Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
  • C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
  • C07D401/12—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings linked by a chain containing hetero atoms as chain links
• • A—HUMAN NECESSITIES
  • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
  • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
  • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
  • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
  • A01N43/54—1,3-Diazines; Hydrogenated 1,3-diazines
• • A—HUMAN NECESSITIES
  • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
  • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
  • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
  • A01N43/64—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with three nitrogen atoms as the only ring hetero atoms
  • A01N43/66—1,3,5-Triazines, not hydrogenated and not substituted at the ring nitrogen atoms
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
  • C07D239/02—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings
  • C07D239/24—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members
  • C07D239/28—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, directly attached to ring carbon atoms
  • C07D239/46—Two or more oxygen, sulphur or nitrogen atoms
  • C07D239/60—Three or more oxygen or sulfur atoms
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D251/00—Heterocyclic compounds containing 1,3,5-triazine rings
  • C07D251/02—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings
  • C07D251/12—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
  • C07D251/26—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with only hetero atoms directly attached to ring carbon atoms
  • C07D251/30—Only oxygen atoms
  • C07D251/34—Cyanuric or isocyanuric esters
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
  • C07D409/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings
  • C07D409/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings linked by a chain containing hetero atoms as chain links

Definitions

• This invention provides compounds of the following Formula I which are useful as herbicides:
• A is O, S, or -N-R 2 in which R 2 is hydrogen, alkyl (for example, methyl or ethyl), -C(O)NH 2 , or -C(O)-alkyl (for example, -C(O)-CH 3 );
• B is -CH-, -CR 4 - or -N-;
• R and R 1 are independently alkyl (for example, methyl), alkoxy (for example, methoxy), haloalkoxy (for example, -OCHF 2 or -OCH 2 CH 2 Cl), or alkylamino (for example, -NHCH 3 or -N(CH 3 ) 2 ); halogen; and
• R 4 is hydrogen, alkyl, phenyl, nitro, cyano, amino, alkoxycarbonyl, or halogen;
• M is hydrogen, alkyl, alkenyl, alkynyl, phenylalkyl, haloalkyl, cyanoalkyl, alkylthioalkyl, dialkylamino- alkyl, alkylsulfonylalkyl, alkoxycarbonylalkyl, carboxy- alkyl, di(alkoxycarbonyl) alkyl, dialkylaminocarbonyl- alkyl, dialkylideneamino, alkylthioalkylideneamino, optionally alkyl substituted ammonium, optionally hydroxyalkyl substituted ammonium, the cation of an alkali or alkaline earth metal, or phenyl optionally substituted with nitro, halo, alkyl, haloalkyl or alkyloxy; and
• Q is Formula II in which X, Y, and P are independently hydrogen, halogen (for example, chlorine and fluorine), lower alkyl (for example, methyl), lower alkoxy (for example, methoxy ), cyano, nitro, amino, lower haloalkyl (for example, trifluoromethyl or difluoromethyl), lower haloalkoxy (for example, trifluoromethoxy or difluoromethoxy), lower alkylthio (for example, methylthio), lower
• alkylsulfonyl for example, methylsulfonyl
• alkylsulfonylamino alkylsulfonyloxy, arylsulfonyloxy, di(aryl sulfonyl) amino, benzylamino, alkylcarbonylamino, aminocarbonylamino, alkoxycarbonyl, alkylcarbonyloxy, alkylsulfonylamino, phenylsulfonylamino, acid salts of the noted amino compounds, lower alkenyl (for example, vinyl or methylvinyl), lower alkynyl (for example, ethynyl or propargyl), lower alkenyloxy (for example, 2- propenyl) or lower alkynyloxy (for example,
• Q is a 5- or 6-membered aromatic heterocyclic ring selected from thiophene, furan, pyrrole, pyrazole, isoxazole, isothiazole, imidazole, oxazole, thiazole, oxadiazole, thiadiazole, triazole, tetrazole, pyridine, pyrimidine, pyrazine, pyridazine and triazine;
• X', Y', W, V, U, X", Y", W, V and Z are independently nitrogen, oxygen, sulfur, -CH- or -CR 3 in which R 3 is halogen (for example, chlorine or fluorine), lower alkyl (for example, methyl or isopropyl), lower alkoxy (for example, methoxy) or lower haloalkoxy (for example, difluoromethoxy).
• R 3 is halogen (for example, chlorine or fluorine), lower alkyl (for example, methyl or isopropyl), lower alkoxy (for example, methoxy) or lower haloalkoxy (for example, difluoromethoxy).
• hydrocarbon moiety of any alkoxy group is a lower alkyl group having less than 6 carbon atoms, and preferably 1 to 3 carbon atoms.
• T is an acid precursor or derivative such as formyl, cyano, methylcarbonyl, dialkoxymethyl, alkyloxycarbonyl, aryloxycarbonyl, alkyl or halogen.
• the carboxy compounds of Formula I may be prepared, depending on the T substituent, by oxidation of the formyl group; hydrolysis of the cyano, aryloxycarbonyl or alkyloxycarbonyl groups; hydrolysis of the
• G is a leaving group such as chloro or
• methylsulfonyl Any of a variety of bases may be used including the alkali or alkaline earth metal carbonates, hydrides, hydroxides, or lower dialkylamines. Specific examples include the carbonates and hydroxides of sodium, potassium, lithium and calcium; the hydrides of sodium, lithium, and potassium; and lithium, sodium, or magnesium diisopropylamide.
• the compounds of Formula I having an oxygen bridge may also be prepared by reacting an optionally
• the optional substituent is preferably in, but not limited to, the 6-position.
• the product of the foregoing reaction would be a 6-optionally substituted salicylaldehyde.
• the 6- optionally substituted salicylaldehyde is in turn reacted with an inorganic base, for example potassium carbonate or sodium hydride, and an appropriately substituted heterocycle having a leaving group, such as chloro or methylsulfonyl, at the 2-position of the heterocyclic ring (for example 4,6-dimethoxy-2- methylsulfonylpyrimidine or 2-chloro-4,6-dimethoxy-
• benzaldehyde for example 6-optionally substituted 2-(4,6- dimethoxypyrimidin-2-yloxy)benzaldehyde or 2-(4,6- dimethoxy-1,3,5-triazin-2-yloxy)benzaldehyde,
• the benzoic acid compounds of Formula I having an oxygen or nitrogen bridge may be prepared by reacting a benzyl 6-substituted salicylate or anthranilate, respectively, with sodium hydride and the appropriately substituted heterocycle (for example 4,6-dimethoxy-2- methylsulfonylpyrimidine) to yield the corresponding benzoate (for example benzyl 6-substituted 2-(4,6- dimethoxypyrimidin-2-yloxy)benzoate or 2-(4,6- dimethoxypyrimidin-2-ylamino) benzoate, respectively).
• the benzoate is subjected to hydrogenolysis in the presence of palladium on carbon to yield the
• benzoic acid for example 6-substituted 2- (4,6-dimethoxypyrimidin-2-yloxy)benzoic acid or 2-(4,6- dimethoxypyrimidin-2-ylamino)benzoic acid,
• the benzoic acid compound of Formula I having a sulfur bridge may be prepared by reacting 6-optionally substituted anthranilic acid hydrochloride with
• diazonium salt 2-carboxy-3-optionally substituted benzenediazonium tetrafluoborate.
• the diazonium salt is in turn reacted with ethylxanthic acid potassium salt to afford the corresponding 6-optionally substituted-2-(ethoxythiocarbonylthio)benzoic acid.
• the benzoic acid is then hydrolyzed to yield the 6- optionally substituted-2-mercaptobenzoic acid.
• the mercaptobenzoic acid is reacted with sodium hydride and an appropriately substituted heterocycle (for example 4,6-dimethoxy-2-methysulfonylpyrimidine) to yield the corresponding benzoic acid of Formula I (for example 6- optionally substituted-2-(4,6-dimethoxypyrimidin-2- ylthio)benzoic acid).
• an appropriately substituted heterocycle for example 4,6-dimethoxy-2-methysulfonylpyrimidine
• the benzoic acid compound of Formula I in which Q is an optionally substituted alkyl or phenyl may also be prepared using a process involving a 2-ethoxycarbony1-3-(optionally substituted phenyl or alkyl) cyclohexen-5-one ester intermediate (intermediate Ila below) as described in F.M. Hauser et al., Synthesis. 10, 814 (1980).
• intermediate Ila 2-ethoxycarbony1-3-(optionally substituted phenyl or alkyl) cyclohexen-5-one ester intermediate
• Intermediate Ila may be prepared by reacting ethyl acetoacetate with the appropriately 3-(optionally substituted alkyl or phenyl)propenal in the presence of a base, such as sodium alkoxide (for example sodium ethoxide), to form the corresponding keto-aldehyde intermediate Ia which, without isolation, is thereafter cyclized by acid catalysis to the corresponding base, such as sodium alkoxide (for example sodium ethoxide), to form the corresponding keto-aldehyde intermediate Ia which, without isolation, is thereafter cyclized by acid catalysis to the corresponding
• a base such as sodium alkoxide (for example sodium ethoxide)
• the cyclohexenone intermediate Ila is then oxidized to the corresponding ethyl salicylate, for example ethyl 6- (optionally substituted phenyl or alkyl) salicylate, which is in turn hydrolyzed by basic catalysis to the corresponding salicylic acid (for example 6-(optionally substituted phenyl or alkyl) salicylic acid).
• ethyl salicylate for example ethyl 6- (optionally substituted phenyl or alkyl) salicylate
• salicylic acid for example 6-(optionally substituted phenyl or alkyl) salicylic acid
• the salicylic acid is then reacted with sodium hydride and the appropriately substituted heterocycle (for example 4,6-dimethoxy-2-methylsulfonylpyrimidine) to yield the corresponding benzoic acid of Formula I (for example 6- (optionally substituted phenyl or alkyl)-2-(4,6- dimethoxypyrimidin-2-yloxy)benzoic acid).
• heterocycle for example 4,6-dimethoxy-2-methylsulfonylpyrimidine
• the cyclohexenone intermediate Ila is reacted with phosphorous pentasulfide or ammonia, respectively, to yield the corresponding thioketo or imino ester (for example 2-ethoxycarbonyl-3- (optionally substituted phenyl or alkyl) cyclohex-5-enthione or 2-ethoxycarbonyl- 3-(optionally substituted phenyl or
• benzoate or anthranilate is subsequently reacted with potassium hydroxide in the presence of 1,4,7,10,13,16- hexaoxacyclooctadecane to yield the corresponding benzoic acid of Formula I (for example 2-mercapto-6- (substituted phenyl or alkyl)benzoic acid or 6- (substituted phenyl or alkyl) anthranilic acid,
• benzoic acid of Formula I for example 2-mercapto-6- (substituted phenyl or alkyl)benzoic acid or 6- (substituted phenyl or alkyl) anthranilic acid
• the starting material may be 2- methoxybenzaldehyde.
• the starting material may be 2- methylthiobenzaldehyde or 2-nitrobenzaldehyde,
• the palladium(II) intermediate is reacted with triphenyl- phosphine and the appropriately Q substituted magnesium bromide to yield the corresponding 6-Q-2-(methoxy-, methylthio-, or nitro-substituted) benzaldehyde.
• the benzaldehyde is reacted with boron tribromide or lithium iodide to cleave the methyl group thereby forming the corresponding salicylaldehyde or 2-mercaptobenzaldehyde, respectively.
• the benzaldehyde is hydrogenated in the presence of
• 6-phenylbenzoic acids for example 6-phenyl-2- (4 ,6-dimethoxypyrimidin-2-yloxy)benzoic acid may be esterified by the reaction of the acid with a halogen containing moiety under basic conditions in an
• the benzoic acid ester may be formed by reacting the benzoyl halide with an alcohol or a phenol.
• the benzoic acid is reacted with an alkylhaloformate such as methyl chloroformate in the presence of base to produce an intermediate mixed anhydride.
• the anhydride is then reacted with an alcohol or phenol to give an ester.
• the 6-phenylbenzoic acid may be esterified by the reaction of the acid with an alcohol or an optionally substituted phenol, for
• 4-nitrophenol and a dehydrating agent such as 1,3-dicyclohexlcarbodiimide or N,N'-carbonyldiimidazole in an appropriate solvent (methylene chloride).
• a dehydrating agent such as 1,3-dicyclohexlcarbodiimide or N,N'-carbonyldiimidazole in an appropriate solvent (methylene chloride).
• the 6- phenylbenzoic acid may be esterified with for example a lower alkyl alcohol by catalysis with acid.
• Alkylideneamino benzoates may be prepared as shown in Example 9 by the reaction of the 4-nitrophenyl benzoate with a ketone oxime in the presence of a base such as potassium carbonate.
• reaction mixture was stirred for one hour, and 90 mL of aqueous 6N hydrochloric acid was added dropwise. Upon completion of addition, the reaction mixture was stirred for one hour, and then it was filtered. The filtrate was diluted with 200 mL of diethyl ether and was washed with an aqueous solution saturated with sodium chloride. The organic layer was dried with magnesium sulfate and filtered. The filtrate was concentrated under reduced pressure to a residue. The residue was subjected to column chromatography on silica gel. Elution was accomplished using heptane followed by 2:1
• reaction mixture was cooled to 15°C, and 419 mL (1.83 mole) of sodium methoxide (25% in methanol) was added dropwise at a rate to maintain the reaction mixture temperature below 20°C. Upon completion of the addition, which required 45 minutes, the reaction mixture was allowed to warm to ambient temperature where it was stirred for 18 hours. After this time the reaction mixture was
• reaction mixture was cooled, and 500 mL of aqueous 1M sodium sulfite solution was added dropwise to destroy excess peroxides present in the reaction mixture.
• reaction mixture was stirred for 15 minutes and then was concentrated under reduced pressure to a residue.
• the residue was stirred in 2500 mL of ethyl acetate and 1500 mL of water. The layers were separated, and the aqueous layer was extracted with 450 mL of ethyl acetate.
• the concentrate was diluted with 50 mL of water and was extracted with two 50 mL portions of ethyl acetate. The aqueous layer was then acidified to pH 3 using aqueous 10% hydrochloric acid and reextracted with three 75 mL portions of ethyl acetate. The combined extracts were concentrated under reduced pressure to a residue. The residue was
• a second reaction mixture containing the reaction of 1.7 grams (0.0078 mole) of 2-methoxy-6-(thien-2- yl)benzaldehyde and 1.7 grams (0.013 mole) of anhydrous lithium iodide, in 10 mL of 2,4,6-trimethylpyridine was also acidified with aqueous 6N hydrochloric acid.
• the two acidified reaction mixtures were combined, and the combination was extracted with diethyl ether and then with ethyl acetate.
• the combined extracts were dried with magnesium sulfate and filtered.
• the filtrate was concentrated under reduced pressure to a residue.
• the residue was subjected to column chromatography on silica gel. Elution was accomplished using 50% heptane in methylene chloride. The appropriate fractions were combined and concentrated under reduced pressure, yielding 0.9 gram of 6-(thien-2-yl) salicylaldehyde.
• the nmr spectrum was consistent with the proposed structure.
• Step D Synthesis of 2-(4,6-dimethoxypyrimidin-2- yloxy)-6-(thien-2-yl)benzaldehyde as an Intermediate Under a nitrogen atmosphere a stirred solution of 0.7 grams (0.003 mole) of 6-(thien-2-yl)salicylaldehyde, 0.5 gram (0.004 mole) of potassium carbonate, and 0.7 gram (0.003 mole) of 4,6-dimethoxy-2- methylsulfonylpyrimidine in 10 mL of dimethylformamide was heated at 80°C for 2 hours. The reaction mixture was taken up in water and an aqueous solution saturated with sodium chloride, and then it was extracted with two portions of ethyl acetate. The combined extracts were dried with magnesium sulfate and filtered. The filtrate was concentrated under reduced pressure to a residue. The residue was evacuated under high vacuum, causing it to solidify. The solid was triturated with cold
• reaction mixture was stirred while being cooled in the ice-salt bath for 1 hour.
• the two reaction mixtures were combined and the combination was filtered through diatomaceous earth.
• Step B Synthesis of bis( ⁇ -acetato-O,O')bis[3- methylthio-2-[(phenylimino)methyl]phenyl-C,N]- dipalladium as an Intermediate
• a stirred mixture of 10.0 grams (0.044 mole) of N-[(2-methylthiophenyl)- methylene]benzeneamine and 10.0 grams (0.044 mole) of palladium(II) acetate in 125 mL of glacial acetic acid is heated at reflux for one hour. After this time the reaction mixture is poured into ice-water.
• reaction mixture Upon completion of addition, the reaction mixture is stirred for one hour, and 90 mL of aqueous 6N hydrochloric acid is added dropwise. Upon completion of addition, the reaction mixture is stirred for one hour and then is filtered. The filtrate is diluted with 200 mL of diethyl ether and is washed with an aqueous solution saturated with sodium chloride. The organic layer is dried with magnesium sulfate and filtered. The filtrate is concentrated under reduced pressure to a residue. The residue is subjected to column
• reaction mixture is taken up in 100 mL of water and extracted with 50 mL of ethyl acetate. The organic layer is dried with magnesium sulfate and filtered. The filtrate is concentrated under reduced pressure, yielding 2-(4,6-dimethoxypyrimidin-2-ylthio)- 6-phenylbenzaldehyde.
• the concentrate is diluted with 50 mL of water and is extracted with two 50 mL portions of ethyl acetate.
• the aqueous layer is then acidified to pH 3 using aqueous 10% hydrochloric acid and reextracted with three 75 mL portions of ethyl acetate.
• the combined extracts are concentrated under reduced pressure, yielding 2-(4,6-dimethoxypyrimidin-2-ylthio)-6- phenylbenzoic acid.
• reaction mixture Under a nitrogen atmosphere, 0.1 gram (0.004 mole) of sodium metal was reacted in 40 mL of ethanol. The solution was stirred, and 13.0 grams (0.100 mole) of ethyl acetoacetate was added. The reaction mixture was cooled in an ice bath, and 13.2 grams (0.100 mole) of trans-cinnamaldehyde in 10 mL of ethanol was added dropwise during a 10 minute period. Upon completion of addition, the reaction mixture was allowed to warm to ambient temperature where it stirred for about 18 hours. After this time the reaction mixture was saturated with gaseous hydrochloric acid and then was allowed to stand for about 65 hours. The reaction mixture was
• reaction mixture was combined with another reaction mixture consisting of the reaction of 1.73 grams (0.0079 mole) of 6-phenylsalicylic acid, 1.70 grams (0.0079 mole) of 4,6-dimethoxy-2- methylsulfonylpyrimidine and 0.78 gram (0.016 mole) of 50-60% sodium hydride in mineral dissolved in 120 mL of tetrahydrofuran.
• the combination was taken up in water and was washed with diethyl ether.
• the aqueous layer was acidified to a pH of 2 with aqueous normal
• Step B Synthesis of ethyl 6-(4-nitrophenyl)salicylate as an intermediate A stirred solution of 15.5 grams (0.054 mole) of 2- ethoxycarbonyl-3-(4-nitrophenyl)cyclohex-5-enone in 40 mL of carbon tetrachloride was cooled in an ice bath, and a solution of 2.8 mL (0.054 mole) of bromine in 40 mL of acetic acid was added in one portion. Upon completion of addition, the reaction mixture was cooled for an additional 40 minutes, and then it was warmed to reflux where it was stirred for about 18 hours.
• reaction mixture was cooled to ambient temperature where it was stirred with 45 mL of water, an additional 45 mL of carbon tetrachloride, and 45 mL of methylene chloride.
• the organic layer was separated was washed with two portions of water and one portion of an aqueous solution saturated with sodium bicarbonate. The mixture was filtered, and the filtrate was concentrated under reduced pressure, yielding 16.4 grams of ethyl 6- (4-nitrophenyl) salicylate.
• Steps A and B of this Example were prepared by the method of Heuser and Pogany Step C Synthesis of 6-(4-nitrophenyl)salicylic acid as an intermediate
• the aqueous concentrate was washed with diethyl ether and then acidified to pH 1 with aqueous 6N hydrochloric acid.
• the mixture was extracted with one portion of ethyl acetate.
• the separation of the aqueous and the organic layers was incomplete.
• the mixture was passed through diatomaceous earth, which resulted in the separation of the layers.
• the organic layer was removed, and the aqueous layer was extracted with two additional portions of ethyl acetate.
• the combined extracts were dried with magnesium sulfate, and the mixture was filtered.
• the filtrate was concentrated under reduced pressure to a solid residue.
• reaction mixture was heated at reflux for two days. After this time the reaction mixture was poured into water. The mixture was
• Step D Synthesis of 2-fluoro-6-(2,4,6- trimethylphenyl)benzaldehyde as an intermediate
• a 9.0 gram (0.02 mole) sample of 2-[2-fluoro-6- (2,4, 6-trimethylphenyl)phenyl]-4,5-dihydro-3,4,4- trimethyloxazolium iodide was completely dissolved in 52 mL of ethanol and, with stirring, 1.1 grams (0.03 mole) of sodium borohydride was cautiously added during a 10 minute period. Upon completion of addition, the reaction mixture was stirred at ambient temperature for two hours. After this time 166 mL of aqueous 3N hydrochloric acid was slowly added.
• This compound was prepared in a manner analogous to that of Example 1, Step H, using 1.3 grams (0.005 mole) of 6-(2,4,6-trimethylphenyl)-salicylaldehyde, 1.2 grams (0.005 mole) of 4,6-dimethoxy-2-methylsulfonylpyrimidine (prepared in Example 1, Steps E-G), and 0.8 gram (0.006 mole) of potassium carbonate in 8.5 mL of
• This compound was prepared in a manner analogous to that of Example 1, Step I, using 1.3 grams (0.003 mole) of 2-(4,6-dimethoxypyrimidin-2-yloxy)-6-(2,4,6- trimethylphenyl)benzaldehyde, 0.8 gram (0.005 mole) of sodium phosphate, dibasic heptahydrate in 22.5 mL of water and 39 mL of acetone.
• the reaction mixture was filtered through diatomaceous earth.
• the filtrate was acidified with concentrated hydrochloric acid and then it was extracted with methylene chloride.
• the extract was washed with an aqueous solution saturated with sodium chloride, and then it was dried with sodium sulfate.
• Step B Synthesis of 2-ethoxycarbonyl-3-(pyridin-4- yl)cyclohex-5-enone as an intermediate
• This compound was prepared in a manner analogous to that of Example 5, Step A, using 21.8 grams (0.163 mole) of 3-(pyridin-4-yl)propenal, 20.6 grams (0.158 mole) of ethyl acetoacetate, 0.8 gram (0.005 mole) of the sodium salt of ethyl acetoacetate in 60 mL of ethanol.
• This compound was prepared in a manner analogous to that of Example 5, Step B, using 38.6 grams (0.158 mole) of 2-ethoxycarbonyl-3-(pyridin-4-yl)cyclohex-5-enone, 8.5 mL (0.160 mole) of bromine, 110 mL of acetic acid and 110 mL of carbon tetrachloride.
• the reaction mixture residue was subjected to column chromatography using silica gel. Elution was accomplished first with methylene chloride, and then with 5% methanol in methylene chloride. The appropriate fractions were combined and concentrated under reduced pressure to a residue.
• a hydrogenfilled balloon was attached to a syringe, and the syringe was inserted through a septum placed over a neck of the reaction vessel.
• the reaction mixture was stirred under the hydrogen atmosphere for about one hour.
• a sample of the reaction mixture was subjected to thin layer chromatography, which indicated that the reaction had gone to completion.
• the reaction vessel was evacuated and filled with nitrogen several times.
• the reaction mixture was filtered through diatomaceous earth and the filtrate was concentrated under reduced pressure to a residual oil. The oil was crystallized with carbon tetrachloride, and the solid was triturated with carbon tetrachloride and hexane.
• acetonitrile was heated at 60oC for about 18 hours. The reaction mixture was cooled, and 50 grams of silica gel was added. The acetonitrile was removed under reduced pressure. The silica gel-reaction mixture was placed on the top of a silica gel column and was eluted with 1:2 - ethyl acetate and hexane. The appropriate fractions were combined and concentrated under reduced pressure to a residual solid. The solid was recrystallized with 1:6 - ethyl acetate and hexane, yielding 11.8 grams of 4- chlorocinnamaldehyde; m.p. 51-56oC. The nmr spectrum was consistent with the proposed structure.
• This compound was prepared in a manner analogous to that of Example 5, Step A, using 11.3 grams (0.071 mole) of 4-chlorocinnamaldehyde, 9.0 grams (0.069 mole) of ethyl acetoacetate, and 0.3 gram (0.002 mole) of the sodium salt of ethyl acetoacetate in 26 mL of ethanol.
• the crude reaction mixture was concentrated under reduced pressure to a residue. The residue was
• Step C Synthesis of ethyl 6-(4-chlorophenyl) salicylate as an intermediate
• the reaction mixture was warmed to 80-85oC where it was stirred for about 18 hours. After this time the reaction mixture was cooled, and 200 mL of diethyl ether was added.
• the solution was washed with three 200 mL portions of water and one portion of an aqueous solution saturated with sodium chloride.
• the organic layer was dried with magnesium sulfate and filtered.
• the filtrate was concentrated under reduced pressure to a residue.
• the residue was subjected to column chromatography on silica gel. Elution was accomplished using 1:4 - ethyl acetate in hexane. The appropriate fractions were combined and concentrated under reduced pressure to a residue. An nmr spectrum of the residue indicated it to be about 80% pure reaction product.
• the residue was subjected to a second column chromatography on silica gel. Elution was accomplished using 7.5:92.5 ethyl acetate in hexane.
• reaction mixture Upon completion of addition the reaction mixture was stirred for about four days. After this time the reaction mixture was poured into aqueous 1N hydrochloric acid. The mixture was extracted with diethyl ether.
• Step G Synthesis of phenylmethyl 2-(4,6-dimethoxy- 1,3,5-triazin-2-yloxy)-6-(4- chlorophenyl)benzoate as an intermediate
• This compound was prepared in a manner analogous to that of Example 7, Step E, using 0.55 gram (0.002 mole) of phenylmethyl 6-(4-chlorophenyl) salicylate, 0.28 gram (0.002 mole) of 2-chloro-4,6-dimethoxy-1,3,5-triazine, and 0.06 gram (0.002 mole) of 60% sodium hydride (in mineral oil) in 5.1 mL of dimethylformamide. Upon completion of addition, the reaction mixture was stirred at ambient temperature for about 18 hours.
• the reaction mixture was poured into water, and the mixture was extracted with ethyl acetate.
• the extract was washed with aqueous 1N hydrochloric acid, with water, and then with an aqueous solution saturated with sodium chloride.
• the organic layer was dried with magnesium sulfate and filtered.
• the filtrate was concentrated under reduced pressure to a residual oil.
• the oil was subjected to column chromatography on silica gel. Elution was accomplished using 1:1.5-ethyl acetate in hexane. The appropriate fractions were combined and concentrated under reduced pressure, yielding 0.63 gram of
• Step H Synthesis of 2-(4,6-dimethoxy-1,3,5-triazin-2- yloxy)-6-(4-chlorophenyl)benzoic acid (Compound 113)
• the mixture was hydrogenated using a Parr hydrogenation apparatus. Upon the completion of the uptake of the theoretical amount of hydrogen gas, the reaction mixture was filtered through diatomaceous earth. The filtrate was washed with methylene chloride, and the ethanol/acetic acid layer was concentrated under reduced pressure to remove the ethanol. The concentrate was shaken with water and ethyl acetate. The organic layer was washed with an aqueous solution saturated with sodium chloride and then was dried with magnesium sulfate. The mixture was filtered, and the filtrate was concentrated under reduced pressure, yielding 0.43 gram of 2-(4,6-dimethoxy-1,3,5-triazin-2-yloxy)-6-(4- chlorophenyl) benzoic acid. The nmr spectrum was consistent with the proposed structure.
• Step A Synthesis of 4-nitrophenyl 2-(4,6- dimethoxypyrimidin-2-yloxy)-6-phenylbenzoate as an intermediate Under a nitrogen atmosphere a stirred solution of 1.0 gram (0.003 mole) of 2-(4,6-dimethoxypyrimidin-2- yloxy)-6-phenylbenzoic (prepared as described in Example 1) in 30 mL of methylene chloride was cooled to 0°C, and 0.3 gram (0.003 mole) of 4-nitrophenol was added. When the phenol had dissolved, 0.6 gram (0.003 mole) of dicyclohexylcarbodiimide (DCC) was added.
• DCC dicyclohexylcarbodiimide
• reaction mixture was stirred at 0oC for one hour, and then was allowed to warm to ambient temperature where it was stirred for an
• Step A Synthesis of 5-chloro-4,6-dimethoxy-2- methylsulfonylpyrimidine as an intermediate Under a nitrogen atmosphere a stirred solution of 9.7 grams (0.045 mole) of 4,6-dimethoxy-2- methylsulfonylpyrimidine and 6.0 grams (0.045 mole) of N-chlorosuccinimide in 25 mL of glacial acetic acid was heated at 95-100oC for three hours. After this time the reaction mixture was allowed to cool to ambient
• This compound was prepared in a manner analogous to that of Example 5, Step D, using 0.50 gram (0.002 mole) of 6-phenylsalicylic acid (prepared as in Example 4, Steps A-C), 0.89 gram (0.004 mole) of 5-chloro-4,6- dimethoxy-2-methylsulfonylpyrimidine, and 0.18 gram (0.006 mole) of 80% sodium hydride in 60 mL of
• the plant test species used in demonstrating the herbicidal activity of compounds of this invention include velvetleaf (AbutiIon theoprasti), blackgrass (Alopecurus m ⁇ osuroides), soybean (Glvcine max),
• Two disposable fiber flats (8 cm x 15 cm x 25 cm) for each rate of application for each candidate herbicide for preemergence testing are filled to an approximate depth of 6.5 cm with steam sterilized sandy loam soil.
• the soil is leveled and impressed with a template to provide six evenly spaced furrows 13 cm long and 0.5 cm deep in each flat. Seeds of corn, wheat, soybean, johnsongrass, and green foxtail are planted in five of the furrows of the first flat (the sixth furrow is left unplanted), and seeds of morningglory, velvetleaf, common cocklebur, blackgrass and common chickweed are planted in the five furrows of the second flat.
• the template is again employed to firmly press the seeds into place.
• a topping soil of equal portions of sand and sandy loam soil is placed uniformly on top of each flat to a depth of approximately 0.5 cm.
• the flats for the preemergence test were first watered and then drenched with a solution of test compound as described below.
• the flats were placed in a greenhouse and watered regularly at the soil surface for 21 days at which time phytotoxicity data were recorded.
• Two flats for each rate of application for each herbicide candidate are also prepared for postemergence application.
• the postemergence flats are prepared in the manner as described above for preemergence flats.
• the flats for the postemergence test were placed in a greenhouse and watered for 8-10 days after which the foliage of the emerged test plants was sprayed with a solution of the test compound. After spraying, the foliage was kept dry for 24 hours and then watered regularly for 21 days after which phytotoxicity data were recorded.
• the candidate herbicides were applied as aqueous acetone solutions at rates equivalent to 8.0 kilograms/hectare (kg/ha) and submultiples thereof, i.e., 4.0 kg/ha, 2.0 kg/ha, and so on.
• Preemergence applications were made as soil drenches using 100 mL of test solution of appropriate concentration for each of the two
• test compound For flats of the size described above, an application rate of 8.0 kg/ha of test compound is equivalent to 0.025 gram/flat.
• a stock solution of 0.2 gram of test compound in 40 mL of acetone containing 0.5% v/v of sorbitan monolaurate emulsifier/solubilizer was
• Percent control is determined by a method similar to the 0 to 100 rating system disclosed in "Research Methods in Weed Science,” 2nd ed., B. Truelove, Ed.; Southern Weed Science Society; Auburn University, Auburn, Alabama, 1977.
• the rating system is as follows:
• the active compounds are formulated into herbicidal compositions by admixture in herbicidally effective amounts with adjuvants and carriers normally employed in the art for facilitating the dispersion of active ingredients for the particular utility desired, recognizing the fact that the formulation and mode of application of a toxicant may affect the activity of the material in a given application.
• the present herbicidal compounds may be formulated as granules of relatively large particle size, as water-soluble or water-dispersible granules, as powdery dusts, as wettable powders, as emulsifiable concentrates, as solutions, or as any of several other known types of formulations, depending on the desired mode of application.
• herbicidal compositions may be applied either as water-diluted sprays, or dusts, or granules to the areas in which suppression of vegetation is desired.
• formulations may contain as little as 0.1%, 0.2% or 0.5% to as much as 95% or more by weight of active ingredient.
• Dusts are free flowing admixtures of the active ingredient with finely divided solids such as talc, natural clays, kieselguhr, flours such as walnut shell and cottonseed flours, and other organic and inorganic solids which act as dispersants and carriers for the toxicant; these finely divided solids have an average particle size of less than about 50 microns.
• a typical dust formulation useful herein is one containing 1.0 part or less of the herbicidal compound and 99.0 parts of talc.
• Wettable powders also useful formulations for both pre- and postemergence herbicides, are in the form of finely divided particles which disperse readily in water or other dispersant.
• the wettable powder is ultimately applied to the soil either as a dry dust or as an emulsion in water or other liquid.
• Typical carriers for wettable powders include Fuller's earth, kaolin clays, silicas, and other highly absorbent, readily wet inorganic diluents.
• Wettable powders normally are prepared to contain about 5-80% of active ingredient, depending on the absorbency of the carrier, and usually also contain a small amount of a wetting, dispersing or emulsifying agent to facilitate dispersion.
• a useful wettable powder formulation contains 80.8 parts of the herbicidal compound, 17.9 parts of
• Palmetto clay 1.0 part of sodium lignosulfonate and 0.3 part of sulfonated aliphatic polyester as wetting agents.
• Other wettable powder formulations are: Component: % by Wt.
• Active ingredient 40 is Active ingredient 40. 00
• ECs emulsifiable concentrates
• ECs emulsifiable concentrates
• ECs emulsifiable concentrates
• these concentrates are dispersed in water or other liquid carrier, and normally applied as a spray to the area to be treated.
• the percentage by weight of the essential active ingredient may vary according to the manner in which the composition is to be applied, but in general comprises 0.5 to 95% of active ingredient by weight of the herbicidal composition.
• Flowable formulations are similar to ECs except that the active ingredient is suspended in a liquid carrier, generally water.
• Flowables like ECs, may include a small amount of a surfactant, and contain active ingredient in the range of 0.5 to 95%, frequently from 10 to 50%, by weight of the composition.
• flowables may be diluted in water or other liquid vehicle, and are normally applied as a spray to the area to be treated.
• Typical wetting, dispersing or emulsifying agents used in agricultural formulations include, but are not limited to, the alkyl and alkylaryl sulfonates and sulfates and their sodium salts; alkylaryl polyether alcohols; sulfated higher alcohols; polyethylene oxides; sulfonated animal and vegetable oils; sulfonated petroleum oils; fatty acid esters of polyhydric alcohols and the ethylene oxide addition products of such esters; and the addition product of long-chain mercaptans and ethylene oxide.
• the surfaceactive agent when used, normally comprises from 1 to 15% by weight of the composition.
• compositions include simple solutions or suspensions of the active ingredient in a relatively non-volatile solvent such as water, corn oil, kerosene, propylene glycol, or other suitable solvents.
• a relatively non-volatile solvent such as water, corn oil, kerosene, propylene glycol, or other suitable solvents.
• Aqueous Suspension % by Wt.
• Active ingredient 40 . 00
• concentrates, flowable concentrates, solutions, etc. may be diluted with water to give a concentration of active ingredient in the range of say 0.1% or 0.2% to 1.5% or 2%.
• the active herbicidal compounds of this invention may be formulated and/or applied with insecticides, fungicides, nematicides, plant growth regulators, fertilizers, or other agricultural chemicals and may be used as effective soil sterilants as well as selective herbicides in agriculture.
• an effective amount and concentration of the active compound is of course employed; the amount may be as low as, for example, about 1 to 250 g/ha, preferably about 4 to 30 g/ha.
• higher application rates for example, four times the rates mentioned above may be employed.
• the active herbicidal compounds of this invention may be used in combination with other herbicides, for example, they may be mixed with, say, an equal or larger amount of a known herbicide such as chloroacetanilide herbicides such as 2-chloro-N-(2,6-diethylphenyl)-N- (methoxymethyl)acetamide (alachlor), 2-chloro-N-(2- ethyl-6-methylphenyl-N-(2-methoxy-1- methylethyl)acetamide (metolachlor), and N-chloroacetyl- N-(2,6-diethylphenyl) glycine (diethatyl-ethyl);
• chloroacetanilide herbicides such as 2-chloro-N-(2,6-diethylphenyl)-N- (methoxymethyl)acetamide (alachlor), 2-chloro-N-(2- ethyl-6-methylphenyl-N-(
• benzothiadiazinone herbicides such as 3-(1-methylethyl)- (1H)-2,1,3-benzothiadiazin-4-(3H)-one-2,2-dioxide
• triazine herbicides such as 6-chloro-N- ethyl-N-(1-methylethyl)-1,3,5-triazine-2,4-diamine

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• 1991
  • 1991-01-30 AU AU73242/91A patent/AU7324291A/en not_active Abandoned
  • 1991-01-30 WO PCT/US1991/000629 patent/WO1991013065A1/en unknown
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