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
  • A01N43/56—1,2-Diazoles; Hydrogenated 1,2-diazoles
• • 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
  • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
  • A01N43/84—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms six-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,4
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
  • C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
  • C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
  • C07D231/14—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three 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, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
  • C07D231/18—One oxygen or sulfur atom
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
  • C07D403/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings
  • C07D403/04—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings directly linked by a ring-member-to-ring-member bond
• • 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
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D413/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
  • C07D413/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings
  • C07D413/04—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings directly linked by a ring-member-to-ring-member bond
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D417/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00
  • C07D417/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings
  • C07D417/04—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings directly linked by a ring-member-to-ring-member bond

Definitions

• the field of the invention contemplated herein pertains to herbicidal compounds generically defined by the above title, to compositions containing same and processes for preparing said compounds.
• substituted-arylpyrazole compounds in the prior art are those having a variety of substituent radicals on the aryl and/or pyrazole moieties of the compound.
• the aryl moeity is a substituted or unsubstituted phenyl radical, in which the substituent radicals are alkyl, cycloalkyl, alkaryl, halogen, trifluoromethyl, heterocyclic or substituted hetero- cyclic, e.g., thienyl or alkyl-substituted furanyl, pyridyl, pyrimidinylurea, etc.
• pyrazolyl radical is substituted in various positions on the N or carbon atoms with alkyl, halogen, alkoxy, heterocycles, S(O) n R members, wherein n is 0-2 and R may be a variety of radicals such as those substituted on the aryl or pyrazole moieties.
• Prior compounds of the above type having utility as herbicides typically require application rates as high as five or ten or more kilograms per hectare to achieve adequate weed control. Accordingly, it is an object of this invention to provide a novel class of arylpyrazole-type compounds having uniquely high phytotoxic unit activity against a spectrum of weeds, including narrovleaf and broadleaf weeds yet maintain a high degree of safety in a plurality of crops, especially small grains and/or row crops such as wheat, barley, corn, soybeans, peanuts, etc.
• This invention relates to herbicidally-active compounds, compositions containing these compounds, processes for making them and herbicidal methods of using same
• R 1 is hydrogen, C 1-5 alkyl optionally substituted with an R 4 member; C 3-8 cycloalkyl or cycloalkenyl optionally substituted with C 1-4 alkyl;
• R 2 is C 1-5 alkyl optionally substituted with an R 4 member
• R 3 is hydrogen or halogen
• R 4 is hydrogen, C 1-8 alkyl, haloalkyl, alkyl- thio, alkoxyalkyl or polyalkoxyalkyl, C 3-8 cycloalkyl, cycloalkenyl, eyeloaIkyalkyl or cycloalkenylalkyl; C 2-8 alkenyl or alkynyl; carbamyl, halogen, amino, nitro, cyano, hydroxy, C 4-10 heterocycle containing 1-4 O, S(O) m and/or N hetero atoms, C 6-12 aryl, aralkyl or alkaryl, -CXYR 8 , -CXR 9 , -CH 2 OCOR 10 , -YR 11 , -NR 12 R 13 , or any two R 4 members may be combined through a saturated and/or unsaturated carbon, and/or hetero atom linkage to form a heterocyclic ring having up to 9 ring members, which may be substituted with any
• X is O, S(O) m , NR 14 or CR 15 R 16 ;
• Y is O or S(O) m or NR 17 ;
• R 8 -R 17 are one of said R 4 members; m is 0-2 and
• n 0-5.
• a preferred subgenus of substituted-arylpyrazolyl compounds in this invention are those according to Formula II
• R 1 , R 2 and R 3 are as defined for Formula I;
• R 5 is independently one of said R 3 members and
• R 6 and R 7 are independently one of said R 4 members or are combined to form a heterocyclic ring having up to 9 members and containing O, N and/or S atoms, which ring may be substituted with alkyl, haloalkyl, alkoxy, alkenyl or alkynyl radicals each having up to 4 carbon atoms; provided that when said two R 6 and R 7 members are combined through a -hetero atom linkage, said heterocyclic ring has at least six ring members.
• Particularly preferred compounds of this invention are those according to Formula III
• R 1 and R 2 are C 1-5 alkyl
• R 3 and R 5 are hydrogen, bromo, chloro or fluoro;
• R 6 is an R 5 member or nitro;
• R 7 is an R 4 member or
• R 1 and R 2 are methyl
• R 3 is hydrogen, bromo or chloro
• R 5 is chloro or fluoro
• R 6 is chloro, fluoro or nitro
• R 7 is a YR 11 member as defined in Formula I or
• Preferred species according to this invention include the following:
• Another aspect of this invention relates to processes for preparing the compounds according to
• substituted-arylpyrazole compounds of Formulae I-III be formulated in compositions containing other herbicidal compounds as co-herbicides, e.g., acetanilides, thiocarbamates, ureas, sulfonylureas, imidazolinones, benzoic acids and their derivatives, diphenyl ethers, salts of glyphosate, etc.
• other herbicidal compounds e.g., acetanilides, thiocarbamates, ureas, sulfonylureas, imidazolinones, benzoic acids and their derivatives, diphenyl ethers, salts of glyphosate, etc.
• herbicidal formulations may be included in such herbicidal formulations as desired and appropriate, e.g., antidotes (safeners) for the herbicide(s), plant disease control agents, such as fungicides, insecticides, nematicides and other pesticides.
• antidotes safeners
• plant disease control agents such as fungicides, insecticides, nematicides and other pesticides.
• alkyl alkenyl
• alkynyl when used either alone or in compound form, e.g., haloalkyl, haloalkenyl, alkoxy, alkoxyalkyl, etc., are intended to embrace linear or branched-chain
• Preferred alkyl members are the lover alkyls having from 1 to 4 carbon atoms and preferred alkenyl and alkynyl members are those having from 2 to 4 carbon atoms.
• haloalkyl is intended to mean alkyl radicals substituted with one or more halogen (chloro, bromo, iodo or fluoro) atoms; preferred members of this class are those having from 1 to 4 carbon atoms, especially the halomethyl radicals, e.g., trifluoro methyl. In polyhaloalkyl members, the halogens can all be the same or mixed halogens.
• alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkylalkyl, cycloalkenyl and cycloalkenylalkyl members include the following:
• Methyl, ethyl the isomeric propyls, butyls, pentyls, hexyls, heptyls, octyls, nonyls, decyls, etc.; vinyl, allyl, crotyl, methallyl, the isomeric butenyls, pentyls, hexenyls, heptenyls, octenyls; ethynyl, the isomeric propynyls, butynyls, pentynyls, hexynyls, etc.; the alkoxy, polyalkoxy, alkoxyalkyl and polyalkoxyalkyl analogs of the foregoing alkyl groups, e.g., methoxy, ethoxy, propoxys, butoxys, pentoxys and hexoxys and corresponding polyalkoxys and alkoxyalkyls
• Representative mon-, di- and tri- haloalkyl members include: chloromethyl, chloroethyl, bromomethyl, bromoethyl, iodomethyl, iodoethyl, chloropropyl, bromopropyl, iodopropyl, 1,1-dichloromethyl, 1,1-dibromomethyl, 1,1-dichloropropyl, 1,2-dibromopropyl, 2,3-dibromopropyl, 1-chloro-2-bromoethyl, 2-chloro-3- bromopropyl, trifluoromethyl, trichloromethyl, etc.
• heterocyclic members include: alkylthiodiazolyl; piperidyl; piperidylalkyl; dioxolanylalkyl, thiazolyl; alkylthiazolyl; benzothiazolyl; halobenzothiazolyl; furyl; alkyl-substituted furyl;
• furylalkyl pyridyl; alkylpyridyl; alkyloxazolyl;
• agriculturallyacceptable salts (of the compounds defined by the above formulae) is meant a salt or salts which readily ionize in aqueous media to form a cation or anion of said compounds and the corresponding salt anion or cation, which salts have no deleterious effect on the herbicidal properties of a given herbicide and which permit formulation of the herbicide composition without undue problems of mixing, suspension, stability, applicator equipment use, packaging, etc.
• herbicide-effective is meant the amount of herbicide required to effect a meaningful injury or destruction to a significant portion of affected undesirable plants or weeds. Although of no hard and fast rule, it is desirable from a commercial viewpoint that 80-85% or more of the weeds be destroyed, although commercially significant suppression of weed growth can occur at much lover levels, particularly with some very noxious, herbicide-resistant plants.
• the compounds according to this invention are suitably prepared by a variety of processes as will be described below.
• the preferred overall process for preparing the compounds of Formulae I-III is best viewed in the separate process steps required to get the necessary intermediates, immediate precursors and end products of the above formulae. Viewed from this perspective, there are at least thirteen main process steps involved and these will be described below.
• the products according to Formulae I-III are prepared by the general "Processes I-XIII" scheme described below; it being expressly understood that various modification obvious to those skilled in the art are contemplated. Specific embodiments are described in Examples 1-27 below.
• radical substituents e.g., R 1 -R 17 , X, Y, etc. have the same meanings as defined for the compounds of Formulae I-III, unless otherwise qualified or limited.
• This process describes the preparation of important intermediate compounds, which are useful in the overall process scheme for producing compounds of Formulae I-III.
• Such intermediate compounds of Formula B belov in which R 3 is H are prepared by this process step.
• the process for the preparation of compounds according to Formula B suitably proceeds from (un) substituted acetophenones of Formula A which are known in the art.
• the process can be carried out in any anhydrous solvent or mixture of such solvents; the preferred solvents are dimethylsulfoxide, toluene, benzene, etc.
• the (un) substituted acetophenones are treated with a strong base such as an alkali hydride or alkali alkoxide with alkali alkoxides such as potassium t-butoxide being preferred.
• the basic mixture is treated with carbon disulfide.
• Reaction temperature is in the range of -100oC to 100oC, preferably -78oC to 50oC. After addition of the carbon disulfide is complete, the reaction may be treated with an alkylhalide,
• alkyldihalide alkylsulfate, dialkylsulfonate or other suitable alkylating agent with the preferred reagent being methyl iodide.
• the reaction period may be chosen from the range of a few minutes to several weeks
• reaction temperature is in the range of
• reaction period may be chosen from the range of a few minutes to several weeks depending on the amounts of reagents, reaction temperature, etc.
• the product is isolated after completion of the reaction by filtration and/or concentration of the reaction mixture. If necessary, the product is purified by standard methods such as extraction, crystallization, column chromatography, etc.
• the resultant pyrazole may be treated with an alkyl halide, alkyl sulfonate or other suitable alkylating agent to obtain compounds of Formula B.
• products of Formula B can be obtained by treatment of the above compound with an alkylating agent such as methyl iodide, benzyl bromide, allyl bromide, dimethyl sulfate, etc.
• alkylating agent such as methyl iodide, benzyl bromide, allyl bromide, dimethyl sulfate, etc.
• the preferred solvents are dimethylsulfoxide, acetone, dimethylformamide, dioxane, etc.
• Reaction temperature is in the range of -78oC to 150oC, preferably 10oC to 100oC.
• the reaction period may be chosen from the range of a few minutes to several weeks depending on the amounts of reagents, reaction temperature, etc.
• the product is isolated after completion of the reaction by filtration and/or concentration of the reaction mixture. If necessary, the product is purified by standard methods such as
• the 2-fluoro-4-chloro-5-methoxyacetophenone used to prepare compound Nos. 4, 9, 10 and 11 in Table 1 by the above process, was prepared from 2-chloro-4-fluoroanisole, which can be obtained from 2-chloro-4-fluoro-phenol by methods known in the art (C. A. Buehler and D. E. Pearson, Survey of Organic Synthesis, pp. 285- 382, Wiley-Interscience, New York, 1970).
• Treatment of 2- chloro-4-fluoroanisole with titanium tetrachloride and dichloromethylmethylether at room temperature gives 2- fluoro-4-chloro-5-methoxybenzaldehyde.
• the 2-fluoro- 4-chloro-5-methoxybenzaldehyde is converted to 2-fluoro- 4-chloro-5-methoxyacetophenone by treatment with methyl Grignard folloved by oxidation using standard methods known in the art.
• This process describes an important step involving oxidation of compounds according to Formula B to prepare compounds according to Formula I.
• the important feature of this process step is the conversion of sulfide derivatives of Formula B to obtain the S,S- dioxide derivatives of Formula I compounds. Accordingly, it will be understood that the oxidation system described below is merely representative, but conceptually any suitable means of accomplishing the intended conversion of sulfide derivatives of Formula B to S,S- dioxide derivatives of Formula I is contemplated herein.
• Oxidation of substituted thiopyrazoles of Formula B can give the corresponding sulfonylpyrazoles of Formula I.
• Any inert solvent may be used in this reaction that does not markedly hinder the reaction from proceeding.
• solvents include, but are not limited to, organic acids, inorganic acids, hydrocarbons, halogenated hydrocarbons, aromatic hydrocarbons, ethers or sulfones.
• Suitable oxidants include, but are not limited to molecular oxygen, organic and inorganic peroxides, organic peracids, inorganic oxides; the preferred reagents being hydrogen peroxide, perbenzoic acids, alkali periodates, alkali permanganates, etc.
• Reaction temperature is in the range of -78oC to 150oC, preferably 10oC to 100oC. The reaction period may be chosen from the range of a few minutes to several weeks depending on the amounts of reagents, reaction
• the product is isolated by diluting the reaction mixture with water and the product is isolated by a method such as crystallization or solvent extraction. If necessary, the product is purified by standard methods.
• any inert solvent may be used in this reaction that does not markedly hinder the reaction from proceeding.
• solvents include, but are not limited to, organic acids, inorganic acids, hydrocarbons, halogenated hydrocarbons, aromatic hydrocarbons, ethers and sulfides, sulfoxides or sulfones.
• Halogenating agents suitable for the above reaction include bromine,
• halogenating agents it is preferable to use an organic peroxide or light as a catalyst.
• the amount of halogenating agent can range from equivalent molar amounts to an excess.
• Reaction temperature is in the range of -100oC to 150oC, preferably 10oC to 100oC.
• the reaction period may be chosen from the range of a few minutes to several weeks or longer depending on the amounts of reagents, reaction temperature, etc.
• the product is isolated by diluting the reaction mixture with water and the product is isolated by a method such as crystallization or solvent extraction. If necessary, the product is purified by standard methods.
• This section describes a process for the preparation of compounds according to Formula I in which one of the R 4 residues is a nitro group (Formula E) starting with compounds according to Formula I.
• Nitrating agents such as concentrated nitric acid, fuming nitric acid, mixtures of nitric acid with concentrated sulfuric acid, alkyl nitrates and acetyl nitrate are suitable for this reaction.
• Solvents such as mineral acids, organic solvents such as acetic anhydride or methylene chloride, and water or mixtures of these solvents may be used.
• the nitrating agent may be used in equimolar amounts or in excess.
• Reaction temperature is in the range of -100oC to 150oC, preferably -10oC to 100oC.
• the reaction period may be chosen from the range of a few minutes to several days depending on the amounts of reagents, reaction temperature, etc.
• the product is isolated by diluting the reaction mixture with water and the product is isolated by a method such as crystallization or solvent extraction. If necessary, the product is purified by standard methods.
• one class of products according to Formula G (one species of Formula II compounds) is prepared by displacement of the Z radical of the corresponding compound of Formula F, wherein Z is any suitable leaving group of the
• Formation of products of Formula G can be carried out by treatment of compounds of Formula F with an alkoxide, thioalkoxide, amine, etc., or an alcohol, mercaptan, amine, etc. in the presence of a base in any suitable solvent.
• the preferred solvents are dimethylsulfoxide, acetone, dimethylformamide, dioxane, water, etc.
• the base may be an organic base (such as a trialkylamine or another organic amine) or an inorganic base (an alkali carbonate such as potassium carbonate or sodium carbonate).
• Reaction temperature is in the range of -100oC to 150oC, preferably -10oC to 100oC.
• the reaction period may be chosen from the range of a few minutes to several weeks depending on the amounts of reagents, reaction temperature, etc.
• the product is isolated after completion of the reaction by filtration and/or concentration of the reaction mixture. If necessary, the product is purified by standard methods such as extraction, crystallization, column chromatography, etc.
• reaction solvent can include either organic or inorganic acids, such as acetic acid or hydrochloric acid, and may be used as concentrated acid solutions or dilute aqueous solutions.
• Reaction temperature is in the range of 0oC to 150oC, preferably 10oC to 100oC. The reaction period may be chosen from the range of a few minutes to several weeks depending on the amounts of reagents, reaction temperature, etc.
• the product is isolated by diluting the reaction mixture with water and the product is isolated by a method such as crystallization or solvent extraction. If necessary, the product is purified by standard methods.
• compounds of Formula H may be reduced by catalytic hydrogenation.
• suitable catalysts include Raney nickel, palladium-carbon, palladium black, palladium on any suitable support, palladium oxide, platinum, platinum black, etc.
• Solvents include any inert solvent which does not markedly hinder the reaction including alcohols, ethers, etc.
• the product is isolated after completion of the reaction by filtration and concentration of the reaction mixture. If necessary, the product is purified by standard methods such as
• the amine radical of the product of step A can be converted to a variety of functional groups, e.g., a halogen (preferred), cyano, hydroxyl, etc., radical by the folloving step in the process.
• any suitable solvent may be employed, although, anhydrous solvents such as anhydrous acetonitrile are preferred.
• a solution or slurry of the product of step A is treated with copper salts including cupric halides, cuprous halides, mixtures of cupric and cuprous halides or other copper salts and their mixtures and with an alkyl nitrite or other organic nitrites, such as t-butylnitrite.
• Reaction temperature is in the range of 0oC to 150oC, preferably 10oC to 100oC.
• the reaction period may be chosen from the range of a few minutes to several weeks depending on the amounts of reagents, reaction tempera- ture, etc.
• the product is isolated after completion of the reaction by filtration and/or
• the product is purified by standard methods such as extraction, crystallization, column chromatography, etc.
• reaction can be carried out as a solution or suspension in any suitable solvent or neat.
• a Levis acid such as, but not limited to, BBr 3 , AlCl 3 , etc. or inorganic acids such as concentrated or aqueous hydrochloric acid, sulfuric acid, hydrobromic acid, etc. can be employed.
• Reaction temperature is in the range of 0oC to 150oC, preferably 10oC to 100oC.
• the reaction period may be chosen from the range of a few minutes to several weeks depending on the amounts of reagents, reaction temperature, etc.
• the product is isolated after completion of the reaction by filtration and/or concentration of the reaction mixture. If necessary, the product is purified by standard methods such as extraction, crystallization, column chromatography, etc.
• formation of products defined above can be carried out by treatment of the starting material with an alkylating agent such as an alkyl halide or alkyl sulfonate, e.g., methyl iodide, allyl bromide, propargyl bromide, methyl phenylsulfonate, etc., or an acylating agent.
• an alkylating agent such as an alkyl halide or alkyl sulfonate, e.g., methyl iodide, allyl bromide, propargyl bromide, methyl phenylsulfonate, etc.
• the reaction may be carried out in any suitable solvent or mixture of solvents, with or without a catalyst, in the presence or absence of a base.
• the preferred solvents are dimethylsulfoxide, acetone, dimethylformamide, dioxane, etc.
• the base may be an organic base (such as a trialkylamine or another organic amine) or an inorganic base (an alkali carbonate such as potassium carbonate or sodium carbonate).
• Reaction temperature is in the range of 0oC to 150oC. preferably 10oC to 100oC.
• the reaction period may be chosen from the range of a few minutes to several weeks depending on the amounts of reagents, reaction temperature, etc. the product is isolated after completion of the reaction by filtration and/or concentration of the reaction mixture. If necessary, the product is purified by standard methods such as extraction, crystallization, column chromatography, etc.
• reaction can be carried out in any suitable solvent or mixture of solvents, with or without a catalyst, in the presence of a base or acid.
• the preferred solvents are water, alcohols, dioxane, dimethylsulfoxide, acetone, dimethylformamide, etc.
• base hydrolysis inorganic bases such as alkali hydroxides are preferred.
• inorganic acids such as concentrated hydrochloric acid or sulfuric acid, organic acids or mixtures of such acids may be employed.
• Reaction temperature is in the range of 0oC to 150oC, preferably 10oC to 100oC. The reaction period may be chosen from the range of a few minutes to several weeks depending on the amounts of reagents, reaction temperature, etc.
• the product is isolated by diluting the reaction mixture with water and/or treating the solution with acid (in the case of base hydrolysis) and the product is isolated by a method such as crystallization or solvent extraction. If necessary the product is purified by standard methods.
• step A The product of step A is converted to compounds of Formula M by esterification or an amide-forming reaction. This may be accomplished directly from compound L or via an alkali metal salt of compound L.
• esterification can be carried out by using an excess of the alcohol corresponding to the objective ester in the presence of a mineral acid (e.g., sulfuric acid).
• a mineral acid e.g., sulfuric acid.
• the amide derivatives can be prepared by treating compound L with the desired amine either neat or in a suitable solvent.
• the esterification or amide-forming reactions can also be carried out in the presence of an inert solvent and a dehydrating agent.
• the product of step A can be converted to an acid halide or anhydride and treated with an alcohol or amine.
• Preparation of the acid halide is carried out in the presence of a halogenating agent such as, but not limited to, thionyl chloride, phosporus pentachloride, oxalyl chloride, etc., with or without an inert solvent. Any inert solvent which does not interfere with the reaction may be employed.
• a catalytic amount of an amine base such as triethylamine, pyridine or dimethylformamide or the like may be added for the purpose of promoting this reaction.
• the reaction temperature is in the range of -20oC to the boiling point of the solvent used, the reaction period ranges from several minutes to 48 hours depending upon the amounts of reactants used and the reaction temperature.
• the excess halogenating reagent and solvent(s) are removed from the reaction product by evaporation or distillation.
• the resultant acid halide may be subjected to an amine or alcohol directly or purified by the usual means.
• the acid halide is treated with an alcohol or amine to give a compound of Formula M.
• Any inert solvent may be employed and a catalytic amount of an amine base such as triethylamine, pyridine or dimethylformamide or the like may be added for the purpose of promoting this reaction.
• the reaction temperature is in the range of -20oC to the boiling point of the solvent used.
• the reaction period ranges from several minutes to 48 hours depending upon the amounts of reactants used and the reaction temperature.
• the product is isolated after completion of the reaction by filtration and/or concentration of the reaction mixture. If necessary, the product is purified by standard methods such as extraction, crystallization, column chromatography, etc.
• This process describes the preparation of compounds of Formulae O, P, Q, R, S or T (Formula II compounds in which the R 7 substituent is alkyl, substituted alkyl, haloalkyl, carboxaldehyde, carboxylic acid or a carboxylic acid derivative such as the previously defined CXYR 8 or CXR 9 ) from compounds of Formula N.
• the radicals R 21 and R 22 are as previously defined for the R 4 members and X 1 and X 2 are halogens. Process schematics are shown below.
• any inert solvent may be used in this reaction that does not markedly hinder the reaction from proceeding.
• solvents include, but are not limited to, organic acids, inorganic acids, hydrocarbons, halogenated hydrocarbons, aromatic hydrocarbons, ethers and sulfides, sulfoxides or sulfones.
• Halogenating agents suitable for the above reaction include bromine, chlorine, N-bromosuccinimide, N-chlorosuccinimide, sulfuryl chloride, etc. With some halogenating agents it is preferable to use an organic peroxide or light as a catalyst.
• the amount of halogenating agent can range from an equal molar amount to an excess. Reaction temperature is in the range of
• reaction period may be chosen from the range of a few minutes to several weeks depending on the amounts of reagents, reaction temperature, etc. After completion of the reaction the product or products are isolated by
• reaction mix- ture diluting the reaction mix- ture with water and the product (s) are isolated by a method such as crystallization or solvent extraction. If necessary the product(s) are purified by standard methods.
• Compounds of Formula 0 can be converted to compounds of Formula P by displacement of the halogen radical X 1 by a suitable nucleophile.
• Formation of products of Formula P can be carried out by treatment of compounds of Formula O with an alkoxide, thioalkoxide, amine, alkyl or aryl anion, etc., or an alcohol, mercaptan, amine, etc. in the presence of a base in any suitable solvent.
• the preferred solvents are dimethylsulfoxide, acetone, dimethylformamide, dioxane, etc.
• the base may be an organic base (such as a trialkylamine or another organic amine) or an inorganic base (an alkali carbonate such as potassium carbonate or sodium carbonate).
• Reaction temperature is in the range of 0oC to 150oC, preferably 10oC to 100oC.
• the reaction period may be chosen from the range of a few minutes to several weeks depending on the amounts of reagents, reaction temperature, etc.
• the product is isolated after completion of the reaction by filtration and/or concentration of the reaction mixture. If necessary, the product is purified by standard methods such as
• Formation of products of Formula R can be carried out by acid hydrolysis of compounds of Formula Q.
• compounds of Formula Q are subjected to an excess of a mineral acid such as hydrochloric acid or sulfuric acid, with a large excess of sulfuric acid being preferred.
• Reaction temperature is in the range of 0oC to the boiling point of the inert solvent, preferably 10oC to 100oC.
• the reaction period may be chosen from the range of a few minutes to several weeks depending on the amounts of reagents, reaction temperature, etc.
• the product or products are isolated by diluting the reaction mixture with water and the product (s) are isolated by a method such as crystallization or solvent extraction. If necessary, the product(s) are purified by standard methods.
• Oxidation of Formula R compounds Any suitable inert solvent may be employed in this reaction including hydrocarbons, aromatic hydrocarbons, pyridine and its derivatives, water, etc. Oxidizing agents employed include but are not limited to peroxides such as
• Reaction temperature is in the range of 0oC to the boiling point of the inert solvent, preferably 10oC to 100oC.
• the reaction period may be chosen from the range of a few minutes to several weeks depending on the amounts of reagents, reaction temperature, etc.
• the product or products are isolated by diluting the reaction mixture with water and the product(s) are isolated by a method such as crys tallization or solvent extraction. If necessary, the product(s) are purified by standard methods.
• the last step of this process is meant to include the transformation of compounds of Formula S to compounds of Formula T by any of the variety of standard techniques for preparation of derivatives of carboxylic acids.
• This process step is an esterification or an amide-forming reaction. This may be accomplished directly from a compound S or via an alkali metal salt of a compound S.
• the esterification can be carried out by using an excess of the alcohol corresponding to the objective ester in the presence of a mineral acid (e.g., sulfuric acid).
• the amide derivatives can be prepared by treating a compound S with the desired amine either neat or in a suitable solvent.
• the esterification or amide-forming reactions can also be carried out in the presence of an inert solvent and a dehydrating agent.
• compounds of Formula S can be nverted to an acid halide or anhydride and treated with an alcohol or amine.
• Preparation of the acid halide is carried out in the presence of a halogenating agent such as, but not limited to, thionyl chloride, phosphorus pentachloride, oxalyl chloride, etc., with or without an inert solvent. Any inert solvent which does not interfere with the reaction may be employed.
• a catalytic amount of an amine base such as triethylamine, pyridine or dimethylformamide or the like may be added for the purpose of promoting this reaction.
• the reaction temperature is in the range of -20oC to the boiling point of the solvent used.
• the reaction period ranges from several minutes to 48 hours depending upon the amounts of reactants used and the reaction temperature.
• the excess halogenating reagent and solvent(s) are removed from the reaction product by evaporation or distillation.
• the resultant acid halide may be subjected to an amine or alcohol directly and purified by the usual means.
• the acid halide is treated with an alcohol or amine to give a compound or Formula T.
• Any inert solvent may be employed and a catalytic amount of an amine base such as triethylamine, pyridine or
• dimethylformamide or the like may be added for the purpose of promoting this reaction.
• the reaction temperature is in the range of -20oC to the boiling point of the solvent used.
• the reaction period ranges from several minutes to 48 hours depending upon the amounts of reactants used and the reaction temperature.
• the product is isolated after completion of the reaction by filtration and/or concentration of the reaction mixture. If necessary, the product is purified by standard methods such as extraction, crystallization, column chromatography, etc.
• This section describes a process for the preparation of compounds according to Formula I in which one of the R 4 residues is a thiol group (Formula U) starting with compounds according to Formula I.
• the desired compounds are obtained by preparation of a halosulfonyl intermediate folloved by reduction to give compounds of Formula U.
• Any solvent may be employed that does not hinder the progress of the reaction such as halogenated hydrocarbons, ethers, alkylnitriles, mineral acids, etc.
• An excess of chlorosulfonic acid is preferred as both the reagent and solvent for the formation of chlorosulfonyl intermediates.
• the reaction temperature is in the range of 25oC to the boiling point of the solvent employed.
• the reaction period may be chosen from the range of a few minutes to several weeks depending on the amounts of reagents, reaction temperature, etc.
• the product or products are isolated by diluting the reaction mixture with water and the product(s) are isolated by a method such as crystallization or solvent extraction. If necessary, the product(s) are purified by standard methods.
• Reduction of the halosulfonyl intermediate can be carried out in inert solvents including either
• reaction solvent can include Reaction temperature is in the range of 0oC to 150oC, preferably 10oC to 100oC.
• the reaction period may be chosen from the range of a few minutes to several weeks depending on the amounts of reagents, reaction temperature, etc.
• the product is isolated by diluting the reaction mixture with water and the product is isolated by a method such as crystallization or solvent extraction. If necessary, the product is purified by standard methods.
• compounds of Formula V (Formula I compounds in which R 2 is CH 2 R 23 where R 23 is one of the previously defined R 4 members) are prepared from compounds of Formula I where R 2 is methyl.
• Any suitable solvent may be employed provided that it is anhydrous, does not react with water, and does not interfere with the course of the reaction.
• anhydrous ethers such as tetrahydrofuran, diethyl ether or polyethers are employed.
• the reaction temperature is usually -100oC to the boiling point of the solvent employed with -78oC to 25oC being preferred.
• the compound of Formula I is treated with a strong base such as an alkyl metal, metal hydride, metal amide, etc., folloved by treatment with an alkylating agent such as an alkyl halide, an alkyl sulfonate, etc.
• the reaction period may be chosen from the range of a few minutes to several weeks depending on the amounts of reagents, reaction temperature, etc.
• the product is isolated by diluting the reaction mixture with water and the product is isolated by a method such as crystallization or solvent extraction. If necessary, the product is purified by standard methods.
• This process step describes the conversion of compounds of Formula W to either compounds of Formulae X or Y.
• the radical R 24 is as previously defined for one of the R 4 members and n is an integer of 0 or 1.
• the nitro radical of compounds according to Formula W is reduced to give an amine derivative which can either be isolated or allowed to cyclize directly to give products of Formulae X or Y depending on the nature of the R 24 radical. In some cases, it may be necessary to carry out the above reactions at elevated temperatures in order to facilitate cyclization of the amine intermediate.
• Reducing agents suitable in an acidic medium include, but are not
• reaction solvent can include either organic or inorganic acids, such as acetic acid or hydrochloric acid, and may be used as concentrated acid solutions or dilute aqueous solutions.
• Reaction temperature is in the range of 0oC to 150oC, preferably 10oC to 100oC.
• the reaction period may be chosen from the range of a few minutes to several weeks depending on the amounts of reagents, reaction temperature, etc.
• compounds of Formula W may be reduced by catalytic hydrogenation.
• suitable catalysts include Raney nickel, palladium-carbon, palladium black, palladium on any suitable support, palladium oxide, platinum, platinum black, etc.
• Solvents include any inert solvent which does not markedly hinder the reaction including alcohols, ethers, etc.
• the product is isolated after completion of the reaction by filtration and concentration of the reaction mixture. If necessary, the product is purified by standard methods such as extraction, crystallization, column chromatography, etc.
• the following Examples 1-27 describe specific working embodiments for the preparation of representative compounds according to this invention. In the examples which follow, where chromatographic purifications were done the adsorbent material was silica.
• a mixture of anhydrous solvents can also be used, e.g., a mixture of DMSO and THF.
• This example describes the preparation of an isomeric mixture of 3-(2,5-difluorophenyl)-1-methyl-5-methylthio-1H-pyrazole and 5-(2,5-difluorophenyl)-1-methyl-3-methylthio-1H-pyrazole.
• This example describes the preparation of 3- (2,4-difluorophenyl)-1-methyl-5-(methylthio)-1H-pyrazole.
• This example describes the preparation of 3- (2,5-difluorophenyl)-1-methyl-5-(methylsulfonyl)-1H-pyrazole.
• This example describes the preparation of 5- (4-chloro-2-fluoro-5-methoxyphenyl)-3-(methylsulfonyl)- 1H-pyrazole.
• This example describes the preparation of 4-chloro-3- (2-fluoro-4-methoxyphenyl) -1-methyl-5- (methylsulfonyl) -1H-pyrazole.
• This example describes the preparation of 4- chloro-3-(2,5-difluorophenyl)-1-methyl-5-(methylsulfonyl)-1H-pyrazole.
• This example describes the preparation of 4-chloro-3-(2-fluoro-4-methoxyphenyl)-1-methyl-5-(methylthio)-1H-pyrazole.
• This example describes the preparation of 4- chloro-3-(2,5-difluoro-4-nitrophenyl)-1-methyl-5- (methylsulfonyl)-1H-pyrazole.
• 1.5 g (4.9 mmole) 4-chloro-3-(2,5-difluorophenyl)-1-methyl-5-(methylsulfonyl)-1H-pyrazole was slowly added to 25 mL of fuming nitric acid. The reaction was stirred at 30oC for 30 minutes. The reaction was poured into 300 mL of ice. The slurry was filtered and the cake washed veil with water and air dried.
• This example describes the preparation of 4-chloro-3-(4-chloro-2-fluoro-5-nitrophenyl)-1-methyl-5- (methylsulfonyl)-1H-pyrazole.
• This example describes the preparation of 4-chloro-3-(2-fluoro-5-methoxy-4-nitrophenyl)-1-methyl-5-(methylsulfonyl)-1H-pyrazole.
• This example describes the preparation of 5- [4-chloro-1-methyl-5-(methylsulfonyl)-1H-pyrazol-3-yl]-4-fluoro-N-(1-methylethyl)-2-nitrobenzenamine.
• This example describes the preparation of 2- chloro-5-[4-chloro-1-methyl-5-(methylsulfonyl)-1H-pyrazol-3-yl]-4-fluoro-N-2-propenylbenzenamine.
• This example describes the preparation of N- [2-chloro-5-[4-chloro-1-methyl-5-(methylsulfonyl)-1H-pyrazol-3-yl]-4-fluorophenyl]-methanesulfonamide.
• This example describes the preparation of 4-chloro-3-(4-chloro-2-fluoro-5-hydroxyphenyl)-1-methyl-5-(methylsulfonyl)-1H-pyrazole.
• This example describes the preparation of 2- chloro-5-[4-chloro-1-methyl-5-(methylsulfonyl)-1H- pyrazol-3-yl]-4-fluoro-N-(1-methylethyl)-benzeneamine.
• This example describes the preparation of 2- (2-chloro-5-(4-chloro-1-methyl-5- (methylsulfonyl) -1H- pyrazol-3-yl) -4-fluorophenoxy) -propanoic acid.
• 2-(2-chloro-5-(4-chloro-1-methyl-5-(methylsulfonyl)-1H-pyrazol-3-yl)-4-fluorophenoxy)-propanoic acid ethyl ester in 20 mL water and 20 mL 1,4-dioxane was added 3.5 mL (8.6 mmole) 10% aqueous NaOH.
• This example describes the preparation of 2- (2-chloro-5-(4-chloro-1-methyl-5-(methylsulfonyl)-1-pyrazol-3-yl)-4-fluorophenoxy)-N-methylpropanamide.
• reaction mixture was a1loved to stir for 30 minutes at room temperature.
• the solution was poured into 150 mL cold water and extracted with ethyl acetate.
• the ethyl acetate extracts vere washed times with brine, dried over anhydrous MgSO 4 , and stripped in vacuo.
• This example describes the preparation of ( ( (2-chloro-5-(4-chloro-1-methyl-5-(methylsulfonyl)-1H-pyrazol-3-yl)-4-fluorophenyl)methyl)thio) acetic acid, ethyl ester.
• This example describes the preparation of 2-chloro-5-(4-chloro-1-methyl-5-(methylsulfonyl)-1H-pyrazol-3-yl)-4-fluoro-N-methylbenzamide.
• This example describes the preparation of 4-chloro-3-(4-chloro-2-fluoro-5-methoxyphenyl)-1-methyl-5-(ethylsulfonyl)-1H-pyrazole and is a specific vorking embodiment of Process XII. All equipment was flame dried un ⁇ er nitrogen.
• This example describes the preparation of 7-[4-chloro-1-methyl-5-(methylsulfonyl)-1H-pyrazol-3-yl]-6-fluoro-2H-1,4-benzothiazin-4(3H)-one and is a specific vorking embodiment of Process XIII.
• the compounds of this invention have been found to be surprisingly effective as herbicides.
• Topsoil is placed in an aluminum pan and compacted to a depth of 0.95 to 1.27 cm from the top of the pan. On the top of the soil is placed a
• Table 5 summarizes the results of the pre-emergence herbicidal activity tests of compounds of this invention against weeds.
• the herbicidal rating shown in Table 5 is the percent inhibition of each plant species.
• topsoil is placed in aluminum pans having holes in the bottom and compacted to a depth of 0.95 to 1.27 cm from the top of the pan.
• a predetermined number of seeds of each of several dicotyledonous and monocotyledonous annual plant species and/or vegetative propagules for the perennial plant species are placed on the soil and pressed into the soil surface. The seeds and/or
• each pan is removed individually to a spraying chamber and sprayed by means of an atomizer, operating at a spray pressure of 170.3 kPa (10 psig) at the application rates noted.
• spray solution is an amount of an emulsifying agent mixture to give a spray solution or suspension which contains about 0.4% by volume of the emulsifier.
• the spray solution or suspension contains a sufficient amount of the candidate chemical in order to give application rates of the active ingredient corresponding to those shown in Table 2, while applying a total amount of solution or suspension equivalent to 1870 L/Ha (200 gallons/acre).
• the pans were returned to the greenhouse and watered as before and the injury to the plants as compared to the control is observed at approximately 10- 14 days (usually 11 days) and in some instances observed again at 24-28 days (usually 25 days) after spraying.
• the post-emergent herbicidal activity shown in Table 6 is the percent inhibition of each plant species.
• compositions of this invention may contain at least one active ingredient and an adjuvant in liquid or solid form.
• compositions are prepared by admixing the active
• extenders, carriers, and conditioning agents to provide compositions in the form of finely-divided particulate solids, granules, pellets, solutions, dispersions or emulsions.
• ingredient could be used with an adjuvant such as a finely-divided solid, a liquid of organic origin, water, a vetting agent, a dispersing agent, an emulsifying agent or any suitable combination of these.
• an adjuvant such as a finely-divided solid, a liquid of organic origin, water, a vetting agent, a dispersing agent, an emulsifying agent or any suitable combination of these.
• Suitable vetting agents are believed to include alkyl benzene and alkyl naphthalene sulfonates, sulfated fatty alcohols, amines or acid amides, long chain acid esters of sodium isothionate, esters of sodium sulfosuccinate, sulfated or sulfonated fatty acid esters, petroleum sulfonates, sulfonated vegetable oils, ditertiary acetylenic glycols, polyoxyethylene
• Preferred dispersants are methyl cellulose, polyvinyl alcohol, sodium lignin sulfonates, polymeric alkyl naphthalene sulfonates, sodium
• Wettable povders are water-dispersible compositions containing one or more active ingredients, an inert solid extender and one or more wetting and dispersing agents.
• the inert sriid extenders are usually of mineral origin such as the natural clays, diatomaceous earth and synthetic minerals derived from silica and the like. Examples of such extenders include kaolinites, attapulgite clay and synthetic magnesium silicate.
• the vettable povders compositions of this invention usually contain from above 0.5 to 60 parts (preferably from 5-20 parts) of active ingredient, from about 0.25 to 25 parts (preferably 1-15 parts) of vetting agent, from about 0.25 to 25 parts (preferably 1.0-15 parts) of dispersant and from 5 to about 95 parts (preferably 5-50 parts) of inert solid extender, all parts being by weight of the total composition. Where required, from about 0.1 to 2.0 parts of the solid inert extender can be replaced by a corrosion inhibitor or anti-foaming agent or both.
• compositions include dust concentrates comprising from 0.1 to 60% by weight of the active ingredient on a suitable extender; these dusts may be diluted for application at concentrations within the range of from about 0.1-10% by weight.
• Aqueous suspensions or emulsions may be prepared by stirring a nonaqueous solution of a water-insoluble active ingredient and an emulsification agent with water until uniform and then homogenizing to give stable emulsion of very finely divided particles.
• the resulting concentrated aqueous suspension is characterized by its extremely small particle size, so that when diluted and sprayed, coverage is very uniform.
• Suitable concentrations of these formulations contain from about 0.1-60%, preferably 5-50% by weight of active ingredient, the upper limit being determined by the solubility limit of active ingredient in the solvent.
• Concentrates are usually solutions of active ingredient in water-immiscible or partially water-immiscible solvents together with a surface active agent.
• Suitable solvents for the active ingredient of this invention include dimethylformamide, dimethylsulfoxide, N-methylpyrrolidone, hydrocarbons, and water-immiscible ethers, esters, or ketones.
• other high-formamide dimethylsulfoxide
• N-methylpyrrolidone hydrocarbons
• water-immiscible ethers esters, or ketones.
• the strength liquid concentrates may be formulated by dissolving the active ingredient in a solvent then diluting, e.g., with kerosene, to spray concentration.
• the concentrate compositions herein generally contain from about 0.1 to 95 parts (preferably 5-60 parts) active ingredient, about 0.25 to 50 parts
• Granules are physically stable particulate compositions comprising active ingredient adhering to or distributed through a basic matrix of an inert, finely-divided particulate extender.
• a surface active agent such as those listed hereinbefore can be present in the composition.
• Natural clays, pyrophyllites, illite, and vermiculite are examples of operable classes of particulate mineral extenders.
• the preferred extenders are the porous, absorptive,
• preformed particles such as preformed and screened particulate attapulgite or heat expanded, particulate vermiculite and the finely-divided clays such as kaolin clays, hydrated attapulgite or bentonitic clays.
• These extenders are sprayed or blended with the active
• the granular compositions of this invention may contain from about 0.1 to about 30 parts by weight of active ingredient per 100 parts by weight of clay and 0 to about 5 parts by weight of surface active agent per 100 parts by weight of particulate clay.
• compositions of this invention can also contain other additaments, for example, fertilizers, other herbicides, other pesticides, safeners and the like used as adjuvants or in combination with any of the above-described adjuvants.
• Chemicals useful in combination with the active ingredients of this invention included, for example, triazines, ureas, sulfonylureas, carbamates, acetamides, acetanilides, uracils, acetic acid or phenol derivatives, thiolcarbamates, triazoles, benzoic acid derivatives, nitriles, heterophenyl ethers, nitrophenyl ethers, diphenyl ethers, pyridines and the like such as:
• 3,5-Pyridinedicarboxylic acid 2-(difluoromethyl)-4-(2-methylpropyl)-6-(trifluoromethyl)-, dimethyl ester;
• 3,5-Pyridinedicarbothioic acid 4-(cyclopropylmethyl)-2- (difluoromethyl)-6-(trifluoromethyl)-, S,S-dimethyl ester;
• Fertilizers useful in combination with the active ingredients include, for example, ammonium nitrate, urea, potash and superphosphate.
• Other useful additaments include materials in which plant organisms take root and grow such as compost, manure, humus, sand and the like.
• Alkyl aryl sulfonate e.g., Morwet D-425
• EO/PO Block Copolymer e.g., Pluronic
• Granular Bentonite (30/60 mesh) 80 .0

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• 1991
  • 1991-08-02 JP JP3513763A patent/JPH05509103A/ja active Pending
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  • 1991-08-02 WO PCT/US1991/005530 patent/WO1992002509A1/en not_active Application Discontinuation
  • 1991-08-02 AU AU84146/91A patent/AU649474B2/en not_active Expired - Fee Related
  • 1991-08-02 CA CA002087260A patent/CA2087260A1/en not_active Abandoned
  • 1991-08-02 EP EP91915235A patent/EP0542872A1/en not_active Withdrawn
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• 1993
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