SCUTT JAMES NICHOLAS (GB)
ROBINSON LOUISA (GB)
TYTE MELLONEY (GB)
MATHEWS CHRISTOPHER JOHN (GB)
SCUTT JAMES NICHOLAS (GB)
ROBINSON LOUISA (GB)
TYTE MELLONEY (GB)
| WO2001017972A2 | 2001-03-15 |
| DE102006000971A1 | 2007-07-12 |
| What is claimed is: 1. A compound of formula I wherein G is hydrogen or an agriculturally acceptable metal, sulfonium, ammonium or latentiating group, R1 is methyl, ethyl, n-propyl, isopropyl, cyclopropyl, halomethyl, haloethyl, vinyl, ethynyl, halogen, CrC2alkoxy or CrC2haloalkoxy, R2 and R3 are independently of each other hydrogen, methyl, ethyl, n-propyl, isopropyl, cyclopropyl, halomethyl, haloethyl, vinyl, propenyl, ethynyl, propynyl, halogen, Ci-C2alkoxy, CrC2haloalkoxy, optionally substituted aryl or optionally substituted heteroaryl, R4 is hydrogen, methyl, ethyl, n-propyl, isopropyl, cyclopropyl, halomethyl, haloethyl, vinyl, propenyl, ethynyl, propynyl, halogen, Ci-C2alkoxy or Ci-C2haloalkoxy, R5 and R9 are independently of each other hydrogen or methyl, R6 is hydrogen optionally substituted CrCβ alkyl, optionally substituted C3-C7 cycloalkyl, optionally substituted aryl, optionally substituted heteroaryl or a group COR10, CO2R11, R7 and R8 are independently of each other, hydrogen, optionally substituted CrCβ alkyl, optionally substituted C3-C7 cycloalkyl, optionally substituted C4-C7 heterocyclyl, optionally substituted aryl or optionally substituted heteroaryl, or any two of R6, R7 and R8 may be joined to form a 4-7 membered carbocyclic ring optionally substituted by one to four C1-C3 alkyl groups or a C4-C7 heterocyclyl containing a heteroatom selected from oxygen or sulfur and optionally substituted by one to four CrC3 alkyl groups, or R6 and R7 form a bond, R10 is optionally substituted CrC6 alkyl or optionally substituted phenyl, and R11 is optionally substituted CrCβ alkyl or optionally substituted phenyl. 2. A compound according to claim 1 , wherein R1 is methyl, ethyl, n-propyl, cyclopropyl, vinyl, ethynyl, halogen, Ci-C2alkoxy or Ci-C2haloalkoxy. 3. A compound according to claim 1 , wherein R2 is methyl, ethyl, halogen, Ci-C2alkoxy, Cr C2haloalkoxy, optionally substituted phenyl, optinally substituted naphthyl or optionally substituted pyridyl. 4. A compound according to claim 1 , wherein R2 is methyl. 5. A compound according to claim 1 , wherein R2 is hydrogen. 6. A compound according to claim 1 , wherein R3 is optionally substituted phenyl, optionally substituted naphthyl or optionally substituted pyridyl. 7. A compound according to claim 1 , wherein R3 is hydrogen. 8. A compound according to claim 1 , wherein R4 is methyl, ethyl, n-propyl, vinyl or ethynyl. 9. A compound according to claim 1 , wherein R4 is hydrogen. 10. A compound according to claim 1 , wherein R5 and R9 are hydrogen. 1 1. A compound according to claim 1 , wherein R6 is C1-C4 alkyl. 12. A compound according to claim 1 , wherein R7 and R8 are independently hydrogen, Ci-C4alkyl, a 5- or 6-membered carbocylic ring optionally substituted once or twice by CrC2alkyl or d- C2alkoxy, a 5- or 6-membered heterocyclyl containing one oxygen atom, or R7 and R8 together with the atom to which they are attached form a 5- or 6-membered carbocyclic ring optionally substituted once or twice by CrC2alkyl or R7 and R8 together with the atom to which they are attached form a 5- or 6-membered heterocyclyl containing one oxygen atom. 13. A compound according to claim 1 , wherein R10 and R11 are independently C1-C4 alkyl. 14. A herbicidal composition, which, in addition to comprising formulation adjuvants, comprises a herbicidally effective amount of a compound of formula I. 15. A method of controlling grasses and weeds in crops of useful plants, which comprises applying a herbicidally effective amount of a compound of formula I, or of a composition comprising such a compound, to the plants or to the locus thereof. |
The present invention relates to novel, herbicidally active isoxazolidine and isoxazoline compounds, and derivatives thereof, to processes for their preparation, to compositions comprising those compounds, and to their use in controlling weeds, especially in crops of useful plants, or in inhibiting undesired plant growth.
Cyclopentanedione compounds having herbicidal action are described, for example, in WO 01/74770 and WO 96/03366.
Novel isoxazolidine and isoxazoline compounds, and derivatives thereof, having herbicidal and growth-inhibiting properties have now been found.
The present invention accordingly relates to compounds of formula I
wherein
G is hydrogen or an agriculturally acceptable metal, sulfonium, ammonium or latentiating group,
R 1 is methyl, ethyl, n-propyl, isopropyl, cyclopropyl, halomethyl, haloethyl, vinyl, ethynyl, halogen,
CrC 2 alkoxy or Ci-C 2 haloalkoxy,
R 2 and R 3 are independently of each other hydrogen, methyl, ethyl, n-propyl, isopropyl, cyclopropyl, halomethyl, haloethyl, vinyl, propenyl, ethynyl, propynyl, halogen, Ci-C 2 alkoxy,
CrC 2 haloalkoxy, optionally substituted aryl or optionally substituted heteroaryl,
R 4 is hydrogen, methyl, ethyl, n-propyl, isopropyl, cyclopropyl, halomethyl, haloethyl, vinyl, propenyl, ethynyl, propynyl, halogen, CrC 2 alkoxy or CrC 2 haloalkoxy,
R 5 and R 9 are independently of each other hydrogen or methyl,
R 6 is hydrogen optionally substituted CrC 6 alkyl, optionally substituted C 3 -C 7 cycloalkyl, optionally substituted aryl, optionally substituted heteroaryl or a group COR 10 , CO 2 R 11 , R 7 and R 8 are independently of each other, hydrogen, optionally substituted C-i-Cβ alkyl, optionally substituted C 3 -C 7 cycloalkyl, optionally substituted C 4 -C 7 heterocyclyl, optionally substituted aryl or optionally substituted heteroaryl, or any two of R 6 , R 7 and R 8 may be joined to form a 4-7 membered carbocyclic ring optionally substituted by one to four C 1 -C 3 alkyl groups or a C 4 -C 7 heterocyclyl containing a heteroatom selected from oxygen or sulfur and optionally substituted by one to four CrC 3 alkyl groups, or R 6 and R 7 form a bond,
R 10 is optionally substituted CrC 6 alkyl or optionally substituted phenyl, and
R 11 is optionally substituted C-i-Cβ alkyl or optionally substituted phenyl.
In the substituent definitions of the compounds of the formula I, each alkyl moiety either alone or as part of a larger group (such as alkoxy, alkylthio, alkoxycarbonyl, alkylcarbonyl, alkylaminocarbonyl, dialkylaminocarbonyl) is a straight or branched chain and is, for example, methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, isopropyl, n-butyl, sec-butyl, isobutyl, fert-butyl or neopentyl. The alkyl groups are suitably CrCβalkyl groups, but are preferably CrC 4 alkyl or CrC 3 alkyl groups, and, more preferably, CrC 2 alkyl groups.
When present, the optional substituents on an alkyl moiety (alone or as part of a larger group such as alkoxy, alkoxycarbonyl, alkylcarbonyl, alkylaminocarbonyl, dialkylaminocarbonyl) include one or more of halogen, nitro, cyano, C 3- C 7 cycloalkyl (itself optionally substituted with Ci-Cβalkyl or halogen), C 5 -C 7 cycloalkenyl (itself optionally substituted with Ci-C 4 alkyl or halogen), hydroxy, Ci-Ci 0 alkoxy, Ci-Ci 0 alkoxy(Ci-Ci 0 )alkoxy, tri(Ci-C 4 )alkylsilyl(CrC 6 )alkoxy, CrC 6 alkoxy- carbonyl(Ci-Cio)alkoxy, CrCiohaloalkoxy, aryl(Ci-C 4 )alkoxy (where the aryl group is optionally substituted), C 3 -C 7 cycloalkyloxy (where the cycloalkyl group is optionally substituted with d- Cβalkyl or halogen), C 3 -Cioalkenyloxy, C 3 -Cioalkynyloxy, mercapto, CrCioalkylthio, Cr Ciohaloalkylthio, aryl(Ci-C 4 )alkylthio (where the aryl group is optionally substituted), C 3 - C 7 cycloalkylthio (where the cycloalkyl group is optionally substituted with CrCβalkyl or halogen), tri(Ci-C 4 )alkylsilyl(CrC 6 )alkylthio, arylthio (where the aryl group is optionally substituted), C r Cβalkylsulfonyl, Ci-Cβhaloalkylsulfonyl, CrCβalkylsulfinyl, CrCβhaloalkylsulfinyl, arylsulfonyl (where the aryl group is optionally substituted), tri(Ci-C 4 )alkylsilyl, aryldi(Ci-C 4 )alkylsilyl, (C r C 4 )alkyldiarylsilyl, triarylsilyl, aryl(Ci-C 4 )alkylthio(CrC 4 )alkyl, aryloxy(CrC 4 )alkyl, formyl, Cr C-ioalkylcarbonyl, HO 2 C, C-i-C-ioalkoxycarbonyl, aminocarbonyl, Ci-Cβalkylaminocarbonyl, di(C1- C6 alkyl)aminocarbonyl, Λ/-(Ci-C 3 alkyl)-Λ/-(d-C 3 alkoxy)aminocarbonyl, d-Cβalkylcarbonyloxy, arylcarbonyloxy (where the aryl group is optionally substituted), di(Ci-C 6 )alkylaminocarbonyloxy, Ci-Cβalkyliminooxy, C 3 -C 6 alkenyloxyimino, aryloxyimino, aryl (itself optionally substituted), heteroaryl (itself optionally substituted), heterocyclyl (itself optionally substituted with d-Cβalkyl or halogen), aryloxy (where the aryl group is optionally substituted), heteroaryloxy, (where the heteroaryl group is optionally substituted), heterocyclyloxy (where the heterocyclyl group is optionally substituted with C-i-Cβalkyl or halogen), amino, C-i-Cealkylamino, di(CrC 6 )alkylamino, C-i-Cealkylcarbonylamino, Λ/-( d-C 6 )alkylcarbonyl-Λ/-( CrC 6 )alkylamino, C 2 -C 6 alkenylcarbonyl, C 2 -C 6 alkynylcarbonyl, Cs-Cealkenyloxycarbonyl, Cs-Cealkynyloxycarbonyl, aryloxycarbonyl (where the aryl group is optionally substituted) and arylcarbonyl (where the aryl group is optionally substituted).
Halogen is fluorine, chlorine, bromine or iodine.
Haloalkyl groups are alkyl groups which are substituted with one or more of the same or different halogen atoms and are, for example, CF 3 , CF 2 CI, CF 2 H, CCI 2 H, FCH 2 , CICH 2 , BrCH 2 , CH 3 CHF, (CHs) 2 CF, CF 3 CH 2 or CHF 2 CH 2 .
In the context of the present specification the term "aryl" refers to aromatic ring systems which may be mono-, bi- or tricyclic. Examples of such rings include phenyl, naphthyl, anthracenyl, indenyl or phenanthrenyl. A preferred aryl group is phenyl.
The term "heteroaryl" preferably refers to an aromatic ring system containing at least one heteroatom and consisting either of a single ring or of two or more fused rings. Preferably, single rings will contain up to three and bicyclic systems up to four heteroatoms which will preferably be chosen from nitrogen, oxygen and sulphur. Examples of such groups include furyl, thienyl, pyrrolyl, pyrazolyl, imidazolyl, 1 ,2,3-triazolyl, 1 ,2,4-triazolyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, 1 ,2,4-oxadiazolyl, 1 ,3,4-oxadiazolyl, 1 ,2,5-oxadiazolyl, 1 ,2,3-thiadiazolyl, 1 ,2,4-thiadiazolyl, 1 ,3,4-thiadiazolyl, 1 ,2,5-thiadiazolyl, pyridyl, pyrimidinyl, pyridazinyl, pyrazinyl, 1 ,2,3-triazinyl, 1 ,2,4-triazinyl, 1 ,3,5-triazinyl, benzofuryl, benzisofuryl, benzothienyl, benzisothienyl, indolyl, isoindolyl, indazolyl, benzothiazolyl, benzisothiazolyl, benzoxazolyl, benzisoxazolyl, benzimidazolyl, 2, 1 ,3-benzoxadiazole, quinolinyl, isoquinolinyl, cinnolinyl, phthalazinyl, quinazolinyl, quinoxalinyl, naphthyridinyl, benzotriazinyl, purinyl, pteridinyl and indolizinyl. Preferred examples of heteroaromatic radicals include pyridyl, pyrimidinyl, triazinyl, thienyl, furyl, oxazolyl, isoxazolyl, 2,1 ,3-benzoxadiazolyl and thiazolyl.
Another group of preferred heteroaryls comprises pyrazolyl, 1 ,2,3-triazolyl, 1 ,2,4-triazolyl, pyridazinyl, pyrazinyl, quinolinyl, isoquinolinyl, cinnolinyl, quinazolinyl or quinoxalinyl. - A -
The term "heterocyclyl" preferably refers to a non-aromatic preferably monocyclic or bicyclic ring systems containing up to 7 atoms including one or more (preferably one or two) heteroatoms selected from O, S and N. Examples of such rings include 1 ,3-dioxolane, oxetane, tetrahydrofuran, morpholine, thiomorpholin and piperazine. When present, the optional substituents on heterocyclyl include CrCβalkyl and d-Cβhaloalkyl as well as those optional substituents given above for an alkyl moiety.
Cycloalkyl includes preferably cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and cycloheptyl. When present, the optional substituents on cycloalkyl include Ci-C 3 alkyl as well as those optional substituents given above for an alkyl moiety.
Carbocyclic rings include aryl, cycloalkyl or carbocyclic groups, and cycloalkenyl groups.
When present, the optional substituents on aryl, heteroaryl and carbocycles are preferably selected independently, from halogen, nitro, cyano, rhodano, isothiocyanato, C-i-Cβalkyl, Ci-C 6 haloalkyl, Ci-C 6 alkoxy(Ci-C 6 ) alkyl, C 2 -C 6 alkenyl, C 2 -C 6 haloalkenyl, C 2 -C 6 alkynyl, C 3 - C 7 cycloalkyl (itself optionally substituted with d-Cβalkyl or halogen), C 5-7 cycloalkenyl (itself optionally substituted with CrC 6 alkyl or halogen), hydroxy, Ci-Ci 0 alkoxy, Ci-Ci 0 alkoxy(Cr Cio)alkoxy, tri(Ci-C 4 )alkylsilyl(CrC6)alkoxy, Ci-C6alkoxycarbonyl(Ci-Cio)alkoxy, d- C-iohaloalkoxy, aryl(Ci-C 4 )alkoxy (where the aryl group is optionally substituted with halogen or CrCβalkyl), C3-C 7 cycloalkyloxy (where the cycloalkyl group is optionally substituted with d- C 6 alkyl or halogen), C 3 -Ci 0 alkenyloxy, C 3 -Ci 0 alkynyloxy, mercapto, CrCi 0 alkylthio, d- C-iohaloalkylthio, aryl(Ci-C 4 )alkylthio, C3-C 7 cycloalkylthio (where the cycloalkyl group is optionally substituted with CrCβalkyl or halogen), tri(Ci-C 4 )-alkylsilyl(CrC6)alkylthio, arylthio, d- Cβalkylsulfonyl, CrCβhaloalkylsulfonyl, CrCβalkylsulfinyl, CrCβhaloalkylsulfinyl, arylsulfonyl, tri(CrC 4 )alkylsilyl, aryldi(CrC 4 )alkylsilyl, CrC 4 alkyldiarylsilyl, triarylsilyl, CrC-ioalkylcarbonyl, HO 2 C, CrCioalkoxycarbonyl, aminocarbonyl, CrCβalkylaminocarbonyl, di(d-C 6 alkyl)- aminocarbonyl, /V-(CrC 3 alkyl)-Λ/-(CrC 3 alkoxy)aminocarbonyl, CrC 6 alkylcarbonyloxy, arylcarbonyloxy, di(Ci-C6)alkylaminocarbonyloxy, aryl (itself optionally substituted with d-Cβalkyl or halogen), heteroaryl (itself optionally substituted with d-Cβalkyl or halogen), heterocyclyl (itself optionally substituted with d-Cβalkyl or halogen), aryloxy (where the aryl group is optionally substituted with CrCβalkyl or halogen), heteroaryloxy (where the heteroaryl group is optionally substituted with CrCβalkyl or halogen), heterocyclyloxy (where the heterocyclyl group is optionally substituted with CrCβalkyl or halogen), amino, CrCβalkylamino, di(Ci-C6)alkylamino, Cr Cβalkylcarbonylamino, Λ/-(Ci-C6)alkylcarbonyl-Λ/-(CrC6)alkylamino, arylcarbonyl, (where the aryl group is itself optionally substituted with halogen or d-Cβalkyl) or two adjacent positions on an aryl or heteroaryl system may be cyclised to form a 5, 6 or 7 membered carbocyclic or heterocyclic ring, itself optionally substituted with halogen or d-Cβalkyl. Further substituents for aryl or heteroaryl include arylcarbonylamino (where the aryl group is substituted by d-Cβalkyl or halogen), (d-CβJalkoxycarbonylamino, (Ci-C6)alkoxycarbonyl-Λ/-(CrC6)alkylamino, aryloxycarbonylamino (where the aryl group is substituted by d-Cβalkyl or halogen), aryloxycarbonyl-Λ/-(Ci-C6)alkylamino, (where the aryl group is substituted by d-Cβalkyl or halogen), arylsulphonylamino (where the aryl group is substituted by d-Cβalkyl or halogen), arylsulphonyl-Λ/-(Ci-C6)alkylamino (where the aryl group is substituted by d-Cβalkyl or halogen), aryl-N-(Ci-C6)alkylamino (where the aryl group is substituted by d-Cβalkyl or halogen), arylamino (where the aryl group is substituted by d-Cβalkyl or halogen), heteroaryl amino (where the heteroaryl group is substituted by d-Cβalkyl or halogen), heterocyclylamino (where the heterocyclyl group is substituted by d-Cβalkyl or halogen), aminocarbonylamino, Cr Cβalkylaminocarbonylamino, di(Ci-C6)alkylaminocarbonylamino, arylaminocarbonylamino where the aryl group is substituted by d-Cβalkyl or halogen), aryl-Λ/- (Ci-Cβjalkylaminocarbonylamino where the aryl group is substituted by CrC 6 alkyl or halogen), d-C 6 alkylaminocarbonyl-Λ/-(d- Cβjalkylamino, di(Ci-C6)alkylaminocarbonyl-Λ/-( d-CβJalkylamino, arylaminocarbonyl-Λ/-(d- C 6 )alkylamino where the aryl group is substituted by CrC 6 alkyl or halogen) and aryl-Λ/-(d- C6)alkylaminocarbonyl-Λ/-(CrC6)alkylamino where the aryl group is substituted by d-Cβalkyl or halogen).
For substituted heterocyclyl groups it is preferred that one or more substituents are independently selected from halogen, C-i-Cβalkyl, d-Cβhaloalkyl, d-Cβalkoxy, d-Cβhaloalkoxy, d-
Cβalkylthio, d-Cβalkylsulfinyl, d-Cβalkylsulfonyl, nitro and cyano. It is to be understood that dialkylamino substituents include those where the dialkyl groups together with the N atom to which they are attached form a five, six or seven-membered heterocyclic ring which may contain one or two further heteroatoms selected from O, N or S and which is optionally substituted by one or two independently selected d-Cβalkyl groups. When heterocyclic rings are formed by joining two groups on an N atom, the resulting rings are suitably pyrrolidine, piperidine, thiomorpholine and morpholine each of which may be substituted by one or two independently selected d- Cβalkyl groups.
The invention relates also to the agriculturally acceptable salts which the compounds of formula I are able to form with transition metal, alkali metal and alkaline earth metal bases, amines, quaternary ammonium bases or tertiary sulfonium bases. Among the transition metal, alkali metal and alkaline earth metal salt formers, special mention should be made of the hydroxides of copper, iron, lithium, sodium, potassium, magnesium and calcium, and preferably the hydroxides, bicarbonates and carbonates of sodium and potassium.
Examples of amines suitable for ammonium salt formation include ammonia as well as primary, secondary and tertiary Ci-Cisalkylamines, Ci-C 4 hydroxyalkylamines and C 2 -C 4 alkoxyalkyl- amines, for example methylamine, ethylamine, n-propylamine, isopropylamine, the four butylamine isomers, n-amylamine, isoamylamine, hexylamine, heptylamine, octylamine, nonylamine, decylamine, pentadecylamine, hexadecylamine, heptadecylamine, octadecylamine, methylethylamine, methylisopropylamine, methylhexylamine, methylnonylamine, methylpentadecylamine, methyloctadecylamine, ethylbutylamine, ethylheptylamine, ethyloctylamine, hexylheptylamine, hexyloctylamine, dimethylamine, diethylamine, di-n- propylamine, di-isopropylamine, di-n-butylamine, di-n-amylamine, di-isoamylamine, dihexyl- amine, diheptylamine, dioctylamine, ethanolamine, n-propanolamine, isopropanolamine, N, N- diethanolamine, Λ/-ethylpropanolamine, Λ/-butylethanolamine, allylamine, n-but-2-enylamine, n- pent-2-enylamine, 2,3-dimethylbut-2-enylamine, dibut-2-enylamine, n-hex-2-enylamine, propylenediamine, trimethylamine, triethylamine, tri-n-propylamine, tri-isopropylamine, tri-n- butylamine, tri-isobutylamine, tri-sec-butylamine, tri-n-amylamine, methoxyethylamine and ethoxyethylamine; heterocyclic amines, for example pyridine, quinoline, isoquinoline, morpholine, piperidine, pyrrolidine, indoline, quinuclidine and azepine; primary arylamines, for example anilines, methoxyanilines, ethoxyanilines, o-, m- and p-toluidines, phenylenediamines, benzidines, naphthylamines and o-, m- and p-chloroanilines; but especially triethylamine, isopropylamine and di-isopropylamine.
Preferred quaternary ammonium bases suitable for salt formation correspond, for example, to the formula [N(R 3 R b R c R d )]OH, wherein R 3 , R b , R c and R d are each independently of the others hydrogen, Ci-C 4 alkyl. Further suitable tetraalkylammonium bases with other anions can be obtained, for example, by anion exchange reactions.
Preferred tertiary sulfonium bases suitable for salt formation correspond, for example, to the formula [SR e R f R g ]OH, wherein R e , R f and R 9 are each independently of the others C 1 -C 4 alkyl. Trimethylsulfonium hydroxide is especially preferred. Suitable sulfonium bases may be obtained from the reaction of thioethers, in particular dialkylsulfides, with alkylhalides, followed by conversion to a suitable base, for example a hydroxide, by anion exchange reactions. It should be understood that in those compounds of formula I, where G is a metal, ammonium or sulfonium as mentioned above and as such represents a cation, the corresponding negative charge is largely delocalised across the 0-C=C-C=O unit.
The compounds of formula I according to the invention also include hydrates which may be formed during the salt formation.
The latentiating groups G are selected to allow its removal by one or a combination of biochemical, chemical or physical processes to afford compounds of formula I where G is H before, during or following application to the treated area or plants. Examples of these processes include enzymatic cleavage, chemical hydrolysis and photoloysis. Compounds bearing such groups G may offer certain advantages, such as improved penetration of the cuticula of the plants treated, increased tolerance of crops, improved compatibility or stability in formulated mixtures containing other herbicides, herbicide safeners, plant growth regulators, fungicides or insecticides, or reduced leaching in soils.
The latentiating group G is preferably selected from the groups CrC 8 alkyl, C 2 -C 8 haloalkyl, phenylC-i-Csalkyl (wherein the phenyl may optionally be substituted by CrC 3 alkyl, Ci-C 3 haloalkyl, CrC 3 alkoxy, CrC 3 haloalkoxy, CrC 3 alkylthio, CrC 3 alkylsulfinyl, Ci-C 3 alkylsulfonyl, halogen, cyano or by nitro), heteroaryld-Csalkyl (wherein the heteroaryl may optionally be substituted by Ci-C 3 alkyl, C r C 3 haloalkyl, C r C 3 alkoxy, C r C 3 haloalkoxy, C r C 3 alkylthio, C r C 3 alkylsulfinyl, C r C 3 alkylsulfonyl, halogen, cyano or by nitro), C 3 -Csalkenyl, C 3 -Cshaloalkenyl, C 3 -Csalkynyl, C(X a )-R a , C(X b )-X c -R b , C(X d )-N(R c )-R d , -SO 2 -R e , -P(X e )(R f )-R 9 or CH 2 -X f -R h wherein X a , X b , X c , X d , X e and X f are independently of each other oxygen or sulfur;
R a is H, CrCi 8 alkyl, C 2 -Ci 8 alkenyl, C 2 -Ci 8 alkynyl, C r Ci 0 haloalkyl, C r Ci 0 cyanoalkyl, C r C-ionitroalkyl, Ci-C-ioaminoalkyl, Ci-C 5 alkylamino(Ci-C 5 )alkyl, C 2 -C 8 dialkylamino(Ci-C 5 )alkyl, C 3 - C 7 cycloalkyl(CrC 5 )alkyl, Ci-C 5 alkoxy(Ci-C 5 )alkyl, C 3 -C 5 alkenyloxy(CrC 5 )alkyl, C 3 -(Cr C 5 )oxyalkyl, Ci-C 5 alkylthio(Ci-C 5 )alkyl, Ci-C 5 alkylsulfinyl(Ci-C 5 )alkyl, Ci-C 5 alkylsulfonyl(Cr C 5 )alkyl, C 2 -C 8 alkylideneaminoxy(Ci-C 5 )alkyl, Ci-C 5 alkylcarbonyl(Ci-C 5 )alkyl, C r C 5 alkoxycarbonyl(CrC 5 )alkyl, aminocarbonyl(Ci-C 5 )alkyl, Ci-C 5 alkylaminocarbonyl(Ci-C 5 )alkyl, C 2 -C 8 dialkylaminocarbonyl(Ci-C 5 )alkyl, Ci-C 5 alkylcarbonylamino(Ci-C 5 )alkyl, N-(Cr C 5 )alkylcarbonyl-Λ/-(Ci-C 5 )alkylamino(Ci-C 5 )alkyl, C 3 -C 6 trialkylsilyl(CrC 5 )alkyl, phenyl(C r C 5 )alkyl (wherein the phenyl may optionally be substituted by Ci-C 3 alkyl, Ci-C 3 haloalkyl, d- C 3 alkoxy, CrC 3 haloalkoxy, CrC 3 alkylthio, CrC 3 alkylsulfinyl, Ci-C 3 alkylsulfonyl, halogen, cyano, or by nitro), heteroaryl(CrC 5 )alkyl, (wherein the heteroaryl may optionally be substituted by Cr C 3 alkyl, C r C 3 haloalkyl, C r C 3 alkoxy, C r C 3 haloalkoxy, C r C 3 alkylthio, C r C 3 alkylsulfinyl, C r C 3 alkylsulfonyl, halogen, cyano, or by nitro), C 2 -C 5 haloalkenyl, C 3 -C 8 cycloalkyl, phenyl or phenyl substituted by CrC 3 alkyl, Ci-C 3 haloalkyl, Ci-C 3 alkoxy, CrC 3 haloalkoxy, halogen, cyano or nitro, heteroaryl or heteroaryl substituted by d-C 3 alkyl, Ci-C 3 haloalkyl, Ci-C 3 alkoxy, Ci-C 3 haloalkoxy, halogen, cyano or nitro,
R b is CrCi 8 alkyl, C 3 -Ci 8 alkenyl, C 3 -Ci 8 alkynyl, C 2 -Ci 0 haloalkyl, Ci-Ciocyanoalkyl, C r Cionitroalkyl, C 2 -Cioaminoalkyl, Ci-C 5 alkylamino(Ci-C 5 )alkyl, C 2 -C 8 dialkylamino(Ci-C 5 )alkyl, C 3 - C 7 cycloalkyl(CrC 5 )alkyl, Ci-C 5 alkoxy(Ci-C 5 )alkyl, C 3 -C 5 alkenyloxy(CrC 5 )alkyl, C 3 - C 5 alkynyloxy(CrC 5 )alkyl, Ci-C 5 alkylthio(Ci-C 5 )alkyl, Ci-C 5 alkylsulfinyl(Ci-C 5 )alkyl, C r C 5 alkylsulfonyl(Ci-C 5 )alkyl, C 2 -C 8 alkylideneaminoxy(Ci-C 5 )alkyl, Ci-C 5 alkylcarbonyl(Ci-C 5 )alkyl, Ci-C 5 alkoxycarbonyl(Ci-C 5 )alkyl, aminocarbonyl(Ci-C 5 )alkyl, Ci-C 5 alkylaminocarbonyl(Cr C 5 )alkyl, C 2 -C 8 dialkylaminocarbonyl(Ci-C 5 )alkyl, Ci-C 5 alkylcarbonylamino(Ci-C 5 )alkyl, N-(Cr C 5 )alkylcarbonyl-Λ/-(Ci-C 5 )alkylamino(Ci-C 5 )alkyl, C 3 -C 6 trialkylsilyl(CrC 5 )alkyl, phenyl(C r C 5 )alkyl (wherein the phenyl may optionally be substituted by Ci-C 3 alkyl, Ci-C 3 haloalkyl, d- C 3 alkoxy, CrC 3 haloalkoxy, CrC 3 alkylthio, CrC 3 alkylsulfinyl, Ci-C 3 alkylsulfonyl, halogen, cyano, or by nitro), heteroarylCrC 5 alkyl, (wherein the heteroaryl may optionally be substituted by Cr C 3 alkyl, C r C 3 haloalkyl, C r C 3 alkoxy, C r C 3 haloalkoxy, C r C 3 alkyl-thio, C r C 3 alkylsulfinyl, C r C 3 alkylsulfonyl, halogen, cyano, or by nitro), C 3 -C 5 haloalkenyl, C 3 -C 8 cycloalkyl, phenyl or phenyl substituted by CrC 3 alkyl, Ci-C 3 haloalkyl, Ci-C 3 alkoxy, CrC 3 haloalkoxy, halogen, cyano or nitro, heteroaryl or heteroaryl substituted by CrC 3 alkyl, Ci-C 3 haloalkyl, Ci-C 3 alkoxy, Ci-C 3 haloalkoxy, halogen, cyano or nitro,
R c and R d are each independently of each other hydrogen, Ci-Ci O alkyl, C 3 -Ci 0 alkenyl, C 3 - Cioalkynyl, C 2 -Ciohaloalkyl, Ci-Ciocyanoalkyl, Ci-Cionitroalkyl, Ci-Cioaminoalkyl, Cr C 5 alkylamino(Ci-C 5 )alkyl, C 2 -C 8 dialkylamino(Ci-C 5 )alkyl, C 3 -C 7 cycloalkyl(CrC 5 )alkyl, C r C 5 alkoxy(CrC 5 )alkyl, C 3 -C 5 alkenyloxy(CrC 5 )alkyl, C 3 -C 5 alkynyloxy(CrC 5 )alkyl, C r C 5 alkylthio(CrC 5 )alkyl, Ci-C 5 alkylsulfinyl(Ci-C 5 )alkyl, Ci-C 5 alkylsulfonyl(Ci-C 5 )alkyl, C 2 - C 8 alkylideneaminoxy(Ci-C 5 )alkyl, Ci-C 5 alkylcarbonyl(Ci-C 5 )alkyl, Ci-C 5 alkoxycarbonyl(Cr C 5 )alkyl, aminocarbonyl(Ci-C 5 )alkyl, Ci-C 5 alkylaminocarbonyl(Ci-C 5 )alkyl, C 2 - C 8 dialkylaminocarbonyl(Ci-C 5 )alkyl, Ci-C 5 alkylcarbonylamino(Ci-C 5 )alkyl, /V-(Cr C 5 )alkylcarbonyl-Λ/-(C 2 -C 5 )alkylaminoalkyl, C 3 -C 6 trialkylsilyl(CrC 5 )alkyl, phenyl(C r C 5 )alkyl (wherein the phenyl may optionally be substituted by CrC 3 alkyl, Ci-C 3 haloalkyl, Ci-C 3 alkoxy, Cr C 3 haloalkoxy, CrC 3 alkylthio, CrC 3 alkylsulfinyl, CrC 3 alkylsulfonyl, halogen, cyano, or by nitro), heteroaryl(CrC 5 )alkyl, (wherein the heteroaryl may optionally be substituted by CrC 3 alkyl, Cr C 3 haloalkyl, C r C 3 alkoxy, C r C 3 haloalkoxy, C r C 3 alkylthio, C r C 3 alkylsulfinyl, C r C 3 alkylsulfonyl, halogen, cyano, or by nitro), C 2 -C 5 haloalkenyl, C 3 -C 8 cycloalkyl, phenyl or phenyl substituted by CrCsalkyl, Ci-C 3 haloalkyl, Ci-C 3 alkoxy, Ci-C 3 haloalkoxy, halogen, cyano or nitro, heteroaryl or heteroaryl substituted by CrC 3 alkyl, Ci-C 3 haloalkyl, CrC 3 alkoxy, Ci-C 3 haloalkoxy, halogen, cyano or nitro, heteroarylamino or heteroarylamino substituted by CrC 3 alkyl, Ci-C 3 haloalkyl, d- C 3 alkoxy, CrC 3 haloalkoxy, halogen, cyano or nitro, diheteroarylamino or diheteroarylamino substituted by CrC 3 alkyl, Ci-C 3 haloalkyl, Ci-C 3 alkoxy, CrC 3 haloalkoxy, halogen, cyano or nitro, phenylamino or phenylamino substituted by Ci-C 3 alkyl, Ci-C 3 haloalkyl, Ci-C 3 alkoxy, d- C 3 haloalkoxy, halogen, cyano or by nitro, diphenylamino or diphenylamino substituted by d- C 3 alkyl, Ci-C 3 haloalkyl, d-C 3 alkoxy, CrC 3 haloalkoxy, halogen, cyano or by nitro or C 3 - dcycloalkylamino, di-C 3 -C 7 cycloalkylamino or C 3 -dcycloalkoxy or R c and R d may join together to form a 3-7 membered ring, optionally containing one heteroatom selected from O or S, R e is d-doalkyl, C2-doalkenyl, C2-doalkynyl, CrCiohaloalkyl, d-docyanoalkyl, d- Cionitroalkyl, Ci-Cioaminoalkyl, Ci-C 5 alkylamino(Ci-C 5 )alkyl, C 2 -C 8 dialkylamino(Ci-C 5 )alkyl, C 3 - C 7 cycloalkyl(CrC 5 )alkyl, Ci-C 5 alkoxy(Ci-C 5 )alkyl, C 3 -C 5 alkenyloxy(CrC 5 )alkyl, C 3 - C 5 alkynyloxy(Ci-C 5 )alkyl, Ci-C 5 alkylthio(Ci-C 5 )alkyl, Ci-C 5 alkylsulfinyl(Ci-C 5 )alkyl, C r C 5 alkylsulfonyl(Ci-C 5 )alkyl, C 2 -C 8 alkylideneaminoxy(Ci-C 5 )alkyl, Ci-C 5 alkylcarbonyl(Ci-C 5 )alkyl, Ci-C 5 alkoxycarbonyl(Ci-C 5 )alkyl, aminocarbonyl(d-C 5 )alkyl, Ci-C 5 alkylaminocarbonyl(Ci- C 5 )alkyl, C 2 -C 8 dialkylaminocarbonyl(Ci-C 5 )alkyl, Ci-C 5 alkylcarbonylamino(Ci-C 5 )alkyl, /V-(Cr C 5 )alkylcarbonyl-Λ/-(Ci-C 5 )alkylamino(Ci-C 5 )alkyl, C 3 -C 6 trialkylsilyl(Ci-C 5 )alkyl, phenyl(C r C 5 )alkyl (wherein the phenyl may optionally be substituted by CrC 3 alkyl, Ci-C 3 haloalkyl, d- C 3 alkoxy, Ci-C 3 haloalkoxy, Ci-C 3 alkylthio, Ci-C 3 alkylsulfinyl, Ci-C 3 alkylsulfonyl, halogen, cyano, or by nitro), heteroaryl(Ci-C 5 )alkyl (wherein the heteroaryl may optionally be substituted by d- C 3 alkyl, C r C 3 haloalkyl, C r C 3 alkoxy, C r C 3 haloalkoxy, C r C 3 alkylthio, C r C 3 alkylsulfinyl, C r C 3 alkylsulfonyl, halogen, cyano, or by nitro), C 2 -C 5 haloalkenyl, C 3 -C 8 cycloalkyl, phenyl or phenyl substituted by Ci-C 3 alkyl, Ci-C 3 haloalkyl, Ci-C 3 alkoxy, Ci-C 3 haloalkoxy, halogen, cyano or nitro, heteroaryl or heteroaryl substituted by CrC 3 alkyl, Ci-C 3 haloalkyl, Ci-C 3 alkoxy, CrC 3 haloalkoxy, halogen, cyano or by nitro, heteroarylamino or heteroarylamino substituted by CrC 3 alkyl, d- C 3 haloalkyl, Ci-C 3 alkoxy, CrC 3 haloalkoxy, halogen, cyano or by nitro, diheteroarylamino or diheteroarylamino substituted by Ci-C 3 alkyl, Ci-C 3 haloalkyl, Ci-C 3 alkoxy, Ci-C 3 haloalkoxy, halogen, cyano or nitro, phenylamino or phenylamino substituted by CrC 3 alkyl, Ci-C 3 haloalkyl, CrC 3 alkoxy, CrC 3 haloalkoxy, halogen, cyano or nitro, diphenylamino, or diphenylamino substituted by CrC 3 alkyl, Ci-C 3 haloalkyl, Ci-C 3 alkoxy, CrC 3 haloalkoxy, halogen, cyano or nitro, or C 3 -C 7 cycloalkylamino, diC 3 -C 7 cycloalkylamino or C 3 -C 7 cycloalkoxy, d-Ci 0 alkoxy, d- Ciohaloalkoxy, CrC 5 alkylamino or C 2 -C8dialkylamino,
R f and R 9 are are each independently of each other d-Ci O alkyl, C 2 -Ci 0 alkenyl, C 2 -Ci 0 alkynyl, d- Cioalkoxy, CrCiohaloalkyl, d-Ciocyanoalkyl, d-donitroalkyl, Ci-Cioaminoalkyl, Cr C 5 alkylamino(Ci-C 5 )alkyl, C 2 -C 8 dialkylamino(Ci-C 5 )alkyl, C 3 -C 7 cycloalkyl(Ci-C 5 )alkyl, C r C 5 alkoxy(CrC 5 )alkyl, C3-C 5 alkenyloxy(Ci-C 5 )alkyl, C3-C 5 alkynyloxy(Ci-C 5 )alkyl, d- C 5 alkylthio(CrC 5 )alkyl, Ci-C 5 alkylsulfinyl(Ci-C 5 )alkyl, Ci-C 5 alkylsulfonyl(Ci-C 5 )alkyl, C 2 - C 8 alkylideneaminoxy(Ci-C 5 )alkyl, Ci-C 5 alkylcarbonyl(Ci-C 5 )alkyl, Ci-C 5 alkoxycarbonyl(Cr C 5 )alkyl, aminocarbonyl(Ci-C 5 )alkyl, Ci-C 5 alkylaminocarbonyl(Ci-C 5 )alkyl, C 2 - C 8 dialkylaminocarbonyl(Ci-C 5 )alkyl, Ci-C 5 alkylcarbonylamino(Ci-C 5 )alkyl, N-(Cr C 5 )alkylcarbonyl-Λ/-(C 2 -C 5 )alkylaminoalkyl, C 3 -C 6 trialkylsilyl(Ci-C 5 )alkyl, phenyl(C r C 5 )alkyl (wherein the phenyl may optionally be substituted by CrC 3 alkyl, d-C 3 haloalkyl, CrC 3 alkoxy, d- C 3 haloalkoxy, CrCsalkylthio, Ci-C 3 alkylsulfinyl, Ci-C 3 alkylsulfonyl, halogen, cyano, or by nitro), heteroaryl(CrC 5 )alkyl (wherein the heteroaryl may optionally be substituted by CrC 3 alkyl, d- C 3 haloalkyl, Ci-C 3 alkoxy, Ci-C 3 haloalkoxy, Ci-C 3 alkylthio, d-C3alkylsulfinyl, Ci-C 3 alkylsulfonyl, halogen, cyano, or by nitro), C 2 -C 5 haloalkenyl, C 3 -C 8 cycloalkyl, phenyl or phenyl substituted by d-C 3 alkyl, d-C3haloalkyl, Ci-C 3 alkoxy, Ci-C 3 haloalkoxy, halogen, cyano or nitro, heteroaryl or heteroaryl substituted by d-C 3 alkyl, d-C 3 haloalkyl, d-C 3 alkoxy, Ci-C 3 haloalkoxy, halogen, cyano or by nitro, heteroarylamino or heteroarylamino substituted by C1-C3 alkyl, d-C3haloalkyl, d-C 3 alkoxy, Ci-C 3 haloalkoxy, halogen, cyano or by nitro, diheteroarylamino or diheteroarylamino substituted by C1-C3 alkyl, d-C3haloalkyl, d-C 3 alkoxy, Ci-C 3 haloalkoxy, halogen, cyano or nitro, phenylamino or phenylamino substituted by d-C 3 alkyl, d-C 3 haloalkyl, CrC 3 alkoxy, d- C 3 haloalkoxy, halogen, cyano or nitro, diphenylamino, or diphenylamino substituted by d- C 3 alkyl, d-C 3 haloalkyl, d-C 3 alkoxy, Ci-C 3 haloalkoxy, halogen, cyano or nitro, or C 3 - dcycloalkylamino, diC3-C 7 cycloalkylamino or C3-C 7 cycloalkoxy, CrCiohaloalkoxy, d- C 5 alkylamino or d-Csdialkylamino, benzyloxy or phenoxy, wherein the benzyl and phenyl groups may in turn be substituted by CrCsalkyl, Ci-C3haloalkyl, Ci-C3alkoxy, Ci-C 3 haloalkoxy, halogen, cyano or nitro, and
R h is CrCioalkyl, C 3 -Cioalkenyl, C 3 -Cioalkynyl, Ci-Ciohaloalkyl, Ci-Ciocyanoalkyl, d- Cionitroalkyl, C 2 -Ci 0 aminoalkyl, Ci-C 5 alkylamino(Ci-C 5 )alkyl, C 2 -C 8 dialkylamino(Ci-C 5 )alkyl, C 3 - C 7 cycloalkyl(CrC 5 )alkyl, Ci-C 5 alkoxy(Ci-C 5 )alkyl, C 3 -C 5 alkenyloxy(CrC 5 )alkyl, C 3 - C 5 alkynyloxy(Ci-C 5 )alkyl, Ci-C 5 alkylthio(Ci-C 5 )alkyl, Ci-C 5 alkylsulfinyl(Ci-C 5 )alkyl, d- C 5 alkylsulfonyl(Ci-C 5 )alkyl, C 2 -C 8 alkylideneaminoxy(Ci-C 5 )alkyl, Ci-C 5 alkylcarbonyl(Ci-C 5 )alkyl, Ci-C 5 alkoxycarbonyl(Ci-C 5 )alkyl, aminocarbonyl(d-C 5 )alkyl, Ci-C 5 alkylaminocarbonyl(Ci- C 5 )alkyl, C 2 -C 8 dialkylaminocarbonyl(Ci-C 5 )alkyl, Ci-C 5 alkylcarbonylamino(Ci-C 5 )alkyl, N-(Ci- C 5 )alkylcarbonyl-Λ/-(Ci-C 5 )alkylamino(Ci-C 5 )alkyl, C 3 -C 6 trialkylsilyl(Ci-C 5 )alkyl, phenyl(C r C 5 )alkyl (wherein wherein the phenyl may optionally be substituted by CrC 3 alkyl, Ci-C 3 haloalkyl, Ci-C 3 alkoxy, Ci-C 3 haloalkoxy, Ci-C 3 alkylthio, Ci-C 3 alkylsulfinyl, d-C 3 alkylsulfonyl, halogen, cyano or by nitro), heteroaryl(Ci-C 5 )alkyl (wherein the heteroaryl may optionally be substituted by CrC 3 alkyl, C r C 3 haloalkyl, C r C 3 alkoxy, C r C 3 haloalkoxy, C r C 3 alkylthio, C r C 3 alkylsulfinyl, C 1 -C3 alkylsulfonyl, halogen, cyano or by nitro), phenoxy(CrC 5 )alkyl (wherein wherein the phenyl may optionally be substituted by CrC 3 alkyl, Ci-C 3 haloalkyl, Ci-C 3 alkoxy, CrC 3 haloalkoxy, Cr C 3 alkylthio, Ci-C 3 alkylsulfinyl, C r C 3 alkylsulfonyl, halogen, cyano or by nitro), heteroaryloxy(d- C 5 )alkyl (wherein the heteroaryl may optionally be substituted by CrC 3 alkyl, Ci-C 3 haloalkyl, Cr C 3 alkoxy, Ci-C 3 haloalkoxy, Ci-C 3 alkylthio, Ci-C 3 alkylsulfinyl, C r C 3 alkylsulfonyl, halogen, cyano or by nitro), C 3 -C 5 haloalkenyl, C 3 -C 8 cycloalkyl, phenyl or phenyl substituted by CrC 3 alkyl, d- C 3 haloalkyl, Ci-C 3 alkoxy, CrC 3 haloalkoxy, halogen or by nitro, or heteroaryl, or heteroaryl substituted by CrC 3 alkyl, Ci-C 3 haloalkyl, Ci-C 3 alkoxy, CrC 3 haloalkoxy, halogen, cyano or by nitro.
In particular, the latentiating group G is a group -C(X a )-R a or -C(X b )-X c -R b , and the meanings of X a , R a , X b , X c and R b are as defined above.
It is preferred that G is hydrogen, an alkali metal or alkaline earth metal, where hydrogen is especially preferred.
Depending on the nature of the substituents, compounds of formula I may exist in different isomeric forms. When G is hydrogen, for example, compounds of formula I may exist in different tautomeric forms:
This invention covers all such isomers and tautomers and mixtures thereof in all proportions. Also, when substituents contain double bonds, cis- and frans-isomers can exist. These isomers, too, are within the scope of the claimed compounds of the formula I.
For the purpose of clarity, a compound of formula I, wherein G is H, is represented as a single tautomer, even if it is present in a different tautomeric form or as a mixture of tautomeric forms.
Preferably, in the compounds of formula I, R 5 I : is, methyl, ethyl, n-propyl, cyclopropyl, vinyl, ethynyl, halogen, Ci-C 2 alkoxy or Ci-C 2 haloalkoxy. More preferably, R 1 is methyl or ethyl. Preferably, R 2 is methyl, ethyl, halogen, Ci-C 2 alkoxy, CrC 2 haloalkoxy, optionally substituted phenyl, optinally substituted naphthyl or optionally substituted pyridyl.
More preferably, R 2 is methyl, optionally substituted phenyl, optionally substituted naphthyl or optionally substituted pyridyl.
Preferred substituents on these phenyl, naphthyl or pyridyl rings R 2 are CrC 2 alkyl, d- C 2 haloalkyl, C r C 2 alkoxy, C r C 2 haloalkoxy, C r C 2 alkylthio, C r C 2 haloalkylthio, C r C 2 alkylsulfinyl, CrC 2 haloalkylsulfinyl, Ci-C 2 alkylsulfonyl, Ci-C 2 haloakylsulfonyl, amino, Ci-C 2 alkylamino, di-Cr C 2 alkylamino, d-C^lkylcarbonylamino, CrC 2 alkoxycarbonylamino, Ci-C 2 alkylsulfonylamino, Cr C 2 haloalkylsulfonylamino, CrC 2 alkylcarbonyl, Ci-C 2 alkoxycarbonyl, aminocarbonyl, Cr C 2 alkylaminocarbonyl, di-Crdalkylaminocarbonyl, Ci-C 2 alkylsulfonoyloxy, Cr C 2 haloalkylsulfonyloxy, formyl, carboxy, halogen, nitro or cyano.
It is also preferred that these phenyl rings R 2 are substituted on two adjacent carbons by -O- CH 2 -O-, -0-CH 2 -CH 2 -O- and 0-CF 2 -O- to form annellated rings.
Even more preferably, R 2 is phenyl subsitituted one to three times by fluorine, chlorine, bromine, methyl, methoxy, trifluorom ethyl, trifluoromethoxy, nitro or cyano.
It is also preferred that R 2 is methyl.
It is also preferred that R 2 is hydrogen.
R 3 is preferably optionally substituted phenyl, optionally substituted naphthyl or optionally substituted pyridyl.
Preferred substituents on these phenyl, naphthyl or pyridyl rings R 3 are CrC 2 alkyl, Cr C 2 haloalkyl, C r C 2 alkoxy, C r C 2 haloalkoxy, C r C 2 alkylthio, C r C 2 haloalkylthio, C r C 2 alkylsulfinyl, CrC 2 haloalkylsulfinyl, Ci-C 2 alkylsulfonyl, Ci-C 2 haloakylsulfonyl, amino, Ci-C 2 alkylamino, di-Cr C 2 alkylamino, Ci-C 2 alkylcarbonylamino, Ci-C 2 alkoxycarbonylamino, Ci-C 2 alkylsulfonylamino, Cr C 2 haloalkylsulfonylamino, CrC 2 alkylcarbonyl, Ci-C 2 alkoxycarbonyl, aminocarbonyl, Cr C 2 alkylaminocarbonyl, di-Ci-C 2 alkylaminocarbonyl, Ci-C 2 alkylsulfonoyloxy, Cr C 2 haloalkylsulfonyloxy, formyl, carboxy, halogen, nitro or cyano.
It is also preferred that these phenyl rings R 3 are substituted on two adjacent carbons by -O- CH 2 -O-, -0-CH 2 -CH 2 -O- and 0-CF 2 -O- to form annellated rings. More preferably, R 3 is phenyl subsitituted one to three times by fluorine, chlorine, bromine, methyl, methoxy, trifluorom ethyl, trifluoromethoxy, nitro or cyano.
Preferably, R 3 is hydrogen.
Preferably, R 4 is methyl, ethyl, n-propyl, vinyl or ethynyl, in particular methyl or ethyl.
It is also preferred that R 4 is hydrogen.
R 5 and R 9 in the compounds of formula I are preferably hydrogen,
Preferably, R 6 is C 1 -C 4 alkyl, and, more preferably, methyl.
Preferably, R 6 and R 7 together with the atoms to which they are joined form a 5- or 6-membered carbocyclic ring optionally substituted by one to four methyl groups.
Preferably, R 7 and R 8 are independently hydrogen, Ci-C 4 alkyl, a 5- or 6-membered carbocylic ring optionally substituted once or twice by CrC 2 alkyl or Ci-C 2 alkoxy, a 5- or 6-membered heterocyclyl containing one oxygen atom, or R 7 and R 8 together with the atom to which they are attached form a 5- or 6-membered carbocyclic ring optionally substituted once or twice by d- C 2 alkyl or R 7 and R 8 together with the atom to which they are attached form a 5- or 6-membered heterocyclyl containing one oxygen atom.
More preferably, R 7 and R 8 are independently hydrogen, methyl, a 5- or 6-membered heterocyclyl containing one oxygen atom, or R 7 and R 8 together form a 5- or 6-membered heterocyclyl containing one oxygen atom.
Preferably, R 10 and R 11 are independently C 1 -C 4 alkyl.
A compound of formula (I) wherein G is d-C 8 alkyl, C 2 -C 8 haloalkyl, phenyld-C 8 alkyl (wherein the phenyl may optionally be substituted by CrC 3 alkyl, d-C 3 haloalkyl, CrC 3 alkoxy, d- Cahaloalkoxy, C-i-Csalkylthio, C-i-Csalkylsufinyl, d-Csalkylsulfonyl, halogen, cyano or by nitro), heteroarylCrC 8 alkyl (wherein the heteroaryl may optionally be substituted by CrC 3 alkyl, d- Cshaloalkyl, d-Csalkoxy, d-Cshaloalkoxy, d-Csalkylthio, d-Csalkylsufinyl, d-C3alkylsulfonyl, halogen, cyano or by nitro), C 3 -C 8 alkenyl, C 3 -C 8 haloalkenyl, C 3 -C 8 alkynyl, C(X a )-R a , C(X b )-X c -R b , C(X d )-N(R c )-R d , -SO 2 -R e , -P(X e )(R f )-R 9 or CH 2 -X f -R h where X a , X b , X c , X d , X e , X f , R a , R b , R c , R d , R e , R f , R 9 and R h are as defined above may be prepared by treating a compound of formula (A), which is a compound of formula (I) wherein G is H, with a reagent G-Z, wherein G-Z is an alkylating agent such as an alkyl halide (the definition of alkyl halides includes simple C-i-Cs alkyl halides such as methyl iodide and ethyl iodide, substituted alkyl halides such as chloromethyl alkyl ethers, Cl- CH 2 -X f -R h , wherein X f is oxygen, and chloromethyl alkyl sulfides Cl- CH 2 -X f -R h , wherein X f is sulfur), a C-i-Csalkyl sulfonate, or a di(Ci-Csalkyl) sulfate, or with a Cβ-Csalkenyl halide, or with a Cβ-Csalkynyl halide, or with an acylating agent such as a carboxylic acid, HO- C(X a )R a , wherein X a is oxygen, an acid chloride, CI-C(X a )R a , wherein X a is oxygen, or acid anhydride, [R a C(X a )] 2 θ, wherein X a is oxygen, or an isocyanate, R C N=C=O, or a carbamoyl chloride, CI-C(X d )-N(R c )-R d (wherein X d is oxygen and with the proviso that neither R c or R d is hydrogen), or a thiocarbamoyl chloride CI-C(X d )-N(R c )-R d (wherein X d is sulfur and with the proviso that neither R c or R d is hydrogen) or a chloroformate, CI-C(X b )-X c -R b , (wherein X b and X c are oxygen), or a chlorothioformate CI-C(X b )-X c -R b (wherein X b is oxygen and X c is sulfur), or a chlorodithioformate CI-C(X b )-X c -R b , (wherein X b and X c are sulfur), or an isothiocyanate, R C N=C=S, or by sequential treatment with carbon disulfide and an alkylating agent, or with a phosphorylating agent such as a phosphoryl chloride, CI-P(X e )(R f )-R 9 or with a sulfonylating agent such as a sulfonyl chloride CI-SO 2 — R e , preferably in the presence of at least one equivalent of base.
formula (A) formula (I)
Depending on the position of the substituent G, the compounds of formula (I) can be present in the form of two isomeric compounds, of formula (IA) and (IB).
formula (IA) formula (1B) This invention covers both a compound of formula (IA) and a compound of formula (IB), together with mixtures of these compounds in any ratio.
The O-alkylation of cyclic 1 ,3-diones is known; suitable methods are described, for example, by T. Wheeler, US4436666. Alternative procedures have been reported by M. Pizzomo and S. Albonico, Chem. Ind. (London), (1972), 425-426; H. Born et al., J. Chem. Soα, (1953), 1779- 1782; M. Constantino et al., Synth. Commun., (1992), 22 (19), 2859-2864; Y. Tian et al., Synth. Commun., (1997), 27 (9), 1577-1582; S. Chandra Roy et al., Chem. Letters, (2006), 35 (1 ), 16-17; P. K. Zubaidha et al., Tetrahedron Lett., (2004), 45, 7187-7188.
The O-acylation of cyclic 1 ,3-diones may be effected by procedures similar to those described, for example, by R. Haines, US4175135, and by T. Wheeler, US4422870, US4659372 and US4436666. Typically diones of formula (A) may be treated with an acylating agent preferably in the presence of at least one equivalent of a suitable base, and optionally in the presence of a suitable solvent. The base may be inorganic, such as an alkali metal carbonate or hydroxide, or a metal hydride, or an organic base such as a tertiary amine or metal alkoxide. Examples of suitable inorganic bases include sodium carbonate, sodium or potassium hydroxide, sodium hydride, and suitable organic bases include trialkylamines, such as trimethylamine and triethylamine, pyridines or other amine bases such as 1 ,4-diazobicyclo[2.2.2]octane and 1 ,8- diazabicyclo[5.4.0]undec-7-ene. Preferred bases include triethylamine and pyridine. Suitable solvents for this reaction are selected to be compatible with the reagents and include ethers such as tetrahydrofuran and 1 ,2-dimethoxyethane and halogenated solvents such as dichloromethane and chloroform. Certain bases, such as pyridine and triethylamine, may be employed successfully as both base and solvent. For cases where the acylating agent is a carboxylic acid, acylation is preferably effected in the presence of a known coupling agent such as 2-chloro-1- methylpyridinium iodide, Λ/,Λ/-dicyclohexylcarbodiimide, 1-(3-dimethylaminopropyl)-3- ethylcarbodiimide and Λ/,Λ/-carbodiimidazole, and optionally in the presence of a base such as triethylamine or pyridine in a suitable solvent such as tetrahydrofuran, dichloromethane or acetonitrile. Suitable procedures are described, for example, by W. Zhang and G. Pugh, Tetrahedron Lett., (1999), 40 (43), 7595-7598; T. lsobe and T. Ishikawa, J. Org. Chem., (1999), 64 (19), 6984-6988 and K. Nicolaou et al., (2005), 127(24), 8872-8888.
Phosphorylation of cyclic 1 ,3-diones may be effected using a phosphoryl halide or thiophosphoryl halide and a base by procedures analogous to those described by L. Hodakowski, US4409153. Sulfonylation of a compound of formula (A) may be achieved using an alkyl or aryl sulfonyl halide, preferably in the presence of at least one equivalent of base, for example by the procedure of C. Kowalski and K. Fields, J. Org. Chem., (1981 ), 46, 197-201.
A compound of formula (A), wherein R 6 and R 7 form a bond, may be prepared by the reaction of a compound of formula (B) with a nitrile oxide of formula (C) in a suitable solvent such as dichloromethane, chloroform or toluene.
formula (B) formula (A) wherein R 6 and R 7 form a bond
A nitrile oxide of formula (C) may be prepared by the dehydration of a nitroalkane of formula (D), in the presence of a dehydrating agent such as phenylisocyanate or 1 ,4-phenylene diisocyanate, or by the dehydrohalogenation of a hydroximoyl halide of formula (E), wherein Hal is a halogen (preferably chlorine or bromine) by contact with a suitable base (such as triethylamine or potassium carbonate), according to known procedures (see, for example, V. Jager and I. Mϋller, Tetrahedron (1985), 41 (17), 3519-3528; E. Kantorowski et al., J. Org. Chem., (1998), 63, 5272- 5274; L. Deng and Y. Hu, Synth. Commun. (2007), 37, 157-163).
R ' dehydrohalogenation dehydration
= N
R B — ≡≡N-O " R -NO,
Hal OH formula (D) formula (C) formula (E)
Preferably the nitrile oxide of formula (C) is not isolated, but instead is prepared in the presence of a compound of formula (B), at a suitable temperature (preferably -20 0 C to 100 0 C), and in a suitable solvent such as dichloromethane, chloroform or toluene, according to known procedures.
In a further approach, additional compounds of formula (A) may be prepared from a compound of formula (B) by reaction with a nitrone of formula (F), optionally in the presence of a suitable solvent (such as dichloromethane, chloroform, acetonitrile and toluene), and optionally in the presence of a Lewis acid catalyst such as aluminium chloride, bismuth(lll) chloride, bismuth(lll) trifluoromethanesulfonate, boron trifluoride, cerium(lll) chloride, copper(l) trifluoromethanesulfonate, diethylaluminium chloride, hafnium(IV) chloride, iron(lll) chloride, lithium perchlorate, lithium trifluoromethanesulfonate, magnesium bromide, magnesium iodide, scandium(lll) trifluoromethanesulfonate, tin(IV) chloride, titanium(IV) chloride, titanium(IV) isopropoxide, trimethyl aluminium, Λ/-trimethylsilyl-bis(trifluoromethanesulfonyl)imide, trimethylsilyl trifluoromethane-sulfonate, ytterbium (III) trifluoromethanesulfonate, zinc bromide, zinc iodide and zirconium (IV) chloride.
formula (A)
Nitrones of formula (F) are known compounds, or may be made by known methods from known compounds (see, for example, N. Langlois and F. Rakotondradany, Tetrahedron, (2000), 56, 2437-2448; S. Kang and W. Kim, Synlett., (1991 ), 520; J. Hwu et al., J. Chem. Soα, Perkin. Trans.1 (1989), 1823-1831 ; O. Exner, Coll. Czech. Chem., (1951 ), 16, 258-267). A compound of formula (A) wherein R 6 is H, may be converted into additional compounds of formula (A) by known transformations (for example, acylation according to the procedure of S. Kang and W. Kim, Synlett., (1991 ), 520).
A compound of formula (B) may be prepared from a compound of formula (G), wherein Hal is bromine or iodine, and a compound of formula (H) according to the procedure of K. Saito and H. Yamachika, US4371711.
oxidation
formula (B)
Compounds of formula (G) are known compounds, (see, for example, M. Muehlebach et al., WO08/071405; M. Muehlebach et ai, WO08/1 10308; M. Muehlebach et ai, WO08/110307; M. Feuerstein et ai., Synthesis, (2004), 8, 1281-1289; T. Maetzke et ai., WO01/017972, R. Fischer et al., WO99/43649), or may be made by known methods from known compounds.
The compounds of formula I according to the invention can be used as crop protection agents in unmodified form, as obtained in the synthesis, but they are generally formulated into crop protection compositions in a variety of ways using formulation adjuvants, such as carriers, solvents and surface-active substances. The formulations can be in various physical forms, for example in the form of dusting powders, gels, wettable powders, coated or impregnated granules for manual or mechanical distribution on target sites, water-dispersible granules, water-soluble granules, emulsifiable granules, water-dispersible tablets, effervescent compressed tablets, water-soluble tapes, emulsifiable concentrates, microemulsifiable concentrates, oil-in-water (EW) or water-in-oil (WO) emulsions, other multiphase systems such as oil/water/oil or water/oil/water products, oil flowables, aqueous dispersions, oily dispersions, suspoemulsions, capsule suspensions, soluble liquids, water-soluble concentrates (with water or a water-miscible organic solvent as carrier), impregnated polymer films or in other forms known, for example, from the Manual on Development and Use of FAO Specifications for Plant Protection Products, 5th Edition, 1999. The active ingredient may be incorporated into microfibers or micro-rods formed of polymers or polymerizable monomers and having diameter of about 0.1 to about 50 microns and aspect ratio of between about 10 and about 1000.
Such formulations can either be used directly or are diluted prior to use. They can then be applied through suitable ground or aerial application spray equipment or other ground application equipment such as central pivot irrigation systems or drip/trickle irrigation means.
Diluted formulations can be prepared, for example, with water, liquid fertilisers, micronutrients, biological organisms, oil or solvents.
The formulations can be prepared, for example, by mixing the active ingredient with formulation adjuvants in order to obtain compositions in the form of finely divided solids, granules, solutions, dispersions or emulsions. The active ingredients can also be contained in fine microcapsules consisting of a core and a polymeric shell. Microcapsules usually have a diameter of from 0.1 to 500 microns. They contain active ingredients in an amount of about from 25 to 95 % by weight of the capsule weight. The active ingredients can be present in the form of liquid technical material, in the form of a suitable solution, in the form of fine particles in solid or liquid dispersion or as a monolithic solid. The encapsulating membranes comprise, for example, natural and synthetic gums, cellulose, styrene-butadiene copolymers or other similar suitable membrane forming material, polyacrylonitrile, polyacrylate, polyester, polyamides, polyureas, polyurethane, aminoplast resins or chemically modified starch or other polymers that are known to the person skilled in the art in this connection.
Alternatively it is possible for fine so called "microcapsules" to be formed wherein the active ingredient is present in the form of finely divided particles in a solid matrix of a base substance, but in that case the microcapsule is not encapsulated with a diffusion limiting membrane as outlined in the preceding paragraph.
The active ingredients may be adsorbed on a porous carrier. This may enable the active ingredients to be released into their surroundings in controlled amounts (e.g. slow release). Other forms of controlled release formulations are granules or powders in which the active ingredient is dispersed or dissolved in a solid matrix consisting of a polymer, a wax or a suitable solid substance of lower molecular weight. Suitable polymers are polyvinyl acetates, polystyrenes, polyolefins, polyvinyl alcohols, polyvinyl pyrrolidones, alkylated polyvinyl pyrrolidones, copolymers of polyvinyl pyrrolidones and maleic anhydride and esters and half- esters thereof, chemically modified cellulose esters like carboxymethyl cellulose, methyl cellulose, hydroxyethyl cellulose, examples of suitable waxes are polyethylene wax, oxidized polyethylene wax, ester waxes like montan waxes, waxes of natural origin like camauba wax, candelilla wax, bees wax etc. Other suitable matrix materials for slow release formulations are starch, stearin, lignin.
The formulation adjuvants suitable for the preparation of the compositions according to the invention are known per se.
As liquid carriers there may be used: water, aromatic solvents such as toluene, m-xylene, o- xylene, p-xylene and mixtures thereof, cumene, aromatic hydrocarbon blends with boiling ranges between 140 and 320 0 C known under various trademarks like Solvesso ® , Shellsol A ® , Caromax ® , Hydrosol ® , paraffinic and isoparaffinic carriers such as paraffin oils, mineral oils, de- aromatized hydrocarbon solvents with boiling ranges between 50 and 320 0 C known for instance under the trademark Exxsol ® , non-dearomatized hydrocarbon solvents with boiling ranges between 100 and 320 0 C known under the tradename Varsol ® , isoparaffinic solvents with boiling ranges between 100 and 320 0 C known under tradenames like Isopar ® or Shellsol T ® , hydrocarbons such as cyclohexane, tetrahydronaphthalene (tetralin), decahydronaphthalene, alpha-pinene, d-limonene, hexadecane, isooctane, ester solvents such as ethyl acetate, n//-butyl acetate, amyl acetate, /-bornyl acetate, 2-ethylhexyl acetate, C 6 - Ci 8 alkyl esters of acetic acid known under the tradename Exxate ® , lactic acid ethylester, lactic acid propylester, lactic acid butylester, benzyl benzoate, benzyl lactate, dipropyleneglycol dibenzoate, dialkyl esters of succinic, maleic and fumaric acid and polar solvents like N-methyl pyrrolidone, N-ethyl pyrrolidone, C 3 -Cis-alkyl pyrrolidones, gamma-butyrolactone, dimethylsulfoxide, N,N-dimethyl- formamide, N,N-dimethylacetamide, N,N-dimethyllactamide, C 4 -C 18 fatty acid dimethylamides, benzoic acid dimethylamide, acetonitrile, acetone, methyl ethyl ketone, methyl-isobutyl ketone, isoamyl ketone, 2-heptanone, cyclohexanone, isophorone, methyl isobutenyl ketone (mesityl oxide), acetophenone, ethylene carbonate, propylene carbonate, butylene carbonate, alcoholic solvents and diluents such as methanol, ethanol, propanol, n/iso-butanol, n/iso-pentanol, 2-ethyl hexanol, n-octanol, tetrahydrofurfuryl alkohol, 2-methyl-2,4-pentanediol, 4-hydroxy-4- methyl-2-pentanon, cyclohexanol, benzyl alcohol, ethylene glycol, ethylene glycol butyl ether, ethylene glycol methyl ether, diethylene glycol, diethylene glycol butyl ether, diethylene glycol ethyl ether, diethylene glycol methyl ether, propylene glycol, dipropylene glycol, dipropylene glycol methyl ether and other similar glycol ether solvents based on ethylene glycol, propylene glycol and butylene glycol feedstocks, triethylene glycol, polyethylene glycol (PEG 400), polypropylenglycols with molecular masses of 400 - 4000, glycerol, glycerol acetate, glycerol diacetate, glycerol triacetate, 1 ,4-dioxane, diethylene glycol abietate, chlorobenzene, chlorotoluene, fatty acid esters such as methyl octanoate, isopropyl myristate, methyl laurate, methyl oleate, mixture of Cs-C-io fatty acid methyl esters, rape seed oil methyl and ethyl esters, soy bean oil methyl and ethyl esters, vegetable oils, fatty acids such as oleic acid, linoleic acid, linolenic acid, esters of phosphoric and phosphonic acid such as triethyl phosphate, C 3 -Ci 8 -tris- alkyl phosphates, alkylaryl phosphates, bis-octyl-octyl phosphonates.
Water is generally the carrier of choice for the dilution of the concentrates.
Suitable solid carriers are, for example, talc, titanium dioxide, pyrophyllite clay, silica (fumed or precipated silica and optionally functionalised or treated, for instance silanised), attapulgite clay, kieselguhr, limestone, calcium carbonate, bentonite, calcium montomorillonite, cottonseed husks, wheatmeal, soybean flour, pumice, wood flour, ground walnut shells, lignin and similar materials, as described, for example, in the EPA CFR 180.1001. (c) & (d).
A large number of surface-active substances can advantageously be used both in solid and in liquid formulations, especially in those formulations which can be diluted with a carrier prior to use. Surface-active substances may be anionic, cationic, amphoteric, non-ionic or polymeric and they may be used as emulsifiying, wetting, dispersing or suspending agents or for other purposes. Typical surface-active substances include, for example, salts of alkyl sulfates, such as diethanolammonium lauryl sulphate; Sodium lauryl sulphate, salts of alkylarylsulfonates, such as calcium or sodium dodecylbenzenesulfonate; alkylphenol-alkylene oxide addition products, such as nonylphenol ethoxylates; alcohol-alkylene oxide addition products, such as tridecyl alcohol ethoxylate; soaps, such as sodium stearate; salts of alkylnaphthalenesulfonates, such as sodium dibutylnaphthalenesulfonate; dialkyl esters of sulfosuccinate salts, such as sodium di(2- ethylhexyl)sulfosuccinate; sorbitol esters, such as sorbitol oleate; quaternary amines, such as lauryl trimethylammonium chloride, polyethylene glycol esters of fatty acids, such as polyethylene glycol stearate; block copolymers of ethylene oxide and propylene oxide; and salts of mono- and di-alkyl phosphate esters; and also further substances described e.g. in "McCutcheon's Detergents and Emulsifiers Annual", MC Publishing Corp., Ridgewood, New Jersey, 1981.
Further adjuvants which can usually be used in pesticidal formulations include crystallisation inhibitors, viscosity-modifying substances, suspending agents, dyes, anti-oxidants, foaming agents, light absorbers, mixing aids, anti-foams, complexing agents, neutralising or pH-modifying substances and buffers, corrosion-inhibitors, fragrances, wetting agents, absorption improvers, micronutrients, plasticisers, glidants, lubricants, dispersants, thickeners, anti-freezes, microbiocides, compatibility agents and solubilisers and also liquid and solid fertilisers.
The formulations may also comprise additional active substances, for example further herbicides, herbicide safeners, plant growth regulators, fungicides or insecticides.
The compositions according to the invention can additionally include an additive (commonly referred to as an adjuvant), comprising a mineral oil, an oil of vegetable or animal origin, alkyl esters of such oils or mixtures of such oils and oil derivatives. The amount of oil additive used in the composition according to the invention is generally from 0.01 to 10 %, based on the spray mixture. For example, the oil additive can be added to the spray tank in the desired concentration after the spray mixture has been prepared. Preferred oil additives comprise mineral oils or an oil of vegetable origin, for example rapeseed oil, olive oil or sunflower oil, emulsifiable vegetable oil, such as AMIGO® (Loveland Products Inc.), alkyl esters of oils of vegetable origin, for example the methyl derivatives, or an oil of animal origin, such as fish oil or beef tallow. A preferred additive contains, for example, as active components essentially 80 % by weight alkyl esters of fish oils and 15 % by weight methylated rapeseed oil, and also 5 % by weight of customary emulsifiers and pH modifiers. Especially preferred oil additives comprise alkyl esters of C8-C 22 fatty acids, especially the methyl derivatives of C 12 -C 1 8 fatty acids, for example the methyl esters of lauric acid, palmitic acid and oleic acid, being important. Those esters are known as methyl laurate (CAS-111-82-0), methyl palmitate (CAS- 112-39-0) and methyl oleate (CAS-112-62-9). A preferred fatty acid methyl ester derivative is AGNIQUE ME 18 RD-F® (Cognis). Those and other oil derivatives are also known from the Compendium of Herbicide Adjuvants, 5th Edition, Southern Illinois University, 2000.
The application and action of the oil additives can be further improved by combining them with surface-active substances, such as non-ionic, anionic, cationic or amphoteric surfactants. Examples of suitable anionic, non-ionic, cationic or amphoteric surfactants are listed on pages 7 and 8 of WO97/34485. Preferred surface-active substances are anionic surfactants of the dodecylbenzylsulfonate type, especially the calcium salts thereof, and also non-ionic surfactants of the fatty alcohol ethoxylate type. Special preference is given to ethoxylated C 12 -C 22 fatty alcohols having a degree of ethoxylation of from 5 to 40. Examples of commercially available surfactants are the Genapol types (Clariant). Also preferred are silicone surfactants, especially polyalkyl-oxide-modified heptamethyltrisiloxanes, which are commercially available e.g. as SILWET L-77®, and also perfluorinated surfactants. The concentration of surface-active substances in relation to the total additive is generally from 1 to 50 % by weight. Examples of oil additives that consist of mixtures of oils or mineral oils or derivatives thereof with surfactants are TURBOCHARGE®, ADIGOR® (both (Syngenta Crop Protection AG), ACTIPRON® (BP Oil UK Limited), AGRI-DEX® (Helena Chemical Company).
The said surface-active substances may also be used in the formulations alone, that is to say without oil additives.
Furthermore, the addition of an organic solvent to the oil additive/surfactant mixture can contribute to a further enhancement of action. Suitable solvents are, for example, SOLVESSO® and AROMATIC® solvents (Exxon Corporation). The concentration of such solvents can be from 10 to 80 % by weight of the total weight. Such oil additives, which may be in admixture with solvents, are described, for example, in US 4 834 908. A commercially available oil additive disclosed therein is known by the name MERGE® (BASF). Further oil additives that are preferred according to the invention are SCORE® and ADIGOR® (both Syngenta Crop Protection AG).
In addition to the oil additives listed above, in order to enhance the activity of the compositions according to the invention it is also possible for formulations of alkylpyrrolidones, (e.g. AGRIMAX® from ISP) to be added to the spray mixture. Formulations of synthetic latices, such as, for example, polyacrylamide, polyvinyl compounds or poly-1-p-menthene (e.g. BOND®, COURIER® or EMERALD®) can also be used.
Such adjuvant oils as described in the preceding paragraphs may be employed as the carrier liquid in which an active compound is dissolved, emulsified or dispersed as appropriate to the physical form of the active compound.
The pesticidal formulations generally contain from 0.1 to 99 % by weight, especially from 0.1 to 95 % by weight, of a compound of formula I and from 1 to 99.9 % by weight of a formulation adjuvant, which preferably includes from 0 to 25 % by weight of a surface-active substance. Whereas commercial products will preferably be formulated as concentrates, the end user will normally employ dilute formulations.
The rate of application of the compounds of formula I may vary within wide limits and depends upon the nature of the soil, the method of application (pre- or post-emergence; seed dressing; application to the seed furrow; no tillage application etc.), the crop plant, the weed or grass to be controlled, the prevailing climatic conditions, and other factors governed by the method of application, the time of application and the target crop. The compounds of formula I according to the invention are generally applied at a rate of 1- 2000 g/ha, preferably 1- 1000 g / ha and most preferably at 1- 500 g / ha.
Preferred formulations have especially the following representative compositions: (% = percent by weight):
Emulsifiable concentrates: active ingredient: 1 to 95 %, preferably 60 to 90 % surface-active agents: 1 to 30 %, preferably 5 to 20 % solvents as liquid carrier: 1 to 80 %, preferably 1 to 35 % Dusts: active ingredient: 0.1 to 10 %, preferably 0.1 to 5 % solid carriers: 99.9 to 90 %, preferably 99.9 to 99 % Suspension concentrates: active ingredient: 5 to 75 %, preferably 10 to 50 % water: 94 to 24 %, preferably 88 to 30 % surface-active agents: 1 to 40 %, preferably 2 to 30 % Wettable powders: active ingredient: 0.5 to 90 %, preferably 1 to 80 % surface-active agents: 0.5 to 20 %, preferably 1 to 15 % solid carriers: 5 to 95 %, preferably 15 to 90 % Granules: active ingredient: 0.1 to 30 %, preferably 0.1 to 15 % solid carriers: 99.5 to 70 %, preferably 97 to 85 %
Waterdispersible granules: active ingredient: 1 to 90 %, preferably 10 to 80 % surface-active agents: 0.5 to 80 %, preferably 5 to 30 % solid carriers: 90 to 10 %, preferably 70 to 30 %
The following Examples further illustrate, but do not limit, the invention.
F1. Emulsifiable concentrates a) b) c) d) active ingredient 5 % 10 % 25 % 50 % calcium dodecylbenzene- sulfonate 6% 8% 6% 8% castor oil polyglycol ether 4 % - 4 % 4 %
(36 mol of ethylene oxide) octylphenol polyglycol ether - 4 % - 2 %
(7-8 mol of ethylene oxide)
NMP - 10% 20% arom. hydrocarbon 85% 68% 65% 16% mixture C9-C12
Emulsions of any desired concentration can be prepared from such concentrates by dilution with water.
F2. Solutions a) b) c) d) active ingredient 5% 10% 50% 90%
1 -methoxy-3-(3-methoxy- propoxy)-propane 40% 50% - polyethylene glycol MW 400 20% 10% - -
NMP - 50% 10% arom. hydrocarbon 35% 30% - - mixture C9-C12
The solutions are suitable for application undiluted or after dilution with water.
F3. Wettable powders a) b) c) d) active ingredient 5% 25% 50% 80% sodium lignosulfonate 4% - 3% - sodium lauryl sulfate 2% 3% - 4% sodium diisobutylnaphthalene- sulfonate - 6% 5% 6% octylphenol polyglycol ether - 1 % 2% -
(7-8 mol of ethylene oxide) highly disperse silicic acid 1 % 3% 5% 10% kaolin 88% 62% 35% _
The active ingredient is thoroughly mixed with the adjuvants and the mixture is thoroughly ground in a suitable mill, yielding wettable powders which can be diluted with water to give suspensions of any desired concentration. F4. Coated granules a) b) c) active ingredient 0.1 % 5% 15 % highly dispersed silica 0.9 % 2% 2 % inorg. carrier 99. 0% 93% 83 %
(diameter 0.1 - 1 mm) e.g. CaCO 3 or SiO 2
The active ingredient is dissolved in methylene chloride, the solution is sprayed onto the carrier and the solvent is subsequently evaporated off in vacuo.
F5. Coated granules a) b) c) active ingredient 0.1 % 5% 15 % polyethylene glycol MW 200 1.0 % 2% 3 % highly dispersed silica 0.9 % 1 % 2 % inorg. carrier 98. 0% 92% 80 %
(diameter 0.1 - 1 mm) e.g. CaCO 3 or SiO 2
The finely ground active ingredient is applied uniformly, in a mixer, to the carrier moistened with polyethylene glycol. Non-dusty coated granules are obtained in this manner.
F6. Extruded granules a) b) c) d) active ingredient 0.1 % 3% 5% 15% sodium lignosulfonate 1.5 % 2% 3% 4% carboxymethylcellulose 1.4 % 2% 2% 2% kaolin 97.0 % 93% 90% 79%
The active ingredient is mixed and ground with the adjuvants and the mixture is moistened with water. The resulting mixture is extruded and then dried in a stream of air.
F7. Water-dispersible granules a) b) c) d) active ingredient 5% 10% 40% 90% sodium lignosulfonate 20% 20% 15% 7% dibutyl naphthalene sulfonate 5% 5% 4% 2%
Gum arabic 2% 1 % 1 % 1 %
Diatomaceous earth 20% 30% 5%
Sodium sulphate 4% 5% kaolin 48 % 30 % 30 %
The active ingredient is mixed and ground with the adjuvants and the mixture is moistened with water. The resulting mixture is extruded and then dried in a stream of air.
F7. Dusts a) b) c) active ingredient 0.1 % 1 % 5 % talcum 39.9 % 49 % 35 % kaolin 60.0 % 50 % 60 %
Ready-to-use dusts are obtained by mixing the active ingredient with the carriers and grinding the mixture in a suitable mill.
F8. Suspension concentrates a) b) c) d) active ingredient 3 % 10 % 25 % 50 % propylene glycol 5 % 5 % 5 % 5 % nonylphenol polyglycol ether - 1 % 2 % -
(15 mol of ethylene oxide) sodium lignosulfonate 3 % 3 % 7 % 6 % heteropolysacharide (Xanthan) 0.2 % 0.2 % 0.2 % 0.2 %
1 ,2-Benzisothiazolin-3-on 0.1 % 0.1 % 0.1 % 0.1 % silicone oil emulsion 0.7 % 0.7 % 0.7 % 0.7 % water 87 % 79 % 62 % 38 %
The finely ground active ingredient is intimately mixed with the adjuvants, yielding a suspension concentrate from which suspensions of any desired concentration can be prepared by dilution with water.
Crops of useful plants in which the compositions according to the invention can be used include especially cereals, in particular wheat and barley, rice, corn, rape, sugarbeet, sugarcane, soybean, cotton, sunflower, peanut and plantation crops.
The term "crops" is to be understood as also including crops that have been rendered tolerant to herbicides or classes of herbicides (for example ALS, GS, EPSPS, PPO and HPPD inhibitors) as a result of conventional methods of breeding or genetic engineering. An example of a crop that has been rendered tolerant e.g. to imidazolinones, such as imazamox, by conventional methods of breeding is Clearfield® summer rape (Canola). Examples of crops that have been rendered tolerant to herbicides by genetic engineering methods include e.g. glyphosate- and glufosinate- resistant maize varieties commercially available under the trade names RoundupReady© and LibertyLink®. The weeds to be controlled may be both monocotyledonous and dicotyledonous weeds, such as, for example, Stellaria, Nasturtium, Agrostis, Digitaria, Avena, Setaria, Sinapis, Lolium, Solanum, Echinochloa, Scirpus, Monochoria, Sagittaria, Bromus, Alopecurus, Sorghum, Rottboellia, Cyperus, Abutilon, Sida, Xanthium, Amaranthus, Chenopodium, Ipomoea, Chrysanthemum, Galium, Viola and Veronica. Control of monocotyledonous weeds, in particular Agrostis, Avena, Setaria, Lolium, Echinochloa, Bromus, Alopecurus and Sorghum is very extensive.
Crops are also to be understood as being those which have been rendered resistant to harmful insects by genetic engineering methods, for example Bt maize (resistant to European corn borer), Bt cotton (resistant to cotton boll weevil) and also Bt potatoes (resistant to Colorado beetle). Examples of Bt maize are the Bt-176 maize hybrids of NK® (Syngenta Seeds). The Bt toxin is a protein that is formed naturally by Bacillus thuringiensis soil bacteria. Examples of toxins and transgenic plants able to synthesise such toxins are described in EP-A-451 878, EP-A-374 753, WO 93/07278, WO 95/34656, WO 03/052073 and EP-A-427 529. Examples of transgenic plants that contain one or more genes which code for an insecticidal resistance and express one or more toxins are KnockOut® (maize), Yield Gard® (maize), NuCOTIN33B® (cotton), Bollgard® (cotton), NewLeaf® (potatoes), NatureGard® and Protexcta®. Plant crops and their seed material can be resistant to herbicides and at the same time also to insect feeding ("stacked" transgenic events). Seed can, for example, have the ability to express an insecticidally active Cry3 protein and at the same time be glyphosate-tolerant. The term "crops" is to be understood as also including crops obtained as a result of conventional methods of breeding or genetic engineering which contain so-called output traits (e.g. improved flavour, storage stability, nutritional content).
Areas under cultivation are to be understood as including land where the crop plants are already growing as well as land intended for the cultivation of those crop plants.
The compounds of formula I according to the invention can also be used in combination with further herbicides. Preferably, in these mixtures, the compound of the formula I is one of those compounds listed in Tables 1 to 30 below. The following mixtures of the compound of formula I are especially important: compound of formula I + acetochlor, compound of formula I + acifluorfen, compound of formula I + acifluorfen-sodium, compound of formula I + aclonifen, compound of formula I + acrolein, compound of formula I + alachlor, compound of formula I + alloxydim, compound of formula I + allyl alcohol, compound of formula I + ametryn, compound of formula I + amicarbazone, compound of formula I + amidosulfuron, compound of formula I + aminopyralid, compound of formula I + amitrole, compound of formula I + ammonium sulfamate, compound of formula I + anilofos, compound of formula I + asulam, compound of formula I + atraton, compound of formula I + atrazine, compound of formula I + azimsulfuron, compound of formula I + BCPC, compound of formula I + beflubutamid, compound of formula I + benazolin, compound of formula I + benfluralin, compound of formula I + benfuresate, compound of formula I + bensulfuron, compound of formula I + bensulfuron-methyl, compound of formula I + bensulide, compound of formula I + bentazone, compound of formula I + benzfendizone, compound of formula I + benzobicyclon, compound of formula I + benzofenap, compound of formula I + bifenox, compound of formula I + bilanafos, compound of formula I + bispyribac, compound of formula I + bispyribac-sodium, compound of formula I + borax, compound of formula I + bromacil, compound of formula I + bromobutide, compound of formula I + bromoxynil, compound of formula I + butachlor, compound of formula I + butafenacil, compound of formula I + butamifos, compound of formula I + butralin, compound of formula I + butroxydim, compound of formula I + butylate, compound of formula I + cacodylic acid, compound of formula I + calcium chlorate, compound of formula I + cafenstrole, compound of formula I + carbetamide, compound of formula I + carfentrazone, compound of formula I + carfentrazone-ethyl, compound of formula I + CDEA, compound of formula I + CEPC, compound of formula I + chlorflurenol, compound of formula I + chlorflurenol-methyl, compound of formula I + chloridazon, compound of formula I + chlorimuron, compound of formula I + chlorimuron-ethyl, compound of formula I + chloroacetic acid, compound of formula I + chlorotoluron, compound of formula I + chlorpropham, compound of formula I + chlorsulfuron, compound of formula I + chlorthal, compound of formula I + chlorthal-dimethyl, compound of formula I + cinidon-ethyl, compound of formula I + cinmethylin, compound of formula I + cinosulfuron, compound of formula I + cisanilide, compound of formula I + clethodim, compound of formula I + clodinafop, compound of formula I + clodinafop-propargyl, compound of formula I + clomazone, compound of formula I + clomeprop, compound of formula I + clopyralid, compound of formula I + cloransulam, compound of formula I + cloransulam-methyl, compound of formula I + CMA, compound of formula I + 4-CPB, compound of formula I + CPMF, compound of formula I + 4-CPP, compound of formula I + CPPC, compound of formula I + cresol, compound of formula I + cumyluron, compound of formula I + cyanamide, compound of formula I + cyanazine, compound of formula I + cycloate, compound of formula I + cyclosulfamuron, compound of formula I + cycloxydim, compound of formula I + cyhalofop, compound of formula I + cyhalofop-butyl, compound of formula I + 2,4-D, compound of formula I + 3,4-DA, compound of formula I + daimuron, compound of formula I + dalapon, compound of formula I + dazomet, compound of formula I + 2,4-DB, compound of formula I + 3,4-DB, compound of formula I + 2,4- DEB, compound of formula I + desmedipham, compound of formula I + dicamba, compound of formula I + dichlobenil, compound of formula I + ortho-dichlorobenzene, compound of formula I + para-dichlorobenzene, compound of formula I + dichlorprop, compound of formula I + dichlorprop-P, compound of formula I + diclofop, compound of formula I + diclofop-methyl, compound of formula I + diclosulam, compound of formula I + difenzoquat, compound of formula I + difenzoquat metilsulfate, compound of formula I + diflufenican, compound of formula I + diflufenzopyr, compound of formula I + dimefuron, compound of formula I + dimepiperate, compound of formula I + dimethachlor, compound of formula I + dimethametryn, compound of formula I + dimethenamid, compound of formula I + dimethenamid-P, compound of formula I + dimethipin, compound of formula I + dimethylarsinic acid, compound of formula I + dinitramine, compound of formula I + dinoterb, compound of formula I + diphenamid, compound of formula I + diquat, compound of formula I + diquat dibromide, compound of formula I + dithiopyr, compound of formula I + diuron, compound of formula I + DNOC, compound of formula I + 3,4-DP, compound of formula I + DSMA, compound of formula I + EBEP, compound of formula I + endothal, compound of formula I + EPTC, compound of formula I + esprocarb, compound of formula I + ethalfluralin, compound of formula I + ethametsulfuron, compound of formula I + ethametsulfuron-methyl, compound of formula I + ethofumesate, compound of formula I + ethoxyfen, compound of formula I + ethoxysulfuron, compound of formula I + etobenzanid, compound of formula I + fenoxaprop-P, compound of formula I + fenoxaprop-P-ethyl, compound of formula I + fentrazamide, compound of formula I + ferrous sulfate, compound of formula I + flamprop-M, compound of formula I + flazasulfuron, compound of formula I + florasulam, compound of formula I + fluazifop, compound of formula I + fluazifop-butyl, compound of formula I + fluazifop-P, compound of formula I + fluazifop-P-butyl, compound of formula I + flucarbazone, compound of formula I + flucarbazone-sodium, compound of formula I + flucetosulfuron, compound of formula I + fluchloralin, compound of formula I + flufenacet, compound of formula I + flufenpyr, compound of formula I + flufenpyr-ethyl, compound of formula I + flumetsulam, compound of formula I + flumiclorac, compound of formula I + flumiclorac-pentyl, compound of formula I + flumioxazin, compound of formula I + fluometuron, compound of formula I + fluoroglycofen, compound of formula I + f I uoroglycof en-ethyl, compound of formula I + flupropanate, compound of formula I + flupyrsulfuron, compound of formula I + flupyrsulfuron- methyl-sodium, compound of formula I + flurenol, compound of formula I + fluridone, compound of formula I + flurochloridone, compound of formula I + fluroxypyr, compound of formula I + flurtamone, compound of formula I + fluthiacet, compound of formula I + fluthiacet-methyl, compound of formula I + fomesafen, compound of formula I + foramsulfuron, compound of formula I + fosamine, compound of formula I + glufosinate, compound of formula I + glufosinate- ammonium, compound of formula I + glyphosate, compound of formula I + halosulfuron, compound of formula I + halosulfuron-methyl, compound of formula I + haloxyfop, compound of formula I + haloxyfop-P, compound of formula I + HC-252, compound of formula I + hexazinone, compound of formula I + imazamethabenz, compound of formula I + imazamethabenz-methyl, compound of formula I + imazamox, compound of formula I + imazapic, compound of formula I + imazapyr, compound of formula I + imazaquin, compound of formula I + imazethapyr, compound of formula I + imazosulfuron, compound of formula I + indanofan, compound of formula I + iodomethane, compound of formula I + iodosulfuron, compound of formula I + iodosulfuron- methyl-sodium, compound of formula I + ioxynil, compound of formula I + isoproturon, compound of formula I + isouron, compound of formula I + isoxaben, compound of formula I + isoxachlortole, compound of formula I + isoxaflutole, compound of formula I + karbutilate, compound of formula I + lactofen, compound of formula I + lenacil, compound of formula I + linuron, compound of formula I + MAA, compound of formula I + MAMA, compound of formula I + MCPA, compound of formula I + MCPA-thioethyl, compound of formula I + MCPB, compound of formula I + mecoprop, compound of formula I + mecoprop-P, compound of formula I + mefenacet, compound of formula I + mefluidide, compound of formula I + mesosulfuron, compound of formula I + mesosulfuron-methyl, compound of formula I + mesotrione, compound of formula I + metam, compound of formula I + metamifop, compound of formula I + metamitron, compound of formula I + metazachlor, compound of formula I + methabenzthiazuron, compound of formula I + methylarsonic acid, compound of formula I + methyldymron, compound of formula I + methyl isothiocyanate, compound of formula I + metobenzuron, compound of formula I + metolachlor, compound of formula I + S-metolachlor, compound of formula I + metosulam, compound of formula I + metoxuron, compound of formula I + metribuzin, compound of formula I + metsulfuron, compound of formula I + metsulfuron-methyl, compound of formula I + MK-616, compound of formula I + molinate, compound of formula I + monolinuron, compound of formula I + MSMA, compound of formula I + naproanilide, compound of formula I + napropamide, compound of formula I + naptalam, compound of formula I + neburon, compound of formula I + nicosulfuron, compound of formula I + nonanoic acid, compound of formula I + norflurazon, compound of formula I + oleic acid (fatty acids), compound of formula I + orbencarb, compound of formula I + orthosulfamuron, compound of formula I + oryzalin, compound of formula I + oxadiargyl, compound of formula I + oxadiazon, compound of formula I + oxasulfuron, compound of formula I + oxaziclomefone, compound of formula I + oxyfluorfen, compound of formula I + paraquat, compound of formula I + paraquat dichloride, compound of formula I + pebulate, compound of formula I + pendimethalin, compound of formula I + penoxsulam, compound of formula I + pentachlorophenol, compound of formula I + pentanochlor, compound of formula I + pentoxazone, compound of formula I + pethoxamid, compound of formula I + petrolium oils, compound of formula I + phenmedipham, compound of formula I + phenmedipham-ethyl, compound of formula I + picloram, compound of formula I + picolinafen, compound of formula I + pinoxaden, compound of formula I + piperophos, compound of formula I + potassium arsenite, compound of formula I + potassium azide, compound of formula I + pretilachlor, compound of formula I + primisulfuron, compound of formula I + primisulfuron-methyl, compound of formula I + prodiamine, compound of formula I + profluazol, compound of formula I + profoxydim, compound of formula I + prometon, compound of formula I + prometryn, compound of formula I + propachlor, compound of formula I + propanil, compound of formula I + propaquizafop, compound of formula I + propazine, compound of formula I + propham, compound of formula I + propisochlor, compound of formula I + propoxycarbazone, compound of formula I + propoxycarbazone-sodium, compound of formula I + propyzamide, compound of formula I + prosulfocarb, compound of formula I + prosulfuron, compound of formula I + pyraclonil, compound of formula I + pyraflufen, compound of formula I + pyraf I uf en-ethyl, compound of formula I + pyrazolynate, compound of formula I + pyrazosulfuron, compound of formula I + pyrazosulfuron-ethyl, compound of formula I + pyrazoxyfen, compound of formula I + pyribenzoxim, compound of formula I + pyributicarb, compound of formula I + pyridafol, compound of formula I + pyridate, compound of formula I + pyriftalid, compound of formula I + pyriminobac, compound of formula I + pyriminobac-methyl, compound of formula I + pyrimisulfan, compound of formula I + pyrithiobac, compound of formula I + pyrithiobac-sodium, compound of formula I + quinclorac, compound of formula I + quinmerac, compound of formula I + quinoclamine, compound of formula I + quizalofop, compound of formula I + quizalofop-P, compound of formula I + rimsulfuron, compound of formula I + sethoxydim, compound of formula I + siduron, compound of formula I + simazine, compound of formula I + simetryn, compound of formula I + SMA, compound of formula I + sodium arsenite, compound of formula I + sodium azide, compound of formula I + sodium chlorate, compound of formula I + sulcotrione, compound of formula I + sulfentrazone, compound of formula I + sulfometuron, compound of formula I + sulfometuron-methyl, compound of formula I + sulfosate, compound of formula I + sulfosulfuron, compound of formula I + sulfuric acid, compound of formula I + tar oils, compound of formula I + 2,3,6-TBA, compound of formula I + TCA, compound of formula I + TCA-sodium, compound of formula I + tebuthiuron, compound of formula I + tepraloxydim, compound of formula I + terbacil, compound of formula I + terbumeton, compound of formula I + terbuthylazine, compound of formula I + terbutryn, compound of formula I + thenylchlor, compound of formula I + thiazopyr, compound of formula I + thifensulfuron, compound of formula I + thifensulfuron-methyl, compound of formula I + thiobencarb, compound of formula I + tiocarbazil, compound of formula I + topramezone, compound of formula I + tralkoxydim, compound of formula I + tri-allate, compound of formula I + triasulfuron, compound of formula I + triaziflam, compound of formula I + tribenuron, compound of formula I + tribenuron-methyl, compound of formula I + tricamba, compound of formula I + triclopyr, compound of formula I + trietazine, compound of formula I + trifloxysulfuron, compound of formula I + trifloxysulfuron-sodium, compound of formula I + trifluralin, compound of formula I + triflusulfuron, compound of formula I + triflusulfuron-methyl, compound of formula I + trihydroxytriazine, compound of formula I + tritosulfuron, compound of formula I + [3-[2-chloro-4-fluoro-5-(1-methyl-6-trifluoromethyl-2,4-diox o-1 , 2,3,4- tetrahydropyrimidin-3-yl)phenoxy]-2-pyridyloxy]acetic acid ethyl ester (CAS RN 353292-31-6), compound of formula I + 4-[(4,5-dihydro-3-methoxy-4-methyl-5-oxo)-1 H-1 ,2,4-triazol-1- ylcarbonylsulfamoyl]-5-methylthiophene-3-carboxylic acid (BAY636), compound of formula I + BAY747 (CAS RN 335104-84-2), compound of formula I + topramezone (CAS RN 210631-68-8), compound of formula I + 4-hydroxy-3-[[2-[(2-methoxyethoxy)methyl]-6-(trifluoromethyl )-3- pyridinyl]carbonyl]-bicyclo[3.2.1]oct-3-en-2-one (CAS RN 352010-68-5), and compound of formula I + 4-hydroxy-3-[[2-(3-methoxypropyl)-6-(difluoromethyl)-3-pyrid inyl]carbonyl]- bicyclo[3.2.1 ]oct-3-en-2-one.
The mixing partners for the compound of formula I may also be in the form of esters or salts, as mentioned e.g. in The Pesticide Manual, 12th Edition (BCPC) 2000.
For applications in cereals, the following mixtures are preferred: compound of formula I + aclonifen, compound of formula I + amidosulfuron, compound of formula I + aminopyralid, compound of formula I + beflubutamid, compound of formula I + benfluralin, compound of formula I + bifenox, compound of formula I + bromoxynil, compound of formula I + butafenacil, compound of formula I + carbetamide, compound of formula I + carfentrazone, compound of formula I + carfentrazone-ethyl, compound of formula I + chlorotoluron, compound of formula I + chlorpropham, compound of formula I + chlorsulfuron, compound of formula I + cinidon-ethyl, compound of formula I + clodinafop, compound of formula I + clodinafop-propargyl, compound of formula I + clopyralid, compound of formula I + 2,4-D, compound of formula I + dicamba, compound of formula I + dichlobenil, compound of formula I + dichlorprop, compound of formula I + diclofop, compound of formula I + diclofop-methyl, compound of formula I + difenzoquat, compound of formula I + difenzoquat metilsulfate, compound of formula I + diflufenican, compound of formula I + diquat, compound of formula I + diquat dibromide, compound of formula I + fenoxaprop-P, compound of formula I + fenoxaprop-P-ethyl, compound of formula I + flamprop-M, compound of formula I + florasulam, compound of formula I + fluazifop-P-butyl, compound of formula I + flucarbazone, compound of formula I + flucarbazone-sodium, compound of formula I + flufenacet, compound of formula I + flupyrsulfuron, compound of formula I + flupyrsulfuron-methyl-sodium, compound of formula I + flurochloridone, compound of formula I + fluroxypyr, compound of formula I + flurtamone, compound of formula I + imazamethabenz- methyl, compound of formula I + imazamox, compound of formula I + iodosulfuron, compound of formula I + iodosulfuron-methyl-sodium, compound of formula I + ioxynil, compound of formula I + isoproturon, compound of formula I + linuron, compound of formula I + MCPA, compound of formula I + mecoprop, compound of formula I + mecoprop-P, compound of formula I + mesosulfuron, compound of formula I + mesosulfuron-methyl, compound of formula I + mesotrione, compound of formula I + metribuzin, compound of formula I + metsulfuron, compound of formula I + metsulfuron-methyl, compound of formula I + pendimethalin, compound of formula I + picolinafen, compound of formula I + pinoxaden, compound of formula I + prodiamine, compound of formula I + propanil, compound of formula I + propoxycarbazone, compound of formula I + propoxycarbazone-sodium, compound of formula I + prosulfocarb, compound of formula I + pyrasulfotole, compound of formula I + pyridate, compound of formula I + pyroxasulfone (KIH-485), compound of formula I + pyroxsulam compound of formula I + sulfosulfuron, compound of formula 1 + tembotrione, compound of formula I + terbutryn, compound of formula I + thifensulfuron, compound of formula I + thiencarbazone, compound of formula I + thifensulfuron-methyl, compound of formula I + topramezone, compound of formula I + tralkoxydim, compound of formula I + tri-allate, compound of formula I + triasulfuron, compound of formula I + tribenuron, compound of formula I + tribenuron-methyl, compound of formula I + trifluralin, compound of formula I + trinexapac-ethyl and compound of formula I + tritosulfuron, where the mixtures comprising a compound of formula (I) + amidosulfuron, compound of formula (I) + aminopyralid, compound of formula (I) + beflubutamid, compound of formula (I) + bromoxynil, compound of formula (I) + carfentrazone, compound of formula (I) + carfentrazone-ethyl, compound of formula (I) + chlorotoluron, compound of formula (I) + chlorsulfuron, compound of formula (I) + clodinafop, compound of formula (I) + clodinafop-propargyl, compound of formula (I) + clopyralid, 2,4-D, compound of formula (I) + dicamba, compound of formula (I) + difenzoquat, compound of formula (I) + difenzoquat metilsulfate, compound of formula (I) + diflufenican, compound of formula (I) + fenoxaprop-P, compound of formula (I) + fenoxaprop-P-ethyl, compound of formula (I) + florasulam, compound of formula (I) + flucarbazone, compound of formula (I) + flucarbazone-sodium, compound of formula (I) + flufenacet, compound of formula (I) + flupyrsulfuron, compound of formula (I) + flupyrsulfuron-methyl-sodium, compound of formula (I) + fluroxypyr, compound of formula (I) + flurtamone, compound of formula (I) + iodosulfuron, compound of formula (I) + iodosulfuron-methyl-sodium, compound of formula (I) + MCPA, compound of formula (I) + mesosulfuron, compound of formula (I) + mesosulfuron-methyl, compound of formula (I) + metsulfuron, compound of formula (I) + metsulfuron-methyl, compound of formula (I) + pendimethalin, compound of formula (I) + picolinafen, compound of formula (I) + pinoxaden, compound of formula (I) + prosulfocarb, compound of formula (I) + pyrasulfotole, compound of formula (I) + pyroxasulfone (KIH-485), compound of formula (I) + pyroxsulam, compound of formula (I) + sulfosulfuron, compound of formula (I) + thifensulfuron, compound of formula (I) + thifensulfuron-methyl, compound of formula (I) + tralkoxydim, compound of formula (I) + triasulfuron, compound of formula (I) + tribenuron, compound of formula (I) + tribenuron-methyl, compound of formula (I) + trifluralin, compound of formula (I) + trinexapac-ethyl and compound of formula (I) + tritosulfuron are particularly preferred.
For applications in rice, the following mixtures are preferred: compound of formula (I) + azimsulfuron, compound of formula (I) + bensulfuron, compound of formula (I) + bensulfuron- methyl, compound of formula (I) + benzobicyclon, compound of formula (I) + benzofenap, compound of formula (I) + bispyribac, compound of formula (I) + bispyribac-sodium, compound of formula (I) + butachlor, compound of formula (I) + cafenstrole, compound of formula (I) + cinosulfuron, compound of formula (I) + clomazone, compound of formula (I) + clomeprop, compound of formula (I) + cyclosulfamuron, compound of formula (I) + cyhalofop, compound of formula (I) + cyhalofop-butyl, compound of formula (I) + 2,4-D, compound of formula (I) + daimuron, compound of formula (I) + dicamba, compound of formula (I) + diquat, compound of formula (I) + diquat dibromide, compound of formula (I) + esprocarb, compound of formula (I) + ethoxysulfuron, compound of formula (I) + fenoxaprop-P, compound of formula (I) + fenoxaprop- P-ethyl, compound of formula (I) + fentrazamide, compound of formula (I) + florasulam, compound of formula (I) + glufosinate-ammonium, compound of formula (I) + glyphosate, compound of formula (I) + halosulfuron, compound of formula (I) + halosulfuron-methyl, compound of formula (I) + imazosulfuron, compound of formula (I) + MCPA, compound of formula (I) + mefenacet, compound of formula (I) + mesotrione, compound of formula (I) + metamifop, compound of formula (I) + metsulfuron, compound of formula (I) + metsulfuron- methyl, compound of formula (I) + n-methyl glyphosate, compound of formula (I) + orthosulfamuron, compound of formula (I) + oryzalin, compound of formula (I) + oxadiargyl, compound of formula (I) + oxadiazon, compound of formula (I) + paraquat dichloride, compound of formula (I) + pendimethalin, compound of formula (I) + penoxsulam, compound of formula (I) + pretilachlor, compound of formula (I) + profoxydim, compound of formula (I) + propanil, compound of formula (I) + pyrazolynate, compound of formula (I) + pyrazosulfuron, compound of formula (I) + pyrazosulfuron-ethyl, compound of formula (I) + pyrazoxyfen, compound of formula (I) + pyribenzoxim, compound of formula (I) + pyriftalid, compound of formula (I) + pyriminobac, compound of formula (I) + pyriminobac-methyl, compound of formula (I) + pyrimisulfan, compound of formula (I) + quinclorac, compound of formula (I) + tefuryltrione, compound of formula (I) + triasulfuron and compound of formula (I) + trinexapac-ethyl, where the mixtures comprising a compound of formula (I) + azimsulfuron, compound of formula (I) + bensulfuron, compound of formula (I) + bensulfuron-methyl, compound of formula (I) + benzobicyclon, compound of formula (I) + benzofenap, compound of formula (I) + bispyribac, compound of formula (I) + bispyribac-sodium, compound of formula (I) + clomazone, compound of formula (I) + clomeprop, compound of formula (I) + cyhalofop, compound of formula (I) + cyhalofop-butyl, compound of formula (I) + 2,4-D, compound of formula (I) + daimuron, compound of formula (I) + dicamba, compound of formula (I) + esprocarb, compound of formula (I) + ethoxysulfuron, compound of formula (I) + fenoxaprop-P, compound of formula (I) + fenoxaprop-P-ethyl, compound of formula (I) + fentrazamide, compound of formula (I) + florasulam, compound of formula (I) + halosulfuron, compound of formula (I) + halosulfuron-methyl, compound of formula (I) + imazosulfuron, compound of formula (I) + MCPA, compound of formula (I) + mefenacet, compound of formula (I) + mesotrione, compound of formula (I) + metsulfuron, compound of formula (I) + metsulfuron-methyl, compound of formula (I) + orthosulfamuron, compound of formula (I) + oxadiargyl, compound of formula (I) + oxadiazon, compound of formula (I) + pendimethalin, compound of formula (I) + penoxsulam, compound of formula (I) + pretilachlor, compound of formula (I) + pyrazolynate, compound of formula (I) + pyrazosulfuron, compound of formula (I) + pyrazosulfuron-ethyl, compound of formula (I) + pyrazoxyfen, compound of formula (I) + pyribenzoxim, compound of formula (I) + pyriftalid, compound of formula (I) + pyriminobac, compound of formula (I) + pyriminobac-methyl, compound of formula (I) + pyrimisulfan, compound of formula (I) + quinclorac, compound of formula (I) + tefuryltrione, compound of formula (I) + triasulfuron and compound of formula (I) + trinexapac-ethyl are particularly preferred.
The compounds of formula I according to the invention can also be used in combination with safeners. Preferably, in these mixtures, the compound of the formula I is one of those compounds listed in Tables 1 to 30 below. The following mixtures with safeners, especially, come into consideration: compound of formula I + cloquintocet-mexyl, compound of formula I + cloquintocet acid and salts thereof, compound of formula I + fenchlorazole-ethyl, compound of formula I + fenchlorazole acid and salts thereof, compound of formula I + mefenpyr-diethyl, compound of formula I + mefenpyr diacid, compound of formula I + isoxad if en-ethyl, compound of formula I + isoxadifen acid, compound of formula I + furilazole, compound of formula I + furilazole R isomer, compound of formula (I) + N-(2-methoxybenzoyl)-4-[(methylaminocarbonyl)amino]benzenesu lfonamide, compound of formula I + benoxacor, compound of formula I + dichlormid, compound of formula I + AD-67, compound of formula I + oxabetrinil, compound of formula I + cyometrinil, compound of formula I + cyometrinil Z-isomer, compound of formula I + fenclorim, compound of formula I + cyprosulfamide, compound of formula I + naphthalic anhydride, compound of formula I + flurazole, compound of formula I + CL 304,415, compound of formula I + dicyclonon, compound of formula I + fluxofenim, compound of formula I + DKA-24, compound of formula I + R-29148 and compound of formula I + PPG-1292. A safening effect can also be observed for the mixtures compound of the formula I + dymron, compound of the formula I + MCPA, compound of the formula I + mecoprop and compound of the formula I + mecoprop-P.
Benoxacor, cloquintocet-mexyl, cyprosulfamide, mefenpyr-diethyl and N-(2-methoxybenzoyl)-4- [(methylaminocarbonyl)amino]benzenesulfonamide are especially preferred, where cloquintocet- mexyl is particularly valuable.
The above-mentioned safeners and herbicides are described, for example, in the Pesticide Manual, Twelfth Edition, British Crop Protection Council, 2000. R-29148 is described, for example by P. B. Goldsbrough et al., Plant Physiology, (2002), Vol. 130 pp. 1497-1505 and references therein, PPG-1292 is known from WO09211761 and N-(2-methoxybenzoyl)-4- [(methylaminocarbonyl)amino]benzenesulfonamide is known from EP365484.
The rate of application of safener relative to the herbicide is largely dependent upon the mode of application. In the case of field treatment, generally from 0.001 to 5.0 kg of safener/ha, preferably from 0.001 to 0.5 kg of safener/ha, and generally from 0.001 to 2 kg of herbicide/ha, but preferably from 0.005 to 1 kg/ha, are applied.
The herbicidal compositions according to the invention are suitable for all methods of application customary in agriculture, such as, for example, pre-emergence application, post-emergence application and seed dressing. Depending upon the intended use, the safeners can be used for pretreating the seed material of the crop plant (dressing the seed or seedlings) or introduced into the soil before or after sowing, followed by the application of the (unsafened) compound of the formula (I), optionally in combination with a co-herbicide. It can, however, also be applied alone or together with the herbicide before or after emergence of the plants. The treatment of the plants or the seed material with the safener can therefore take place in principle independently of the time of application of the herbicide. The treatment of the plant by simultaneous application of herbicide and safener (e.g. in the form of a tank mixture) is generally preferred. The rate of application of safener relative to herbicide is largely dependent upon the mode of application. In the case of field treatment, generally from 0.001 to 5.0 kg of safener/ha, preferably from 0.001 to 0.5 kg of safener/ha, are applied. In the case of seed dressing, generally from 0.001 to 10 g of safener/kg of seed, preferably from 0.05 to 2 g of safener/kg of seed, are applied. When the safener is applied in liquid form, with seed soaking, shortly before sowing, it is advantageous to use safener solutions which contain the active ingredient in a concentration of from 1 to 10 000 ppm, preferably from 100 to 1000 ppm.
It is preferred to apply the other herbicide together with one of the safeners mentioned above. The following Examples illustrate the invention further but do not limit the invention.
Preparation Examples:
Those skilled in the art will appreciate that certain compounds described below are β-ketoenols, and as such may exist as a single tautomer or as a mixture of keto-enol and diketone tautomers, as described, for example by J. March, Advanced Organic Chemistry, third edition, John Wiley and Sons. The compounds shown below, and in Table T1 are drawn in the diketone form, but it should be inferred that this description covers both the diketone form and any possible enols which could arise through tautomerism. Where more than one tautomer is observed in proton NMR, the data shown are for the mixture of tautomers. Furthermore, some of the compounds shown below are drawn as single enantiomers for the purposes of simplicity, but unless specified as single enantiomers, these structures should be construed as representing a mixture of enantiomers. Additionally, some of the compounds can exist as diastereoisomers, and it should be inferred that these can be present as a mixture of diastereoisomers or as any possible single diastereoisomer. Within the detailed experimental section the diketone tautomer is chosen for naming purposes, even if the predominant tautomer is the enol form.
Example 1 : Preparation of (3aS * ,6aR * )-5-(4'-chloro-4-ethylbiphen-3-yl)-2,3,3-trimethyl-3a, 6a- tetrahvdrocvclopentard1isoxazole-4,6-dione.
Step 1 : Preparation of (4'-chloro-4-ethylbiphen-3-yl)furan-2-ylmethanol.
About 10 ml of a solution of 3-bromo-4'-chloro-4-ethylbiphenyl (40.0 g, 135.3 mmol) in tetrahydrofuran (200 ml) is added to magnesium turnings in a dry flask, followed by a crystal of iodine. The mixture is allowed to stand without stirring for 30 minutes, then stirred once and warmed until the orange coloured mixture becomes colourless. The remainder of the solution of 3-bromo-4'-chloro-4-ethylbiphenyl in tetrahydrofuran is added dropwise over 30 minutes with external heating applied as necessary to maintain the mixture at gentle reflux. Once the addition is complete, the mixture is heated to reflux for 2-3 hours, until only trace residues of magnesium remain. The mixture is cooled to room temperature, and then cooled further in an ice-bath. A solution of 2-furaldehyde (13.05 g, 135.8 mmol) in tetrahydrofuran (80 ml) is added dropwise over 35 minutes, and the mixture is stirred at room temperature overnight.
A second batch of material is prepared in the same way, using identical quantities of reagents and solvents, before the two batches are treated according to the procedure below.
A solution of saturated aqueous ammonium chloride (500 ml) is added to each of the mixtures prepared above, the mixtures are combined, stirred vigorously, and then allowed to stand. The two phases are separated, and the aqueous phase is extracted with ethyl acetate. The organic extracts are combined, washed with brine, dried over anhydrous magnesium sulfate, filtered and the filtrate is evaporated under reduced pressure. The residue is purified by column chromatography on silica gel to give (4'-chloro-4-ethylbiphen-3-yl)furan-2-ylmethanol (67.18 g) as a yellow oil. Step 2: Preparation of 5-(4'-chloro-4-ethylbiphen-3-yl)-4-hydroxycyclopent-2-enone.
A solution of (4'-chloro-4-ethylbiphen-3-yl)furan-2-ylmethanol (67.18 g, 214.8 mmol) in acetone (1340 ml) and water (235 ml) is heated to 55 0 C and 30 drops of polyphosphoric acid are added. The mixture is stirred at 55 0 C for 25 hours, then cooled to room temperature. The reaction mixture is concentrated under reduced pressure to remove most of the acetone then ethyl acetate (600 ml) is added, and the reaction mixture is partitioned. The aqueous phase is extracted into ethyl acetate and the organic solutions are combined, washed with saturated aqueous sodium bicarbonate solution and brine, dried over anhydrous magnesium sulfate, filtered and the filtrate is concentrated under reduced pressure. The residue is purified by column chromatography on silica gel to give 5-(4'-chloro-4-ethylbiphen-3-yl)-4-hydroxy-cyclopent-2-enone (59.84 g) as a brown oil.
Step 3: Preparation of 2-(4'-chloro-4-ethylbiphen-3-yl)cyclopent-4-ene-1 ,3-dione.
A 1.67 molar solution of Jones' reagent is prepared by adding chromium trioxide (72 g, 720 mmol) to an ice-cold mixture of concentrated sulphuric acid (72 ml) and water (360 ml) and stirring until dissolution is complete.
Jones' reagent (126 ml of 1.67 M solution, 210.4 mmol) prepared according to the procedure described above, is added dropwise over 30 minutes to a cooled (ice-bath) solution of 5-(4'- chloro-4-ethylbiphen-3-yl)-4-hydroxycyclopent-2-enone (59.84 g, 191.3 mmol) in acetone (615 ml). The mixture is stirred for 20 minutes, then the cooling bath is removed and the mixture is stirred for 1 hour at room temperature, lsopropanol (500 ml) is added to the yellow slurry and the mixture is stirred at room temperature for 2 hours. The mixture is diluted with ethyl acetate and washed with brine, dried over anhydrous magnesium sulfate, filtered and the filtrate is evaporated under reduced pressure to give 2-(4'-chloro-4-ethylbiphen-3-yl)cyclopent-4-ene-1 ,3-dione (47.94 g) as a yellow solid.
Ste p 4 : P re pa ration of (3aS * ,6aR * )-5-(4'-chloro-4-ethylbiphen-3-yl)-2,3,3-trimethyl-3a, 6a- tetrahydrocyclopenta[d]isoxazole-4,6-dione.
Anhydrous potassium carbonate (400 mg, 2.9 mmol) is added to a solution of N- methylhydroxylamine hydrochloride (120 mg, 3.6 mmol) and 2-(4'-chloro-4-ethylbiphen-3- yl)cyclopent-4-ene-1 ,3-dione (300 mg, 0.97 mmol) in acetone at 4O 0 C. The mixture is stirred and heated at 4O 0 C for 18 hours, then cooled to room temperature. The mixture is partitioned between dichloromethane and dilute aqueous potassium carbonate solution. The organic phase is discarded. The aqueous phase is acidified to pH 1 by addition of 2M aqueous hydrochloric acid, and extracted into dichloromethane. The organic extract is washed with brine, dried over anhydrous magnesium sulfate, filtered and the filtrate is evaporated under reduced pressure. The residue is purified by column chromatography on silica gel to give (3aS*,6aR*)-5-(4'-chloro-4- ethylbiphen-S-yl^.S.S-trimethyl-Sa.δa-tetrahydrocyclo-penta ^lisoxazole^.δ-dione.
Example 2: Preparation of (3aS * ,6aR * )-2,3,3-trimethyl-5-(2,4,6-trimethylphenyl)-3a,6a- tetrahydrocvclopentard1isoxazole-4,6-dione.
Step 1 : Preparation of (2,4, 6-trimethylphenyl)furan-2-ylmethanol.
A solution of 2,4,6-trimethyl-1-bromobenzene (30.9 g,155 mmol) in tetrahydrofuran (100 ml) is added slowly to magnesium turnings (3.77 g, 155 mmol), until the magnesium is just covered. A small quantity of iodine is added and the mixture is allowed to stand at room temperature for 25 minutes and then heated and stirred until the brown colour is lost. The remainder of the aryl bromide solution is added dropwise over a 20 minute period, with occasional heating to maintain the formation of the Grignard reagent solution. The reaction is stirred at room temperature for 1 hour. A solution of furfural (12.8 ml, 155 mmol) in tetrahydrofuran (70 ml) is added dropwise, and once the addition is complete, the reaction is stirred at room temperature for 2 hours. The reaction is quenched by cautious addition of excess saturated ammonium chloride solution, then extracted into ethyl acetate, washed with brine, dried over anhydrous magnesium sulfate, filtered and concentrated under reduced pressure. Purification by column chromatography on silica gel affords (2,4,6-trimethylphenyl)furan-2-ylmethanol.
Step 2: Preparation of 5-(2,4,6-trimethylphenyl)-4-hydroxycyclopent-2-enone.
A solution of (2,4,6-trimethylphenyl)furan-2-ylmethanol (27.8 g, 129 mmol) in acetone (730 ml) and water (100 ml) is heated to 55 0 C and polyphosphoric acid (2 g) is added. The mixture is stirred at 55 0 C for 7 hours, then cooled to room temperature overnight. The reaction mixture is concentrated under reduced pressure to remove most of the acetone then ethyl acetate (500 ml) is added, and the reaction mixture is partitioned. The aqueous phase is extracted into ethyl acetate and the organic solutions are combined, washed with saturated aqueous sodium bicarbonate solution and brine, dried over anhydrous magnesium sulfate, filtered and the filtrate is concentrated under reduced pressure. The residue is purified by column chromatography on silica gel to give 5-(2,4,6-trimethylphenyl)-4-hydroxycyclopent-2-enone.
Step 3: Preparation of 2-(2,4,6-trimethylphenyl)cyclopent-4-ene-1 ,3-dione.
Jones' reagent (138 ml of 1.67 M solution, 230 mmol) is added dropwise over 40 minutes to a cooled (ice-bath) solution of 5-(2,4,6-trimethylphenyl)-4-hydroxycyclopent-2-enone (49.66 g, 230 mmol) in acetone (600 ml). The mixture is stirred for 1 hour, lsopropanol (100 ml) is added and the mixture is stirred at room temperature for 2 hours. The mixture is diluted with ethyl acetate and washed with brine, dried over anhydrous magnesium sulfate, filtered and the filtrate is evaporated under reduced pressure to give 2-(2,4,6-trimethylphenyl)cyclopent-4-ene-1 ,3-dione.
Step 4: Preparation of (3aS * ,6aR * )-2,3,3-trimethyl-5-(2,4,6-trimethylphenyl)-3a,6a- tetrahydrocyclopenta[d]isoxazole-4,6-dione.
A mixture of N-methylhydroxylamine hydrochloride (175 mg, 2.1 mmol), 2-(2,4,6- trimethylphenyl)cyclopent-4-ene-1 ,3-dione (300 mg, 1.4 mmol) and anhydrous potassium carbonate (580 mg, 4.2 mmol) in acetone (10 ml) is stirred at room temperature for 8 days. The reaction mixture is partitioned between dichloromethane and water. The organic phase is discarded. The aqueous phase is acidified to pH 1 using 2M aqueous hydrochloric acid and extracted into dichloromethane. The organic extracts are washed with brine, dried over anhydrous magnesium sulfate, filtered and the filtrate is evaporated under reduced pressure. The residue is purified by column chromatography on silica gel to give (3aS * ,6aR * )-2,3,3-trimethyl-5- (2,4,6-trimethylphenyl)-3a,6a-tetrahydrocyclopenta[d]isoxazo le-4,6-dione.
Example 3: Preparation of (3aS * ,6aR * )-5-(4'-chloro-4-ethylbiphen-3-v)-3-ethyl-3a,6a- dihvdrocvclopentard1isoxazole-4,6-dione.
Triethylamine (4 drops, excess) is added to a mixture of 1 ,4-phenylene diisocyanate (320 mg, 2.0 mmol), 1-nitropropane (0.06 ml, 0.66 mmol) and 2-(4'-chloro-4-ethylbiphen-3-yl)cyclopent-4-ene- 1 ,3-dione (200 mg, 0.64 mmol) in tetrahydrofuran (7 ml) under an atmosphere of nitrogen. The reaction mixture is heated to reflux for 22 hours then cooled to room temperature and diluted with dichloromethane. The mixture is stirred for 1 hour, then water (1 ml) is added and the mixture stirred for an additional 1 hour. The precipitate is removed by filtration and the filtrate is dried over anhydrous magnesium sulfate, filtered and the filtrate is concentrated under reduced pressure. The residue is purified by column chromatography on silica gel to give (3aS * ,6aR * )-5- (4'-chloro-4-ethylbiphen-3-y)-3-ethyl-3a,6a-dihydrocyclopent a[d]isoxazole-4,6-dione.
Additional compounds in Table T1 below were prepared by similar methods using appropriate starting materials.
It should be noted that certain compounds of the invention exist as a mixture of isomers noted above, under the conditions used to obtain the 1 H NMR data. Where this has occurred, the characterising data are reported for all isomers present at ambient temperature in the specified solvent. Unless otherwise stated, proton NMR spectra were recorded at ambient temperature.
Compounds characterised by HPLC-MS were analysed using a Waters 2795 HPLC equipped with a Waters Atlantis dC18 column (column length 20 mm, internal diameter of column 3 mm, particle size 3 micron, temperature 40 0 C), Waters photodiode array and Micromass ZQ2000. The analysis was conducted using a three minute run time, according to the following gradient table:
Solvent A: H 2 O containing 0.1 % HCOOH Solvent B: CH 3 CN containing 0.1 % HCOOH
The characteristic values obtained for each compound were the retention time (rt, recorded in minutes) and the molecular ion (typically the cation MH + ), as listed in Table T1.
Table T1
physical
s), 7.14 br. s), 1.15
H, d), (1 H, br. H, br.
The compounds of the following Tables 1 to 30 can be obtained in an analogous manner.
Table 1 covers compounds of the following type
,1 wherein R , R , R and R are as defined in Table 1.
Table 1
Table 2 covers compounds of the following type
wherein R 1 , R 2 , R 3 and R 4 are as defined in Table 1.
Table 3 covers compounds of the following type
wherein R 1 , R 2 , R 3 and R 4 are as defined in Table 1. Table 4 covers compounds of the following type
wherein R 1 , R 2 , R 3 and R 4 are as defined in Table 1. Table 5 covers compounds of the following type wherein R 1 , R 2 , R 3 and R 4 are as defined in Table 1. Table 6 covers compounds of the following type
,1 wherein R', R^, R ό and R 4 are as defined in Table 1. Table 7 covers compounds of the following type
wherein R 1 , R 2 , R 3 and R 4 are as defined in Table 1.
Table 8 covers compounds of the following type
wherein R 1 , R 2 , R 3 and R 4 are as defined in Table 1. Table 9 covers compounds of the following type
Table 10 covers compounds of the following type
Table 1 1 covers compounds of the following type
wherein R 1 , R 2 , R 3 and R 4 are as defined in Table 1. Table 12 covers compounds of the following type
wherein R 1 , R 2 , R 3 and R 4 are as defined in Table 1.
Table 13 covers compounds of the following type
wherein R 1 , R 2 , R 3 and R 4 are as defined in Table 1. Table 14 covers compounds of the following type
wherein R 1 , R 2 , R 3 and R 4 are as defined in Table 1. Table 15 covers compounds of the following type
wherein R 1 , R 2 , R 3 and R 4 are as defined in Table 1. Table 16 covers compounds of the following type
wherein R 1 , R 2 , R 3 and R 4 are as defined in Table 1. Table 17 covers compounds of the following type
wherein R 1 , R 2 , R 3 and R 4 are as defined in Table 1. Table 18 covers compounds of the following type
wherein R 1 , R 2 , R 3 and R 4 are as defined in Table 1. Table 19 covers compounds of the following type
wherein R 1 , R 2 , R 3 and R 4 are as defined in Table 1. Table 20 covers compounds of the following type
wherein R 1 , R 2 , R 3 and R 4 are as defined in Table 1. Table 21 covers compounds of the following type
Table 22 covers compounds of the following type
Table 23 covers compounds of the following type
wherein R 1 , R 2 , R 3 and R 4 are as defined in Table 1. Table 24 covers compounds of the following type
wherein R 1 , R 2 , R 3 and R 4 are as defined in Table 1. Table 25 covers compounds of the following type wherein R 1 , R 2 , R 3 and R 4 are as defined in Table 1. Table 26 covers compounds of the following type
wherein R 1 , R 2 , R 3 and R 4 are as defined in Table 1. Table 27 covers compounds of the following type
wherein R 1 , R 2 , R 3 and R 4 are as defined in Table 1. Table 28 covers compounds of the following type
wherein R 1 , R 2 , R 3 and R 4 are as defined in Table 1. Table 29 covers compounds of the following type
wherein R 1 , R 2 , R 3 and R 4 are as defined in Table 1. Table 30 covers compounds of the following type wherein R 1 , R 2 , R 3 and R 4 are as defined in Table 1.
Biological Examples Test Example 1
Seeds of a variety of test species were sown in standard soil in pots. After cultivation for one day (pre-emergence) or after 8 days cultivation (post-emergence) under controlled conditions in a glasshouse (at 24/16 0 C, day/night; 14 hours light; 65 % humidity), the plants were sprayed with an aqueous spray solution derived from the formulation of the technical active ingredient in acetone / water (50:50) solution containing 0.5% Tween 20 (polyoxyethelyene sorbitan monolaurate, CAS RN 9005-64-5). The test plants were then grown in a glasshouse under controlled conditions in a glasshouse (at 24/16 0 C, day/night; 14 hours light; 65 % humidity) and watered twice daily. After 13 days for pre and post-emergence, the test was evaluated (100 = total damage to plant; 0 = no damage to plant).
Test plants:
Amaranthus retroflexus (AMARE), Setaria faberi (SETFA), Alopecurus myosuroides (ALOMY),
Echinochloa crus-galli (ECHCG), and Avena fatua (AVEFA)
Pre-Emergence Activity
Post-Emergence Activity
Next Patent: POINT-FASTENED ADHESIVE BOND AND METHOD FOR PRODUCING AN ADHESIVE BOND