FUNGICIDES This invention relates to the use of certain aminothiophene compounds for combating phytopathogenic diseases of plants and harvested food crops, to fungicidal compositions containing these compounds, processes for preparing these compounds and to some of the compounds themselves.

It is known from US 3,989, 505 to use certain 2-aminothiophenes as ripeners for sugarcane and from US 5,422, 335 to use other 2-aminothiophenes as herbicide antidotes.

Other 2-aminothiophenes are disclosed as being useful for controlling pests on domestic animals and livestock (see, for example, WO 01/36415, WO 01/40223 and WO 01/46165). It is known from EP 0,253, 259 that certain N- (3-cyano-2-thienyl) carbamates are active against phytopathogenic fungi. In EP 0,737, 682 various (hetero) aryl thiophene carboxamide derivatives were shown to be useful for protecting plants from fungal attack. Pyridine thiophene carboxamide derivatives are disclosed in DE 100,63, 868 as being useful in the control of microorganisms, for example fungi, and insects. In the J.

Indian Chem. Soc., vol. LV, August 1978,822-825, various 2-amino 4,5, 6, 7-tetrahydro- benzo [b] thiophenes are reported as being evaluated for their pharmacological, antibacterial, antifungal and antitubercular activities. In the Archiv der Pharmazie (Wei7heim, Germany2, vol. 312, no. 9,1979, 726-33, 2-aminothiophene derivatives are reported to have been evaluated as a pesticide. In the J. Agric. Food Chem., vol. 51, no. 2, 2003,362-368, a thienyl thiobenzamide was evaluated for its fungistatic activity against phytopathogenic fungi.

Surprisingly it was found that the following 2-aminothiophene derivatives are especially potent in combating phytopathogenic diseases of plants and harvested food crops.

According to the present invention, there is provided a method of combating phytopathogenic diseases on plants and harvested food crops which comprises applying to a plant, to the seed of a plant, to the locus of the plant or seed or to a harvested food crop a fungicidally effective amount of a compound of the general formula (1) :

wherein: R1 and R2 are independently H, halo, C1-8 alkyl, C3-6 cycloalkyl, hydroxy(C1-8) alkyl, Cl 4 alkoxy (C1-8) alkyl, C1-4 alkoxycarbonyl (C1-8) alkyl, Ci. s alkoxy, C1-8 alkylcarbonyl, C1-8 alkoxycarbonyl, di (CI 4) alkylaminocarbonyl, cyano, nitro, amino, aryl, aryloxy or heterocyclyl, or Rl and R2 join together to form a C3-6 alkylene or C3-6 alkenylene group in which one of the carbon atoms is optionally replaced by an oxygen or nitrogen atom and in which two non-adjacent carbon atoms or a non-adjacent carbon atom and nitrogen atom are optionally further linked by a 1-3 alkylene or Cl 3 alkenylene group, or any two adjacent carbon atoms of the C3-6 alkylene or C3-6 alkenylene group are optionally further joined by another C3-6 alkylene or C3-6 alkenylene group, any of the carbon atoms of the C3-6 alkylene, C3-6 alkenylene, C1-3 alkylene or C1-3 alkenylene groups being optionally substituted with one, two or three substituents selected independently from halo, C1-6 alkyl, C1-6 alkoxy, cyano, nitro, C1-6 alkylenedioxy or aryl, and where a nitrogen atom replaces a carbon atom on the first C3-6 alkylene or C3-6 alkenylene group joining together the R1 and R2 group and is not linked to a non-adjacent carbon atom with a C1-3 alkylene or C1-3 alkenylene group, the nitrogen atom is optionally substituted with C1-3 alkyl, halo (Ci-8) alkyl, 2-8 alkenyl, 2-8 alkynyl, C1-8 alkoxycarbonyl, aryl or aryl (Cl-4) alkyl- aminocarbonyl, or R1 and R2 join together to form an optionally substituted fused aromatic ring; R3 is H, halo, cyano, nitro, C1-6 alkyl, halo (Cl-6) alkyl, 2-6 alkenyl, 2-6 alkynyl, aryl- (C2-4) alkenyl, aryl (C2-4) alkynyl, aryl, arylcarbonyl, heteroarylcarbonyl, C1-6 alkylcarbonyl, halo (C1-6)alkylcarbonyl, C1-6 alkoxycarbonyl, carboxy,-CONR4R5 where R4 and Rs are <BR> <BR> <BR> independently H, Cl alkyl, halo (Cl-4) alkyl or phenyl (Cl-4) alkyl, -S (O) nR4 where n is 0,1 or 2 and R4 has the meaning already given or-P (O) m (OR4) 2 where m is 0 or 1 and R4 has the meaning already given; X is O, S or NR6 where R6 is H or Cl 4 alkyl ;

Y is H, C1-8 alkyl, halo (Ci-s) alkyl, hydroxy (Cl-4) alkyl, mercapto (C1-4) alkyl, hydroxyhalo- (Cl-4) alkyl, C1-4 alkoxy(C1-4)alkyl, C1-4 alkylthio(C1-4) alkyl, C1-4 alkoxyhalo (C1-4)alkyl, C1-4 alkoxycarbonyl(C1-4) alkyl, arylhalo (C1-8) alkyl, C1-8 alkylthio, halo (CI-8) alkylthio, C3-6 cycloalkyl (Cl 4) alkyl (especially C3-6 cycloalkylmethyl), cyano (C1-4) alkyl, aryl (C1-4)- alkyl (especially arylmethyl), C1-6 alkenyloxy (C1-4) alkyl, C1-6 alkenylthio (Cl 4) alkyl, C4-6 cycloalkyl, heterocyclyl (Cl 4) alkyl (especially heterocyclylmethyl), heterocyclylthio (C1-4)- alkyl (especially heterocyclylthiomethyl), carboxy (C1-4)alkylthio(C1-4)alkyl, C1-4 alkoxy- carbonyl(C1-4) alkylthio (Cl 4) alkyl, N,N-di(C1-6) alkylaminothiocarbonylthio (Cl 4) alkyl, -(CH2)pCR7=CR8R9 where R7 is H, halo, C1-6 alkyl, C1-4 alkylcarbonyl, C1-4 alkoxy- carbonyl, cyano or nitro, R8 and R9 are independently H, halo, C16 alkyl, 2-6 alkenyl, N,N-di(C1-6) alkylamino, aryl or heteroaryl, and p is 0,1 or 2 (especially 0), -OCHR10C#CR11 or -SCHR10C#CR11 where Rl° and Rll are independently H, tri (C1-4)- alkylsilyl, C1-6 alkyl or aryl,-C=CRl2 where R12 is H, tri (C1-4)alkylsilyl, C1-6 alkyl or aryl, where R13 is H, halo, C14 alkyl or aryl, R14 is H, halo or C14 alkyl and Rls is H, halo or C1-4 alkyl, or-CHRl6S-S (O) qR17 where q is 0,1 or 2, R16 is H or Cl4 alkyl, Rl7 is H or Cl 4 alkyl or, where q is 3, R17 may also be a cation; and Z is H, C1-6 alkyl, C1-4 alkoxy(C1-4)alkyl, C1-4 alkylcarbonyl, halo (Cl-4) alkylcarbonyl, C1-4 alkoxycarbonyl or halo (Cl 4) alkoxycarbonyl; any of the foregoing aryl, heteroaryl or heterocyclyl groups being optionally substituted.

Except where otherwise stated, alkyl groups and alkyl moieties of alkoxy, alkylthio, etc. , suitably contain from 1 to 8, typically from 1 to 6, for example 1 to 4, carbon atoms in the form of straight or branched chains. Examples are methyl, ethyl, fa- and iso-propyl and rz-, sec-, iso-and tert-butyl, n-pentyl and n-hexyl.

Similarly, alkenyl and alkynyl moieties suitably contain from 2 to 8, typically from 2 to 6, for example 2 to 4, carbon atoms in the form of straight or branched chains.

Examples are ethenyl, allyl, ethynyl, propargyl, butynyl and pentynyl.

Halo includes fluoro, chloro, bromo and iodo. Most commonly it is fluoro, chloro or bromo and usually fluoro or chloro. Haloalkyl groups and moieties may be mono-or polyhalogenated. A typical haloalkyl group is chloromethyl or trifluoromethyl.

Aryl is usually phenyl but also includes naphthyl, anthryl and phenanthryl.

Heterocyclyl includes aromatic heterocyclic groups, referred to as heteroaryl groups, and non-aromatic heterocyclic groups. Typically they are 5-or 6-membered aromatic or non-aromatic rings containing one or more 0, N or S heteroatoms which may be fused to one or more other aromatic or heteroaromatic or other heterocyclic rings, such as a benzene ring. Examples are thienyl, furyl, pyrrolyl, isoxazolyl, oxazolyl, thiazolyl, oxadiazolyl, pyrazolyl, imidazolyl, triazolyl, isothiazolyl, tetrazolyl, thiadiazolyl, pyridyl, pyrimidinyl, pyrazinyl, pyridazinyl, triazinyl, benzofuryl, benzothienyl, dibenzofuryl, benzothiazolyl, benzoxazolyl, benzimidazolyl, indolyl, quinolinyl, quinoxalinyl, thiazolo- pyridyl, dihydropyrindyl, pyrazolopyrimidinyl, thienopyrimidinyl, isothiazolopyrimidinyl, pyrrolidinyl, tetrahydroquinolinyl, quinazolinyl, azepinyl, azepanyl, succinimido, piperidino, morpholinyl, thio-morpholinyl and morpholino groups and, where appropriate, N-oxides (especially pyridine-N-oxide) and salts thereof. Other examples include fully and partially hydrogenated thienyl, furyl, pyrrolyl, thiazolyl, oxazolyl, oxazinyl, thiazinyl, pyridinyl and azepinyl.

Any of the aryl, heteroaryl or heterocyclyl values may be optionally substituted.

Except where otherwise stated, substituents which may be present include one or more of the following: halo, hydroxy, mercapto, C18 alkyl (especially methyl and ethyl), 2-6 alkenyl (especially allyl), 2-6 alkynyl (especially propargyl), Cl 6 alkoxy (especially methoxy), 2-6 alkenyloxy (especially allyloxy), 2-6 alkynyloxy (especially propargyl- oxy), halo (Ci-s) alkyl (especially trifluoromethyl), halo (Cl-6) alkoxy (especially trifluoro- methoxy), Ci-6 alkylthio (especially methylthio and ethylthio), 2-6 alkenylthio (especially allylthio), 2-6 alkynylthio (especially propargylthio), hydroxy (Ci-6) alkyl, C14 alkoxy- (Cl 4) alkyl, Cl 4alkoxy (Cl 4) alkoxy, C3-6 cycloalkyl (especially cyclohexyl), C3-6 cyclo- alkyl (Cl alkyl, optionally substituted aryl (especially optionally substituted phenyl), optionally substituted heterocyclyl (especially optionally substituted thienyl, furyl, pyridyl or pyrimidinyl), optionally substituted aryloxy (especially optionally substituted phenoxy), optionally substituted heterocyclyloxy (especially optionally substituted

pyridyloxy or pyrimidinyloxy), optionally substituted arylthio (especially optionally substituted phenylthio), optionally substituted heterocyclylthio (especially optionally substituted pyridylthio or pyrimidinylthio), optionally substituted aryl (CI-4) alkyl (especially optionally substituted benzyl, phenethyl or phenyl n-propyl), optionally substituted heterocyclyl (Cl-4) alkyl (especially optionally substituted furfuryl, tetrahydrofurfuryl, pyridyl (C1_4) alkyl or pyrimidinyl (Cl 4) alkyl), optionally substituted aryl (C2-4) alkenyl (especially optionally substituted phenylethenyl), optionally substituted heterocyclyl (C2-4) alkenyl (especially optionally substituted pyridylethenyl or pyrimidinyl- ethenyl), optionally substituted aryl (Cl-4) alkoxy (especially optionally substituted benzyloxy and phenethyloxy), optionally substituted heterocyclyl (Cl-4) alkoxy (especially optionally substituted pyridyl (CI-4) alkoxy or pyrimidinyl (Cl 4) alkoxy), optionally substituted aryloxy (C1-4) alkyl (especially optionally substituted phenoxymethyl), optionally substituted heterocyclyloxy (Cl-4) alkyl (especially optionally substituted pyridyloxy (Cl-4) alkyl or pyrimidinyloxy (Cl 4) alkyl), optionally substituted aryl-(C1-4)- alkylthio (especially optionally substituted benzylthio and phenethylthio), optionally substituted heterocyclyl (C1-4) alkylthio (especially optionally substituted pyridyl (C1-4)- alkylthio or pyrimidinyl (Cl-4) alkylthio), optionally substituted arylthio (CI-4) alkyl (especially optionally substituted phenylthiomethyl), optionally substituted heterocyclyl- thio (CI 4) alkyl (especially optionally substituted pyridylthio (C1-4) alkyl or pyrimidinylthio- (Cl-4) alkyl), optionally substituted arylamino (Ci-4) alkyl (especially optionally substituted anilinomethyl), optionally substituted heterocyclylamino (Cl 4) alkyl (especially optionally substituted pyridylamino (Cl 4) alkyl or pyrimidinylamino (Cl 4) alkyl), acyloxy, including Ci. 4 alkanoyloxy (especially acetyloxy) and benzoyloxy, cyano, isocyano, thiocyanato, isothiocyanato, nitro, NR'R", -NHCOR', -NHCONR'R", -CONR'R", -COOR', -SO2R, -SO2NR'COR",-OSO2R',-COR',-CR'=NR"or-N=CR'R"in which R'and R"are independently hydrogen, Cl4 alkyl, halo (Cl 4) alkyl, C1-4 alkoxy, halo (Cl 4) alkoxy, C1-4 alkylthio, C3-6 cycloalkyl, C3-6 cycloalkyl (Cl 4) alkyl, phenyl or benzyl, any of the afore mentioned aryl, heterocyclyl, phenyl or benzyl groups being optionally substituted with halogen, hydroxy, Cl 4 alkyl or Cl alkoxy. Preferably the aryl, heteroaryl or heterocyclyl moieties may be substituted with one or more of the following: halo, hydroxy, mercapto, C1-8 alkyl (especially methyl and ethyl), 2-6 alkenyl (especially allyl), 2-6 alkynyl

(especially propargyl), C16 alkoxy (especially methoxy), 2-6 alkenyloxy (especially allyloxy), 2-6 alkynyloxy (especially propargyloxy), halo (Cl-8) alkyl (especially trifluoromethyl), halo (Ci-6) alkoxy (especially trifluoromethoxy), C1-6 alkylthio (especially methylthio and ethylthio), 2-6 alkenylthio (especially allylthio), 2-6 alkynylthio (especially propargylthio), hydroxy (Cl 6) alkyl, C14 alkoxy (Cl4) alkyl, C1-4alkoxy- (Ci-4) alkoxy, C3-6 cycloalkyl (especially cyclohexyl), C3-6 cycloalkyl (Ci-4) alkyl, optionally substituted aryl (especially optionally substituted phenyl), optionally substituted heterocyclyl (especially optionally substituted thienyl, furyl, pyridyl or pyrimidinyl), optionally substituted aryl (C1-4) alkyl (especially optionally substituted benzyl, phenethyl or phenyl n-propyl), optionally substituted heterocyclyl (Cl4) alkyl (especially optionally substituted furfuryl, tetrahydrofurfuryl, pyridyl (Cl 4) alkyl or pyrimidinyl (Cl 4) alkyl), optionally substituted arylamino (Cl-4) alkyl (especially optionally substituted anilinomethyl), optionally substituted heterocyclylamino (Cl4) alkyl (especially optionally substituted pyridylamino (C1-4) alkyl or pyrimidinylamino (C1-4)- alkyl), cyano, amino, any of the afore mentioned aryl or heterocyclyl groups being optionally substituted with halogen, hydroxy, C14 alkyl or Cl4 alkoxy.

Typically, when Rl and R2 are not joined to form an alicyclic ring system, they are independently H, halo (for example, chloro and iodo), C18 alkyl (for example, methyl, ethyl, n-propyl, n-butyl, iso-butyl, tert-butyl and iso-amyl, n-pentyl and 1, 1-dimethyl- propyl), C3-6 cycloalkyl (for example, cyclopropyl), hydroxy (Ci-s) alkyl (for example, hydroxymethyl), C1-4 alkoxy (C1-8) alkyl (for example, methoxymethyl), Cl4 alkoxy- carbonyl (Cl-8) alkyl (for example, methoxycarbonylmethyl), C1-8 alkoxy (for example, methoxy), C1_8 alkylcarbonyl (for example acetyl), C1-8 alkoxycarbonyl (for example, methoxycarbonyl and ethoxycarbonyl), di (Cl-) alkylaminocarbonyl (for example, diethyl- aminocarbonyl), cyano, nitro, amino, aryl (for example, phenyl, 4-chlorophenyl, 4- methoxyphenyl and 2-fluoro-4-chloro-5-methoxyphenyl), aryloxy (for example, phenoxy) or heterocyclyl (for example, 2-thienyl and morpholino).

However, of particular interest are compounds where R1 and R2 are joined to fonn a C3-6 alkylene or C3-6 alkenylene group in which one of the carbon atoms is optionally replaced by an oxygen or nitrogen atom and in which two non-adjacent carbon atoms or a non-adjacent carbon atom and nitrogen atom are optionally further linked by a C1-3

alkylene or C1-3 alkenylene group (for example, a butylen group in which the first and fourth carbon atom are linked by a methylene group, a pentylene group in which the second and fifth carbon atom are linked by a methylene group or an aminopropylene group in which the nitrogen atom is linked to the third propylene carbon atom by an ethylene group), or any two adjacent carbon atoms of the C3-6 alkylene or C3-6 alkenylene group are optionally further joined by another C3-6 alkylene or C3-6 alkenylene group, any of the carbon atoms of the C3-6 alkylene, C3-6 alkenylene, C1-3 alkylene or C1-3 alkenylene groups being optionally substituted with one, two or three substituents selected independently from halo, C16 alkyl (for example, methyl, ethyl and tert-butyl), Cri-6 alkoxy, cyano, nitro, Ci-6 alkylenedioxy (for example, ethylenedioxy) or aryl (for example, phenyl), and where a nitrogen atom replaces a carbon atom on the first C3-6 alkylene or C3-6 alkenylene group joining together the R1 and R2 group and is not linked to a non-adjacent carbon atom with a C1-3 alkylene or C1-3 alkenylene group, the nitrogen atom is optionally substituted with C1-8 alkyl, halo (Cl-8) alkyl (for example, trifluoroethyl), C2-8 alkenyl (for example, allyl), C2-8 alkynyl (for example, propargyl), C18 alkoxycarbonyl (for example, tert-butoxycarbonyl), aryl or aryl (Cl4) alkyl- aminocarbonyl (for example, benzylaminocarbonyl). Examples of groups that R1 and R2 join to form are trimethylene, tetramethylene, 1-methyltetramethylene, 2-methyltetra- methylene, 2-ethyltetramethylene, 2-tert-butyltetramethylene, 2-phenyltetramethylene, 1-methyl-3, 3-dimethyltetramethylene, 1,1-dimethyl-3, 3-dimethyltetramethylene, 1,2- tetramethylenetetramethylene, pentamethylene, hexamethylene, methyleneoxyethylene and N-tert-butoxycarbonylmethylene-aminoethylene.

When Rl and R2 join together to form an optionally substituted fused aromatic ring, the fused ring is typically a fused benzene ring but may be a fused naphthyl or other fused aromatic ring. Optional substituents include those listed above as suitable substituents for aryl, heteroaryl and heterocyclyl values.

Typically R3 is H, halo (for example, bromo and iodo), cyano, nitro, C1-6 alkyl, halo (Ci-6) alkyl, 2-6 alkenyl (for example ethenyl), 2-6 alkynyl (for example, ethynyl and pent-1-ynyl), aryl (C2-4) alkenyl, aryl (C2-4) alkynyl (for example, 2-phenylethynyl), aryl, especially phenyl optionally substituted with halo, C14 alkyl, halo (C1-4) alkyl or C1-4 alkoxy (for example, phenyl, 4-chlorophenyl, 2,4-dichlorophenyl, 4-methylphenyl, 3-

trifluoromethylphenyl, 4-trifluoromethylphenyl, 2-methoxy-5-fluorophenyl and 2,4- dimethoxyphenyl), arylcarbonyl, especially benzoyl in which the phenyl ring is optionally substituted with halo, particularly fluoro or chloro, or Cl4 alkoxy (for example, 4- chlorobenzoyl, 3-fluorobenzoyl, 4-fluorobenzoyl, 2-fluoro-4-chlorobenzoyl and 4- methoxybenzoyl), heteroarylcarbonyl (for example, 2-thienylcarbonyl), C1-6 alkyl- carbonyl (for example, tert-butylcarbonyl), halo (C1-6) alkylcarbonyl (for example, chloro- acetyl), C16 alkoxycarbonyl (for example, methoxycarbonyl, ethoxycarbonyl and tert- butoxycarbonyl), carboxy,-CONR4R5 where R4 and R 5 are independently H, C1-4 alkyl, halo (Cl-4) alkyl or phenyl (C1-4) alkyl (for example, aminocarbonyl and benzylamino- carbonyl), -S (O),, nR4 where n is 0,1 or 2 and R4 has the meaning already given (e. g. methylsulfone) or-P (O) m (OR4) 2 where m is 0 or 1 and R4 has the meaning already given (e. g. dimethylphosphate). Of particular interest as values of R3 are cyano, C14 alkoxy- carbonyl, benzoyl in which the phenyl ring is optionally substituted with halo, heteroaryl- carbonyl in which the heteroaryl is optionally substituted with one or more halo. Of more particular interest as values of R3 are cyano or benzoyl in which the phenyl ring is optionally substituted with one or more halo.

Typically X is O, S or NH, normally O.

Z is usually H but other values include C1-4 alkyl (for example, methyl), C14 alkoxy (Cl 4) alkyl (for example, methoxymethyl), C14 alkylcarbonyl (for example, acetyl) halo (Cl4) alkylcarbonyl (for example, chloroacetyl) and C1-4 alkoxycarbonyl (for example, tert-butoxycarbonyl).

Y is typically H, C1-8 alkyl (for example, methyl, ethyl, n-propyl, iso-propyl and 3-n-pentyl), halo (Ci-8) alkyl (for example, chloromethyl, bromomethyl, iodomethyl, 1- chloroethyl, 2-chloroethyl, 1-bromoethyl, 2-bromoethyl, dichloromethyl, 1,2-dichloro- ethyl, 1,2-dibromoethyl, 1-chloro-n-propyl, 3-chloro-n-propyl, 1-bromo-n-propyl, 1,3- dibromoprop-1-yl, 2,3-dibromoprop-2-yl, 1, 3-dichloro-2-methyl-prop-2-yl, chloro-tert- butyl, trifluoromethyl, trichloromethyl, tribromomethyl, 1,1, 2, 2-tetrafluoroethyl, 1, 1, 1, 3,3, 3-hexafluoroprop-2-yl and heptafluoropropyl), hydroxy (Ci-4) alkyl (for example, hydroxymethyl), mercapto (Cl 4) alkyl (for example, mercaptomethyl), hydroxyhalo- (Cl 4) alkyl (for example, l-hydroxy-tetrafluoroethyl), Cl4 alkoxy (Cl 4) alkyl, C14 alkyl- thio (Cl4) alkyl, Cl4 alkoxyhalo (Ci-4) alkyl (for example, 1-methoxy-1, 2,2, 2-tetrafluoro-

ethyl), Cl4 alkoxycarbonyl (Cl-4) alkyl (e. g. 2-ethoxycarbonylethyl), arylhalo (CI-8) alkyl (e. g. phenylchloromethyl), C1-8 alkylthio (for example, ethylthio), halo (CI-8) alkylthio, C3-6 cycloalkyl (C1-4) alkyl especially C3-6 cycloalkylmethyl, cyano (Cl-4) alkyl (for example cyanomethyl), aryl (C1-4) alkyl especially arylmethyl (for example, benzyl), C1-6 alkenyl- oxy (Cl-4) alkyl, C1-6 alkenylthio (C1-4) alkyl (e. g. allylthiomethyl), C4-6 cycloalkyl (e. g. cyclopentyl), adamantyl, heterocyclyl (C1-4) alkyl (for example, 4-methylpiperidinoethyl, 4-methyl-piperazin-1-ylethyl, morpholinoethyl and 2,6-dimethylmorpholinoethyl), especially heterocyclylmethyl (for example, 3-phenyl-isoxazol-5-ylmethyl) and particularly N-linked heterocyclylmethyl (for example, 1-tetrazolylmethyl, 2-tetrazolyl- methyl, 5- (4-methoxyphenyl)-tetrazol-2-ylmethyl, 2,6-dimethylmorpholinomethyl, succinimidomethyl, 1,2, 4-triazol-1-ylmethyl, 5-phenyltetrazol-1-ylmethyl, 5-phenyl- tetrazol-2-ylmethyl, 4-methylpiperidinomethyl, 4-methylpiperazin-1-ylmethyl, phthalimidomethyl, azepanylmethyl and 3-tert-butyl-hydantoin-1-ylmethyl), heterocyclylthio (Cl4) alkyl especially heterocyclylthiomethyl (for example, 5-thien-2-yl- 1,3, 4-oxadiazol-2-ylthiomethyl, 5-benzyl-1,3, 4-oxadiazol-2-ylthiomethyl, 5-phenyl-1,3, 4- oxadiazol-2-ylthiomethyl, 5- (4-hydroxyphenyl)-1, 3, 4-oxadiazol-2-ylthiomethyl, 5- (4- methoxyphenyl) -1,3, 4-oxadiazol-2-ylthiomethyl, 4-methyl-5-iso-propyl-1, 2,4-triazol-3- ylthiomethyl, 5-benzyl-4-methyl-1, 2,4-triazol-3-ylthiomethyl, 5-benzyl-4-ethyl-1, 2,4- triazol-3-ylthiomethyl, 5-benzyl-4-phenyl-1, 2,4-triazol-3-ylthiomethyl, 5-methyl-4- phenyl-1,2, 4-triazol-3-ylthiomethyl, 4-ethyl-5-phenyl-1,2, 4-triazol-3-ylthiomethyl, 3- (2- chlorophenyl)-1H-1, 2,4-triazol-5-ylthiomethyl, 5- (2-bromophenyl)-4-methyl-1, 2,4- triazol-3-ylthiomethyl, 5-(4-chlorophenyl)-4-ethyl-1, 2, 4-triazol-3-ylthiomethyl, 5-(4- chloroanilinomethyl)-4-methyl-1, 2, 4-triazol-3-ylthiomethyl, 4-methyl-5-thien-2-yl-1, 2, 4- triazol-3-ylthiomethyl, 4-ethyl-5-thien-2-yl-1,2, 4-triazol-3-ylthiomethyl, 4-cyclohexyl-5- methyl-1,2, 4-triazol-3-ylthiomethyl, 5-benzyl-4-cyclohexyl-1, 2,4-triazol-3-ylthiomethyl, 4-ethyl-5-pyrid-4-yl-1, 2,4-triazol-3-ylthiomethyl, 4-pyrid-3-yl-1,2, 4-triazol-3- ylthiomethyl, 3-pyrid-3-yl-lH-1, 2,4-triazol-5-ylthiomethyl, 3-(m-tolyl)-lH-1, 2,4-triazol- 5-ylthiomethyl, 5-(2-methoxyphenyl)-4-methyl-1, 2,4-triazol-3-ylthiomethyl, 4-ethyl-5- (4- methoxyphenyl)-1, 2,4-triazol-3-ylthiomethyl, 5- (4-methoxyphenyl)-4-phenyl-1, 2,4- triazol-3-ylthiomethyl, 5- (4-hydroxyphenyl)-4-phenyl-1, 2,4-triazol-3-ylthiomethyl, 3- (2- hydroxyphenyl)-1H-1, 2,4-triazol-5-ylthiomethyl, 1-methyl-imidazol-2-ylthiomethyl, 5-

(4-chlorophenyl)-lH-imidazol-2-ylthiomethyl, 5-(4-fluorophenyl)-1-methyl-imidazol-2- ylthiomethyl, 5-phenyl-1-tetrahydrofurfuryl-imidazol-2-ylthiomethyl, 5-chloro-lH-benz- imidazol-2-ylthiomethyl, thiazol-2-ylthiomethyl, 5-trifluoromethyl-pyrid-2-ylthiomethyl, 3-cyano-6-methylpyrid-2-ylthiomethyl, 3-cyano-4, 6-dimethylpyrid-2-ylthiomethyl, 5- methyl-6-ethyl-3-cyanopyrid-2-ylthiomethyl, 3-cyano-4,5, 6-trimethylpyrid-2-ylthio- methyl, 3-cyano-6-thien-2-yl-pyrid-2-ylthiomethyl, 3-cyano-6-methyl-4-thien-2-yl-pyrid- 2-ylthiomethyl, 6-amino-3, 5-dicyano-pyrid-2-ylthiomethyl, 6-amino-3, 5-dicyano-4- phenyl-pyrid-2-ylthiomethyl, 3-cyano-6-ethyl-5-methyl-pyrid-2-ylthiomethyl, 1-oxy- pyrid-2-ylthiomethyl, thiazolo [4,5-b] pyrid-2-ylthiomethyl, 3-cyano-6, 7-dihydro-5H- [1] pyrind-2-ylthiomethyl, pyrimidin-2-ylthiomethyl, 4-methyl-pyrimidin-2-yltliiomethyl, 4, 6-dimethyl-pyrimidin-2-ylthiomethyl, 4-trifluoromethyl-pyrimidin-2-ylthiomethyl, 6- (2,2, 2-trifluoroethoxy-pyrimidin-4-ylthiomethyl, 4, 6-diamino-pyrimidin-2-ylthiomethyl, <BR> <BR> <BR> <BR> 4-amino-5-cyano-pyrimidin-2-ylthiomethyl, 2-amino-5-cyano-6-methylthiopyrimidin-4- ylthiomethyl, 1-phenyl-pyrazolo [3, 4-d] pyrimidin-4-ylthiomethyl, 5,6-dimethyl- thieno [2, 3-d] pyrimidin-4-ylthiomethyl, 3- (4-fluorophenyl)-isothiazolo [4,5-d] pyrimidin- 7-ylthiomethyl, 3,5-dihydroxy-1, 2, 4-triazin-6-ylthiomethyl, 5,6-di (2-furyl)-1, 2,4-triazin- 3-ylthiomethyl, 4,5-diphenyl-oxazol-2-ylthiomethyl, benzoxazol-2-ylthiomethyl, 6- methoxy-2-methyl-quinolin-4-ylthiomethyl, 3-cyano-7-methyl-quinolin-2-ylthiomethyl, 3-cyano-8-methyl-quinolin-2-ylthiomethyl, 3-cyano-5,6, 7,8-tetrahydroquinolin-2-ylthio- methyl, 3-methyl-quinazolin-4-on-2-ylthiomethyl, 3-furfuryl-quinazolin-4-on-2- ylthiomethyl, 5-phenoxymethyl-4-ethyl-1, 2,4-triazol-3-ylthiomethyl, 5-methyl-1, 3,4- thiadiazol-2-ylthiomethyl, 5-propargylthio-1, 3, 4-thiadiazol-2-ylthiomethyl and 6,7- dihydro-5H-cyclopenta [4,5] thieno [2,3-d] pyrimidin-4-ylthiomethyl), carboxy (C1-4)- alkylthio (Cl-) alkyl especially carboxymethylthiomethyl, alkoxycarbonyl (C1-4)- alkylthio (Cl-) alkyl especially ethoxycarbonylmethylthiomethyl, N,N-di(C1-6) alkyl- aminothiocarbonylthio (CI-4) alkyl especially N,N-diethylaminothiocarbonylthiomethyl, -(CH2)pCR7=CR8R9 where p is 0,1 or 2 (especially 0), R7 is H, halo, C1-6 alkyl, C1-4 alkylcarbonyl, C1-4 alkoxycarbonyl, cyano or nitro and R8 and R9 are independently H, halo, C1-6 alkyl, C2-6 alkenyl, N,N-di(C1-6)alkylamino, aryl or heteroaryl (for example, ethenyl, 1-chloroethenyl, 2-chloroethenyl, trichloroethenyl, 1-bromoethenyl, propenyl, propen-2-yl, penta-1, 3-dienyl, 2-methylpropenyl, but-3-enyl, 2- (2-furyl) ethenyl, 2-

dimethylamino-1-methoxycarbonylethenyl, 2-dimethylamino-1-ethoxycarbonylethenyl, 1-methoxycarbonyl-2-phenylethen-1-yl, 2- (4-fluorophenyl)-1-ethoxycarbonylethenyl and 1-cyano-2-(4-methoxyphenyl)ethenyl), -OCHR10C#CR11 or -SCHR10C#CR11 where Rlo and Rll are independently H, tri (Cl4) alkylsilyl, C16 alkyl or aryl (for example propargyloxy, but-2-ynyloxy, but-3-yn-2-yloxy, 1-methylpropargyloxy, 3-phenyl- propargyloxy, 1-phenylpropargyloxy, 3-trimethylsilylpropargyloxy, pent-2-ynyloxy, hex- 2-ynyloxy, hex-3-yn-2-yloxy, 4-methylpentyn-3-yloxy, 1-methylpent-2-ynyloxy, 5- methylhex-l-yn-3-yloxy and 2-methylhex-5-yn-2-yloxy),-C-CR12 where R12 is H, CI-6 alkyl, trialkylsilyl or aryl (for example, ethynyl, prop-1-ynyl, trimethylsilylethynyl and 2,5-dichlorophenylethynyl), where R13 is H, halo (for example, Br), C14 alkyl or aryl, R14 is H, halo (for example, Br) or Cl4 alkyl and Rls is H, halo or Cl4 alkyl (for example, cyclopropyl, 1-methyl-2, 2- dibromocyclopropyl and 2-phenylcyclopropyl), or-CHRl6S-S (O) qRl7 where q is 0,1 or 2, R16 is H or C1-4 alkyl, R17 is H or C1-4 alkyl or, where q is 3, R17 may also be a cation (e. g. sulfothiomethyl).

The method of this aspect of the invention is particularly useful for controlling Botrytis pathogens, especially Botrytis cinerea (grey mould), and Septoria pathogens, especially Septoria tritici (leaf blotch), on various host plants and harvested crops.

In one aspect the invention provides a method of combating phytopathogenic diseases on plants and harvested food crops, which comprises applying to a plant, to the seed of a plant, to the locus of the plant or seed or to a harvested food crop a fungicidally effective amount of a compound of the general formula (1) wherein: Rl and R2 are independently H, C1-6 alkyl or C3-6 cycloalkyl, or Rl and R2 join together to form a C3-6 alkylene group in which one of the carbon atoms is optionally replaced by an oxygen atom and in which two non-adjacent carbon atoms are optionally further linked by a C1-3 alkylene group, or any two adjacent carbon atoms of the C3-6 alkylene group are optionally further joined by another C3-6 alkylene group, any of the carbon atoms of the C3-6 alkylene or 1-3 alkylene groups being optionally

substituted with one or two Cl-6 alkyl groups, or Rl and R2 join together to form an optionally substituted fused aromatic ring.

In another aspect the invention provides a method of combating phytopathogenic diseases on plants and harvested food crops, which comprises applying to a plant, to the seed of a plant, to the locus of the plant or seed or to a harvested food crop a fungicidally effective amount of a compound of the general formula (1) wherein: Rl and R2 are independently H or Cl-4 alkyl, or Rl and R2 join together to form a C3-6 alkylene group in which one of the carbon atoms is optionally replaced by an oxygen, any of the carbon atoms of the C3-6 alkylene group being optionally substituted with one or two C1_6 alkyl groups, or Rl and R2 join together to form an optionally substituted fused aromatic ring.

In yet another aspect the invention provides a method of combating phytopatho- genic diseases on plants and harvested food crops, which comprises applying to a plant, to the seed of a plant, to the locus of the plant or seed or to a harvested food crop a fungicidally effective amount of a compound of the general formula (1) wherein R3 is cyano, Cl4 alkoxycarbonyl, benzoyl in which the phenyl ring is optionally substituted with one or more halo, or heteroarylcarbonyl in which the heteroaryl is optionally substituted with one or more halo; preferably R3 is cyano or benzoyl in which the phenyl ring is optionally substituted with one or more halo.

In a further aspect the invention provides a method of combating phytopathogenic diseases on plants and harvested food crops, which comprises applying to a plant, to the seed of a plant, to the locus of the plant or seed or to a harvested food crop a fungicidally effective amount of a compound of the general formula (1) wherein X is O.

In yet a further aspect the invention provides a method of combating phytopatho- genic diseases on plants and harvested food crops, which comprises applying to a plant, to the seed of a plant, to the locus of the plant or seed or to a harvested food crop a fungicidally effective amount of a compound of the general formula (1) wherein Z is H, Cl4 alkylcarbonyl or halo (Cl 4) alkylcarbonyl; most preferably Z is H.

In another aspect the invention provides a method of combating phytopathogenic diseases on plants and harvested food crops, which comprises applying to a plant, to the seed of a plant, to the locus of the plant or seed or to a harvested food crop a fungicidally

effective amount of a compound of the general formula (1) wherein Y is C1-6 alkyl, halo (C1-6)alkyl, C1-6 alkylthio, C1-6 alkenylthiomethyl, C3-6 cycloalkyl, heterocyclylmethyl, heterocyclylthiomethyl, carboxymethylthiomethyl, Cl4 alkoxy- carbonylmethylthiomethyl, N,N-di(C1-6) alkylaminothiocarbonylthiomethyl, -(CH2) pCR7=CR8R9 where R7 is H, halo or Cl4 alkyl, R8 and R9 are independently H or Cl4 alkyl and p is 0, -OCHR10C#CR11 where R10 and R11 are independently H, tri (C1-4)- alkylsilyl, C1-4 alkyl or phenyl, or-C--CRl2 where Rl2 is H, tri (Cl4) alkylsilyl or phenyl optionally substituted with one or more halo ; preferably Y is halo (Ci-4) alkyl, C1-6 alkenyl- thiomethyl, C3-6 cycloalkyl, tetrazolylmethyl optionally substituted with aryl, heterocyclylthiomethyl, C1-4 alkoxycarbonylmethylthiomethyl, N,N-di(C1-6)alkylamino- thiocarbonylthiomethyl,-(CH2) pCR7=CR8R9 where R7 is halo, R8 and R9 are H and p is 0, -OCHRl°C_CRl l where Rl° and Rl l are independently H or C1-4 alkyl, or-C-CRI2 where R12 is H.

Most preferably Y is halo (Cl4) alkyl, especially chloromethyl.

Even more preferably Y is-OCHRl°C-CRll where Rl° and R'1 are independently H or Cl4 alkyl.

The method of this aspect of the invention is particularly useful for controlling Botrytis pathogens, especially Botrytis cinerea (grey mould), and Septoria pathogens, especially Septoria tritici (leaf blotch), on various host plants and harvested crops.

In another aspect the invention provides a method of combating phytopathogenic diseases on plants and harvested food crops, which comprises applying to a plant, to the seed of a plant, to the locus of the plant or seed or to a harvested food crop a fungicidally effective amount of a compound of the general formula (1) wherein: Rl and R2 are independently H, halo, C1-8 alkyl, C3-6 cycloalkyl, hydroxy(C1-8)alkyl, C1-4 alkoxy (C1-8) alkyl, C1-4 alkoxycarbonyl (C1-8)alkyl, C1-8 alkoxy, C1-8 alkylcarbonyl, C1-8 alkoxycarbonyl, di (C1-4) alkylaminocarbonyl, cyano, nitro, amino, aryl, aryloxy or heterocyclyl, or Rl and R2 join together to form a C3-6 alkylene group in which one of the carbon atoms is optionally replaced by an oxygen or nitrogen atom and in which two non-adjacent carbon atoms or a non-adjacent carbon atom and nitrogen atom are optionally further linked by a C1-3 alkylene bridge, any of the carbon atoms of the C3-6 alkylene group being optionally

substituted with halo, a Cl4 alkyl group, a Cl4 alkylenedioxy group or an aryl group, or any two adjacent carbon atoms of the C3-6 alkylene group being further joined by another C3-6 alkylene group, and where a nitrogen atom replaces a carbon atom on the C3-6 alkylene group and is not linked to a non-adjacent carbon atom with a Cl 3 alkylene bridge, the nitrogen atom is optionally substituted with C1-8 alkyl, halo (C1-8)alkyl, C2-8 alkenyl, C2-8 alkynyl, aryl, C1-8 alkoxycarbonyl or aryl (C1-4)alkylaminocarbonyl ; or R1 and R2 join together to form an optionally substituted fused aromatic ring; R3 is H, halo, cyano, nitro, 2-6 alkyl, halo (C1-6)alkyl, C2-6 alkenyl, 2-6 alkynyl, aryl- (C2-4) alkenyl, aryl (C2-4) alkynyl, aryl, arylcarbonyl, aryl (C1-4) alkylaminocarbonyl, heteroarylcarbonyl, Cz4 alkylcarbonyl, Cz4 alkylcarbonyloxy, Cl 4 alkoxycarbonyl, carboxy,-CONR4R5 where R4 and Rs are independently H, C1-4 alkyl or phenyl (C1-4)- alkyl,-S (o) nR4 where n is 0,1 or 2 and R4 has the meaning already given or P (O)m(OR4) 2 where m is 0 or 1 and R4 has the meaning already given; X is O, S or NR6 where R6 is H or Cl4 alkyl ; Y is H, C1-8 alkyl, halo (C1-8)alkyl, hydroxy(C1-4) alkyl, mercapto (C1-4) alkyl, hydroxyhalo- (Cl4) alkyl, C1-4 alkoxy (Cl-4) alkyl, 1-4 alkoxyhalo (Ci-4) alkyl, arylhalo (C1-8)alkyl, C1-8 alkoxy, halo (C1-8) alkoxy, C1_8 alkylthio, C3_6 cycloalkyl (1-4) alkyl (especially C3-6 cycloalkylmethyl), aryl, cyano (Cl4) alkyl, aryl (Ci4) alkyl (especially arylmethyl), aryloxyalkyl (especially aryloxymethyl), arylamino, adamantyl, heterocyclyl, heterocyclyl (Cl-4) alkyl (especially heterocyclylmethyl), heterocyclylthio (C1-4)alkyl (especially heterocyclylthiomethyl), heterocyclylamino, carboxymethylthiomethyl, C1-4 alkylcarbonylthiomethyl, arylaminocarbonylmethylthiomethyl, C1-4 alkylcarbonyl, halo (C1-4) alkylcarbonyl, C1-4 alkoxycarbonyl, halo (Cl 4) alkoxycarbonyl, carboxy, heterocyclylcarbonyl, arylcarbonyloxymethyl, heterocyclylaminocarbonylalkyl in which the alkyl group is optionally substituted with halo, -(CH2)pCR7=CR8R9 where R7 is H, halo, C1-6 alkyl, C1-4 alkylcarbonyl, C1-4 alkoxycarbonyl, cyano or nitro, R and R9 are independently H, halo, 2-6 alkenyl, aryl or heteroaryl, and p is 0,1 or 2 (especially 0), -OCHR10C#CR11 or -SCHR10C#CR11 where R10 and Rll are independently H, C1-6 alkyl or aryl, -C#CR12 where Rl2 is H, tri (C1-4)alkylsilyl, C1-6 alkyl or aryl,

where R13 is H, halo, C14 alkyl or aryl, Rl4 is H, halo or Cl4 alkyl and Rls is H, halo or C1-4 alkyl, or -CHR16S-S(O)qR17 where q is 0,1 or 2, R16 is H or C14 alkyl, Rl7 is H or Cl4 alkyl or, where p is 3, R17 may also be a cation; and Z is H, C1-6 alkyl, C1-4alkoxy(C1-4) alkyl, C1-4 alkylcarbonyl, halo (Cl 4) alkylcarbonyl, Cl4 alkoxycarbonyl, halo (CI-4) alkoxycarbonyl; any of the foregoing aryl, heteroaryl or heterocyclyl groups being optionally substituted.

In yet another aspect the invention provides a method of combating phytopatho- genic diseases on plants and harvested food crops, which comprises applying to a plant, to the seed of a plant, to the locus of the plant or seed or to a harvested food crop a fungicidally effective amount of a compound of the general formula (1) wherein: Rl and R2 are independently H, C1-6 alkyl, C1-4 alkoxycarbonyl, hydroxy (C1-4) alkyl, C1-4 alkoxy (CI 4) alkyl or aryl, or Rl and R2 are join together to form a C3-6 alkylene group in which one of the carbon atoms is optionally replaced by an oxygen or a nitrogen atom and in which any of the carbon atoms is optionally substituted by a C14 alkyl group or any two adjacent carbon atoms are further joined by another C3-6 alkylene group and, where a nitrogen atom replaces a carbon atom, the nitrogen atom is optionally substituted with C14 alkoxycarbonyl; R3 is H, halo, 2-6 alkenyl, 2-6 alkynyl, cyano, C1-4 alkylcarbonyl, halo (C1-4)- alkylcarbonyl, C14 alkoxycarbonyl, aminocarbonyl, phenyl optionally substituted with halo, benzoyl in which the phenyl ring is optionally substituted with halo, thienyl- carbonyl; X is O or NH ; Y is H, C1-6 alkyl, halo (CI-8) alkyl, C1-4 alkoxy, halo (Cl4) alkoxy, Cl4 alkylthio, Cl4 alkylcarbonyl, heterocyclyl (C1-4) alkyl, heterocyclylthiomethyl, the acid or a salt of sulfothiomethyl, carboxymethylthiomethyl,-CR7=R8R9 where R7 is H and R8 and R9 are independently H, halo or C2-6 alkenyl, -OCHR10C#CR11 where R10 and R11 are independently H, C1-6 alkyl or aryl,-C=CR12 where. Rla is H or trialkylsilyl, or

where R13 is H, halo or aryl, R14 is H or halo and Rl5 is H or C1-4 alkyl ; and Z is H or C14 alkylcarbonyl ; any of the foregoing aryl, heteroaryl or heterocyclyl groups being optionally substituted.

In another aspect the invention provides a method of combating phytopathogenic diseases on plants and harvested food crops which comprises applying to a plant, to the seed of a plant, to the locus of the plant or seed or to a harvested food crop a fungicidally effective amount of a compound of the general formula (1) wherein : Rl and R2 are independentlyH, Cl-6 alkyl, C14 alkoxycarbonyl or Cl 4 alkoxy (C1-4) alkyl, or Rl and R2 join together to form a C3-6 alkylene group in which one of the carbon atoms is optionally replaced by an oxygen atom and in which any of the carbon atoms is optionally substituted by a Cl 4 alkyl group or any two adjacent carbon atoms are further joined by another C3-6 alkylene group; R3 is H, cyano, C14 alkylcarbonyl, halo (Ci-4) alkylcarbonyl, C1-4 alkoxycarbonyl, aminocarbonyl, benzoyl in which the phenyl ring is optionally substituted with halo or thienylcarbonyl; X is O ; Y is halo (Cl-8) alkyl, heterocyclylmethyl, heterocyclylthiomethyl, the acid or a salt of sulfothiomethyl,-CR7--R8R9 where R7 is H and R8 and R9 are independently H or halo, -OCHR10C#CR11 where Rl° and Rll are independently H, C1-6 alkyl or aryl, or-C_CRl2 where R12 is H or trialkylsilyl; and Z is H ; any of the foregoing aryl, heteroaryl or heterocyclyl groups being optionally substituted.

The method of this other aspect of the invention is also particularly useful for controlling Botrytis pathogens, especially Botrytis cinerea (grey mould), on various host plants and harvested crops.

The compounds of the formula (1) where Y is -OCHR10C#CR11 where R10 and Rl l are independently H, Cl 6 alkyl or aryl, are novel compounds and also form part of this invention.

Thus, in another aspect, the invention provides a compound of the formula (1) wherein: R1 and R2 are independently H, halo, C1-8 alkyl, C3-6 cycloalkyl, hydroxy(C1-8) alkyl, C1-4 alkoxy (C1-8)alkyl, C1-4 alkoxycarbonyl (Cl-8) alkyl, C1-8 alkoxy, C1-8 alkylcarbonyl, C1-8 alkoxycarbonyl, di (Cl4) alkylaminocarbonyl, cyano, nitro, amino, aryl, aryloxy or heterocyclyl, or Rl and R2 join together to form a C3-6 alkylene or C3-6 alkenylene group in which one of the carbon atoms is optionally replaced by an oxygen or nitrogen atom and in which two non-adjacent carbon atoms or a non-adjacent carbon atom and nitrogen atom are optionally further linked by a Cl 3 alkylene or C1-3 alkenylene group, or any two adjacent carbon atoms of the C3-6 alkylene or C3-6 alkenylene group are optionally further joined by another C3-6 alkylene or C3-6 alkenylene group, any of the carbon atoms of the C3-6 alkylene, C3-6 alkenylene, C1-3 alkylene or 1-3 alkenylene groups being optionally substituted with one, two or three substituents selected independently from halo, CI-6 alkyl, C1-6 alkoxy, cyano, nitro, C1-6 alkylenedioxy or aryl, and where a nitrogen atom replaces a carbon atom on the first C3-6 alkylene or C3-6 alkenylene group joining together the Rl and R2 group and is not linked to a non-adjacent carbon atom with a C1-3 alkylene or C1-3 alkenylene group, the nitrogen atom is optionally substituted with C1-8 alkyl, halo (C1-8) alkyl, 2-8 alkenyl, 2-8 alkynyl, C1-8 alkoxycarbonyl, aryl or aryl (Cl4) alkyl- aminocarbonyl, or Rl and R2 join together to form an optionally substituted fused aromatic ring; R3 is H, halo, cyano, nitro, C1-6 alkyl, halo (C1-6)alkyl, C2-6 alkenyl, 2-6 alkynyl, aryl- (C2-4) alkenyl, aryl (C2-4) alkynyl, aryl, arylcarbonyl, heteroarylcarbonyl, Cl-6 alkylcarbonyl, Cl-6 allcylcarbonyloxy, C16 alkoxycarbonyl, carboxy,-CONR4R5 where R4 and Rus are independently H, C1-4 alkyl, halo (Cl-4) alkyl or phenyl (Cl4) alkyl,-S (0) nR where n is 0,1 or 2 and R4 has the meaning already given, or P (0) m (OR) 2 where m is 0 or 1 and R4 has the meaning already given; X is O, S or NR6 where R6 is H or C14 alkyl ; Y is -OCHR10C#CR11 where R10 and R11 are independently H, tri (C1-4) alkylsilyl, C1-6 allcyl or aryl; and

Z is H, C1-6 alkyl, C1-4alkoxy(C1-4) alkyl, Cl4 alkylcarbonyl, halo (Cl 4) alkyl-carbonyl, Cl4 alkoxycarbonyl or halo (Cl4) alkoxycarbonyl; any of the foregoing aryl, heteroaryl or heterocyclyl groups being optionally substituted; except that when R2, R3, R11 and Z are H, X is O and Rl° is methyl, R1 is not chloro.

In one aspect the invention provides a compound of the general formula (1) wherein: Rl and R2 are independently H, C1-6 alkyl or C3-6 cycloalkyl, or Rl and R2 join together to form a C3-6 alkylene group in which one of the carbon atoms is optionally replaced by an oxygen atom and in which two non-adjacent carbon atoms are optionally further linked by a C1-3 alkylene group, or any two adjacent carbon atoms of the C3-6 alkylene group are optionally further joined by another C3-6 alkylene group, any of the carbon atoms of the C3-6 alkylene or C1-3 alkylene groups being optionally substituted with one or two C1-6 alkyl groups, or R1 and R2 join together to form an optionally substituted fused, aromatic ring.

In another aspect the invention provides a compound of the general formula (1) wherein: Rl and R2 are independently H or Cl4 alkyl, or Rl and R2 join together to form a C3-6 alkylene group in which one of the carbon atoms is optionally replaced by an oxygen, any of the carbon atoms of the C3-6 alkylene group being optionally substituted with one or two C1-6 alkyl groups, or Rl and R2 join together to form an optionally substituted fused aromatic ring.

In yet another aspect the invention provides a compound of the general formula (1) wherein R3 is cyano, Cl4 alkoxycarbonyl, benzoyl in which the phenyl ring is optionally substituted with one or more halo, or heteroarylcarbonyl in which the heteroaryl is optionally substituted with one or more halo; preferably R3 is cyano or benzoyl in which the phenyl ring is optionally substituted with one or more halo.

In a further aspect the invention provides a compound of the general formula (1) wherein X is O.

In yet a further aspect the invention provides a compound of the general formula (1) wherein Z is H, Cl4 alkylcarbonyl or halo (C1-4) alkylcarbonyl; most preferably Z is H.

In another aspect the invention provides a compound of the general formula (1) wherein Y is -OCHR10C#CR11 where R10 and R11 are independently H or C1-4 alkyl.

Thus, in yet another aspect, the invention provides a compound of the formula (1) wherein: Ri and R are independently H, halo, C1-8 alkyl, C3-6 cycloalkyl, hydroxy(C1-8)alkyl, C1-4 alkoxy (C1-8) alkyl, Cl4 alkoxycarbonyl (Cl-$) alkyl, Cl-8 alkoxy, C1-8 alkylcarbonyl, C1-8 alkoxycarbonyl, di (Cl4) alkylaminocarbonyl, cyano, nitro, amino, aryl, aryloxy or heterocyclyl, or R1 and R2 join together to form a C3-6 alkylene group in which one of the carbon atoms is optionally replaced by an oxygen or nitrogen atom and in which two non-adjacent carbon atoms or a non-adjacent carbon atom and nitrogen atom are optionally further linked by a C1-3 alkylene bridge, any of the carbon atoms of the C3-6 alkylene group being optionally substituted with halo, a Cl4 alkyl group, an ethylenedioxy group or an aryl group, or any two adjacent carbon atoms of the 3-6 alkylene group being further joined by another C3-6 alkylene group, and where a nitrogen atom replaces a carbon atom on the C3-6 alkylene group and is not linked to a non-adjacent carbon atom with a 1-3 alkylene bridge, the nitrogen atom is optionally substituted with C1-8 alkyl, halo (Cl_$) alkyl, C2-8 alkenyl, C2-8 alkynyl, aryl, C1-8 alkoxycarbonyl or aryl (Cl4) alkylaminocarbonyl; or Ri and R2 join together to form an optionally substituted fused aromatic ring; R3 is H, halo, cyano, nitro, C2-6 alkyl, halo (Ci-6) alkyl, 2-6 alkenyl, 2-6 alkynyl, aryl- (C2-4) alkenyl, aryl (C2-4) alkynyl, aryl, arylcarbonyl, heteroarylcarbonyl, C1-4 alkylcarbonyl, Cl4 alkylcarbonyloxy, C1-4 alkoxycarbonyl, carboxy, -CONR4R5 where R4 and R5 are independently H, C1-4 alkyl or phenyl (Cl-4) alkyl, -S (O) nR4 where n is 0,1 or 2 and R4 has the meaning already given or P (O)m(OR4)2 where m is 0 or 1 and R4 has the meaning already given; X is O, S or NR6 where R6 is H or C1-4 alkyl; Y is-OCHRl°C-CRll where Rl° and Rl l are independently H, 1. 6 alkyl or aryl; and Z is H, C1-6 alkyl, C1-4 alkoxy (Cl4) alkyl, C1-4 alkylcarbonyl, halo (C1-4) alkylcarbonyl, Cl4 alkoxycarbonyl, halo (C1-4) allcoxycarbonyl ; any of the foregoing aryl, heteroaryl or heterocyclyl groups being optionally substituted; except that when R2, R3, R11 and Z are H, X is O and R'° is methyl, Ru ils not chloro.

This aspect of the invention includes compounds as defined above where R1 and R2 are independently H, C1-8 alkyl, C3-6 cycloalkyl, hydroxy (Cl 8) alkyl, C1-4 alkoxy- (Cl 8) alkyl, C14 alkoxycarbonyl (Cl 8) alkyl, C18 alkoxy, C1-8 alkylcarbonyl, C18 alkoxycarbonyl, di (C1-8) alkylaminocarbonyl, cyano, nitro, amino, aryl, aryloxy or heterocycyl, or R2 is halo.

In yet another aspect the invention provides a compound of the formula (1) wherein: Rl and R2 are independently H, C1-6 alkyl, C3-6 cycloalkyl, C1-4 alkoxycarbonyl, hydroxy- (Cl4) alkyl, Cl 4 alkoxy (Cl4) alkyl or aryl, or Rl and R2 are join together to form a C3-6 alkylene group in which one of the carbon atoms is optionally replaced by an oxygen or a nitrogen atom and in which any of the carbon atoms is optionally substituted by a Cl 4 alkyl group or any two adjacent carbon atoms are further joined by another C3-6 alkylene group and, where a nitrogen atom replaces a carbon atom, the nitrogen atom is optionally substituted with C1-4 alkoxy- carbonyl; R3 is H, halo, 2-6 alkenyl, 2-6 alkynyl, cyano, C1-4 alkylcarbonyl, halo (Cl4) alkyl- carbonyl, Cl4 alkoxycarbonyl, aminocarbonyl, phenyl optionally substituted with halo, benzoyl in which the phenyl ring is optionally substituted with halo, thienylcarbonyl; X is O or NH ; Y is -OCHR10C#CR11 where R10 and R11 are independently H, C1-6 alkyl or aryl; and Z is H or C1-4 alkylcarbonyl; any of the foregoing aryl, heteroaryl groups being optionally substituted.

In still yet another aspect the invention provides a compound of the formula (1) wherein: R1 and R2 are independently H, C1-6 alkyl, C1-4 alkoxycarbonyl or C1-4 alkoxy (Cl4) alkyl, or Rt and R2 join together to form a C3-6 alkylene group in which one of the carbon atoms is optionally replaced by an oxygen atom and in which any of the carbon atoms is optionally substituted by a C1-4 alkyl group or any two adjacent carbon atoms are further joined by another C3-6 alkylene group ; R3 is H, cyano, C1-4 alkylcarbonyl, halo (CI4) alkylcarbonyl, C14 alkoxycarbonyl,

aminocarbonyl, benzoyl in which the phenyl ring is optionally substituted with halo or thienylcarbonyl; X is O ; Y is-OCHRl°C_CRl l where Rl° and Rl l are independently H, C1-6 alkyl or optionally substituted aryl; and Z is H.

In yet another aspect the invention provides a compound of the formula (1) wherein: Ri and R2 are independently H, C1-6 alkyl, C1-4 alkoxycarbonyl or C14 alkoxy (C1-4) alkyl, or Rl and R2 join together to form a C3-6 alkylene group in which one of the carbon atoms is optionally replaced by an oxygen atom and in which any of the carbon atoms is optionally substituted by a 1-4 alkyl group or any two adjacent carbon atoms are further joined by another C3-6 alkylene group; R3 is cyano ; X is O ; Y is-OCHRl°C-CRll where R10 and Rll are independently H, C1-6 alkyl or phenyl which is optionally substituted with halo, Cl 4 alkyl, halo (Cl4) alkyl or Cl4 alkoxy ; and ZisH.

Typically, Rl and R2 are independently H or Cl-6 alkyl or join together to form a 3-4 alkylene group.

In addition, the following compounds listed in Table 1 to Table 140 below are amongst the compounds that are novel and form a further part of the present invention.

These are compounds 2-69,2-174, 2-192,3-524, 3-558,7-69, 12-69,14-3, 14-15,14-35, 14-43,14-50, 14-53,14-57, 14-58,14-59, 14-62,14-64, 14-122,14-131, 14-136,14-149, 14-164,14-169, 14-182, 14-192,14-195, 14-203,14-211, 14-219,14-221, 14-252,14- 263,14-265, 14-270,14-281, 14-288, 14-307,14-318, 14-322,14-334, 14-336,14-348, 14-365,14-404, 14-425,14-439, 14-461,14-465, 14-481,14-489, 14-494,14-506, 14- 524, 14-538, 14-540,14-553, 14-556,14-558, 14-559, 14-565, 14-566,14-567, 14-568, 14-569,14-571, 14-572,15-69, 15-291,16-58, 16-69, 16-174,16-192, 16-465,16-516, 16-524,16-538, 16-558,17-69, 18-69,19-69, 24-69,28-69, 29-69,31-43, 33-69,36-69,

40-524,40-558, 41-69,47-69, 50-69,56-69, 58-524,58-558, 59-194,59-368, 61-69,62- 69,63-69, 64-69,66-69, 71-69, 71-174, 71-192,72-69, 76-69,77-69, 79-69,80-69, 84- 69,86-69, 86-253,86-368, 88-69, 90-69,91-69, 92-69,93-69, 98-69,108-69, 109-69, 110-69,113-69, 117-69,121-69, 123-69,127-35, 127-43,127-53, 127-182,127-219, 127-252,127-334, 127-445,129-69, 132-69,134-32, 134-34,134-43, 134-57,134-116, 134-122,134-130, 134-137,134-156, 134-178,134-186, 134-248,134-259, 134-260, 134-262,134-292, 134-303,134-335, 134-345,134-361, 134-384,134-386, 134-445, 134-525,134-579, 136-69,137-69 and 140-69.

Compounds that may be used in the invention are illustrated in Table 1 to Table 140 below. Characterising data is given in the Examples and in Table 141 and Table 142 which come after the Examples.

Table 1 The compounds in Table 1 are of the general formula (1) where Y is 3, 5-dihydroxy-1, 2,4- triazin-6-ylthiomethyl, and R1, R2, R3, X and Z have the values given in the table. RlR2R3X Z CpdNo -(CH2)2CH(CH3)CH2- 4-Cl-C6H4CO O H 1 (CH3)2CH CH3 C6H5CO O H 2 morpholino CH3 (CH2) 3 CH3CH, OCO p H 3 # CH2 # 3-F-C6H4CO -CH-(CH2)2-CH- O H 4 CH3CH2 H SO2CH3 O H 5 CH3 CH3CH2 4-Cl-C6H4 p H 6 -CH2O(CH2)2- 4-F-C6H4CO O H 7 (CH3)2CH CH3 CH3CH2OCO O H 8 -(CH2)3- 4-F-C6H4CO O H 9 CH3CH2 CH3CH2 CH3CH20CO O H 10 CH3CH2 CH3(CH2)2 4-F-C6H4CO O H 11 CH3 (CH3)2CH 2-thienyl-CO O H 12 -CH2O(CH2)2- CONH2 O H 13 H CH3CH2 CN O H 14 CH3 CH3CH2 CN O H 15 CH3 CH3(CH2)3 CH3CH2OCO O H 16 -(CH2)4- CH3CH2OCO O CH3 17 CH3 (CH3) 3C CN O H 18 CN 4-CH3O-C6H4 C6H5CO O H 19 -(CH2)2CH(CH3)CH2- C6H5CO O H 20 CH3CH2 H 4-Cl-C6H4CO 0 H 21 (CH3)2CH 3-F-C6H4CO O H 22 -CH=CH-CH=CH- (CH3) 3COCO 0 H 23 -(CH2)3CF2- CH3CH2OCO O H 24 CH3CH2 cyclopropyl CH3CH2OCO 0 H 25 -CH=CH-CH=CH- 4-Cl-C6H4CO O H 26 CH3CH2 CH3CH2 4-F-C6H4CO O H 27 CH3CH2 H CH3CH2OCO O ClCH2CO 28 CH3CH2 H HOCO O H 29 (CH3)2CH CH3 2-thienyl-CO O H 30 (CH3) 2CH (CH3)3C CN O H 31 CH3OCH2 cyclopropyl 4-Cl-C6H4 O CH3 32 CH3 (CH3) 3C 2-thienyl-CO O H 33 -(CH2)4- C6H5C#C O (CH3)3COCO 34 C6H5O CH3(CH2)3 CH3CH2OCO O H 35 CH3CH2 CH3 (CH2) 2 2-thienyl-CO O H 36 -(CH2)3- C6H5CO O CH3 37 (CH3)2CHCH2 CH3CH2OCO O H 38 -CH2CH(CH2CH3)(CH2)2- CN O H 39 CH3 CH3CH2 HOCO O H 40 -(CH2)3CHF- C6H5CO O H 41 CH3 (CH3)3C 4-F-C6H4CO O H 42 -(CH2)4- (CH3)3COCO O H 43 CH3 CH3 4-F-C6H4CO 0 H 44 H CH3(CH2)2 C6H5CO O H 45 -(CH2)3- PO(OCH3)2 O H 46 RlR2R3X Z CpdNo CH3 (CH3)3C CH3CH2OCO O H 47 CH3CH2 cyclopropyl 4-F-C6H4CO O H 48 CH3 (CH2)2 CH3CH2 CH3CH2OCO O H 49 # CH2 # - CH- (CH2) 2-CH- O H 50 -CH=CH-CH=CH- CH=C O H 51 (CH3) 2CH H C6H5CO O H 52 CH3CH2 CN O H 53 -CH2CH(CH3)(CH2)2- 3-F-C6H4CO O H 54 (CH3)2CH CH3(CH2)2 2-thienyl-CO O H 55 - CH=CH-CH=CH-CH3CH2OCO 0 CH3 56 CH30CO CH30CH2 H O H 57 C6H5 H CN 0 H 58 CH30 CH3OCOCH2 CN O H 59 (CH3) 2CH CH3CH2 CN O H 60 (CH2) 3-CH_C O H 61 CN 4-CH3O-C6H4 H O H 62 -CH20 (CH2) 2-3-F-C6H4CO O H 63 CH3CH2OCO CH3 2-CH30-5-F-C6H3 O H 64 HOCH2 cyclopropyl CN O H 65 -(CH2)5- 4-F-C6H4CO O H 66 CH3(CH2)2 2-thienyl-CO O H 67 CH3CH2 (CH3)2CH 2-thienyl-CO O H 68 -(CH2)4- CN O H 69 cyclopropyl cyclopropyl CN O H 70 CH30CO cyclopropyl CN 0 H 71 CH3CH2 cyclopropyl 3-F-C6H4CO O H 72 - (CH2)3- CH3CH2OCO O H 73 -CH2O(CH2)2- CH2=CH O H 74 (CH3)2CH cyclopropyl 3-F-C6H4CO O H 75 (CH3)2CH H 4-F-C6H4CO O H 76 (CH3)2CH H PO (OCH3) 2 O H 77 - (CH2)3CHF- CN O H 78 C6H5CO O H 79 -(CH2)3- C6H5CO O H 80 -CH2CH(CH2CH3)(CH2)2- 3-F-C6H4CO O H 81 -CH=CH-CH=CH- 4-F-C6H4CO O H 82 (CH3)2CH H CH3CH2OCO O H 83 CH3(CH2)2 CH3CH2OCO O H 84 H CH3(CH2)2 CH3CH2OCO O H 84 (CH3)2CH (CH3)2CH CH3CH2OCO O H 85 -(CH2)5- CH3CH2OCO O ClCH2CO 86 CH3 CH3CH2 CONH2 O H 87 CH3CH2 3-F-C6H4CO O H 88 -CH2O(CH2)2- 4-Cl-C6H4CO O H 89 -(CH2)3CH(CH3)- C6H5CO O H 90 (CH3) 2CH (CH3)2CH 4-F-C6H4CO O H 91 (CH3)3C 2-thienyl-CO O H 92 R1 R2 R3 X Z CpdNo (CH3)2CH H CH2=CH O H 93 (CH3)2CH H 2-thienyl-CO O H 94 -(CH2)3CHF- CH3CH2OCO O H 95 -(CH2)4- CH3CH2OCO O ClCH2CO 96 CH3 cyclopropyl 2-thienyl-CO O H 97 (CH3)2CH H Br O H 98 -CH2CH(CH3)(CH2)2- CH3CH2OCO O H 99 (CH3)2CH CH3 4-F-C6H4CO O H 100 - (CH2) s- C6H5CO O H 101 H (CH3)3C C6H5CO O H 102 -(CH2)5- CH3CH2OCO O CH3 103 -(CH2) 3CH (CH3)-2-thienyl-CO O H 104 (CH3)2CH H (CH3)3CCO O H 105 H H 4-F-C6H4CO O H 106 CH3 CH3(CH2)2 4-F-C6H4CO O H 107 (CH2)3CF2- C6H5CO O H 108 CH3 CH3CH2 2-thienyl-CO O H 109 (CH3) 2CHCH2 (CH3)2CH(CH2)2 C6H5CO O H 110 -(CH2) 6 CN O H 111 (CH3)2CH (CH3)2CH CN O H 112 -CH3CH (CH3) (CH2)2- SO2CH3 O H 113 -CH2O(CH2)2- 4-Cl-C6H4 O H 114 -CH20 (CH2) 2-I O H 115 CH30CO cyclopropyl 4-Cl-C6H4 p H 116 CH3OCO cyclopropyl C6H5CO O H 117 H CH3(CH2)2 4-F-C6H4CO O H 118 -CH2N(CH2C#CH)(CH2)2- C6H5CO O H 119 -(CH2)3CF2- CN O H 120 # CH2 # -CH2CH-(CH2)2-CH- 2-thienyl-CO O H 121 CH3CH2OCO CH3 Br O H 122 CH2C(CH3)2CH2 CH3CH2OCO # # O O -CH2-C-(CH3)2- O H 123 -(CH2)5- Br O H 124 -CH20 (CH2) 2-HOCO O H 125 CH3CH2 H CN 0 ClCH2CO 126, -(CH2)2CH (CH3) CH2- SO2CH3 O H 127 -(CH2)3- CN O ClCH2CO 128 CH3CH2 (CH3)3C C6H5CO O H 129 CH3OCO CH3OCH2 I O H 130 C6H5O CH3(CH2)3 CN O H 131 C6H5O CH3 (CH2) 3 CN O H 131 r (CH2)4# CH3CH2OCO -(CH2)2CH-CH- O H 132 (CH3)3C H C6H5CO O H 133 CH3CH2 H 2-thienyl-CO 0 H 134 -CF2(CH2)3- C6H5CO O H 135 R1 R2 R3 X Z CpdNo #(CH2)2# -CH-N-CHCH2- # COOCH2CH3 CN'O H 136 CH3CH2OCO CH3 2,4-diCH3O-C6H3 O H 137 -(CH2)5- C6H5CO O ClCH2CO 138 -(CH2)3- HOCO O H 139 CH3CH2 cyclopropyl CN O H 140 CH3 H CH3CH2OCO O H 141 -(CH2)2CH(CH3)CH2- CN O H 142 -(CH2)5- C6H5CO O CH3 143 -CH20 (CH2) 2-SO2CH3 O H 144 CH3OCO cyclopropyl CH3CH2OCO O H 145 CH3 CH3(CH2)2 2-thienyl-CO O H 146 # CH2 # C6H5CO -CH-(CH2)2-CH- O H 147 H H 3-F-C6H4CO O H 148 CH3(CH2)2 CH3(CH2)3 CN O H 149 CH3 CH3CH2 (CH3)3COCO O H 150 -(CH2)4- C6H5CO O H 151 -(CH2)2CH(CH3)CH2- PO(OCH3)2 O H 152 CH3CH2 (CH3)2CH 4-F-C6H4CO O H 153 CH3CH2 CH3CH2 CN O H 154 (CH3) 2CH cyclopropyl CN O H 155 -(CH2)4- 4-CF3-C6H4 O H 156 H cyclopropyl 2-thienyl-CO O H 157 CH3CH2 H PO(OCH3)2 O H 158 -CH2O(CH2)2- (CH3)3CCO O H 159 #(CH2)4# CH3CH2OCO -CH-CH(CH2)2- O H 160 CH3CH2 H I O H 161 H C6H5 C6H5CO O H 162 H (CH3) 3C CN O H 163 - (CH2) 4- CN 0 CICH2CO 164 CH3 CH3CH2 PO(OCH3)2 O H 165 -(CH2)5- (CH3)3CCO O H 166 (CH3)2CH cyclopropyl 2-thienyl-CO O H 167 (CH3)2CH CH3CH2 3-F-C6H4CO O H 168 CH3CH2OCO CH3 3-CF3-C6H4 O H 169 (CH3) 2CH CH3 (CH2) 2 CN O H 170 -(CH2)3- 4-Cl-C6H4CO O H 171 CH3CH2 CH3(CH2)2 C6H5CO O H 172 -CH=CH-CH=CH- CN O CH3 173 -(CH2)5- CN O H 174 (CH3)2CH H (CH3)3COCO O H 175 CH3CH2 H C6H5CO O ClCH2CO R1 R2 R3 X Z CpdNo # (CH2) 27 CH3CHOCO -CH-N-CHCH2- COOCH. CH, Q H 177 -(CH2)4- 3-CF3-C6H4 O H 178 CH3CH2 (CH3)2CH 3-F-C6H4CO O H 179 (CH3)2CH (CH3)2CH 3-F-C6H4CO O H 180 -CH=CH-CH=CH- PO(OCH3)2 O H 181 morpholino CH3 CH3CH20CO p H 182 -(CH2)3- CN O CH3 183 CH3 CH3CH2 CH3CH2OCO O H 184 -CH2O(CH2)2- CH3CH2OCO O ClCH2CO 185 CH30CO cyclopropyl Br 0 H 186 CH3CH2 H H O H 187 -(CH2)3- I O H 188 -(CH2)4- C6H5CO O CH3 189 -(CH2)4- SO2CH3 O H 190 -CH2O(CH2)2- Br O H 191 -(CH2)4- CN O CH3 192 -CHF(CH2)3- C6H5CO O H 193 -(CH2)4- CH3CH2OCO O H 194 -CH2N (COOC (CH3) 3) (CH2)2- CN O H 195 -CH2N (COOC (CH3) 3) (CH2)2- C6H5CO O H 196 H (CH3)2CH CH3CH2OCO O H 197 -(CH2)3- CONH2 O H 18 CH3 H 2-thienyl-CO O H 199 CH3CH2 (CH3)3C CH3CH2OCO O H 200 - (CH2)2CH(CH3)CH2- CN O CH3 201 CH3CH2 CH3 (CH2) 2 CH3CH20CO 0 H 202 #(CH2)2# -N-(CH2)2-CH- CN O H 203 CN 4-CH3O-C6H4 CH3CH2OCO O H 204 H CH3 (CH2) 2 CN O H 205 #CH2# CH3CH2OCO -CH2CH-(CH2)2-CH- O H 206 (CH3)2CH (CH3)3C C6H5CO O H 207 -(CH2)6- 2-thienyl-CO O H 208 - (CH2) 2CH (CH3) CH2- CH2=CH 0 H 209 (CH3) 2CH (CH3)3C 3-F-C6H4CO O H 210 CH3CH2OCO CH3 4-CF3-C6H4 O H 211 -(CH2)4- Br O H 212 CH3OCO CH3OCH2 CH3CH2OCO O H 213 -(CH2)3CH(CH3)- CH3CH2OCO O H 214 CH3CH2 (CH3)3C 3-F-C6H4CO O H 215 - (CH2) 2CH (CH3) CH2- 4-Cl-C6H4 O H 216 H H CN O H 217 CN 4-CH30-C6H4 CN O H 218 R1 R2 R3 X Z Cpd No kCH2) 4-HOCO O H 219 CH3 cyclopropyl 4-F-C6H4CO p H 220 morpholino CH3CH2 CH3CH2OCO O H 221 -(CH2)2CH(CH3)CH2- CN O ClCH2CO 222 - CH=CH-CH=CH-g O H 223 -(CH2)5- 4-Cl-C6H4CO O H 224 -CH2CH(CH2CH3)(CH2)2- 2-thienyl-CO O H 225 -CH2O(CH2)2- C6H5CO O CH3 226 -CH2CH (CH3) (CH2) 2- 4-Cl-C6H4 O H 227 -(CH2)3- CH2=CH O H 228 CH3 CH3CH2 4-F-C6H4CO O H 229 CH3 CH3 3-thienyl-CO O H 230 CH3 H C6H5CO O H 231 (CH3)3C CH3CH2OCO O H 232 HOCH2 cyclopropyl C6H5CO O H 233 CH3CH2 H CH=C O H 234 H CH3 CN O H 235 H (CH3) 2CHCH2 CN O H 236 -CH2CH(CH3)(CH2)2- C6H5CO O ClCH2CO 237 -CH2O(CH2)2- CH3CH2OCO O CH3 238 - CH=CH-CH=CH-CH3CH2OCO p CICH2CO 239 C6H5CO -N-(CH2)2-CH- O H 240 -(CH2)6- 4-F-C6H4CO O H 241 H C6H5 CN O H 242 -(CH2)2CH (CH3) CH2- CH3CH2OCO O CH3 243 -CH=CH-CH=CH- 2-thienyl-CO O H 244 -(CH2)5- CONH2 O H 245 -(CH2)6- 3-F-C6H4CO O H 246 -(CH2)5- CH#C O H 247 -(CH2)4- CH3(CH2)2C#C O H 248 H H 2-thienyl-CO O H 249 cyclopropyl cyclopropyl CH3CH2OCO O H 250 -(CH2)5- SO2CH3 O H 251 -CH2O(CH2)2- CH3CH2OCO O H 252 CH3 CH3 CN O H 253 CH3 CH3 3-F-C6H4CO O H 254 -CH2N(CH2C#CH)(CH2)2- CH3CH2OCO O H 255 -CH=CH-CH=CH- 3-F-C6H4CO O H 256 CH3 cyclopropyl CN O H 257 CH3CH2 C6H5CO O H 258 -(CH2) 4-CH2=CH O H 259 CH30CO cyclopropyl I O H 260 (CH3) 2CH CH3 3-F-C6H4CO O H 261 CH30CO CH3OCH2 CH=C O H 262 #(CH2)4# -(CH2)2CH-CH- CN O H 263 RlR2R3X Z CpdNp - (CH2) 2CH (CH3) CH2- I O H 264 #(CH2)2# -CH-N-CHCH2- # CH2CF3 CN O H 265 CH3(CH2)2 CH3(CH2)3 C6H5CO O H 266 -CH2O(CH2)2- C6H5CO O H 267 -CF2(CH2)2CF2- C6H5CO O H 268 CH3CH2OCO CH3 H O H 269 CH3CH2 H CN O H 270 (CH3)2CH (CH3)2CH C6H5CO O H 271 -CF2(CH2)2CF2- CH3CH2OCO O H 272 -CH2CH (CH3) (CH2)2- I O H 273 -CH2CH(CH3)(CH2)2- CH#C O H 274 CH3 (CH3)3C C6H5CO O H 275 -CH2CH(CH3)(CH2)2- CH3CH2OCO O ClCH2CO -CH2CH(CH3)(CH2)2- CN O ClCH2CO CH3CH2 H C6H5CO O CH3 CH3 CH3CH2 C6H5CO O CH3 CH3CH2 H 4-Cl-C6H4 O H 280 CH3CH2OCO CH3 2, 4-diCl-C6H3 O H 281 CH3CH2 CH3CH2 C6H5CO O H 282 -(CH2)4- 2-thienyl-CO O H 283 CH3 CH3(CH2)2 C6H5CO O H 284 CH3CH2 H 3-F-C6H4CO O H 285 #(CH2)4# 3-F-C6H4CO -CH-CH(CH2)2- O H 286 CH3 CH3CH2 SO2CH3 O H 287 #(CH2)2# CH3CH2OCO -N-(CH2)2-CH- O H 288 -CH=CH-CH=CH- 4-Cl-C6H4 O H 289 (CH3) 2CH (CH3)3C CH3CH2OCO O H 290 - CH=CBr-CH=CH-H O H 291 CH3CH2OCO CH3 CH2=CH O H 292 H (CH3) 2CHCH2 C6H5CO O H 293 HOCH2 cyclopropyl CH3CH2OCO O H 294 CH3 CH3CH2 CN O ClCH2CO CH3CH2 H C6H5CO O H 296 -CF2(CH2)3- CN O H 297 (CH3)2CH H CH=C O H 298 C6H5O CH3CH2 C6H5CO O H 299 -(CH2)5- 4-Cl-C6H4 O H 300 (CH3) 2CHCH2 (CH3) 2CH (CH2)2 CH3CH2OCO O H 301 H cyclopropyl 4-F-C6H4CO O H 302 -(CH2)4- C6H5C#C O H 303 CH3CH2 CH3 4-F-C6H4CO O H 304 CH3 CH3 C6H5CO O H 305 R1 R2 R3 X Z Cpd No -(CH2)3CH(CH3)- 3-F-C6H4CO O H 306 H cyclopropyl CN O H 307 CH3CH2 (CH3)2CH CN O H 308 -CH=CH-CH=CH- CN O ClCH2CO 309 (CH3)3C H CH3CH2OCO O H 310 CH3CH2 CH3 C6H5CO O H 311 CH3CHz H CONH2 O H 312 -CH2O(CH2)2- CN O CH3 313 -(CH2)2CH(CH3)CH2- C6H5CO O ClCH2CO 314 - (CH2) 2CH (CH3) CH2- (CH3) 3CCo O H 315 -CH2CH(C6H5)(CH2)2- CN O H 316 -CH2CH(CH3)(CH202- (CH3)3COCO O H 317 CH2 C (CH3) 2CIi, | | O# #O -CH2-C-(CH2)2- CN O H 318 CH3 (CH3)2CH C6H5CO O H 319 -(CH2)3CH(CH3)- 4-F-C6H4CO O H 320 -(CH2)4- CN NH H 321 -CH=CH-CH=CH- Br O H 322 -CH2CH(C6H5)(CH2)2- CH3CH2OCO O H 323 C6H5 H CH3CH2OCO O H 324 -(CH2)5- PO(OCH3)2 O H 325 (CH3)2CH H 3-F-C6H4CO O H 326 - (CH2) 2CH (CH3) CH2- CONH2 O H 327 # CH2 # 4-F-C6H4CO -CH-(CH2)2-CH- O H 328 CH3CH2 CH3CH2 3-F-C6H4CO O H 329 -CF2(CH2)3- CH3CH2OCO O H 330 -CH2O(CH2)2- (CH3)3COCO O H 331 - CH20 (CH2) 2-2-thienyl-CO 0 H 332 -CH2CH (CH3) (CH2)2- CH2=CH O H 333 -CH2O(CH2)2- CN O H 334 -(CH2)4- CH#C O H 335 -CH2N(CH2C#CH)(CH2)2- CN O H 336 #(CH2)4# C6H5CO -(CH2)2CH-CH- O H 337 CH3 CH3(CH2)2 CN O H 338 CH3CH2OCO CH3 CH3CH2OCO O H 339 -CH2CH(CH2CH3)(CH2)2- CH3CH2OCO O H 340 -(CH2)3- C6H5CO O ClCH2CO 341 #CH2# 4-F-C6H4CO -CH2CH-(CH2)2-CH- O H 342 CH3CH2 H (CH3) 3CCO p H 343 (CH3)2CH H 4-Cl-C6H4CO O H 344 - (CH2) 4- CH2=CH O (CH3)3COCO 345 -CF2(CH2)2CF2- CN O H 346 R1 R2 R3 X Z Cpd No CH3 CH3 (CH2)3 CN O H 347 (CH3CH2)2NCO CH3 H O H 348 H CH3 C6H5CO O H 349 -CH2CH(CH3)(CH2)2- HOCO O H 350 -CH2CH(C6H5)(CH2)2- C6H5CO O H 351 -CH2CH(CH3)(CH2)2- (CH3)3CCO O H 352 - (CH2)5- CN O ClCH2CO 353 CH, 3-F-C6H4CO -CH2CH-(CH2)2-CH- O H 354 -CH=CH-CH=CH- SO2CH3 O H 355 (CH3) 2CH H HOCO O H 356 CH3CH2 CH3CH2 2-thienyl-CO O H 357 CH3 CH3 (CH2) 3 C6H5CO O H 358 CH3CH2 H 4-Cl-C6H4 O H 359 -(CH2)4- 3-F-C6H4CO O H 360 HOCH2 CH3 2, 4-diCH30-C6H3 O H 361 -CH2-CH(CH3)(CH2)2- CN O H 362 H O H 363 CH3 H 4-F-C6H4C0 O H 364 #(CH2)4# -CH-CH(CH2)2- CN O H 365 -CHF(CH2)3- CH3CH2OCO O H 366 #CH2# C6H5CO CH2CH-(CH2)2-CH- O H 367 -(CH2)3- CN O H 368 (CH3) 2CH H CN O CH3 369 CH3CH2 H CH2=CH O H 370 -CH2O(CH2)2- C6H5CO O ClCH2CO 371 H (CH3)3C 4-F-C6H4CO O H 372 -CH2CH(CH2CH3)(CH2)2- 4-F-C6H4CO O H 373 r (CH2)4# -CH-CH(CH2)2- 2thienyl-CO O H 374 - 4-PO (OCH3) 2 O H 375 #(CH2)2# CH3CH2OCO -CH-N-CHCH2- # CH. CF, Q H 376 -CH2CH (CH3) (CH2) 2- CH3CH2OCO O CH3 377 (CH3) H H I O H 378 CH3 CH3CH2 C6H5CO O H 379 CH3 (CH2)2 CH3(CH2)3 CH3CH2OCO O H 380 -CH=CH-CH=CH- CONH2 O H 381 CH3 CH3CH2 C6H5CO O CICH2CO 382 CH3 H 3-F-C6H4CO O H 383 CH3CH2OCO CH3 4-Cl-C6H4 O H 384 CH3CH2 cyclopropyl C6H5CO O H 385 -(CH2)4- I O H 386 R1 R2 R3 X Z Cpd No -CH=CH-CH=CH- C6H5CO O CICH2CO 387 CH3CH2 CH3 CN O H 388 H CH3 CH3CH20CO p H 389 -(CH2)4- CONH2 O H 390 -(CH2)6- CONH2 O H 391 CH3OCO CH3OCH2 C6H5CO O H 392 CH3CH2 (CH3) 2CH CH3CH2OCO O H 393 H H CH3CH2OCO O H 394 -CH2CH(CH3)(CH2)2- CN O CH3 395 CH3CH2 (CH3) 3C 2-thienyl-CO O H 396 CH3CH2 (CH3)3C CN O H 397 CH3 CH3CH2 CH3CH2OCO O CH3 398 H C6H5 CH3CH2OCO O H 399 CH3CH2 Br 0 H 400 (CH3) 2CH H CH3CH2OCO O CH3 401 H 4-F-C6H4 CH3CH2OCO O H 402 -(CH2)2CH(CH3)CH2- (CH3)3COCO O H 403 CH3CH2 CH3(CH2)2 CN O H 404 -CH2CH (CH3) (CH2) 2- Br O H 405 -(CH2)6 C6H5CO O H 406 (CH3) 2CH CH3 (CH2) 2 3-F-C6H4CO O H 407 CH3 CH3 CH3CH2OCO O H 408 -CH2CH(CH3)(CH2)2- PO(OCH3)2 O H 409 CH3CH2 H CH3CH2OCO O H 410 CH3 (CH3)2CH 4-F-C6H4CO O H 411 CH3 CH3 (CH2)2 CH3CH2OCO O H 412 -(CH2)2CH (CH3) Chez- HOCO O H 413 CH3CH2 CH3 CH3CH2OCO O H 414 #(CH2)4# C6H5CO -CH-CH(CH2)2- O H 415 (CH3)2CH CH3CH2 4-F-C6H4CO O H 416 CH3CH2 H 4-F-C6H4CO O H 417 -CH=CH-CH=CH- HOCO O H 418 #(CH2)2# C6H5CO -CH-N-CHCH2- # CH2CF3 O H 419 - CH, CH (CH3) (CH2) 2- C6H5CO O H 420 -(CH2)2CH (CH3) CH2- CH3CH2OCO O ClCH2CO 421 (CH3) 2CH H H O H 422 - (CH2) zCH (CH3) CH2- 3-F-C6H4CO O H 423 CH3 CH3CH2 Br O H 424 (CH3)2CHCH2 (CH3)2CH(CH2)2 CN O H 425 -CH=CH-CH=CH- CH2=CH O H 426 -(CH2)4- 4-Cl-C6H4CO O H 427 CH3CH2 H CH3CH2OCO O CH3 428 (CH3) 2CH (CH3) 2CH 2-thienyl-CO 0 H 429 RlR2R3X Z CpdNo H CH3CH2 2-thienyl-CO O H 430 H (CH3) 2CH 4-F-C6H4CO p H 431 CH3 (CH3) 3C 3-F-C6H4CO p H 432 (CH3) 2CH (CH3) 3C 4-F-C6H4CO O H 433 CH30CO CH3OCH2 CN 0 H 434 CH3 CH3CH2 CN O CH3 435 -CH2O(CH2)2- CN O ClCH2CO 436 cyclopropyl cyclopropyl C6H5CO O H 437 CH3 CH3(CH2)2 3-F-C6H4CO O H 438 (CH2) 4-2-F-4-Cl-C6H3CO O H 439 CH3CH2 CH3CH2OCO O H 440 -(CH2)3- CH3CH2OCO O CH3 441 -(CH2)2CH(CH3)CH2- H O H 442 CH3 (CH3) 2CH CN O H 443 -(CH2)4- 4-F-C6H4CO O H 444 CH3OCO cyclopropyl H O H 445 (CH3) 2CH H CONH2 O H 446 -(CH2)3- (CH3)3COCO O H 447 (CH3)2CH CH3CH2 2-thienyl-CO O H 448 CH3 cyclopropyl 3-F-C6H4CO O H 449 -(CH2) 3-SO2CH3 O H 450 CH3 (CH3)2CH 3-F-C6H4CO O H 451 -CH=CH-CH=CH- I O H 452 -(CH2)3- 3-F-C6H4CO O H 453 CH3CH2 cyclopropyl 2-thienyl-CO O H 454 (CH2) 4-4-Cl-C6H4 O H 455 -CH2CH (CH3) (CH2) 2- H O H 456 -CH=CH-CH=CH- C6H5CO O H 457 (CH3)2CH H SO2CH3 O H 458 CH3 (CH2) 2 CH3CH2 C6H5CO O H 459 C6H5O CH3CH2 CH3CH2OCO O H 460 -CH2N(COOC (CH3) 3) (CH2) 2- CH3CH2OCO O H 461 -CH2CH (CH3) (CH2) 2- 4-Cl-C6H4CO O H 462 -(CH2)5- CH3CH2OCO O H 463 -(CH2)2CH(CH3)CH2- 2-thienyl-CO O H 464 # CH2 # -CH2CH-(CH2)2-CH- CN O H 465 (CH3)3C 3-F-C6H4CO O H 466 CH3CH2 (CH3) 2CH C6H5CO O H 467 (CH3) 2CH CH3 CN O H 468 (CH3) 2CH CH3(CH2)2 CH3CH2OCO O H 469 (CH3) 2CH H C6H5CO O CH3 470 -CH=CH-CH=CH- (CH3)3CCO O H 471 -CH2CH(CH3)(CH2)2- C6H5CO O CH3 472 -CH=CH-CH=CH- C6H5CO O CH3 473 # (CH2)4 # 4-F-C6H4CO -CH-CH(CH2)2 O H 474 RlR2R3X Z CpdNo H CH3 4-F-C6H4CO O H 475 (CH3) 2CH cyclopropyl C6H5CO O H 476 CH3 CH3CH2 CH3CH2OCO O ClCH2CO CH3 cyclopropyl CH3CH2OCO O H 478 -CH2CH (CH3) (CH2)2- CONH2 O H 479 CH3 (CH3)2CH CH3CH2OCO O H 480 - CH=CH-CH=CH-CN O H 481 (CH3)2CH H CH3CH2OCO O ClCH2CO 482 (CH3)2CH H C6H5CO O ClCH2CO 483 CH3 CH3CH2 CH2=CH O H 484 CH3CH2 CH3 2-thienyl-CO O H 485 # -(CH2)3- 2-thienyl-CO O H 486 -(CH2)4- CN S H 487 (CH3)2CH CH3(CH2)2 4-F-C6H4CO O H 488 -(CH2)4- (CH3)3CCO O H 489 (CH3)2CH CH3(CH2)2 C6H5CO O H 490 -(CH2)6 CH3CH2OCO O H 491 CH3 CH3CH2 4-Cl-C6H4CO p H 492 -CH2O(CH2)2- PO (OCH3) 2 O H 493 CH3CH2OCO CH3 4-CH3-C6H4 O H 494 CH3CH2OCO CH3CN O H 495 CH3CH2OCO CH3 C6H5CO O H 496 CH3CH2 H CN O CH3 497 -(CH2)2CH(CH3)CH2- Br O H 498 H (CH3)2CH C6H5CO O H 499 2-thienyl-CO O H 500 -(CH2)3- Br O H 501 -CH2O(CH2)2- CH#C O H 502 # CH2 # -CH-(CH2)2-CH- 2-thienyl-CO O H 503 CH3CH2 CH3(CH2)2 3-F-C6H4CO O H 504 H CH3(CH2)2 3-FC6H4CO O H 505 -(CH2) 3CH (CH3)- CN O H 506 H CH3CH2 4-F-C6H4CO O H 507 -CH2O(CH2)2- H O H 508 # (CH2)2 # C6H5CO -CH-N-CHCH2- # COOCH2CH3 O H 509 -(CH2)5- (CH3)3COCO O H 510 (CH3) zea cyclopropyl CH3CH2OCO O H 511 H cyclopropyl C6H5CO O H 512 -(CH2)2CH(CH3)CH2- C6H5CO O CH3 513 -CHF(CH2)3- CN O H 514 CH, C(CH3)2CH2 C6H5CO | | O O # # -CH2-C-(CH2)2- O H 515 R1 R2 R3 X Z Cpd No -CH=CH-CH=CH- CH3CH2OCO O H 516 -(CH2)3- CH3CH2OCO O ClCH2CO 517 CH3CH2 CH3 3-F-C6H4CO O H 518 ClCH2CO (CH3)2CH H CN O 519 H 4-F-C6H4 C6H5CO O H 520 - (CH2)4- H O H 521 - (CH2) 5- H O H 522 CH3 CH3CH2 H 0 H 523 (CH3)2CH H CN O H 524 HOCH2 cyclopropyl 4-Cl-C6H4 O H 525 -(CH2)5- CN O CH3 526 -(CH2)5- I O H 527 CH3 CH3CH2 3-F-C6H4CO O H 528 - (CH2) 5- HOCO 0 H 529 -(CH2)5- CH2=CH O H 530 (CH3)2CH (CH3)3C 2-thienyl-CO O H 531 2-thienyl-CO O H 532 - (CH2) 3- (CH3)3CCO O H 533 CH3CH2 (CH3)3C 4-F-C6H4CO O H 534 (CH3)2CH CH3CH2 CH3XH2OCO O H 535 - CH2CH (CH3) (CH2) 2- 2-thienyl-CO O H 536 -(CH2)4- C6H5CO O ClCH2CO 537 (CH3) 3C H CN O H 538 CH3 CHCH2 CH3(CH2)2 CH3CH2 CN O H 540 -(CH2)2CH(CH3)CH2- 4-F-C6H4CO O H 541 CH3 CH3CH2 I O H 542 CH3 3-F-C6H4CO H O H 543 -(CH2)2CH(CH3)CH2- CH#C O H 544 CH3 CH3CH2 (CH3)3CCO O H 545 -(CH2)3- 4-Cl-C6H4 O H 546 - (CH2) 5- 2-thienyl-CO O H 547 (CH3) 2CH CH3CH2 C6H5CO O H 548 H cyclopropyl 3-F-C6H4CO p H 549 CH3 cyclopropyl C6H5CO O H 550 -(CH2)5- 3-F-C6H4CO O H 551 (CH3)2CH cyclopropyl 4-F-C6H4CO O H 552 H (CH3)2CH CN O H 553 -(CH2)2CH(CH3)CH2- CH3CH2OCO O H 554 # CH2 # CH3CH2OCO #CH#(CH2)2#CH# O H 555 -CH2CH(C6H5)(CH2)2- CN O ClCH2CO 556 H cyclopropyl CH3CH2OCO O H 557 CH3 H CN O H 558 H 4-F-C6H4 CN O H 559 -CH2CH (CH3) (CH2) 2- 4-F-C6H4CO O H 560 C6H5 H C6H5CO O H 561 R1 R2 R3 X Z Cpd No (CH3CH2)2NCO CH3 CN O H 562 -CH2CH(CH2CH3)(CH2)2- C6H5CO O H 563 CH3CH2 H (CH3) 3COCO p H 564 -CH2N(CONHCH2C6H5)(CH2)2- CN O H 565 - (CH2)4- C6H5CH2NHCO O H 566 H H CH3OCO O H 567 CH2 - CH2 | | O# #O #CH2#C#(CH2)2# CN O H 568 CH3(CH2)3 CH3CH2 CN- O H 569 CH3 CH3(CH2)4 CN- O H 570 -CH (CH3) CH2C (CH3) 2CH2- CN O H 571 -C(CH3)2CH2C(CH3)2CH2- CN O H 572 -CH2CH (C (CH3) 3)(CH2)2- CN O H 573 -CH, CH (C (CH3) 2CH2CH3) (CH2)2- CN O H 574 -(CH2)4- CH3 OCO O H 575 -(CH2)4- CH3(CH2)2C#C O (CH3) 3COCO 576

Table 2 Table 2 consists of 576 compounds of the general formula (1), where Y is 1,2- dichloroethyl, and Rl, R, R3, X and Z have the values listed in Table 1. Thus compound 1 of Table 2 is the same as compound 1 of Table 1 except that in compound 1 of Table 2 Y is 1,2-dichloroethyl instead of 3, 5-dihydroxy-1, 2, 4-triazin-6-ylthiomethyl. Similarly, compounds 2 to 576 of Table 2 are the same as compounds 2 to 576 of Table 1, respectively, except that in the compounds of Table 2 Y is 1,2-dichloroethyl instead of 3,5-dihydroxy-1, 2s4-triazin-6-ylthiomethyl.

Table 3 Table 3 consists of 576 compounds of the general formula (1), where Y is iso-propyl, and Rl, R2, R3, X and Z have the values listed in Table 1. Thus compound 1 of Table 3 is the same as compound 1 of Table 1 except that in compound 1 of Table 3 Y is iso-propyl instead of 3, 5-dihydroxy-1, 2,4-triazin-6-ylthiomethyl. Similarly, compounds 2 to 576 of Table 3 are the same as compounds 2 to 576 of Table 1, respectively, except that in the compounds of Table 3 Y is iso-propyl instead of 3, 5-dihydroxy-1, 2,4-triazin-6- ylthiomethyl.

Table 4 Table 4 consists of 576 compounds of the general formula (1), where Y is allylthiomethyl, and Ru, R2, R3, X and Z have the values listed in Table 1. Thus compound 1 of Table 4 is the same as compound 1 of Table 1 except that in compound 1 of Table 4 Y is allylthiomethyl instead of 3, 5-dihydroxy-1, 2,4-triazin-6-ylthiomethyl.

Similarly, compounds 2 to 576 of Table 4 are the same as compounds 2 to 576 of Table 1, respectively, except that in the compounds of Table 4 Y is allylthiomethyl instead of 3, 5-dihydroxy-1, 2, 4-triazin-6-ylthiomethyl.

Table 5 Table 5 consists of 576 compounds of the general formula (1), where Y is fa-propyl, and Rl, R2, R3, X and Z have the values listed in Table 1. Thus compound 1 of Table 5 is the same as compound 1 of Table 1 except that in compound 1 of Table 5 Y is n-propyl instead of 3, 5-dihydroxy-1, 2,4-triazin-6-ylthiomethyl. Similarly, compounds 2 to 576 of Table 5 are the same as compounds 2 to 576 of Table 1, respectively, except that in the

compounds of Table 5 Y is n-propyl instead of 3, 5-dihydroxy-1, 2,4-triazin-6- ylthiomethyl.

Table 6 Table 6 consists of 576 compounds of the general formula (1), where Y is penta-1, 3-dien- 1-yl, and R1, R2, R3, X and Z have the values listed in Table 1. Thus compound 1 of Table 6 is the same as compound 1 of Table 1 except that in compound 1 of Table 6 Y is penta-1, 3-dien-1-yl instead of 3, 5-dihydroxy-1, 2, 4-triazin-6-ylthiomethyl. Similarly, compounds 2 to 576 of Table 6 are the same as compounds 2 to 576 of Table 1, respectively, except that in the compounds of Table 6 Y is penta-1, 3-dien-1-yl instead of 3,5-dihydroxy-1, 2,4-triazin-6-ylthiomethyl.

Table 7 Table 7 consists of 576 compounds of the general formula (1), where Y is 2,5- dichlorophenylethynyl, and Rl, R2, R3, X and Z have the values listed in Table 1. Thus compound 1 of Table 7 is the same as compound 1 of Table 1 except that in compound 1 of Table 7 Y is 2, 5-dichlorophenylethynyl instead of 3, 5-dihydroxy-1, 2,4-triazin-6- ylthiomethyl. Similarly, compounds 2 to 576 of Table 7 are the same as compounds 2 to 576 of Table 1, respectively, except that in the compounds of Table 7 Y is 2,5- dichlorophenylethynyl instead of 3,5-dihydroxy-1, 2,4-triazin-6-ylthiomethyl.

Table 8 Table 8 consists of 576 compounds of the general formula (1), where Y is cyclopentyl, and Rl, R2, R3, X and Z have the values listed in Table 1. Thus compound 1 of Table 8 is the same as compound 1 of Table 1 except that in compound 1 of Table 8 Y is cyclopentyl instead of 3, 5-dihydroxy-1, 2,4-triazin-6-ylthiomethyl. Similarly, compounds 2 to 576 of Table 8 are the same as compounds 2 to 576 of Table 1, respectively, except that in the compounds of Table 8 Y is cyclopentyl instead of 3, 5-dihydroxy-1, 2,4-triazin- 6-ylthiomethyl.

Table 9 Table 9 consists of 576 compounds of the general formula (1), where Y is 5- (4'- chlorophenyl)-4-ethyl-1, 2, 4-triazol-3-ylthiomethyl, and Rl, R2, R3, X and Z have the values listed in Table 1. Thus compound 1 of Table 9 is the same as compound 1 of Table 1 except that in compound 1 of Table 9 Y is 5- (4'-chlorophenyl)-4-ethyl-1, 2,4-

triazol-3-ylthiomethyl instead of 3, 5-dihydroxy-1, 2, 4-triazin-6-ylthiomethyl. Similarly, compounds 2 to 576 of Table 9 are the same as compounds 2 to 576 of Table 1, respectively, except that in the compounds of Table 9 Y is 5- (4'-chlorophenyl)-4-ethyl- 1,2, 4-triazol-3-ylthiomethyl instead of 3, 5-dihydroxy-1, 2,4-triazin-6-ylthiomethyl.

Table 10 Table 10 consists of 576 compounds of the general formula (1), where Y is thiazol-2- ylthiomethyl, and Rl, R2, R3, X and Z have the values listed in Table 1. Thus compound 1 of Table 10 is the same as compound 1 of Table 1 except that in compound 1 of Table 10 Y is thiazol-2-ylthiomethyl instead of 3, 5-dihydroxy-1, 2, 4-triazin-6-ylthiomethyl.

Similarly, compounds 2 to 576 of Table 10 are the same as compounds 2 to 576 of Table 1, respectively, except that in the compounds of Table 10 Y is thiazol-2-ylthiomethyl instead of 3,5-dihydroxy-1, 2,4-triazin-6-ylthiomethyl.

Table 11 Table 11 consists of 576 compounds of the general formula (1), where Y is 5-benzyl- 1, 3,4-oxadiazol-2-ylthiomethyl, and Rl, R2, R3, X and Z have the values listed in Table 1.

Thus compound 1 of Table 11 is the same as compound 1 of Table 1 except that in compound 1 of Table 11 Y is 5-benzyl-1, 3, 4-oxadiazol-2-ylthiomethyl instead of 3,5- dihydroxy-1, 2,4-triazin-6-ylthiomethyl. Similarly, compounds 2 to 576 of Table 11 are the same as compounds 2 to 576 of Table 1, respectively, except that in the compounds of Table 11 Y is 5-benzyl-1, 3,4-oxadiazol-2-ylthiomethyl instead of 3, 5-dihydroxy-1, 2,4- triazin-6-ylthiomethyl.

Table 12 Table 12 consists of 576 compounds of the general formula (1), where Y is 3-phenyl- prop-2-yn-1-yloxy, and Ru, R2, R3, X and Z have the values listed in Table 1. Thus compound 1 of Table 12 is the same as compound 1 of Table 1 except that in compound 1 of Table 12 Y is 3-phenylprop-2-yn-1-yloxy instead of 3, 5-dihydroxy-1, 2, 4-triazin-6- ylthiomethyl. Similarly, compounds 2 to 576 of Table 12 are the same as compounds 2 to 576 of Table 1, respectively, except that in the compounds of Table 12 Y is 3- phenylprop-2-yn-1-yloxy instead of 3, 5-dihydroxy-1, 2, 4-triazin-6-ylthiomethyl.

Table 13 Table 13 consists of 576 compounds of the general formula (1), where Y is 4-pyrid-3-yl- 1, 2,4-triazol-3-ylthiomethyl, and Rl, R2, R3, X and Z have the values listed in Table 1.

Thus compound 1 of Table 13 is the same as compound 1 of Table 1 except that in compound 1 of Table 13 Y is 4-pyrid-3-yl-1, 2, 4-triazol-3-ylthiomethyl instead of 3,5- dihydroxy-1, 2, 4-triazin-6-ylthiomethyl. Similarly, compounds 2 to 576 of Table 13 are the same as compounds 2 to 576 of Table 1, respectively, except that in the compounds of Table 13 Y is 4-pyrid-3-yl-1, 2,4-triazol-3-ylthiomethyl instead of 3, 5-dihydroxy-1, 2,4- triazin-6-ylthiomethyl.

Table 14 Table 14 consists of 576 compounds of the general formula (1), where Y is chloromethyl, and Rl, R2, R3, X and Z have the values listed in Table 1. Thus compound 1 of Table 14 is the same as compound 1 of Table 1 except that in compound 1 of Table 14 Y is chloromethyl instead. of 3, 5-dihydroxy-1, 2,4-triazin-6-ylthiomethyl. Similarly, compounds 2 to 576 of Table 14 are the same as compounds 2 to 576 of Table 1, respectively, except that in the compounds of Table 14 Y is chloromethyl instead of 3,5- dihydroxy-1,2, 4-triazin-6-ylthiomethyl.

Table 15 Table 15 consists of 576 compounds of the general formula (1), where Y is 1,3- dibromopropyl, and Rl, R2, R3, X and Z have the values listed in Table 1. Thus compound 1 of Table 15 is the same as compound 1 of Table 1 except that in compound 1 of Table 15 Y is 1,3-dibromopropyl instead of 3, 5-dihydroxy-1, 2,4-triazin-6- ylthiomethyl. Similarly, compounds 2 to 576 of Table 15 are the same as compounds 2 to 576 of Table 1, respectively, except that in the compounds of Table 15 Y is 1,3- dibromopropyl instead of 3,5-dihydroxy-1, 2,4-triazin-6-ylthiomethyl.

Table 16 Table 16 consists of 576 compounds of the general formula (1), where Y is but-2-yn-1- yloxy, and R1, R2, R3, X and Z have the values listed in Table 1. Thus compound 1 of Table 16 is the same as compound 1 of Table 1 except that in compound 1 of Table 16 Y is but-2-yn-1-yloxy instead of 3, 5-dihydroxy-1, 2,4-triazin-6-ylthiomethyl. Similarly, compounds 2 to 576 of Table 16 are the same as compounds 2 to 576 of Table 1,

respectively, except that in the compounds of Table 16 Y is but-2-yn-1-yloxy instead of 3, 5-dihydroxy-1, 2, 4-triazin-6-ylthiomethyl.

Table 17 Table 17 consists of 576 compounds of the general formula (1), where Y is 2- ethoxycarbonylethyl, and Rl, R, R3, X and Z have the values listed in Table 1. Thus compound 1 of Table 17 is the same as compound 1 of Table 1 except that in compound 1 of Table 17 Y is 2-ethoxycarbonylethyl instead of 3, 5-dihydroxy-1, 2,4-triazin-6- ylthiomethyl. Similarly, compounds 2 to 576 of Table 17 are the same as compounds 2 to 576 of Table 1, respectively, except that in the compounds of Table 17 Y is 2- ethoxycarbonylethyl instead of 3, 5-dihydroxy-1, 2, 4-triazin-6-ylthiomethyl.

Table 18 Table 18 consists of 576 compounds of the general formula (1), where Y is propen-2-yl, and Rl, R2, R3, X and Z have the values listed in Table 1. Thus compound 1 of Table 18 is the same as compound 1 of Table 1 except that in compound 1 of Table 18 Y is propen-2-yl instead of 3, 5-dihydroxy- I 2, 4-triazin-6-ylthiomethyl. Similarly, compounds 2 to 576 of Table 18 are the same as compounds 2 to 576 of Table 1, respectively, except that in the compounds of Table 18 Y is propen-2-yl instead of 3, 5-dihydroxy-1, 2,4- triazin-6-ylthiomethyl.

Table 19 Table 19 consists of 576 compounds of the general formula (1), where Y is l-chloro-n-. prop-1-yl, and Rl, R2, R3, X and Z have the values listed in Table 1. Thus compound 1 of Table 19 is the same as compound 1 of Table 1 except that in compound 1 of Table 19 Y is 1-chloro-n-prop-1-yl instead of 3, 5-dihydroxy-1, 2,4-triazin-6-ylthiomethyl. Similarly, compounds 2 to 576 of Table 19 are the same as compounds 2 to 576 of Table 1, respectively, except that in the compounds of Table 19 Y is 1-chloro-n-prop-l-yl instead of 3, 5-dihydroxy-1, 2, 4-triazin-6-ylthiomethyl.

Table 20 Table 20 consists of 576 compounds of the general formula (1), where Y is 4-methyl- pyrimidin-2-ylthiomethyl, and Rl, R2, R3, X and Z have the values listed in Table 1. Thus compound 1 of Table 20 is the same as compound 1 of Table 1 except that in compound 1 of Table 20 Y is 4-methyl-pyrimidin-2-ylthiomethyl instead of 3, 5-dihydroxy-1, 2,4-

triazin-6-ylthiomethyl. Similarly, compounds 2 to 576 of Table 20 are the same as compounds 2 to 576 of Table 1, respectively, except that in the compounds of Table 20 Y is 4-methyl-pyrimidin-2-ylthiomethyl instead of 3, 5-dihydroxy-1, 2,4-triazin-6- ylthiomethyl.

Table 21 Table 21 consists of 576 compounds of the general formula (1), where Y is 1-chloroeth- 1-yl, and R1, R2, R3, X and Z have the values listed in Table 1. Thus compound 1 of Table 21 is the same as compound 1 of Table 1 except that in compound 1 of Table 21 Y is 1-chloroeth-1-yl instead of 3, 5-dihydroxy-1, 2,4-triazin-6-ylthiomethyl. Similarly, compounds 2 to 576 of Table 21 are the same as compounds 2 to 576 of Table 1, respectively, except that in the compounds of Table 21 Y is 1-chloroeth-1-yl instead of 3, 5-dihydroxy-1, 2,4-triazin-6-ylthiomethyl.

Table 22 Table 22 consists of 576 compounds of the general formula (1), where Y is 5- (4- methoxyphenyl) -tetrazol-2-ylmethyl, and R, R2, R3, X and Z have the values listed in Table 1. Thus compound 1 of Table 22 is the same as compound 1 of Table 1 except that in compound 1 of Table 22 Y is 5- (4-methoxyphenyl)-tetrazol-2-ylmethyl instead of 3,5- dihydroxy-1, 2, 4-triazin-6-ylthiomethyl. Similarly, compounds 2 to 576 of Table 22 are the same as compounds 2 to 576 of Table 1, respectively, except that in the compounds of Table 22 Y is 5- (4-methoxyphenyl)-tetrazol-2-ylmethyl instead of 3, 5-dihydroxy- 1,2, 4-triazin-6-ylthiomethyl.

Table 23 Table 23 consists of 576 compounds of the general formula (1), where Y is 3- (4- fluorophenyl) -isothiazolo [4,5-d] pyrimidin-7-ylthiomethyl, and R, R2, R3, X and Z have the values listed in Table 1. Thus compound 1 of Table 23 is the same as compound 1 of Table 1 except that in compound 1 of Table 23 Y is 3- (4-fluorophenyl)-isothiazolo- [4,5-d] pyrimidin-7-ylthiomethyl instead of 3, 5-dihydroxy-1, 2,4-triazin-6-ylthiomethyl.

Similarly, compounds 2 to 576 of Table 23 are the same as compounds 2 to 576 of Table 1, respectively, except that in the compounds of Table 23 Y is 3- (4-fluorophenyl)- isothiazolo [4,5-d] pyrimidin-7-ylthiomethyl instead of 3, 5-dihydroxy-1, 2,4-triazin-6- ylthiomethyl.

Table 24 Table 24 consists of 576 compounds of the general formula (1), where Y is pent-2-yn-1- yloxy, and Rl, R2, R3, X and Z have the values listed in Table 1. Thus compound 1 of Table 24 is the same as compound 1 of Table 1 except that in compound 1 of Table 24 Y is pent-2-yn-1-yloxy instead of 3, 5-dihydroxy-1, 2,4-triazin-6-ylthiomethyl. Similarly, compounds 2 to 576 of Table 24 are the same as compounds 2 to 576 of Table 1, respectively, except that in the compounds of Table 24 Y is pent-2-yn-1-yloxy instead of 3, 5-dihydroxy-1, 2,4-triazin-6-ylthiomethyl.

Table 25 Table 25 consists of 576 compounds of the general formula (1), where Y is 3-cyano-6- methylpyrid-2-ylthiomethyl, and Rl, R, R3, X and Z have the values listed in Table 1.

Thus compound 1 of Table 25 is the same as compound 1 of Table 1 except that in compound 1 of Table 25 Y is 3-cyano-6-methylpyrid-2-ylthiomethyl instead of 3,5- dihydroxy-1, 2,4-triazin-6-ylthiomethyl. Similarly, compounds 2 to 576 of Table 25 are the same as compounds 2 to 576 of Table 1, respectively, except that in the compounds of Table 25 Y is 3-cyano-6-methylpyrid-2-ylthiomethyl instead of 3, 5-dihydroxy-1, 2,4- triazin-6-ylthiomethyl.

Table 26 Table 26 consists of 576 compounds of the general formula (1), where Y is chloro-tert- butyl, and Rl, R, R3, X and Z have the values listed in Table 1. Thus compound 1 of Table 26 is the same as compound 1 of Table 1 except that in compound 1 of Table 26 Y is chloro-tert-butyl instead of 3, 5-dihydroxy-1, 2,4-triazin-6-ylthiomethyl. Similarly, compounds 2 to 576 of Table 26 are the same as compounds 2 to 576 of Table 1, respectively, except that in the compounds of Table 26 Y is chloro-tert-butyl instead of 3, 5-dihydroxy-1, 2,4-triazin-6-ylthiomethyl.

Table 27 Table 27 consists of 576 compounds of the general formula (1), where Y is 6-methoxy-2- methyl-quinolin-4-ylthiomethyl, and Rl, R, R3, X and Z have the values listed in Table 1. Thus compound 1 of Table 27 is the same as compound 1 of Table 1 except that in compound 1 of Table 27 Y is 6-methoxy-2-methyl-quinolin-4-ylthiomethyl instead of 3, 5-dihydroxy-1, 2,4-triazin-6-ylthiomethyl. Similarly, compounds 2 to 576 of Table 27

are the same as compounds 2 to 576 of Table 1, respectively, except that in the compounds of Table 27 Y is 6-methoxy-2-methyl-quinolin-4-ylthiomethyl instead of 3,5- dihydroxy-1, 2, 4-triazin-6-ylthiomethyl.

Table 28 Table 28 consists of 576 compounds of the general formula (1), where Y is 5- trifluoromethyl-pyrid-2-ylthiomethyl, and Rl, R2, R3, X and Z have the values listed in Table 1. Thus compound 1 of Table 28 is the same as compound 1 of Table 1 except that in compound 1 of Table 28 Y is 5-trifluoromethyl-pyrid-2-ylthiomethyl instead of 3,5- dihydroxy-1, 2,4-triazin-6-ylthiomethyl. Similarly, compounds 2 to 576 of Table 28 are the same as compounds 2 to 576 of Table 1, respectively, except that in the compounds of Table 28 Y is 5-trifluoromethyl-pyrid-2-ylthiomethyl instead of 3, 5-dihydroxy-1, 2,4- triazin-6-ylthiomethyl.

Table 29 Table 29 consists of 576 compounds of the general formula (1), where Y is prop-1-enyl, and Rl, R2, R3, X and Z have the values listed in Table 1. Thus compound 1 of Table 29 is the same as compound 1 of Table 1 except that in compound 1 of Table 29 Y is prop- 1-enyl instead of 3, 5-dihydroxy-1, 2, 4-triazin-6-ylthiomethyl. Similarly, compounds 2 to 576 of Table 29 are the same as compounds 2 to 576 of Table 1, respectively, except that in the compounds of Table 29 Y is prop-1-enyl instead of 3, 5-dihydroxy-1, 2,4-triazin-6- ylthiomethyl.

Table 30 Table 30 consists of 576 compounds of the general formula (1), where Y is 3- (2- hydroxyphenyl)-lH-1, 2,4-triazol-5-ylthiomethyl, and Rl, R2, R3, X and Z have the values listed in Table 1. Thus compound 1 of Table 30 is the same as compound 1 of Table 1 except that in compound 1 of Table 30 Y is 3- (2-hydroxyphenyl)-IH-1, 2,4-triazol-5- ylthiomethyl instead of 3, 5-dihydroxy-1, 2,4-triazin-6-ylthiomethyl. Similarly, compounds 2 to 576 of Table 30 are the same as compounds 2 to 576 of Table 1, respectively, except that in the compounds of Table 30 Y is 3-(2-hydroxyphenyl)-lH-1, 2, 4-triazol-5- ylthiomethyl instead of 3,5-dihydroxy-1, 2,4-triazin-6-ylthiomethyl.

Table 31 Table 31 consists of 576 compounds of the general formula (1), where Y is hydrogen, and Rl, R, R3, X and Z have the values listed in Table 1. Thus compound 1 of Table 31 is the same as compound 1 of Table 1 except that in compound 1 of Table 31 Y is hydrogen instead of 3, 5-dihydroxy-1, 2,4-triazin-6-ylthiomethyl. Similarly, compounds 2 to 576 of Table 31 are the same as compounds 2 to 576 of Table 1, respectively, except that in the compounds of Table 31 Y is hydrogen instead of 3, 5-dihydroxy-1, 2,4-triazin-6- ylthiomethyl.

Table 32 Table 32 consists of 576 compounds of the general formula (1), where Y is 5-benzyl-4- methyl-1, 2,4-triazol-3-ylthiomethyl, and R1, R, R3, X and Z have the values listed in Table 1. Thus compound 1 of Table 32 is the same as compound 1 of Table 1 except that in compound 1 of Table 32 Y is 5-benzyl-4-methyl-1, 2, 4-triazol-3-ylthiomethyl instead of 3, 5-dihydroxy-1, 2, 4-triazin-6-ylthiomethyl. Similarly, compounds 2 to 576 of Table 32 are the same as compounds 2 to 576 of Table 1, respectively, except that in the compounds of Table 32 Y is 5-benzyl-4-methyl-1, 2, 4-triazol-3-ylthiomethyl instead of 3, 5-dihydroxy-1, 2,4-triazin-6-ylthiomethyl.

Table 33 Table 33 consists of 576 compounds of the general formula (1), where Y is phenylchloromethyl, and Rl, R2, R3, X and Z have the values listed in Table 1. Thus compound 1 of Table 33 is the same as compound 1 of Table 1 except that in compound 1 of Table 33 Y is phenylchloromethyl instead of 3, 5-dihydroxy-1, 2,4-triazin-6- ylthiomethyl. Similarly, compounds 2 to 576 of Table 33 are the same as compounds 2 to 576 of Table 1, respectively, except that in the compounds of Table 33 Y is phenylchloromethyl instead of 3,5-dihydroxy-1, 2,4-triazin-6-ylthiomethyl.

Table 34 Table 34 consists of 576 compounds of the general formula (1), where Y is 6-amino-3, 5- dicyano-pyrid-2-ylthiomethyl, and Rl, R, R3, X and Z have the values listed in Table 1.

Thus compound 1 of Table 34 is the same as compound 1 of Table 1 except that in compound 1 of Table 34 Y is 6-amino-3, 5-dicyano-pyrid-2-ylthiomethyl instead of 3,5- dihydroxy-l, 2,4-triazin-6-ylthiomethyl. Similarly, compounds 2 to 576 of Table 34 are

the same as compounds 2 to 576 of Table 1, respectively, except that in the compounds of Table 34 Y is 6-amino-3, 5-dicyano-pyrid-2-ylthiomethyl instead of 3, 5-dihydroxy- 1,2, 4-triazin-6-ylthiomethyl.

Table 35 Table 35 consists of 576 compounds of the general formula (1), where Y is 5- (4- methoxyphenyl)-4-phenyl-1, 2, 4-triazol-3-ylthiomethyl, and Rl, R2, R3, X and Z have the values listed in Table 1. Thus compound 1 of Table 35 is the same as compound 1 of Table 1 except that in compound 1 of Table 35 Y is 5- (4-methoxyphenyl)-4-phenyl-1, 2,4- triazol-3-ylthiomethyl instead of 3, 5-dihydroxy-1, 2,4-triazin-6-ylthiomethyl. Similarly, compounds 2 to 576 of Table 35 are the same as compounds 2 to 576 of Table 1, respectively, except that in the compounds of Table 35 Y is 5- (4-methoxyphenyl)-4- phenyl-1, 2,4-triazol-3-ylthiomethyl instead of 3,5-dihydroxy-1, 2,4-triazin-6-ylthiomethyl.

Table 36 Table 36 consists of 576 compounds of the general formula (1), where Y is ethynyl, and Rl, R2, R3, X and Z have the values listed in Table 1. Thus compound 1 of Table 36 is the same as compound 1 of Table 1 except that in compound 1 of Table 36 Y is ethynyl instead of 3, 5-dihydroxy-1, 2,4-triazin-6-ylthiomethyl. Similarly, compounds 2 to 576 of Table 36 are the same as compounds 2 to 576 of Table 1, respectively, except that in the compounds of Table 36 Y is ethynyl instead of 3, 5-dihydroxy-1, 2,4-triazin-6- ylthiomethyl.

Table 37 Table 37 consists of 576 compounds of the general formula (1), where Y is 4,5-diphenyl- oxazol-2-ylthiomethyl, and Rl, R2, R3, X and Z have the values listed in Table 1. Thus compound 1 of Table 37 is the same as compound 1 of Table 1 except that in compound 1 of Table 37 Y is 4, 5-diphenyl-oxazol-2-ylthiomethyl instead of 3, 5-dihydroxy-1, 2,4- triazin-6-ylthiomethyl. Similarly, compounds 2 to 576 of Table 37 are the same as compounds 2 to 576 of Table 1, respectively, except that in the compounds of Table 37 Y is 4,5-diphenyl-oxazol-2-ylthiomethyl instead of 3, 5-dihydroxy-1, 2,4-triazin-6- ylthiomethyl.

Table 38 Table 38 consists of 576 compounds of the general formula (1), where Y is 3-cyano- 4,5, 6-trimethylpyrid-2-ylthiomethyl, and R1, R2, R3, X and Z have the values listed in Table 1. Thus compound 1 of Table 38 is the same as compound 1 of Table 1 except that in compound 1 of Table 38 Y is 3-cyano-4n5 6-trimethylpyrid-2-ylthiomethyl instead of 3, 5-dihydroxy-1, 2, 4-triazin-6-ylthiomethyl. Similarly, compounds 2 to 576 of Table 38 are the same as compounds 2 to 576 of Table 1, respectively, except that in the compounds of Table 38 Y is 3-cyano-4,5, 6-trimethylpyrid-2-ylthiomethyl instead of 3,5- ,.. dihydroxy-1, 2,4-triazin-6-ylthiomethyl.

Table 39 Table 39 consists of 576 compounds of the general formula (1), where Y is 5-chloro-lH- benzimidazol-2-ylthiomethyl, and Rl, R2, R3, X and Z have the values listed in Table 1.

Thus compound 1 of Table 39 is the same as compound 1 of Table 1 except that in compound 1 of Table 39 Y is 5-chloro-lH-benzimidazol-2-ylthiomethyl instead of 3,5- dihydroxy-1, 2,4-triazin-6-ylthiomethyl. Similarly, compounds 2 to 576 of Table 39 are the same as compounds 2 to 576 of Table 1, respectively, except that in the compounds of Table 39 Y is 5-chloro-1H-benzimidazol-2-ylthiomethyl instead of 3, 5-dihydroxy- 1,2, 4-triazin-6-ylthiomethyl.

Table 40 Table 40 consists of 576 compounds of the general formula (1), where Y is 3-7z-pentyl, and R', R2, R3, X and Z have the values listed in Table 1. Thus compound 1 of Table 40 is the same as compound 1 of Table 1 except that in compound 1 of Table 40 Y is 3-n- pentyl instead of 3, 5-dihydroxy-1, 2,4-triazin-6-ylthiomethyl. Similarly, compounds 2 to 576 of Table 40 are the same as compounds 2 to 576 of Table 1, respectively, except that in the compounds of Table 40 Y is 3-n-pentyl instead of 3, 5-dihydroxy-1, 2,4-triazin-6- ylthiomethyl.

Table 41 Table 41 consists of 576 compounds of the general formula (1), where Y is 1- phenylprop-2-yn-1-yloxy, and Ru, R, R3, X and Z have the values listed in Table 1. Thus compound 1 of Table 41 is the same as compound 1 of Table 1 except that in compound 1 of Table 41 Y is l-phenylprop-2-yn-1-yloxy instead of 3, 5-dihydroxy-1, 2,4-triazin-6-

ylthiomethyl. Similarly, compounds 2 to 576 of Table 41 are the same as compounds 2 to 576 of Table 1, respectively, except that in the compounds of Table 41 Y is 1- phenylprop-2-yn-1-yloxy instead of 3, 5-dihydroxy-1, 2,4-triazin-6-ylthiomethyl.

Table 42 Table 42 consists of 576 compounds of the general formula (1), where Y is 3-chloro-n- prop-1-yl, and R1, R2, R3, X and, Z have the values listed in Table 1. Thus compound 1 of Table 42 is the same as compound 1 of Table 1 except that in compound 1 of Table 42 Y is 3-chloro-n-prop-1-yl instead of 3, 5-dihydroxy-1, 2,4-triazin-6-ylthiomethyl. Similarly, compounds 2 to 576 of Table 42 are the same as compounds 2 to 576 of Table 1, respectively, except that in the compounds of Table 42 Y is 3-chloro-n-prop-1-yl instead of 3, 5-dihydroxy-1, 2,4-triazin-6-ylthiomethyl.

Table 43 Table 43 consists of 576 compounds of the general formula (1), where Y is 3-cyano-6- methyl-4-thien-2-yl-pyrid-2-ylthiomethyl, and Ru, R2, R3, X and Z have the values listed in Table 1. Thus compound 1 of Table 43 is the same as compound 1 of Table 1 except that in compound 1 of Table 43 Y is 3-cyano-6-methyl-4-thien-2-yl-pyrid-2-ylthiomethyl instead of 3, 5-dihydroxy-1, 2,4-triazin-6-ylthiomethyl. Similarly, compounds 2 to 576 of Table 43 are the same as compounds 2 to 576 of Table 1, respectively, except that in the compounds of Table 43 Y is 3-cyano-6-methyl-4-thien-2-yl-pyrid-2-ylthiomethyl instead of 3, 5-dihydroxy-1, 2,4-triazin-6-ylthiomethyl.

Table 44 Table 44 consists of 576 compounds of the general formula (1), where Y is 5- (2- bromophenyl)-4-methyl-1, 2,4-triazol-3-ylthiomethyl, and Ru, R, R3, X and Z have the values listed in Table 1. Thus compound 1 of Table 44 is the same as compound 1 of Table 1 except that in compound 1 of Table 44 Y is 5-(2-bromophenyl)-4-methyl-1, 2,4- triazol-3-ylthiomethyl instead of 3, 5-dihydroxy-1, 2,4-triazin-6-ylthiomethyl. Similarly, compounds 2 to 576 of Table 44 are the same as compounds 2 to 576 of Table 1, respectively, except that in the compounds of Table 44 Y is 5- (2-bromophenyl)-4-methyl- 1, 2,4-triazol-3-ylthiomethyl instead of 3, 5-dihydroxy-1, 2,4-triazin-6-ylthiomethyl.

Table 45 Table 45 consists of 576 compounds of the general formula (1), where Y is 5- (4- fluorophenyl)-l-methyl-imidazol-2-ylthiomethyl, and Ru, R2, R3, X and Z have the values listed in Table 1. Thus compound 1 of Table 45 is the same as compound 1 of Table 1 except that in compound 1 of Table 45 Y is 5- (4-fluorophenyl)-1-methyl-imidazol-2- ylthiomethyl instead of 3, 5-dihydroxy-1, 2,4-triazin-6-ylthiomethyl. Similarly, compounds 2 to 576 of Table 45 are the same as compounds 2 to 576 of Table 1, respectively, except that in the compounds of Table 45 Y is 5-(4-fluorophenyl)-1-metl1yl-imidazol-2- ylthiomethyl instead of 3,5-dihydroxy-1, 2,4-triazin-6-ylthiomethyl.

Table 46 Table 46 consists of 576 compounds of the general formula (1), where Y is 4-ethyl-5- thien-2-yl-1, 2,4-triazol-3-ylthiomethyl, and Ru, R2, R3, X and Z have the values listed in Table 1. Thus compound 1 of Table 46 is the same as compound 1 of Table 1 except that in compound 1 of Table 46 Y is 4-ethyl-5-thien-2-yl-1, 2,4-triazol-3-ylthiomethyl instead of 3, 5-dihydroxy-1, 2,4-triazin-6-ylthiomethyl. Similarly, compounds 2 to 576 of Table 46 are the same as compounds 2 to 576 of Table 1, respectively, except that in the compounds of Table 46 Y is 4-ethyl-5-thien-2-yl-1, 2, 4-triazol-3-ylthiomethyl instead of 3, 5-dihydroxy-1, 2, 4-triazin-6-ylthiomethyl.

Table 47 Table 47 consists of 576 compounds of the general formula (1), where Y is 4- trifluoromethyl-pyrimidin-2-ylthiomethyl, and R, R2, R3, X and Z have the values listed in Table 1. Thus compound 1 of Table 47 is the same as compound 1 of Table 1 except that in compound 1 of Table 47 Y is 4-trifluoromethyl-pyrimidin-2-ylthiomethyl instead of 3, 5-dihydroxy-1, 2, 4-triazin-6-ylthiomethyl. Similarly, compounds 2 to 576 of Table 47 are the same as compounds 2 to 576 of Table 1, respectively, except that in the compounds of Table 47 Y is 4-trifluoromethyl-pyrimidin-2-ylthiomethyl instead of 3,5- dihydroxy-1, 2,4-triazin-6-ylthiomethyl.

Table 48 Table 48 consists of 576 compounds of the general formula (1), where Y is 4-ethyl-5- pyrid-4-yl-1, 2,4-triazol-3-ylthiomethyl, and Rl, R2, R3, X and Z have the values listed in Table 1. Thus compound 1 of Table 48 is the same as compound 1 of Table 1 except that

in compound 1 of Table 48 Y is 4-ethyl-5-pyrid-4-yl-1, 2, 4-triazol-3-ylthiomethyl instead of 3, 5-dihydroxy-1, 2, 4-triazin-6-ylthiomethyl. Similarly, compounds 2 to 576 of Table 48 are the same as compounds 2 to 576 of Table 1, respectively, except that in the compounds of Table 48 Y is 4-ethyl-5-pyrid-4-yl-1, 2,4-triazol-3-ylthiomethyl instead of 3, 5-dihydroxy-1, 2, 4-triazin-6-ylthiomethyl.

Table 49 Table 49 consists of 576 compounds of the general formula (1), where Y is 4-ethyl-5- phenyl-1, 2, 4-triazol-3-ylthiomethyl, and Rl, R2, R3, X and Z have the values listed in Table 1. Thus compound 1 of Table 49 is the same as compound 1 of Table 1 except that in compound 1 of Table 49 Y is 4-ethyl-5-phenyl-1, 2,4-triazol-3-ylthiomethyl instead of 3, 5-dihydroxy-1, 2,4-triazin-6-ylthiomethyl. Similarly, compounds 2 to 576 of Table 49 are the same as compounds 2 to 576 of Table 1, respectively, except that in the compounds of Table 49 Y is 4-ethyl-5-phenyl-1, 2,4-triazol-3-ylthiomethyl instead of 3,5- dihydroxy-1,2, 4-triazin-6-ylthiomethyl.

Table 50 Table 50 consists of 576 compounds of the general formula (1), where Y is 1,2- dibromoprop-2-yl, and Ru, R2, R3, X and Z have the values listed in Table 1. Thus compound 1 of Table 50 is the same as compound 1 of Table 1 except that in compound 1 of Table 50 Y is 1, 2-dibromoprop-2-yl instead of 3, 5-dihydroxy-1, 2, 4-tliazin-6- ylthiomethyl. Similarly, compounds 2 to 576 of Table 50 are the same as compounds 2 to 576 of Table 1, respectively, except that in the compounds of Table 50 Y is 1,2- dibromoprop-2-yl instead of 3, 5-dihydroxy-1, 2,4-triazin-6-ylthiomethyl.

Table 51 Table 51 consists of 576 compounds of the general formula (1), where Y is 2,2-dibromo- 1-methyl-cyclopropyl, and Rl, R2, R3, X and Z have the values listed in Table 1. Thus compound 1 of Table 51 is the same as compound 1 of Table 1 except that in compound 1 of Table 51 Y is 2, 2-dibromo-1-methyl-cyclopropyl instead of 3, 5-dihydroxy-1, 2,4- triazin-6-ylthiomethyl. Similarly, compounds 2 to 576 of Table 51 are the same as compounds 2 to 576 of Table 1, respectively, except that in the compounds of Table 51 Y is 2, 2-dibromo-1-methyl-cyclopropyl instead of 3, 5-dihydroxy-1, 2,4-triazin-6- ylthiomethyl.

Table 52 Table 52 consists of 576 compounds of the general formula (1), where Y is 5- (4- methoxyphenyl)-1, 3,4-oxadiazol-2-ylthiomethyl, and Rl, R2, R3, X and Z have the values listed in Table 1. Thus compound 1 of Table 52 is the same as compound 1 of Table 1 except that in compound 1 of Table 52 Y is 5-(4-methoxyphenyl)-1, 3,4-oxadiazol-2- ylthiomethyl instead of 3, 5-dihydroxy-1, 2, 4-triazin-6-ylthiomethyl. Similarly, compounds 2 to 576 of Table 52 are the same as compounds 2 to 576 of Table 1, respectively, except that in the compounds of Table 52 Y is 5- (4-methoxyphenyl)-1, 3,4-oxadiazol-2- ylthiomethyl instead of 3, 5-dihydroxy-1, 2,4-triazin-6-ylthiomethyl.

Table 53 Table 53 consists of 576 compounds of the general formula (1), where Y is 5-benzyl-4- cyclohexyl-1, 2,4-triazol-3-ylthiomethyl, and Rl, R2, R3, X and Z have the values listed in Table 1. Thus compound 1 of Table 53 is the same as compound 1 of Table 1 except that in compound 1 of Table 53 Y is 5-benzyl-4-cyclohexyl-1, 2,4-triazol-3-ylthiomethyl instead of 3, 5-dihydroxy-1, 2,4-triazin-6-ylthiomethyl. Similarly, compounds 2 to 576 of Table 53 are the same as compounds 2 to 576 of Table 1, respectively, except that in the compounds of Table 53 Y is 5-benzyl-4-cyclohexyl-1, 2,4-triazol-3-ylthiomethyl instead of 3, 5-dihydroxy-1, 2,4-triazin-6-ylthiomethyl.

Table 54 Table 54 consists of 576 compounds of the general formula (1), where Y is 3-cyano-6- thien-2-yl-pyrid-2-ylthiomethyl, and Rl, R2, R3, X and Z have the values listed in Table 1.

Thus compound 1 of Table 54 is the same as compound 1 of Table 1 except that in compound 1 of Table 54 Y is 3-cyano-6-thien-2-yl-pyrid-2-ylthiomethyl instead of 3,5- dihydroxy-1, 2, 4-triazin-6-ylthiomethyl. Similarly, compounds 2 to 576 of Table 54 are the same as compounds 2 to 576 of Table 1, respectively, except that in the compounds of Table 54 Y is 3-cyano-6-thien-2-yl-pyrid-2-ylthiomethyl instead of 3, 5-dihydroxy- 1,2, 4-triazin-6-ylthiomethyl.

Table 55 Table 55 consists of 576 compounds of the general formula (1), where Y is 5-methyl-4- phenyl-l, 2,4-triazol-3-ylthiomethyl, and Rl, R2, R3, X and Z have the values listed in Table 1. Thus compound 1 of Table 55 is the same as compound 1 of Table 1 except that

in compound 1 of Table 55 Y is 5-methyl-4-phenyl-1, 2,4-triazol-3-ylthiomethyl instead of 3, 5-dihydroxy-1, 2,4-triazin-6-ylthiomethyl. Similarly, compounds 2 to 576 of Table 55 are the same as compounds 2 to 576 of Table 1, respectively, except that in the compounds of Table 55 Y is 5-methyl-4-phenyl-1, 2, 4-triazol-3-ylthiomethyl instead of 3, 5-dihydroxy-1, 2,4-triazin-6-ylthiomethyl.

Table 56 Table 56 consists of 576 compounds of the general formula (1), where Y is tetrazol-2- ylmethyl, and Ru, R2, R3, X and Z have the values listed in Table 1. Thus compound 1 of Table 56 is the same as compound 1 of Table 1 except that in compound 1 of Table 56 Y is tetrazol-2-ylmethyl instead of 3, 5-dihydroxy-1, 2,4-triazin-6-ylthiomethyl. Similarly, compounds 2 to 576 of Table 56 are the same as compounds 2 to 576 of Table 1, respectively, except that in the compounds of Table 56 Y is tetrazol-2-ylmethyl instead of 3,5-dihydroxy-1, 2, 4-triazin-6-ylthiomethyl.

Table 57 Table 57 consists of 576 compounds of the general formula (1), where Y is 3-cyano- 5,6, 7, 8-tetrahydroquinolin-2-ylthiomethyl, and Ru, R2, R3, X and Z have the values listed in Table 1. Thus compound 1 of Table 57 is the same as compound 1 of Table 1 except that in compound 1 of Table 57 Y is 3-cyano-5,6, 7,8-tetrahydroquinolin-2-ylthiomethyl instead of 3, 5-dihydroxy-1, 2,4-triazin-6-ylthiomethyl. Similarly, compounds 2 to 576 of Table 57 are the same as compounds 2 to 576 of Table 1, respectively, except that in the compounds of Table 57 Y is 3-cyano-5,6, 7, 8-tetrahydroquinolin-2-ylthiomethyl instead of 3, 5-dihydroxy-1, 2,4-triazin-6-ylthiomethyl.

Table 58 Table 58 consists of 576 compounds of the general formula (1), where Y is ethyl, and Rl, R2, R3, X and Z have the values listed in Table 1. Thus compound 1 of Table 58 is the same as compound 1 of Table 1 except that in compound 1 of Table 58 Y is ethyl instead of 3, 5-dihydroxy-1, 2, 4-triazin-6-ylthiomethyl. Similarly, compounds 2 to 576 of Table 58 are the same as compounds 2 to 576 of Table 1, respectively, except that in the compounds of Table 58 Y is ethyl instead of 3, 5-dihydroxy-1, 2,4-triazin-6-ylthiomethyl.

Table 59 Table 59 consists of 576 compounds of the general formula (1), where Y is hydroxymethyl, and Rl, R2, R3, X and Z have the values listed in Table 1. Thus compound 1 of Table 59 is the same as compound 1 of Table 1 except that in compound 1 of Table 59 Y is hydroxymethyl instead of 3, 5-dihydroxy-1, 2,4-triazin-6-ylthiomethyl.

Similarly, compounds 2 to 576 of Table 59 are the same as compounds 2 to 576 of Table 1, respectively, except that in the compounds of Table 59 Y is hydroxymethyl instead of 3,5-dihydroxy-1, 2, 4-triazin-6-ylthiomethyl.

Table 60 Table 60 consists of 576 compounds of the general formula (1), where Y is ethenyl, and Ru, R2, R3, X and Z have the values listed in Table 1. Thus compound 1 of Table 60 is the same as compound 1 of Table 1 except that in compound 1 of Table 60 Y is ethenyl instead of 3, 5-dihydroxy-1, 2, 4-triazin-6-ylthiomethyl. Similarly, compounds 2 to 576 of Table 60 are the same as compounds 2 to 576 of Table 1, respectively, except that in the compounds of Table 60 Y is ethenyl instead of 3, 5-dihydroxy-1, 2,4-triazin-6- ylthiomethyl.

Table 61 Table 61 consists of 576 compounds of the general formula (1), where Y is 2- chloroethen-1-yl, and R1, R2, R3, X and Z have the values listed in Table 1. Thus compound 1 of Table 61 is the same as compound 1 of Table 1 except that in compound 1 of Table 61 Y is 2-chloroethen-1-yl instead of 3, 5-dihydroxy-1, 2,4-triazin-6- ylthiomethyl. Similarly ; compounds 2 to 576 of Table 61 are the same as compounds 2 to 576 of Table 1, respectively, except that in the compounds of Table 61 Y is 2- chloroethen-1-yl instead of 3, 5-dihydroxy-1, 2,4-triazin-6-ylthiomethyl.

Table 62 Table 62 consists of 576 compounds of the general formula (1), where Y is 3- trimethylsilyl-prop-2-yn-1-yloxy, and Rl, R2, R3, X and Z have the values listed in Table 1. Thus compound 1 of Table 62 is the same as compound 1 of Table 1 except that in compound 1 of Table 62 Y is 3-trimethylsilyl-prop-2-yn-1-yloxy instead of 3,5- dihydroxy-1, 2,4-triazin-6-ylthiomethyl. Similarly, compounds 2 to 576 of Table 62 are the same as compounds 2 to 576 of Table 1, respectively, except that in the compounds

of Table 62 Y is 3-trimethylsilyl-prop-2-yn-1-yloxy instead of 3, 5-dihydroxy-1, 2,4- triazin-6-ylthiomethyl.

Table 63 Table 63 consists of 576 compounds of the general formula (1), where Y is 1-oxy-pyrid- 2-ylthiomethyl, and Rl, R2, R3, X and Z have the values listed in Table 1. Thus compound 1 of Table 63 is the same as compound 1 of Table 1 except that in compound 1 of Table 63 Y is l-oxy-pyrid-2-ylthiomethyl instead of 3, 5-dihydroxy-1, 2,4-triazin-6- ylthiomethyl. Similarly, compounds 2 to 576 of Table 63 are the same as compounds 2 to 576 of Table 1, respectively, except that in the compounds of Table 63 Y is l-oxy-pyrid- 2-ylthiomethyl instead of 3,5-dihydroxy-1, 2,4-triazin-6-ylthiomethyl.

Table 64 Table 64 consists of 576 compounds of the general formula (1), where Y is 2- dimethylamino-1-ethoxycarbonylethen-l-yl, and Rl, R2, R3, X and Z have the values listed in Table 1. Thus compound 1 of Table 64 is the same as compound 1 of Table 1 except that in compound 1 of Table 64 Y is 2-dimethylamino-1-ethoxycarbonylethen-1-yl instead of 3, 5-dihydroxy-1, 2,4-triazin-6-ylthiomethyl. Similarly, compounds 2 to 576 of Table 64 are the same as compounds 2 to 576 of Table 1, respectively, except that in the compounds of Table 64 Y is 2-dimethylamino-1-ethoxycarbonylethen-l-yl instead of 3,5- dihydroxy-1, 2,4-triazin-6-ylthiomethyl.

Table 65 Table 65 consists of 576 compounds of the general formula (|1), where Y is 2-chloroeth- 1-yl, and Rl, R2, R3, X and Z have the values listed in Table 1. Thus compound 1 of Table 65 is the same as compound 1 of Table 1 except that in compound 1 of Table 65 Y is 2-chloroeth-1-yl instead of 3, 5-dihydroxy-1, 2,4-triazin-6-ylthiomethyl. Similarly, compounds 2 to 576 of Table 65 are the same as compounds 2 to 576 of Table 1, respectively, except that in the compounds of Table 65 Y is 2-chloroeth-1-yl instead of 3,5-dihydroxy-1, 2,4-triazin-6-ylthiomethyl.

Table 66 Table 66 consists of 576 compounds of the general formula (1), where Y is 5-methyl- hex-l-yn-3-yloxy, and R', R2, R3, X and Z have the values listed in Table 1. Thus compound 1 of Table 66 is the same as compound 1 of Table 1 except that in compound

1 of Table 66 Y is 5-methyl-hex-1-yn-3-yloxy instead of 3, 5-dihydroxy-1, 2,4-triazin-6- ylthiomethyl. Similarly, compounds 2 to 576 of Table 66 are the same as compounds 2 to 576 of Table 1, respectively, except that in the compounds of Table 66 Y is 5-methyl- hex-1-yn-3-yloxy instead of 3,5-dihydroxy-1, 2, 4-triazin-6-ylthiomethyl.

Table 67 Table 67 consists of 576 compounds of the general formula (1), where Y is ethoxycarbonylmethylthiomethyl, and Ru, R2, R3, X and Z have the values listed in Table 1. Thus compound 1 of Table 67 is the same as compound 1 of Table 1 except that in compound 1 of Table 67 Y is ethoxycarbonylmethylthiomethyl instead of 3, 5-dihydroxy- 1, 2,4-triazin-6-ylthiomethyl. Similarly, compounds 2 to 576 of Table 67 are the same as compounds 2 to 576 of Table 1, respectively, except that in the compounds of Table 67 Y is ethoxycarbonylmethylthiomethyl instead of 3, 5-dihydroxy-1, 2, 4-triazin-6-ylthiomethyl.

Table 68 Table 68 consists of 576 compounds of the general formula (1), where Y is 5-thien-2-yl- 1, 3,4-oxadiazol-2-ylthiomethyl, and Rl, R2, R3, X and Z have the values listed in Table 1.

Thus compound 1 of Table 68 is the same as compound 1 of Table 1 except that in compound 1 of Table 68 Y is 5-thien-2-yl-1, 3,4-oxadiazol-2-ylthiomethyl instead of 3,5- dihydroxy-1, 2,4-triazin-6-ylthiomethyl. Similarly, compounds 2 to 576, of Table 68 are the same as compounds 2 to 576 of Table 1, respectively, except that in the compounds of Table 68 Y is 5-thien-2-yl-1, 3,4-oxadiazol-2-ylthiomethyl instead of 3, 5-dihydroxy- 1, 2,4-triazin-6-ylthiomethyl.

Table 69 Table 69 consists of 576 compounds of the general formula (1), where Y is dichloromethyl, and Rl, R2, R3, X and Z have the values listed in Table 1. Thus compound 1 of Table 69 is the same as compound 1 of Table 1 except that in compound 1 of Table 69 Y is dichloromethyl instead of 3, 5-dihydroxy-1, 2,4-triazin-6-ylthiomethyl.

Similarly, compounds 2 to 576 of Table 69 are the same as compounds 2 to 576 of Table 1, respectively, except that in the compounds of Table 69 Y is dichloromethyl instead of 3, 5-dihydroxy-1, 2,4-triazin-6-ylthiomethyl.

Table 70 Table 70 consists of 576 compounds of the general formula (1), where Y is sulfothiomethyl thiosulfuric acid methyl, and Rl, R2, R3, X and Z have the values listed in Table 1. Thus compound 1 of Table 70 is the same as compound 1 of Table 1 except that in compound 1 of Table 70 Y is sulfothiomethyl instead of 3, 5-dihydroxy-1, 2,4-triazin-6- ylthiomethyl. Similarly, compounds 2 to 576 of Table 70 are the same as compounds 2 to 576 of Table 1, respectively, except that in the compounds of Table 70 Y is sulfothiomethyl instead of 3,5-dihydroxy-1, 2,4-triazin-6-ylthiomethyl.

Table 71 Table 71 consists of 576 compounds of the general formula (1), where Y is 1- chloroethen-1-yl, and Rl, R2, R3, X and Z have the values listed in Table 1. Thus compound 1 of Table 71 is the same as compound 1 of Table 1 except that in compound 1 of Table71 Yis l-chloroethen-l-ylinsteadof3, 5-dihydroxy-1, 2, 4-triazin-6- ylthiomethyl. Similarly, compounds 2 to 576 of Table 71 are the same as compounds 2 to 576 of Table 1, respectively, except that in the compounds of Table 71 Y is 1- chloroethen-1-yl instead of 3,5-dihydroxy-1, 2,4-triazin-6-ylthiomethyl.

Table 72 Table 72 consists of 576 compounds of the general formula (1), where Y is thiazolo [4,5-b] pyrid-2-ylthiomethyl, and Rl, R2, R3, X and Z have the values listed in Table 1. Thus compound 1 of Table 72 is the same as compound 1 of Table 1 except that in compound 1 of Table 72 Y is thiazolo [4,5-b] pyrid-2-ylthiomethyl instead of 3,5- dihydroxy-1, 2,4-triazin-6-ylthiomethyl. Similarly, compounds 2 to 576 of Table 72 are the same as compounds 2 to 576 of Table 1, respectively, except that in the compounds of Table 72 Y is thiazolo [4,5-b] pyrid-2-ylthiomethyl instead of 3, 5-dihydroxy-1, 2,4- triazin-6-ylthiomethyl.

Table 73 Table 73 consists of 576 compounds of the general formula (1), where Y is 3-cyano-6,7- dihydro-5H-[l] pyrind-2-ylthiomethyl, and Rl, R2, R3, X and Z have the values listed in Table 1. Thus compound 1 of Table 73 is the same as compound 1 of Table 1 except that in compound 1 of Table 73 Y is 3-cyano-6, 7-dihydro-SH-[l] pyrind-2-ylthiomethyl instead of 3, 5-dihydroxy-1, 2, 4-triazin-6-ylthiomethyl. Similarly, compounds 2 to 576 of

Table 73 are the same as compounds 2 to 576 of Table 1, respectively, except that in the compounds of Table 73 Y is 3-cyano-6, 7-dihydro-5H-[l] pyrind-2-ylthiomethyl instead of 3, 5-dihydroxy-1, 2,4-triazin-6-ylthiomethyl.

Table 74 Table 74 consists of 576 compounds of the general formula (1), where Y is 1,1, 1,3, 3,3- hexafluoroprop-2-yl, and R1, R2, R3, X and Z have the values listed in Table 1. Thus compound 1 of Table 74 is the same as compound 1 of Table 1 except that in compound 1 of Table 74 Y is 1, 1, 1, 3,3, 3-hexafluoroprop-2-yl instead of 3, 5-dihydroxy-1, 2,4-triazin- 6-ylthiomethyl. Similarly, compounds 2 to 576 of Table 74 are the same as compounds 2 to 576 of Table 1, respectively, except that in the compounds of Table 74 Y is 1,1, 1,3, 3, 3-hexafluoroprop-2-yl instead of 3,5-dihydroxy-1, 2, 4-triazin-6-ylthiomethyl.

Table 75 Table 75 consists of 576 compounds of the general formula (1), where Y is 3-furfuryl- quinazolin-4-on-2-ylthiomethyl, and Ru, R2, R3, X and Z have the values listed in Table.

1. Thus compound 1 of Table 75 is the same as compound 1 of Table 1 except that in compound 1 of Table 75 Y is 3-furfuryl-quinazolin-4-on-2-ylthiomethyl instead of 3,5- dihydroxy-1, 2,4-triazin-6-ylthiomethyl. Similarly, compounds 2 to 576 of Table 75 are the same as compounds 2 to 576 of Table 1, respectively, except that in the compounds of Table 75 Y is 3-furfuryl-quinazolin-4-on-2-ylthiomethyl instead of 3, 5-dihydroxy- 1,2, 4-triazin-6-ylthiomethyl.

Table 76 Table 76 consists of 576 compounds of the general formula (1), where Y is 1-bromoeth- 1-yl, and Ru, R2, R3, X and Z have the values listed in Table 1. Thus compound 1 of Table 76 is the same as compound 1 of Table 1 except that in compound 1 of Table 76 Y is 1-bromoeth-1-yl instead of 3, 5-dihydroxy-1, 2,4-triazin-6-ylthiomethyl. Similarly, compounds 2 to 576 of Table 76 are the same as compounds 2 to 576 of Table 1, respectively, except that in the compounds of Table 76 Y is 1-bromoeth-l-yl instead of 3, 5-dihydroxy-1, 2,4-triazin-6-ylthiomethyl.

Table 77 Table 77 consists of 576 compounds of the general formula (1), where Y is 1,2, 4-triazol- 1-ylinethyl, and RI, R, R3, X and Z have the values listed in Table 1. Thus compound 1

of Table 77 is the same as compound 1 of Table 1 except that in compound 1 of Table 77 Y is 1,2, 4-triazol-1-ylmethyl instead of 3, 5-dihydroxy-1, 2,4-triazin-6-ylthiomethyl.

Similarly, compounds 2 to 576 of Table 77 are the same as compounds 2 to 576 of Table 1, respectively, except that in the compounds of Table 77 Y is 1,2, 4-triazol-1-ylmethyl instead of 3, 5-dihydroxy-1, 2,4-triazin-6-ylthiomethyl.

Table 78 Table 78 consists of 576 compounds of the general formula (1), where Y is 5-benzyl-4- phenyl-1, 2,4-triazol-3-ylthiomethyl, and Ru, R, R3, X and Z have the values listed in Table 1. Thus compound 1 of Table 78 is the same as compound 1 of Table 1 except that in compound 1 of Table 78 Y is 5-benzyl-4-phenyl-1, 2,4-triazol-3-ylthiomethyl instead of 3, 5-dihydroxy-1, 2, 4-triazin-6-ylthiomethyl. Similarly, compounds 2 to 576 of Table 78 are the same as compounds 2 to 576 of Table 1, respectively, except that in the compounds of Table 78 Y is 5-benzyl-4-phenyl-1, 2,4-triazol-3-ylthiomethyl instead of 3,5-dihydroxy-1, 2,4-triazin-6-ylthiomethyl.

Table 79 Table 79 consists of 576 compounds of the general formula (1), where Y is 4-methyl- pent-l-yn-3-yloxy, and Ru, R2, R3, X and Z have the values listed in Table 1. Thus compound 1 of Table 79 is the same as compound 1 of Table 1 except that in compound 1 of Table 79 Y is 4-methyl-pent-1-yn-3-yloxy instead of 3, 5-dihydroxy-1, 2,4-triazin-6- ylthiomethyl. Similarly, compounds 2 to 576 of Table 79 are the same as compounds 2 to 576 of Table 1, respectively, except that in the compounds of Table 79 Y is 4-methyl- pent-1-yn-3-yloxy instead of 3,5-dihydroxy-1, 2,4-triazin-6-ylthiomethyl.

Table 80 Table 80 consists of 576 compounds of the general formula (1), where Y is trimethylsilylethynyl, and Ru, R2, R3, X and Z have the values listed in Table 1. Thus compound 1 of Table 80 is the same as compound 1 of Table 1 except that in compound 1 of Table 80 Y is trimethylsilylethynyl instead of 3, 5-dihydroxy-1, 2,4-triazin-6- ylthiomethyl. Similarly, compounds 2 to 576 of Table 80 are the same as compounds 2 to 576 of Table 1, respectively, except that in the compounds of Table 80 Y is trimethylsilylethynyl instead of 3, 5-dihydroxy-1, 2,4-triazin-6-ylthiomethyl.

Table 81 Table 81 consists of 576 compounds of the general formula (1), where Y is 5- (4- chloroanilinomethyl)-4-methyl-1, 2, 4-triazol-3-ylthiomethyl, and R, R2, R3, X and Z have the values listed in Table 1. Thus compound 1 of Table 81 is the same as compound 1 of Table 1 except that in compound 1 of Table 81 Y is 5- (4-chloroanilinomethyl)-4-methyl- 1,2, 4-triazol-3-ylthiomethyl instead of 3, 5-dihydroxy-1, 2, 4-triazin-6-ylthiomethyl.

Similarly, compounds 2 to 576 of Table 81 are the same as compounds 2 to 576 of Table 1, respectively, except that in the compounds of Table 81 Y is 5- (4-chloroanilinomethyl)- 4-methyl-1,2, 4-triazol-3-ylthiomethyl instead of 3,5-dihydroxy-1, 2, 4-triazin-6- ylthiomethyl.

Table 82 Table 82 consists of 576 compounds of the general formula (1), where Y is cyanomethyl, and Rl, R2, R3, X and Z have the values listed in Table 1. Thus compound 1 of Table 82 is the same as compound 1 of Table 1 except that in compound 1 of Table 82 Y is cyanomethyl instead of 3, 5-dihydroxy-1, 2, 4-triazin-6-ylthiomethyl. Similarly, compounds 2 to 576 of Table 82 are the same as compounds 2 to 576 of Table 1, respectively, except that in the compounds of Table 82 Y is cyanomethyl instead of 3, 5-dihydroxy-1, 2,4- triazin-6-ylthiomethyl.

Table 83 Table 83 consists of 576 compounds of the general formula (1), where Y is tetrazol-1- ylmethyl, and R1, R2, R3, X and Z have the values listed in Table 1. Thus compound 1 of Table 83 is the same as compound 1 of Table 1 except that in compound 1 of Table 83 Y is tetrazol-1-ylmethyl instead of 3, 5-dihydroxy-1, 2, 4-triazin-6-ylthiomethyl. Similarly, compounds 2 to 576 of Table 83 are the same as compounds 2 to 576 of Table 1, respectively, except that in the compounds of Table 83 Y is tetrazol-1-ylmethyl instead of 3,5-dihydroxy-1, 2, 4-triazin-6-ylthiomethyl.

Table 84.

Table 84 consists of 576 compounds of the general formula (1), where Y is 1-bromo-n- prop-1-yl, and Rl, R2, R3, X and Z have the values listed in Table 1. Thus compound 1 of Table 84 is the same as compound 1 of Table 1 except that in compound 1 of Table 84 Y is 1-bromo-n-prop-1-yl instead of 3, 5-dihydroxy-1, 2, 4-triazin-6-ylthiomethyl. Similarly,

compounds 2 to 576 of Table 84 are the same as compounds 2 to 576 of Table 1, respectively, except that in the compounds of Table 84 Y is 1-bromo-n-prop-l-yl instead of 3,5-dihydroxy-1, 2,4-triazin-6-ylthiomethyl.

Table 85 Table 85 consists of 576 compounds of the general formula (1), where Y is 4-methyl-5- iso-propyl-1, 2, 4-triazol-3-ylthiomethyl, and R1, R2, R3, X and Z have the values listed in Table 1. Thus compound 1 of Table 85 is the same as compound 1 of Table 1 except that in compound 1 of Table 85 Y is 4-methyl-5-iso-propyl-1, 2,4-triazol-3-ylthiomethyl instead of 3, 5-dihydroxy-1, 2, 4-triazin-6-ylthiomethyl. Similarly, compounds 2 to 576 of Table 85 are the same as compounds 2 to 576 of Table 1, respectively, except that in the compounds of Table 85 Y is 4-methyl-5-iso-propyl-1, 2, 4-triazol-3-ylthiomethyl instead of 3,5-dihydroxy-1, 2, 4-triazin-6-ylthiomethyl.

Table 86 Table 86 consists of 576 compounds of the general formula (1), where Y is propargyloxy, and R1, R2, R3, X and Z have the values listed in Table 1. Thus compound 1 of Table 86 is the same as compound 1 of Table 1 except that in compound 1 of Table 86 Y is propargyloxy instead of 3, 5-dihydroxy-1, 2,4-triazin-6-ylthiomethyl. Similarly, compounds 2 to 576 of Table 86 are the same as compounds 2 to 576 of Table 1, respectively, except that in the compounds of Table 86 Y is propargyloxy instead of 3,5- dihydroxy-1, 2,4-triazin-6-ylthiomethyl.

Table 87 Table 87 consists of 576 compounds of the general formula (1), where Y is 3-cyano-8- methyl-quinolin-2-ylthiomethyl, and Rl, R2, R3, X and Z have the values listed in Table 1. Thus compound 1 of Table 87 is the same as compound 1 of Table 1 except that in compound 1 of Table 87 Y is 3-cyano-8-methyl-quinolin-2-ylthiomethyl instead of 3,5- dihydroxy-1, 2,4-triazin-6-ylthiomethyl. Similarly, compounds 2 to 576 of Table 87 are the same as compounds 2 to 576 of Table 1, respectively, except that in the compounds of Table 87 Y is 3-cyano-8-methyl-quinolin-2-ylthiomethyl instead of 3,5-dihydroxy- 1,2, 4-triazin-6-ylthiomethyl.

Table 88 Table 88 consists of 576 compounds of the general formula (1), where Y is 2- (4- fluorophenyl)-l-ethoxycarbonylethen-l-yl, and Rl, R2, R3, X and Z have the values listed in Table 1. Thus compound 1 of Table 88 is the same as compound 1 of Table 1 except that in compound 1 of Table 88 Y is 2-(4-fluorophenyl)-1-ethoxycarbonylethen-1-yl instead of 3, 5-dihydroxy-1, 2,4-triazin-6-ylthiomethyl. Similarly, compounds 2 to 576 of Table 88 are the same as compounds 2 to 576 of Table 1, respectively, except that in the compounds of Table 88 Y is 2- (4-fluorophenyl)-1-ethoxycarbonylethen-1-yl instead of 3,5-dihydroxy-1, 2,4-triazin-6-ylthiomethyl.

Table 89 Table 89 consists of 576 compounds of the general formula (1), where Y is 4,6-diamino- pyrimidin-2-ylthiomethyl, and Rl, R2, R3, X and Z have the values listed in Table 1. Thus compound 1 of Table 89 is the same as compound 1 of Table 1 except that in compound 1 of Table 89 Y is 4,6-diamino-pyrimidin-2-ylthiomethyl instead of 3, 5-dihydroxy-1, 2,4- triazin-6-ylthiomethyl. Similarly, compounds 2 to 576 of Table 89 are the same as compounds 2 to 576 of Table 1, respectively, except that in the compounds of Table 89 Y is 4, 6-diamino-pyrimidin-2-ylthiomethyl instead of 3, 5-dihydroxy-1, 2,4-triazin-6- ylthiomethyl.

Table 90 Table 90 consists of 576 compounds of the general formula (1), where Y is 5- propargylthio-1, 3,4-thiadiazol-2-ylthiomethyl, and Rl, R, R3, X and Z have the values listed in Table 1. Thus compound 1 of Table 90 is the same as compound 1 of Table 1 except that in compound 1 of Table 90 Y is 5-propargylthio-1, 3,4-thiadiazol-2- ylthiomethyl instead of 3, 5-dihydroxy-1, 2,4-triazin-6-ylthiomethyl. Similarly, compounds 2 to 576 of Table 90 are the same as compounds 2 to 576 of Table 1, respectively, except that in the compounds of Table 90 Y is 5-propargylthio-1, 3,4-thiadiazol-2-ylthiomethyl instead of 3, 5-dihydroxy-1, 2,4-triazin-6-ylthiomethyl.

Table 91 Table 91 consists of 576 compounds of the general formula (1), where Y is prop-l-yn-l- yl, and Rl, R2, R3, X and Z have the values listed in Table 1. Thus compound 1 of Table 91 is the same as compound 1 of Table 1 except that in compound 1 of Table 91 Y is

prop-1-yn-1-yl instead of 3, 5-dihydroxy-1, 2, 4-triazin-6-ylthiomethyl ; Similarly, compounds 2 to 576 of Table 91 are the same as compounds 2 to 576 of Table 1, respectively, except that in the compounds of Table 91 Y is prop-1-yn-l-yl instead of 3,5- dihydroxy-1, 2,4-triazin-6-ylthiomethyl.

Table 92 Table 92 consists of 576 compounds of the general formula (1), where Y is bromomethyl, and Ru, R2, R3, X and Z have the values listed in Table 1. Thus compound 1 of Table 92 is the same as compound 1 of Table 1 except that in compound 1 of Table 92 Y is bromomethyl instead of 3, 5-dihydroxy-1, 2,4-triazin-6-ylthiomethyl. Similarly, compounds 2 to 576 of Table 92 are the same as compounds 2 to 576 of Table 1, respectively, except that in the compounds of Table 92 Y is bromomethyl instead of 3,5- dihydroxy-1, 2,4-triazin-6-ylthiomethyl.

Table 93 Table 93 consists of 576 compounds of the general formula (1), where Y is 6- (2, 2,2- trifluoroethoxy)-pyrimidin-4-ylthiomethyl and Rl, R2, R3, X and Z have the values listed in Table 1. Thus compound 1 of Table 93 is the same as compound 1 of Table 1 except that in compound 1 of Table 93 Y is 6- (2, 2, 2-trifluoroethoxy)-pyrimidin-4-ylthiomethyl instead of 3, 5-dihydroxy-1, 2, 4-triazin-6-ylthiomethyl. Similarly, compounds 2 to 576 of Table 93 are the same as compounds 2 to 576 of Table 1, respectively, except that in the compounds of Table 93 Y is 6- (2, 2, 2-trifluoroethoxy)-pyrimidin-4-ylthiomethyl instead of 3, 5-dihydroxy-1, 2,4-triazin-6-ylthiomethyl.

Table 94 Table 94 consists of 576 compounds of the general formula (1), where Y is 2- phenylcyclopropyl, and Rl, R, R3, X and Z have the values listed in Table 1. Thus compound 1 of Table 94 is the same as compound 1 of Table 1 except that in compound 1 of Table 94 Y is 2-phenylcyclopropyl instead of 3, 5-dihydroxy-1, 2,4-triazin-6- ylthiomethyl. Similarly, compounds 2 to 576 of Table 94 are the same as compounds 2 to 576 of Table 1, respectively, except that in the compounds of Table 94 Y is 2- phenylcyclopropyl instead of 3, 5-dihydroxy-1, 2,4-triazin-6-ylthiomethyl.

Table 95 Table 95 consists of 576 compounds of the general formula (1), where Y is carboxymethylthiomethyl, and Ru, R, R3, X and Z have the values listed in Table 1. Thus compound 1 of Table 95 is the same as compound 1 of Table 1 except that in compound 1 of Table 95 Y is carboxymethylthiomethyl instead of 3, 5-dihydroxy-1, 2,4-triazin-6- ylthiomethyl. Similarly, compounds 2 to 576 of Table 95 are the same as compounds 2 to 576 of Table 1, respectively, except that in the compounds of Table 95 Y is carboxymethylthiomethyl instead of 3, 5-dihydroxy-1, 2,4-triazin-6-ylthiomethyl.

Table 96 Table 96 consists of 576 compounds of the general formula (1), where Y is 3-cyano-7- methyl-quinolin-2-ylthiomethyl, and Rl, R2, R3, X and Z have the values listed in Table 1. Thus compound 1 of Table 96 is the same as compound 1 of Table 1 except that in compound 1 of Table 96 Y is 3-cyano-7-methyl-quinolin-2-ylthiomethyl instead of 3,5- dihydroxy-1, 2,4-triazin-6-ylthiomethyl. Similarly, compounds 2 to 576 of Table 96 are the same as compounds 2 to 576 of Table 1, respectively, except that in the compounds of Table 96 Y is 3-cyano-7-methyl-quinolin-2-ylthiomethyl instead of 3, 5-dihydroxy- 1,2, 4-triazin-6-ylthiomethyl.

Table 97 Table 97 consists of 576 compounds of the general formula (1), where Y is 3-cyano-4,6- dimethylpyrid-2-ylthiomethyl, and Rl, R2, R3, X and Z have the values listed in Table 1.

Thus compound 1 of Table 97 is the same as compound 1 of Table 1 except that in compound 1 of Table 97 Y is 3-cyano-4, 6-dimethylpyrid-2-ylthiomethyl instead of 3,5- dihydroxy-1, 2, 4-triazin-6-ylthiomethyl. Similarly, compounds 2 to 576 of Table 97 are the same as compounds 2 to 576 of Table 1, respectively, except that in the compounds of Table 97 Y is 3-cyano-4,6-dimethylpyrid-2-ylthiomethyl instead of 3, 5-dihydroxy- 1,2, 4-triazin-6-ylthiomethyl.

Table 98 Table 98 consists of 576 compounds of the general formula (1), where Y is 2- dimethylamino-1-methoxycarbonylethen-l-yl, and Rl, R2, R3, X and Z have the values listed in Table 1. Thus compound 1 of Table 98 is the same as compound 1 of Table 1 except that in compound 1 of Table 98 Y is 2-dimethylamino-1-methoxycarbonylethen-1-

yl instead of 3, 5-dihydroxy-1, 2,4-triazin-6-ylthiomethyl. Similarly, compounds 2 to 576 of Table 98 are the same as compounds 2 to 576 of Table 1, respectively, except that in the compounds of Table 98 Y is 2-dimethylamino-1-methoxycarbonylethen-1-yl instead of 3,5-dihydroxy-1, 2,4-triazin-6-ylthiomethyl.

Table 99 Table 99 consists of 576 compounds of the general formula (1), where Y is 2,6- dimethylmorpholinomethyl, and Rl, R2, R3, X and Z have the values listed in Table 1.

Thus compound 1 of Table 99 is the same as compound 1 of Table 1 except that in compound 1 of Table 99 Y is 2,6-dimethylmorpholinomethyl instead of 3, 5-dihydroxy- 1, 2,4-triazin-6-ylthiomethyl. Similarly, compounds 2 to 576 of Table 99 are the same as compounds 2 to 576 of Table 1, respectively, except that in the compounds of Table 99 Y is 2,6-dimethylmorpholinomethyl instead of 3, 5-dihydroxy-1, 2,4-triazin-6-ylthiomethyl.

Table 100 Table 100 consists of 576 compounds of the general formula (1), where Y is 2-amino-5- cyano-6-methylthiopyrimidin-4-ylthiomethyl, and Ru, R, R3, X and Z have the values listed in Table 1. Thus compound 1 of Table 100 is the same as compound 1 of Table 1 except that in compound 1 of Table 100 Y is 2-amino-5-cyano-6-methylthiopyrimidin-4- ylthiomethyl instead of 3, 5-dihydroxy-1, 2,4-triazin-6-ylthiomethyl. Similarly, compounds 2 to 576 of Table 100 are the same as compounds 2 to 576 of Table 1, respectively, except that in the compounds of Table 100 Y is 2-amino-5-cyano-6-methylthiopyrimidin- 4-ylthiomethyl instead of 3, 5-dihydroxy-1, 2, 4-triazin-6-ylthiomethyl.

Table 101 Table 101 consists of 576 compounds of the general formula (1), where Y is 3-pyrid-3-yl- lH-1, 2,4-triazol-5-ylthiomethyl, and R', R2, R3, X and Z have the values listed in Table 1. Thus compound 1 of Table 101 is the same as compound 1 of Table 1 except that in compound 1 of Table 101 Y is 3-pyrid-3-yl-lH-1, 2,4-triazol-5-ylthiomethyl instead of 3, 5-dihydroxy-1, 2,4-triazin-6-ylthiomethyl. Similarly, compounds 2 to 576 of Table 101 are the same as compounds 2 to 576 of Table 1, respectively, except that in the compounds of Table 101 Y is 3-pyrid-3-yl-lH-1, 2,4-triazol-5-ylthiomethyl instead of 3,5- dihydroxy-1,2, 4-triazin-6-ylthiomethyl.

Table 102 Table 102 consists of 576 compounds of the general formula (1), where Y is N- succinimidomethyl, and Rl, R2, R3, X and Z have the values listed in Table 1. Thus compound 1 of Table 102 is the same as compound 1 of Table 1 except that in compound 1 of Table 102 Y is N-succinimidomethyl instead of 3, 5-dihydroxy-1, 2,4-triazin-6- ylthiomethyl. Similarly, compounds 2 to 576 of Table 102 are the same as compounds 2 to 576 of Table 1, respectively, except that in the compounds of Table 102 Y is N- succinimidomethyl instead of 3,5-dihydroxy-1, 2,4-triazin-6-ylthiomethyl.

Table 103 Table 103 consists of 576 compounds of the general formula (1), where Y is 3-cyano-6- ethyl-5-methyl-pyrid-2-ylthiomethyl, and Ru, R2, R3, X and Z have the values listed in Table 1. Thus compound 1 of Table 103 is the same as compound 1 of Table 1 except that in compound 1 of Table 103 Y is 3-cyano-6-ethyl-5-methyl-pyrid-2-ylthiomethyl instead of 3, 5-dihydroxy-1, 2,4-triazin-6-ylthiomethyl. Similarly, compounds 2 to 576 of Table 103 are the same as compounds 2 to 576 of Table 1, respectively, except that in the compounds of Table 103 Y is 3-cyano-6-ethyl-5-methyl-pyrid-2-ylthiomethyl instead of 3,5-dihydroxy-1, 2, 4-triazin-6-ylthiomethyl.

Table 104 Table 104 consists of 576 compounds of the general formula (1), where Y is 5-phenyl- tetrazol-2-ylmethyl, and Rl, R2, R3, X and Z have the values listed in Table 1. Thus compound 1 of Table 104 is the same as compound 1 of Table 1 except that in compound 1 of Table 104 Y is 5-phenyl-tetrazol-2-ylmethyl instead of 3, 5-dihydroxy-1, 2,4-triazin- 6-ylthiomethyl. Similarly, compounds 2 to 576 of Table 104 are the same as compounds 2 to 576 of Table 1, respectively, except that in the compounds of Table 104 Y is 5- phenyl-tetrazol-2-ylmethyl instead of 3,5-dihydroxy-1, 2,4-triazin-6-ylthiomethyl.

Table 105 Table 105 consists of 576 compounds of the general formula (1), where Y is pyrimidin-2- ylthiomethyl, and Rl, R2, R3, X and Z have the values listed in Table 1. Thus compound 1 of Table 105 is the same as compound 1 of Table 1 except that in compound 1 of Table 105 Y is pyrimidin-2-ylthiomethyl instead of 3, 5-dihydroxy-1, 2,4-triazin-6-ylthiomethyl.

Similarly, compounds 2 to 576 of Table 105 are the same as compounds 2 to 576 of

Table 1, respectively, except that in the compounds of Table 105 Y is pyrimidin-2- ylthiomethyl instead of 3, 5-dihydroxy-1, 2,4-triazin-6-ylthiomethyl.

Table 106 Table 106 consists of 576 compounds of the general formula (1), where Y is 5- (4- hydroxyphenyl)-1, 3,4-oxadiazol-2-ylthiomethyl, and RI, R2, R3, X and Z have the values listed in Table 1. Thus compound 1 of Table 106 is the same as compound 1 of Table 1 except that in compound 1 of Table 106 Y is 5- (4-hydroxyphenyl)-1, 3,4-oxadiazol-2- ylthiomethyl instead of 3, 5-dihydroxy-1, 2, 4-triazin-6-ylthiomethyl. Similarly, compounds 2 to 576 of Table 106 are the same as compounds 2 to 576 of Table 1, respectively, except that in the compounds of Table 106 Y is 5- (4-hydroxyphenyl)-1, 3,4-oxadiazol-2- ylthiomethyl instead of 3, 5-dihydroxy-1, 2,4-triazin-6-ylthiomethyl.

Table 107 Table 107 consists of 576 compounds of the general formula (1), where Y is 2-methyl- prop-1-enyl, and R1, R, R3, X and Z have the values listed in Table 1. Thus compound 1 of Table 107 is the same as compound 1 of Table 1 except that in compound 1 of Table 107 Y is 2-methyl-prop-1-enyl instead of 3, 5-dihydroxy-1, 2,4-triazin-6-ylthiomethyl.

Similarly, compounds 2 to 576 of Table 107 are the same as compounds 2 to 576 of Table 1, respectively, except that in the compounds of Table 107 Y is 2-methyl-prop-1- enyl instead of 3, 5-dihydroxy-1, 2,4-triazin-6-ylthiomethyl.

Table 108 Table 108 consists of 576 compounds of the general formula (1), where Y is 1,2- dibromoethyl, and Rl, R2, R3, X and Z have the values listed in Table 1. Thus compound 1 of Table 108 is the same as compound 1 of Table 1 except that in compound 1 of Table 108 Y is 1,2-dibromoethyl instead of 3, 5-dihydroxy-1, 2,4-triazin-6-ylthiomethyl.

Similarly, compounds 2 to 576 of Table 108 are the same as compounds 2 to 576 of Table 1, respectively, except that in the compounds of Table 108 Y is 1,2-dibromoethyl instead of 3,5-dihydroxy-1, 2, 4-triazin-6-ylthiomethyl.

Table 109 Table 109 consists of 576 compounds of the general formula (1), where Y is hex-3-yn-2- yloxy, and Rl, R2, R3, X and Z have the values listed in Table 1. Thus compound 1 of Table 109 is the same as compound 1 of Table 1 except that in compound 1 of Table 109

Y is hex-3-yn-2-yloxy instead of 3, 5-dihydroxy-1, 2,4-triazin-6-ylthiomethyl. Similarly, compounds 2 to 576 of Table 109 are the same as compounds 2 to 576 of Table 1, respectively, except that in the compounds of Table 109 Y is hex-3-yn-2-yloxy instead of 3, 5-dihydroxy-1, 2,4-triazin-6-ylthiomethyl.

Table 110 Table 110 consists of 576 compounds of the general formula (1), where Y is but-3-yn-2- yloxy, and Ru, R2, R3, X and Z have the values listed in Table 1. Thus compound 1 of Table 110 is the same as compound 1 of Table 1 except that in compound 1 of Table 110 Y is but-3-yn-2-yloxy instead of 3, 5-dihydroxy-1, 2, 4-triazin-6-ylthiomethyl. Similarly, compounds 2 to 576 of Table 110 are the same as compounds 2 to 576 of Table 1, respectively, except that in the compounds of Table 110 Y is but-3-yn-2-yloxy instead of 3, 5-dihydroxy-1, 2,4-triazin-6-ylthiomethyl.

Table 111 Table 111 consists of 576 compounds of the general formula (1), where Y is 5-phenyl-1- tetrahydrofurfuryl-imidazol-2-ylthiomethyl, and Rl, R2, R3, X and Z have the values listed in Table 1. Thus compound 1 of Table 111 is the same as compound 1 of Table 1 except that in compound 1 of Table 111 Y is 5-phenyl-1-tetrahydrofurfuryl-imidazol-2- ylthiomethyl instead of 3, 5-dihydroxy-1, 2,4-triazin-6-ylthiomethyl. Similarly, compounds 2 to 576 of Table 111 are the same as compounds 2 to 576 of Table 1, respectively, except that in the compounds of Table 111 Y is 5-phenyl-1-tetrahydrofurfuryl-imidazol- 2-ylthiomethyl instead of 3, 5-dihydroxy-1, 2,4-triazin-6-ylthiomethyl.

Table 112 Table 112 consists of 576 compounds of the general formula (1), where Y is 1-methyl- imidazol-2-ylthiomethyl, and Rl, R2, R3, X and Z have the values listed in Table 1. Thus compound 1 of Table 112 is the same as compound 1 of Table 1 except that in compound 1 of Table 112 Y is 1-methyl-imidazol-2-ylthiomethyl instead of 3, 5-dihydroxy-1, 2,4- triazin-6-ylthiomethyl. Similarly, compounds 2 to 576 of Table 112 are the same as compounds 2 to 576 of Table 1, respectively, except that in the compounds of Table 112 Y is l-methyl-imidazol-2-ylthiomethyl instead of 3, 5-dihydroxy-1, 2,4-triazin-6- ylthiomethyl.

Table 113 Table 113 consists of 576 compounds of the general formula (1), where Y is 4-methyl-5- thien-2-yl-1, 2,4-triazol-3-ylthiomethyl, and Ru, R2, R3, X and Z have the values listed in Table 1. Thus compound 1 of Table 113 is the same as compound 1 of Table 1 except that in compound 1 of Table 113 Y is 4-methyl-5-thien-2-yl-1, 2, 4-triazol-3-ylthiomethyl instead of 3, 5-dihydroxy-1, 2,4-triazin-6-ylthiomethyl. Similarly, compounds 2 to 576 of Table 113 are the same as compounds 2 to 576 of Table 1, respectively, except that in the compounds of Table 113 Y is 4-methyl-5-thien-2-yl-1, 2,4-triazol-3-ylthiomethyl instead of 3, 5-dihydroxy-1, 2,4-triazin-6-ylthiomethyl.

Table 114 Table 114 consists of 576 compounds of the general formula (1), where Y is 3- (2- chlorophenyl)-lH-1, 2, 4-triazol-5-ylthiomethyl, and Rl, R2, R3, X and Z have the values listed in Table 1. Thus compound 1 of Table 114 is the same as compound 1 of Table 1 except that in compound 1 of Table 114 Y is 3- (2-chlorophenyl)-17 :/-l, 2,4-triazol-5- ylthiomethyl instead of 3, 5-dihydroxy-1, 2,4-triazin-6-ylthiomethyl. Similarly, compounds 2 to 576 of Table 114 are the same as compounds 2 to 576 of Table 1, respectively, except that in the compounds of Table 114 Y is 3- (2-chlorophenyl)-17 :/-l, 2,4-triazol-5- ylthiomethyl instead of 3, 5-dihydroxy-1, 2,4-triazin-6-ylthiomethyl.

Table 115 Table 115 consists of 576 compounds of the general formula (1), where Y is 4, 6- dimethyl-pyrimidin-2-ylthiomethyl, and Rl,. R2, R3, X and Z have the values listed in Table 1. Thus compound 1 of Table 115 is the same as compound 1 of Table 1 except that in compound 1 of Table 115 Y is 4,6-dimethyl-pyrimidin-2-ylthiomethyl instead of 3, 5-dihydroxy-1, 2, 4-triazin-6-ylthiomethyl. Similarly, compounds 2 to 576 of Table 115 are the same as compounds 2 to 576 of Table 1, respectively, except that in the compounds of Table 115 Y is 4, 6-dimethyl-pyrimidin-2-ylthiomethyl instead of 3,5- dihydroxy-1,2, 4-triazin-6-ylthiomethyl.

Table 116 Table 116 consists of 576 compounds of the general formula (1), where Y is 5-benzyl-4- ethyl-1, 2,4-triazol-3-ylthiomethyl, and Rl, R2, R3, X and Z have the values listed in Table 1. Thus compound 1 of Table 116 is the same as compound 1 of Table 1 except that in

compound 1 of Table 116 Y is 5-benzyl-4-ethyl-1, 2,4-triazol-3-ylthiomethyl instead of 3, 5-dihydroxy-1, 24-hiazin-6-ylthiomethyl. Similarly, compounds 2 to 576 of Table 116 are the same as compounds 2 to 576 of Table 1, respectively, except that in the compounds of Table 116 Y is 5-benzyl-4-ethyl-1, 2,4-triazol-3-ylthiomethyl instead of 3,5-dihydroxy-1, 2, 4-triazin-6-ylthiomethyl.

Table 117 Table 117 consists of 576 compounds of the general formula (1), where Y is hex-2-yn-1- yloxy, and Ru, R2, R3, X and Z have the values listed in Table 1. Thus compound 1 of Table 117 is the same as compound 1 of Table 1 except that in compound 1 of Table 117 Y is hex-2-yn-1-yloxy instead of 3, 5-dihydroxy-1, 2, 4-triazin-6-ylthiomethyl. Similarly, compounds 2 to 576 of Table 117 are the same as compounds 2 to 576 of Table 1, respectively, except that in the compounds of Table 117 Y is hex-2-yn-1-yloxy instead of 3,5-dihydroxy-1, 2,4-triazin-6-ylthiomethyl.

Table 118 Table 118 consists of 576 compounds of the general formula (1), where Y is 3-(m-tolyl)- lH-1, 2, 4-triazol-5-ylthiomethyl, and Rl, R2, R3, X and Z have the values listed in Table 1. Thus compound 1 of Table 118 is the same as compound 1 of Table 1 except that in compound 1 of Table 118 Y is 3-(m-tolyl)-lH-1, 2,4-triazol-5-ylthiomethyl instead of 3,5- dihydroxy-1, 2, 4-triazin-6-ylthiomethyl. Similarly, compounds 2 to 576 of Table 118 are the same as compounds 2 to 576 of Table 1, respectively, except that in the compounds of Table 118 Y is 3-(m-tolyl)-lH-1, 2, 4-triazol-5-ylthiomethyl instead of 3, 5-dihydroxy- 1,2, 4-triazin-6-ylthiomethyl.

Table 119 Table 119 consists of 576 compounds of the general formula (1), where Y is 4-ethyl-5- (4- methoxyphenyl)-1, 2, 4-triazol-3-ylthiomethyl, and Rl, R2, R3, X and Z have the values listed in Table 1. Thus compound 1 of Table 119 is the same as compound 1 of Table 1 except that in compound 1 of Table 119 Y is 4-ethyl-5- (4-methoxyphenyl)-1, 2, 4-triazol- 3-ylthiomethyl instead of 3, 5-dihydroxy-1, 2,4-triazin-6-ylthiomethyl. Similarly, compounds 2 to 576 of Table 119 are the same as compounds 2 to 576 of Table 1, respectively, except that in the compounds of Table 119 Y is 4-ethyl-5- (4-methoxy-

phenyl) -1,2, 4-triazol-3-ylthiomethyl instead of 3,5-dihydroxy-1, 2,4-triazin-6- ylthiomethyl.

Table 120 Table 120 consists of 576 compounds of the general formula (1), where Y is N, N- diethylaminothiocarbonylthiomethyl, and Rl, R2, R3, X and Z have the values listed in Table 1. Thus compound 1 of Table 120 is the same as compound 1 of Table 1 except that in compound 1 of Table 120 Y is N, N-diethylaminothiocarbonylthiomethyl instead of 3, 5-dihydroxy-1, 2, 4-triazin-6-ylthiomethyl. Similarly, compounds 2 to 576 of Table 120 are the same as compounds 2 to 576 of Table 1, respectively, except that in the compounds of Table 120 Y is N, N-diethylaminothiocarbonylthiomethyl instead of 3,5- dihydroxy-l, 2,4-triazin-6-ylthiomethyl.

Table 121 Table 121 consists of 576 compounds of the general formula (1), where Y is but-3-en-1- yl, and Rl, R2, R3, X and Z have the values listed in Table 1. Thus compound 1 of Table 121 is the same as compound 1 of Table 1 except that in compound 1 of Table 121 Y is but-3-en-1-yl instead of 3, 5-dihydroxy-1, 2, 4-triazin-6-ylthiomethyl. Similarly, compounds 2 to 576 of Table 121 are the same as compounds 2 to 576 of Table 1, respectively, except that in the compounds of Table 121 Y is but-3-en-1-yl instead of 3,5- dihydroxy-1, 2,4-triazin-6-ylthiomethyl.

Table 122 Table 122 consists of 576 compounds of the general formula (1), where Y is benzoxazol- 2-ylthiomethyl, and Rl, Ra,, R3, X and Z have the values listed in Table 1. Thus compound 1 of Table 122 is the same as compound 1 of Table 1 except that in compound 1 of Table 122 Y is benzoxazol-2-ylthiomethyl instead of 3, 5-dihydroxy-1, 2,4-triazin-6- ylthiomethyl. Similarly, compounds 2 to 576 of Table 122 are the same as compounds 2 to 576 of Table 1, respectively, except that in the compounds of Table 122 Y is benzoxazol-2-ylthiomethyl instead of 3,5-dihydroxy-1, 2,4-triazin-6-ylthiomethyl.

Table 123 Table 123 consists of 576 compounds of the general formula (1), where Y is 1-bromo- ethen-1-yl, and RI, R2, R3, X and Z have the values listed in Table 1. Thus compound 1 of Table 123 is the same as compound 1 of Table 1 except that in compound 1 of Table

123 Y is 1-bromo-ethen-l-yl instead of 3, 5-dihydroxy-1, 2,4-triazin-6-ylthiomethyl.

Similarly, compounds 2 to 576 of Table 123 are the same as compounds 2 to 576 of Table 1, respectively, except that in the compounds of Table 123 Y is 1-bromo-ethen-l-yl instead of 3, 5-dihydroxy-1, 2,4-triazin-6-ylthiomethyl.

Table 124 Table 124 consists of 576 compounds of the general formula (1), where Y is 3-methyl- quinazolin-4-on-2-ylthiomethyl, and Rl, R2, R3, X and Z have the values listed in Table 1. Thus compound 1 of Table 124 is the same as compound 1 of Table 1 except that in compound 1 of Table 124 Y is 3-methyl-quinazolin-4-on-2-ylthiomethyl instead of 3,5- dihydroxy-1, 2,4-triazin-6-ylthiomethyl. Similarly, compounds 2 to 576 of Table 124 are the same as compounds 2 to 576 of Table 1, respectively, except that in the compounds of Table 124 Y is 3-methyl-quinazolin-4-on-2-ylthiomethyl instead of 3, 5-dihydroxy- 1,2, 4-triazin-6-ylthiomethyl.

Table 125 Table 125 consists of 576 compounds of the general formula (1), where Y is 5-phenyl- 1, 3,4-oxadiazol-2-ylthiomethyl, and Rl, R2, R3, X and Z have the values listed in Table 1.

Thus compound 1 of Table 125 is the same as compound 1 of Table 1 except that in compound 1 of Table 125 Y is 5-phenyl-1, 3,4-oxadiazol-2-ylthiomethyl instead of 3,5- dihydroxy-l, 2,4-triazin-6-ylthiomethyl. Similarly, compounds 2 to 576 of Table 125 are the same as compounds 2 to 576 of Table 1, respectively, except that in the compounds of Table 125 Y is 5-phenyl-1, 3,4-oxadiazol-2-ylthiomethyl instead of 3, 5-dihydroxy- 1,2, 4-triazin-6-ylthiomethyl.

Table 126 Table 126 consists of 576 compounds of the general formula (1), where Y is 5- (4- chlorophenyl)-lH-imidazol-2-ylthiomethyl, and Rl, R2, R3, X and Z have the values listed in Table 1. Thus compound 1 of Table 126 is the same as compound 1 of Table 1 except that in compound 1 of Table 126 Y is 5-(4-chlorophenyl)-lH-imidazol-2- ylthiomethyl instead of 3, 5-dihydroxy-1, 2,4-triazin-6-ylthiomethyl. Similarly, compounds 2 to 576 of Table 126 are the same as compounds 2 to 576 of Table 1, respectively, except that in the compounds of Table 126 Y is 5- (4-chlorophenyl)-IH-imidazol-2- ylthiomethyl instead of 3, 5-dihydroxy-1, 2, 4-triazin-6-ylthiomethyl.

Table 127 Table 127 consists of 576 compounds of the general formula (1), where Y is cyclopropyl, and Rl, RZ, R3, X. and Z have the values listed in Table 1. Thus compound 1 of Table 127 is the same as compound 1 of Table 1 except that in compound 1 of Table 127 Y is cyclopropyl instead of 3, 5-dihydroxy-1, 2, 4-triazin-6-ylthiomethyl. Similarly, compounds 2 to 576 of Table 127 are the same as compounds 2 to 576 of Table 1, respectively, except that in the compounds of Table 127 Y is cyclopropyl instead of 3, 5-dihydroxy- 1,2, 4-triazin-6-ylthiomethyl.

Table 128 Table 128 consists of 576 compounds of the general formula (1), where Y is 5- (2- methoxyphenyl)-4-methyl-1, 2,4-triazol-3-ylthiomethyl, and Ru, R2, R3, X and Z have the values listed in Table 1. Thus compound 1 of Table 128 is the same as compound 1 of Table 1 except that in compound 1 of Table 128 Y is 5- (2-methoxyphenyl)-4-methyl- 1,2, 4-triazol-3-ylthiomethyl instead of 3,5-dihydroxy-1, 2,4-triazin-6-ylthiomethyl.

Similarly, compounds 2 to 576 of Table 128 are the same as compounds 2 to 576 of Table 1, respectively, except that in the compounds of Table 128 Y is 5- (2-methoxy- phenyl) -4-methyl-1,2, 4-triazol-3-ylthiomethyl instead of 3,5-dihydroxy-1, 2, 4-triazin-6- ylthiomethyl.

Table 129 Table 129 consists of 576 compounds of the general formula (1), where Y is iodomethyl, and Ru, R2, R3, X and Z have the values listed in Table 1. Thus compound 1 of Table 129 is the same as compound 1 of Table 1 except that in compound 1 of Table 129 Y is iodomethyl instead of 3, 5-dihydroxy-1, 2,4-triazin-6-ylthiomethyl. Similarly, compounds 2 to 576 of Table 129 are the same as compounds 2 to 576 of Table 1, respectively, except that in the compounds of Table 129 Y is iodomethyl instead of 3, 5-dihydroxy- 1,2, 4-triazin-6-ylthiomethyl.

Table 130 Table 130 consists of 576 compounds of the general formula (1), where Y is 5- (4- hydroxyphenyl)-4-phenyl-1, 2,4-triazol-3-ylthiomethyl, and RI, R2, R3, X and Z have the values listed in Table 1. Thus compound 1 of Table 130 is the same as compound 1 of Table 1 except that in compound 1 of Table 130 Y is 5- (4-hydroxyphenyl)-4-phenyl-

1,2, 4-triazol-3-ylthiomethyl instead of 3,5-dihydroxy-1, 2,4-triazin-6-ylthiomethyl.

Similarly, compounds 2 to 576 of Table 130 are the same as compounds 2 to 576 of Table 1, respectively, except that in the compounds of Table 130 Y is 5- (4-hydroxy- phenyl)-4-phenyl-1, 2,4-triazol-3-ylthiomethyl instead of 3,5-dihydroxy-1, 2,4-triazin-6- ylthiomethyl.

Table 131 Table 131 consists of 576 compounds of the general formula (1), where Y is 5,6- dimethyl-thieno [2, 3-d] pyrimidin-4-ylthiomethyl, and Rl, R2, R3, X and Z have the values listed in Table 1. Thus compound 1 of Table 131 is the same as compound 1 of Table 1 except that in compound 1 of Table 131 Y is 5, 6-dimetliyl-thieno [2,3-d] pyrimidin-4- ylthiomethyl instead of 3, 5-dihydroxy-1, 2,4-triazin-6-ylthiomethyl. Similarly, compounds 2 to 576 of Table 131 are the same as compounds 2 to 576 of Table 1, respectively, except that in the compounds of Table 131 Y is 5,6-dimethyl-thieno [2,3-d] pyrimidin-4- ylthiomethyl instead of 3, 5-dihydroxy-1, 2, 4-triazin-6-ylthiomethyl.

Table 132 Table 132 consists of 576 compounds of the general formula (1), where Y is 1- methoxycarbonyl-2-phenylethen-1-yl, and Rl, R, R3, X and Z have the values listed in Table 1. Thus compound 1 of Table 132 is the same as compound 1 of Table 1 except that in compound 1 of Table 132 Y is 1-methoxycarbonyl-2-phenylethen-1-yl instead of 3, 5-dihydroxy-1, 2,4-triazin-6-ylthiomethyl. Similarly, compounds 2 to 576 of Table 132 are the same as compounds 2 to 576 of Table 1, respectively, except that in the compounds of Table 132 Y is 1-methoxycarbonyl-2-phenylethen-1-yl instead of 3,5- dihydroxy-1, 2,4-triazin-6-ylthiomethyl.

Table 133 Table 133 consists of 576 compounds of the general formula (1), where Y is 5-methyl- 1, 3,4-thiadiazol-2-ylthiomethyl, and Ru, R2, R3, X and Z have the values listed in Table 1.

Thus compound 1 of Table 133 is the same as compound 1 of Table 1 except that in compound 1 of Table 133 Y is 5-methyl-1, 3,4-thiadiazol-2-ylthiomethyl instead of 3,5- dihydroxy-1, 2, 4-triazin-6-ylthiomethyl. Similarly, compounds 2 to 576 of Table 133 are the same as compounds 2 to 576 of Table 1, respectively, except that in the compounds

of Table 133 Y is 5-methyl-1, 3,4-thiadiazol-2-ylthiomethyl instead of 3, 5-dihydroxy- 1,2, 4-triazin-6-ylthiomethyl.

Table 134 Table 134 consists of 576 compounds of the general formula (1), where Y is methyl, and Ru, W,, R3, X and Z have the values listed in Table 1. Thus compound 1 of Table 134 is the same as compound 1 of Table 1 except that in compound 1 of Table 134 Y is methyl instead of 3, 5-dihydroxy-1, 2,4-triazin-6-ylthiomethyl. Similarly, compounds 2 to 576 of Table 134 are the same as compounds 2 to 576 of Table 1, respectively, except that in the compounds of Table 134 Y is methyl instead of 3, 5-dihydroxy-1, 2,4-triazin-6- ylthiomethyl.

Table 135 Table 135 consists of 576 compounds of the general formula (1), where Y is 5,6-di (2- furyl)-1, 2, 4-triazin-3-ylthiomethyl, and Rl, R, R3, X and Z have the values listed in Table 1. Thus compound 1 of Table 135 is the same as compound 1 of Table 1 except that in compound 1 of Table 135 Y is 5,6-di (2-furyl)-1, 2,4-triazin-3-ylthiomethyl instead of 3, 5-dihydroxy-1, 2, 4-triazin-6-ylthiomethyl. Similarly, compounds 2 to 576 of Table 135 are the same as compounds 2 to 576 of Table 1, respectively, except that in the compounds of Table 135 Y is 5,6-di (2-furyl)-1, 2, 4-triazin-3-ylthiomethyl instead of 3,5- dihydroxy-1, 2,4-triazin-6-ylthiomethyl.

Table 136 Table 136 consists of 576 compounds of the general formula (1), where Y is trichloroethenyl, and Rl, R2, R3, X and Z have the values listed in Table 1. Thus compound 1 of Table 136 is the same as compound 1 of Table 1 except that in compound 1 of Table 136 Y is trichloroethenyl instead of 3, 5-dihydroxy-1, 2,4-triazin-6- ylthiomethyl. Similarly, compounds 2 to 576 of Table 136 are the same as compounds 2 to 576 of Table 1, respectively, except that in the compounds of Table 136 Y is trichloroethenyl instead of 3,5-dihydroxy-1, 2, 4-triazin-6-ylthiomethyl.

Table 137 Table 137 consists of 576 compounds of the general formula (1), where Y is ethylthio, and R', R2, R3, X and Z have the values listed in Table 1. Thus compound 1 of Table 137 is the same as compound 1 of Table 1 except that in compound 1 of Table 137 Y is

ethylthio instead of 3, 5-dihydroxy-1, 2,4-triazin-6-ylthiomethyl. Similarly, compounds 2 to 576 of Table 137 are the same as compounds 2 to 576 of Table 1, respectively, except that in the compounds of Table 137 Y is ethylthio instead of 3, 5-dihydroxy-1, 2,4-triazin- 6-ylthiomethyl.

Table 138 Table 138 consists of 576 compounds of the general formula (1), where Y is 4- methylpiperidinoethyl, and Rl, R2, R3, X and Z have the values listed in Table 1. Thus compound 1 of Table 138 is the same as compound 1 of Table 1 except that in compound 1 of Table 138 Y is 4-methylpiperidinoethyl instead of 3, 5-dihydroxy-1, 2,4-triazin-6- ylthiomethyl. Similarly, compounds 2 to 576 of Table 138 are the same as compounds 2 to 576 of Table 1, respectively, except that in the compounds of Table 138 Y is 4- methylpiperidinoethyl instead of 3, 5-dihydroxy-1, 2,4-triazin-6-ylthiomethyl.

Table 139 Table 139 consists of 576 compounds of the general formula (1), where Y is azepan-1- ylmethyl, and R, R2, R3, X and Z have the values listed in Table 1. Thus compound 1 of Table 139 is the same as compound 1 of Table 1 except that in compound 1 of Table 139 Y is azepan-1-ylmethyl instead of 3, 5-dihydroxy-1, 2,4-triazin-6-ylthiomethyl. Similarly, compounds 2 to 576 of Table 139 are the same as compounds 2 to 576 of Table 1, respectively, except that in the compounds of Table 139 Y is azepan-1-ylmethyl instead of 3,5-dihydroxy-1, 2,4-triazin-6-ylthiomethyl.

Table 140 Table 140 consists of 576 compounds of the general fonnula (1), where Y is 1,3- dichloro-2-methyl-prop-2-yl, and Ru, R2, R3, X and Z have the values listed in Table 1.

Thus compound 1 of Table 140 is the same as compound 1 of Table 1 except that in compound 1 of Table 140 Y is 1, 3-dichloro-2-methyl-prop-2-yl instead of 3, 5-dihydroxy- 1, 2, 4-tliazin-6-ylthiomethyl. Similarly, compounds 2 to 576 of Table 140 are the same as compounds 2 to 576 of Table 1, respectively, except that in the compounds of Table 140 Y is 1, 3-dichloro-2-methyl-prop-2-yl instead of 3, 5-dihydroxy-1, 2,4-triazin-6- ylthiomethyl.

Compounds of formula (1) may be prepared by the reaction of an aminothiophene (2) with an acyl chloride of formula (3), conveniently in 1,4-dioxane. This process has the advantage that it may be conducted in the absence of a base. It also has the advantage that it may be conducted at a temperature of from 0°C to 40°C and conveniently, at room temperature.

The aminothiophene (2) may be obtained by known literature methods using, for example, the Gewald synthesis involving the reaction of a cyclic or acyclic ketone with malononitrile (to form compounds where R3 is cyano) or with cyanoacetic acid or ester (to form compounds where R3 is a carboalkoxy group). The general methodology of the Gewald synthesis and references to it are discussed in US 4,013, 681 and detailed preparative methods are given here in the Preparative Examples that follow. Further compounds of formula (1) may be prepared by using standard chemical modification techniques, several of which are described in more detail in the Examples.

The compounds of formula (1) are active fungicides and may be used to control one or more of the following pathogens: Pyricularia oryzae (Magnaporthe grisea) on rice and wheat and other Pyricularia spp. on other hosts; Puccinia triticina (or recondita) Puccinia striiformis and other rusts on wheat, Puccinia hordei, Puccinia striiformis and other rusts on barley, and rusts on other hosts (for example turf, rye, coffee, pears, apples, peanuts, sugar beet, vegetables and ornamental plants); Eiysiphe cichoracearum on cucurbits (for example melon); Blumeria (or Erysiphe) graminis (powdery mildew) on barley, wheat, rye and turf and other powdery mildews on various hosts, such as Sphaerotheca maculais on hops, Sphaerotheca fusca (Sphaerotheca fuliginea) on cucurbits (for example cucumber), Leveillula taurica on tomatoes, aubergine and green pepper, Podosphaera leucotricha on apples and Uncinula necator on vines; Cochliobolus spp., Helminthosporium spp., Dreelislera spp. (Pyrenophora spp.), Rhynchospo7 ium spp., Mycosphaerella graminicola (Septoria tritici) and Phaeosphaeria nodorunz

(Stagonospora nodorum or Septo7-ia nodorum), Pseudocercosporella hefpotrichoides and Gaeumannomyces graminis on cereals (for example wheat, barley, rye), turf and other hosts; Cercospora arachidicola and Cercosporidium personatum on peanuts and other Cercospora spp. on other hosts, for example sugar beet, bananas, soya beans and rice; Botrytis cinerea (grey mould) on tomatoes, strawberries, vegetables, vines and other hosts and other Botrytis spp. on other hosts; Alternaria spp. on vegetables (for example carrots), oil-seed rape, apples, tomatoes, potatoes, cereals (for example wheat) and other hosts; Venturia spp. (including Venturia inaequalis (scab) ) on apples, pears, stone fruit, tree nuts and other hosts ; Cladosporium spp. on a range of hosts including cereals (for example wheat) and tomatoes; Monilinia spp. on stone fruit, tree nuts and other hosts; Didymella spp. on tomatoes, turf, wheat, cucurbits and other hosts; Phoma spp. on oil-seed rape, turf, rice, potatoes, wheat and other hosts; Aspergillus spp. and Aureobasidium spp. on wheat, lumber and other hosts; Ascochyta spp. on peas, wheat, barley and other hosts ; Stemphylium spp. (Pleospora spp. ) on apples, pears, onions and other hosts; summer diseases (for example bitter rot (Glomerella cingulata), black rot or frogeye leaf spot (Botryosphaeria obtusa), Brooks fruit spot (Mycosphaerella pomi), Cedar apple rust (Gymnosporangium junipe7i-virginianae), sooty blotch (Gloeodes pomigena), flyspeck (Schizothyrium pomi) and white rot (Bottyosphaeria dothidea)) on apples and pears; Plasmopara viticola on vines; other downy mildews, such as Uremia lactucae on lettuce, Peronospora spp. on soybeans, tobacco, onions and other hosts, Pseudoperonospora humuli on hops and Pseudoperonospora cubensis on cucurbits; Pythium spp. (including Pythiunz ultimum) on turf and other hosts; Phytophthora infestans on potatoes and tomatoes and other Phytophthora spp. on vegetables, strawberries, avocado, pepper, ornamentals, tobacco, cocoa and other hosts; Tlianatephorus eucuineris on rice and turf and other Rhizoctonia spp. on various hosts such as wheat and barley, peanuts, vegetables, cotton and turf ; Sclerotinia spp. on turf, peanuts, potatoes, oil-seed rape and other hosts; Sclerotium spp. on turf, peanuts and other hosts; Gibberella fujikuroi on rice; Colletotrichum spp. on a range of hosts including turf, coffee and vegetables; Laetisaria fuciformis on turf ; Mycosphaerella spp. on bananas, peanuts, citrus, pecans, papaya and other hosts; Diaporthe spp. on citrus, soybean, melon, pears, lupin and other hosts; Elsinoe spp. on citrus, vines, olives, pecans, roses and other

hosts; Verticillium spp. on a range of hosts including hops, potatoes and tomatoes; Pyrenopeziza spp. on oil-seed rape and other hosts; Oncobasidium theobromae on cocoa <BR> <BR> <BR> <BR> causing vascular streak dieback; Fusarium spp. , Typhula spp. , Microdochium nivale,<BR> <BR> <BR> <BR> <BR> Ustilago spp. , Urocystis spp. , Tilletia spp. and Claviceps purpurea on a variety of hosts but particularly wheat, barley, turf and maize; Ramularia spp. on sugar beet, barley and other hosts; post-harvest diseases particularly of fruit (for example Penicillium digitatum, Penicillium italicum and Trichoderma viride on oranges, Colletotrichum musae and Gloeosporiun7 musarum on bananas and Botrytis cinerea on grapes); other pathogens on vines, notably Eutypa lata, Guignardia bidwellii, Phellinus igniarus, Phomopsis viticola, Pseudopeziza tracheiphila and Stereum hirsutum ; other pathogens on trees (for example Lophodermium seditiosum) or lumber, notably Cephaloascus fragrans, Ceratocystis spp. , Ophiostoma piceae, Penicillium spp. , Trichoderma pseudokoningii, Trichoderma viride, Trichoderma harzianum, Aspergillus niger, Leptographium lindbergi and Aureobasidium pullulans ; and fungal vectors of viral diseases (for example Polymyxa graminis on cereals as the vector of barley yellow mosaic virus (BYMV) and PolJmyxa betae on sugar beet as the vector of rhizomania).

The compounds of formula (1) are particularly useful for controlling Botrytis pathogens, especially Botfytis cinerea (grey mould), and Septoria pathogens, especially Septoria tritici (leaf blotch), on various host plants and harvested crops.

The invention therefore provides the use of the compounds of formula (1) for combating or controlling phytopathogenic diseases on plants and harvested foodstuffs.

The term"plant"as used herein includes seedlings, bushes and trees. Furthermore, the fungicidal method of the invention includes protectant, curative, systemic, eradicant and antisporulant treatments.

The compounds of formula (1) are preferably used for agricultural, horticultural and turfgrass purposes in the form of a composition.

In order to apply a compound of formula (1) to a plant, to a seed of a plant, to the locus of the plant or seed or to soil or any other growth medium, a compound of formula (1) is usually formulated into a composition which includes, in addition to the compound of formula (1), a suitable inert diluent or carrier and, optionally, a surface active agent (SFA). SFAs are chemicals that are able to modify the properties of an interface (for

example, liquid/solid, liquid/air or liquid/liquid interfaces) by lowering the interfacial tension and thereby leading to changes in other properties (for example dispersion, emulsification and wetting). It is preferred that all compositions (both solid and liquid formulations) comprise, by weight, 0.0001 to 95%, more preferably 1 to 85%, for example 5 to 60%, of a compound of formula (1). The composition is generally used for the control of fungi such that a compound of formula (1) is applied at a rate of from 0. 1 g tolOkg per hectare, preferably from lg to 6kg per hectare, more preferably from lg to lkg per hectare.

When used in a seed dressing, a compound of formula (1) is used at a rate of O. OOOlg to lOg (for example O. OOlg or 0. 05g), preferably 0. 005g to lOg, more preferably 0. 005g to 4g, per kilogram of seed.

In another aspect the present invention provides a fungicidal composition comprising a fungicidally effective amount of a compound of formula (1) and a suitable carrier or diluent therefor.

In a still further aspect-the invention provides a method of combating and controlling fungi at a locus, which comprises treating the fungi, or the locus of the fungi with a fungicidally effective amount of a composition comprising a compound of formula (1).

The compositions can be chosen from a number of formulation types, including dustable powders (DP), soluble powders (SP), water soluble granules (SG), water dispersible granules (WG), wettable powders (WP), granules (GR) (slow or fast release), soluble concentrates (SL), oil miscible liquids (OL), ultra low volume liquids (UL), emulsifiable concentrates (EC), dispersible concentrates (DC), emulsions (both oil in water (EW) and water in oil (EO)), micro-emulsions (ME), suspension concentrates (SC), aerosols, fogging/smoke formulations, capsule suspensions (CS) and seed treatment formulations. The formulation type chosen in any instance will depend upon the particular purpose envisaged and the physical, chemical and biological properties of the compound of formula (1).

Dustable powders (DP) may be prepared by mixing a compound of formula (1) with one or more solid diluents (for example natural clays, kaolin, pyrophyllite, bentonite, alumina, montmorillonite, kieselguhr, chalk, diatomaceous earths, calcium

phosphates, calcium and magnesium carbonates, sulphur, lime, flours, talc and other organic and inorganic solid carriers) and mechanically grinding the mixture to a fine powder.

Soluble powders (SP) may be prepared by mixing a compound of formula (1) with one or more water-soluble inorganic salts (such as sodium bicarbonate, sodium carbonate or magnesium sulphate) or one or more water-soluble organic solids (such as a polysaccharide) and, optionally, one or more wetting agents, one or more dispersing agents or a mixture of said agents to improve water dispersibility/solubility. The mixture is then ground to a fine powder. Similar compositions may also be granulated to form water soluble granules (SG).

Wettable powders (WP) may be prepared by mixing a compound of formula (1) with one or more solid diluents or carriers, one or more wetting agents and, preferably, one or more dispersing agents and, optionally, one or more suspending agents to facilitate the dispersion in liquids. The mixture is then ground to a fine powder. Similar compositions may also be granulated to form water dispersible granules (WG).

Granules (GR) may be formed either by granulating a mixture of a compound of formula (1) and one or more powdered solid diluents or carriers, or from pre-fonned blank granules by absorbing a compound of formula (1) (or a solution thereof, in a suitable agent) in a porous granular material (such as pumice, attapulgite clays, fuller's earth, kieselguhr, diatomaceous earths or ground corn cobs) or by adsorbing a compound of formula (1) (or a solution thereof, in a suitable agent) on to a hard core material (such as sands, silicates, mineral carbonates, sulphates or phosphates) and drying if necessary.

Agents which are commonly used to aid absorption or adsorption include solvents (such as aliphatic and aromatic petroleum solvents, alcohols, ethers, ketones and esters) and sticking agents (such as polyvinyl acetates, polyvinyl alcohols, dextrins, sugars and vegetable oils). One or more other additives may also be included in granules (for example an emulsifying agent, wetting agent or dispersing agent).

Dispersible Concentrates (DC) may be prepared by dissolving a compound of formula (1) in water or an organic solvent, such as a ketone, alcohol or glycol ether.

These solutions may contain a surface active agent (for example to improve water dilution or prevent crystallisation in a spray tank).

Emulsifiable concentrates (EC) or oil-in-water emulsions (EW) may be prepared by dissolving a compound of formula (1) in an organic solvent (optionally containing one or more wetting agents, one or more emulsifying agents or a mixture of said agents).

Suitable organic solvents for use in ECs include aromatic hydrocarbons (such as alkylbenzenes or alkylnaphthalenes, exemplified by SOLVESSO 100, SOLVESSO 150 and SOLVESSO 200; SOLVESSO is a Registered Trade Mark), ketones (such as cyclohexanone or methylcyclohexanone), alcohols (such as benzyl alcohol, furfuryl alcohol or butanol), N-alkylpyrrolidones (such as N-methylpyrrolidone or N-octyl- pyrrolidone), dimethyl amides of fatty acids (such as C8-CIo fatty acid dimethylamide) and chlorinated hydrocarbons. An EC product may spontaneously emulsify on addition to water, to produce an emulsion with sufficient stability to allow spray application through appropriate equipment. Preparation of an EW involves obtaining a compound of formula (1) either as a liquid (if it is not a liquid at room temperature, it may be melted at a reasonable temperature, typically below 70°C) or in solution (by dissolving it in an appropriate solvent) and then emulsifying the resultant liquid or solution into water containing one or more SFAs, under high shear, to produce an emulsion. Suitable solvents for use in EWs include vegetable oils, chlorinated hydrocarbons (such as chlorobenzenes), aromatic solvents (such as alkylbenzenes or alkylnaphthalenes) and other appropriate organic solvents that have a low solubility in water.

Microemulsions (ME) may be prepared by mixing water with a blend of one or more solvents with one or more SFAs, to produce spontaneously a thermodynamically stable isotropic liquid formulation. A compound of formula (1) is present initially in either the water or the solvent/SFA blend. Suitable solvents for use in MEs include those hereinbefore described for use in in ECs or in EWs. An ME may be either an oil-in-water or a water-in-oil system (which system is present may be determined by conductivity measurements) and may be suitable for mixing water-soluble and oil-soluble pesticides in the same formulation. An ME is suitable for dilution into water, either remaining as a microemulsion or forming a conventional oil-in-water emulsion.

Suspension concentrates (SC) may comprise aqueous or non-aqueous suspensions of finely divided insoluble solid particles of a compound of formula (1). SCs may be prepared by ball or bead milling the solid compound of formula (1) in a suitable medium,

optionally with one or more dispersing agents, to produce a fine particle suspension of the compound. One or more wetting agents may be included in the composition and a suspending agent may be included to reduce the rate at which the particles settle.

Alternatively, a compound of formula (1) maybe dry milled and added to water, containing agents hereinbefore described, to produce the desired end product.

Aerosol formulations comprise a compound of formula (1) and a suitable propellant (for example 7l-butane). A compound of formula (1) may also be dissolved or dispersed in a suitable medium (for example water or a water miscible liquid, such as 7z- propanol) to provide compositions for use in non-pressurised, hand-actuated spray pumps.

A compound of formula (1) may be mixed in the dry state with a pyrotechnic mixture to form a composition suitable for generating, in an enclosed space, a smoke containing the compound.

Capsule suspensions (CS) may be prepared in a manner similar to the preparation of EW formulations but with an additional polymerisation stage such that an aqueous dispersion of oil droplets is obtained, in which each oil droplet is encapsulated by a polymeric shell and contains a compound of formula (1) and, optionally, a carrier or diluent therefor. The polymeric shell may be produced by either an interfacial polycondensation reaction or by a coacervation procedure. The compositions may provide for controlled release of the compound of formula (1) and they may be used for seed treatment. A compound of formula (1) may also be formulated in a biodegradable polymeric matrix to provide a slow, controlled release of the compound.

A composition may include one or more additives to improve the biological performance of the composition (for example by improving wetting, retention or distribution on surfaces; resistance to rain on treated surfaces; or uptake or mobility of a compound of formula (1) ). Such additives include surface active agents, spray additives based on oils, for example certain mineral oils or natural plant oils (such as soy bean and rape seed oil), and blends of these with other bio-enhancing adjuvants (ingredients which may aid or modify the action of a compound of formula (1)).

A compound of formula (1) may also be formulated for use as a seed treatment, for example as a powder composition, including a powder for dry seed treatment (DS), a

water soluble powder (SS) or a water dispersible powder for slurry treatment (WS), or as a liquid composition, including a flowable concentrate (FS), a solution (LS) or a capsule suspension (CS). The preparations of DS, SS, WS, FS and LS compositions are very similar to those of, respectively, DP, SP, WP, SC and DC compositions described above.

Compositions for treating seed may include an agent for assisting the adhesion of the composition to the seed (for example a mineral oil or a film-forming barrier).

Wetting agents, dispersing agents and emulsifying agents may be SFAs of the cationic, anionic, amphoteric or non-ionic type.

Suitable SFAs of the cationic type include quaternary ammonium compounds (for example cetyltrimethyl ammonium bromide), imidazolines and amine salts.

Suitable anionic SFAs include alkali metals salts of fatty acids, salts of aliphatic monoesters of sulphuric acid (for example sodium lauryl sulphate), salts of sulphonated aromatic compounds (for example sodium dodecylbenzenesulphonate, calcium dodecylbenzenesulphonate, butylnaphthalene sulphonate and mixtures of sodium di- isopropyl-and tri-isopropyl-naphthalene sulphonates), ether sulphates, alcohol ether sulphates (for example sodium laureth-3-sulphate), ether carboxylates (for example sodium laureth-3-carboxylate), phosphate esters (products from the reaction between one or more fatty alcohols and phosphoric acid (predominately mono-esters) or phosphorus pentoxide (predominately di-esters), for example the reaction between lauryl alcohol and tetraphosphoric acid; additionally these products may be ethoxylated), sulphosuc- cinamates, paraffin or olefine sulphonates, taurates and lignosulphonates.

Suitable SFAs of the amphoteric type include betaines, propionates and glycinates.

Suitable SFAs of the non-ionic type include condensation products of alkylene oxides, such as ethylene oxide, propylene oxide, butylene oxide or mixtures thereof, with fatty alcohols (such as oleyl alcohol or cetyl alcohol) or with alkylphenols (such as octylphenol, nonylphenol or octylcresol) ; partial esters derived from long chain fatty acids or hexitol anhydrides; condensation products of said partial esters with ethylene oxide; block polymers (comprising ethylene oxide and propylene oxide); alkanolamides; simple esters (for example fatty acid polyethylene glycol esters); amine oxides (for example lauryl dimethyl amine oxide); and lecithins.

Suitable suspending agents include hydrophilic colloids (such as polysaccharides, polyvinylpyrrolidone or sodium carboxymethylcellulose) and swelling clays (such as bentonite or attapulgite).

A compound of formula (1) may be applied by any of the known means of applying fungicidal compounds. For example, it may be applied, formulated or unformulated, to any part of the plant, including the foliage, stems, branches or roots, to the seed before it is planted or to other media in which plants are growing or are to be planted (such as soil surrounding the roots, the soil generally, paddy water or hydroponic culture systems), directly or it may be sprayed on, dusted on, applied by dipping, applied as a cream or paste formulation, applied as a vapour or applied through distribution or incorporation of a composition (such as a granular composition or a composition packed in a water-soluble bag) in soil or an aqueous environment.

A compound of formula (1) may also be injected into plants or sprayed onto vegetation using electrodynamic spraying techniques or other low volume methods, or applied by land or aerial irrigation systems.

Compositions for use as aqueous preparations (aqueous solutions or dispersions) are generally supplied in the form of a concentrate containing a high proportion of the active ingredient, the concentrate being added to water before use. These concentrates, which may include DCs, SCs, ECs, EWs, MEs SGs, SPs, WPs, WGs and CSs, are often required to withstand storage for prolonged periods and, after such storage, to be capable of addition to water to form aqueous preparations which remain homogeneous for a sufficient time to enable them to be applied by conventional spray equipment. Such aqueous preparations may contain varying amounts of a compound of formula (1) (for example 0.0001 to 10%, by weight) depending upon the purpose for which they are to be used.

A compound of formula (1) may be used in mixtures with fertilisers (for example nitrogen-, potassium-or phosphorus-containing fertilisers). Suitable formulation types include granules of fertiliser. The mixtures suitably contain up to 25% by weight of the compound of formula (1).

The invention therefore also provides a fertiliser composition comprising a fertiliser and a compound of formula (1).

The compositions of this invention may contain other compounds having biological activity, for example micronutrients or compounds having similar or complementary fungicidal activity or which possess plant growth regulating, herbicidal, insecticidal, nematicidal or acaricidal activity.

By including another fungicide, the resulting composition may have a broader spectrum of activity or a greater level of intrinsic activity than the compound of formula (1) alone. Further the other fungicide may have a synergistic effect on the fungicidal activity of the compound of formula (1).

The compound of formula (1) may be the sole active ingredient of the composition or it may be admixed with one or more additional active ingredients such as a pesticide, fungicide, synergist, herbicide or plant growth regulator where appropriate.

An additional active ingredient may: provide a composition having a broader spectrum of activity or increased persistence at a locus; synergise the activity or complement the activity (for example by increasing the speed of effect or overcoming repellency) of the compound of formula (1); or help to overcome or prevent the development of resistance to individual components. The particular additional active ingredient will depend upon the intended utility of the composition.

Examples of fungicidal compounds which may be included in the composition of the invention are AC 382042 (N-(l-cyano-1, 2-dimethylpropyl)-2-(2, 4-dichlorophenoxy) propionamide), acibenzolar-S-methyl, alanycarb, aldimorph, anilazine, azaconazole, azafenidin, azoxystrobin, benalaxyl, benomyl, benthiavalicarb, biloxazol, bitertanol, blasticidin S, boscalid (new name for nicobifen), bromuconazole, bupirimate, captafol, captan, carbendazim, carbendazim chlorhydrate, carboxin, carpropamid, carvone, CGA 41396, CGA 41397, chinomethionate, chlorbenzthiazone, chlorothalonil, chlorozolinate, clozylacon, copper containing compounds such as copper oxychloride, copper oxyquino- late, copper sulphate, copper tallate, and Bordeaux mixture, cyamidazosulfamid, cyazofamid (IKF-916), cyflufenamid, cymoxanil, cyproconazole, cyprodinil, debacarb, di-2-pyridyl disulphide 1, 1'-dioxide, dichlofluanid, diclocymet, diclomezine, dicloran, diethofencarb, difenoconazole, difenzoquat, diflumetorim, O, O-di-iso-propyl-S-benzyl thiophosphate, dimefluazole, dimetconazole, dimethirimol, dimethomorph, dimoxystrobin, diniconazole, dinocap, dithianon, dodecyl dimethyl ammonium chloride,

dodemorph, dodine, doguadine, edifenphos, epoxiconazole, ethaboxam, ethirimol, ethyl (Z)-N-benzyl-N ([methyl (methyl-thioethylideneaminooxycarbonyl) amino] thio)-ß- alaninate, etridiazole, famoxadone, fenamidone, fenarimol, fenbuconazole, fenfuram, fenhexamid, fenoxanil (AC 382042), fenpiclonil, fenpropidin, fenpropimorph, fentin acetate, fentin hydroxide, ferbam, ferimzone, fluazinam, fludioxonil, flumetover, flumorph, fluoroimide, fluoxastrobin, fluquinconazole, flusilazole, flusulfamide, flutolanil, flutriafol, folpet, fosetyl-aluminium, fuberidazole, furalaxyl, furametpyr, guazatine, hexaconazole, hydroxyisoxazole, hyinexazole, imazalil, imibenconazole, iminoctadine, iminoctadine triacetate, ipconazole, iprobenfos, iprodione, iprovalicarb, isopropanyl butyl carbamate, isoprothiolane, kasugamycin, kresoxim-methyl, LY186054, LY211795, LY 248908, mancozeb, maneb, mefenoxam, mepanipyrim, mepronil, metalaxyl, metalaxyl M, metconazole, metiram, metiram-zinc, metominostrobin, metrafenone, MON65500 (N-allyl-4, 5-dimethyl-2-trimethylsilylthiophene-3- carboxamide), myclobutanil, NTN0301, neoasozin, nickel dimethyldithiocarbamate, nitrothale-isopropyl, nuarimol, ofurace, organomercury compounds, orysastrobin, oxadixyl, oxasulfuron, oxolinic acid, oxpoconazole, oxycarboxin, pefurazoate, penconazole, pencycuron, phenazin oxide, phosphorus acids, phthalide, picoxystrobin, polyoxin D, polyram, probenazole, prochloraz, procymidone, propamocarb, propamocarb hydrochloride, propiconazole, propineb, propionic acid, proquinazid, prothioconazole, pyraclostrobin, pyrazophos, pyrifenox, pyrimethanil, pyroquilon, pyroxyfur, pyrrolnitrin, quaternary ammonium compounds, quinomethionate, quinoxyfen, quintozene, silthiofam (MON 65500), S-imazalil, simeconazole, sipconazole, sodium pentachlorophenate, spiroxamine, streptomycin, sulphur, tebuconazole, tecloftalam, tecnazene, tetraconazole, thiabendazole, thifluzamide, 2- (thiocyanomethylthio) benzothiazole, thiophanate-methyl, thiram, tiadinil, timibenconazole, tolclofos-methyl, tolylfluanid, triadimefon, triadimenol, triazbutil, triazoxide, tricyclazole, tridemorph, trifloxystrobin, triflumizole, triforine, triticonazole, validamycin A, vapam, vinclozolin, XRD-563, zineb, ziram, zoxamide and compounds of the formulae :

The compounds of formula (1) may be mixed with soil, peat or other rooting media for the protection of plants against seed-borne, soil-borne or foliar fungal diseases.

Some mixtures may comprise active ingredients, which have significantly different physical, chemical or biological properties such that they do not easily lend themselves to the same conventional formulation type. In these circumstances other formulation types may be prepared. For example, where one active ingredient is a water insoluble solid and the other a water insoluble liquid, it may nevertheless be possible to disperse each active ingredient in the same continuous aqueous phase by dispersing the solid active ingredient as a suspension (using a preparation analogous to that of an SC) but dispersing the liquid active ingredient as an emulsion (using a preparation analogous to that of an EW). The resultant composition is a suspoemulsion (SE) formulation.

The invention is illustrated by the following Examples in which the following abbreviations are used: conc. = concentrated m. p. = melting point equiv. = equivalent ppm = parts per million dec. = decomposes s = singlet br s = broad singlet d = doublet t = triplet br t = broad triplet dd = doublet of doublets q = quartet qt = quartet of triplets m = multiplet NMR = nuclear magnetic resonance TLC = thin layer chromatography DMSO = dimethylsulphoxide DMF = N, N-dimethylformamide THF = tetrahydrofuran TFA = trifluoroacetic acid DCM = dichloromethane HOBT =1-hydroxybenzotriazole DMAP = 4-dimethylaminopyridine DBU = 1, 8-diazabicyclo [5.4. 0] undec-7-ene DDQ = 2,3-dichloro-5, 6-dicyano-1, 4-EDCI = 1-ethyl-3-1\4N-dimethylamino- benzoquinone propylcarbodiimide hydrochloride TPP = triphenyl phosphine PREPARATIVE EXAMPLES The following Examples illustrate the preparation of aminothiophenes of general formula (2).

EXAMPLE A This Example describes the general methodology for the Gewald synthesis from cyclic and acyclic ketones.

A = O, C, NH or NHCO2tBu X = CN, COOEt The appropriate cyclic ketone (60 mmol), cyanoacetic acid ethyl ester or malononitrile (60 mmol) and sulphur (60 mmol) were dissolved in ethanol (50ml). The mixture was warmed to 50°C and, once the solubilisation of sulphur was complete, morpholine (l lg) was added dropwise. The reaction mixture was kept at 50°C until the absence of starting material was confirmed by TLC (usually between 1 and 3 hours). Once cooled to room temperature, the desired aminothiophene precipitated, was filtered, and washed with ethanol until the mother liquor became colourless.

The decalin thiophene AO was obtained using the general procedure from octahydro- naphthalen-2-one in 90 % yield as a single regioisomer. m. p. 135-136°C ; IH NMR 8H (300MHz, CDC13) : 4.65 (2H, s) and 2.9-1. 0 (14H, m) ppm; fizz (-ve ion): 231 (M-H) 100%.

The aminothiophene BO was obtained using the general procedure from tetrahydro-4H- pyran-4-one in 87% yield.

1H NMR 5H (300MHz, CDCl3) : 5.50 (2H, s), 4.55 (2H, s), 3. 8 (2H, t) and 2.7 (2H, m) ppm.

The aminothiophene CO was obtained using the general procedure from tetrahydro-4H- pyran-4-one in 77% yield. m. p. 117-118°C ; 'H NMR 5H (300MHz, CDC13) : 6.00 (2H, s), 4.55 (2H, s), 4.35 (2H, q), 3.9 (2H, t), 2.8 (2H, m) and 1.35 (3H, t) ppm.

The aminothiophene HO was obtained using the general procedure from 4-oxo- piperidine-1-carboxylic acid ter-butyl ester as white crystals in 77% yield. m. p. 151-152°C ; . tH NMR AH (300MHz, d6-DMSO): 7.2 (2H, s), 4.05 (2H, s), 3.95 (2H, q), 3.3 (2H, t), 2.45 (2H, t), 1.20 (9H, s) and 1.05 (3H, t) ppm.

The aminothiophene JO was obtained using the general procedure from cyclohexanone as yellow crystals in 97% yield.

IH NMR 8H (300MHz, CDC13) : 6.5-5. 5 (2H, br s), 4.3 (2H, q), 2.7 (2H, m), 2.45 (2H, m), 1.75 (4H, m) and 1.45 (3H, t) ppm.

EXAMPLE B This Example describes the general methodology for the Gewald synthesis from certain acyclic ketones.

The appropriate ß-keto ester (200 mmol), cyanoacetic acid (18g, 212 mmol), ammonium acetate (3.87g) and acetic acid (6g) were stirred at room temperature for 5 hours in toluene (100ml). The reaction mixture was poured into saturated aqueous ammonium chloride and extracted with ethyl acetate. After drying over magnesium sulphate and concentration under reduced pressure, the remaining oil was dissolved in ethanol (100ml). Sulphur (4g) was added, followed by the dropwise addition of diethylamine (13ml) to give a red solution, which was stirred at room temperature for 16 hours. The reaction mixture was poured into saturated aqueous ammonium chloride and extracted with ethyl acetate. After drying over magnesium sulphate and concentration under reduced pressure, the remaining oil was purified by flash chromatography, using ethyl acetate: hexane (2: 1, by volume) as eluant, to yield the desired aminothiophene.

The aminothiophene DO was obtained using the general procedure as yellowish crystals (11. 9g, 40 %). m. p. 131-132°C ; 1H NMR 8H (300MHz, CDC13) : 6.8 (1H, s), 4.7 (2H, s), 4.3 (2H, s), 3.8 (3H, s) and 3.45 (3H, s) ppm ; m/z (-ve ion): 200 (M-H) 100%.

EXAMPLE C This Example illustrates the preparation of 2-amino-4,5, 6,7- tetrahydrobenzo [b] thiophene-3-carbonitrile (aminothiophene EO) To a stirred solution of cyclohexanone (10. 4ml, 0. 10 mol) in ethanol (300ml) were added sulphur (3.52g, O. llmol), malononitrile (6.60g, 0.10 mol) and diethylamine (10. 30ml, 0. 10mol). The reaction mixture was heated at 70°C for 17 hours. The mixture was allowed to cool to room temperature and the solvent removed under reduced pressure.

The residue was partitioned between water and ethyl acetate and the aqueous extracted with further ethyl acetate. The combined organic extracts were washed with brine, dried over magnesium sulphate and evaporated to dryness under reduced pressure to give the desired product (16. 7g, 94%) as a brown solid.

1H NMR #H (400MHz, CDCl3): 4.60 (2H, br s), 2.50 (4H, m) and 1.80 (4H, m) ppm.

EXAMPLE D This Example illustrates the preparation of 2-amino-4, 5,6, 7-tetrahydro- benzo [b] thiophene-3-carboxylic acid tert-butyl ester (aminothiophene FO)

To a stirred solution of cyclohexanone (5. 20ml, 50 mmol) in ethanol (150ml) were added sulphur (1.77g, 55 mmol), ter-butyl cyanoacetate (7-25mol, 50 mmol) and diethylamine (5. 15ml, 50 mmol). The reaction mixture was heated at 70°C for 17 hours and then allowed to cool to room temperature. The mixture was reduced to approximately half its volume under reduced pressure, diluted with water and extracted with ethyl acetate. The combined organic extracts were washed with brine, dried over magnesium sulphate and evaporated to dryness under reduced pressure to give a yellow/brown oil (14.2g).

Chromatography of the crude product over silica, using 30% ether in hexane (by volume) as eluant, gave the desired product (10. 5g, 83%) as a yellow oil.

1H NMR 5H (400MHz, CDC13) : 5.85 (2H, br s), 2.65 (2H, m), 2.50 (2H, m), 1.75 (4H, m) and 1. 55 (9H, s) ppm.

EXAMPLE E This example illustrates the preparation of 1- (2-amino-4, 5,6, 7-tetrahydro- benzo [b] thiophen-3-yl)-2, 2-dimethyl-propan-1-one (aminothiophene GO) To a stirred solution of cyclohexanone (520u. l, 5 mmol) in ethanol (15ml) were added sulphur (176mg, 5.5 mmol), 4, 4-dimethyl-3-oxo-pentanenitrile (436µl, 5 mmol) and morpholine (436p1, 5 mmol). The reaction mixture was heated at 70°C for 17 hours, then allowed to cool to room temperature, diluted with water and extracted with ethyl acetate.

The combined organic extracts were washed with brine, dried over magnesium sulphate

and evaporated to dryness under reduced pressure to give a brown oil (1. llg).

Chromatography of the crude product over silica, using 20% ether in hexane (by volume) as eluant, gave the desired product (225mg, 19%) as a yellow oil.

'H NMR 8H (400MHz, CDC13) : 4.00 (2H, br s), 2.55 (2H, m), 2.40 (2H, m), 1.80 (2H, m), 1.70 (2H, m) and 1.20 (9H, s) ppm.

EXAMPLE F This Example illustrates the preparation of 2-amino-5,6, 7, 8-tetrahydro-4H- cyclohepta [b] thiophene-3-carbonitrile (aminothiophene KO) To a stirred solution of cycloheptanone (5. 90ml, 50 mmol) in ethanol (200ml) were added sulphur (1.76g, 55 mmol), malononitrile (3.30g, 50 mmol) and morpholine (4. 80ml, 5.5 mmol). The reaction mixture was stirred at 70°C for 17 hours, then allowed to cool to room temperature. The solvent was removed under reduced pressure, the residue dissolved in ethyl acetate and washed with water and brine. The organic phase was dried over magnesium sulphate and evaporated to dryness under reduced pressure to give the desired product (9.58g, 99%) as a brown solid.

1H NMR 8H (400MHz, CDC13) : 4.50 (2H, br s), 2.60 (4H, m), 1.85 (2H, m), 1.65 (4H, m) ppm.

EXAMPLE G This Example illustrates the preparation of 2-amino-5-tert-butyl-thiophene-3-carbonitrile (aminothiophene LO)

To a stirred suspension of 3, 3-dimethyl-butyraldehyde (4. 25ml, 33.9 mmol) and sulphur (1. 08g, 33.9 mmol) in DMF (20ml) at 0°C was added triethylamine (2. 88ml, 21 mmol) dropwise over 30 minutes. The reaction mixture was allowed to warm to room temperature over 1 hour and then a solution of malononitrile (2.24g, 33.9 mmol) in DMF (10ml) was added dropwise. The mixture was stirred at room temperature for 17 hours and then poured into iced water. The resultant solid was removed by filtration, washed with cold water and air-dried to give the desired product (4.84g, 79%) as a pale brown solid. m. p. 125.0-127. 0 °C (dec.).

EXAMPLE H This Example illustrates the preparation of 2-methylamino-4, 5,6, 7- tetrahydrobenzo [b] thiophene-3-carbonitrile (aminothiophene MO) Preparation of (3-cyano-4,5, 6, 7-tetrahydrobenzo [b] thiophen-2-yl) -carbamic acid tert- butyl ester To a stirred solution of aminothiophene EO (prepared as described in Example C; 1.79g, 10 mmol,) in acetonitrile (75ml) were added DMAP (lOOmg) and di-tert-butyl dicarbonate (2.40g, 10.5 mmol). The reaction mixture was stirred at room temperature for 65 hours after which further di-tert-butyl dicarbonate (2.40g, 10.5 mmol) and DMAP (100mg) were added. The mixture was stirred at room temperature for a further 17 hours.

The solvent was removed under reduced pressure and the residue partitioned between water and ethyl acetate. The aqueous was further extracted with ethyl acetate. The combined organic extracts were washed with brine, dried over magnesium sulphate and evaporated to dryness under reduced pressure to give a brown oil (2.40g).

Chromatography of the crude product over silica, using 40% ether in hexane (by volume) as eluant, gave the desired product (1.25g, 45%) as an off-white solid.

1H NMR 8H (400MHz, CDC13) : 7.45 (1H, br s), 2.60 (4H, m), 1.80 (4H, m) and 1.55 (9H, s) ppm.

Preparation of (3-cyano-4,5, 6,7-tetrahydrobenzo [b] thiophen-2-yl)-methylcarbamic acid tert-butyl ester

To a stirred solution of (3-cyano-4,5, 6,7-tetrahydrobenzo [b] thiophen-2-yl) -carbamic acid tert-butyl ester (278mg, 1 mmol) in dry THF (20ml) under a nitrogen atmosphere at room temperature was added in a single portion, sodium hydride (60% suspension in mineral oil; 60mg, 1.5 mmol). The reaction mixture was stirred at room temperature for 30 minutes, then methyl iodide (311111, 5 mmol) was added and the mixture stirred at room temperature for a further 18 hours. The reaction was quenched with water and extracted with ethyl acetate. The combined organic extracts were washed with brine, dried over magnesium sulphate and evaporated to dryness under reduced pressure to give the desired product (257mg, 88%) as an off-white solid.

1H NMR 5H (400MHz, CDC13) : 3.35 (3H, s), 2.65 (4H, m), 1.80 (4H, m) and 1.50 (9H, s) ppm.

Preparation of 2-methylamino-4,5, 6,7-tetrahydrobenzo [b] thiophene-3-carbonitrile (aminothiophene MO)

To a stirred solution of (3-cyano-4, 5,6, 7-tetrahydrobenzo [b] thiophen-2-yl)-methyl- carbamic acid tert-butyl ester (197mg, 6.8 mmol,) in DCM (5ml) was added TFA (lml).

The reaction mixture was stirred at room temperature for 2 hours and then the solvent was removed under reduced pressure. The residue was dissolved in ethyl acetate and

washed with saturated aqueous sodium hydrogen carbonate, water and brine. The organic phase was dried over magnesium sulphate and evaporated to dryness under reduced pressure to give the desired product (126mg, 98%) as an orange solid.

'H NMR 6. (400MHz, CDC13) : 4.85 (1H, br s), 2.95 (3H, d), 2.50 (4H, m) and 1.80 (4H, m) ppm.

EXAMPLE I This Example illustrates the preparation of 5-amino-3-methylthiophene-2-carboxylic acid ethyl ester (aminothiophene NO) Preparation of 4-cyano-3-methylbut-3-enoic acid ethyl ester

3-Oxo-butyric acid ethyl ester (39g, 0.3 mol) was dissolved in toluene (150ml) in the presence of cyanoacetic acid (27.2g, 0.32 mol), ammonium acetate (5.8g, 0.075 mol) and acetic acid (8. 6ml, 0.15 mol). The mixture was heated at reflux for 7 hours with continuous distillation of water. The reaction mixture was then concentrated under reduced pressure to remove the toluene and poured into concentrated aqueous ammonium chloride. The mixture was extracted with ethyl acetate, and the organic phase dried over magnesium sulphate and concentrated under reduced pressure to give the desired product as a 60: 40 mixture of two isomers (44.4g, 97%).

IH NMR on (400MHz, CDC13) : 5.35 (1H, 2 s), 4.2 (2H, 2 q), 3.45 and 3. 2 (2H, 2 s), 2.2 and 2.0 (3H, 2 s) and 1.3 (3H, 2 t) ppm.

Preparation of 5-amino-3-methylthiophene-2-carboxylic acid ethyl ester (aminothiophene NO)

4-Cyano-3-methylbut-3-enoic acid ethyl ester (42.1g, 275 mmol) was dissolved in ethanol (200ml) and sulphur (8.8g, 276 mmol) added. Diethylamine (28. 5ml, 276 mmol) was added slowly to the reaction mixture, keeping the temperature below 40°C during the addition. The dark reaction mixture was stirred at room temperature for 5 hours, then poured into concentrated aqueous ammonium chloride and extracted with ethyl acetate. The organic phase was dried over magnesium sulphate and concentrated to dryness under reduced pressure. The residual brown oil was purified by column chromatography on silica, with hexane: ethyl acetate (3: 1, by volume) as eluant, to provide the desired product (18. 5g, 30%) as a colourless oil.

IH NMR AH (300MHz, CDC13) : 5.9 (1H, s), 4.3 (2H, q), 4.5-2. 8 (2H, br s), 2.4 (3H, s) and 1.3 (3H, t) ppm.

EXAMPLE J This Example illustrates the preparation of 5-amino-4-iodo-3-methylthiophene-2- carboxylic acid ethyl ester (aminothiophene PO) Preparation of 5-tert-butoxycarbonylamino-3-methylthiophene-2-carboxylic acid ethyl ester Aminothiophene NO (prepared as described in Example 1 ; 3.89g, 21 mmol) was dissolved in acetonitrile (50ml) in the presence of di-tert-butyl dicarbonate (4.7g, 21 mmol).

Catalytic DMAP was added to the reaction mixture before stirring at 50°C for 3 hours.

The reaction mixture was then poured into water and extracted with ethyl acetate. The organic phase was dried over magnesium sulphate and concentrated to dryness under reduced pressure. The residual oil was purified by column chromatography, using hexane: ethyl acetate (4: 1, by volume) as eluant, to give the desired product (2. 0g, 33%) as yellow crystals. m. p. 133-134°C ;

'H NMR AH (400MHz, CDC13) : 7.2 (1H, br s), 6.3 (1H, s), 4.3 (2H, q), 2.45 (3H, s), 1.55 (9H, s) and 1. 3 (3H, t) ppm.

Preparation of 5-amino-4-iodo-3-methylthiophene-2-carboxylic acid ethyl ester (aminothiophene PO) To a solution of 5-tert-butoxycarbonylamino-3-methylthiophene-2-carboxylic acid ethyl ester (1. 91g, 6.7 mmol) in acetic acid (30ml) at room temperature was added slowly a solution of iodine monochloride (0. 34ml, 6.7 mmol) in acetic acid (20ml). The reaction mixture was stirred for 1 hour, then poured into ice and extracted with ethyl acetate. The organic phase was washed with 10% aqueous sodium thiosulphate and water, dried over magnesium sulphate and concentrated to dryness under reduced pressure. The residual solid was purified by column chromatography, using hexane: ethyl acetate (6: 1, by volume) as eluant, to give 5-tert-butoxycarbonylamino-4-iodo-3-methylthiophene-2- carboxylic acid ethyl ester (1.03g, 30%) as orange crystals and 5-amino-4-iodo-3- methylthiophene-2-carboxylic acid ethyl ester (aminothiophene PO) (0.78g, 30%).

5-tert-Butoxycarbonylamino-4-iodo-3-methylthiophene-2-carbox ylic acid ethyl ester: m. p. 111-112°C ; 'H NMR on (400MHz, CDC13) : 7.3 (1H ; br s), 4.3 (2H, q), 2.55 (3H, s), 1.55 (9H, s) and 1.3 (3H, t) ppm.

Aminothiophene PO : m. p. 104-105°C ; 1H NMR 8H (400MHz, CDC13) : 4.55 (2H, br s), 4.3 (2H, q), 2.5 (3H, s) and 1.3 (3H, t) ppm.

EXAMPLE K This Example illustrates the preparation of 5-amino-4- (2, 4-dichlorophenyl) -3- methylthiophene-2-carboxylic acid ethyl ester (aminothiophene QO)

Aminothiophene PO (prepared as described in Example J; 156mg, 0.5 mmol), 2,4- dichlorophenylboronic acid (96mg, 0.5 mmol), tetrakis (triphenylphosphine) palladium (40mg), toluene (2. 5ml), aqueous sodium carbonate (2M; 0. 5ml) and ethanol (0. 6ml) were placed in a 5ml microwave reactor. The reaction mixture was heated under microwave conditions (sealed tube) at 100°C for 10 min. The mixture was then poured into saturated aqueous ammonium chloride and extracted with ethyl acetate. The organic phase was dried over magnesium sulphate and concentrated to dryness under reduced pressure. The residual oil was purified by column chromatography, using hexane: ethyl acetate (3: 1, by volume) as eluant, to give the desired product (99mg, 60%) as a yellow oil.

1H NMR 8H (400MHz, CDC13) : 7.6 (1H, d), 7.45 (1H, dd), 7.2 (1H, d), 4.3 (2H, q), 4.1 (2H, br s), 2.20 (3H, s) and 1.3 (3H, t) ppm.

EXAMPLE L This Example illustrates the preparation of 2-amino-4-butyl-5-phenoxy-thiophene-3- carbonitrile (aminothiophene RO) Preparation of l-phenoxy-hexan-2-ol

A solution of phenol (18.8g, 0.2 mol) in ethylmethylketone (200ml) was treated with caesium carbonate (6. 5g, 0.02 mol) and butyloxirane (48ml, 0.4 mol). The reaction mixture was stirred for 20 hours at 90°C, cooled and poured into ice and ethyl acetate.

The organic phase was washed with 4N aqueous sodium hydroxide and water, dried over magnesium sulphate and concentrated under reduced pressure. The remaining oil was taken up in cold petroleum ether and filtered to give the desired alcohol (19.4g, 50%) as beige crystals.

Preparation of l-phenoxy-hexan-2-one A solution of oxalyl chloride (11. 5ml, 132 mmol) in DCM (130ml) was cooled under nitrogen to-78°C. DMSO (15. 8ml, 224 mmol) in DCM (50ml) was slowly added at - 78°C. The reaction mixture was stirred for 15 min at-78°C, then l-phenoxy-hexan-2-ol (19.4g, 100 mmol) in DCM (50ml) was added dropwise over 30 min. After the addition, the reaction mixture was stirred for a further 30 min at-78°C and triethylamine (94ml, 0.67 mol) then added. The reaction mixture was allowed to warm slowly to room temperature, then poured into an ice-water mixture and extracted with ethyl acetate. The organic phase was washed with water, dried over magnesium sulphate and concentrated to dryness under reduced pressure to provide the desired product as an oil (19. 2g ; 100%).

1H NMR 8H (400MHz, CDC13) : 7.4 (2H, dd), 6.95 (1H, t), 6.8 (2H, d), 4.55 (2H, s), 2.6 (2H, t), 1.6 (2H, qt), 1.3 (2H, m) and 0.85 (3H, t) ppm.

Preparation of 2-amino-4-butyl-5-phenoxy-thiophene-3-carbonitrile (aminothiophene RO)

l-Phenoxy-hexan-2-one (5.76g, 30 mmol) was dissolved in ethanol (50ml) in the presence of malononitrile (2. 0g, 30 mmol). The temperature was kept at 25°C and sulphur (0.96g, 30 mmol) added to the reaction mixture to give a yellow suspension.

Morpholine (3. 4ml, 39 mmol) was slowly added to the reaction mixture. The temperature was kept below 40°C during the addition and the reaction mixture was then stirred at room temperature for 1 hour. The reaction mixture was poured into concentrated aqueous ammonium chloride and extracted with ethyl acetate. The organic phase was dried over'magnesium sulphate and concentrated to dryness under reduced pressure. The residual brown oil was purified by column chromatography on silica, with hexane: ethyl acetate (4: 1, by volume) as eluant, to yield the desired product (1.9g, 25%) as a reddish oil.

1H NMR on (400MHz, CDC13) : 7.35 (2H, t), 7.1 (1H, t), 6.95 (2H, d), 4.6 (2H, br s), 2.4 (2H, t), 1.6 (2H, m), 1.3 (2H, m) and 0.85 (3H, t) ppm.

EXAMPLE M This Example illustrates the preparation of 2-amino-4-methyl-5-morpholino-thiophene-3- carboxylic acid ethyl ester (aminothiophene SO) Preparation of 4- (2-oxo-propoxy)-benzonitrile

Chloroacetone (8. 8ml, 110 mmol), 4-cyanophenol (11.9g, 100 mmol) and potassium carbonate (20.7g, 150 mmol) were heated at reflux in acetonitrile for 5 hours. The reaction mixture was cooled, poured into concentrated aqueous ammonium chloride and extracted with ethyl acetate. The organic phase was dried over magnesium sulphate and concentrated to dryness under reduced pressure. The residual brown oil was purified by column chromatography on silica, with hexane: ethyl acetate (6: 1, by volume) as eluant, to provide the desired product as an oil (15. 4g, 80%).

1H NMR 8H (300MHz, CDC13) : 7.4 (2H, d), 6.6 (2H, d), 4.25 (2H, s) and 2. 5 (3H, s) ppm.

Preparation of 2-amino-4-methyl-5-morpholino-thiophene-3-carboxylic acid ethyl ester (aminothiophene SO) 4- (2-Oxo-propoxy)-benzonitrile (2.28g, 13 mmol) was dissolved in ethanol (5ml) in the presence of cyanoacetic acid ethyl ester (1. 4ml, 13 mmol). The temperature was kept at 25°C and sulphur (0.42g, 13 mmol) added to the reaction mixture, followed by the slow addition of morpholine (1. 5ml, 17 mmol). The temperature was kept below 40°C for one hour and the reaction mixture then warmed to 50°C for 90 min. The reaction mixture was poured into a mixture of ice and concentrated aqueous ammonium chloride and

extracted with ethyl acetate. The organic phase was dried over magnesium sulphate and concentrated to dryness under reduced pressure. The remaining brown oil was purified by column chromatography on silica, with hexane: ethyl acetate (3: 1, by volume) as eluant, to provide the desired product (0.27g, 8%). m. p. 193-194°C ; 'H NMR 8H (300MHz, CDC13) : 4.7 (2H, s), 4.3 (2H, q), 3.8 (4H, t), 2.75 (4H, t), 2.1 (3H, s) and 1. 4 (3H, t) ppm.

EXAMPLE N This Example illustrates the preparation of 3-bromo-benzo [b] thiophen-2-ylamine (aminothiophene TO) Preparation of 3-bromo-2-nitro-benzo [b] thiophene

To a stirred solution of 3-bromo-benzo [b] thiophene (2. 62ml, 0.02 mol) in dry DCM (20ml) at 10°C was added portionwise nitronium tetrafluoroborate (2.66g, 0.02 mol). The reaction temperature was kept below 25°C during the addition by the use of an ice bath.

The mixture was allowed to warm to room temperature and stirred for a further 5 hours. The reaction mixture was cautiously quenched with water and extracted with DCM. The organic extract was washed with water, dried over magnesium sulphate and evaporated to dryness under reduced pressure to give an orange solid (4.64g). Chromatography of the crude material, using 5% ether in hexane (by volume) as eluant, gave the crude product (470mg).

Preparation of 3-bromo-benzo [b] thiophen-2-ylamine (aminothiophene TO)

To a stirred suspension of crude 3-bromo-2-nltro-benzo [b] thiophene (470mg) in isopropanol (9ml) and water (lml) was added iron powder (915mg, 16.4 mmol) and cone. HC1 (2 drops). The reaction mixture was heated at reflux for 3 hours, allowed to cool to room temperature, then filtered through a pad of celite and washed with isopropanol and ethyl acetate. The solvent was removed under reduced pressure to give a black solid (518mg). Chromatography of the crude material, using 10% ether in hexane (by volume) as eluant, gave the desired product (30mg) as a brown oil. m/z (+ve ion): 228 (MH+, 79Br, 100%) 230 (MH+, 8lBr, 100%).

EXAMPLE O This Example illustrates the preparation of 2-amino-benzo [b] thiophene-3-carboxylic acid ethyl ester (aminothiophene UO).

To a stirred suspension of 2-acetylamino-benzo [b] thiophene-3-carboxylic acid ethyl ester (Compound No. 516 of Table 134, prepared as described in Example 27; 85mg, 0.323 mmol) in toluene (15ml) was added pyrrolidine (400u. l). The reaction mixture was heated at 100°C for 6 hours, then further pyrrolidine (400u. l) was added and heating continued at 100°C for 17 hours. The mixture was allowed to cool to room temperature, quenched with brine and extracted with ether. The combined organic extracts were dried over magnesium sulphate and evaporated to dryness under reduced pressure to give an off- white solid (104mg). Chromatography of the crude material, using 20% ether in hexane (by volume) as eluant, gave the desired product as a white solid (39mg, 55%).

'H NMR 8H (400MHz, CDC13) : 8.10 (1H, d), 7.50 (1H, d), 7.30 (1H, t), 7.10 (1H, t), 6.50 (2H, br s), 4.40 (2H, q) and 1.45 (3H, t) ppm.

EXAMPLE P This Example illustrates the preparation of 2-amino-benzo [b] thiophene-3-carbonitrile (aminothiophene VO)

To crude N- (3-cyano-benzo [b] thiophen-2-yl) -acetamide (Compound No. 481 of Table 134, prepared as described in Example 28; 500mg) in toluene (30ml) was added pyrrolidine (3ml). The mixture was heated at reflux for 2 hours and allowed to cool to room temperature overnight. The reaction mixture was diluted with brine and extracted with ether. The combined organic extracts were dried over magnesium sulphate and evaporated to dryness under reduced pressure to give a dark red solid (197mg).

Chromatography of the crude material, using 35% ether in hexane (by volume) as eluant, gave the desired product (22mg, 4%) as a purple solid.

1H NMR 5H (400MHz, CDC13) : 7.55 (2H, d), 7.35 (1H, t), 7.20 (1H, t) and 5.10 (2H, br s) ppm.

EXAMPLE Q This Example illustrates the preparation of 2-amino-4, 5,6, 7-tetrahydro- benzo [b] thiophene-3-carboxylic acid amide (aminothiophene WO) A solution of aminothiophene EO (prepared as described in Example C; 500mg, 2.8 mmol) in concentrated sulphuric acid (5ml) was stirred at room temperature for 65 hours.

The reaction mixture was poured cautiously into ice-cold aqueous potassium carbonate, diluted with water and extracted with ethyl acetate. The combined organic extracts were

washed with water and brine, dried over magnesium sulphate and evaporated to dryness under reduced pressure to give the desired product (383mg, 70%) as an off-white solid.

'H NMR 8H (400MHz, CDC13) : 6.15 (2H, br s), 4.40 (2H, b-r s), 2. 65 (2H, m), 2.50 (2H, m) and 1.80 (4H, m) ppm.

The following table provides the melting points for additional aminothiophenes prepared by similar methods.

TABLE A Aminothiophene No. Structure Melting Point °C AAO 138-139 N S/\NH2 ABO 146-147 AC0 XNH2 JL o NH N ADO N 203-204 N NH, AEO\198-201 AEO 198-201 CN nu 2 AFO 170-171 s nu d r S NH2 0 Aminothiophene No. Structure Melting Point °C AGO 118-119 con \O NH2 N AHA 127-128 N S NH2 AJ0 MCF3 61-62 nu2 NHz O AK0 XNH2 130-134 Zu ALO P 188. 5-192 CON N NH2 SCN 115. 5-118 _nu2 ANO 105-106 CN nu2 Aminothiophene No. Structure Melting Point °C APO 161-162 N% N AQO 81-82 I \ 0. NH2 c54 ARO N 133-134 AR0 \ NU2

EXAMPLE 1 This Example describes the general procedure for the preparation of amides of the formula (1) (Compounds Nos. 57,131, 252,281, 334,365 and 461 of Table 14, Compound No. 334 of Table 127, and Compound No. 194 of Table 134)

The appropriate aminothiophene (1 equiv. ) was dissolved in dioxane (2ml per mmol aminothiophene). The appropriate acyl chloride (1.15 equiv. ) was added slowly at room temperature. The reaction is exothennic and the temperature of the reaction mixture may rise to 40°C. After 2 to 4 hours, the amide usually appeared as a suspension and was filtered from the reaction mixture and washed in hexane. If the amide did not precipitate, the reaction mixture was poured into saturated aqueous ammonium chloride and extracted with ethyl acetate. After drying over magnesium sulphate and concentration under reduced pressure, the residual solid was taken up in hexane or an ether/hexane mixture and filtered to give the desired product.

Compound No. 365 of Table 14 Using the general procedure 2-chloro-N-(3-cyano-4, 5, 5a, 6,7, 8,9, 9a-octahydro- naphtho [1, 2-b] thiophen-2-yl)-acetamide (Compound No. 365 of Table 14) was obtained from aminothiophene AO in 30 % yield. m. p. 173-174°C ; 1H NMR AH (300MHz, CDC13) : 9.25 (1H, s), 4.25 (2H, s) and 3.0-1. 0 (14H, m) ppm; m/z (-ve ion): 307 (M-H) 100%.

Compound No. 334 of Table 14 Using the general procedure 2-chloro-N-(3-cyano-4, 7-dihydro-5H-thieno [2,3-c] pyran-2- yl) -acetamide (Compound No. 334 of Table 14) was obtained from aminothiophene BO in 93% yield. m. p. 241-242°C ; 1H NMR OH (300MHz, d6-DMSO): 12.0 (1H, s), 4.55 (2H, s), 4. 45 (2H, s), 3.8 (2H, t) and 2.55 (2H, m) ppm; m/z (-ve ion): 255 (M-H) 100%.

Compound No. 252 of Table 14 Using the general procedure 2-(2-chloroacetylamino)-4, 7-dihydro-5H-thieno [2,3-c] pyran- 3-carboxylic acid ethyl ester (Compound No. 252 of Table 14) was obtained from aminothiophene CO in 93% yield. m. p. 160-161°C ; 1H NMR #H (300MHz, CDCl3) : 12.1 (1H, s), 4.7 (2H, m), 4.4 (2H, q), 4.30 (2H, s), 3.9 (2H, t), 2.9 (2H, m) and 1.4 (3H, t) ppm; m/z (-ve ion): 302 (M-H) 100%. . O', 1 N Cl vs O Compound No. 57 of Table 14

Using the general procedure 5- (2-chloroacetylamino)-3-methoxymethyl-thiophene-2- carboxylic acid methyl ester (Compound No. 57 of Table 14) was obtained from aminothiophene DO in 36% yield. m. p. 166-167°C ; 'H NMR on (300MHz, CDC13) : 9. 1 (1H, s), 6.9 (1H, s), 4.8 (2H, s), 4.3 (2H, s), 3.85 (3H, s) and 3. 45 (3H, s) ppm; m/z (-ve ion): 276 (M-H) 100%. N 0 rr. 4 0H Compound No. 334 of Table 127

Using the general procedure cyclopropanecarboxylic acid (3-cyano-4, 7-dihydro-5H- thieno [2,3-c] pyran-2-yl) -amide (Compound No. 334 of Table 127) was obtained from aminothiophene BO in 80% yield. m. p. 240-241°C ; tH NMR aH (300MHz, CDC13) : 8.9 (1H, s), 4.7 (2H, s), 4.0 (2H, t), 2.7 (2H, t), 1.75 (1H, m), 1.2 (2H, m) and 1.0 (2H, m) ppm; m/z (-ve ion): 255 (M-H) 100%.

Compound No. 461 of Table 14 Using the general procedure 2-(2-chloroacetylamino)-4, 7-dihydro-5H-thieno [2,3- c] pyridine-3,6-dicarboxylic acid 6-te7 » t-butyl ester 3-ethyl ester (Compound No. 461 of Table 14) was obtained from aminothiophene HO as beige crystals in 71% yield. m. p. 140-141°C ; 1H NMR #H(300MHz, d6-DMSO): 11.75 (1H, s), 4.75 (2H, s), 4.6 (2H, s), 4.45 (2H, q), 3.7 (2H, t), 2.9 (2H, m), 1.5 (9H, s) and 1.45 (3H, t) ppm; m/z (-ve ion) : 401 (M-H) 100%.

Compound No. 194 of Table 134 Using the general procedure 2-acetylamino-4, 5,6, 7-tetrahydro-benzo [b] thiophene-3- carboxylic acid ethyl ester (Compound No. 194 of Table 134) was obtained from aminothiophene JO as beige crystals in 92% yield. m. p. 119-120°C ; 'H NMR 5H (300MHz, CDC13) : 11.3 (1H, s), 4. 3 (2H, q), 2.8 (2H, m), 2.65 (2H, m), 2.25 (3H, s), 1.8 (4H, m) and 1.40 (3H, t) ppm.

Compound No. 281 of Table 14 Using the general procedure 5- (2-chloroacetylamino)-4- (2, 4-dichlorophenyl)-3- methylthiophene-2-carboxylic acid ethyl ester (Compound No. 281 of Table 14) was obtained from aminothiophene QO as beige crystals in 79% yield. m. p. 160-161°C ; IH NMR on (300MHz, CDC13) : 8.6 (1H, br s), 7.65 (1H, d), 7.45 (1H, dd), 7.2 (1H, d), 4. 35 (2H, q), 4.2 (2H, s), 2.25 (3H, s) and 1.4 (3H, t) ppm. N O S NH A o Cl Compound No. 131 of Table 14

Using the general procedure N- (4-butyl-3-cyano-5-phenoxy-thiophen-2-yl)-2- chloroacetamide (Compound No. 131 of Table 14) was obtained from aminothiophene RO as beige crystals in 70% yield. m. p. 103-105°C ; IH NMR 5H (300MHz, CDCl3) : 9.2 (1H, br s), 7.35 (2H, t), 7.1 (1H, t), 6.95 (2H, d), 4.3 (2H, s), 2.55 (2H, t), 1.6 (2H, m), 1.3 (2H, m) and 0.85 (3H, t).

EXAMPLE 2 This Example describes an alternative general procedure for the preparation of amides of the formula (1) (Compounds Nos. 43,69, 174,322, 481 and 538 of Table 14, Compound No. 69 of Table 108 and Compound No. 194 of Table 134)

To a stirred solution of the appropriate aminothiophene (1 equiv. ) in 1,4-dioxane (5ml per mmol aminothiophene) was added portionwise the appropriate acyl chloride (1.15 equiv. ). The reaction mixture was stirred at room temperature for 17-65 hours. The solvent was removed under reduced pressure, the residue triturated with hexane, a hexane/ether mixture or ether, and filtered to give the desired product.

Compound No. 69 of Table 14 Using the alternative general procedure 2-chloro-N- (3-cyano-4, 5,6, 7-tetrahydro- benzo [b] thiophen-2-yl) -acetamide (Compound No. 69 of Table 14) was obtained from aminothiophene EO as a pale pink solid in 91% yield.

1H NMR on (400MHz, CDC13) : 9.25 (1H, br s), 4.25 (2H, s), 2.60 (4H, m) and 1.80 (4H, m) ppm.

Compound No. 69 of Table 108

Using the alternative general procedure ()-2, 3-dibromo-N- (3-cyano-4, 5,6, 7-tetrahydro- benzo [b] thiophen-2-yl)-propionamide (Compound No. 69 of Table 108) was obtained from aminothiophene EO as an off-white solid in 88% yield.

'H NMR on (400MHz, CDC13) : 9.70 (1H, br s), 4.75 (1H, m), 4.10 (1H, m), 3.80 (1H, m), 2.65 (4H, m) and 1.85 (4H, m) ppm.

Compound No. 43 of Table 14 Using the alternative general procedure 2-(2-chloroacetylamino)-4, 5,6, 7-tetrahydro- benzo [b] thiophene-3-carboxylic acid tert-butyl ester (Compound No. 43 of Table 14) was obtained from aminothiophene FO as a pale brown solid in 41% yield.

'H NMR on (400MHz, CDC13) : 12.10 (1H, br s), 4.25 (2H, s), 2.75 (2H, m), 2.65 (2H, m), 1.80 (4H, m) and 1.55 (9H, m) ppm.

Compound No. 174 of Table 14 Using the alternative general procedure 2-chloro-N- (3-cyano-5, 6,7, 8-tetrahydro-4H- cyclohepta [b] thiophen-2-yl)-acetamide (Compound No. 174 of Table 14) was obtained from aminothiophene KO as a brown solid in 97% yield.

IH NMR on (400MHz, CDC13) : 9.20 (1H, br s), 4.30 (2H, s), 2.75 (4H, m), 1.90 (2H, m) and 1.65 (4H, m) ppm.

Compound No. 538 of Table 14 Using the alternative general procedure N-(5-tert-butyl-3-cyano-thiophen-2-yl)-2- chloroacetamide (Compound No. 538 of Table 14) was obtained from aminothiophene L0, following column chromatography, as a pale brown semi-solid in 57% yield.

IH NMR on (400MHz, CDC13) : 9.25 (1H, br s), 6.70 (1H, s), 4. 30 (2H, s) and 1.35 (9H, s) ppm.

Compound No. 322 of Table 14 Using the alternative general procedure N- (3-bromo-benzo [b] thiophen-2-yl)-2- chloroacetamide (Compound No. 322 of Table 14) was obtained from aminothiophene TO as a purple solid in 27% yield.

IH NMR 8H (400MHz, CDC13) : 9.80 (1H, br s), 8.15 (1H, d), 7.70 (1H, d), 7.45 (1H, d), 7.40 (1H, d) and 4. 30 (2H, s) ppm.

Compound No. 481 of Table 14 Using the alternative general procedure 2-chloro-N- (3-cyano-benzo [b] thiophen-2-yl)- acetamide (Compound No. 481 of Table 14) was obtained from aminothiophene VO as an off-white solid in 60% yield. m. p. &gt;250 °C. o 0 I y" S 0 Compound No. 194 of Table 134

Using the alternative general procedure 2-acetylamino-4,5, 6,7-tetrahydro- benzo [b] thiophene-3-carboxylic acid ethyl ester (Compound No. 194 of Table 134) was obtained from aminothiophene JO as a yellow solid in 89% yield.

IH NMR 8H (400MHz, CDC13) : 11.20 (1H, br s), 4.30 (2H, q), 2.75 (2H, m), 2.60 (2H, m), 2.25 (3H, s), 1.75 (4H, m) and 1.35 (3H, t) ppm.

EXAMPLE 3 This Example describes a further general procedure for the preparation of amides of the formula (1) (Compounds Nos. 192 and 489 of Table 14 and N- (3-cyano-4, 5,6, 7- tetrahydro-benzo [b] thiophen-2-yl)-malonamic acid ethyl ester)

To a stirred solution of the appropriate aminothiophene (1 equiv. ) in 1,4-dioxane (8ml per mmol of aminothiophene) was added the appropriate acyl chloride (1.2 equiv. ). The reaction was stirred at room temperature for 17-65 hours, diluted with water and extracted with ethyl acetate. The combined organic extracts were washed with brine, dried over magnesium sulphate and evaporated to dryness under reduced pressure to give the crude product. Chromatography over silica gave the desired product. 0 N H 0 C ! 6 ci Compound No. 489 of Table 14'

Using the further general procedure 2-chloro-N-[3-(2, 2-dimethylpropionyl) -4,5, 6,7- tetrahydrobenzo [b] thiophen-2-yl] -acetamide (Compound No. 489 of Table 14) was obtained from aminothiophene GO as a pale brown solid in 23% yield.

'H NMR 8H (400MHz, CDC13) : 9.10 (1H, br s), 4.20 (2H, s), 2.70 (2H, m), 2.50 (2H, m), 1.80 (4H, m) and 1.25 (9H, s) ppm.

Compound No. 192 of Table 14 Using the further general procedure 2-chloro-N-(3-cyano-4, 5,6, 7-tetrahydro- benzo [b] thiophen-2-yl)-N-methyl-acetamide (Compound No. 192 of Table 14) was obtained from aminothiophene MO as a colourless oil in 41% yield.

1H NMR 8H (400MHz, CDC13) : 4.10 (2H, s), 3.35 (3H, s), 2.70 (4H, m) and 1.90 (4H, m) ppm.

Using the further general procedure N- (3-cyano-4, 5,6, 7-tetrahydro-benzo [b] thiophen-2- yl) -malonamic acid ethyl ester was obtained from aminothiophene EO as an off-white solid in 68% yield.

IH NMR 8H (400MHz, CDC13) : 10.60 (1H, br s), 4.30 (2H, q), 3.55 (2H, s), 2.60 (4H, m), 1.85 (4H, m) and 1.35 (3H, t) ppm.

EXAMPLE 4 This Example describes an additional general procedure for the preparation of amides of the formula (1) (Compound No. 390 of Table 14 and Compound No. 69 of Table 134)

To a stirred solution of the appropriate aminothiophene (1 equiv. ) in 1,4-dioxane (5ml per mmol of aminothiophene) was added the appropriate acyl chloride (1.2 equiv. ). The reaction mixture was stirred at room temperature for 17 hours and then diluted with ether or hexane. The resultant precipitate was removed by filtration, washed with ether and air- dried to give the desired product.

Compound No. 390 of Table 14 Using the additional general procedure 2- (2-chloroacetylamino)-4, 5,6, 7-tetrahydro- benzo [b] thiophene-3-carboxylic acid amide (Compound No. 390 of Table 14) was obtained from aminothiophene WO as an off-white solid in 52% yield. m. p. 242-245°C (dec.).

Compound No. 69 of Table 134 Using the additional general procedure N- (3-cyano-4, 5,6, 7-tetrahydro-benzo [b] thiophen- 2-yl)-acetamide (Compound No. 69 of Table 134) was obtained from aminothiophene EO as a pale yellow solid in 80% yield.

'H NMR 8H (400MHz, CDC13) : 8.50 (1H, br s), 2.60 (4H, m), 2.25 (3H, s) and 1.80 (4H, m) ppm.

EXAMPLE 5 This Example illustrates the preparation of 2- (2-chloroacetylamino)-4-methyl-5 - morpholino-thiophene-3-carboxylic acid ethyl ester (Compound No. 182 of Table 14)

Under nitrogen, aminothiophene AAO (700mg, 2.58 mmol) was dissolved in THF (10ml). Sodium hydride (60% dispersion in mineral oil; 120mg, 3 mmol) was added, followed after 30 min by the slow addition of chloroacetyl chloride (240 ut, 3 mmol).

The reaction mixture turned orange and a precipitate appeared after 2 hours. The reaction mixture was poured into saturated aqueous ammonium chloride and extracted with ethyl acetate. The organic phase was dried over magnesium sulphate and concentrated to dryness under reduced pressure. The remaining oil was purified by column chromatography on silica, with hexane: ethyl acetate (3: 1, by volume) as eluant, to provide the desired product (450mg, 50%). m. p. 105-106°C ; 'H NMR 5. (300MHz, CDC13) : 12.2 (1H, br s), 4.4 (2H, q), 4.25 (2H, s), 3.8 (4H, t), 2.9 (4H, t), 2. 3 (3H, s) and 1.4 (3H, t) ppm.

EXAMPLE 6 This Example illustrates the preparation of N-(4, 5,6, 7-tetrahydrobenzo [b] thiophen-2-yl)-- acetamide (Compound No. 521 of Table 134)

4,5, 6,7-Tetrahydrobenzo [b] thiophen-2-ylamine (obtained as described in the literature by the hydrolysis and decarboxylation of aminothiophene J0 ; 1.53g, 10 mmol) was treated in DCM (50ml) with acetic anhydride (l. lml, 12 mmol) in the presence of a catalytic amount of DMAP. The reaction mixture was stirred for 2 hours at room temperature and

poured into an ice-water mixture. The mixture was extracted with ethyl acetate, and the organic extracts dried over magnesium sulphate and concentrated to dryness under reduced pressure to provide the desired product (1.76g, 90%). m. p. 156-157°C ; IH NMR BH (300MHz, CDC13) : 8.3 (1H, s), 6.3 (1H, s), 2.7 (2H, m), 2.5 (2H, m), 2.2 (3H, s) and 1. 8 (4H, m) ppm.

EXAMPLE 7 This Example illustrates the preparation of 2-chloro-N- (3-cyano-4, 5,6, 7-tetrahydro- benzo [b] thiophen-2-yl) -acetamidine (Compound No. 321 of Table 14) To a stirred solution of aminothiophene EO (178mg, 1 mmol) in chloroacetonitrile (5ml) under an atmosphere of nitrogen was added tin (IV) chloride (1171, 1 mmol) and the reaction mixture heated at reflux for 17 h. The reaction mixture was allowed to cool to room temperature, diluted with water and extracted with ethyl acetate. The combined organic extracts were washed with water and brine, dried over magnesium sulphate and evaporated to dryness under reduced pressure to give a brown solid (451mg).

Chromatography of the crude product, using 25% ether in hexane to 100% ether (by volume) as eluant, gave the desired product (151mg, 60%) as a brown solid. m. p. 164.5-168. 0°C.

EXAMPLE 8 This Example illustrates the preparation of 3-trimethylsilanylpropynoic acid (3-cyano- 4,5, 6,7-tetrahydrobenzo [b] thiophen-2-yl) amide (Compound No. 69 of Table 80)

3- (Trimethylsilyl) propynoic acid (l. Og, 7 mmol) was dissolved in DCM (lOml) under nitrogen and cooled to 0°C. Oxalyl chloride (0. 6ml, 7 mmol) was added dropwise, keeping the temperature below 5°C. The solution became orange. At the end of the addition, the mixture was maintained at room temperature for one hour, then aminothiophene EO (1.25g, 7 mmol) was added as a solution in THF (10ml). The reaction mixture was stirred for 4 hours at room temperature and then treated with saturated aqueous ammonium chloride and extracted with DCM. The combined organic extracts were dried over magnesium sulphate and evaporated under reduced pressure.

Purification of the residue by flash chromatography gave the desired product (0.25g, 15%) as an amorphous solid.

'H NMR 8H (300MHz, CDC13) : 8.55 (1H, br s), 2.6 (4H, m), 1.85 (4H, m) and 0.3 (9H, s) ppm; ni/z (-ve ion): 301 (M-H).

EXAMPLE 9 This. Example describes the preparation of but-2-ynoic acid (3-cyano-4,5, 6,7-tetrahydro- benzo [b] thiophen-2-yl) amide (Compound No. 69 of Table 91) Butynoic acid (295mg, 3.5 mmol) was dissolved in THF (lOml) at room temperature.

Oxalyl chloride (300gui, 3.5 mmol) was added and the reaction mixture stirred at room

temperature for 1 hour until no more gas was evolved. One drop of DMF was added to the reaction mixture before adding dropwise a solution of aminothiophene EO (623mg, 3.5 mmol) in THF (lOml). The mixture was stirred for another hour at room temperature, poured into saturated aqueous ammonium chloride and extracted with ethyl acetate. The combined organic extracts were dried over magnesium sulphate and evaporated under reduced pressure. The residual solid was purified by flash chromatography to give the desired product (120mg, 14% yield). m. p. 202-206°C ; 'H NMR 8H (300MHz, CDC13) : 11.2 (1H, s), 2.6 (4H, m), 1.7 (3H, s) and 1.6 (4H, m) ppm.

EXAMPLE 10.

This Example describes the preparation of propynoic acid (3-cyano-4,5, 6, 7-tetrahydro- benzo [b] thiophen-2-yl) amide (Compound No. 69 of Table 36)

Propynoic acid (345p1, 5.6 mmol) was stirred in DCM (lSml) under nitrogen. Amino- thiophene EO (l. Og, 5.6 mmol) was added to the reaction mixture, which was then cooled to 0-5°C. Dicyclohexyl carbodiimide (1. 16g, 5.6 mmol) in DCM (5ml) was added dropwise to the reaction mixture. After the addition was complete, the mixture was stirred for 2 hours at room temperature, then poured into saturated aqueous ammonium chloride and extracted with DCM. The combined organic extracts were dried over magnesium sulphate and evaporated under reduced pressure. The remaining oil was purified by chromatography, using hexane: ethyl acetate (3: 1, by volume) as eluant, to afford the desired product as yellow crystals (115mg, 10% yield). m. p. 209-210°C ; IH NMR AH (300MHz, CDC13) : 8.7 (1H, s), 3.2 (1H, s), 2.6 (4H, m) and 1.8 (4H, m) ppm; m/z (-ve ion): 229 (M-H) 100%.

EXAMPLE 11 This Example illustrates the preparation of (3-cyano-4, 5,6, 7-tetrahydro- benzo [b] thiophen-2-yl)-carbamic acid prop-2-ynyl ester (Compound No. 69 of Table 86) To a stirred solution of aminothiophene EO (200mg, 1.7 mmol) in 1,4-dioxane (10mol) was added propargyl chlorofonnate (122µl, 1.25 mol) in a single portion. The reaction mixture was stirred at room temperature for 65 hours, then diluted with water and extracted with ethyl acetate. The combined organic extracts were washed with brine, dried over magnesium sulphate and evaporated to dryness under reduced pressure to give a brown oil (334mg). Chromatography of the crude product over silica, using 75% DCM in hexane then 100% DCM (by volume) as eluant, gave the desired product as an off- white solid (217mg, 71%).

IH NMR 8H (400MHz, CDC13) : 7.75 (1H, br s), 4.85 (2H, s), 2.60 (5H, m) and 1.85 (4H, m) ppm.

EXAMPLE 12 This Example illustrates the preparation of 2- (but-2-ynyloxycarbonylamino)- benzo [b] thiophene-3-carboxylic acid ethyl ester (Compound No. 516 of Table 16) To a stirred solution of aminothiophene UO (lOOmg, 0.45 mmol) in 1,4-dioxane (10ml) was added 2-butynyl chlorofonnate (60p1, 0.5 mmol). The reaction mixture was stirred at

room temperature for 65 hours and then evaporated to dryness under reduced pressure to give a brown solid (114mg). Chromatography of the crude product, using 25% ether in hexane (by volume) as eluant, gave the desired product as an off-white solid (1 1mg, 8%). lH NMR 5H (400MHz, CDC13) : 11.10 (1H, br s), 8.25 (1H, d), 7.70 (1H, d), 7.40 (1H, t), 7. 30 (1H, t), 4.85 (2H, m) 4.45 (2H, q), 1.90 (3H, m) and 1.50 (3H, t) ppm.

EXAMPLE 13 This Example illustrates the preparation of (3-cyano-4,5, 6, 7-tetrahydro- benzo [b] thiophen-2-yl)-thiocarbamic acid S-ethyl ester (Compound No. 69 of Table 137) To a stirred solution of aminothiophene EO (200mg, 1.7 mmol) in 1,4-dioxane (5ml) was added ethyl chlorothiolformate (156mg, 1.25 mmol). The reaction mixture was stirred at room temperature for 17 hours and then the solvent was removed under reduced pressure.

The residue was partitioned between water and ethyl acetate. The aqueous was extracted with further ethyl acetate and the combined organic extracts were dried over magnesium sulphate and evaporated to dryness under reduced pressure. Chromatography of the crude product over silica, using 100% DCM then 5% methanol in DCM (by volume) as eluant, gave the desired product (34mg, 11 %).

IH NMR 5. (500MHz, CH3CN): 9.30 (1H, br s), 2.90 (2H, q), 2.60 (4H, m), 1.80 (4H, m) and 1. 25 (3H, t) ppm.

EXAMPLE 14 This Example illustrates the preparation of N-(3-cyano-5, 6-dihydro-4H- cyclopenta [b] thiophen-2-yl)-2-hydroxyacetamide (Compound No. 368 of Table 59)

A stirred suspension of 2-chloro-N- (3-cyano-5, 6-dihydro-4H-cyclopenta [b] thiophen-2- yl)-acetamide (Compound No. 368 of Table 14, prepared by the general method described in Example 2; 243mg, 1.01 mmol) in water (2ml) and fonnamide (10ml) was heated at 110°C for 3 hours. The reaction mixture was allowed to cool to room temperature, diluted with water and extracted with ethyl acetate. The combined organic extracts were washed with water and brine, dried over magnesium sulphate and evaporated to dryness under reduced pressure to give a brown solid (340mg).

Chromatography of the crude product, using 75% ether in hexane (by volume) as eluant, gave the desired product (78mg, 35%) as a yellow solid.

IH NMR 8H (400MHz, CDC13) : 9.85 (1H, br s), 5.60 (1H, t), 4.25 (2H, d), 2.90 (2H, m), 2.80 (2H, m) and 2.45 (2H, m) ppm.

EXAMPLE 15 This Example illustrates the preparation of N-(3-cyano-4, 5,6, 7-tetrahydro-benzo [b] thio- phen-2-yl)-2-tetrazol-2-yl-acetamide and N-(3-cyano-4, 5,6, 7-tetrahydro-benzo [b] thio- phen-2-yl)-2-tetrazol-1-yl-acetamide (Compounds No. 69 of Tables 56 and 83 respectively)

To a stirred solution of 2-chloro-N-(3-cyano-4, 5,6, 7-tetrahydro-benzo [b] thiophen-2-yl)- acetamide (Compound No. 69 of Table 14, prepared as described in Example 2; 255mg, 1 mmol) in acetonitrile (20ml) was added potassium carbonate (276mg, 2 mmol) and 1-H tetrazole (77mg, 1.1 mmol). The reaction mixture was heated at reflux for 17 hours, allowed to cool to room temperature, diluted with water and extracted with DCM. The combined organic extracts were dried over magnesium sulphate and evaporated to dryness under reduced pressure to give the desired product as a 1: 1 mixture of isomers (138mg, 48%).

IHNMR BH (400MHz, d6-DMSO): 9.05 (1H, s), 8.60 (1'H, s), 5.80 (2'H, s), 5.60 (2H, s), 2.80-2. 55 (4H + 4'H, m) and 1.85 (4H + 4'H, m) ppm.

EXAMPLE 16 This Example illustrates the preparation of N-(3-cyano-4, 5,6, 7-tetrahydro- benzo [b] thiophen-2-yl)-2- [6- (2, 2, 2-trifluoroethoxy)-pyrimidin-4-ylsulfanyl]-acetamide (Compound No. 69 of Table 93)

A solution of 2-chloro-N- (3-cyano-4, 5,6, 7-tetrahydro-benzo [b] thiophen-2-yl)-acetamide (Compound No. 69 of Table 14, prepared as described in Example 2; 100mg, 0.39 mmol) in acetone (4ml) was added to a mixture of 6- (2, 2, 2-trifluoro-ethoxy)-pyrimidine-4-thiol (84mg, 4 mmol) and potassium carbonate (138mg, 1 mmol). The reaction mixture was heated at reflux for 2.5 hours and allowed to cool to room temperature overnight. The solvent was removed under reduced pressure and the residue partitioned between water and ethyl acetate. The aqueous was further extracted with ethyl acetate and the combined organic extracts washed with brine, dried over magnesium sulphate and evaporated to dryness under reduced pressure. Chromatography of the crude material, using 25% ethyl acetate in hexane (by volume) as eluant, gave the desired product (148 mg, 89%).

1H NMR 8H (400MHz, CDC13) : 11.60 (1H, br s), 9.00 (1H, s), 6.85 (1H, s), 4.85 (2H, q), 3.90 (2H, s), 2. 70-2. 50 (4H, m) and 1.80 (4H, m) ppm.

EXAMPLE 17 This Example illustrates the preparation of 2-bromo-N- (3-cyano-4, 5,6, 7-tetrahydro- benzo [b] thiophen-2-yl) -acrylamide (Compound No. 69 of Table 123) To a stirred suspension of ()-2, 3-dibromo-N- (3-cyano-4, 5,6, 7-tetrahydro- benzo [b] thiophen-2-yl)-propionamide (Compound No. 69 of Table 108, prepared as described in Example 2; 390mg, 1 mmol) in acetonitrile (5ml) was added DBU (3001, 2 mmol). The resultant pale brown solution was stirred at room temperature for 1.5 hours, diluted with water and extracted with ethyl acetate. The combined organic extracts were

washed with 2M HC1, water and brine, dried over magnesium sulphate and evaporated to dryness to give the desired product as a yellow solid (248mg, 80%).

'H NMR 8H (400MHz, CDC13) : 9.40 (1H, br s), 7.20 (1H, s), 6.25 (1H, s), 2.65 (4H, m) and 1.85 (4H, m) ppm.

EXAMPLE 18 This Example illustrates the preparation of 2- (3-cyano-4, 5,6, 7-tetrahydro- benzo [b] thiophen-2-ylcarbamoyl)-3- (4-fluorophenyl)-acrylic acid ethyl ester (Compound No. 69 of Table 88) To a stirred solution of N-(3-cyano-4, 5,6, 7-tetrahydro-benzo [b] thiophen-2-yl)-malonamic acid ethyl ester (prepared as described in Example 3; 500mg, 1.7 mmol) in 1,4-dioxane was added 4-fluorobenzaldehyde (182, 1, 1.7 mmol) and piperidine (0. 15ml). The reaction mixture was heated at reflux for 4 hours and then evaporated to dryness under reduced pressure to give a yellow solid (708mg). Chromatography of the crude product, using 25% ether in hexane (by volume) as eluant, gave the desired product (64mg, 9%) as a yellow solid. m. p. 113.5-117. 5 °C.

EXAMPLE 19 This Example illustrates the preparation of 2-(2-chloroacetylamino)-4, 5,6, 7-tetrahydro- benzo [b] thiophene-3-carboxylic acid (Compound No. 219 of Table 14)

To a stirred solution of 2- (2-chloroacetylamino)-4, 5,6, 7-tetrahydrobenzo [b] thiophene-3- carboxylic acid tert-butyl ester (Compound No. 43 of Table 14, prepared as described in Example 2; 200mg, 0.61 mmol) in DCM (10ml) was added TFA (0. 5ml). The reaction mixture was stirred at room temperature for 1.5 hours. Additional TFA (0. 5ml) was added and the mixture stirred at room temperature for a further 15 hours. The mixture was evaporated to dryness under reduced pressure to give the desired product as a pale brown solid (165mg, 100%).

'H NMR on (400MHz, CDC13) : 12.00 (1H, br s), 6.00 (1H + H20, br s), 4.30 (2H, s), 2.85 (2H, m), 2.65 (2H, m) and 1.80 (4H, m) ppm.

EXAMPLE 20 This Example illustrates the preparation of 2- (2-chloroacetylamino)-4, 5,6, 7-tetrahydro- benzo [b] thiophene-3-carboxylic acid benzylamide (Compound No. 566 of Table 14)

To a stirred suspension of 2- (2-chloroacetylamino)-4, 5,6, 7-tetrahydrobenzo [b] thiophene- 3-carboxylic acid (Compound No. 219 of Table 14, prepared as described in Example 19; 100mg, 0.44 mmol) in DCM (8ml) was added EDCI (115mg, 0.6 mmol) and HOBT (81mg, 0.6 mmol). The resultant solution was stirred at room temperature for 5 minutes.

Benzylamine (50µl, 0.45 mmol) was added and a precipitate immediately resulted. The reaction mixture was stirred at room temperature for 17 hours, diluted with water and

extracted with ethyl acetate. The combined organic extracts were washed with water and brine, dried over magnesium sulphate and evaporated to dryness under reduced pressure to give a brown solid (149mg). Chromatography of the crude product over silica, using first 25% ether in hexane then 100% ether (by volume) as eluant, gave the desired product as an off-white solid (30mg, 19%).

1H NMR 8H (400MHz, CDC13) : 13.00 (1H, br s), 7.40-7. 25 (5H, m), 6.20 (1H, br t), 4.65 (2H, d), 4.25 (2H, s), 2.70 (4H, m) and 1.80 (4H, m) ppm.

EXAMPLE 21 This Example illustrates the preparation of 2-acetylamino-4, 5,6, 7-tetrahydro- benzo [b] thiophene-3-carboxylic acid (Compound No. 219 of Table 134) 2-Acetylamino-4,5, 6,7-tetrahydro-benzo [b] thiophene-3-carboxylic acid ethyl ester (Compound No. 194 of Table 134, prepared as described in Examples 1 and 2; 70g, 0.26 mol) was added to a mixture of 1N aqueous sodium hydroxide (350ml) and ethanol (350ml). The suspension was dissolved by warming to 80°C for 2 hours. The solution was acidified to pH 4 and the cooled reaction mixture extracted with ethyl acetate. The combined organic extracts were dried over magnesium sulphate and evaporated under reduced pressure to yield the desired product as colourless solid (40g, 64% yield). m. p. 228-230°C.

EXAMPLE 22 This Example illustrates the preparation of N- (4, 5,6, 7-tetrahydrobenzo [b] thiophen-2-yl)- acetamide (Compound No. 521 of Table 134)

To 2-acetylamino-4, 5,6, 7-tetrahydro-benzo [b] thiophene-3-carboxylic acid (Compound No. 219 of Table 134, prepared as described in Example 21 ; 38g, 0.16 mol) in quinoline (75ml) was added copper (<200 mesh; 10. 5g). The reaction mixture was heated to 150°C for 2 hours and ethanol (350ml) then added, the temperature being maintained at 80°C for 3 hours. The remaining black suspension was purified by chromatography, using hexane : ethyl acetate (1: 1, by volume) as eluant, to provide the desired product as beige crystals (21g, 66% yield). m. p. 156-157°C ; 1H NMR 8H (300MHz, CDC13) : 8.3 (1H, s), 6.3 (1H, s), 2.7 (2H, m), 2.5 (2H, m), 2.2 (3H, s) and 1.8 (4H, m) ppm.

EXAMPLE 23 This Example illustrates the preparation of N- (3-iodo-4, 5,6, 7-tetrahydro- benzo [b] thiophen-2-yl)-acetamide (Compound No. 386 of Table 134)

N- (4, 5,6, 7-Tetrahydrobenzo [b] thiophen-2-yl)-acetamide (Compound No. 521 of Table 134, prepared as described in Examples 6 and 22; 9.95g, 51 mmol) was suspended in acetic acid (100ml). A solution of iodine monochloride (8.3g, 51 mmol) in acetic acid (35ml) was added slowly at room temperature. The resulting dark solution was stirred at room temperature for 30 minutes and then poured into cold 10% aqueous sodium thiosulphate. The suspension was filtered, the solid washed with water and hexane, and dried to give the desired product as a white solid (13g, 79% yield). m. p. 132-133°C ;

'H NMR 8H (300MHz, d6-DMSO): 9.6 (1H, s), 2.4 (2H, m), 2.1 (2H, m), 1.9 (3H, s) and 1.5 (4H, m) ppm.

EXAMPLE 24 This Example illustrates the preparation of N-(3-ethynyl-4, 5,6, 7-tetrahydro-benzo [ b] thiophen-2-yl) -acetamide (Compound No. 335 of Table 134) Preparation of N-(3-trimethylsilanylethynyl-4, 5,6, 7-tetrahydro-benzo [ b] thiophen-2-yl)-acetamide N- (3-Iodo-4, 5,6, 7-tetrahydro-benzo [b] thiophen-2-yl) -acetamide (Compound 386 of Table 134, prepared as described in Example 23; 3. 21g, 10 mmol) was dissolved in DMF (36ml) in the presence of PdCl2 (TPP) 2 (585mg) and copper iodide (336mg). Ethynyl trimethylsilane (3ml, 21 mmol) was added at 5°C and the reaction mixture kept at room temperature for 1 hour. The reaction mixture was poured into saturated aqueous ammonium chloride and extracted with ethyl acetate. The combined organic extracts were dried over magnesium sulphate and evaporated under reduced pressure to leave an oil, which was purified by chromatography, using hexane: ethyl acetate (2: 1, by volume) as eluant, to afford the desired product as a yellow oil (3.15g, quantitative).

1H NMR 8H (300MHz, CDC13) : 8.05 (1H, s), 2.65 (2H, m), 2.55 (2H, m), 2.2 (3H, s), 1.8 (4H, in) and 0.25 (9H, s) ppm; m/z (-ve ion): 290 (M-H) 100%.

Preparation of N-(3-ethynyl-4757677-tehrahydro-benzo [b] thiophen-2-yl)-acetamide (Compound No. 335 of Table 134)

N- (3-Trimethylsilanylethynyl-4, 5,6, 7-tetrahydro-benzo [b] thiophen-2-yl)-acetamide (2. 91g, 10 mmol) was dissolved in methanol (250ml) in the presence of potassium carbonate (1. 38g, 10 mmol). After 1 hour, the reaction mixture was poured into saturated aqueous ammonium chloride and extracted with ethyl acetate. The combined organic extracts were dried over magnesium sulphate and evaporated under reduced pressure to leave a solid, which was suspended in hexane, filtered and washed with hexane to give the desired product (1. 5g, 66% yield).

1H NMR on (300MHz, CDC13) : 8.05 (1H, s), 3.5 (1H, s), 2.65 (2H, m), 2.55 (2H, m), 2.2 (3H, s) and 1.8 (4H, m) ppm; m/z (-ve ion): 218 (M-H) 100%.

EXAMPLE 25 This Example illustrates the preparation of N- (3-vinyl-4, 5,6, 7-tetrahydrobenzo [b] thio- phen-2-yl) -acetamide (Compound No. 259 of Table 134) N-(3-Iodo-4, 5,6, 7-tetrahydrobenzo [b] thiophen-2-yl)-acetamide (Compound 386 of Table 134, prepared as described in Example 23; 1.45g, 4.5 mmol) was dissolved in acetonitrile (50ml) in the presence of PdCl2 (TPP) 2 (250mg) and tributylvinyltin (2.14g, 6.75 mmol).

The reaction mixture was heated at reflux under nitrogen for 20 hours and then cooled, saturated aqueous ammonium chloride added, and the mixture extracted with ethyl acetate. The combined organic extracts were dried over magnesium sulphate and

evaporated under reduced pressure to give a solid, which was taken up in ether and filtered to give the desired product (800mg, 80%). m. p. 150-151°C.

EXAMPLE 26 This Example illustrates the preparation of acetyl- (3-vinyl-4, 5,6, 7-tetrahydro- benzo [b] thiophen-2-yl)-carbamic acid tert-butyl ester (Compound No. 345 of Table 134) N- (3-Vinyl-4, 5,6, 7-tetrahydrobenzo [b] thiophen-2-yl) -acetamide (Compound No. 259 of Table 134, prepared as described in Example 25; 880mg, 4 mmol) was treated in acetonitrile (lOml) with di-tert-butyl dicarbonate (0.98g, 4.5 mmol) in the presence of a catalytic amount of DMAP. The initial suspension became a solution at room temperature after 10 minutes. The reaction mixture was stirred for one hour at room temperature and poured into water. The mixture was extracted with ethyl acetate and the combined organic extracts dried over magnesium sulphate and concentrated to dryness under reduced pressure to give the desired product as a brown oil (1.28g, quantitative).

'H NMR on (300MHz, CDC13) : 6.82 (1H, dd); 5.4 (1H, d); 5.25 (1H, d); 2.75 (2H, m), 2.6 (2H, m), 2.5 (3H, s), 1.8 (4H, m) and 1.45 (9H, s) ppm.

EXAMPLE 27 This Example illustrates the preparation of 2-acetylamino-benzo [b] thiophene-3- carboxylic acid ethyl ester (Compound No. 516 of Table 134)

To a stirred solution of 2-acetylamino-4, 5,6, 7-tetrahydro-benzo [b] thiophene-3-carboxylic acid ethyl ester (Compound No. 194 of Table 134, prepared as described in Examples 1 and 2; 535mg, 2 mmol) in fluorobenzene (15ml) under an atmosphere of nitrogen was added DDQ (603mg, 3 mmol). The reaction mixture was heated at reflux for 1.75 hours and then allowed to cool to room temperature overnight. The mixture was quenched with saturated aqueous sodium hydrogen carbonate and extracted with ethyl acetate. The combined organic extracts were washed with brine, dried over magnesium sulphate and evaporated to dryness under reduced pressure to give a pale yellow solid (582mg).

Chromatography of the crude material, using first 25% ether in hexane then 5% methanol in DCM (by volume) as eluant, gave the desired product as a pale yellow solid (84mg, 16%).

1H NMR 8H (400MHz, CDC13) : 11.80 (1H, br s), 8.30 (1H, d), 7.75 (1H, d), 7.40 (1H, t), 7.30 (1H, t), 4.50 (2H, q), 2.35 (3H, s) and 1.55 (3H, t) ppm.

EXAMPLE 28 This Example illustrates the preparation of N-(3-cyano-benzo [b] thiophen-2-yl)-acetamide (Compound No. 481 of Table 134) To a stirred suspension of N-(3-cyano-4, 5,6, 7-tetrahydro-benzo [b] thiophen-2-yl)- acetamide (Compound No. 69 of Table 134, prepared as described in Example 4; 734mg, 3. 37 mmol) in fluorobenzene (25ml) under an atmosphere of nitrogen was added DDQ (1. 14g, 5.06 mmol). The reaction mixture was heated at reflux for 6 hours, then allowed to cool to room temperature, quenched with saturated aqueous sodium hydrogen carbonate and extracted with ethyl acetate. The combined organic extracts were washed with brine, dried over magnesium sulphate and evaporated to dryness under reduced pressure to give the crude desired product as a 57: 43 mixture with the starting material.

This crude mixture was carried forward without purification.

Table 141 This table gives characterising NMR data for other compounds listed in Tables 1-140. Table No. -NMR Data Compound No. 1H NMR chemical shifts in ppm from TMS 2-69 AH (400MHz, CDC13) 9. 40 (1H, br s), 4.80 (1H, t), 4. 10 (2H, d), 2.65 (4H, m), 1.85 (4H, m). AH (400MHz, CDC13) 7.70 (1H, br s), 7.45 (2H, 12-69 m), 7.30 (3H, m), 5.10 (2H, s), 2.60 (4H, m), 1.80 (4H, m). 14-15 #H (400MHz, CDCl3) 9.20 (1H, br s), 4.25 (2H, s), 2. 60 (2H, q), 2.30 (3H, s), 1.20 (3H, t). 14-347 & 14-540SH (400MHz, CDC13) 7.70 (1H, br s), 7.45 (2H, (63 : 37) m), 7. 30 (3H, m), 5.10 (2H, s), 2.60 (4H, m), 1.80 (4H, m). 14-568 AH (400MHz, CDC13) 9.35 (1H, br s), 4. 30 (2H, s), 4. 05 (4H, s), 2.90 (2H, s), 2.85 (2H, t), 1.95 (2H, t). 14-569 & 14-570 #H (400MHz, CDCl3) diagnostic signals 9.30 (1H + (60: 40) 1'H, br s), 4. 30 (2H, s), 4.15 (2'H, s), 2.30 (3H, s). 16-192 #H (400MHz, CDCl3) 4.70 (2H, s), 3.40 (3H, s), 2. 65 (4H, m), 1.90 (3H, s), 1.80 (4H, m). 17-69 #H (400MHz, CDCl3) 7.75 (1H, br s), 6.60 (1H, q), 2.60 (4H, m), 1.90 (3H, d), 1. 80 (4H, m). 28-69 #H (500MHz, CH3CN) 8.95 (1H, s), 7.90 (1H, d), 7.50 (1H, d), 4.00 (2H, s), 2.60 (2H, m), 2.50 (2H, m), 1.80 (4H, m). 31-43 8H (400MHz, CDCl3) 11.35 (1H, br s), 8.45 (1H, s), 2.75 (2H, m), 2.65 (2H, m), 1.80 (4H, m), 1.60 (9H, m). 42-253 8H (400MHz, CDCl3) 8.75 (1H, br s), 3.65 (2H, m), 2.70 (2H, m), 2.25 (3H, s), 2.20 (2H, m), 2.15 (3H, s). 47-69 AH (500MHz, CH3CN) 8.90 (1H, d), 7.50 (1H, d), 4. 05 (2H, s), 2.55 (2H, m), 2.50 (2H, m), 1.80 (4H, m). 59-194 8H (400MHz, CDCl3) 12.00 (1H, br s), 4.35 (4H, m), 2.80 (2H, m), 2.65 (3H, m), 1.80 (4H, m), 1.40 (3H, t). Table No. -NMR Data Compound No. 1H NMR chemical shifts in ppm from TMS 63-69 BH (500MHz, CH3CN) 8.05 (1H, d), 7.65 (1H, d), 7.20 (1H, t), 7.05 (1H, t), 3.70 (2H, s), 2.50 (4H, m), 1.80 (4H, m). 71-192 8H (400MHz, CDC13) 5.85 (1H, s), 5.70 (1H, s), 3.45 (3H, s), 2.75 (2H, m), 2.65 (2H, m), 1.85 (4H, m). 72-69 8H (500MHz, CH3CN) 8.45 (1H, d), 8.20 (1H, d), 7.40 (1H, m), 4.20 (2H, s), 2.55 (2H, m), 2.50 (2H, m), 1. 80 (4H, m). 8H (400MHz, CDC13) 10.20 (1H, br s), 8.30 (1H, 77-69 s), 8.10 (1H, s), 5.15 (2H, s), 2.60 (4H, m), 1.80 (4H, m). 90-69 #H (400MHz, CDCl3) 10.80 (1H, br s), 4. 15 (2H, s), 4.10 (2H, s), 2.65 (2H, m), 2.60 (2H, m), 2.35 (1H, m), 1. 80 (4H, m). 113-69 8H (SOOMHz, CH3CN) 7.60 (1H, d), 7.50 (1H, d), 7.20 (1H, t), 3.95 (2H, s), 3.70 (3H, s), 2.55 (2H, m), 2.50 (2H, m), 1.80 (4H, m). 121-69 8n (400MHz, CDC13) 8.60 (1H, br s), 5.85 (1H, m), 5.15 (1H, d), 5.10 (1H, d), 2.60 (6H, m), 2. 50 (2H, m), 1.80 (4H, m). 127-43 8H (400MHz, CDC13) 11.50 (1H, br s), 2.75 (2H, m), 2.60 (2H, m), 1.80 (4H, m), 1.65 (1H, m), 1. 60 (9H, s), 1.15 (2H, m), 0.90 (2H, m). 127-194 8H (400MHz, CDC13) 11.20 (1H, br s), 4. 35, (2H, q), 2.80 (2H, m), 2.60 (2H, m), 1.75 (4H, m), 1.65 (1H, m), 1.40 (3H, t), 1.15 (2H, m), 0.90 (2H, m). 127-219 8H (400MHz, CDCl3) 11.30 (1H, br s), 2.85 (2H, m), 2.65 (2H, m), 1. 80 (4H, m), 1.70 (1H, m), 1.15 (2H, m), 0. 95 (2H, m). 134-43 AH (400MHz, CDC13) 11.40 (1H, br s), 2.75 (2H, m), 2.65 (2H, m), 2.25 (3H, s), 1.80 (4H, m), 1.55 (9H, s). 134-292 8H (400MHz, CDCl3) 8.15 (1H, br s), 6.5 (1H, dd), 5.65 (1H, d), 5.4 (1H, d), 4.25 (2H, q), 2.5 (3H, s), 2.25 (3H, s), 1.35 (3H, t). 134-576 8H (400MHz, CDC13) 2.70 (2H, m), 2.55 (2H, m), 2.50 (3H, s), 2.35 (2H, t), 1.80 (4H, m), 1.55 (2H, n, 1.45 (9H, s), 0.95 (3H, t). 140-69 8H (SOOMHz, CH3CN) 8.90 (1H, br s), 3.85 (4H, m), 2.55 (4H, m), 1.80 (4H, m), 1.45 (3H, m).

Table 142 This table gives melting point data for compounds listed in Tables 1-140. Table No.-Melting Point °C Table No.-Melting Point °C Compound No. Compound No. 2-174 149-151 2-192 109-111. 5 3-69 197-199 3-524 107. 5-109 3-558 135-137. 5 7-69 >230 14-3 107-108 14-35 88-89 14-50 138. 5-140 1. 4-53 134-135 14-57 166-167 14-58 207-208. 5 14-59 177-178 14-62 221-222 14-64 160-161 14-122 131-133 14-131 103-105 14-136 191-194 14-149 101-103. 5 14-169 161-162 14-182 105-106 14-195 >265 14-203 >250 14-211 182-183 14-221 111-112 14-235 206. 5-209 14-242 216. 5-217. 5 14-252 160-161 14-263 147-148 14-265 223. 5-227 14-269 166-167 14-270 158. 5-161 14-281 160-161 14-288 114-115 14-307 214. 5-216 14-318 205-207 14-321 164. 5-168 14-334 241-242 14-336 >260 14-348 162-163 14-365 173-174 14-390 242-245 14-404 125. 5-128 14-425 132-134 14-427 146-148. 5 14-439 173-175 14-461 140-141 14-465 92. 5-93.5 14-481 250-250 14-494 189-190 14-495 201-203 14-516 159. 5-160 Table No.-Melting Point °C Table No.-Melting Point °C Compound No. Compound No. 14-524 127.5-130.5 14-553 159. 5-161 14-558 191-192. 5 14-559 216. 5-219 14-562 155-156 14-565 237-238 15-69 155-156. 5 15-291 162-162 16-58 154-156 16-69 163. 5-164.5 16-174 139-142 16-465 157-159. 5 16-524 102-105 16-538 119-121 16-558 160-164. 5 17-69 136. 5-138. 5 18-69 128-133 19-69 102-106 21-69 190-192 24-69 137-139. 5 29-69 186-187 33-69-127-129. 5 36-69 209-210 37-69 162. 5-166 40.-69 184-187. 5 40-524 104-105. 5 40-558 102-107 41-69 129-132. 5 50-69 170-172. 5 58-69 184. 5-187.5 58-524 102. 5-106 58-558 140. 5-143 61-69 219-220 62-69 132-136. 5 64-69 141. 5-143 66-69 104-106 71-69 150-153 71-174 95. 5-101.5 76-69 211-213 79-69 131. 5-132.5 84-69 138. 5-141 86-253 149-151 86-368 156-158 88-69 113. 5-117.5 91-69 202-206 92-69 191-193. 5 98-69 142-144 107-69 189-190 108-69 210-213. 5 109-69 150. 5-153.5 110-69 126. 5-128. 5 115-69 203. 5-207.5 117-69 131-132. 5 122-69 215-217 123-69 153. 5-155. 5 127-35 147-149 Table No.-Melting Point °C Table No.-Melting Point °C Compound No. Compound No. 127-53 164-166 127-182 103-105 127-252 133-134 127-334 240-241 127-445 196-197 127-521 188-193 129-69 214. 5-218. 5 132-69 182-183 134-32 114-115 134-34 110-111 134-57 167-168 134-116 164-165 134-122 160-162 134-130 142-143 134-137 70-75 134-156 137-138 134-178 176-177 134-186 153-154 134-194 119-120 134-212 151-152 134-219 228-230 134-248 123-124 134-259 150-151 134-260 143-144 134-262 172-173 134-269 176-178 134-303 120-121 134-335 165-166 134-361 185-186 134-362 232-232 134-384 188-190 134-386 132-133 134-445 208-209 134-521 156-157 134-525 148-149 136-69 202-203

EXAMPLE 29 This Example illustrates the fungicidal properties of the compounds of the invention against the pathogens Botrytis cinerea (grey mould) and Pseudocercosporella herpotrichoides (eyespot'Rye Pathotype').

Liquid culture tests were conducted in 96 well plates using artificial media (Vogel's minimal media) inoculated with spores of the pathogens Bot7ytis cinerea (BOTRCI) and Pseudocercosporella he7potrichodes (PSDCHR).

The test compounds were individually formulated as a solution in acetone and sufficient of each formulation was added to the Vogel's minimal media to provide the

required concentration. After 24 hours, the acetone was evaporated from the plates in a class 2 cabinet for 1 hour. The plates were then inoculated by adding a mixture of fungal inoculum (spores of BOTRCI and PSDCHR), dispersed in sterile media, to individual wells. The plates were then incubated at 22°C until assessment 6 days later. The liquid culture assays were assessed visually.

The following compounds (shown as table number first, followed by hyphen and the number of the compound) showed 90% or more disease control against BOTRCI at a concentration of 10 ppm : Compound Nos. 1-69,2-69, 2-174,3-69, 3-253,3-368, 3-524, 4-69,4-174, 4-368,10-69, 13-69, 14-15, 14-39, 14-50,14-69, 14-151,14-163, 14-164,14-174, 14-194,14-217, 14- 235,14-252, 14-253,14-270, 14-285,14-307, 14-322,14-334, 14-362,14-368, 14-390, 14-404,14-425, 14-444,14-465, 14-481,14-486, 14-489,14-506, 14-524, 14-538, 14- 553,14-558, 16-69,16-174, 16-524,16-558, 17-69,20-69, 22-69,23-69, 24-69,27-69, 28-69,30-69, 31-38,34-368, 35-69,36-69, 40-15,40-69, 40-524,44-69, 45-69,47-69, 48-69,49-69, 52-69,54-69, 55-69,56-69, 57-69,58-69, 58-142,58-174, 60-69,65-69, 67-174,68-362, 70-69,71-69, 71-174,72-69, 73-69,75-69, 76-69,76-174, 78-69,81-69, 85-69,86-69, 86-253,86-368, 87-69,89-69, 90-69,92-69, 93-69,96-69, 99-174,100- 495,104-69, 106-69,108-69, 109-69,110-69, 112-69,113-69, 114-69,116-69, 117-69, 118-69,120-174, 122-368,123-69, 124-69,126-69, 127-69,127-252, 127-410,127-521, 128-69,129-69, 130-69,133-69, 134-463 and 135-69.

The following compounds (shown as table number first, followed by hyphen and the number of the compound) showed less than 90% but more than 50% disease control against BOTRCI at a concentration of 1 Oppm : Compound Nos. 5-69,6-368, 9-69, 11-69, 12-69,14-57, 14-111, 14-149,14-318, 14-427, 14-540,19-69, 25-368,32-69, 34-69,38-69, 39-69,43-368, 46-362,53-69, 57-368,58- 524,63-69, 82-368,88-69, 94-69, 97-368, 101-69, 103-368,105-69, 111-69,119-69, 122-69, 122-362, 125-69, 127-15, 127-174, 127-334,127-368 and 131-253.

The following compounds (shown as table number first, followed by hyphen and the number of the compound) showed 90% or more disease control against PSDCHR at a concentration of 10 ppm :

Compound Nos. 2-69,2-174, 3-69,3-524, 5-69,14-15, 14-69,14-151, 14-174,14-217, 14-235,14-253, 14-285,14-334, 14-362,14-368, 14-481,14-486, 14-495,14-558, 14- 567,16-69, 22-69,24-69, 36-69,58-69, 58-142,60-69, 65-69,71-69, 71-174,76-69, 86- 69, 92-69, 93-69,100-495, 104-69, 108-69, 109-69,110-69, 122-368,123-69, 127-15, 127-174,127-252, 127-368, 127-410 and 129-69.

The following compounds (shown as table number first, followed by hyphen and the number of the compound) showed less than 90% but more than 50% disease control against PSDCHR at a concentration of lOppm : Compound Nos. 4-368,13-69, 14-192,14-270, 14-307, 14-321,14-444, 14-524,14-553, 16-524,40-69, 40-524,56-69, 76-174,78-69, 86-253,86-368, 94-69,113-69, 117-69, 126-69,127-69 and 135-69.

EXAMPLE 30 This Example illustrates further the fungicidal properties of compounds of formula (1). The compounds were tested against Plasmopara viticola and Puccinia triticina, two foliar fungal diseases of plants. The technique employed was as follows.

Plants were either grown in John Innes Potting Compost (No. l or 2) in 4cm diameter, 3. 5cm depth minipots or in an artificial, cellulose based growing medium in plugs. The test compounds were individually formulated as a solution either in acetone or acetone/ethanol (1: 1 by volume), which was diluted in reverse osmosis water to a concentration of lOOppm (that is, lmg of compound in a final volume of 10ml) immediately before use. When foliar sprays were applied to monocotyledonous crops, TWEEN 20 (0.05% by volume) was added. TWEEN is a registered trade mark.

Individual compounds of formula (1) were applied as a foliar application, where the chemical solution was applied to the foliage of the test plants by spraying the plant to maximum droplet retention. In the case of Plasmopara viticola (PLASVI), each treatment was applied to two replicate vines grown in soil and, in the case of Puccinia triticina (PUCCRT), each treatment was applied to three wheat plants grown in two replicate cellulose plugs. The plants were inoculated with a calibrated fungal spore suspension one day after chemical application.

After chemical application and inoculation, the plants were incubated under high humidity conditions and then put into an appropriate environment to allow infection to proceed, until the disease was ready for assessment. For Plasmopara viticola, the plants were reincubated under high humidity conditions for 24hours prior to assessment. The time period between chemical application and assessment varied from five to fourteen days according to the disease and environment. However, each individual disease was assessed after the same time period for all compounds.

Assessments were performed on a single leaf of each of the two replicate plants for Plasmopara viticola. For Puccinia tritici7ia assessments were carried out collectively on the plants in each replicate cellulose medium plug.

The disease level present (that is, the percentage leaf area covered by actively sporulating disease) or percentage of infected plants per pot or plug was assessed visually.

For each treatment, the assessed values for all its replicates were meaned to provide mean disease values. Untreated control plants were assessed in the same manner. The data were then processed by the method described below, providing a PRCO (Percentage Reduction from Control) value.

Assessment Method This method uses banded assessment values. The mean disease values are banded in the manner shown below. If the disease level value falls exactly mid-way between two of the points, the result will be the lower of the two points.

0 = 0% disease present 10 = 5.1-10% disease present 1 = 0. 1-1% disease present 20 = 10.1-20% disease present 3 = 1. 1-3% disease present 30 = 20.1-30% disease present 5 = 3.1-5% disease present 60 = 30.1-60% disease present 90 = 60.1-100% disease present An example of a typical banded calculation is as follows: Mean disease level for treatment A = 25% Therefore banded mean disease level for treatment A = 30 Mean disease level on untreated controls = 85%

Therefore banded mean disease level on untreated controls = 90 PRCO =100-{Banded mean disease level for treatment A 3 x 100 {Banded mean disease level on untreated controls} = 100- (30 x 100) = 66.7 90 The PRCO is then rounded to the nearest whole number. Thus, in this particular example, the PRCO result is 67.

The following compounds (shown as table number first, followed by hyphen and the number of the compound) showed 90% or more disease control against PLASVI at a concentration of 100 ppm: Compound Nos. 2-174,14-57, 14-69, 14-111, 14-198,14-235, 14-253,14-265, 14-270, 14-318,14-321, 14-334,14-368, 14-427,14-461, 14-465,14-524, 14-553,14-556, 14- 558,14-568, 14-571,15-69, 33-69,36-69, 41-69,59-194, 60-69,65-174, 67-69,67-174, 71-69,71-174, 74-69,74-368, 82-575,88-69, 91-69,92-69, 110-69,115-69, 123-69, 129-69 and 138-69.

The following compounds (shown as table number first, followed by hyphen and the number of the compound) showed less than 90% but more than 50% disease control against PLASVI at a concentration of 100ppm : Compound Nos. 2-192, 3-524,14-15, 14-50,14-58, 14-136,14-163, 14-307,14-404, 14- 506,14-538, 14-540,14-559, 31-43, 42-174,50-69, 69-111,69-362, 69-573,71-192, 109-69,120-174, 121-69 and 140-69.

The following compounds (shown as table number first, followed by hyphen and the number of the compound) showed 90% or more disease control against PUCCRT at a concentration of 100 ppm : Compound Nos. 14-57,14-136, 14-163,14-235, 14-270,14-465, 14-506,14-524, 14- 558,14-568, 14-571, 14-572 and 60-69.

The following compounds (shown as table number first, followed by hyphen and the number of the compound) showed less than 90% but more than 50% disease control against PUCCRT at a concentration of 100ppm :

Compound Nos. 14-59,14-174, 14-318,14-321, 14-334,14-439, 14-489,14-538, 14-573, 14-574,59-194, 71-69,74-368, 91-69,92-69, 104-69,138-69 and 139-69.

EXAMPLE 31 This Example still further illustrates the fungicidal properties of compounds. of formula (1).

The compounds were tested in a nutrient broth or leaf disk assay, using the methods described below.

Botrytis cinerea (grey mould): Conidia of the fungus from cryogenic storage were directly mixed into nutrient broth (PDB potato dextrose broth). After placing a (DMSO) solution of the test compounds into a microtiter plate (96-well format) the nutrient broth containing the fungal spores was added. The test plates were incubated at 24°C and the inhibition of growth was determined photometrically after 72 hrs.

Septoria tritici (leaf blotch): Conidia of the fungus from cryogenic storage were directly mixed into nutrient broth (PDB potato dextrose broth). After placing a (DMSO) solution of the test compounds into a microtiter plate (96-well format) the nutrient broth containing the fungal spores was added. The test plates were incubated at 24°C and the inhibition of growth was determined photometrically after 72 hrs.

Pyricularia ofyzae (rice blast): Conidia of the fungus from cryogenic storage were directly mixed into nutrient broth (PDB potato dextrose broth). After placing a (DMSO) solution of the test compounds into a microtiter plate (96-well format) the nutrient broth containing the fungal spores was added. The test plates were incubated at 24°C and the inhibition of growth was determined photometrically after 72 hrs.

Botrytis cinerea (grey mould): Bean leaf disks were placed on agar in multiwell plates (24-well format) and sprayed with the test solutions. After drying, the leaf disks were inoculated with a spore suspension of the fungus. After appropriate incubation the activity of the compounds was assessed 4 days after inoculation for preventive fungicidal activity.

Eiysiphe granziiiisfsp. hordei (Barley powdery mildew): Barley leaf segments were placed on agar in multiwell plates (24-well fonnat) and inoculated by dusting with freshly propagated spores from infected barley leaves. 24 hours after inoculation the leaf disks

are sprayed with the test solutions. After appropriate incubation the activity of the compounds was assessed 6 days after inoculation as curative fungicidal activity.

Erysiphe graminisfsp. tritici (Wheat powdery mildew): Wheat leaf segments were placed on agar in multiwell plates (24-well fonnat) and sprayed with the test solutions.

After drying, the leaf disks were inoculated by dusting with freshly propagated spores from infected wheat leaves. After appropriate incubation the activity of the compounds was assessed 6 days after inoculation as preventive fungicidal activity.

The following compounds (shown as table number first, followed by hyphen and the number of the compound) gave greater than 60% control of the following fungal infections at 20ppm: Botrytis cinerea (nutrient broth) : 2-69,3-69, 3-524,4-69, 4-174, 4-368, 7-69,10-69, 14- 15,14-50, 14-69, 14-149, 14-151,14-164, 14-174,14-217, 14-252, 14-253, 14-269,14- 270,14-307, 14-322,14-362, 14-368,14-390, 14-404,14-425, 14-427,14-444, 14-465, 14-481,14-486, 14-506,14-524, 14-538,14-540, 14-553,14-558, 16-69,16-524, 20-69, 22-69,24-69, 28-69, 36-69, 40-524,42-174, 50-69,52-69, 56-69,58-69, 58-142,60-69, 63-69,67-174, 70-69,71-69, 71-174,76-69, 80-69,92-69, 93-69,99-174, 104-69,105- 69,109-69, 110-69,113-69, 118-69,120-174, 122-69,123-69, 126-69,127-69, 127-252, 127-410,129-69, 133-69,134-212, 134-259,134-345 and 135-69.

Septoria tritici : 2-69, 2-174,4-368, 7-69,10-69, 14-15,14-39, 14-50, 14-69,14-136, 14- 149,14-163, 14-174,14-192, 14-194,14-217, 14-219,14-253, 14-269, 14-270, 14-288, 14-307,14-334, 14-362,14-368, 14-390,14-404, 14-427,14-444, 14-465,14-481, 14- 486,14-489, 14-524,14-538, 14-540, 14-553, 14-558,14-571, 15-69,16-69, 16-524,22- 69,24-69, 28-69,33-69, 36-69,40-524, 41-69,42-174, 52-69,58-142, 60-69,61-69, 67- 174,69-15, 70-69,71-69, 71-174,71-192, 74-368,76-69, 80-69, 86 69, 91-69,93-69, 99-174,102-69, 104-69,109-69, 110-69,113-69, 118-69, 120-174,122-69, 123-69,127- 69,127-219, 127-410,129-69, 132-69,134-156, 134-259,134-345, 134-384 and 135-69.

Pyricularia oryzae : 2-69,2-174, 3-524,4-368, 5-69,7-69, 14-15,14-50, 14-53,14-64, 14-69,14-122, 14-131,14-149, 14-151,14-163, 14-164,14-174, 14-182,14-192, 14-194, 14-217,14-219, 14-242,14-253, 14-269,14-270, 14-281,14-307, 14-362,14-368, 14- 390,14-404, 14-427,14-444, 14-465, 14-486, 14-506,14-524, 14-538,14-540, 14-553, 14-558,14-559, 14-569,14-571, 14-574,15-69, 16-465,16-524, 18-69,33-69, 36-69,

40-524,41-69, 42-174,58-524, 59-194,60-69, 61-69,66-69, 69-15,69-39, 69-174,69- 362,71-69, 71-174,71-192, 74-69,74-368, 79-69,80-69, 82-194,82-575, 84-69,86-69, 88-69,98-69, 110-69, 118-69, 123-69,127-219, 127-410,129-69, 132-69,134-116, 134- 303,134-345, 134-384 and 140-69.

The following compounds (shown as table number first, followed by hyphen and the number of the compound) gave greater than 60% control of the following fungal infections at 200ppm: Botrytis chorea (leaf disk): 2-69,2-174, 4-368,8-390, 14-15,14-50, 14-62, 14-69, 14- 151,14-174, 14-253,14-270, 14-307,14-322, 14-334,14-362, 14-365,14-368, 14-390, 14-427,14-444, 14-461,14-465, 14-486, 14-558, 16-69,22-69, 26-69,36-69, 42-69,42- 174,51-69, 71-69,71-174, 76-69,79-69, 80-69,94-362, 95-111,102-69, 118-69,123-69, 127-69,127-142, 127-174,132-69, 134-57,134-194, 134-259,134-260, 134-335,134- 386,134-525 and 135-69.

Erysiphe graminis f : sp. hordei : 4-174,14-39, 14-53,14-57, 14-64, 14-111, 14-194,14- 211, 14-252,14-253, 14-281,14-334, 14-336, 14-391, 14-444,14-568, 14-571, 14-573, 14-574,16-192, 16-558,37-69, 40-39,42-368, 52-69,58-142, 58-174,58-558, 59-368, 65-362,66-69, 69-573,70-69, 71-174,74-69, 76-174,77-69, 94-174,105-69, 107-69, 110-69,118-69, 120-174,123-69, 126-69,127-53, 127-111,127-368, 127-390,134-57, 134-122,134-194, 134-219,134-259, 134-260,134-269, 134-292,134-345, 134-361, 134-384,134-445, 134-521 and 134-525.

Erysiphe graminisfsp. tritici : 3-524,4-174, 14-62, 14-64,14-163, 14-1, 69,14-211, 14- 242,14-263, 14-348,14-558, 14-571,15-69, 16-69,16-192, 16-516,19-69, 33-69,52-69, 58-573, 69-174, 71-69,71-174, 74-69,80-69, 88-69, 118-69, 123-69,129-69, 134-32, 134-122,134-186, 134-248,134-260, 134-303,134-345, 134-384,134-576 and 140-69.