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WO1989000991A1 - Sulfonamides herbicides - Google Patents

Sulfonamides herbicides Download PDF

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Publication number
WO1989000991A1
WO1989000991A1 PCT/US1988/002459 US8802459W WO8900991A1 WO 1989000991 A1 WO1989000991 A1 WO 1989000991A1 US 8802459 W US8802459 W US 8802459W WO 8900991 A1 WO8900991 A1 WO 8900991A1
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Prior art keywords
och
alkyl
compound according
amino
alkoxy
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PCT/US1988/002459
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English (en)
Inventor
Morris Padgett Rorer
Original Assignee
E.I. Du Pont De Nemours And Company
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Filing date
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Application filed by E.I. Du Pont De Nemours And Company filed Critical E.I. Du Pont De Nemours And Company
Priority to AU21334/88A priority Critical patent/AU611191B2/en
Publication of WO1989000991A1 publication Critical patent/WO1989000991A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D521/00—Heterocyclic compounds containing unspecified hetero rings
    • 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
    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
    • A01N47/28—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N<
    • A01N47/36—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N< containing the group >N—CO—N< directly attached to at least one heterocyclic ring; Thio analogues thereof

Definitions

  • This invention pertains to compounds of Formula I, including their agriculturally suitable salts, herbicidal compositions containing said compounds and use thereof as preemergent herbicides, postemergent herbicides and/or plant growth regulants.
  • the compounds will be described and claimed with respect to Formula I, it being understood that all salts are included as well.
  • the compounds are:
  • E is a single bond or -CH 2 -;
  • T 1 is selected from CN, F, Cl, Br, SCN, N 3 , C 1 to C 2 alkoxy, C 1 to C 2 thioalkyl, NH(C 1 to C 2 alkyl), N(C 1 to C 2 alkyl) 2 , N(OCH 3 )CH 3 and H 2 ) 3 or A ;
  • T 2 is selected from H; C 1 to C 3 alkyl optionally substituted with CN, OCH 3 , SCH 3 or halogen; eyelopropyl; F; Cl; Br; CN; SCN; N 3 ; C 1 to C 2 alkoxy; C 1 to C 2 thioalkyl; NH(C 1 to C 2 alkyl); N(C 1 to C 2 alkyl) 2 ; N(OCH 3 )CH 3 and H 2 ) 3 or 4; R 1 is selected from H, C 1 to C 3 alkyl, C 1 to C 3 haloalkyl, halogen, CN, nitro, C 1 to C 3 alkoxy, C 1 to C 3 haloalkoxy, C 1 to C 3 alkylthio, C 1 to C 3 alkylsulfinyl, C 1 to C 3 alkylsulfonyl, SCF 2 H, NH 2 , NHCH 3 , N(CH3) 2 or
  • R 2 is selected from H, F, Cl, Br, C 1 to C 2 alkyl, C 1 to C 2 haloalkyl or C 1 to C 2 alkoxy;
  • R 3 is selected from H, C 1 to C 3 alkyl, C 1 to C 2 haloalkyl, C 3 to C 4 alkenyl, C 3 to C 4 alkynyl, CH 2 CN, phenyl and phenyl substituted by F, Cl, CH 3 or OCH 3 ; n is 0 or 1;
  • R is H or CH 3 ;
  • W is O or S; A is selected from h h
  • X is selected from H, C 1 to C 4 alkyl, C 1 to C 4 alkoxy, C 1 to C 4 haloalkoxy, C 1 to C 4 haloalkyl, C 1 to C 4 haloalkylthio, C 1 to C 4 alkylthio, halogen, C 2 to C 5 alkoxyalkyl, C 2 to C 5 alkoxyalkoxy, amino, C 1 to C 3 alkylamino, diC 1 to C 3 alkyl) amino or C 3 to C 5 eyeloalkyl;
  • Y is selected from H, C 1 to C 4 alkyl, C 1 to C 4 alkoxy, C 1 to C 4 haloalkoxy, C 1 to C 4 haloalkylthio, C 1 to C 4 alkylthio, C 2 to C 5 alkoxyalkyl, C 2 to C 5 alkoxyalkoxy, amino, C 1 to C 3 alkylamino, di(C 1 to C 3 alkyl) amino, C
  • m 2 or 3;
  • L 1 and L 2 are independently O or S;
  • R a is H or C 1 to C 3 alkyl;
  • R b and R c are independently C 1 to C 3 alkyl; Z is CH or N; Z 1 is CH or N; Y 1 is O or CH 2 ;
  • X 1 is CH 3 , OCH 3 , OC 2 H 5 or OCF 2 H;
  • X 2 is CH 3 , C 2 H 5 or CH 2 CF 3 ;
  • Y 2 is OCH 3 , OC 2 H 5 , SCH 3 , SC 2 H 5 , CH 3 or CH 2 CH 3 ;
  • X 3 is CH 3 or OCH 3 ;
  • Y 3 is H or CH 3 ;
  • X 4 is CH 3 , OCH 3 , OC 2 H 5 , CH 2 OCH 3 or Cl; and Y 4 is CH 3 , OCH 3 , OC 2 H 5 or Cl; provided that
  • alkyl used either alone or in compound words such as “alkylthio” or “haloalkyl,” denotes straight chain or branched alkyl, such as methyl, ethyl, n-propyl, isopropyl or the different butyl and pentyl isomers.
  • Alkoxy denotes methoxy, ethoxy, n-propyl- oxy, isopropyloxy and the different butyl isomers.
  • Alkenyl denotes straight chain or branched alkenes, such as 1-propenyl, 2-propenyl, 3-propenyl and the different butenyl and pentenyl isomers.
  • Alkynyl denotes straight chain or branched alkynes, such as ethynyl, 1-propynyl, 2-pro ⁇ ynyl and the different butynyl and pentynyl isomers.
  • Alkylsulfonyl denotes methylsulfonyl, ethylsulfonyl and the different propylsulfonyl isomers,
  • Preferred Compounds A are compounds of Formula I wherein: E is a single bond;
  • Preferred Compounds B are compounds of Formula I wherein:
  • E is CH 2 or J is J-6; and W is O.
  • Preferred Compounds C are compounds A wherein:
  • R 1 is selected from H, F, Cl, Br, CH 2 CN, CH 3 , OCH 3 , SCH 3 or OCF 2 H;
  • R 2 is selected from H, F, Cl, Br or CH 3 ;
  • X is selected from C 1 to C 2 alkyl, C 1 to C 2 alkoxy, Cl, F, Br, I, OCF 2 H, CH 2 F, CF 3 , OCH 2 CH 2 F, OCH 2 CHF 2 , OCH 2 CF 3 , CH 2 Cl and CH 2 Br;
  • Preferred Compounds D are compounds C wherein: A is A-1; n is O;
  • X is selected from CH 3 , OCH 3 , OCH 2 CH 3 , Cl or OCF 2 H;
  • Y is selected from CH 3 , OCH 3 , C 2 H 5 , CH 2 OCH 3 , NHCH 3 , CH(OCH 3 ) 2 and cyclopropyl.
  • Preferred Compounds E are compounds D wherein: R is H;
  • T 1 is selected from CN, Cl and C 1 to C 2 alkoxy; and T 2 is selected from H, C 1 to C 3 alkyl, cyclopropyl, Cl, CN and C 1 to C 2 alkoxy.
  • J is J-1 to J-5 and J-7 to J-13.
  • Specifically preferred compounds are:
  • Equation 1 illustrates the reaction of sulfonamides II with the phenol ester of the appropriate carbamie acid or thiocarbamic acid of
  • the reaction of Equation 1 is best carried out at about -5° to 25°C is an inert solvent such as dioxane or acetonitrile for 1 to 24 hours, optionally under an inert atmosphere and in the presence of an equimolar quantity of DBU.
  • the desired products of Formula I can be conveniently isolated by acidifying the reaction solution with aqueous hydrochloric acid or acetic acid and filtration. Alternatively, the aqueous layer can be extracted with a solvent such as methylene chloride. Drying and evaporating the solvent affords the desired product.
  • phenylcarbamate and phenylthiocarbamate intermediates of Formula III can be prepared by methods, or obvious modifications thereof, described in South African Patent Application 82/5671 and South African Patent Application 82/5045.
  • Equation 2 illustrates the reaction of sulfonylisocyanates and sulfonylisothiocyanates of Formula IV with the appropriate heterocyclic amines of Formula V.
  • Equation 2 The reaction of Equation 2 is best carried out in an inert solvent such as methylene chloride, tetrahydrofuran, toluene or acetonitrile at a temperature between about 0° and 80°C.
  • an inert solvent such as methylene chloride, tetrahydrofuran, toluene or acetonitrile at a temperature between about 0° and 80°C.
  • DABCO 1,4-diazabicyclo[2.2.2] octane
  • the products can be isolated by simple filtration. Soluble products can be isolated by evaporation of the solvent and trituration of the residue with solvents such as 1-chlorobutane, diethyl ether or ethyl acetate, and filtration.
  • sulfonamides are converted to isolatable n-butylsulfonylureas which are reacted further with phosgene and a tertiary amine catalyst to form sulfonyl isocyanates.
  • the analogous one-step procedure can be employed by using the method described in U.S. Patent 4,238,621.
  • sulfonamides can be reacted with thionyl chloride to form intermediate N-sulfinylsulfonamides, which upon exposure to phosgene in the presence of a catalytic amount of pyridine, provide sulfonyl isocyanates.
  • thionyl chloride to form intermediate N-sulfinylsulfonamides, which upon exposure to phosgene in the presence of a catalytic amount of pyridine, provide sulfonyl isocyanates.
  • Equation 3 The reaction of Equation 3 is carried out at about 20° to 100°C in an inert solvent such as p-dioxane for 0.5 to 24 hours. Additional details concerning the general coupling reaction to prepare sulfonylureas can be found in EPA 44,807.
  • the product is isolated by evaporation of the reaction solvent and purified by trituration of the residue with solvents such as 1-chlorobutane or ethyl ether, and filtration, or by chromatography procedures on silica gel.
  • Phenylcarbamates and phenylthiocarbamates of Formula VI are prepared by methods described, or obvious modifications thereof, in U.S. Patent 4,443,243, EPA 44,808 or South African Patent Application 82/5042.
  • Equation 4 illustrates the reaction of sulfonamides of Formula Ia with appropriate salts or amines to form corresponding sulfonamides of Formula lb.
  • P is SO 2 NHCNR-A
  • A, Alk, R and R 1 are as previously defined;
  • M is Na + or K + ;
  • Ta is CN, SCN, N 3 , C 1 to C 3 alkoxy, C 1 to C 2 thioalkyl, or F;
  • Tb is NH(C 1 to C 2 alkyl), N(C 1 to C 2 alkyl) 2 , N(OCH 3 )CH 3 , or CH 2 ) 3 or 4 ;
  • Tc is Ta or Tb.
  • the reaction of Equation 4 is effected by reacting Ia with at least one molar equivalent of salt M-Ta (at least two molar equivalents when Ta is an alkoxide or mercaptide) in an inert solvent such as acetone, methyl ethyl ketone, tetrahydrofuran, dioxane, methanol, dimethylformamide (DMF), dimethylsulfone or dimethylsulfoxide.
  • an inert solvent such as acetone, methyl ethyl ketone, tetrahydrofuran, dioxane, methanol, dimethylformamide (DMF), dimethylsulfone or dimethylsulfoxide.
  • the reaction is carried out at about 20° to 140°C for 1 to 24 hours, and optionally in the presence of a phase transfer catalyst such as a crown ether.
  • Products lb (Tc is Ta) are isolated by addition of water, acidification if Ta is alkoxide or mercaptide, and filtration. Alternatively, the aqueous suspension is extracted with a solvent such as methylene chloride, dried and the solvent evaporated to yield crude lb. Product lb can be purified further by trituration with a solvent such as 1-chlorobutane, ethyl acetate or diethyl ether, and filtration, or by chromatography procedures on silica gel.
  • a solvent such as 1-chlorobutane, ethyl acetate or diethyl ether
  • products lb (Tc is Tb) can be prepared by reacting Ia with amines, H-Tb, preferably an excess of about 2 to 20 mole equivalents, in an inert solvent such as tetrahydrofuran, p-dioxane, methanol, methylene chloride or DMF. The reactions are carried out at about 0°C to 100°C for 1 to 24 hours. Work-up is as described above.
  • the intermediate sulfonamides of Formula II are conveniently prepared by amination of the corresponding sulfonyl chlorides with anhydrous ammonia or aqueous ammonium hydroxide by general methods known in the art, e.g., Crossley et al., J. Am. Chem. Soc., 60. pages 2223 to 2224 (1938); Pailer, Monatsh. 92, pages 677 to 683 (1961); and U.S. Patent 4,511,392.
  • sulfonamides of Formula II can also be prepared by deprotection of t-butylsulfonamides of Formula VIII. Equation 6
  • Equation 6 The reaction of Equation 6 is conveniently carried out in excess trifluoroacetic acid (TFA) according to the procedure of Catt et al., J. Org. Chem., 39. pages 566 to 568 (1974), or with polyphosphorie acid (PPA) according to procedures of Loiliano, J. Org. Chem., 36, pages 1843 to 1845 (1971).
  • t-butylsulfonamide VIII can be treated with a catalytic amount of p-toluene sulfonic acid (p-TSA) in a solvent such as toluene or xylenes at reflux temperatures for 1 to 24 hours to yield II.
  • Intermediate sulfonyl chlorides of Formula Vila are preferably prepared by oxidative-ehlorination of an appropriate thioether of Formula IX, as shown below in Equation 7.
  • Equation 7 is carried out by contacting a suspension of thioether IX in a solvent such as acetic or propionic acid in the presence of at least 2.5 equivalents of water and 3.0 equivalents of chlorine at about -20° to 30°C for 0.2 to 5 hours.
  • the reaction mixture is poured into ice-water and the product is isolated by filtration or extraction with a solvent such as methylene chloride.
  • the extraction product is optionally washed with aqueous sodium bicarbonate until neutral or slightly basic to litmus, then dried, and the solvent is evaporated to yield a product sufficiently pure to be carried directly on to the next step.
  • reaction of thioether IX, wherein R 4 is benzyl or hydrogen, with a hypochlorite solution, i.e., NaOCl can provide sulfonyl chloride Vila.
  • a hypochlorite solution i.e., NaOCl
  • Mercaptans or thioethers can also be transformed to sulfonyl fluorides by reaction with chlorine and potassium hydrogen difluoride, which on further reaction with ammonia or ammonium hydroxide can provide sulfonamides; see, e.g.. Brown et al., J. Chem. Soc. Perkins Trans I. pages 522 to 527 (1972).
  • Sulfonyl chlorides, Vila can also be prepared by diazotization reactions, as illustrated in Equation 8.
  • amine hydrochloride salt is diazotized with an alkylnitrite in an organic solvent, such as acetonitrile or acetone, and the resulting diazonium salt is reacted with sulfur dioxide and cupric chloride to yield Vila. Doyle, J. Org. Chem., 42, pages 2426 to 2431 (1977) and ibid, pages 2431 to
  • sulfonyl chlorides Vila can be prepared by aqueous diazotization; for additional details, see EPA 83,975 and 85,476.
  • Aromatic amines of Formual X can be prepared from the corresponding nitro compounds by various known reduction procedures, e.g., Preparative Organic Chemistry. 4 Ed., pages 557 to 563, John Wiley and Sons, New York and London, Hilgetag et al., Eds., and EPA 207,894.
  • Sulfonyl chlorides of Formula Vllb can be prepared from compounds of Formula XI as shown in Equation 9 and described in U.S. Patent 4,420,325.
  • J is as previously defined and [X] is a suitable halogenating agent, such as N-bromosuccinimide.
  • Thioethers of Formula IX are important intermediates for preparing compounds of this invention and can be prepared by a variety of general methods known in the art. Several such procedures a re described below in Equations 10 through 15 .
  • Equation 10 illustrates the preparation of thioethers of Formula IXa, containing an alpha-chlorooxime moiety, from carboxylic acids of Formula XII. Subsequent reaction of IXa with appropriate salts, M-Ta, or amines, H-Tb, provides thioethers of Formula IXb.
  • R 1 , R 4 , Alk, M, Ta, Tb and Tc are as previously defined; and [X] is as defined below.
  • Suitable halogenating agents include phosphorous pentachloride or phosphorous pentabromide in an inert solvent such as benzene or chloroform at about 5° to 40°C for 1 to 24 hours; or phosgene, preferably, or thionyl chloride and a catalytic amount of DMF in an inert solvent such as methylene chloride, benzene or chlorobenzene at about 10° to 130°C for 0.5 to 24 hours; or more preferably equimolar amounts of triphenylphosphine and carbon tetraehloride (or carbon tetrabromide) in an inert solvent such as acetonitrile at about 0°C to 80°C for 1 to 24 hours.
  • Compounds of Formula IXa are isolated by evaporation of reaction media under vacuum and can be purified by optionally treatment with water followed by chromatography procedures on silica gel.
  • the reactions of Equation 10b are carried out by the general procedures described in
  • Equation 11 illustrates the preparation of thioethers of Formula IXc, containing an alpha-cyanooxime moiety, f rom corresponding aldehydes of Formula XIII.
  • alkyInitrite NaOCH 3 , CH 3 OH, H 3 O;
  • Equation 11 M-Alk, base IXc wherein R 1 , R 4 , M and Alk are as previously defined.
  • the reactions 1) to 4) of Equation 11 are carried out by generally known methods, to provide uncapped oximes of Formula IXc, wherein Alk is H.
  • Subsequent reaction of the uncapped oximes by generally known methods with a suitable base and reagents, M-Alk, in an inert solvent provides capped oximes IXc.
  • Suitable bases and solvents include potassium tert-butoxide in DMF or sodium methoxide in methanol.
  • Reactions 4) and 5) of Equation 11 are further illustrated in Example 7.
  • Equation 12 illustrates the preparation of aldooximes and ketooximes of Formula IXd.
  • R 2 , R 4 and Alk are as previously defined;
  • T d is C 1 to C 3 alkyl, optionally substituted with OCH 3 or SCH 3 ; or cyclopropyl;
  • Td' is Td or CF 3 , CF 2 CF 3 , CF 2 CF 2 CF 3 , or H
  • T e is T d ' or CO 2 H
  • T e ' is T d '.
  • Equation 12a 2-fluoropyridine XIV is metallated with lithium diisopropyl amide (LDA) according to the procedure of Gungor, et al.,
  • aldo or keto-thioethers in Equation 12b can be reacted with hydroxylamine followed by a suitable base and an alkylating reagent, M-Alk, to provide capped oximes Ixd.
  • Suitable bases and solvents are described in Equation 11.
  • Oximes of Formula IXd, wherein Te' is CH 2 CN can be prepared in a two-step procedure from an appropriate 2-benzylthio-3-pyridyl-carboxylate ester using generally known methods.
  • reaction of the ester with a suitable base such as sodium hydride and acetonitrile in an inert solvent such as tetrahydrofuran can provide the corresponding 3-ketoacetonitrile, which on subsequent reaction with an appropriate alkoxyamine, or more preferably, its hydrochloride salt, in an inert solvent such as methanol or DMF can provide IXd (Te' is CH 2 CN).
  • Pyridyl alkyl ketones described in Equations 12a and 12b can also be prepared by reaction of appropriate pyridyl acid chlorides with alkyl Grignard reagents. For details see, for example, Japanese Patent Application 60-253,531.
  • Equations 13 and 14 illustrate the preparation of thiophene carboxylic acids of Formula IXe and IXf.
  • the acids can be used as intermediates for preparing compounds analogous to those described in Equation 10. Also, reduction of the acids or their esters can provide methyl alcohols for analogous reactions described in Equation 11.
  • Equation 13 and 14 metal-halogen exchange or metallation with carbon dioxide or a disulfide by known methods provides carboxylic acids IXe and IXf. Starting with 3,4- dibromo-thiophene, and carrying out the reactions of Equation 13, can provide the 3,4- substituted isomer of acid IXe. Further details pertaining to the preparation and functional group manipulation of thiophenes are found in U.S. Patent 4,481,029 and Knight, et al., J. Chem. Soc. Perkin Trans I. pages 791 to 794, (1983). Equation 15 illustrates the preparation of some pyrazolethioethers of Formula IXg, which can undergo further reactions analogous to those described in Equations 10, 11 and 12.
  • Tf is H, C 1 to C 3 alkyl, optionally substituted with OCH 3 , SCH 3 or halogen; cyclopropyl, OH or OCH 3 , and R 2 , R 3 and R 4 are as previously defined.
  • the compounds of Formula XVI in Equation 15 are known or can be prepared by known methods; see, for example, Kviko et al., Zhurnal Org. Khimi, 5, pages 1685 to 1692 (1969); Koshelev et al., Ibid. 8, pages 1750 to 1754 (1972); and Japanese Patent Application 57-228261.
  • the t-butylsulfonamides of Formulas XIX, XXI and XXIII are useful intermediates for preparing compounds of this invention and they can be prepared by known methods or simple modifications thereof. Several such .methods are illustrated in Equations 16, 17 and 18. wherein Tf is as previously defined.
  • bromide XVIII Preparation of intermediates such as bromide XVIII can be found in EPA 95,925. Exposure of bromide XVIII to BuL; followed by treatment with an appropriate acid chloride, DMF or carbon dioxide yields XIX.
  • Equation 17 the isomeric 5-keto-4-sulfonamide is prepared as outlined, while in Equation 18, the isomeric 4-keto-3-sulfonamide XXIII is prepared as outlined.
  • Equation 2 above can be prepared by methods known in the literature, or simple modifications thereof, by those skilled in the art.
  • EPA 84,224 and Braker et al., J. Chem. Soc, 69, 3072 (1947) describe methods for preparing aminopyridines and triazines substituted by acetal groups such as dialkoxymethyl or 1,3-dioxolan-2-yl, among other groups.
  • South African Patent Application Nos. 82/5045 and 82/5671 describe methods for preparing aminopyrimidines and triazines substituted by haloalkyl or haloalkylthio groups such as OCH 2 CH 2 F, OCH 2 CF 3 , SCF 2 H, and OCF 2 H.
  • South African Patent Application 83/7434 describes methods for the synthesis of cyclopropylpyrimidines and triazines substituted by such groups as alkyl, haloalkyl, alkoxy, haloalkoxy, alkylamino, dialkylamino or alkoxyalkyl.
  • the 5,6-dihydrofuro[2,3-d]pyrimidine-2- amines, the cyclopenta[d]pyrimidines-2-amines (V, A is A-2) and the 6,7-dihydro-5H-pyrano[2,3-d]pyrimidin-2- amines (V, A is A-3) can be prepared as described in EPA 15,683.
  • the furo[2,3-d]pyrimidin-2-amines (V, A is A-4) are described in EPA 46,677.
  • Compounds of Formula V, where A is A-7, are described in EPA 125,864.
  • Compounds of Formula V, where A is A-5 are described in EPA 73,562.
  • Formula I are also useful herbicides and can be prepared in a number of ways known to the art.
  • metal salts can be made by contacting compounds of Formula I with a solution of an alkali or alkaline earth metal salt having a sufficiently basic anion (e.g., hydroxide, alkoxide, or carbonate).
  • Quaternary amine salts can be made by similar techniques.
  • Salts of compounds of Formula I can also be prepared by exchange of one cation for another.
  • Cationic exchange can be effected by direct contact of an aqueous solution of a salt of a compound of Formula I (e.g., alkali or quaternary amine salt) with a solution containing the cation to be exchanged. This method is most effective when the desired salt containing the exchanged cation is insoluble in water and can be separated by filtration.
  • a salt of a compound of Formula I e.g., alkali or quaternary amine salt
  • Exchange can also be effected by passing an aqueous solution of a salt of a compound of Formula I (e.g., an alkali metal or quaternary amine salt) through a column packed with a cation exchange resin containing the cation to be exchanged for that of the original salt and the desired product is eluted from the column.
  • a salt of a compound of Formula I e.g., an alkali metal or quaternary amine salt
  • a cation exchange resin containing the cation to be exchanged for that of the original salt and the desired product is eluted from the column.
  • Acid addition salts useful in this invention, can be obtained by reacting a compound of Formula I with a suitable acid, e.g., p-toluenesulfonic acid, trichloroacetic acid or the like.
  • a suitable acid e.g., p-toluenesulfonic acid, trichloroacetic acid or the like.
  • Example 3 in 100 ml of tetrahydrofuran, cooled at
  • Example 3 By the procedure of Example 3, 11 g of the product of Example 7 was reacted with 2.2 g of water and 9.9 ml of chlorine in 125 ml of glacial acetic acid. After work-up, 2-[cyano(methoxyimino)methyl]- benzenesulfonyl chloride was obtained as a crude oil.
  • Example 8 By the procedure of Example 5, 0.4 g of the product of Example 8 was reacted with 0.51 g of phenyl (4,6-dimethoxy-1,3,5-triazin-2-yl)carbamate and
  • Useful formulations of the compounds of Formula I can be prepared in conventional ways. They include dusts, granules, pellets, solutions, suspensions , emulsions , wettable powders , emulsifiable concentrates and the like. Many of these may be applied directly. Sprayable formulations can be extended in suitable media and used as spray volumes of from a few liters to several hundred liters per hectare. High strength compositions are primarily useadi as intermediates for further formulation.
  • the formulations broadly, contain about 0.1% to 99% by weight of active ingredient(s) and at least one of these carriers: (a) about 0.1% to 20% surfactant(s) and (b) about 1% to 99.9% solid or liquid inert diluent(s). More specifically, they will contain these ingredients in the following approximate proportions: Weight Percent*
  • Active ingredient plus at least one of a Surfactant or a Diluent equals 100 weight percent.
  • Lower or higher levels of active ingredient can, of course, be present depending on the intended use and the physical properties of the compound. Higher ratios of surfactant to active ingredient are sometimes desirable, and are achieved by incorporation into the formulation or by tank mixing.
  • Typical solid diluents are described in Watkins, et al., "Handbook of Insecticide Dust Diluents and Carriers", 2nd Ed., Dorland Books, Caldwell, New Jersey, but other solids, either mined or manufactured, may be used. The more absorptive diluents are preferred for wettable powders and the denser ones for dusts.
  • Typical liquid diluents and solvents are described in Marsden, “Solvents Guide”, 2nd Ed., Interscience, New York, 1950. Solubility under 0.1% is preferred for suspension concentrates; solution concentrates are preferably stable against phase separation at 0°C.
  • compositions are well known. Solutions are prepared by simply mixing the ingredients. Fine solid compositions are made by blending and, usually, grinding as in a hammer or fluid energy mill. Suspensions are prepared by wet milling (see, for example. Littler, U.S. Patent 3,060,084). Granules and pellets may be made by spraying the active material upon preformed granular carriers or by agglomeration techniques. See
  • the surfactant is sprayed upon the active ingredient in a blender and the mixture sifted through a U.S.S. No. 40 sieve (0.42 mm openings) prior to packaging.
  • the concentrate may be formulated further for practical use.
  • the ingredients are thoroughly blended.
  • the liquid surfactant is added by spraying upon the solid ingredients in the blender. After grinding in a hammer mill to produce particles essentially all below 100 microns, the material is reblended and sifted through a U.S.S. No. 50 sieve (0.3 mm opening) and packaged.
  • polyacrylic acid thickener 0 . 3% dodecylphenol polyethylene glycol ether 0 . 5% disodium phosphate 1 .
  • the ingredients are blended and ground together in a sand mill to produce particles essentially all under 5 microns in size.
  • the ingredients are combined and ground together in a sand mill to produce particles essentially all below 3 microns.
  • the product can be used directly, extended with oils, or emulsified in water.
  • Example 15 The ingredients are ground together in a sand mill until the solid particles have been reduced to under about 5 microns.
  • the resulting thick suspension may be applied directly, but preferably after being extended with oils or emulsified in water.
  • the ingredients are ground together in a ball or roller mill until the solid particles have been reduced to diameters under 10 microns.
  • the ingredients are thoroughly blended, passed through an air mill, to produce an average particle size under 15 microns, reblended, and sifted through a U.S.S. No. 50 sieve (0.3 mm opening) before packaging.
  • the ingredients are blended, coarsely hammer-milled and then air milled to produce particles of active essentially all below 10 microns in diameter.
  • the product is reblended before packaging.
  • the ingredients are blended, hammer-milled and then moistened with about 12% water.
  • the mixture is extruded as cylinders about 3 mm diameter which are cut to produce pellets about 3 mm long. These may be used directly after drying, or the dried pellets may be crushed to pass a U.S.S. No. 20 sieve (0.84 mm openings).
  • Example 21 The ingredients are blended and then ground in a hammer-mill to produce particles with an average particle size less than 25 microns in diameter. The material is reblended and sifted through a U.S.S. No. 50 sieve (0.3 mm opening) before being packaged.
  • Example 21 The ingredients are blended and then ground in a hammer-mill to produce particles with an average particle size less than 25 microns in diameter. The material is reblended and sifted through a U.S.S. No. 50 sieve (0.3 mm opening) before being packaged.
  • Example 21 Example 21
  • the rates of application for the compounds of the invention are determined by a number of factors, including their use as plant growth modifiers or as herbicides, the crop species involved, the types of weeds to be controlled, weather and climate, formulations selected, mode of application, amount of foliage present, etc.
  • the subject compounds should be applied at levels of around 0.001 to 20 kg/ha, the lower rates being suggested for use on lighter soils and/or those having a low organic matter content, for plant growth modification or for situations where only short-term persistence is required, such as a herbicide for fallow land.
  • the compounds of the invention may be used in combination with any other commercial herbicide, representative examples of which are those of the sulfonylurea, triazine, triazole, uracil, urea, amide, diphenyl ether, carbamate, imidazolinone, cineole and bipyridylium types.
  • any other commercial herbicide representative examples of which are those of the sulfonylurea, triazine, triazole, uracil, urea, amide, diphenyl ether, carbamate, imidazolinone, cineole and bipyridylium types.
  • lactofen ( ⁇ )-2-ethoxy-1-methyl-2-oxoethyl 5-[2- chloro-4-(trifluoromethyl)phenoxy]- 2-nitrobenzoate lenaci1 3-cyclohexyl-6,7-dihydro-1H-cyclopenta- pyrimidine-2,4(3H,5H)-dione linuron N'-(3,4-dichlorophenyl)-N-methoxy-N- methylurea
  • MCPB 4-(4-chloro-2-methylphenoxy)butanoic acid mecoprop ( ⁇ )-2-(4-chloro-2-methylphenoxy)- propanoic acid mefluidide N-[2,4-dimethyl-5-[[(trifluoromethyl)- sulfonyl]amino]phenyl]acetamide methal- N-(2-methyl-2-propenyl)-2,6-dinitro-N- propalin propyl-4-(trifluoromethyl)benzenamide methabenz1,3-dimethyl-3-(2-benzothiazolyl)urea thiazuron metham methylcarbamodithioic acid methazole 2-(3,4-dichlorophenyl)-4-methyl-1,2,4- oxadiazolidine-3,5-dione methoxuron N'-(3-chloro-4-methoxyphenyl)-N,N- dimethylurea metolachlor 2-chlor
  • PPG-1013 5-[2-chloro-4-(trifluoromethyl)- phenoxy]-2-nitroacetophenone oxime-O-acetic acid, methyl ester procyazine 2-[[4-chloro-6-(cyclopropylamino)-1,3,5- triazine-2-yl]amino]-2-methylpropanenitrile profluralin N-(cyclopropylmethyl)-2,6-dinitro-N-propyl-4- (trifluoromethyl)benzenamine prometon 6-methoxy-N,N'-bis(1-methylethyl)-1,3,5- triazine-2,4-diamine prometryn N,N'-bis(1-methylethyl)-6-(methylthio)- 1,3,5-triazine-2,4-diamine pronamide 3,5-dichloro-N-(1,1-dimethyl-2-propynyl)benzamide propachlor 2-chloro-N-
  • the second pot was planted with green foxtail (Setaria viridis), cocklebur (Xanthium pensylvanicum), morningglory (Ipomoea hederacea), cotton (Gossypium hirsutum), johnsongrass (Sorghum halepense), barnyardgrass (Echinochloa crus-galli), corn (Zea mays), soybean (Glycine max), and giant foxtail (Setaria faberi).
  • green foxtail Setaria viridis
  • cocklebur Xanthium pensylvanicum
  • morningglory Ipomoea hederacea
  • cotton Gossypium hirsutum
  • johnsongrass Sorghum halepense
  • barnyardgrass Echinochloa crus-galli
  • corn Zea mays
  • soybean Glycine max
  • giant foxtail Setaria faberi
  • the third pot was planted with wheat (Triticum aestivum), barley (Hordeum vulgare), wild buckwheat (Polygonum convolvulus), cheatgrass (Bromus secalinus) or downy brome (Bromus tectorum), sugarbeet (Beta vulgaris), wild oat (Avena fatua), common chickweed (Stellaria media) or field violet (Viola arvensis), blackgrass (Alopecurus myosuroides), and rape (Brassica napus).
  • the plants were grown for approximately fourteen days, then sprayed postemergence with the chemicals dissolved in a nonphytotoxic solvent.
  • Three round pans (25 cm diameter by 12.5 cm deep) were filled with Sassafras sandy loam soil.
  • One pan was planted with nutsedge tubers, crabgrass, sicklepod, jimsonweed, velvetleaf, lambsquarters, rice, and teaweed.
  • the second pot was planted with green foxtail, cocklebur, morningglory, cotton, johnsongrass, barnyardgrass, corn, soybean, and giant foxtail.
  • the third pot was planted with wheat, barley, wild buckwheat, cheatgrass or downy brome, sugarbeet, wild oat, chickweed or field violet, blackgrass, and rape.
  • the three pans were sprayed preemergence with the chemicals dissolved in a non-phytotoxic solvent.
  • Treated plants and controls were maintained in the greenhouse for approximately 24 days, then all rated plants were compared to controls and visually rated for plant response.
  • the Corn and Sorghum Herbicide Test included the following species in both the preemergence and postemergence evaluations:
  • Postemergence plantings were grown in Sassafras sandy loam soil. Corn and soybeans were grown in separate 25 cm diameter containers. Sorghum and the seven grass weed species were grown in two 18 cm diameter containers, 4 species per container. The seven broadleaf weed species were also grown in two 18 cm diameter containers, 4 species in one container, 3 species in the second container.
  • One additional planting of corn in an 18 cm diameter container was made. The soil surface of this additional container of corn was covered with the absorbent, perlite, before spray treatment so that test chemicals would enter the plant only via the foliage. The plants were grown 10-21 days, dependent upon the species and then sprayed postemergence with the test chemicals dissolved in a nonphytotoxic solvent.
  • Preemergence Preemergence plantings were grown in fertilized Tama silt loam soil. These plantings are identical to those described in the postemergence section, with the exception of the corn planting having perlite covering the soil surface. These plantings were made the day of or the day before spraying the test chemicals dissolved in a nonphytotoxic solvent. Evaluation
  • Cotton (Coker 315) Gossypium hirsutum 2
  • Airlite plastic pots were partially filled with Tama silt loam soil and the soil saturated with water.
  • Japonica and Indica rice seedlings at the 2.0 to 2.5 leaf stage were transplanted into 1/3 of the pots.
  • Into another third of the pots were transplanted seedling or sprouted tubers of water plantain (Alisma trivale), Scripus (Scirpus paludosus), Cyperus (Cyperus esculentus), and arrowhead (Sagittaria spp.).
  • the remaining pots were planted with barnyardgrass (Echinochloa crus-galli) seeds and sprouted tubers of water chestnut (Eleocharis spp.).
  • Approximate planting depths were corn and soybeans - 3 to 4 cm; morningglory, cocklebur, and nutsedge - 2.5 to 3 cm; velvetleaf, sicklepot, and sesbania - 2 cm; all other species - 0.5 cm.
  • test chemicals were dissolved/suspended in a nonphytotoxic solvent in concentrations required to obtain the desired rate of application.
  • the solutions or suspensions were then applied as soil/foliage sprays to the young plants (postemergence phase) and to the soil surfaces of the freshly planted containers (preemergence phase).
  • Application was made utilizing an automatic spray machine at a spray volume of 374 liters per hectare.
  • the containers were transferred to a greenhouse and subsequently watered on a demand basis, taking care not to wet the foliage of the plants in the postemergence phase of the test.
  • the following species were included in the test: APPROXIMATE GROWTH STAGE AT POST
  • a third pot was prepared with the following species.
  • Preemergence treaments were prepared immediately before herbicide application in the same manner as described for the postemergence treatments.
  • Application of the herbicide was accomplished by first diluting the technical material in a nonphytotoxic solvent and applying over the surface of the plants and soil of all six components using a belt sprayer. After treatment, all components were removed to the greenhouse where they were maintained for 21 days at temperatures of 19°C night and 30°C day with a 16-hour photoperiod and a relative humidity of 45 to 80 percent. At this time, all species were rated using a visual scale of 0 representing no control and 100 representing complete control. Test results are summarized in Table G.

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  • Chemical & Material Sciences (AREA)
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  • Engineering & Computer Science (AREA)
  • Dentistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Pest Control & Pesticides (AREA)
  • Agronomy & Crop Science (AREA)
  • Plural Heterocyclic Compounds (AREA)
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  • Pyridine Compounds (AREA)

Abstract

Sulfonamides herbicides de formule générale (I), dans laquelle J, W, R et A sont décrits plus particulièrement dans la description, des composés et des compositions pour l'agriculture contenant de tels sulfonamides étant utiles en tant qu'herbicides préémergents ou postémergents ou les deux, ou en tant que régulateurs de la croissance des plantes. Leur utilisation est également décrite.
PCT/US1988/002459 1987-07-27 1988-07-25 Sulfonamides herbicides WO1989000991A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU21334/88A AU611191B2 (en) 1987-07-27 1988-07-25 Herbicidal sulfonamides

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US7819187A 1987-07-27 1987-07-27
US078,191 1987-07-27

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WO1989000991A1 true WO1989000991A1 (fr) 1989-02-09

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0159576A2 (fr) * 1984-04-10 1985-10-30 Bayer Ag 2-(Alkoximinoalkyloxycarbonyl)-phénylsulfonyl-urées
EP0164017A2 (fr) * 1984-06-04 1985-12-11 Bayer Ag Phénylsulfonylurées substituées
EP0164269A2 (fr) * 1984-06-07 1985-12-11 E.I. Du Pont De Nemours And Company Sulfonamides herbicides
EP0205348A2 (fr) * 1985-06-12 1986-12-17 E.I. Du Pont De Nemours And Company Sulfonamides comme herbicides

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0159576A2 (fr) * 1984-04-10 1985-10-30 Bayer Ag 2-(Alkoximinoalkyloxycarbonyl)-phénylsulfonyl-urées
EP0164017A2 (fr) * 1984-06-04 1985-12-11 Bayer Ag Phénylsulfonylurées substituées
EP0164269A2 (fr) * 1984-06-07 1985-12-11 E.I. Du Pont De Nemours And Company Sulfonamides herbicides
EP0205348A2 (fr) * 1985-06-12 1986-12-17 E.I. Du Pont De Nemours And Company Sulfonamides comme herbicides

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JPH02504275A (ja) 1990-12-06
EP0386001A1 (fr) 1990-09-12

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