This invention relates to certain novel substituted furanyloxy-and thienyloxyazines, to the preparation of such compounds, to herbicidal compositions containing such compounds, and to a method of combating undesired plant growth using such compounds.

Pyridines, pyrimidines and their derivatives have many uses in the pharmaceutical area as well as in agriculture (herbicides, fungicides, acaricides, anthelmintics, bird repellents), as reagents, intermediates and chemicals for the polymer and textile industry.

Selective herbicides the active ingredients of which are pyridine derivatives, and particularly 2,6-substituted pyridines, are known from EP0572093, EP0692474 and WO 94/22833.

The European patent application EP0693490 discloses 2-phenyloxy- 6-thienylmethyloxypyridines.

The European patent application EP 0694538 discloses herbicidal 2- benzyloxy-4-phenoxypyrimidines.

Herbicidal 2,6-disubstituted pyridines and 2,4-disubstituted pyrimidines are described in EP 0 723 960. Said compounds contain a heteroaryloxy group in the 2 or 6 position wherein the heteroaryl moiety contains at least one nitrogen atom.

The European patent application EP 0 447 004 discloses similar 6- phenyloxypyrid-2-carboxamides.

Although many of these disclosed pyridine and pyrimidine compounds demonstrate efficacious control of a variety of weeds, said compounds are not completely satisfactory with regard to crop selectivity and consequently may have limited application in agricultural practice.

However, disubstituted pyridine and pyrimidine derivatives containing a furanyloxy or thienyloxy group have not yet been described.

It has now been found that the furanyl-and thienyloxyazine compounds of the present invention are particularly useful as crop- selective herbicidal agents.

The compounds according to the present invention combine high herbicidal activity with the necessary selectivity and enhanced soil degradation.

SUMMARY OF THE INVENTION We have now found that, surprisingly, furanyl-and thienyloxyazines show excellent herbicidal activity at low dosages combined with higher selectivity in crops than those disclosed in the aforementioned patent applications.

Accordingly, the present invention provides novel compounds of the general formula I

R'each independently represent a halogen atom; an optionally substituted alkyl, alkenyl, alkynyl, alkoxy, alkoxyalkyl, alkoxyalkoxy, alkoxycarbonyl, alkanoyloxy or are group; a haloalkyl, haloalkoxy, formyl, cyano or SF5 group; a-S (O) P-R3 group, in which p is 0,1 or 2, and R3 represents an alkyl or haloalkyl group;-NR4R5, in which R4 and R5 each independently represent a hydrogen atom, an alkyl, alkenyl, aralkyl or aryl group; Y'and Y2each independently represent O or S; one of the groups X', X2 and X3 represents N or CR2 and the others represent CR2, in which R each independently represent a hydrogen atom, a nitro group or has the meaning given for R'; R represents an organic radical which is bonded directly or via an oxy, mercapto, carbamoyl, thiocarbamoyl, imidoyl or thioimidoyl group; and m is 0 or an integer from 1 to 3.

The compounds show excellent selective herbicidal activity in certain crops, such as maize and rice, and enhanced soil degradation.

The present invention also provides a compound of formula IIIA wherein R'is as defined hereinabove for formula 1.

It is another object of the invention to provide methods for controlling undesired plant growth by contacting said plants with a herbicidally effective amount of the new compounds.

Further provided are selective herbicidal compositions and methods for the control of monocotyledenous and dicotyledenous plant species and processes to prepare herbicidal compounds of formula I employing the intermediate of formula IIIA.

Those and other objects and features of the invention will become more apparent from the detailed description set forth hereinbelow.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Improved crop production methods and new, effective herbicidal agents are continually being sought by agriculturalists around the world.

Surprisingly, the formula I furanyloxy and thienyloxy compounds of the invention demonstrate excellent control of a wide variety of monocotyledenous and dicotyledenous weeds. Advantageously, the formula I compounds of the invention also demonstrate crop selectivity, particularly cereal crop selectivity, and especially corn selectivity.

Generally, if any of the above mentioned moieties comprises an alkyl, alkenyl or alkynyl group, such groups, unless otherwise specified, may be linear or branched and may contain 1 to 6, preferably 1 to 4, carbon atoms. Examples of such groups are methyl, ethyl, propyl, vinyl, allyl, propargyl, isopropyl, butyl, isobutyl and tertiary-butyl groups. The alkyl portion of a haloalkyl, haloalkoxy, haloalkylthio, alkylthio or alkoxy group suitably has from 1 to 4 carbon atoms, preferably 1 or 2 carbon atoms. The number of carbon atoms in the alkoxyalkyl, alkoxyalkoxy or dialkoxyalkyl groups is up to 6, preferably up to 4, e. g. methoxymethyl, methoxymethoxy, methoxyethyl, ethoxymethyl, ethoxyethoxy, dimethoxymethyl.

"Halogen"means a fluorine, chlorine, bromine or iodine atom, preferably fluorine, chlorine or bromine. Haloalkyl moieties of any groups within the definitions used herein and as such can contain one or more halogen atoms, preferably an alkyl group of formula CH2, 111, wherein from 1 to 2n +1 hydrogen atoms are replace by a halogen atom, preferably a fluorine atom. Haloalkyl, haloalkoxy and haloalkylthio are preferably mono-, di-, tri-or perfluoroalkyl,-alkoxy and-alkylthio, especially trifluoromethyl, chlorodifluoromethyl, pentafluoroethyl, trifluoromethoxy, difluoromethoxy, difluoromethylthio, trifluoromethylthio, 2,2,2-trifluoroethyl, 1,1,1-trifluoroprop-2-yl or 2,2,2-trifluoroethoxy groups.

R preferably represents a group of formula-Z-B, wherein Z represents-O-,-S-,-OCH2-,-SCH2-,-CO-NR'5-,-CS-NR'8-,-C (OR'5) =N-,-

C (SR'5) =N- or a single bond, in which R'8 represents preferably a hydrogen atom or an optionally substituted alkyl group, and B represents an optionally substituted aryl group or an optionally substituted 5-or-6- membered heteroaryl group. In the event that Z represents a simple bond B is preferably an optionally substituted phenyl group. In the event that Z represents a carboxamide group of

formula-CO-NR'8-, B may also represent an optionally substituted<BR> <BR> <BR> <BR> <BR> aralkyl, alkyl, cycloalkyl, cycloalkylalkyl, heterocyclyl, alkenyl, alkynyl, alkoxy, alkenyloxy, alkynyloxy, alkoxyalkyl, alkoxyalkoxy, alkylcarbonyl, alkoxycarbonyl or a haloalkyl, ahaloalkoxy or haloalkyithio group; or B and R18 together with the interjacent nitrogen atom form a nitrogen containing heterocyclic ring.

An aryl group as substituent or part of other substituents is suitably an optionally substituted phenyl or naphthyl group. An heteroaryl group as substituent or part of other substituents is suitably an optionally substituted 5-or 6-membered heterocyclus containing one or more heteroatoms selected from nitrogen, oxygen and sulfur, at least 1 oxygen, 1 sulfur atom or 1 to 3 nitrogen atoms being preferred. Examples of such groups are thienyl, furanyl, pyrazolyl, imidazolyl, triazolyl, tetrazolyl, thiazolyl, pyridyl, pyrazinyl, pyrimidyl, pyridazinyl, and triazinyl groups. 5- or 6-membered heterocycles may be fused with a benzene ring.

"Aryl"and"heteroaryl"preferably represent a phenyl, pyridyl, thienyl or pyrazolyl group being substituted by one or more of the same or different substituents selected from halogen atoms, alkyl groups, alkoxy groups, cyano groups, haloalkyl groups, haloalkoxy groups, alkylthio groups, haloalkylthio groups and SFs groups.

When any groups are designated as being optionally substituted, the substituent groups which are optionally present may be any of those customarily employed in the modification and/or development of pesticidal compounds and are especially substituents that maintain or enhance the herbicidal activity associated with the compounds of the present invention, or influence persistence of action, soil or plant penetration, or any other desirable property of such herbicidal compounds.

There may be one or more of the same or different substituents present in each part of the molecules. In relation to moieties defined above as comprising an optionally substituted alkyl group, including alkyl parts of haloalkyl, alkoxy, alkylthio, haloalkoxy, alkylamino and

dialkylamino groups, specific examples of such substituents include phenyl, halogen atoms, nitro, cyano, hydroxyl, C1-4-alkoxy, C1-4-haloalkoxy and groups.

In relation to moieties defined above as comprising an optionally substituted aryl or heteroaryl group, optional substituents include halogen, especially fluorine, chlorine and bromine atoms, and nitro, cyano, amino, hydroxy, phenoxy, C1-4-haloalkyl,C1-4-haloalkenyl,C1-4-alkoxy, C1-4-alkylsulfonylandhalosulfanylC1-4-haloalkoxy,C1-4-haloal kylthio, groups such as SFS. In the case of phenyl-groups 1 to 5 substituents may suitably be employed, in the case of thienyl-groups 1 to 3 substituents may suitably be employed, 1 or 2 substituents being preferred.

Typically haloalkyl, haloalkoxy and haloalkylthio groups are trifluoromethyl, pentafluoroethyl, 2,2,2-trifluoroethyl, 1,1,1-trifluoroprop-2- yl, trifluoromethoxy, difluoromethoxy, 2,2,2-trifluoroethoxy and trifluoromethylthio groups.

R'is preferably a halogen atom, a C1-C6alkyl group optionally substituted with one or more halogen atoms, C,-C4alkoxy, C,-C4haloalkoxy, C,-C4alkoxycarbonyl, OH, CN, NO2, CX'R9, R'°SO,, or phenyl groups, a C2-C6alkenyl group optionally substituted with one or more halogen atoms, C,-C4alkoxy, C,-C4haloalkoxy, C,-C4alkoxycarbonyl, OH, CN, NO2, CX'R9, R'°SO,, or phenyl groups, a C3-C6alkynyl group optionally substituted with one or more halogen atoms, C,-C4alkoxy, C,-C4haloalkoxy, C,-C4alkoxycarbonyl, OH, CN, R10SOz,orphenylgroups,NO2,CX'R9, a C,-C6alkoxy group optionally substituted with one or more halogen atoms, C,-C4alkoxy, C,-C4haloalkoxy, C,-C4alkoxycarbonyl, OH, CN, R10SOz,orphenylgroups,NO2,CX'R9; a phenyl group optionally substituted with one or more halogen atoms, C,-C4alkoxy, C,-C4haloalkoxy, C,-C4alkoxycarbonyl, OH, CN, R10SOz,orphenylgroups,orNO2,CX'R9,

a R'°S (O) y, N11R12, NO2, CN, CX'R9, C02R'3 or OCOR'4group, in which X'is each independently orNNR16R17;NOR15 R9, R'3, R'4 and R'5 are each independently H or C1-C4alkyl optionally substituted with one or more halogen, phenyl or furyl groups; R'°, R", R12, R16 and R17 are each independently H, C,-C4alkyl or C,- C4alkoxy; and y is each independently 0 or an integer of 1 or 2.

R2 is preferably a hydrogen or halogen atom, a C,-Calkyl group optionally substituted with one or more halogen atoms, C,-C4alkoxy, C,-C4haloalkoxy, C,-C4alkoxycarbonyl, OH, CN, NO2, CX'R9, R10SOz, or phenyl groups, a C2-C6alkenyl group optionally substituted with one or more halogen atoms, C1-C4alkoxy, OH,CN,C1-C4alkoxycarbonyl, R10SOz,orphenylgroups,NO2,CX'R9, a C3-C6alkynyl group optionally substituted with one or more halogen atoms, C1-C4alkoxycarbonyl,OH,CN,C1-C4haloalkoxy, NO2, CX'R9, R'°SO,, or phenyl groups, a Ci-Ceaikoxy group optionally substituted with one or more halogen atoms, C1-C4alkoxycarbonyl,OH,CN,C1-C4haloalkoxy, NO2, CX'R9, R'°SO,, or phenyl groups, or a CN,CX'R9,CO2R13orformamidinegroup,inNR11R12, which X'is each independently orNNR16R17;NOR15 R9, R'3, R'4 and R'5 are each independently H or C,-C4alkyl optionally substituted with one or more halogen, phenyl or furyl groups; R'°, R", R'2, R16 and R"are each independently H, C1-C4alkyl or Ci- C4alkoxy, and y is each independently 0 or an integer of 1 or 2.

R3 is preferably a C1-C6alkyl group optionally substituted with one or more halogen atoms, preferably fluorine atoms.

R4 and R5 are each independently preferably a hydrogen atom, a C,- Cgatkyt group, optionally substituted with one or more phenyl groups, a C2- C6alkenyl group or a phenyl group.

Y'is preferably S; y2 is preferably 0; Y2 is preferably attached at the 3-position of the furanyl or thienyl group.

Preferably m is 0,1 or 2, in particular 1. When m is at least 1, one substituent R'is most preferably located at the 5-position.

At least two of the groups X'through X3 represents CR2. Preferably X3orX1,X2andX3denoteCR2.X2and X'is preferably N or CR2, in particular N, CH or CF; and X3 preferably is CR2.

The furanyl or thienyl group may be attached in the 2-or 3-position with respect to the oxygen or sulfur atom. 3-thienyl groups are preferred.

Particularly preferred are the compounds of formula IA. wherein R', R and X1 through X3 have the meaning given hereinabove.

Furthermore preferred are the compounds of formula 11, wherein X'X3, R'and m have the meaning given hereinabove; and B represents an optionally substituted aryl group, an optionally substituted 5-or 6-membered nitrogen-containing heteroaromatic group or an optionally substituted thienyl group, and

Z represents a single bond, an oxygen or sulfur atom or a-OCH2-or- SCH2-group.

In formula I the organic radical R preferably represents a group of formula-Z-B, in which Z represents-O-or-OCH2-and B represents a group selected from the formulae a, b, c or d: wherein R6 and R7 each independently represent a hydrogen atom or halogen atom or an optionally substituted alkyl or alkoxy group, o is 1 or 2 and q is R6 and R7 are each independently preferably a hydrogen atom or halogen atom, a Ci-Cgaikyi group optionally substituted with one or more halogen atoms, C1-C4alkoxy, OH,CN,NO2,C1-C4alkoxycarbonyl, orphenylgroups,orCX'R9,R10SOz, a C,-C6alkoxy group optionally substituted with one or more halogen atoms, C1-C4alkoxycarbonyl,OH,CN,NO2,C1-C4haloalkoxy, CX'R9, R10SOz, or phenyl groups, Particularly preferred are the compounds of formula #A1 wherein B, X'through X3 have the meaning given and Z is-O-or-OCH2-, in particular wherein X3 represents CR2.

The compounds of formula IA1a are most preferred:

wherein either R1 and R2 each independently represent a halogen atom; an optionally substituted alkyl, alkenyl, alkinyl, alkoxy, alkoxyalkyl or alkoxyalkoxy group; a haloalkyl, haloalkoxy, cyano, formyl or SF5 group; a-S (O) p-R3 group, in which p is 0,1 or 2, and R3 represents an alkyl or haloalkyl group;-NR4R5 group, in which R4 and R5 each independently represent a hydrogen atom, an alkyl, alkenyl, aralkyl or aryl group; or R'is as described above and R2 is hydrogen; R6 and R7 each independently represent a hydrogen or halogen atom, or an alkyl or haloalkyl group; R2'represents a hydrogen or fluorine atom; and s is 0 or 1; and q is 1, 2 or 3.

At least one of R6 and R7 preferably represents a hydrogen, if s is 1, or R5 is attached in the 4-position and represents a hydrogen atom, and R7 is attached in the 2-or 3-position and represents a halogen atom or a haloalkyl group, if is s is 0.

Furthermore preferred are the compounds of formula IA1 b wherein R', R2 and R2'have the meaning given above for formula IA1 a ; R6 represents a hydrogen or halogen atom or a haloalkyl group; W represents a N or S atom,

T represents a-CH-,-CH-CH-or a-N (CH3)-group, and s is 0 or 1.

Suitably, R'represents a halogen atom or an optionally substituted alkyl, alkoxy, alkyl thio or cyano group.

Preferably, R'represents an optionally substituted C, 6 alkyl, C, 6 alkoxy or C, 6 alkylthio group which is unsubstituted, or substituted by one or more moieties independently selected from halogen atoms. In particular R'denotes a fluorine or chlorine atom or a methyl, ethyl, iso-propyl or tert- butyl, methoxy, trifluoromethyl, perfluoroethyl, trifluormethoxy, difluoromethoxy, trifluormethylthio or difluoromethylthio group.

Preferably, R'represents a cyano group or a C, 6 alkyl, C, 6 alkoxy or C,-6 alkylthio group which is unsubstituted, or substituted by one or more moieties independently selected from halogen atoms. In particular R2 denotes a fluorine or chlorine atom or a methyl, ethyl, methoxy, methylthio or a cyano group.

The invention is exemplified by the following specific compounds: 2,6-bis- (5-trifluoromethylthien-3-yloxy)-4-methylpyridine, 2- (4- fluorobenzyloxy)-4-methyl-6- (5-trifluoromethylthien-3-yloxy)-pyridine, 2- (3,4-difluorobenzyloxy)-4-methyl-6- (5-trifluoromethylthien-3-yloxy)- pyridine, 2- (2, 4-difluorobenzyloxy)-4-methyl-6- (5-trifluoromethylthien-3- <BR> <BR> yloxy)-pyridine, 4-methyl-2- (3-trifluoromethylphenoxy)-6- (5-<BR> <BR> trifluoromethylthien-3-yloxy)-pyridine, 4-cyano-2- (3, 4-dichlorophenoxy)-6-<BR> <BR> (5-trifluoromethylthien-3-yloxy)-pyridine, 2- (3, 4-dichlorophenoxy)-4- methyl-6- (5-trifluoromethylthien-3-yloxy)-pyridine, 3,5-difluoro-2- (4- <BR> <BR> fluorobenzyloxy)-4-methyl-6- (5-trifluoromethylthien-3-yloxy)-pyridine, 3, 5-<BR> <BR> difluoro-2- (3, 4-difluorophenoxy)-4-methyl-6- (5-trifluoromethylthien-3- yloxy)-pyridine,3,5-difluoro-2- (3-chloro-4-fluorophenoxy)-4-methyl-6- (5- <BR> <BR> trifluoromethylthien-3-yloxy)-pyridine, 2-benzyloxy-4-cyano-6- (5-<BR> <BR> trifluoromethylthien-3-yloxy)-pyridine, 2-benzyloxy-4-methyl-6- (5-<BR> <BR> trifluoromethylthien-3-yloxy)-pyridine, 2- (3-chloro-4-fluorophenoxy)-4-<BR> <BR> methyl-6- (5-trifluoromethylthien-3-yloxy)-pyridine, 4-methyl-2- (thien-2-

ylmethyloxy)-6- (5-trifluoromethylthien-3-yloxy)-pyridine, 2- (2,4- <BR> <BR> difluorobenzyloxy)-4-methoxy-6- (5-trifluoromethylthien-3-yloxy)-pyridine,<BR> <BR> 2- (4-fluorobenzyloxy)-4-methoxy-6- (5-trifluoromethylthien-3-yloxy)- pyridine, 4-methoxy-2- (3-trifluoromethylphenyloxy)-6- (5- trifluoromethylthien-3-yloxy)-pyridine,3,5-difluoro-2-(3-flu orophenoxy)-6- (5-trifluoromethylthien-3-yloxy)-4-methoxypyridine, 2-benzyloxy-3,5- difluoro-6- (5-trifluoromethylthien-3-yloxy)-4-methoxypyridine, 3,5-difluoro- <BR> <BR> 2- (3-chlorophenoxy)-4-methoxy-6- (5-trifluoromethylthien-3-yloxy)-pyridine,<BR> <BR> 2-benzyloxy-4-methoxy-6- (5-trifluoromethylthien-3-yloxy)-pyridine, 2- (3,4- dichlorophenoxy)-4-methoxy-6- (5-trifluoromethylthien-3-yloxy)-pyridine, 2- <BR> <BR> (3-chloro-4-fluorophenoxy)-4-methoxy-6- (5-trifluoromethylthien-3-yloxy)- pyridine, 2- (2, 4-difluorobenzyloxy)-6- (5-trifluoromethylthien-3-yloxy)- pyridine, 2- (4-fluorobenzyloxy)-6- (5-trifluoromethylthien-3-yloxy)-pyridine, <BR> <BR> 2- (3-trifluoromethylphenyloxy)-6- (5-trifluoromethylthien-3-yloxy)-pyridine, 2-(3,4-difluorophenoxy)-3,4,5-trifluoro-6-(5-trifluoromethyl thien-3-yloxy)- pyridine, 2-(3,4-difluoroebnzyloxy)-3,4,5-trifluoro-6-(5-trifluoromelt hylthien- 3-yloxy)-pyridine, 2,4-bis (5-trifluoromethylthienyl-3-oxy)-6- methoxypyrimidine, 2-benzyloxy-6-methoxy-4- (5-trifluoromethylthienyl-3- oxy)-pyrimidine,2-benzylthio-4-methyl-6-(5-trifluoromelthylt hienyl-3-oxy)- pyridine, 4-methyl-2- (3-trifluormethylphenylthio)-6- (5-trifluoromethylthienyl- 3-oxy)-pyridine, 2- (2-chloropyrid-4-yloxy)- 4-methyl-6- (5- <BR> <BR> trifluoromethylthienyl-3-oxy)-pyridine, 2- (2-trifluoromethylpyrid-4-yloxy)-4-<BR> <BR> methyl-6- (5-trifluoromethylthienyl-3-oxy)-pyridine, 2- (2-<BR> <BR> difluoromethoxypyrid-4-yloxy)-4-methyl-6- (5-trifluoromethylthienyl-3-oxy)- pyridine, 4-methyl-2-(1-methyl-3-trifluoromethylpyrazol-5-yloxy)-6-(5- trifluoromethylthienyl-3-oxy)-pyridine; 2,6-bis- (5-trifluoromethylthien-3- <BR> <BR> yloxy)-3,5-difluoro-4-methylpyridine, 2-benzyloxy-3, 5-difluoro-4-methyl-6-<BR> <BR> (5-trifluoromethylthien-3-yloxy)-pyridine, 4-cyano-2- (2-methylbenzyloxy)-6-<BR> <BR> (5-trifluoromethylthien-3-yloxy)-pyridine, 4-cyano-2- (thien-2-ylmethoxy)-6- (5-trifluoromethylthien-3-yloxy)-pyridine, 2,6-bis- (5-trifluoromethylthien-3- yloxy)-3, 5-difluoropyridine, 2-benzyloxy-3, 5-difluoro-6- (5-

trifluoromethylthien-3-yloxy)-pyridine, 2-benzyloxy-4-cyano-3, 5-difluoro-6- (5-trifluoromethylthien-3-yloxy)-pyridine, 2-benzyloxy-4-formyl-6- (5- trifluoromethylthien-3-yloxy)-pyridine, 2,6-bis- (5-trifluoromethylthien-3- <BR> <BR> yloxy)-4-cyanopyridine, 4-cyano-2- (4-fluorobenzyloxy)-6- (5-<BR> <BR> trifluoromethylthien-3-yloxy)-pyridine, 4-cyano-2- (3-fluorobenzyloxy)-6- (5-<BR> <BR> trifluoromethylthien-3-yloxy)-pyridine, 2-benzyloxy-6- (5-<BR> <BR> trifluoromethylthien-3-yloxy)-pyridine, 4-chloro-2- (4-fluorobenzyloxy)-6- (5-<BR> <BR> trifluoromethylthien-3-yloxy)-pyridine, 2-benzyloxy-4-fluoro-6- (5-<BR> <BR> trifluoromethylthien-3-yloxy)-pyridine, 2- (5-chlorothien-2-ylmethyloxy)-6- (5- trifluoromethylthienyl-3-oxy)-4-methylpyridine and 4-cyano-2- (5- fluorothien-2-ylmethoxy)-6- (5-trifluoromethylthienyl-3-oxy)-pyridine.

In formula I the organic radical R preferably represents a group of formula-Z-B, in which Z represents-single bond and B represents a group selected from the formulae c, d or e: wherein R and R7 each independently represent a hydrogen atom or halogen atom or an optionally substituted alkyl or alkoxy group, o is 1 or 2 and q is 1,2,3 or 4.

Particularly preferred are the compounds of formula 12, R', X', R2 y1, y2 and m are as defined in any of claims 1 to 7; n is 0 or an integer from 1 to 5;

R5 each independently represent a halogen atom, a C1-C6alkyl group optionally substituted with one or more halogen atom, C,-C4alkoxy, C,-C4haloalkoxy, C,-C4alkoxycarbonyl, OH, CX'R9, CN, NO2, phenylgroups,R10S(O)yor a C2-C6alkenyl group optionally substituted with one or more halogen atom, C,-C4alkoxy, C,-C4haloalkoxy, C,-C4alkoxycarbonyl, OH, CX'R9, CN, orphenylgroups,NO2,R10S(O)y a C3-C6alkynyl group optionally substituted with one or more halogen atom, C,-C4alkoxy, C,-C4haloalkoxy, C,-C4alkoxycarbonyl, OH, CX'R9, CN, orphenylgroups,NO2,R10S(O)y a C,-C6alkoxy group optionally substituted with one or more halogen atom, C,-C4alkoxy, C,-C4haloalkoxy, C,-C4alkoxycarbonyl, OH, CX'R9, CN, NO2, R10S(O) y or phenyl groups, R'°S (O) y} NR11R12, NO2, CN, CX'R9, CO2R13 or OCOR14 ; X'X'is each independently orNNR16R17;NOR15 R9, R'3, R'4 and R'5 are each independently H or C1-C4alkyl optionally substituted with one or more halogen, phenyl or furyl groups; R'°, R", R'2, R16 and R17 are each independently H, C,-C4alkyl or C,- C4alkoxy; y is each independently 0 or an integer of 1 or 2.

In particular preferred are the compounds of formula IA2 wherein R', R2, R8, X', m and n are as defined hereinabove, in particular wherein m is 1, and R'is attached to the 5-position of the thienyloxy ring; n is 1; and R5 is attached to the 4-position of the phenyl group.

Another group of preferred compounds having the structure of formula 12 are those compounds wherein R1 is C1-C4haloalkyl, C1- C4haloalkylcarbonyl, C,-C4alkylsulfonyl or C,-C4haloalkylsulfonyl,

preferably CF3, COCF3, CF3SO2, CH3SO2, CF2C1 or CHF2; R2 are each independently H, halogen, C,-C4alkoxy or C,-C4alkyl optionally substituted with one or more C,-C4alkoxy groups; and R8 is CF3.

Examples of specific compounds of formula 12 include, but are not limited to: 4-methyl-2-(α,α,α-trifluoro-p-tolyl)-6-{[5-(trifluorometh yl?)-3-thienyl]oxy}- pyrimidine;4-methoxy-2-(α,α,α-trifluoro-p-tolyl)-6-{[5-(t rifluromethyl-3- thienyl] oxy} pyrimidine; 5-ethyl-2- (a, a, α-trifluoro-p-tolyl)-6-{[5- (trifluoromethyl-3-thienyl] oxy} pyrimidine; 4-methyl-6-(α,α,α-trifluoro-p- tolyl)-2- { [5- (trifluoromethyl)-3-thienyl] oxy} pyrimidine; 5-methyl-2-(α,α,α- trifluoro-p-tolyl)-6-{[5-(trfluoromethyl-3-thienyl]oxy} pyrimidine; 5-ethyl-2- (a, a, a-trifluoro-p-tolyl)-6- { [5- (trifluoromethyl-sulfonyl) 3- thienyl] oxy} pyrimidine; 4-ethyl-2- (a, a, a-trifluoro-p-tolyl)-6- { [5- (trifluoro- methyl-3-thienyl] oxy} pyrimidine; 2- (a, a, α-trifluoro-p-tolyl)-6-{[5-(trifluoro- methyl-3-thienyl]oxy}pyrimdine;4-n-propyl-2-(α,α,α-triflu oro-p-toyl)-6-{[5- (trifluoromethyl-3-thienyl]oxy}pyrimidine;4-chloro-5-ethyl-2 -(α,α,α-trfluoro- <BR> <BR> p-tolyl)-6-{[5-(trifluormethyl-3-thienyl]oxy}pyridmidine;4-c hloro-2-(α,α,α- trifluoro-p-tolyl)-6-{[5-(trifluoromethyl-3-thienyl] oxy} pyrimidine; 4- (methoxymelthyl)-2-(α,α,α-trifluoro-p-tolyl)-6-{[5-(trifl uoromethyl-3- thienyl] oxy} pyrimidine; 4-methyl-2- (a, a, α-trifluoro-p-tolyl)-6-{[5-(hydroxy- methyl)-3-thienyl] oxy} pyrimidine; 4-(difluoromethyl)-2-(α,α,α-trifluoro-p- tolyl)-6- { [5- (trifluoromethyl-3-thienyl] oxy} pyrimidine; 4-methyl-6-(α, a, a- trifluoro-p-tolyl)-2- { [5- (trifluoromethyl-3-thienyl] oxy} pyridine; 4-cyano-6- (α,α,α-trifluoro-p-tolyl)-2-{[5-(trifluoromelthyl-3-thien yl]oxy} pyridine; 2- (a, a, a-trifluoro-p-tolyl)-6- { [5- (trifluoromethyl-3-thienyl] oxy} pyridine; 3- methyl-6- (a, a, a-trifluoro-p-tolyl)-2- { [5- (trifluoromethyl-3- thienyl] oxy} pyridine; 3-methyl-6-(α, a, a-trifluoro-p-tolyl)-2- [ (5-formyl-3- thienyl) oxy] pyridine; 4-cyano-6- (a, a, a-trifluoro-p-tolyl)-2- { [5- (methyl- sulfonyl)-3-thienyl] oxy} pyridine; 2- (a, a, a-trifluoro-p-tolyl)-6- { [5- <BR> <BR> (trifluoromelthylsulfonyl)-3-thienyl]oxy}pyridine;5-ethyl-2- (α,α,α-trifluoro-p- tolyl)-6- { [5- (trifluoromethylsulfonyl)-3-thienyl] oxy} pyrimidine; 5-methyl-2-

(a, a, a-trifluoro-p-tolyi)-6- { [5- (methylsulfonyl)-3-thienyl] oxy} pyrimidine; 4- methoxy-2- (a, a, a-trifluoro-p-tolyl)-6- [ (5-formyl-3-thienyl) oxy] pyrimidine; 4- ethyl-2-(α,α,α-trifluoro-p-tolyl)-6-{[5-(methylsulfonyl)- 3- thienyl] oxy} pyrimidine; 4-methyl-2-(α,α,α-trifluoro-p-tolyl)-6-{[5-(trifluoro- methylsulfonyl)-3-thienyl] oxy} pyrimidine; 4-cyano-2- (a, a, a-trifluoro-p-tolyl)- <BR> <BR> <BR> <BR> 6-{[5-(methylsulfonyl)-3-thienyl]oxy}pyrimidine;5-methoxymet hyl-2-(α,α,α- trifluoro-p-tolyl)-6-{[5-(trifluoromethylsulfonyl)-3-thienyl ]oxy}pyrimidine,4- fluoro-2-(awasa-trifluoro-p-tolyl)-6-{[5-(trifluoromethyl)-3 - thienyl] oxy} pyrimidine, 4-methylamino-2- (a, a, a-trifluoro-p-tolyl)-6-{[5- <BR> <BR> <BR> <BR> (trifluoromethyl)-3-thienyl] oxy} pyrimidine, 4-methyl-2-(4-chlorophenyl)-6- {[5-(trifluoromethyl)-3-thienyl] oxy} pyrimidine, 5-methyl-4-fluoro-2-(α, a, a- trifluoro-p-tolyl)-6- { [5- (trifluoromethyl)-3-thienyl] oxy} pyrimidine, 5-methyl-2- (5-chlorophenyl)-6-{[5-(trifluoromelthyl)-3-thienyl]oxy}pyri midine,2-(4- chlorophenyl)-6- { [5- (trifluoromethyl)-3-thienyl] oxy} pyrimidine, 4-methyl-6- (4-chlorophenyl)-2- { [5- (trifluoromethyl)-3-thienyl] oxy} pyridine, 4-methyl-2- (4-tert-butylphenyl)-6-{[5-(trifluoromethyl)-3-thienyl]oxy}p yrimidine,4- methyl-3,5-difluoro-2-(4-trifluoromethylphenyl)-6-{[5-(trifl uoromethyl)-3- thienyl]oxy}pyridine,4-methyl-2-(3-thienyl)-6-{[5-(trifluoro methyl)-3- thienyl] oxy} pyrimidine, 5-methyl-2- (2-thienyl)-6- { [5- (trifluoromethyl)-3- thienyl] oxy} pyrimidine, 2-(5-chloro-2-thienyl)-6-{[5-(trifluoromethyl)-3- thienyl] oxy} pyrimidine, 4-methoxy-2-(5-chloro-3-thienyl)-6-{[5- <BR> <BR> <BR> <BR> (trifluoromethyl)-3-thienyl] oxy} pyrimidine, 4-methyl-2- (5-trifluoromethyl-2-<BR> <BR> <BR> <BR> <BR> <BR> <BR> thienyl)-6- oxy} pyrimidine, 2-(5- trifluoromethyl-3-thienyl)-6-{[5-(trifluoromethyl)-3-thienyl ] oxy} pyrimidine,{[5-(trifluoromethyl)-3-thienyl] oxy} pyrimidine, 4- <BR> <BR> <BR> <BR> methyl-2- (3-thienyl)-6- { [5- (trifluoromethyl)-3-thienyl] oxy} pyridine, and 2- (2-<BR> <BR> <BR> <BR> <BR> <BR> thienyl)-6- { [5- (trifluoromethyl)-3-thienyl] oxylpyridine,.

Furthermore preferred are the compounds of formula 13,

wherein R', R2 and m are as defined hereinabove, and o is 0 or an integer from 1 to 3, R13 and R'9 each independently represent a hydrogen atom or an optionally substituted aryl, aralkyl, alkyl, cycloalkyl, cycloalkylalkyl, heteroaryl, heterocyclyl, alkenyl, alkinyl, alkoxy, alkenyloxy, alkynyloxy, alkoxyalkyl, alkoxyalkoxy, alkylcarbonyl, alkoxycarbonyl or a haloalkyl, haloalkoxy or haloalkylthio group; or a-S (O) P R3 group, in which p is 0,1 or 2 and R3 represents an alkyl or haloalkyl group, or a-NR"R'group, in which R4 and R5 each independently represent a hydrogen atom, an alkyl, alkenyl, aralkyl or aryl group; or R13 and R'9 together with the interjacent nitrogen atom form a nitrogen containing heterocyclic ring; and W represents an oxygen or sulphur atom.

Particularly preferred are the compounds of formula IA3 wherein R', R2, R'8, R'9, W and o are as defined hereinabove.

Most preferred are the compounds of formula IA3a

wherein R1 and R2 are as definedhereinabove and R'9 represents an optionally substituted aryl, alkyl, cycloalkyl or haloalkyl group.

Examples of specific compounds of formula 13 include, but are not limited to: 6- (5-trifluoromethylthien-3-yloxy)-pyrid-2-ylcarboxanilide; 6- (5- trifluoromethylthien-3-yloxy)-pyrid-2-yl N- (4-fluorophenyl) carboxamide; 6- (5-trifluoromethylthien-3-yloxy)-pyrid-2-yl N-(cyclopropyl) carboxamide; 6- (5- trifluormethylthien-3-yloxy)-pyrid-2-ylN-(2,2,2-trifluoroeth yl) carboxamide; 6- (5-trifluoromethylthien-3-yloxy)-pyrid-2-yl N-methyl carboxamide; 6- (5-trifluoromethylthien-3-yloxy)-pyrid-2-yl N-ethyl carboxamide; N-allyl carboxamide; 6- (5-trifluoromethylthien-3-yloxy)-pyrid-2-yl N-propyl carboxamide; 6- (5-trifluoromethylthien-3-yloxy)-pyrid-2-yl N-isopropyl carboxamide; 6- (5-trifluoromethylthien-3-yloxy)-pyrid-2-yi N- (2-fluoroethyl) carboxamide; 6- (5-trifluoromethylthien-3-yloxy)-pyrid-2-yl N- (2,4- difluorophenyl) carboxamide; 6- (5-trifluoromethylthien-3-yloxy)-pyrid-2-yl N- (cyclobutyl) carboxamide; 6-(5-trifluoromethylthien-3-yloxy)-pyrid-2-yl N- (2,2-dichlorocyclopropyl) carboxamide; 6- (5-trifluoromethylthien-3-yloxy)- pyrid-2-yl N- (2-methylpropyl) carboxamide; 6- (5-trifluoromethylthien-3- yloxy)-pyrid-2-yl N- (1-methylpropyl) carboxamide; 6- (5- trifluoromethylthien-3-yloxy)-pyrid-2-yl N- (cyclopropylmethyl) carboxamide; 6- (5-trifluoromethylthien-3-yloxy)-pyrid-2-yl N-tert-butyl carboxamide; 6- (5- trifluoromethylthien-3-yloxy)-pyrid-2-yl N- (3-fluorophenyl) carboxamide; 6- (5-trifluoromethylthien-3-yloxy)-pyrid-2-yl N-methyl-N- (4-fluorophenyl) carboxamide; 6- (5-trifluoromethylthien-3-yloxy)-pyrid-2-yl N-methyl-N- (cyclopropyl) carboxamide; 6-(5-trifluoromelthylthien-3-yloxy)-pyrid-2-yl N- methyl-N-(2, 2,2-trifluoroethyl) carboxamide; 6- (5-trifluoromethylthien-3- yloxy)-pyrid-2-yl N-methyl-N-phenyl carboxamide; 6- (5- trifluoromethylthien-3-yloxy)-4-methylpyrid-2-yl N- (4-fluorophenyl) carboxamide; 6- (5-trifluoromethylthien-3-yloxy)-4-methoxypyrid-2-yl N- (4- fluorophenyl) carboxamide; 6- (5-trifluoromethylthien-3-yloxy)-4-

fluoropyrid-2-yl N- (4-fluorophenyl) carboxamide; 6- (5-trifluoromethylthien- 3-yloxy)-4-chloropyrid-2-yl N- (4-fluorophenyl) carboxamide, <BR> <BR> N- (4-fluorophenyl)-4-methyl-2- (5-trifluoromethylthienyl-3-oxy)-6-pyridine carboxamide, N- (2,2,2-trifluoroethyl)-4-methoxy-2- (5- trifluoromethylthienyl-3-oxy)-6-pyridine carboxamide, and N-methyl-N- cyclopropyl-4-cyano-2- (5-trifluoromethylthienyl-3-oxy)-6-pyridine carboxamide.

The compounds are oils, gums, or crystalline solid materials. They are superior through their valuable herbicidal properties. For example, they can be used in agriculture or related fields for the control of undesired plants. The compounds of general formula I according to the invention possess a high herbicidal activity within a wide concentration range and at low dosages, and may be used in agriculture without any difficulties, in particular for the selective control of undesired plants such <BR> <BR> as Alopecurus myosuroides, Echinochloa crus-galli, Setaria viridis, Galium aparine, Stellaria media, Veronica persica, Lamium purpureum, Viola arvensis, Abutilon theophrasti, Ipomoea purpurea and Amaranthus retroflexus Panicum dichotomiflorum by pre-and post-emergence application, particularly in certain crops, such as maize, cotton, wheat, and rice.

The compounds of formula according to the present invention can be prepared by conventional methods, particularly as follows: reacting a compound of formula 11 in which R, X', X2 and X3 are as defined hereinabove for formula 1, and L represents a leaving group, with a compound of formula III or a metal salt thereof

in which R', Y', y2 and m are as defined hereinabove for formula 1.

(A) A suitable process for the preparation of the compounds of general formula 11 comprises the reaction of a compound of formula IV: in which Y', R', R2, X', X2, X3 and m have the meaning given, with a compound of general formula V, in which B and Z have the meaning given, or a metal salt thereof.

(B) The compounds of formula IV may be prepared from the compounds of the general formula VI, in which X', X'and X'have the meaning given and L is a leaving group with a compound of formula III, or a metal salt thereof.

(C) A suitable process for the preparation of the compounds of general formula 11 comprises the reaction of a compound of formula VII : in which B, X', X2, X3 and Z have the meaning given and L is a leaving group, with a compound of general formula III or a metal salt thereof.

(D) The compounds of formula 12 may be prepared by reacting a compound of formula 112

wherein L is F, Cl or Br and X', R3 and n are as described for formula 11 and R2a and R2b have the meaning given for R2, with at least one molar equivalent of a compound of formula 111, in the presence of a base and optionally a solvent.

(E) Alternatively, compounds of formula 12 may be prepared by reacting a compound of formula 112 wherein R2b is F, Cl or Br with at least 2 molar equivalents of a compound of formula III in the presence of a base and optionally a solvent to form a dithienyl (or furyl) oxy or-thioxy intermediate compound of formula Vlil wherein Y1, Y2, X1, R', R2, R8, m and n are as described for formula 12.

Using conventional methods, the 4-thienyloxy group of the intermediate formula VIII compound may be displaced by an alkanol or alkylthiol to give compounds of formula I wherein R2 is alkoxy or alkylthio, or hydrolytically cleaved to give compounds of formula I wherein R2 is hydrogen. The reaction scheme is shown in flow diagram 1, wherein the alkanol or alkylthiol is an alkanol and the alkanol is methanol.

FLOW DIAGRAM I Y' Yz'R' Rm ra 2a R J y R 2a R 2b R 2a (Rl) m 2 + (R 8)"m 2 (R y L N base y N (111) (112) solvent (Vill) o CH3 X/| H2, Pd-C R2a H w R2a/X 8 N I Y m r 6 (Rr a J Y/

Preferred formula VIII compounds of the invention are those compounds wherein Y2 is O ; Y1 is S; X'is N or CR2; and R2 is hydrogen.

More preferred compounds of formula VIII are those compounds having the structure of formula VIIIA

wherein X', R'and R3 are as described for formula 12.

Particularly preferred are those compounds wherein R'is CF3 or CH3SO2 ; R2 is hydrogen; R8 is CF3; X'is N or CR2; and R2 is hydrogen.

The present invention relates to the novel compounds of formula VIII.

(F) A suitable process for the preparation of the compounds of general formula 13 comprises the reaction of a compound of formula 113: in which R2, W and o have the meaning given for formula 13 and R'is a halogen atom or a hydroxy or alkoxy group; and L is a leaving group or a group of

in which R'and m have the meaning given, with a compound of general formula IX, HNR 18 R'9 (IX) in which R13 and R'9 have the meaning given, and, in the event that L represents a leaving group, reacting the resulting product with a compound of formula III, or a metal salt thereof.

(G) Alternatively a compound of the general formula 114, in which R2 and o have the meaning given; and L is a leaving group is reacted with a compound of formula 111, or a metal salt thereof and the resulting compound of formula X

in which R', R2, m and o have the meaning given, is hydrolyzed to yield a compound of formula 113. Furthermore, the invention relates to the novel compounds of formula X, preferably wherein Y'is S <BR> y2 iS 0, and<BR> <BR> mis1 or2.

Most preferred are the compounds of formula XA: Compounds of formula III wherein Y2 is O may be prepared according to conventional procedures such as the conjugative addition of the appropriately substituted butenoate of formula XI with a glycolate or thioglycolate of formula XII in the presence of a base to form a thienyl- (or furyl)-2-carboxylate compound of formula XIII. The formula XIII compound may then be hydrolyzed to the corresponding carboxylic acid of formula XIV, which may then be decarboxylated to form the desired formula III compound wherein the hydroxyl group is attached in the 3 position. The reaction sequence is shown in flow diagram 11.

FLOW DIAGRAM il OH 0CH3 0ms base (R1) mC 0 solvent 1'CO CH (Xll) (Xl) (Xlil) (XIII) (XII) hydrolysis OH OH (III) (XIV) (111) (FIV) (III) (XIV)

The present invention provides a compound of formula IIIA wherein R'has the meaning given hereinabove.

Compounds of formula IIIA are preferred, wherein R'is CN, R3SOP, C1-C6alkyl optionally substituted with one or more halogen, C1-C4- C1-C4alkoxycarbonyl,alkoxy,C1-C4haloalkoxy, phenyl optionally substituted with one or more halogen, C,-C4alkyl or C,-C4haloalkyl groups, OH, CHO, CN, NO2, or R10SOy groups, C,-C4alkoxy optionally substituted with one or more halogen, OH, CHO, CN, NO2or R10SOy groups, R3 and R'° are independently C,-C4alkyl or C1-C4haloalkyl ; p and y are independently 0 or an integer of 1 or 2.

Preferred compounds of formula IIIA are those compounds wherein R'is C1-C4haloalkylsulfonylandmorepreferablywhereinC1-C4haloalkyl or CF3orCF3SO2.R1is Compounds of formula IIIA are particularly useful for preparing many of the herbicidal compounds of formula IA when employed in the processes illustrated hereinabove.

Furthermore, the invention relates to a process for the preparation of the compounds of formula IIIA, in which R'is as defined hereinabove for formula 1, which comprises the steps of (a) saponification of a compound of formula XIII in which R'is as described for formula IIIA ; R'is C, 6 alkyl; and PG represents a hydrogen atom or a protecting group, to obtain a compound of formula XIVA

(b) decarboxylation of the compound of formula XIVA; and (c) optionally cleaving of the protecting group.

PG represents a protecting group, in particular a benzyl group. The deprotection method depends on the protecting group used. When the protecting group represents a benzyl group, treatment with iodotrimethylsilane in tetrachloromethane is preferred.

The reactions according to (A), (B), (C), (D), (E) and (G) may be carried out in the absence or presence of a solvent which promotes the reaction or at least does not interfere with it. Preferred are polar, aprotic or protic solvents, suitably being N, N-dimethylformamide, dimethylsulfoxide, sulfolane, acetonitrile, methyl ethyl ketone, or an ether, such as tetrahydrofurane or dioxane, or alcoholes, or water, or mixtures thereof.

The reactions are carried out at a temperature between ambient temperature and the reflux temperature of the reaction mixture, preferably at elevated temperature, especially at reflux temperature. Conveniently substantially equimolar amounts of reactants are used. It may be expedient, however, to use one reactant in excess.

The reactions may be carried out in the presence of a basic compound such as an alkali hydroxide, bicarbonate or carbonate, e. g. sodium or potassium hydroxide, bicarbonate or carbonate, an alkali alkoxide, e. g. sodium ethoxide, or an organic base such as triethylamine.

A hydroxy compound used in the above reactions may be present in form of a salt, preferably as a salt of an alkali metal, particularly of sodium or potassium. The presence of a copper salt may be suitable.

Suitable leaving groups L are e. g. alkyl-and arylsulfonyl, alkyl-and arylsulfonyloxy, perfluoroalkylsulfonyloxy, nitro groups and halogen atoms, particularly fluorine, chlorine and bromine atoms.

The metal salts are conveniently generated by reaction of the hydroxythiophene of formula III or B-Z-H compounds of formula IV, the alcools or thiols with a suitable metal base, a metal carbonate or hydride.

The prepared compounds of formula I may be isolated and purified using conventional methods and techniques.

The starting compounds for the preparation of compounds of this invention can be prepared according to known methods.

For compounds of formula 11, IV, or VI certain substituents R2 like alkyl, alkoxy, alkylthio, alkylamino, dialkylamino, amino or halo, can be introduced onto the pyridine ring by displacement of a alkyl-or arylsulfonyl, alkyl-or arylsulfonyloxy, nitro, or halogen group. Halogen atoms may also be introduced by diazotization of an amino group. The diazotization reaction may be carried out in an aqueous medium and the diazonium compound can be reacted e. g. with CuCI, CuBr, CuCN or KI to introduce the chlorine, bromine, iodine atom or the cyano group.

Conveniently substantially equimolar amounts of compounds of formula 113 and IX are used for the preparation of the compounds of formula 13 according to (F). It may be expedient, however, to use one reactant in excess, suitably the amine of formula IX.

When R'in formula 113 represents a halogen atom, the reaction is suitably carried out at a temperature in the range 0 to 50 °C, preferably at

ambient temperature, and suitably in the presence of a base, for example potassium carbonate or, preferably an amine base, such as triethylamine, or excess amine of formula 111.

When R'in formula 113 represents an alkoxy group, the reaction is suitably carried out at a temperature in the range 0 to 100 °C, preferably at reflux temperature of the reaction medium, and suitably in the absence of a base. The reaction may be carried out with or without solvent. If a solvent is utilise, then a high boiling solvent is the most suitable type of solvent.

The reactions between formula 113 and formula IX may be carried out in the presence of a basic compound such as an alkali hydroxide, bicarbonate or carbonate, e. g. sodium or potassium hydroxide, bicarbonate or carbonate, an alkali alkoxide, e. g. sodium ethoxide, or an organic base such as triethylamine.

The compounds used as starting material are partly known and partly novel. The intermediate compounds of formula VI are known for example from GB 2 285 045. Intermediates of formula 11 are known from WO 94/22833, EP 0 447 004, EP 0 572 093, EP 0 693 490, EP 0 692 474, EP 0 694 538, EP 0 707 001, EP 0 723 960, and GB 2 285 045.

The present invention also provides the use of the compounds of formula I as herbicides. Further, in accordance with the invention there is provided a method of combating undesired plant growth at a locus by treating the locus with a composition according to the invention or an effective amount of a compound of formula 1. As a useful action is by foliar spray application, the locus is most suitably the plants in a crop area, typical crops being cereals, maize, soya bean, sunflower or cotton.

However, application may also be to the soil for those compounds having pre-emergence herbicidal action, or to the water of paddy rice fields. The dosage of active ingredient used may, for example be in the range of from 0.005 to 3 kg/ha, preferably 0.01 to 1 kg/ha.

The compounds of general formula I have been found to have herbicidal activity. Accordingly, the invention further provides a herbicidal composition which comprises an active ingredient, which is at least one compound of formula I as defined above, and one or more carriers. A method of making such a composition is also provided which comprises bringing a compound of formula I as defined above into association with the carrier (s). Such a composition may contain a single active ingredient or a mixture of several active ingredients of the present invention. It is also envisaged that different isomers or mixtures of isomers may have different levels or spectra of activity and thus compositions may comprise individual isomers or mixtures of isomers.

A composition according to the invention preferably contains from 0.5% to 95% by weight (w/w) of active ingredient.

A carrier in a composition according to the invention is any material with which the active ingredient is formulated to facilitate application to the locus to be treated, which may for example be a plant, seed or soil, or to facilitate storage, transport or handling. A carrier may be a solid or a liquid, including material which is normally a gas but which has been compressed to form a liquid.

The compositions may be manufactured into e. g. emulsion concentrates, solutions, oil in water emulsions, wettable powders, soluble powders, suspension concentrates, dusts, granules, water dispersible granules, micro-capsules, gels and other formulation types by well- established procedures. These procedures include intensive mixing and/or milling of the active ingredients with other substances, such as filles, solvents, solid carriers, surface active compounds (surfactants), and optionally solid and/or liquid auxilaries and/or adjuvants. The form of application such as spraying, atomizing, dispersing or pouring may be chosen like the compositions according to the desired objectives and the given circumstances.

Solvents may be aromatic hydrocarbons, e. g. Solvessos 200, substituted naphthalenes, phthalic acid esters, such as dibutyl or dioctyl phthalate, aliphatic hydrocarbons, e. g. cyclohexane or paraffins, alcools and glycols as well as their ethers and esters, e. g. ethanol, ethyleneglycol mono-and dimethyl ether, ketones such as cyclohexanone, strongly polar solvents such as N-methyl-2-pyrrolidone, or y-butyrolactone, higher alkyl pyrrolidones, e. g. n-octylpyrrolidone or cyclohexylpyrrolidone, epoxidized plant oil esters, e. g. methylated coconut or soybean oil ester and water.

Mixtures of different liquids are often suitable.

Solid carriers, which may be used for dusts, wettable powders, water dispersible granules, or granules, may be mineral filles, such as calcite, talc, kaolin, montmorillonite or attapulgite. The physical properties may be improved by addition of highly dispersed silica gel or polymers. Carriers for granules may be porous material, e. g. pumice, kaolin, sepiolite, bentonite; non-sorptive carriers may be calcite or sand. Additionally, a multitude of pre-granulated inorganic or organic materials may be used, such as dolomite or crushed plant residues.

Pesticidal compositions are often formulated and transported in a concentrated form which is subsequently diluted by the user before application. The presence of small amounts of a carrier which is a surfactant facilitates this process of dilution. Thus, preferably at least one carrier in a composition according to the invention is a surfactant. For example, the composition may contain at two or more carriers, at least one of which is a surfactant.

Surfactants may be nonionic, anionic, cationic or zwitterionic substances with good dispersing, emulsifying and wetting properties depending on the nature of the compound according to general formula I to be formulated. Surfactants may also mean mixtures of individual surfactants.

The compositions of the invention may for example be formulated as wettable powders, water dispersible granules, dusts, granules, solutions,

emulsifiable concentrates, mulsions, suspension concentrates and aerosols. Wettable powders usually contain 5 to 90% w/w of active ingredient and usually contain in addition to solid inert carrier, 3 to10% w/w of dispersing and wetting agents and, where necessary, 0 to 10% w/w of stabilizer (s) and/or other additives such as penetrants or stickers. Dusts are usually formulated as a dust concentrate having a similar composition to that of a wettable powder but without a dispersant, and may be diluted in the field with further solid carrier to give a composition usually containing 0.5 to 10% w/w of active ingredient. Water dispersible granules and granules are usually prepared to have a size between 0.15 mm and 2.0 mm and may be manufactured by a variety of techniques. Generally, these types of granules will contain 0.5 to 90% w/w active ingredient and 0 to 20% w/w of additives such as stabilizer, surfactants, slow release modifiers and binding agents. The so-called"dry flowables"consist of relatively small granules having a relatively high concentration of active ingredient.

Emulsifiable concentrates usually contain, in addition to a solvent or a mixture of solvents, 1 to 80% w/v active ingredient, 2 to 20% w/v emulsifiers and 0 to 20% w/v of other additives such as stabilizers, penetrants and corrosion inhibitors. Suspension concentrates are usually milled so as to obtain a stable, non-sedimenting flowable product and usually contain 5 to 75% w/v active ingredient, 0.5 to 15% w/v of dispersing agents, 0.1 to 10% w/v of suspending agents such as protective colloids and thixotropic agents, 0 to 10% w/v of other additives such as defoamers, corrosion inhibitors, stabilizers, penetrants and stickers, and water or an organic liquid in which the active ingredient is substantially insoluble; certain organic solids or inorganic salts may be present dissolve in the formulation to assist in preventing sedimentation and crystalization or as antifreeze agents for water.

Aqueous dispersions and mulsions, for example compositions obtained by diluting the formulated product according to the invention with water, also lie within the scope of the invention.

Of particular interest in enhancing the duration of the protective activity of the compounds of this invention is the use of a carrier which will provide slow release of the pesticidal compounds into the environment of a plant which is to be protected as disclosed for example by U. S patent no.

5,705,174.

The biological activity of the active ingredient can also be increased by including an adjuvant in the spray dilution. An adjuvant is defined here as a substance which can increase the biological activity of an active ingredient but is not itself significantly biologically active. The adjuvant can either be included in the formulation as a coformulant or carrier, or can be added to the spray tank together with the formulation containing the active ingredient.

As a commodity the compositions may preferably be in a concentrated form whereas the end user generally employs diluted compositions. The compositions may be diluted to a concentration down to 0.001% of active ingredient. The doses usually are in the range from 0.01 to 10 kg a. i./ha.

Examples of formulations according to the invention are: Emulsion Concentrate (EC) Active Ingredient Compound of Example 11 30 % (w/v) Emulsifier (s) Atloxe 4856 B/Atloxs 4858 B 1) 5 % (w/v) (mixture containing calcium alkyl aryl sulfonate, fatty alcohol ethoxylates and light aromatics/mixture containing calcium alkyl aryl sulfonate, fatty alcohol ethoxylates and light aromatics) <BR> Solvent Shellsole A 2) to 1000 ml (mixture of Cg-C, o aromatic hydrocarbons) Suspension Concentrate (SC) Active Ingredient Compound of Example 11 50 % (w/v) Dispersing agent Soprophor"FL 3) 3 % (w/v) (polyoxyethylene polyaryl phenyl ether phosphate amine salt) Antifoaming agent Rhodorsilo 422 3) 0. 2 % (nonionic aqueous mulsion of (w/v) polydimethylsiloxanes) Structure agent 4)0.2%S (Xanthan gum) (w/v) Antifreezing agent Propylene glycol 5 % (w/v) Biocidal agent Proxel# 5) 0.1 % (aqueous dipropylene glycol solution (w/v) containing 20% 1,2-benisothiazolin-3-one) Water to 1000 mi Wettable Powder (WP) Active Ingredient Compound of Example 12 60 % (w/w) Wetting agent Atloxs 4995 1) 2 % (w/w) (polyoxyethylene alkyl ether) Dispersing agent 6)3%(w/w)D-60 (mixture of sodium salts of condensed naphthalene sulfonic acid and alkylarylpolyoxy acetates Carrier/Filler Kaolin 35 % (w/w) Water Dispersible Granules (WG) Active Ingredient Compound of Example 12 50 % (w/w) <BR> <BR> <BR> D-34506)8%(w/w)Dispersing/Witcosperse# Binding agent (mixture of sodium salts of condensed naphthalene sulfonic acid and alkyl sulfonates) <BR> <BR> <BR> <BR> Wetting agent Morwete EFW 6) 2 % (w/w) (formaldehyde condensation product) Antifoaming agent Rhodorsile EP 6703 3) 1 % (w/w) (encapsulated silicone) Disintegrant AgrimerATF2%(w/w) (cross-linked homopolymer of N-vinyl-2-

pyrrolidone) Carrier/Filler Kaolin 35 % (w/w) available from ICI Surfactants <BR> 2) available from Deutsche Shell AG<BR> 3) available from Rhodia (former Rhône-Poulenc)<BR> 4) available from Kelco Co.<BR> <P>5) available from Zeneca<BR> 6) available from Witco<BR> 7) available from International Speciality Products The compositions of this invention can also comprise other compounds having biological activity, e. g. compounds having similar or complementary pesticidal activity or compounds having plant growth regulating, fungicidal or insecticidal activity. These mixtures of pesticides can have a broader spectrum of activity than the compound of general formula I alone. Furthermore, the other pesticide can have a synergistic effect on the pesticidal activity of the compound of general formula 1.

The active ingredients according to the invention can be employed alone or as formulations in combination with conventional herbicides.

Such combinations of at least two herbicides can be included in the formulation or also added in a suitable form with the preparation of the tank mix. For such mixtures at least one of the following known herbicides can be used: amethydione, metabenzthiazuron, metamitron, metribuzin, 2,4-D, 2,4-DB, 2,4-DP, alachlor, alloxydim, asulam, atrazin, bensulfuron, bentazon, bifenox, bromoxynil, butachlor, chloridazon, chlorimuron, chlorpropham, chlorsulfuron, chlortoluron, cinmethylin, clopyralid, cyanazin, cycloate, cycloxydim, dichlobenil, diclofop, eptame, ethiozin, fenoxaprop, fluazifop, fluometuron, fluridone, fluroxypyr, fomesafen, glyphosate, haloxyfop, hexazinone, imazamethabenz, imazapyr, imazaquin, imazethapyr, ioxynil, isoproturon, lactofen, MCPA, MCPP,

mefenacet, metazachlor, metolachlor, metsulfuron, molinate, norflurazon, oryzalin, oxyfluorfen, pendimethalin, picloram, pretilachlor, propachlor, pyridate, quizalofopethyl, sethoxydim, simetryne, terbutryne, thiobencarb, triallate, trifluralin, diflufenican, propanil, triclopyr, dicamba, desmedipham, acetochlor, fluoroglycofen, halosafen, tralkoxydim, amidosulfuron, cinosulfuron, nicosulfuron, pyrazosulfuron, oxasulfuron, azimsulfuron, thiameturon, thifensulfuron, triasulfuron, tribenuron, esprocarb, prosulfocarb, terbutylazin, benfuresate, clomazone, di-methazone, dithiopyr, isoxaben, quinchlorac, qinmerac, sulfosate, cyclosulfamuron, imazamox, imazamethapyr, flamprop-M-methyl, flamprop-M-isopropyl, picolinafen, thiafluamide, isoxaflutole, flurtamone, daimuron, bromobutide, methyidimron, dimethenamid, sulcotrione, sulfentrazone, oxadiargyl, acifluorfen, cafenstrole, carfentrazone, diuron, glufosinate.

Mixtures with other active ingredients like fungicides, insecticides, acaricides and nematicides are possible.

For a more clear understanding of the invention, specific examples are set forth below. These examples are merely illustrations and are not to be understood as limiting the scope and underlying principles of the invention in any way. Various modifications of the invention in addition to those shown and described herein will become apparent to those skilled in the art from the following examples and foregoing description. Such modifications are also intended to fall within the scope of the appended claims.

The structures of the compounds prepared in the following examples were addition confirmed by NMR and mass spectrometry.

Example 1: Preparation of Method A 1A EthLr 3-methoxy-3-trifluoromethylacrylate Cesium carbonate (132.8 g) was added to a mixture of ethyl 4,4,4- trifluoroacetoacetate (75.0 g) and dimethylformamide (400 ml). The reaction mixture was heated to 70 °C for 30 minutes. A mixture of methyl tosylate (83.4 g) and dimethylformamide (150 ml) was added to the resulting reaction mixture within 40 minutes. The mixture was heated for 3 hours and cooled to room temperature. Upon dilution with water (800 ml) the reaction mixture was extracted with diethyl ether three times. The combined organic phases were washed with water and dried. The mixture was concentrated and the residue distille under reduced pressure to yield the product as a clear liquid (48.5 g, 60 %) with a boiling point of 62- <BR> <BR> <BR> 70 °C at 12 mm.<BR> <BR> <BR> <BR> <BR> <P>1B Methyl (3-hydroxy-5-trifluoromethylthien-2-yl)-carboxylate A solution of 1M potassium hydroxide in methanol (30 mi) is added to a cooled mixture of 1A (4.6 g), methyl thioglycolate (2.46 g) and methanol (10 ml). The resulting reaction mixture was stirred for 24 hours at room temperature. Then the mixture was poured on ice and acidified with 6N sulfuric acid (pH = 2). The mixture is extracted with diethyl ether twice. The combined organic phases were washed with water and dried.

The mixture was concentrated and the residue is distille under reduced pressure to yield the product as a clear liquid (3.4 g, 65 %) with a boiling point of 42-45 °C at 0.10 mm.

1C (3-Hydroxy-5-trifluoromethylthien-2-yl)-carboxylic acid A mixture of 1 B (2.38 g) and methanol (20 ml) was added to a stirred solution of sodium hydroxide (1.68 g) in water (20 ml). The reaction mixture was heated at reflux for 3 hours. The reaction mixture was cooled to room temperature and concentrated in vacuo. The concentrate was cooled to 5 °C and acidified with concentrated HCI (3.5 ml). The resulting

suspension was stirred at 5 °C for 30 minutes. The solid was collecte by filtration, washed with water, then dried in vacuo at 35-40 °C to give the free acid (1.45 g, 65 %).

1 D 3-Hydroxy-5-trifluoromethylthiophen 1 C (1.80 g) was slowly heated under argon. Evolution of gas was observed at 90 °C. Heating was continued for addition 3.5 hours at 90°C. The resulting oil was distille under reduced pressure (boiling point 70-74 °C at 4 mm) to yield 1.18 g (82 %) of compound 1 D.

Method B 1E Methyl (3-benzyloxy-5-trifluoromethylthien-2-yl)-carboxylate A mixture of 1 B (5.0 g) and dimethylformamide (50 ml) is treated with sodium hydride (1.06 g). Benzylbromide (3.15 ml) was slowly added to the resulting reaction mixture and stirred at room temperature for 20 hours.

The reaction mixture was poured into water. The mixture was extracted with diethyl ether twice. The combined organic phases were washed with water, dried and concentrated in vacuo. The crude product was chromatographed (hexane/dichloromethane, 1/1) to give the product as a white solid (4.5 g, 64 %) with a melting point of 52-53.5 °C.

1 F (3-Benzyloxv-5-trifluoromethylthien-2-yl)-carboxylic acid A mixture of 1 E (3.80 g) and tetrahydrofuran (12 mi) was heated to reflux in 2N sodium hydroxide (12 ml) for 12 hours. Then the mixture was poured on ice and acidified with 6N sulfuric acid (pH = 1-2). The mixture is extracted with diethyl ether twice. The combined organic phases were washed with water and dried. The mixture was concentrated and the residue is distille under reduced pressure to yield the product as a white solid (3.22 g, 89 %) with a melting point of 142-144 °C.

1 G 3-Benzvioxv-5-trifluoromethylthiophen A mixture of 1 F (14.5 g) and quinoline (50 ml) was treated with copper powder (4.57 g) and heated to 150 °C. The reaction mixture is heated for 25 minutes at 150 °C and cooled to room temperature. The mixture was filtered and washed with water. Aqueous quinoline was acidified with 6N HCI (pH = 2) and extracted with diethyl ether twice. The combined organic phases were washed with water and dried. The mixture was concentrated and the residue was chromatographed to yield a yellow liquid (8.74 g, 71 %).

1 D 3-Hydroxy-5-trifluoromethylthiophene A mixture of 1G (7.75 g) and tetrachloromethane (50 ml) was treated with iodotrimethylsilane (12.30 ml) and heated to 60 °C for 12 hours. The reaction mixture was stirred at room temperature for 12 hours. Water (50 ml) was added and the resulting reaction mixture was extracted with dichloromethane three times. The combined organic phases were washed with water and dried. The crude reaction mixture was eluted through hexane (100 g/silica gel) to remove benzyliodide and then with diethyl ether. The etheral phases were concentrated and distille in vacuo to give the product (3.33 g, 74 %) having a boiling point of 65-66 °C at 4 mm.

Analogously is obtainned 4-hydroxy-2- (methylsulfonyl) thiophene, mp 109- 111 °C.

Example 2A: Preparation of 2.6-bis j5-trifluoromethylthienyrl-3-oxy)-4- methylpvridine A mixture of 2, 6-dichloro-4-methylpyridine (0.1 mol), 1 D (potassium salt, 0.22 mol), and potassium carbonate (0.22 mol) in anhydrous sulfolane (70 ml) is heated to 80 °C for 4 hours and then to 100 °C for 3 hours. The reaction mixture is diluted with pentane/ethyl acetate (1/1 by volume).

After filtration through a bed of silica gel the filtrate is washed 8 times with

water. The organic layer is dried with anhydrous magnesium sulfate and filtered over silica gel. Now the solvent is removed and the residue is washed with diisopropyl ether. After drying, the product is obtained as an off-white wax of melting point 38-39 °C.

Example 2B By analogy to Example 2A, 2,6-bis- (5-trifluoromethylthienyl-3-oxy)-4- cyanopyridine can be obtained. This compound has a melting point of about 103-104 °C. It is identical to the compound of Example 2A, except for the cyano (in Example 2A, there is a methyl) substituent at the 4- position of the pyridine ring.

Example 3: Preparation of 2-(3. 4-difluorobenzyloxy)-6-(5- trifluoromethvlthienyl-3-oxy)-4-methylpnridine To 0.34g potassium tert-butylate (3 mmol) in 10 ml dry diglyme are added 0.51 g (3 mmol) 1 D. After stirring at room temperature for 30 min., 0.55g (2 mmol) 2-bromo-4-methyl-6- (3, 4-difluorobenzyloxy)-pyridine (prepared analogously to the method disclosed in WO 94/22833), 0.3g CuBr and a catalytic amount of 18-crown-6 ether are added. The mixture is heated to 130°C under nitrogen atmosphere for 16 hrs. Another 0.51g hydroxythiophene and 0.34 g potassium tert-butylate are added and heating is continued for 16hrs. The mixture is diluted with toluene, washed with water and purified by flash chromatography.

Yield 0.35 g oil

Example 4: Preparation of 3.5-difluoro-2-(4-fluorobenzyloxv)-4- methvl-6-(5-trifluoromethylth ienvl-3-oxy)-pyridine 4A 4-methyl-2,3.5-trifluoro-6- (5-trifluoromethylthienyl-3-oxy)-pyridine A mixture of 4-methyl-2,3,5,6-tetrafluoropyridine (20 mmol, 3.3 g), sodium hydride (23 mmol) and 1 D (22 mmol, 3.7 g) in anhydrous acetonitrile (100 ml) is stirred at room temperature for 5 hours. The solvent is removed under reduced pressure. Pentane/ethyl acetate (1/1 by volume) is added to the residue and the mixture is washed twice with 2N sodium hydroxide and 5 times with water. After drying of the organic layer, the solvent is removed and the product is purified by flash chromatography and distillation under reduced pressure: One obtains the product as an oil (2.75 g, b. p. 110°C at 0.0015 mbar).

4B 3,5-Difluoro-6- (4-fluorophenoxy)-4-methyl-2-5-trifluoromethyl- thienvl-3-oxy)pyridine A mixture of 4A (0.85 g, 2.7 mmol), 60% sodium hydride (0.13 g, 3.3 mmol) and 4-fluorobenzylalcohol (3,0 mmol) in anhydrous sulfolane (3 ml) is heated to 85°C for 5 hours. The reaction mixture is diluted with pentane/ethyl acetate (1/1 by volume) and filtered through a bed of silica gel. The filtrate is washed 5 times with water, the organic layer is dried with anhydrous magnesium sulfate, and the solvents are removed in vacuo. The residue is purified by a flash silica gel chromatography using pentane/toluene in a ratio of 4/1.0.6 g (53% yield) of 4B are obtained as a colourless oil.

Examples 5-34: Further Examples are prepared according to the general method of Example 3 or 4 and are listed in Table 1.

Table 1 Ex. No. R2 R6 R7 R2' s melting point <BR> (°C)<BR> <BR> 5 CH3 F 2-F H 1 55-57<BR> <BR> 6 CH3 F H H 1 oil<BR> <BR> 7 CH3 H 3-CF3 H 0 oil Cl3-ClH0oil8CN 9 CH3 F 3-F F 0 oil F3-ClF0oil10CH3 <BR> <BR> 11 CN H H H 1 oil<BR> <BR> 12 CH3 H H H 1 oil Cl3-ClH0oil13CH3 F3-ClH0oil14CH3 F2-FH115CH3O <BR> <BR> 16 CH30 F H H 1<BR> <BR> 17 CH30 H 3-CF3 H 0<BR> <BR> 18 CH30 F 3-F F 0 FHF119CH3O F3-ClF020CH3O HHH121CH3O Cl3-ClH022CH3O

Ex. No. R2 R6 R7 R2x s melting point (°C) 23 CH30 F 3-Cl H 0 24 H F 2-F H 1 25 H F H H 1 26 H H 3-CF3 H 0 27 F F 3-F F 0 28 CN H H F 1 83 29 CN F H H 1 oil 30 CN H 2-F H 1 oil 31 CH3 H H F 1 oil 32 CN H 2-CH3 H 1 78 33 H H H H 1 oil 34 CN H 3-CF3 H 0 oil 35 CH3 H H F 1 oil 36 H H H F 1 52 37 CHO H H H 1 oil 38 CN H F H 1 oil 39 CN H 3-F H 1 oil 40 H H H H 1 oil Example 41A: Preparation of 2-(thien-2-ylmethyloxy)-6-(5- <BR> <BR> <BR> <BR> trifluoromethylthienyl-3-oxy !-4-methylpyridine<BR> <BR> <BR> <BR> <BR> 2-bromo-4-methyl-6- (thien-2-ylmethoxy)-pyridine is reacted with 1D as described in example 3. After cooling, the reaction mixture is diluted with pentane/ethyl acetate (1/1 by volume) and filtered through a bed of silica gel. The filtrate is washed 6 times with water. The organic layer is

dried with anhydrous magnesium sulfate, filtered and the solvents evaporate in vacuo. Purification by flash chromatography (2 times: silica gel, pentane/ethyl acetate 8/2 v/v and silica gel: toluene) gives the title compound as a colourless oil.

Example 41 B By analogy to Example 41A, 4-cyano-2- (thien-2-ylmethoxy)-6- (5- trifluoromethylthienyl-3-oxy)-pyridine can be obtained. This compound has a melting point of about 54 °C. It is identical to the compound of Example 35A, except for the cyano (in Example 35A, there is a methyl) substituent at the 4-position of the pyridine ring.

Examples 42-55: Further Examples are prepared according to the general method of Examples 3 to 4 and are listed in Table 2.

Table 2 Ex. No. R2 B R2'X'Z s 1-CH3-3-CF3-pyazol-5-ylHCHO042CH3 1-CH3-3-CF3-pyazol-5-ylFCFO043CH3 1-CH3-3-CF3-pyazol-5-ylHCHO044CH3O 1-CH3-3-CF3-pyazol-5-ylFCFO045CH3O 46 CH3 phenyl H CH S 1, oil 3-CF3-phenylHCHS047CH3 <BR> <BR> <BR> <BR> 48 CH30 5-CF3-thien-3-yl H N O 0<BR> <BR> <BR> <BR> 49 CH30 phenyl H N 0 1 2-Cl-pyrid-4-ylHCHO050CH3 2-CF3-pyrid-4-ylHCHO051CH3 2-CF2H-O-pyrid-4-ylHCHO052CH3 5-CF3-thien-3-ylFCFO0,m.p.43°C53CH3 54 H 5-CF3-thien-3-yl F CF O 0, oil 55 CN 5-CF3-thien-3-yl H CH O 0, m. p. 103-104 oc

EXAMPLE 56 56A Preparation of p- (Trifluoromethyl) benzamidine Hydrochloride A stirred solution of p- (trifluoromethyl) benzonitrile (100 g, 0.585 mol) in toluene is treated with NaNH2 (38 g, 0.878 mol, 90% pure) and dibenzo-18-crown-6 (1.5 g), heated at reflux temperatures for 4 hours, cooled to 10°C and treated slowly with 175 ml of concentrated HCI over a 30 minute period. The resultant reaction mixture is filtered and the filtercake is washed with toluene and dried to give a powdery yellowish solid. The solid is dissolve in ethanol and filtered. The filtrate is concentrated in vacuo to give a yellow solid residue. The residue is slurried in ethyl acetate and filtered. The filtercake is washed with ether and dried to give the title product as a yellow solid, 132.3 g (quantitative yield).

56B 6-Hvdroxy-5-methyl-2-a, a. a-trifluoro-p-tolyl) pyrimidine A mixture of 56A (31.7 g, 0.141 mol) and a 25% NaOCH3 solution in methanol (60.9 g, 0.282 mol NaOCH3) is stirred for 10 minutes, treated with methyl 2-formylpropionate (14.9 g, 0.128 mol) and stirred at ambient temperatures until reaction is complete by HPLC. The resultant reaction mixture is concentrated in vacuo to give a solid residue. The residue is treated with 1 N NaOH, acidified with 10% HCI to pH 4 and filtered. The filtercake is washed with water and dried in vacuo to give the title product as a white solid, 30.35 g (85% yield), mp 273-275°C.

56C Substituted 6-hyd roxy-2-(a, a, a-trifluoro-p-tolyl ! pyrimidine Using essentially the same procedure described in Example 56B and substituting the appropriate acetate or malonate reagent, the following substituted 2-hydroxypyrimidines are obtained.

Table 3

Reagent R2b R2a mp °C yield (%) methylpropionylacetate C2 H 181 86 ethyl butyrylacetate n-C3H7 H 138-141 59 ethyl acetoacetate CH3 H 209 93 methyl 4-methoxyacetoacetate CH2OCH3 H 180-182 82 dimethyl ethylmalonate OH C2 >270 64 dimethyl malonate OH H >275 56 56D 6-Chloro-5-methvl-2-(a, a, a-trifluoro-p-tolyl) pyrimidine A mixture of 56B (5.00 g, 18.7 mmol) and 10 ml of PORC13 is heated at reflux temperatures for 2 hours, allowed to cool to room temperature overnight and concentrated in vacuo to a thick paste residue. The residue is diluted with water and extracted with ethyl acetate.

The ethyl acetate extracts are combined, dried with brine and concentrated in vacuo to afford the title product as a tan solid, 2.72 g mp110-112°C.(51%yield) 56E Substituted 6-chloro-2- (a a. a-trifluoro-p-tolyl) pvrimidines Using essentially the same procedure described in Example 56D and employing the appropriately substituted 6-hydroxypyrimidine, the following compounds are obtained.

Table 4

mp(°C)yield(%)R2bR2a C2H5 H 85 r-r-A H 01 80 CH3 H 62 91 Cl H ol 73 a C2 77-78 51 CH2OCH3 H oi 81 EXAMPLE 57: Preparation of 4-Methyl-2-(a. a, a-trifluoro-p-tolyl)-6d [5- <BR> <BR> <BR> <BR> (trifluoromethyl)-3-thienyl]pyrimidine<BR> <BR> <BR> <BR> <BR> <BR> <BR> <BR> A mixture of 1D (0.50 g, 2.98 mmol) and 56D (0.31g, 2.98 mmol) in dimethylformamide is treated with K2CO3 (0.62 g, 4.47 mmol), heated at 100°C for 17 hours, cooled to room temperature and diluted with water.

The resultant reaction mixture is extracted with ether. The ether extracts are combined, washed sequentially with water and brine, dried over MgSO4 and concentrated in vacuo to give a brown solid residue. The residue is chromatographed (silica gel, ethyl acetate/hexanes, 20/80) to <BR> <BR> <BR> give the title product as a light yellow solid, 0.88 g (73% yield), mp 83.5-<BR> <BR> <BR> <BR> <BR> <BR> 85°C.

EXAMPLE 58-71: Preparation of Substituted 6-(Thienyloxy)- pyrimidines Using essentially the same procedure described in Example 57 and employing the appropriate 6-chloro-pyrimidine and 3-hydroxythiophene reactants the following compounds are obtained.

Table 5 Example R2bmp(°C)yield(%)R2a Number <BR> <BR> <BR> <BR> <BR> 58 CH3S02 H CH3 145-146 35<BR> <BR> <BR> <BR> <BR> <BR> <BR> 59 CF3 CH3 H 85-86 72<BR> <BR> <BR> <BR> <BR> <BR> <BR> 60 CH3S02 CH3 H 156-158 57 HC2H%61-636561CF3 62 CF3 H n-C3H7 53-54. 5 52 63 CF3 C2H5 Cl 82.5-85 72 <BR> <BR> <BR> <BR> 64 CF3 H Cl 85-86 75<BR> <BR> <BR> <BR> <BR> <BR> <BR> 65 CF3 H CH20CH3 oil 58<BR> <BR> <BR> <BR> <BR> <BR> <BR> 66 C02CH3 H CH3 120-122 52 HCH3106-1086267CH2OH 68 CHO H CH3 152-153.5 89 HCH3203-2048669CO2H <BR> <BR> <BR> 70 CHF2 H CH3 57-58 54<BR> <BR> <BR> <BR> <BR> <BR> 71 CF3 H H 61-63 53

EXAMPLE 72 72A 2- (a. a. a-Trifluoro-p-tolvl)-4, 6-diff5- (trifluoromethyl)-3- thienyl] oxy} pyrimidine A mixture of 4, 6-dichloro-2- (a, a, a-trifluoro-p-tolyl) pyrimidine (2.15 g, 7.34 mmol) and 1D (2.47 g, 14.7 mmol) in dimethylformamide is treated with K2CO3 (2.52 g, 18.3 mmol), heated at 100°C for 3 hours, cooled to room temperature, poured onto water and neutralized with 6N HCL to pH 6-7. The resultant reaction mixture is extracted with ether. The ether extracts are washed sequentially with water and brine, dried over MgS04 and concentrated in vacuo to give a yellow solid residue. The residue is purified by flash chromatography (silica gel, methylene chloride) to afford the title product as an off-white solid, 3.03 g (74%), mp 93-95°C.

72B4-Methoxy-2-(α,α,α-trifluoro-p-tolyl)-6-{[5-(triflu oromethyl)-3- thienyl] oxy} pvrimidine A solution of 72A (1.50 g, 2.70 mmol) in dimethylformamide is treated with 25% NaOCH3 in methanol (0.58 g, 2.70 mmol), heated to 60°C for 1.5 hours, cooled to room temperature, poured onto water and acidified to pH 5 with 6N HCI. The resultant reaction mixture is extracted with ether. The ether extracts are combined, washed sequentially with water and brine, dried over MgSO4 and concentrated in vacuo to give a solid residue. The residue is chromatographed (silica gel, ethyl acetate/hexanes, 3/97) to afford the title product as a white solid, 0.58 g (51% yield), mp 91-93°C.

EXAMPLEof5-Ethyl-2-(α,α,α-trifluoro-p-tolyl)-6-{[5-Pre paration (trifluoromethyl)-3-thienyl] oxy} pyrimidine A solution of 4-chloro-5-ethyl-2- (a, a, a-trifluoro-p-tolyl)-6- { [5- (trifluoromethyl)-3-thienyl] oxy} pyrimidine (1.06 g, 2.34 mmol) in a 1: 1

mixture of methanol: ethyl acetate is treated with triethylamine (0.80 ml, 5.86 mmol) and 10% Pd-C (0.32 g, 30 wt%). The resultant mixture is placed on a PARR hydrogenator at 50 psi for 2 hours (reaction is complete by TLC). The resultant mixture is filtered. The filtrate is concentrated. The concentrate is dissolved in ethyl acetate/chloroform and chromatographed (silica gel, methylene chloride/hexanes, 20/80) to give the title product as a white solid, 0.69 g (70%), mp 67-68°C.

EXAMPLE 74 74A 6-Bromo-4-melthyl-2-{[5-(trifluoromelthyl)-3-thienyl]oxy}pyr idine A solution of 2-bromo-6-fluoro-4-methylpyridine (1.00 g, 5.26 mmol) and 1 D (0.88 g, 5.26 mmol) in dimethylformamide is treated with K2CO3 (1.09 g, 7.89 mmol), heated at 80°C for 23 hours, cooled to room temperature, poured onto water, acidified to pH 5-6 with 6N HCI and extracted with ether. The ether extracts are combined, washed sequentially with water and brine, dried over MgSO4 and concentrated in vacuo to give a residue. The residue is chromatographed (silica gel, ethyl acetate/hexanes, 3/97) to afford the title produce as a yellow oil, 1.16 g (65% yield.

74B 4-Methya. a, a-trifluoro-p-tolyl)-2- [55- (trifluoromethyl)-3- thienyloxy} pyridine A solution of 74A (1.16 g, 3.43 mmol) in dimethoxyethane is treated with tetrakis (triphenylphosphine) Pd (79 mg,. 069 mmol), stirred at room temperature for 30 minutes under N2, treated with a, a, a-trifluoro-p- tolylboronic acid (0.72 g, 3.77 mmol), NaHCO3 (0.95 g, 11.32 mmol) and water, heated at reflux temperature for 1.5 hours, cooled to room temperature, diluted with a mixture of ethyl acetate and water to give a two phase mixture. The phases are separated and the organic phase is set aside. The aqueous phase is extracted with ethyl acetate. The ethyl acetate extracts are combined with the organic phase, washed

sequentially with water and brine, dried over MgSO4 and concentrated in vacuo to give an amber oil residue. The residue is chromatographed (silica gel, ethyl acetate/hexanes, 5/95) to give the title product as a clear oil, which solidifie upon drying in a Kugelrohr, to a waxy white solid, 1.22 g (88% yield), mp 52.5-55.5°C.

EXAMPLE 75 and 76: Preparation of Substituted 2- (Thienyloxy)pyridines Using essentially the same procedures described in Examples 74A and 74B and employing the appropriately substituted 2,6-dihalopyridine substrate and phenylboronic acid, the compounds shown in Table 6 are obtained.

Table 6

Example mp Number R'R2a R2b (°C) 75 CF3 H CN 86 76 CF3 H H 61-63 Example 77: Preparation of N- (4-ftuorophenv !)-2-f5- trifluoromethvlthienyl-3-oxy)-6-pyridinecarboxamide 77A 2-(5-Trifluoromethylthienyl-3-oxy)-6-cyanopyridine A mixture of 1D (5.00 g), 2-chloro-6-cyanopyridine (4.13 g), potassium carbonate (4.52 g) and dimethylsulfoxide (50 ml) was heated under reflux for 4 hours and cooled to room temperature. The reaction

mixture was poured into ice/water (200 ml) and acidified with 6N HCI (pH = 6-7). The reaction mixture was extracted with diethyl ether three times.

The combined organic phases were washed with water and concentrated.

The resulting crude product was reacted without further purification.

77B 2-(5-Trifluoromethylthienyl-3-oxv)-6-pyridinecarboxylicacid A mixture of 77A (6.80 g) and dioxane (100 ml) was treated with concentrated HCI (100 ml) and heated under reflux for 2 hours. The mixture was cooled to room temperature, basified with 3N sodium hydroxide (pH = 9) and extracted with diethyl ether. The organic phase was discarged, the aqueous phase acidified with 6N HCI (pH = 2) and extracted with diethyl ether 3 times. The combined organic phases were washed with water, dried, concentrated and recrystallized from <BR> <BR> <BR> <BR> dichloromethane/hexane to yield 5.50 g (76 %) of a brown solid, having a melting point of 91-92 °C.

77C 2- (5-trifluoromethylthienyl-3-oxy)-6-pyridinecarboxyl chloride A mixture of 76B (5.5 g), toluene (100 ml) and thionyl chloride (2.80 ml) was heated to 75-80 °C for 12 hours. The reaction mixture was concentrated in vacuo and toluene (50 ml) added to the residual oil. The oil was dried in vacuo to afford 5.43 g of crude 76C.

77D N- (4-fluorophenyl)-2- (5-trifluoromethylthienyl-3-oxy)-6- pyridinecarboxamide A mixture of 76C (1.30 g) and tetrahydrofuran (20 ml) was added to a mixture of p-fluoroaniline (0.40 ml), triethylamine (0.88 ml) and tetrahydrofuran (20 ml). The reaction mixture was stirred at room temperature for 6.5 hours and poured into water. The reaction mixture was extracted with diethyl ether twice. The combined organic phases were dried and concentrated. The crude product was <BR> <BR> <BR> chromatographed (ethyl acetate/hexane, 20/80) to give 0.97 g (60 %) of the desired product having a melting point of 135-136.5 °C Examples 78-118: Further compounds are prepared according to the general methods of Example 77 are listed in Table 7.

Table 7 Example melting point (° C) No. R'8 R'9 cyclopropyl107-10978H phenyl117-11979H 80 H 2,2,2-trifluoroethyl 96-98 81 H 2, 4-difluorophenyl 130 <BR> <BR> <BR> <BR> <BR> 82 H benzyl<BR> <BR> <BR> <BR> <BR> <BR> <BR> <BR> <BR> 83 4-chloro-2-fluorophenyi<BR> <BR> <BR> <BR> <BR> <BR> <BR> <BR> 84 2-fluorophenyl 2,4-dichlorophenyl85H 86H2,6-dif)uoropheny) 87 H 3-fluorophenyl 107-109 4-methylphenyl88H 4-trifluoromelthylphenyl89H Example melting point (° C) No. R'8 R'9 90 H 2,4,5-trifluorophenyl 91 H 4-chlorophenyl 92 H 2, 4-dimethylphenyl 93 H 4-trifluoromethoxyphenyl 94 H n-butyl 107-109 95 H s-butyl 83-85 96 H tert-butyl 65-67 97 H ethyl semi-solid propyl120-12298H 99 H allyl 118 100 H i-propyl 111-114 101 H n-pentyl 102 H n-hexyl 103 H n-heptyl 104 H n-octyl 105 H cyclobutyl 115-117 106 H cyclopentyl 107 H cyclohexyl oil 108H 2,2-dichlorocyclopropylmethyl 109 H 1,1,1-trifluoroprop-2-yl 110 H anilino 111 H methyl 87 112 H 2-fluoroethyl 105-107 113 H cyclopropylmethyl Example melting point (° C) No. R18 R'9 114 CH3 4-fluorophenyl semi-solid 115 CH3 cyclopropyl semi-solid 116 CH3 phenyl semi-solid 117 CH3 2,2,2-trifluoroethyl oil 118 H 2-methylpropyl 100-102 Herbicidal Activity To evaluate their herbicidal activity, compounds according to the invention are tested using a representative range of plants: Plant Species Used ABUTH Abutilon theophrasti velvetleaf ALOMY Alopecurus myosuroides blackgrass AMBEL Ambrosia artemisiifolia, L ragweed CASOB Senna obtusifolia sicklepod CHEAL Chenopodium album lambsquarters DIGSA Digitaria sanguinalis crabgrass ECHCG Echinichloa crus-galli barnyardgrass GALAP Galium aparine cleaver GLXMA Glycine max soybeans IPOHE Ipomoea hederacea morning glory MATIN Matricaria inodora mayweed PANDI Panicum Panicum dichotomiflorum SETVI Setaria viridis green foxtail TRZAW Tritium aestivum winter wheat ZEAMX Zea mays maize

The pre-emergence tests involve spraying a liquid formulation of the compound onto the soil in which the seeds of the plant species mentioned above has recently been sown. The soil used in the tests is a sandy loam.

The formulations used in the tests are prepared from solutions of the test compounds in acetone containing 0.4% by weight of an alkylphenol/ethylene oxide condensate available under the trade mark TRITON X-155. These acetone solutions are diluted with water and the resulting formulations applied at dosage levels corresponding to dose rates between 0.4 kg and 0.0125 kg, of active material per hectare in a volume equivalent to 900 litres per hectare. In these tests untreated sown soil are used as controls.

The herbicidal effects of the test compounds are assessed visually twenty-one days after spraying the foliage and the soil and visual ratings are made using the rating scale shown below.

Rating Scale % Control Rating (As Compared To Check) 9 100 8 91-99 7 80-90 6 65-79 5 45-64 4 30-44 3 16-29 2 6-15 <BR> 1 1-5<BR> 0 No Effect The results of the pre-emergence assessment are set out in Tables 8 to 11.

Table 8 Assessment (pre-emergence application) 21 days after treatment (dose rate 0.4 kq/ha) Example G T Z A E S A C G I M L R E L C E B A A P A X Z A O H T U S L O T M A M M C V T O A H A W X Y G I H B P E N 2 4 6 6 9 9 9 9 9 7 9 9 3 5 5 5 9 9 9 9 9 9 8 4 5 5 4 9 9 9 8 9 8 8 9 5 5 3 5 9 9 9 8 9 8 9 9 6 69999X8994 7 1 4 3 9 8 9 7 7 6 8 8 2 3 3 7 9 9 3 5 1 9 9 599997985 10 3 4 4 9 9 9 5 9 3 9 11 599999991 12 4 2 5 9 9 9 9 8 8 9

13 4 3 2 8 8 9 8 9 8 9 14 3 3 3 9 8 9 9 9 5 9 29 2 1 4 9 8 9 6 9 1 8 X = no value The compounds of the formula 11 have high activities against many weeds and show clearly improved selectivity in important crops (maize, soybeans, wheat, barley) when compared to the corresponding compounds of the state of the art having a 3-trifluormethylphenoxy moiety instead of the 5-trifluoromethyl-thienyl-3-oxy-group according to the invention.

Table 9 Pre-emergence Herbicidal Evaluation of Test Compounds Example Rate A A I E P G Z Number kg/ha B M P C A O E U B O H N S A T E H C D H M H L E G I I X <BR> <BR> <BR> <BR> 57 0. 2500 9. 0 9. 0 9. 0 9. 0 9. 0 5. 0 0.1250 9.0 9.0 9.0 9.0 9.0 0.0 66 0.2000 4.0 1.0 3.0 2.0 2.0 0.0 67 0.2000 1.0 3.0 0.0 1.0 3.0 0.0 68 0.2000 2.0 0.0 1.0 4.0 4.0 0.0 69 0.2000 0.0 1.0 1.0 2.0 2.0 0.0 70 0.2000 7.0 7.0 7.0 9.0 9.0 2.0 0.1000 6.0 5. 0 6. 0 1.0 Table 10 Pre-emergence Herbicidal Evaluation of Test Compounds Example Rate A A I M D E S Z Number kg/ha B M P A I C E E <BR> <BR> <BR> <BR> U B O T G H T A<BR> <BR> <BR> <BR> <BR> <BR> T E H I S C V M<BR> <BR> <BR> <BR> <BR> <BR> H L E N A G I X<BR> <BR> <BR> <BR> <BR> <BR> 58 0. 4000 8. 0 7. 0 9. 0 4. 0 9. 0 1. 5 0.1000 5.0 3. 0 9. 0 3. 0 5. 0 1.5 0.0250 4.0 3. 0 8. 0 1. 0 2. 0 1.0 59 0.4000 9.0 9. 0 5.0 0.1000 7.0 9. 0 4.0 0.0250 9.0 9. 0 8. 0 6. 0 8. 0 3.0 60 0.4000 2.0 8. 0 4. 0 6. 0 0.5 0.1000 1.0 8. 0 2. 0 3. 0 0.5 0.0250 1.0 4. 0 1. 0 2. 0 0.0 61 0.4000 9.0 9. 0 8. 0 9. 0 9. 0 4.0 0.1000 4.0 6. 0 8. 0 7. 0 9. 0 3.0 0.0250 4.0 6. 0 8. 0 6. 0 9. 0 2.0 62 0.4000 5.0 7. 0 8. 0 7. 0 9. 0 2.5 0.1000 3.0 3. 0 8. 0 5. 0 9. 0 1.0 0.0250 2.0 2. 0 5. 0 2. 0 6. 0 1.0 63 0.4000 0.0 3. 0 0. 0 0. 0 0.0 0.1000 0.0 0. 0 1. 0 0. 0 0. 0 0.0 64 0.4000 4.0 8.0 8.0 8.0 9.0 4.0 0.1000 3.0 7.0 8.0 7.0 9.0 3.0 0.0250 2.0 3.0 8.0 5.0 9.0 2.0 72 0.4000 9.0 9.0 9.0 8.0 9.0 4.0 0.1000 7.0 5.0 8.0 7.0 9.0 3.0 0.0250 6.0 4.0 8.0 6.0 9.0 2.0 73 0.4000 9.0 9.0 9.0 8.0 9.0 9.0 4.0 0.1000 6.0 8.0 3.0 8.0 8.0 9.0 2.5 0.0250 5.0 7.0 3.0 8.0 6.0 9.0 2.0 75 0.4000 8.0 9.0 3.0 9.0 8.0 5.0 9.0 2.0 0.1000 3.0 7.0 1.0 9.0 4.0 1.0 5.0 1.0 0.0250 0.0 3.0 1.0 6.0 1.0 0.0 1.0 1.0 76 0.4000 9.0 8.0 9.0 9.0 9.0 9.0 9.0 4.0 0.1000 9.0 8.0 9.0 9.0 9.0 8.0 9.0 3.0 0.0250 5.0 8.0 2.0 8.0 8.0 4.0 9.0 2.0 Table 11 Assessment (pre-emergence application) 21 days after treatment Example Dose kg/ha A A C I M A S G T Z B M H P A L E L R E <BR> <BR> <BR> U B E O T O T X Z A<BR> <BR> <BR> <BR> <BR> T E A H I M V M A M<BR> <BR> <BR> <BR> <BR> H L L E N Y I A W X No. 77 0. 400 5 8 9 6 9 9 9 1 2 2 0.100 4 6 9 4 8 5 9 1 0 1 0.025 3 5 8 2 7 2 4 1 0 1 No. 78 0.400 8 7 9 2 9 9 9 6 4 4

0.100 4 3 8 1 8 6 7 2 1 3 0.025 1 2 8 0 6 2 3 2 0 1 No. 79 0.400 6 8 9 2 8 8 9 1 2 2 0.100 2 6 9 1 8 5 8 1 1 1 0.025 2 5 8 1 7 2 3 0 0 0 No. 80 0.400 9 8 9 5 9 9 9 6 2 4 0.100 6 7 9 2 8 8 9 4 0 2 0.025 4 6 9 X 8 4 9 3 0 1 X = no value The compounds of the formula 13 have shown to clearly improve selectivity in important crops (maize, soybeans, wheat, barley) when compared to the corresponding compounds of the state of the art having a central 3-trifluormethylphenoxy moiety instead of the 5-trifluoromethyl- thienyl-3-oxy-group according to the invention. At the dose of 25 g/ha, which was well tolerated in maize and wheat, the compound of example 80 demonstrated good overall levels of weed control while conventional herbicides were not sufficiently selective in these crops.

The post-emergence herbicidal activity of the compounds of the present invention is demonstrated by the following test, wherein a variety of monocotyledonous and dicotyledonous plants are treated with formulations prepared from solutions of the test compounds in acetone containing 0,4 % by weight of an alkylphenol/ethylene oxide condensate available under the trade mark TRITON X-1 55. These acetone solutions were diluted with water and the resulting formulations applied at dosage levels equivalent of about 0.4 to 0.2 kg per hectare of test compound per pot. After spraying the plants are placed on greenhouse benches and are cared for in the usual manner, commensurate with conventional greenhouse practices. From 2 to 4 weeks after treatment, the seedling plants are examined and rated according to the rating system provided below.

%Control Rating (As Compared To Check) 9 100 8 91-99 7 80-90 6 65-79 5 45-64 4 30-44 3 16-29 2 6-15 1 1-5 0 No Effect The resuits of the tests are set out in Tables 12 to 15 below. The compounds of the invention showed good performance on monocotyledonous and dicotyledonous weeds: Table 12 Post-emergence application 21 days after treatment (dose rate: 0. 4 kg/ha) Example G T Z A E S A C G I M L R E L C E B A A P A X Z A O H T U S L O T<BR> M A M M C V T O A H<BR> A W X Y G I H B P E N<BR> 2 8 4 6 8 8 8 6 8 7 9 6 3 7 5 6 8 8 9 7 7 8 9 7 4 58885X7X55

5 58987X7X65 6 8 4 5 8 8 9 6 7 7 9 6 9 7 5 6 8 8 9 6 5 8 9 6 12 7 4 6 8 8 9 6 7 8 9 7 X = no value Table 13 Post-emergence Herbicidal Evaluation of Test Compounds Example Rate A A I E P Number kg/ha B M P C A U B O H N T E H C D <BR> H L E G !<BR> 57 0. 2500 9. 0 9. 0 9. 0 9. 0 66 0.2000 4.0 4.0 2.0 3.0 2.0 67 0.2000 4.0 3.0 4.0 2.0 3.0 68 0.2000 3.0 3.0 4.0 3.0 2.0 69 0.2000 2.0 3.0 4.0 3.0 3.0 70 0.2000 7.0 7.0 7.0 6.0 5.0 Table 14 Post-emergence Herbicidal Evaluation of Test Compounds Example Rate A A G I L M D E S Number kg/ha B M A P A A I C E U B L O M T G H T <BR> T E A H P I S C V<BR> H L P E U N A G 1 58 0. 400 5. 0 4.0 8.0 6. 0 4. 0 6. 0 59 0.400 8.0 6.0 7.5 9.0 7.5 8.5 7.5 60 0.400 5.0 4.0 6.0 9.0 8.0 5.0 7.0 61 0.400 7.0 6.0 7.0 9.0 7.0 8.0 6.0 62 0.400 6.0 5.0 7.0 9.0 7.0 7.0 7.0 63 0.400 0.0 4.0 2.0 3.0 3.0 0.0 0.0 64 0.400 5.0 7.0 8.0 9.0 8.0 8.0 8.0 72 0.400 7.0 6.0 7.0 9.0 7.0 8.0 6.0 73 0.400 7.0 6.0 8.0 9.0 7.0 8.0 7.0 74 0.400 7.0 5.0 7.0 9.0 7.0 8.0 6.0 75 0.400 8.0 7.0 7.0 9.0 8.0 7.0 8.0 76 0.400 9.0 8.0 8.0 9.0 8.0 9.0 8.0 Table 15 Post-emergence application Example Dose H T Z C G I L D E S kg/ha O R E A A P A I C E ASLOMGHTRZ MOAHPSCVVA W W X B P E U A G 334797789770.4 78 0.4 4 4 3 7 8 9 8 7 8 9 79 0.4 3 2 3 7 8 9 7 7 8 9 80 0.4 3 2 3 5 7 8 8 7 8 9