Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
  • C07C303/36—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of amides of sulfonic acids
  • C07C303/38—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of amides of sulfonic acids by reaction of ammonia or amines with sulfonic acids, or with esters, anhydrides, or halides thereof
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
  • C07C303/02—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of sulfonic acids or halides thereof
  • C07C303/22—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of sulfonic acids or halides thereof from sulfonic acids, by reactions not involving the formation of sulfo or halosulfonyl groups; from sulfonic halides by reactions not involving the formation of halosulfonyl groups
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof
  • C07C309/01—Sulfonic acids
  • C07C309/28—Sulfonic acids having sulfo groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton
  • C07C309/57—Sulfonic acids having sulfo groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton containing carboxyl groups bound to the carbon skeleton
  • C07C309/59—Nitrogen analogues of carboxyl groups
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C311/00—Amides of sulfonic acids, i.e. compounds having singly-bound oxygen atoms of sulfo groups replaced by nitrogen atoms, not being part of nitro or nitroso groups
  • C07C311/65—N-sulfonylisocyanates
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C327/00—Thiocarboxylic acids
  • C07C327/02—Monothiocarboxylic acids
  • C07C327/04—Monothiocarboxylic acids having carbon atoms of thiocarboxyl groups bound to hydrogen atoms or to acyclic carbon atoms
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
  • C07D239/02—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings
  • C07D239/24—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members
  • C07D239/28—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, directly attached to ring carbon atoms
  • C07D239/46—Two or more oxygen, sulphur or nitrogen atoms
  • C07D239/52—Two oxygen atoms
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D327/00—Heterocyclic compounds containing rings having oxygen and sulfur atoms as the only ring hetero atoms
  • C07D327/02—Heterocyclic compounds containing rings having oxygen and sulfur atoms as the only ring hetero atoms one oxygen atom and one sulfur atom
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D327/00—Heterocyclic compounds containing rings having oxygen and sulfur atoms as the only ring hetero atoms
  • C07D327/02—Heterocyclic compounds containing rings having oxygen and sulfur atoms as the only ring hetero atoms one oxygen atom and one sulfur atom
  • C07D327/04—Five-membered rings

Definitions

• the invention relates to new substituted benzamides and the technical field of chemical processing for preparing substituted benzamides which can be employed for preparing herbicidally active sulfonylurea compounds, intermediates or products intended for use in crop protection.
• an object of the present invention is to provide new sulfobenzamides that can advantageously be used for the preparation of herbicidally active sulfonylureas and their prescursors such as sulfochlorides or sulfonamides.
• Another object of the present invention is to provide an improved process for the preparation of herbicidally active sulfonylureas and their prescursors such as sulfochlorides or sulfonamides.
• the present invention thus relates to new 4-nitro-2-sulfobenzamides of the formula
• R 1 is an unsubstituted or substituted hydrocarbon or radical having a total of 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms
• R 2 is an unsubstituted or substituted hydrocarbon radical having a total of
• the group NR 1 R 2 is a heterocydic ring having 3 to 8 ring atoms which is unsubstituted or substituted and contains the nitrogen atom of the group NR 1 R 2 as ring heteroatom and may also contain one or two further ring heteroatoms from the group consisting of N, O and S, and
• Q is H, or a cation like an alkali or alkaline earth metal cation, e.g. Li, Na,
• K, Mg or Ca or an ammonium- or phosphonium-cation e.g. R 4 N, R 3 NH, R 2 NH 2 , RNH 3 , NH 4 , R 4 P, wherein R are identical or different unsubstituted or substituted hydrocarbon radicals having 1 to 24 carbon atoms, e.g.
• C C 18 -alkyl C 2 -C 18 -alkenyl, C 2 -C 18 -alkynyl or C 5 - C 18 -cycloalkyl, each of the 4 latter radicals being unsubstituted or substituted by one or more radicals from the group consisting of halogen, C 6 -C 10 -aryl, C 1 -C 4 -alkoxy, C,-C 4 -ha.oalkoxy, C r C 4 -alkylthio, mono- and di-(C r C 4 -alkyl)-amino, cyano, azido, formyl, (C C 4 -alkyl)- carbonyl, (C r C 4 -alkoxy)-carbonyl, C 1 -C 4 -alkylsulfinyl and C,-C 4 - alkylsulfonyl, or R is phenyl which is unsubstituted or substituted by radicals
• the present invention relates to compounds of the formula (I), wherein
• R 1 is C 2 -C 6 -alkenyl, C 2 -C 6 -alkynyl or C 5 -C 6 -cycloalkyl, each of the four latter radicals being unsubstituted or substituted by one or more radicals from the group consisting of halogen, C ⁇ C ⁇ -alkoxy, C,- C 4 -haloalkoxy, C ⁇ C ⁇ alkylthio, mono- and di-(C 1 -C 4 -alkyl)-amino, cyano, azido, formyl, (C ⁇ C ⁇ alkylJ-carbonyl, (C ⁇ C ⁇ -alkoxy ⁇ carbonyl, C ⁇ O t -alkylsulfinyl and C.,-C 4 -alkylsulfonyl, or is phenyl which is unsubstituted or substituted by radicals from the group consisting of halogen, C C 4 -alkyl, C ⁇ C ⁇ alkoxy,
• R 2 is C,-C 6 -alkyl, C 2 -C 6 -alkenyl, C 2 -C 6 -alkynyl or C 5 -C 6 -cycloalkyl, each of the four latter radicals being unsubstituted or substituted by one or more radicals from the group consisting of halogen, C r C 4 -alkoxy, C C 4 -haloalkoxy, C ⁇ C ⁇ alkylthio, mono- and di-(C 1 -C 4 -alkyl)-amino, cyano, azido, formyl, (C ⁇ C ⁇ alkyl ⁇ carbonyl, (C r C 4 -alkoxy)-carbonyl, C ⁇ C ⁇ alkylsulfinyi and C 1 -C 4 -alkylsulfonyl, or the group
• NR 1 R 2 is a heterocydic ring of 4, 5 or 6 ring atoms which may contain up to two further ring heteroatoms from the group consisting of N and O in the ring and which is unsubstituted or substituted by one or more C ⁇ C 4 -alkyl radicals, and
• Q is H or an alkali or alkaline earth metal cation or an ammonium- or phosphonium-cation, preferably an alkalimetal kation like Li, Na or K.
• R 2 is C 1 -C 4 -alkyl, especially methyl or ethyl, and
• Q is H, Na or K.
• Examples of compounds of the formula (I) are: N,N-dimethyl 4-nitro-2-sulfobenzamide potassium salt N,N-dimethyl 4-nitro-2-sulfobenzamide sodium salt N,N-dimethyl 4-nitro-2-suifobenzamide N,N-diethyl 4-nitro-2-sulfobenzamide potassium salt N,N-diethyl 4-nitro-2-sulfobenzamide sodium salt N,N-diethyl 4-nitro-2-sulfobenzamide N,N-methylethyl 4-nitro-2-sulfobenzamide potassium salt N,N-methylethyl 4-nitro-2-sulfobenzam.de sodium salt N,N-methylethyl 4-nitro-2-sulfo benzamide
• radicals alkyl, alkoxy, haloalkyl, haloalkoxy, alkylamino and alkylthio and their unsaturated and/or substituted counterparts may in each case be straight-chain or branched in the carbon framework. Unless indicated specifically, preference is given in the case of these radicals to the lower carbon frameworks, e.g. those having 1 to 4 carbon atoms, or, in the case of unsaturated groups, having 2 to 4 carbon atoms.
• Alkyl radicals both alone and in the composite definitions such as alkoxy, haloalkyl, etc., are for example methyl, ethyl, n-propyl, isopropyl, n-butyl isobutyl, tert-butyl or 2-butyl, pentyls, hexyls, such as n-hexyl, isohexyl and 1 ,3-dimethylbutyl, and heptyls, such as n-heptyl, 1- methylhexyl and 1 ,4-dimethylpentyl; alkenyl and alkynyl radicals have the meaning of the possible unsaturated radicals corresponding to the alkyl radicals; alkenyl is for example allyl, 1-methylprop-2-en-1-yl, 2-methylprop-2-en-1-yl, but-2-en-1-yl, but-3- en-1-yl, 1-methylbut-3-en-1-y
• Halogen is for example fluorine, chlorine, bromine or iodine.
• Haloaryl, haloalkyl, haloalkenyl and haloalkynyl are aryl, alkyl, alkenyl and, respectively, alkynyl which are partially or completely substituted by halogen, preferably by fluorine, chlorine and/or bromine, in particular by fluorine or chlorine, examples being CF 3 , CHF 2 , CH 2 F, CF 3 CF 2 , CH 2 FCHCI, CCI 3 , CHCI 2 , CH 2 CH 2 CI;
• haloalkoxy is for example OCF 3 , OCHF 2 , OCH 2 F, CF 3 CF 2 O, OCH 2 CF 3 and OCH 2 CH 2 CI; corresponding comments apply to haloalkenyl and other halogen-substituted radicals.
• a hydrocarbon radical is a straight-chain, branched or cyclic and saturated or unsaturated aliphatic or aromatic hydrocarbon radical, for example alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl or aryl, preferably alkyl, alkenyl or alkynyl having up to 12 carbon atoms or cycloalkyl having 5 or 6 ring atoms, or phenyl; corresponding comments apply to a hydrocarbonoxy radical.
• a heterocydic radical or ring can be saturated, unsaturated or heteroaromatic; it contains one or more ring heteroatoms, preferably from the group consisting of N, O and S; it preferably has 5 or 6 members and contains 1 , 2 or 3 ring heteroatoms.
• the radical may for example be a heteroaromatic radical or ring (heteroaryl) as defined above, or is a partially hydrogenated radical such as oxiranyl, pyrrolidinyl, piperidyl, piperazinyl, dioxolanyl, morpholinyl, and tetrahydrofuryl.
• Suitable substituents for a substituted heterocydic radical are those mentioned below, and also oxo.
• the oxo group may also be on the ring heteroatoms, which may exist in various oxidation states in the case, for example, of N and S.
• Substituted radicals such as substituted hydrocarbon radicals, e.g. substituted alkyl, alkenyl, alkynyl, aryl, phenyl and benzyl, or substituted heteroaryl, a substituted bicyclic radical or ring or a substituted bicyclic radical, with or without aromatic components, are for example a substituted radical derived from the unsubstituted parent structure, the substituents being for example one or more, preferably 1 , 2 or 3, radicals from the group consisting of halogen, alkoxy, haloalkoxy, alkylthio, hydroxyl, amino, nitro, cyano, azido, alkoxycarbonyl, alkylcarbonyl, formyl, carbamoyl, mono- and dialkylaminocarbonyl, substituted amino such as acylamino, mono- and dialkylamino, and alkylsulfinyl, haloalkylsuifinyl, alky
• radicals containing carbon atoms preference is given to those having 1 to 4 carbon atoms, especially 1 or 2 carbon atoms.
• substituents from the group consisting of halogen, e.g. fluorine and chlorine, C r C 4 -alkyl, preferably methyl or ethyl, C C 4 -haloalkyl, preferably trifluoromethyl, C r C 4 - alkoxy, preferably methoxy or ethoxy, C C 4 -haloalkoxy, nitro and cyano.
• substituents methyl, methoxy and chlorine are particularly preferred.
• Aryl is a mono-, bi- or polycylic aromatic system such as phenyl, naphtyl, indenyl or fluorenyl, preferably phenyl.
• Substituted or unsubstituted phenyl is preferably phenyl which is unsubstituted or is substituted one or more times, preferably up to three times, by identical or different radicals from the group consisting of halogen, C,-C 4 - alkyl, C r C 4 -alkoxy, C C 4 -haloalkyl, C C 4 -haloalkoxy and nitro, examples being o-, m- and p-tolyl, dimethylphenyls, 2-, 3- and 4-chlorophenyl, 2-, 3- and 4-trifluoro- and -trichlorophenyl, 2,4-, 3,5- 2,5- and 2,3-dichlorophenyl, and o-, m- and p- methoxyphen
• An acyl radical is the radical of an organic acid, for example the radical of a carboxylic acid, and radicals of acids derived therefrom, such as of thiocarboxylic acid, of unsubstituted or N-substituted iminocarboxylic acids, or is a radical of carbonic acid monoesters, of unsubstituted or N-substituted carbamic acid, sulfonic acids, sulfinic acids, phosphonic acids, phosphinic acids.
• Acyl is for example formyl, alkylcarbonyl such as (C,-C 4 -alkyl)-carbonyl, phenylcarbonyl, where the phenyl ring can be substituted, for example, as shown above for phenyl, or alkyloxycarbonyl, phenyloxycarbonyl, benzyloxycarbonyl, alkylsulfonyl, alkylsulfinyl, N-alkyl-1- iminoalkyl and other radicals of organic acids.
• amide among others includes amides such as: dimethyl formamide, diethyl formamide, dimethyl acetamide, N-methyl formanilide, N-methyl acetanilide, 4-formyl morpholine, N-formyl piperidine, N-formyl pyrolidine or mixtures thereof.
• phase transfer catalyst among others includes ammonium or phosphonium compounds preferably hydrocarbylammonium or hydrocarbylphosphonium compounds such as: tetraalkylammonium such as tetrabutylammonium, tetraethylammonium, tetramethylammonium, cetyltrimethylammonium or methyltrioctylammoniumchlo de (Alliquat® 336), benzyltriethylammonium, benzyltrimethylammonium, or tetraphenylphosphonium, each as chloride, bromide, hydrogensulfate, sulfate or mixtures thereof.
• tetraalkylammonium such as tetrabutylammonium, tetraethylammonium, tetramethylammonium, cetyltrimethylammonium or methyltrioctylammoniumchlo de (Alliquat® 336)
• tertiary amine among others includes alkylamines such as: triethylamine, tributylamine, benzyldialkylamine, N-alkyimorpholine, N- alkylpiperidine, N-alkylpyrrolidine, or aromatic amines such as pyridine, 2 or 3 or 4- methylpyridine, 2,3 or 2,4 or 2,5 or 2,6 or 3,4 or 3,5-dimethylpyridine, N,N- dialkylaniline, e.g. N,N-dimethylaniline, or mixtures thereof.
• alkylamines such as: triethylamine, tributylamine, benzyldialkylamine, N-alkyimorpholine, N- alkylpiperidine, N-alkylpyrrolidine, or aromatic amines such as pyridine, 2 or 3 or 4- methylpyridine, 2,3 or 2,4 or 2,5 or 2,6 or 3,4 or 3,5-dimethylpyridine, N,N- dialkylani
• activation reagent means a reagent that is capable of converting an acid into the acid-chloride or acid-anhydride or similarly reactive derivatives of the acid, and amongst others includes phosgene, thionyl chloride, phosphorous oxychloride, phosphorous trichloride, phoshorous pentachlo de, sulforyl chloride, or mixtures thereof.
• acylation reagent means a reagent that is capable of substituting hydrogen by an acyl radical and among others includes formic acid and C,-C 8 -carboxylic acid anhydrides, e.g. acetic anhydride or formic acetic anhydride.
• aryl among others includes nitrobenzene, toluene, xylene, chiorobenzene and dichlorobenzene.
• alkyl among others includes pentane, hexane, dichloromethane and dichloroethane.
• ester among other includes ethylacetate, propylacetate and butyiacetate.
• ether among others includes dibutylether, dipropylether, dioxane and tetrahydrofurane.
• nitrile among others includes acetonit le, propionitrile and benzonit le.
• carboxylic acid among others includes formic acid, acidic acid, propionic acid and butyric acid.
• carbonate among others includes diethylcarbonate.
• amide among others includes N-methylpyrolidone, dimethylformamide and dimethylacetamide.
• sulfone among others includes dimethylsulfone.
• ketone among others includes acetone, ethylmethylketone, diethylketone and cyclohexanone.
• carbamate among others include trimethylcarbamate.
• alcohol among others includes methanol, ethanol, propanol and butanol.
• the benzamides of the formula (I) of the present invention can be obtained for example by reaction of the appropriately substituted amine of the formula NHR 1 R 2 or a salt thereof wherein R 1 and R 2 are defined as in formula (I), with the anhydride of the formula (II).
• Reaction of the anhydride of the formula (II) with between 1 and 10 equivalents, preferably 1 and 4 equivalents and especially 1 to 2 equivalents of an appropriately substituted amine (NHR 1 R 2 ) affords in the presence or preferably in the absence of a tertiary amine the desired benzamides of the formula (I) in excellent yields.
• the reaction may be carried out at temperatures between about -50 and 300°C, preferably -20 and 180°C, in solvents or mixtures of solvents such as but not limited to unsubstituted or substituted hydrocarbones such as unsubstituted or substituted aryls (e.g. alkylaryls or haloaryls) or unsubstituted or substituted alkyls (e.g. haloalkyls), esters and ethers, at atmospheric, reduced or increased pressure.
• solvents or mixtures of solvents such as but not limited to unsubstituted or substituted hydrocarbones such as unsubsti
• the anhydride of the formula (II) can also be obtained from the reaction of the diacid of the formula (III) with possibly up to 4 equivalents, preferably 1 to 2 equivalents of an activation reagent, preferably thionyl chloride or phosgene, possibly in the presence of a phase transfer catalyst, preferably benzyltriethylammonium chloride, and optionally in the presence an amide catalyst, preferably dimethyl formamide, and optionally in the presence a tertiary amine catalyst, preferably pyridine. Thereafter of the excess reagent is removed by, for example but not limited to, distillation at or above atmospheric pressure or under vacuum.
• the reaction may carried out, in solvents or mixtures of solvents such as but not limited to: unsubstituted or substituted hydrocarbones such as unsubstituted or substituted aryls (e.g. alkylaryls or haloaryls) or unsubstituted or substituted alkyls (e.g. haloalkyls), carbonates, carbamates, esters, ethers, and sulfones, at, above or below their boiling point at atmospheric, reduced or increased pressure, at temperatures between about 0°C to 300°C, preferably between 40°C to 150°C.
• solvents or mixtures of solvents such as but not limited to: unsubstituted or substituted hydrocarbones such as unsubstituted or substituted aryls (e.g. alkylaryls or haloaryls) or unsubstituted or substituted alkyls (e.g. haloalkyls), carbonates, carbamates,
• the anhydride of the formula (II) can also be obtained by reaction of a dichloride of the formula (IV) with a diacid of the formula (111).
• the dichloride of the formula (IV) (or other doubly activated isomers or derivatives thereof such as disclosed in DE 2616611 , see e.g.
• formula (V) therein) may, after removal of excess reagent by, for example but not limited to, distillation at or above atmospheric pressure or under vacuum, be reacted with fresh diacid of the formula (III) or a salt thereof, other carboxylic acids (RCO 2 H, where R is C C 8 -alkyl), or other molecules capable of supplying the necessary oxygen atom, such as sulfoxides or tertiary N-oxides, optionally in the presence of a tertiary amine, preferably pyridine.
• the reaction may be carried out in solvents or mixtures of solvents such as but not limited to: unsubstituted or substituted hydrocarbones such as unsubstituted or substituted aryls (e.g.
• alkylaryls or haloaryls or unsubstituted or substituted alkyls (e.g. haloalkyls), carbonates, carbamates, amides, esters, ethers, nitriles and sulfones, at, above or below their boiling point at atmospheric, reduced or increased pressure, at temperatures between about 0°C to 300°C, preferably between 40°C to 150°C, to produce the anhydride of the formula (II) in excellent yield.
• benzamides of the formula (I) of the present invention can also be obtained by direct reaction of a diacid of the formula (III) or a salt thereof,
• Q and Q 2 are identical or different and are H or a cation like an alkali or alkaline earth metal cation, e.g. Li, Na, K, Mg or Ca or an ammonium- or phosphoniumcation, e.g. R 4 N, R 3 NH, R 2 NH 2 , RNH 3 , NH 4 , R 4 P, wherein R are identical or different unsubstituted or substituted hydrocarbon radicals having 1 to 24 carbon atoms, e.g.
• the reaction is carried out optionally in the presence of a phase transfer catalyst, preferably benzyltriethylammonium chloride, and optionally in the presence of a tertiary amine catalyst.
• a phase transfer catalyst preferably benzyltriethylammonium chloride
• a tertiary amine catalyst preferably benzyltriethylammonium chloride
• the reaction may be carried out in substance or in solvents such as but not limited to unsubstituted or substituted hydrocarbones such as unsubstituted or substituted aryls (e.g. alkylaryls or haloaryls) or unsubstituted or substituted alkyls (e.g.
• haloalkyls carbonates, carbamates, esters, ethers, nitrites and sulfones, at, above or below their boiling point at atmospheric, reduced or increased pressure, at temperatures between about 0°C to 300°C, preferably between 40°C to 150°C, and renders the benzamides of the formula (I) in excellent yields.
• the benzamides of the formula (I) may be isolated by techniques commonly practised in the laboratory and known to those skilled in the art such as filtration, or they may be further reacted without isolation.
• the benzamides of the formula (I) are valuable intermediates for the preparation of various products such as sulfonylareas intended for use in crop protection.
• the nitrobenzamides of the formula (I) can be converted into the corresponding aminobenzamides of the formula (V), wherein Q, R 1 and R 2 are defined as in formula (I).
• the hydrogenation may be carried out with hydrogen or a hydrogen source such as cyclohexadiene, in the presence of a metal catalyst like: Pd/C, Pt/C, Ru/C or Raney-Ni alone or in combination, possibly in the presence of other metal derivatives such as the oxides of or the salts of the metals manganese, molybdenum, tungsten, iron and cobalt in which the metal is present as cation, oxoanion or polyoxoanion, in an inert solvent or solvent mixture thereof, such as but nor limited to: water, alcohols, ethers, carboxylic acids and ketones, alone or as mixtures, or as mixtures with the solvents used in the preparation of the benzamides of the formula (I), at temperatures between about -30°C to 300°C
• the benzamides of the formula (I) may also be hydrogenated and subsequently or simultaneously (reductive acylation) be reacted with an acylating reagent.
• the benzamides of the formula (I) may be reacted with hydrogen or a hydrogensource such as cyclohexadiene, in the presence of a) a metal catalyst like: Pd/C, Pt/C, Ru/C or Raney-Ni alone or in combination, possibly in the presence of other metal derivatives such as the oxides of or the salts of the metals manganese, molybdenum, tungsten, iron and cobalt in which the metal is present as cation, oxoanion or polyoxoanion, and b) an acylating agent such as formic acid and/or an C C 8 -carboxylic acid anhydride, optionally in other solvents or mixture of solvents, such as but not limited to: alkylaryi, aryl, carbonate, carbamate, ester,
• alkylaryls or haloaryls or unsubstituted or substituted alkyls (e.g. haloalkyls), carbonates, carbamates, esters, ethers, ketones, nitriles and sulfones, at temperatures between about -30°C to 300°C and preferably between -10°C and 150°C, to form the corresponding acylamido derivatives of the formula (VI), where Q, R 1 and R 2 are defined in formula (I) and A is an acyl radical, preferably a formyl radical or a C,-C 8 - hydrocarbyl-carbonyl radical, such as a branched or straight chain C,-C 8 -alkyl-carbonyl radical.
• A is an acyl radical, preferably a formyl radical or a C,-C 8 - hydrocarbyl-carbonyl radical, such as a branched or straight chain C,-C 8 -alkyl-carbonyl radical.
• the benzamide of the formula (I) may be reacted with an activation reagent, preferably thionyl chloride or phosgene, in the presence of an amide catalyst, preferably dimethyl formamide, optionally in the presence of a phase transfer catalyst, preferably benzylthethylammonium chloride, and optionally in the presence of a tertiary amine catalyst, preferably pyridine, to form in excellent yields the sulfonyl chlorides of the formula (VII), where R 1 and R 2 are defined as in formula (I).
• an activation reagent preferably thionyl chloride or phosgene
• an amide catalyst preferably dimethyl formamide
• a phase transfer catalyst preferably benzylthethylammonium chloride
• a tertiary amine catalyst preferably pyridine
• the excess reagent is removed by, for example but not limited to: distillation at or above atmospheric pressure or under vacuum, in solvents such as but not limited to unsubstituted or substituted hydrocarbones such as unsubstituted or substituted aryls (e.g. alkylaryls or haloaryls) or unsubstituted or substituted alkyls (e.g. haloalkyls), esters, carbonates and ethers, at or below their boiling point at atmospheric, reduced or increased pressure, at temperatures between about 0°C to 200°C, preferably between 50°C and 150°C.
• solvents such as but not limited to unsubstituted or substituted hydrocarbones such as unsubstituted or substituted aryls (e.g. alkylaryls or haloaryls) or unsubstituted or substituted alkyls (e.g. haloalkyls), esters, carbonates and ethers, at or below their
• the compound of the formula (VII) may be isolated by techniques commonly practiced in the laboratory and to those skilled in the art such as filtration.
• the sulfonyl chlorides of the formula (VII) may also be further reacted, preferably without further isolation at temperatures between about -100°C to 200°C, preferably -30°C to 100°C with ammonia, primary or secondary amines, optionally in the presence of a tertiary amine, preferably pyridine, to give in excellent yields the corresponding sulfonamides of the formula (VIII), where R and R 2 are defined as in formula (I) and where R 4 and R 5 are hydrogen or C r C 12 -hydrocarbon radical like straight or branched chain C r C 12 -alkyl, C.,-C 12 -alkenyl or C,-C 12 - alkynyi, C 6 -C 12 -aryl or heteroaryl, where the ring or chain may contain one or more of the following substituent
• the sulfonyl chlorides of the formula (VII) may also be reacted with cyanate salts (e.g. MOCN, where M is a cation like an alkali or alkaline earth metal cation, such as Li, Na, K, Mg or Ca or an ammonium- or phosphoniumcation), possibly in the presence of a phase transfer catalyst (including in addition to those previously described polyethylene, glycols and polyethers), and optionally in the presence of a tertiary amine catalyst, preferably pyridine, triethylamine or tributylamine, or mixtures thereof, at temperatures between about -100°C to 150°C, preferably -30°C to 100°C to form in excellent yields the sulfonyl isocyanates of the formula (IX-A) or (IX-B), where R 1 and R 2 are defined as in formula (I) and Z in formula (IX-B) is a tertiary ammonium radical obtained from
• the sulfonyl isocyanate of the formula (IX-B) may be obtained if the reaction is carried out in the presence of a nucleophilic tertiary amine catalyst
• the sulfonamides of the formula (VIII) may be isolated by techniques commonly practised in the laboratory and known to those skilled in the art such as filtration or they may be further reacted without isolation.
• the sulfonamides of the formula (VIII) are valuable intermediates for the preparation of various products such as sulfonylareas intended for use in crop protection.
• the sulfonamides of the formula (VIII) can be converted into the corresponding sulfonamides of the formula (V * ), wherein R 1 ,R 2 , R 4 and R 5 are defined as in formula (VIII).
• the hydrogenation may be carried out with hydrogen or a hydrogen source such as cyclohexadiene in the presence of a metal catalyst like: Pd/C, Pt/C, Ru/C or Raney-Ni alone or in combination, possibly in the presence of other metal derivatives such as the oxides of or the salts of the metals manganese, molybdanum, tungsten, iron and cobalt in which the metal is present as cation, oxoanion or polyoxoanion, in an inert solvent or solvent mixture thereof, such as but nor limited to: water, alcohols, unsubstituted or substituted hydrocarbones such as unsubstituted or substituted aryls (e.g.
• alkylaryls or haloaryls or unsubstituted or substituted alkyls (e.g. haloalkyls), ethers, carbonates, carbamates, esters, nitriles, sulfones, carboxylic acids and ketones, alone or as mixtures, or as mixtures with the solvents used in the preparation of the sulfonamides of the formula (VIII), at temperatures between about -30°C to 300°C and preferably between -10°C and 150°C.
• the sulfonamides of the formula (VIII) may also be hydrogenated and subsequently or simultaneously (reductive acylation) be reacted with an acylating reagent.
• the sulfonamides of the formula (VIII) may be reacted with hydrogen or a hydrogensource such as cyclohexadiene in the presence of a) a metal catalyst like: Pd/C, Pt/C, Ru/C or Raney-Ni alone or in combination, possibly in the presence of other metal derivatives such as the oxides of or the salts of the metals manganese, molybdanum, tungsten, iron and cobalt in which the metal is present as cation, oxoanion or polyoxoanion, and b) an acylating reagent such as formic acid and/or an C,-C 8 -carboxylic acid anhydride, optionally in other solvents or mixture of solvents, such as but not limited to: unsubstituted or substituted
• alkylaryls or haloaryls or unsubstituted or substituted alkyls (e.g. haloalkyls), carbonates, carbamates, esters, ethers, ketones, nitriles and sulfones, at temperatures between about -30°C to 300°C and preferably between -10°C and 150°C, to form the corresponding acylamido derivatives of the formula (VI*), where R 1 , R 2 , R 4 and R 5 are defined as in formula (VIII) and A is an acyl radical, preferably a formyl radical or a C r C 8 hydrocarbyl-carbonyl radical, such as a branched or straight chain C r C 8 -alkyl-carbonyl radical.
• A is an acyl radical, preferably a formyl radical or a C r C 8 hydrocarbyl-carbonyl radical, such as a branched or straight chain C r C 8 -alkyl-
• the sulfonamide of the formula (VIM) and the sulfonyl isocyanates of the formula (IX-A) and (IX-B) can be advantageously used to prepare in excellent yields sulfonylureas which exhibit herbicidal activity.
• herbicidal sulfonylareas are sulfonylareas of the formulas (XII) and (XIV) below, such as N-(4,6- dimethoxypyrimidin-2-ylaminocarbonyl)-2-(N,N-dimethylaminocarbonyl)-5-(N- methoxycarbonylamino)benzenesulfonamide, N-(4,6-dimethoxypyrimidin-2- ylaminocarbonyl)-2-(N,N-dimethylaminocarbonyl)-5-(N-propionyl- amino)benzenesulfonamide sodium salt, N-(4,6-dimethoxypyrimidin-2- ylaminocarbonyl)-2-(N,N-dimethylaminocarbonyl)-5-(N- formylamino)benzenesulfonamide, N-(4,6-dimethoxypyrimidin-2-ylaminocarbonyl)-2
• the sulfonylareas can form salts where the hydrogen of the -SO 2 -NH- group is replaced by an agriculturally suitable cation.
• These salts are, for example, metal salts, in particular alkali metal salts or alkaline-earth metal salts, in particular sodium salts and potassium salts, or else ammonium salts or salts with organic amines.
• salt formation can be carried out by adding an acid to basic groups, such as, for example, amino and alkylamino. Suitable acids for this purpose are strong inorganic and organic acids, for example HCI, HBr, H 2 SO 4 or HNO 3 .
• the sulfonamide of the formula (VIII) can be reacted as described above
• R 1 and R 2 are defined as in formula (I), R 4 and R 5 are hydrogen or a C ⁇ C ⁇ -hydrocarbon radical and A* is hydrogen or an acyl radical, and then reacting the compound of the formula (A) previously obtained with
• M is H, C 1 -C 4 -alkyl or a metal cation
• X and Y independently of one another are halogen, C,-C 6 -alkyl, alkoxy, C C 6 -alkylthio, each of the three latter radicals being unsubstituted or substituted by one or more radicals from the group consisting of halogen, C,-C 4 -aIkoxy and C 1 -C 4 -alkylthio, or are C 3 -C 6 -cycloalkyl, C 2 -C 6 -alkenyl, C 2 -C 6 -alkynyl, C 3 -C B - alkenyloxy or C 3 -C 6 -alkynyloxy, and
• Z is CH or N
• a solvent or mixture of solvents such as but not limited to unsubstituted or substituted hydrocarbones such as unsubstituted or substituted aryls (e.g. alkylaryls or haloaryls) or unsubstituted or substituted alkyls (e.g. haloalkyls), esters, ethers, amides, nitriles and ketones, and optionally in the presence of a base such as but not limited to carbonates, alkoxides, hydroxides or tertiary amines, or
• X and Y independently of one another are halogen, C C 6 -alkyl, C,-C 6 - alkoxy, C r C 6 -alkylthio, each of the three latter radicals being unsubstituted or substituted by one or more radicals from the group consisting of halogen, C,-C 4 -alkoxy and C,-C 4 -alkylthio, or are C 3 -C 6 -cycloalkyl, C 2 -C 6 -alkenyl, C 2 -C 6 -alkynyl, C 3 -C 6 - alkenyloxy or C 3 -C 6 -alkynyloxy, and Z is CH or N,
• a solvent or mixture of solvents such as but not limited to unsubstituted or substituted hydrocarbones such as unsubstituted or substituted aryls (e.g. alkylaryls or haloaryls) or unsubstituted or substituted alkyls (e.g. haloalkyls), esters, ethers and nitriles,
• R 1 , R 2 and R 4 are defined as in formula (VIII) and M, X, Y and Z are defined as in formula (X) and A* is hydrogen or an acyl group.
• Ar is unsubstituted or substituted phenyl
• M is H, C r C 4 -alkyl or a metal cation
• X and Y independently of one another are halogen, C 1 -C 6 -alkyl, C,-C 6 - alkoxy, each of the three latter radicals being unsubstituted or substituted by one or more radicals from the group consisting of halogen, C C 4 -alkoxy and C ⁇ C ⁇ alkylthio, or are C 3 -C 6 -cycloalkyl, C 2 -C 6 -alkenyl, C 2 -C 6 -alkynyl, C 3 -C 6 - alkenyloxy or C 3 -C 6 -alkynyloxy, and
• Z is CH or N, or
• X and Y independently of one another are halogen, C 1 -C 6 -alkyl, C,-
• Z is CH or N, or as described in WO 00/05220 which is fully incorporated herewith by reference with an activation reagent such as phosgene and an amine to give a compound of the formula (IX-A) or (IX-B)
• R 1 and R 2 are defined as in formula (I) in claims 1 to 3, and then reacting the compound of the formula (IX) previously obtained with a compound of the formula (XI * )
• M is H, C ⁇ C ⁇ alkyl or a metal cation
• X and Y independently of one another are halogen, C,-C 6 -alkyl, C 1 -C 6 - alkoxy, each of the three latter radicals being unsubstituted or substituted by one or more radicals from the group consisting of halogen, C C 4 -alkoxy and C ⁇ C ⁇ alkylthio, or are C 3 -C 6 -cycloalkyl, C 2 -C 6 -alkenyl, C 2 -C 6 -alkynyl, C 3 -C 6 - alkenyloxy or C 3 -C 6 -alkynyloxy, and
• Z is CH or N, at a temperature of fer example about -50 - 150°C, at atmospheric, reduced or increased pressure, optionally in the presence of a solvent or mixture of solvent such as but not limited to unsubstituted or substituted hydrocarbones such as unsubstituted or substituted aryls (e.g. alkylaryls or haloaryls) or unsubstituted or substituted alkyls (e.g. haloalkyls), esters, ethers and nitriles,
• a solvent or mixture of solvent such as but not limited to unsubstituted or substituted hydrocarbones such as unsubstituted or substituted aryls (e.g. alkylaryls or haloaryls) or unsubstituted or substituted alkyls (e.g. haloalkyls), esters, ethers and nitriles,
• R 1 , R 2 and R 4 are defined as in formula (VIII) and M, X, Y and Z are defined as in formula (X).
• nitrophenyl-sulfonylureas of the formula (XII) or a salt thereof can be further transformed into the corresponding aminophenyl-sulfonylureas of the formula (XIV) or salts thereof
• R 1 , R 2 and R 4 are defined as in formula (VIII) and M, X, Y and Z are defined as in formula (X) and A * is H, by hydrogenation, e.g. as described above for compounds of the formula (I) and (VIII) or as described in WO 97/16419 which is herewith fully incorporated by reference.
• the hydrogenation may be carried out with hydrogen or a hydrogen source such as cyclohexadiene in the presence of a metal catalyst like: Pd/C, Pt/C, Ru/C or Raney-Ni alone or in combination, possibly in the presence of other metal derivatives such as the oxides of or the salts of the metals manganese, molybdanum, tungsten, iron and cobalt in which the metal is present as cation, oxoanion or polyoxoanion, in an inert solvent or solvent mixture thereof, such as but nor limited to: water, alcohols, unsubstituted or substituted hydrocarbones such as unsubstituted or substituted aryls (e.g.
• alkylaryls or haloaryls or unsubstituted or substituted alkyls (e.g. haloalkyls), ethers, carbonates, carbamates, esters, nitriles, sulfones, carboxylic acids and ketones, at temperatures between about -30°C to 300°C and preferably between -10°C and 150°C.
• the reaction may be carried out with hydrogen or a hydrogen source such as cyclohexadiene in the presence of a) a metal catalyst like: Pd/C, Pt/C, Ru/C or Raney-Ni alone or in combination, possibly in the presence of other metal derivatives such as the oxides of or the salts of the metals manganese, molybdanum, tungsten, iron and cobalt in which the metal is present as cation, oxoanion or polyoxoanion, and b) an acylating reagent such as formic acid and/or an C 1 -C 8 -carboxylic acid anhydride, optionally in other solvents or mixture of solvents, such as but not limited to: unsubstituted or substituted hydrocarbones such as unsubstituted or substituted aryls (e.g.
• alkylaryls or haloaryls or unsubstituted or substituted alkyls (e.g. haloalkyls), carbonates, carbamates, esters, ethers, ketones, nitriles and sulfones, at temperatures between about -30°C to 300°C and preferably between -10°C and 150°C, to form the corresponding acylamidophenyl-sulfonylurea of the formula (XIV) or a salt thereof.

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