CA1230593A - Process for the preparation of aryloxybenzoic acids containing a sulphonamide group - Google Patents
Process for the preparation of aryloxybenzoic acids containing a sulphonamide groupInfo
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- CA1230593A CA1230593A CA000454361A CA454361A CA1230593A CA 1230593 A CA1230593 A CA 1230593A CA 000454361 A CA000454361 A CA 000454361A CA 454361 A CA454361 A CA 454361A CA 1230593 A CA1230593 A CA 1230593A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom 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
- C07D213/62—Oxygen or sulfur atoms
- C07D213/63—One oxygen atom
- C07D213/64—One oxygen atom attached in position 2 or 6
- C07D213/643—2-Phenoxypyridines; Derivatives thereof
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/582—Recycling of unreacted starting or intermediate materials
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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Abstract
ABSTRACT
A PROCESS FOR THE PREPARATION OF ARYLOXYBENZOIC ACIDS
CONTAINING A SULPHONAMIDE GROUP
A process for the preparation of herbicidal aryloxybenzoic acids containing a sulphonamide group by reacting an aryloxybenzoic acid halide, which may be impure, with a sulphonamide in the presence of a halogenating agent such as P(0)C13.
A PROCESS FOR THE PREPARATION OF ARYLOXYBENZOIC ACIDS
CONTAINING A SULPHONAMIDE GROUP
A process for the preparation of herbicidal aryloxybenzoic acids containing a sulphonamide group by reacting an aryloxybenzoic acid halide, which may be impure, with a sulphonamide in the presence of a halogenating agent such as P(0)C13.
Description
1~30593 DESCRIPTION
PROCESS FOR THE PREPARATION OF ARYLOXYBENZOIC ACIDS
CONTAINING A SULPHONAMIDE GROUP
The present invention relates to an improved process for the preparation of certain aryloxybenzoic acid derivatives containing a sulphonamide group and having herbicidal properties.
Herbicidal phenoxybenzoic acid derivatives containing a sulphonamide group (or N-sulphonylphenoxy-benzamides) are known from European Patent Applications Nos.
3,416 and 23,392 and Japanese Patent Application No.
82/106,654.
These patent applications disclose a number of products of this type, and particularly products of the general formula:
C B Co-NH-So2-R3 D ~ O ~ (I) and their salts, in which:
A is hydrogen; fluorine; chlorine; bromine; iodine; a nitro group; -N=NCF3;H2PO3 and its alkyl esters wherein the alkyl group contains from 1 to 4 carbon atoms; NH2; NHOH; N2; a carboxy group or one of its functional derivatives (e.g.
esters, amides and alkali metal, alkaline earth metal, ammonium and amine salts); a monoalkylamino or dialkylamino group; an NH-CO-Rl group in which Rl is an alkyl or alkoxy or monoalkylamino or dialkylamino group; an alkyl group;
trialkylammonium; NHSO2 in which R2 is an alkyl group or a phenyl group; NHCONHSO2R2, in which R2 is as hereinbefore defined; alkylthio; alkylsulphinyl: alkylsulphonyl;
dialkylsulphonium; cyanosulphonyl; hydroxy; alkanoyloxy;
alkoxy; alkoxy substituted by an alkoxycarbonyl group; SH;
nitroso ; -SCN; an azide group; CF3; -N=N-P-(OCH3)2, o or acyl;
B is a hydrogen, fluorine, chlorine, bromine or iodine atom, or an alkyl, alkoxy, alkylsulphinyl, alkylsulphonyl, CF3, NO2, CN, NH2, NHCORl, wherein R is as hereinbefore defined, or CONH2 group;
C is a hydrogen or halogen atom or an alkyl or dialkylamino group;
D is a fluorine, chlorine, bromine or iodine atom or a CF3, alkylthio, alkylsulphinyl, alkylsulphonyl, haloalkyl, sulphamoyl, formyl, alkylcarbonyl, CN or dimethylamino group;
E is hydrogen or a haloalkyl, alkoxy, alkylsulphinyl, alkylsulphonyl, CN, CF3, NH2, CONH2, or NH-CO-Rl group, in which Rl is as hereinbefore defined;
W is a trivalent nitrogen atom or a -C(G)= group in which G has one of the meanings given for B;
R3 is a phenyl, pyridyl or thienyl group optionally substituted by one or more halogen atoms, alkyl groups or nitro groups; or an alkenyl or alkynyl radical having 2 to 4 lZ3(~593 carbon atoms or an alkyl radical containing 1 to 4 carbon atoms optionally substituted by one or more fluorine, chlorine, bromine or iodine atoms, preferably CF3, or by one or more of the following substituents: carboxy, alkoxycarbonyl containing from 2 to 5 carbon atoms, alkylcarbonyl containing from 2 to 5 carbon atoms, monoalkylcarbamoyl or dialkylcarbamoyl in which the alkyl groups contain from 1 to 4 carbon atoms, alkylthio, alkyl~
sulphinyl, alkylsulphonyl, each having from 1 to 4 carbon 10 atoms, alkylcarbonyloxy containing from 2 to 5 carbon atoms, alkylcarbonylamino containing from 2 to 5 carbon atoms, or cyano.
In this specification and the accompanying claims alkyl groups and moieties, unless otherwise specified, are lS straight- or branched-chain and preferably contain from 1 to 4 carbon atoms.
According to the known processes, the products of general formula (I) can be prepared by reacting, between 25 and 140C, an acid halide intetmediate of the general formula:
D ~0 ~X ( I l ) in which X is chlorine, bromine or iodine, and A, B, C, D, E
and W have the meanings already indicated, with a sulphonamide of the general formula:
PROCESS FOR THE PREPARATION OF ARYLOXYBENZOIC ACIDS
CONTAINING A SULPHONAMIDE GROUP
The present invention relates to an improved process for the preparation of certain aryloxybenzoic acid derivatives containing a sulphonamide group and having herbicidal properties.
Herbicidal phenoxybenzoic acid derivatives containing a sulphonamide group (or N-sulphonylphenoxy-benzamides) are known from European Patent Applications Nos.
3,416 and 23,392 and Japanese Patent Application No.
82/106,654.
These patent applications disclose a number of products of this type, and particularly products of the general formula:
C B Co-NH-So2-R3 D ~ O ~ (I) and their salts, in which:
A is hydrogen; fluorine; chlorine; bromine; iodine; a nitro group; -N=NCF3;H2PO3 and its alkyl esters wherein the alkyl group contains from 1 to 4 carbon atoms; NH2; NHOH; N2; a carboxy group or one of its functional derivatives (e.g.
esters, amides and alkali metal, alkaline earth metal, ammonium and amine salts); a monoalkylamino or dialkylamino group; an NH-CO-Rl group in which Rl is an alkyl or alkoxy or monoalkylamino or dialkylamino group; an alkyl group;
trialkylammonium; NHSO2 in which R2 is an alkyl group or a phenyl group; NHCONHSO2R2, in which R2 is as hereinbefore defined; alkylthio; alkylsulphinyl: alkylsulphonyl;
dialkylsulphonium; cyanosulphonyl; hydroxy; alkanoyloxy;
alkoxy; alkoxy substituted by an alkoxycarbonyl group; SH;
nitroso ; -SCN; an azide group; CF3; -N=N-P-(OCH3)2, o or acyl;
B is a hydrogen, fluorine, chlorine, bromine or iodine atom, or an alkyl, alkoxy, alkylsulphinyl, alkylsulphonyl, CF3, NO2, CN, NH2, NHCORl, wherein R is as hereinbefore defined, or CONH2 group;
C is a hydrogen or halogen atom or an alkyl or dialkylamino group;
D is a fluorine, chlorine, bromine or iodine atom or a CF3, alkylthio, alkylsulphinyl, alkylsulphonyl, haloalkyl, sulphamoyl, formyl, alkylcarbonyl, CN or dimethylamino group;
E is hydrogen or a haloalkyl, alkoxy, alkylsulphinyl, alkylsulphonyl, CN, CF3, NH2, CONH2, or NH-CO-Rl group, in which Rl is as hereinbefore defined;
W is a trivalent nitrogen atom or a -C(G)= group in which G has one of the meanings given for B;
R3 is a phenyl, pyridyl or thienyl group optionally substituted by one or more halogen atoms, alkyl groups or nitro groups; or an alkenyl or alkynyl radical having 2 to 4 lZ3(~593 carbon atoms or an alkyl radical containing 1 to 4 carbon atoms optionally substituted by one or more fluorine, chlorine, bromine or iodine atoms, preferably CF3, or by one or more of the following substituents: carboxy, alkoxycarbonyl containing from 2 to 5 carbon atoms, alkylcarbonyl containing from 2 to 5 carbon atoms, monoalkylcarbamoyl or dialkylcarbamoyl in which the alkyl groups contain from 1 to 4 carbon atoms, alkylthio, alkyl~
sulphinyl, alkylsulphonyl, each having from 1 to 4 carbon 10 atoms, alkylcarbonyloxy containing from 2 to 5 carbon atoms, alkylcarbonylamino containing from 2 to 5 carbon atoms, or cyano.
In this specification and the accompanying claims alkyl groups and moieties, unless otherwise specified, are lS straight- or branched-chain and preferably contain from 1 to 4 carbon atoms.
According to the known processes, the products of general formula (I) can be prepared by reacting, between 25 and 140C, an acid halide intetmediate of the general formula:
D ~0 ~X ( I l ) in which X is chlorine, bromine or iodine, and A, B, C, D, E
and W have the meanings already indicated, with a sulphonamide of the general formula:
2 2 (III) in which R3 is as hereinbefore defined, generally in the presence of an acid acceptor, especially a tertiary amine such as N,N-dimethylaniline or pyridine, or an alkali metal carbonate such as anhydrous potassium carbonate or an alkali metal fluoride such as caesium fluoride.
The compounds of general formula (I) can then be alkylated in a known manner, for example by reaction with a diazoalkane containing ~rom 1 to 4 carbon atoms, so as to give the corresponding products which are substituted on the nitrogen atom of the sulphonamide group by an alkyl group containing from 1 to 4 carbon atoms; the hydrogen atom of this same nitrogen atom can also be replaced by an alkali metal atom such as, e.g. sodium, for example by reaction with lS basic alkali metal reagents.
This known process for condensing the compounds of general formulae (II) and (III) has various disadvantages, in particular poor yields. It is believed that, in general, it is the presence of an acid acceptor which lowers the yield because it favours the diacylation reaction. Moreover, the use of an acid acceptor makes the isolation and the purification of the final products more difficult and more costly.
An objective of the invention is to remedy these disadvantages of the known processes.
The process of the present invention enables the lZ3(~S93 of general formula (I) to be prepared from reactants of the general formula:
C B COOH
D ~ O ~ A (IV) (wherein the various symbols are as hereinbefore defined) of technical or industrial grades.
In practice, the latter problem is all the more important because this type of acid of general formula (IV) is liable to contain a considerable number of impurities as a result of the number and the nature of the reactions used in its manufacture. Thus, by way of a non-limiting example, it may be indicated that acifluorfen of the formula:
Cl CooH
CF3~ 0 {~ N02 (V) i.e. 5-[2'-chloro-4'-(trifluoromethyl)phenoxy]-2-nitrobenzoic acid, can be prepared by coupling an alkali metal meta-cresolate with a 3,4-dihalotrifluoromethylbenzene, followed by oxidation of the CH3 group to a carboxylic acid group and then nitration. During such a sequence of reactions, the number of isomers and other undesirable compounds progressively increases and a large number of acids is often detected in acifluorfen of ordinary quality, and especially the following acids:
2-ni~ro-3-12'-chloro-4'-(trifluoromethyl)phenoxy]benzoic acid in an amount which can easily reach 16~ by weight, 2-nitro-5-~3~593 [2'-chloro-5'-(trifluoromethyl)phenoxy]benzoic acid and 4-nitro-5-[2'-chloro-4'-(trifluoromethyl)phenoxy]benzoic acid, it being easily possible for these two acids to be present in quantities of up to 3~ by weight, as well as a series of other acids, in amounts which can also range up to 3~, this amount frequently being lower, however, for example less than 0.5~, such as for example the following acids
The compounds of general formula (I) can then be alkylated in a known manner, for example by reaction with a diazoalkane containing ~rom 1 to 4 carbon atoms, so as to give the corresponding products which are substituted on the nitrogen atom of the sulphonamide group by an alkyl group containing from 1 to 4 carbon atoms; the hydrogen atom of this same nitrogen atom can also be replaced by an alkali metal atom such as, e.g. sodium, for example by reaction with lS basic alkali metal reagents.
This known process for condensing the compounds of general formulae (II) and (III) has various disadvantages, in particular poor yields. It is believed that, in general, it is the presence of an acid acceptor which lowers the yield because it favours the diacylation reaction. Moreover, the use of an acid acceptor makes the isolation and the purification of the final products more difficult and more costly.
An objective of the invention is to remedy these disadvantages of the known processes.
The process of the present invention enables the lZ3(~S93 of general formula (I) to be prepared from reactants of the general formula:
C B COOH
D ~ O ~ A (IV) (wherein the various symbols are as hereinbefore defined) of technical or industrial grades.
In practice, the latter problem is all the more important because this type of acid of general formula (IV) is liable to contain a considerable number of impurities as a result of the number and the nature of the reactions used in its manufacture. Thus, by way of a non-limiting example, it may be indicated that acifluorfen of the formula:
Cl CooH
CF3~ 0 {~ N02 (V) i.e. 5-[2'-chloro-4'-(trifluoromethyl)phenoxy]-2-nitrobenzoic acid, can be prepared by coupling an alkali metal meta-cresolate with a 3,4-dihalotrifluoromethylbenzene, followed by oxidation of the CH3 group to a carboxylic acid group and then nitration. During such a sequence of reactions, the number of isomers and other undesirable compounds progressively increases and a large number of acids is often detected in acifluorfen of ordinary quality, and especially the following acids:
2-ni~ro-3-12'-chloro-4'-(trifluoromethyl)phenoxy]benzoic acid in an amount which can easily reach 16~ by weight, 2-nitro-5-~3~593 [2'-chloro-5'-(trifluoromethyl)phenoxy]benzoic acid and 4-nitro-5-[2'-chloro-4'-(trifluoromethyl)phenoxy]benzoic acid, it being easily possible for these two acids to be present in quantities of up to 3~ by weight, as well as a series of other acids, in amounts which can also range up to 3~, this amount frequently being lower, however, for example less than 0.5~, such as for example the following acids
3-12'-chloro-S'-(trifluoromethyl)phenoxy]benzoic acid, 3-[2'-chloro-4'-(trifluoromethyl)phenoxy]benzoic acid and 2,4-dinitro-5-[2'-chloro-4'-(trifluoromethyl)phenoxy]benzoic acid, as well as
4-[2'-chloro-4'-(trifluromethyl)phenoxy]nitrobenzene and 2-nitro-5-[2'-chloro-4'-(trifluoromethyl)phenoxy]toluene.
The process of the invention permits the preparation of products of general formula (I) having high purity from starting materials of low purity which comprise impurities in addition to the compound of general formula (IV).
The present invention provides a process for the preparation of a compound of general formula (I) wherein the various symbols are as hereinbefore defined which comprises reacting an acid halide of general formula (II) with a sulphonamide of general formula (III), wherein, in both, the various symbols are as defined and X is preferably a chlorine atom in the liquid phase, in the presence of a halogenating agent, preferably a phosphorated chlorinating (or chloride-forming) agent and at a temperature which is such 123(~593 that the hydrogen halide which is formed during the reaction is progressively removed from the reaction medium in a gaseous form as it is formed.
According to a preferred embodiment of the process according to the invention, the acid halide of general formula (II) which is used is one which has been prepared by halogenating an acid of general formula (IV) by means of a known halogenating agent.
According to an embodiment of the invention, there is employed [for reacting with the sulphonamide of general formula (III)] an acid halide of general formula (II) of technical or industrial quality, that is to say containing up to 20% by weight and possibly up to, but preferably less than, 30% by weight of impurities. Such impurities are, for example, the impurities derived from the reaction of a halogenating agent with an acid of general formula (IV) of technical or industrial quality, containing up to 20% by weight and possibly up to, but preferably less than, 30~ by weight of impurities. These impurities in the acid halide of general formula (II) are, therefore, chiefly products whose formula is similar to that of the compound of general formula (II~, but differing particularly in the number and the position of the substituents. These impurities are therefore essentially compounds containing the group of the formula:
~ ~ (A) which carries one or more substituents, or specifically the lZ305~3 group of the formula:
Cl ~0~ (O
¢F3 which carries one or more additional substituents.
The process of the invention comprising the reaction of the compounds of general formulae (II) and (III) is preferably carried out in the absence of an acid acceptor;
furthermore, the presence of a solvent is optional.
A sub-group of compounds of general formula (I) for the preparation of which the process according to the invention is especially suitable and advantageous, consists of the compounds of general formula ~I) in which A is the NO2 group or a hydrogen or chlorine atom; B is a halogen atom and more particularly a chlorine atom; C and E are hydrogen atoms; D is the CF3 group; R is an alkyl group preferably having 1 to 4 carbon atoms, particularly CH3; and W is -CH=, and more especially 5-[2'choro-4'-(trifluoromethyl)phenoxy]-2-nitro-~-methanesulphonylbenzamide..
The preferred reactants of general formulae (II) and ~III) are naturally chosen so that the symbols which appear in their formula have a meaning which is similar to that just given for the products of general formula (I).
Among the halogenating agents which may be employed there may be mentioned: P(O)C13, PC13, P(O)Br3 or PBr3;
P(O)C13 is preferred.
The molar ratio of (II) to (III) is generally lZ3l:~S93 between 0.8 and 1.2, preferably btween 0.9 and 1.1; more especially, these reactants are in stoichiometric proportions.
The molar ratio of the halogenating agent relative to the halide of general formula (II) generally varies between 0.1 and 5. The halogenating agent can be present in large excess, e.g. the molar ratio relative to the acid halide (II) may exceed 5 and may be as much as 20; it can then serve as a solvent for the reaction. In that case, it can be recovered by distillation from the reaction mixture for the purpose of subsequent recycling.
The reactants can also be dissolved in an inert solvent which has a boiling point above the reaction temperature, for example a liquid aliphatic or aromatic, chlorinated or unchlorinated hydrocarbon such as benzene, toluene, xylenes, mixed xylenes, cumene, 1,2-dichloro-ethane, chlorobenzene or, for example, a nitrile such as acetonitrile; a mixture of several solvents can also be employed. The use of an inert solvent has the practical advantage of permitting better heat transfer in a process on an industrial scale; it also makes it possible to avoid local overheating of the reaction medium.
As hereinbefore indicated, the temperature at which the process according to the invention is carried out is such that the hydrogen halide formed during the reaction is removed from the reaction medium in a gaseous form concurrently with its production. This temperature, ~Z3~593 moreover, lies below the decomposition temperature of the compounds of general formulae (II), (III) and (I) involved in the process; in the case where a solvent is employed, the reaction temperature is advantageously less than or equal to the boiling point of this solvent which can, moreover, consist of an excess of the halogenating agent as has already been indicated. The temperature is therefore generally between 70 and 180C. In the absence of a solvent, the preferred temperature is between 80 and 120C: in the presence of a solvent (particularly in the case of cumene which boils at 153C), the temperature is advantageously between 80 and 150C.
At the end of the reaction the product of general formula (I) can be isolated by methods known per se. By the term "methods known per se" as used in the present specification is meant methods heretofore used or described in the chemical literature.
The process according to the invention is distinguished by the simplicity of the method by which the final product is recovered because the latter is insoluble in the halogenating agent with the result that this recovery is usually confined to a filtration. This filtration can also be facilitated by the addition of a non-solvent.
The acid halide of general formula (II) can be prepared by any method known ~ se from the acid of general formula (IV). In general, the procedure is a reaction of an acid of general formula (IV) with a halogenating agent such 123~S93 as those mentioned hereinbefore. ~he reaction can, if appropriate, be carried out in situ, and catalysts, e.g.
dimethylformamide, can also be employed.
The acid halide of general formu~a (II) can be:
- separated and purified, or - separated in the crude state without purification, or - prepared _ situ in the reaction solvent, without being separated, before being placed in the presence of the sulphonamide of general formula (III).
The following non-limitative examples illustrate the present invention.
Example 1:
Cl COCl CF - ~ - ~ ~ ~ NO2 + CH352NH2 9O~C
Cl CoNHso2cH3 3 ~ ~ ~ ~ NO2 + H Cl (VI)
The process of the invention permits the preparation of products of general formula (I) having high purity from starting materials of low purity which comprise impurities in addition to the compound of general formula (IV).
The present invention provides a process for the preparation of a compound of general formula (I) wherein the various symbols are as hereinbefore defined which comprises reacting an acid halide of general formula (II) with a sulphonamide of general formula (III), wherein, in both, the various symbols are as defined and X is preferably a chlorine atom in the liquid phase, in the presence of a halogenating agent, preferably a phosphorated chlorinating (or chloride-forming) agent and at a temperature which is such 123(~593 that the hydrogen halide which is formed during the reaction is progressively removed from the reaction medium in a gaseous form as it is formed.
According to a preferred embodiment of the process according to the invention, the acid halide of general formula (II) which is used is one which has been prepared by halogenating an acid of general formula (IV) by means of a known halogenating agent.
According to an embodiment of the invention, there is employed [for reacting with the sulphonamide of general formula (III)] an acid halide of general formula (II) of technical or industrial quality, that is to say containing up to 20% by weight and possibly up to, but preferably less than, 30% by weight of impurities. Such impurities are, for example, the impurities derived from the reaction of a halogenating agent with an acid of general formula (IV) of technical or industrial quality, containing up to 20% by weight and possibly up to, but preferably less than, 30~ by weight of impurities. These impurities in the acid halide of general formula (II) are, therefore, chiefly products whose formula is similar to that of the compound of general formula (II~, but differing particularly in the number and the position of the substituents. These impurities are therefore essentially compounds containing the group of the formula:
~ ~ (A) which carries one or more substituents, or specifically the lZ305~3 group of the formula:
Cl ~0~ (O
¢F3 which carries one or more additional substituents.
The process of the invention comprising the reaction of the compounds of general formulae (II) and (III) is preferably carried out in the absence of an acid acceptor;
furthermore, the presence of a solvent is optional.
A sub-group of compounds of general formula (I) for the preparation of which the process according to the invention is especially suitable and advantageous, consists of the compounds of general formula ~I) in which A is the NO2 group or a hydrogen or chlorine atom; B is a halogen atom and more particularly a chlorine atom; C and E are hydrogen atoms; D is the CF3 group; R is an alkyl group preferably having 1 to 4 carbon atoms, particularly CH3; and W is -CH=, and more especially 5-[2'choro-4'-(trifluoromethyl)phenoxy]-2-nitro-~-methanesulphonylbenzamide..
The preferred reactants of general formulae (II) and ~III) are naturally chosen so that the symbols which appear in their formula have a meaning which is similar to that just given for the products of general formula (I).
Among the halogenating agents which may be employed there may be mentioned: P(O)C13, PC13, P(O)Br3 or PBr3;
P(O)C13 is preferred.
The molar ratio of (II) to (III) is generally lZ3l:~S93 between 0.8 and 1.2, preferably btween 0.9 and 1.1; more especially, these reactants are in stoichiometric proportions.
The molar ratio of the halogenating agent relative to the halide of general formula (II) generally varies between 0.1 and 5. The halogenating agent can be present in large excess, e.g. the molar ratio relative to the acid halide (II) may exceed 5 and may be as much as 20; it can then serve as a solvent for the reaction. In that case, it can be recovered by distillation from the reaction mixture for the purpose of subsequent recycling.
The reactants can also be dissolved in an inert solvent which has a boiling point above the reaction temperature, for example a liquid aliphatic or aromatic, chlorinated or unchlorinated hydrocarbon such as benzene, toluene, xylenes, mixed xylenes, cumene, 1,2-dichloro-ethane, chlorobenzene or, for example, a nitrile such as acetonitrile; a mixture of several solvents can also be employed. The use of an inert solvent has the practical advantage of permitting better heat transfer in a process on an industrial scale; it also makes it possible to avoid local overheating of the reaction medium.
As hereinbefore indicated, the temperature at which the process according to the invention is carried out is such that the hydrogen halide formed during the reaction is removed from the reaction medium in a gaseous form concurrently with its production. This temperature, ~Z3~593 moreover, lies below the decomposition temperature of the compounds of general formulae (II), (III) and (I) involved in the process; in the case where a solvent is employed, the reaction temperature is advantageously less than or equal to the boiling point of this solvent which can, moreover, consist of an excess of the halogenating agent as has already been indicated. The temperature is therefore generally between 70 and 180C. In the absence of a solvent, the preferred temperature is between 80 and 120C: in the presence of a solvent (particularly in the case of cumene which boils at 153C), the temperature is advantageously between 80 and 150C.
At the end of the reaction the product of general formula (I) can be isolated by methods known per se. By the term "methods known per se" as used in the present specification is meant methods heretofore used or described in the chemical literature.
The process according to the invention is distinguished by the simplicity of the method by which the final product is recovered because the latter is insoluble in the halogenating agent with the result that this recovery is usually confined to a filtration. This filtration can also be facilitated by the addition of a non-solvent.
The acid halide of general formula (II) can be prepared by any method known ~ se from the acid of general formula (IV). In general, the procedure is a reaction of an acid of general formula (IV) with a halogenating agent such 123~S93 as those mentioned hereinbefore. ~he reaction can, if appropriate, be carried out in situ, and catalysts, e.g.
dimethylformamide, can also be employed.
The acid halide of general formu~a (II) can be:
- separated and purified, or - separated in the crude state without purification, or - prepared _ situ in the reaction solvent, without being separated, before being placed in the presence of the sulphonamide of general formula (III).
The following non-limitative examples illustrate the present invention.
Example 1:
Cl COCl CF - ~ - ~ ~ ~ NO2 + CH352NH2 9O~C
Cl CoNHso2cH3 3 ~ ~ ~ ~ NO2 + H Cl (VI)
5-[2'-Chloro-4'-(trifluoromethyl)phenoxy]-2-nitrobenzoic acid 15 chloride (16.79; 0.044 mol) and methanesulphonamide (4.2 9;
0.044 mol) are suspended in P(0)C13 i.e. phosphoryl chloride (20 cc). The reaction mixture is heated for 1 hour at 90C
with stirring. After adding toluene (50 cc) the precipitate formed is filtered off and then washed with toluene.
A white solid consisting of 5-l2'-choro-4'-(tri-fluoromethyl)phenoxy]-2-nitro-N-methanesulphonyl benzamide (16.49; 0.034 mol; yield 85%), of the formula (VI), m.p.
203C is thus obtained. The structure of this product is confirmed by infrared and by nuclear magnetic resonance (NMR).
123~593 Example 2:
5-C2'-Chloro-4'-~trifluoromethyl)phenoxy~-2-nitro-benzo;c ac;d chlor;de (19 9; 0.05 mol) and methanesul-phonamide (4.759; 0.05 mol) are suspended in a mixture of P(O)Cl3 (14 cc) and toluene (35 cc). The reaction mixture is heated for 3 hours at 100C ~ith stirring.
After adding toluene (50 cc) the precipitate formed is filtered off and then uashed with toluene.
A uhite solid consisting of 5-~2'-chloro-4'-(tri-fluoromethyl)phenoxy~-2-nitro-N-methanesulphonyl benzamide ~14.7 9; 0.034 mol; yield 67X), of the formula (VI), m.p.
198C, is thus obtained. The structure of this product is confirmed by infrared and by NMR.
Example 3:
5-t2'-Chloro-4'-(trifluoromethyl)phenoxy]-2-nitro-benzoic acid chloride (7.6 9; 0.02 mol) and methanesul-phonamide (1.9 9; 0.02 mol) are dissolved ;n a mi~ture of P(O)Cl3 (2 cc) and acetonitrile (20 cc). The reaction m;xture ;s boiled under reflux for 2 hours 30 minutes ~;th st;rr;ng, and ;s then concentrated to dryness. The crude mater;al obta;ned ;s rccrystallised from a mixture of toluene and ethyl acetate (95/5).
A uh;te sol;d consist;ng of 5-C2'-chloro-4'-(tri-fluoromethyl)phenoxy~-2-nitro-N-methanesulphonyl benz-amide (7.6 9; 0.0173 mol; yield 87X), of the formula (VI),m.p. 215C, is thus obtained. The structure of this product ;s confirmed by infrared and by NMR.
;lZ3~)S93 ExampLe 4:
5-C2'-Chloro-4'-(trifluoromethyl)phenoxy~-2-nitro-benzoic acid t36.1 9; 0.1 mol) is suspended in a mixture of toluene (60 cc) and dimethylformamide (DMF) (1 cc). The reaction mixture is heated to 55C with stirring. A
solution of thionyl chloride (11.9 g; 0.1 mol) in toluene (15 cc) is then added. When gas ceases to be evolved, the reaction mixture is heated to 90C, before adding methanesulphonamide (9.5 9; 0.1 moL). P(O)Cl3 (27 cc) is then run in over a period of 10 minutes, and the reac-tion mixture is then heated at 105C for 2 hours. Af-ter cooling, the precipitate formed is filtered off and then washed ~ith toluene.
A white solid consisting of 5-C2'-chloro-4'-(tri-fluoromethyl)phenoxy]-2-nitro-N-methanesulphonyl benzamide (23.8 9; 0.054 moL; yield 54%~, of the formula (VI), m.p.
200C is thus obtained. The structure of this product is confirmed by infrared and by NMR.
Example 5:
This exampLe illustrates the preparation of benz-amide of the formula (VI) starting from impure phenoxy-benzoic acid. The purity of the starting phenoxybenzoic acid was determined by high performance liquid phase chromatography (abbreviated to HPLC); this HPLC was per-formed under the following conditions:
- column 20 cm in Length, 4 mm in diameter, - packing of silica on which a stationary phase contain-123~593 1 ~, ing an amine group has been grafted (the chromatographytakes pl-ace by a partit;on bet~een the stat;onary phase and the eluant) eluant: a mixture of 2,2,4-trimethylpentane, 2-propanol and acet;c acid in constant volume proportions of 42/4û/18 respect;vely - flow rate 2 cc/min.
The purity of the react;on product ~as also deter-mined by HPLC under similar conditions except for varying 1û the proport;ons of the components of the eluant mixture between the outset and the end of the chromatography, from a ratio of 35/50/5 to 56/20/24 (elution gradient).
The accuracy of these chromatographic methods ~as checked by the use of standards corresponding to the sam-ples of each of the ;mpur;t;es mentioned, taken separateLy.
The percentages sho~n belo~ are percentages by~eight. The "technica ~grade" acid employed containS:
- 80.9% of 5-C2'-chLoro-4'-(trifluoromethyl)phenoxy]-2-nitrobenzoic acid of the formula (V), - 8.2X of 3-C2'-chloro-4'-(trifluoromethyl)phenoxy]-2-nitrobenzoic acid, - ~.3% of 5-C2'-chloro-4'-(trifluoromethyl)phenoxy]-4-nitrobenzoic acid, - less than 1X of 5-C2'-chloro-5'-(trifluoromethyl)phenoxy~-2-nitrobenzoic acid, and - less than 1Z of 3-C2'-chloro-4'-(trifluoromethyl)phenoxy~
benzoic acid.
.
Techn;cal-grade ac;d (38 9) of the composition specified above is suspended in a mixture of 1,2-dichloro-ethane (1ûO cc), thionyl chloride (10.3 cc; 0.109 mol) and dimethyl~ormamide (1 cc). The reaction mixture is heated grad-ually with stirring to the boil under reflux. Refluxing is con-tinued for 1 hour after gas evolution has ended, and the material is then concentrated to dr~ness. The residue (4û 9) is dissolved in toluene (75 cc)~ after ~hich methane-sulphonamide (10 9; 0.105 mol) and R(O)Cl3 (25 cc) are added. The reaction mixture is then heated to the boil under reflux for 3 hours ~ith stirring. After cooling, the precipitate formed is filtered off and then ~ashed w;th toluene.
A ~hite solid consisting of 5-~2'-chloro-4'-(tri-fluoromethyl)phenoxy~-2-nitro-N-methanesulphonyl benzamide (28 9) of the formula (VI), m.p. 200C, is thus ob-tained. The structure of this product is confirmed by infrared and by NMR. Its purity, as determined by HPLC, is 90%.
gL23~593 - 15a -SfJPI'l,E~ 'rARY DISCLOSU~E
~ he ~ollowing Example 111UGtrate3 the proce3s Or the pre~ent in~ention in which, ln general formulae ~I~ and ~II), t3 hydrog~n, B is chlorine, C 13 hydrosen, D is trl~l~oromethyl, 3 ~ hydrogen, W ~g a -C~)= grou~, X in general formula ~II) 19 chlorine, and R3 ln ~ormulae tI) and ~ 3 ~ethyl. The halogenating agent i3 ph~8phO
chlorlde.
Exam~le 6 5-~2'-Chlbro-4'-(tri~luoromethyl~phenoxy]-benzo1c acid chlor~de ~8,4gS 0.025 mole) o~ the formul~:
Cl CCCl ~ ~/
, ~ethane~ulphonamlde ~2. 4g; 0 . 02S mole) and phosphar~ll chlor~de ~12c~ were a~ded to a 5ac~ reactor wi~h he~tlng and stir~lng. T~ reactlon mlxtu~e was heated for 1 hour at 90C
and then cooledS toluene ~Occ) and then petroleum ether ~3~cc) wera ad2~d. ~ho mlxtu~e thu~ oo~alned was ~iltered, washed with p2troleum ether a~d dried to o~taln 5-~'-chloro-4l-~trlfluoromethyl)phenoxy~ methar~esulphon~l benzamlde (~.7g: yield 8g~: melting point about 163C) o. the ormula:
Cl ~ Co~ o2-c.i3 C~3 ~ ~ ~
. ~
0.044 mol) are suspended in P(0)C13 i.e. phosphoryl chloride (20 cc). The reaction mixture is heated for 1 hour at 90C
with stirring. After adding toluene (50 cc) the precipitate formed is filtered off and then washed with toluene.
A white solid consisting of 5-l2'-choro-4'-(tri-fluoromethyl)phenoxy]-2-nitro-N-methanesulphonyl benzamide (16.49; 0.034 mol; yield 85%), of the formula (VI), m.p.
203C is thus obtained. The structure of this product is confirmed by infrared and by nuclear magnetic resonance (NMR).
123~593 Example 2:
5-C2'-Chloro-4'-~trifluoromethyl)phenoxy~-2-nitro-benzo;c ac;d chlor;de (19 9; 0.05 mol) and methanesul-phonamide (4.759; 0.05 mol) are suspended in a mixture of P(O)Cl3 (14 cc) and toluene (35 cc). The reaction mixture is heated for 3 hours at 100C ~ith stirring.
After adding toluene (50 cc) the precipitate formed is filtered off and then uashed with toluene.
A uhite solid consisting of 5-~2'-chloro-4'-(tri-fluoromethyl)phenoxy~-2-nitro-N-methanesulphonyl benzamide ~14.7 9; 0.034 mol; yield 67X), of the formula (VI), m.p.
198C, is thus obtained. The structure of this product is confirmed by infrared and by NMR.
Example 3:
5-t2'-Chloro-4'-(trifluoromethyl)phenoxy]-2-nitro-benzoic acid chloride (7.6 9; 0.02 mol) and methanesul-phonamide (1.9 9; 0.02 mol) are dissolved ;n a mi~ture of P(O)Cl3 (2 cc) and acetonitrile (20 cc). The reaction m;xture ;s boiled under reflux for 2 hours 30 minutes ~;th st;rr;ng, and ;s then concentrated to dryness. The crude mater;al obta;ned ;s rccrystallised from a mixture of toluene and ethyl acetate (95/5).
A uh;te sol;d consist;ng of 5-C2'-chloro-4'-(tri-fluoromethyl)phenoxy~-2-nitro-N-methanesulphonyl benz-amide (7.6 9; 0.0173 mol; yield 87X), of the formula (VI),m.p. 215C, is thus obtained. The structure of this product ;s confirmed by infrared and by NMR.
;lZ3~)S93 ExampLe 4:
5-C2'-Chloro-4'-(trifluoromethyl)phenoxy~-2-nitro-benzoic acid t36.1 9; 0.1 mol) is suspended in a mixture of toluene (60 cc) and dimethylformamide (DMF) (1 cc). The reaction mixture is heated to 55C with stirring. A
solution of thionyl chloride (11.9 g; 0.1 mol) in toluene (15 cc) is then added. When gas ceases to be evolved, the reaction mixture is heated to 90C, before adding methanesulphonamide (9.5 9; 0.1 moL). P(O)Cl3 (27 cc) is then run in over a period of 10 minutes, and the reac-tion mixture is then heated at 105C for 2 hours. Af-ter cooling, the precipitate formed is filtered off and then washed ~ith toluene.
A white solid consisting of 5-C2'-chloro-4'-(tri-fluoromethyl)phenoxy]-2-nitro-N-methanesulphonyl benzamide (23.8 9; 0.054 moL; yield 54%~, of the formula (VI), m.p.
200C is thus obtained. The structure of this product is confirmed by infrared and by NMR.
Example 5:
This exampLe illustrates the preparation of benz-amide of the formula (VI) starting from impure phenoxy-benzoic acid. The purity of the starting phenoxybenzoic acid was determined by high performance liquid phase chromatography (abbreviated to HPLC); this HPLC was per-formed under the following conditions:
- column 20 cm in Length, 4 mm in diameter, - packing of silica on which a stationary phase contain-123~593 1 ~, ing an amine group has been grafted (the chromatographytakes pl-ace by a partit;on bet~een the stat;onary phase and the eluant) eluant: a mixture of 2,2,4-trimethylpentane, 2-propanol and acet;c acid in constant volume proportions of 42/4û/18 respect;vely - flow rate 2 cc/min.
The purity of the react;on product ~as also deter-mined by HPLC under similar conditions except for varying 1û the proport;ons of the components of the eluant mixture between the outset and the end of the chromatography, from a ratio of 35/50/5 to 56/20/24 (elution gradient).
The accuracy of these chromatographic methods ~as checked by the use of standards corresponding to the sam-ples of each of the ;mpur;t;es mentioned, taken separateLy.
The percentages sho~n belo~ are percentages by~eight. The "technica ~grade" acid employed containS:
- 80.9% of 5-C2'-chLoro-4'-(trifluoromethyl)phenoxy]-2-nitrobenzoic acid of the formula (V), - 8.2X of 3-C2'-chloro-4'-(trifluoromethyl)phenoxy]-2-nitrobenzoic acid, - ~.3% of 5-C2'-chloro-4'-(trifluoromethyl)phenoxy]-4-nitrobenzoic acid, - less than 1X of 5-C2'-chloro-5'-(trifluoromethyl)phenoxy~-2-nitrobenzoic acid, and - less than 1Z of 3-C2'-chloro-4'-(trifluoromethyl)phenoxy~
benzoic acid.
.
Techn;cal-grade ac;d (38 9) of the composition specified above is suspended in a mixture of 1,2-dichloro-ethane (1ûO cc), thionyl chloride (10.3 cc; 0.109 mol) and dimethyl~ormamide (1 cc). The reaction mixture is heated grad-ually with stirring to the boil under reflux. Refluxing is con-tinued for 1 hour after gas evolution has ended, and the material is then concentrated to dr~ness. The residue (4û 9) is dissolved in toluene (75 cc)~ after ~hich methane-sulphonamide (10 9; 0.105 mol) and R(O)Cl3 (25 cc) are added. The reaction mixture is then heated to the boil under reflux for 3 hours ~ith stirring. After cooling, the precipitate formed is filtered off and then ~ashed w;th toluene.
A ~hite solid consisting of 5-~2'-chloro-4'-(tri-fluoromethyl)phenoxy~-2-nitro-N-methanesulphonyl benzamide (28 9) of the formula (VI), m.p. 200C, is thus ob-tained. The structure of this product is confirmed by infrared and by NMR. Its purity, as determined by HPLC, is 90%.
gL23~593 - 15a -SfJPI'l,E~ 'rARY DISCLOSU~E
~ he ~ollowing Example 111UGtrate3 the proce3s Or the pre~ent in~ention in which, ln general formulae ~I~ and ~II), t3 hydrog~n, B is chlorine, C 13 hydrosen, D is trl~l~oromethyl, 3 ~ hydrogen, W ~g a -C~)= grou~, X in general formula ~II) 19 chlorine, and R3 ln ~ormulae tI) and ~ 3 ~ethyl. The halogenating agent i3 ph~8phO
chlorlde.
Exam~le 6 5-~2'-Chlbro-4'-(tri~luoromethyl~phenoxy]-benzo1c acid chlor~de ~8,4gS 0.025 mole) o~ the formul~:
Cl CCCl ~ ~/
, ~ethane~ulphonamlde ~2. 4g; 0 . 02S mole) and phosphar~ll chlor~de ~12c~ were a~ded to a 5ac~ reactor wi~h he~tlng and stir~lng. T~ reactlon mlxtu~e was heated for 1 hour at 90C
and then cooledS toluene ~Occ) and then petroleum ether ~3~cc) wera ad2~d. ~ho mlxtu~e thu~ oo~alned was ~iltered, washed with p2troleum ether a~d dried to o~taln 5-~'-chloro-4l-~trlfluoromethyl)phenoxy~ methar~esulphon~l benzamlde (~.7g: yield 8g~: melting point about 163C) o. the ormula:
Cl ~ Co~ o2-c.i3 C~3 ~ ~ ~
. ~
Claims (26)
1. A process for the preparation of a compound of the general formula:
(I) in which:
A is hydrogen; fluorine; chlorine; bromine; iodine; a nitro group; -N=NCF3; H2PO3 and its alkyl esters wherein the alkyl group contains from 1 to 4 carbon atoms; NH2; NHOH; N?;
a carboxy group or one of its functional derivatives; a monoalkylamino or dialkylamino group; an NH-CO-R1 group in which R1 is an alkyl or alkoxy or monoalkylamino or dialkylamino group; an alkyl group; trialkylammonium; NHSO2R2 in which R2 is an alkyl group or a phenyl group; NHCONHSO2R2, in which R2 is as hereinbefore defined; alkylthio;
alkylsulphinyl; alkylsulphonyl; dialkylsulphonium;
cyanosulphonyl; hydroxy; alkanoyloxy; alkoxy, alkoxy substituted by an alkoxycarbonyl group; SH; nitroso; -SCN;
azide; CF3; or acyl;
B is a hydrogen, fluorine, chlorine, bromine or iodine atom, or an alkyl, alkoxy, alkylsulphinyl, alkylsulphonyl, CF3, NO2, CN, NH2, NHCOR wherein R1 is as hereinbefore defined or CONH2 group;
C is a hydrogen or halogen atom or an alkyl or dialkylamino group;
D is a fluorine, chlorine, bromine or iodine atom or a CF3, alkylthio, alkylsulphinyl, alkylsulphonyl, haloalkyl, sulphamoyl, formyl, alkylcarbonyl, CN or dimethylamino group, E is hydrogen or a haloalkyl, alkoxy, alkylsulphinyl, alkylsulphonyl, CN, CF3, NH2, CONH2, or NH-CO-R1 group, wherein R1 is as hereinbefore defined;
W is a trivalent nitrogen atom or a -C(G)= group in which G has one of the meanings given for B;
R3 is a phenyl, pyridyl or thienyl group optionally substituted by one or more halogen atoms, alkyl groups or nitro groups; or an alkenyl or alkynyl radical having 2 to 4 carbon atoms or an alkyl radical containing 1 to 4 carbon atoms optionally substituted by one or more fluorine, chlorine, bromine or iodine atoms, or by one or more of the following substituents: carboxy, alkoxycarbonyl containing from 2 to 5 carbon atoms, alkylcarbonyl containing from 2 to 5 carbon atoms, monoalkylcarbamoyl or dialkylcarbamoyl in which the alkyl groups contain from 1 to 4 carbon atoms, alkylthio, alkylsulphinyl, alkylsulphonyl, each having from 1 to 4 carbon atoms, alkylcarbonyloxy containing from 2 to 5 carbon atoms, alkylcarbonylamino containing from 2 to 5 carbon atoms, or cyano, which comprises reacting an acid halide of the general formula:
(II) with a sulphonamide of the general formula:
R3-SO-2-NH2 (III) in which A, B, C, D, E and W are as hereinbefore defined, and X is chlorine, bromine or iodine, in the liquid phase in the presence of a halogenating agent and at a temperature such that the hydrogen halide formed during the reaction is removed progressively from the reaction medium in a gaseous form as it is formed.
(I) in which:
A is hydrogen; fluorine; chlorine; bromine; iodine; a nitro group; -N=NCF3; H2PO3 and its alkyl esters wherein the alkyl group contains from 1 to 4 carbon atoms; NH2; NHOH; N?;
a carboxy group or one of its functional derivatives; a monoalkylamino or dialkylamino group; an NH-CO-R1 group in which R1 is an alkyl or alkoxy or monoalkylamino or dialkylamino group; an alkyl group; trialkylammonium; NHSO2R2 in which R2 is an alkyl group or a phenyl group; NHCONHSO2R2, in which R2 is as hereinbefore defined; alkylthio;
alkylsulphinyl; alkylsulphonyl; dialkylsulphonium;
cyanosulphonyl; hydroxy; alkanoyloxy; alkoxy, alkoxy substituted by an alkoxycarbonyl group; SH; nitroso; -SCN;
azide; CF3; or acyl;
B is a hydrogen, fluorine, chlorine, bromine or iodine atom, or an alkyl, alkoxy, alkylsulphinyl, alkylsulphonyl, CF3, NO2, CN, NH2, NHCOR wherein R1 is as hereinbefore defined or CONH2 group;
C is a hydrogen or halogen atom or an alkyl or dialkylamino group;
D is a fluorine, chlorine, bromine or iodine atom or a CF3, alkylthio, alkylsulphinyl, alkylsulphonyl, haloalkyl, sulphamoyl, formyl, alkylcarbonyl, CN or dimethylamino group, E is hydrogen or a haloalkyl, alkoxy, alkylsulphinyl, alkylsulphonyl, CN, CF3, NH2, CONH2, or NH-CO-R1 group, wherein R1 is as hereinbefore defined;
W is a trivalent nitrogen atom or a -C(G)= group in which G has one of the meanings given for B;
R3 is a phenyl, pyridyl or thienyl group optionally substituted by one or more halogen atoms, alkyl groups or nitro groups; or an alkenyl or alkynyl radical having 2 to 4 carbon atoms or an alkyl radical containing 1 to 4 carbon atoms optionally substituted by one or more fluorine, chlorine, bromine or iodine atoms, or by one or more of the following substituents: carboxy, alkoxycarbonyl containing from 2 to 5 carbon atoms, alkylcarbonyl containing from 2 to 5 carbon atoms, monoalkylcarbamoyl or dialkylcarbamoyl in which the alkyl groups contain from 1 to 4 carbon atoms, alkylthio, alkylsulphinyl, alkylsulphonyl, each having from 1 to 4 carbon atoms, alkylcarbonyloxy containing from 2 to 5 carbon atoms, alkylcarbonylamino containing from 2 to 5 carbon atoms, or cyano, which comprises reacting an acid halide of the general formula:
(II) with a sulphonamide of the general formula:
R3-SO-2-NH2 (III) in which A, B, C, D, E and W are as hereinbefore defined, and X is chlorine, bromine or iodine, in the liquid phase in the presence of a halogenating agent and at a temperature such that the hydrogen halide formed during the reaction is removed progressively from the reaction medium in a gaseous form as it is formed.
2. A process according to claim 1 wherein R3 represents CF3.
3. A process according to claim 1 or 2 in which A is NO2 or a hydrogen or chlorine atom B is a halogen atom, C and are hydrogen atoms, D is a trifluoromethyl group, and W is -CH=.
4. A process according to claim 1 in which is a chlorine atom and R3 is an alkyl group.
5. A process according to claim 1 in which R3 is an alkyl group containing from 1 to 4 carbon atoms.
6. A process according to claim 1 in which R3 is CH3.
7. A process according to claim 1, wherein X in the compound of general formula (II) is a chlorine atom.
8. A process according to claim 1, in which the starting material comprises, in addition to the acid halide of general formula (II), up to 30% by weight of impurities.
9. A process according to claim 1 in which the starting material comprises, in addition to the acid halide of general formula (II), up to 20% by weight of impurities.
10. A process according to claim 1, wherein the starting material comprises, in addition to the acid halide of general formula (II), impurities which are mainly compounds containing a group of the formula:
which carries one or more substituents.
which carries one or more substituents.
11. A process according to claim 10, in which the starting material comprises, in addition to the acid halide of general formula (II), impurities which are mainly compounds containing a group of the formula:
which carries one or more substituents.
which carries one or more substituents.
12. A process according to claim 1, in which the halogenating agent is P(0)C13, PC13, P(0)Br3, or PBr3.
13. A process according to claim 1, in which the halogenating agent is P(0)C13.
14. A process according to claim 1, which is carried out in the absence of an acid acceptor.
15. A process according to claim 1, in which the molar ratio of the sulphonamide of general formula (III) depicted in claim 1 relative to the acid halide of general formula (II) depicted in claim 1 is between 0.8 and 1.2.
16. A process according to claim 1, in which the molar ratio of the sulphonamide of general formula (III) depicted in claim 1 relative to the acid halide of general formula (II) depicted in claim 1 is between 0.9 and 1.1.
17. A process according to claim 1 in which the molar ratio of the halogenating agent relative to the acid halide of general formula (II) depicted in claim 1 is between 0.1 and 20.
18. A process according to claim 1 in which the molar ratio of the halogenating agent relative to the acid halide of general formula (II) depicted in claim 1 is between 0.1 and 5.
19. A process according to claim 1, which is carried out in the presence of an inert solvent.
20. A process according to claim 19, in which the solvent is a liquid aliphatic or aromatic, chlorinated or non-chlorinated hydrocarbon, or a nitrile.
21. A process according to claim 1, in which the reaction temperature is below the decomposition temperature of the compounds of general formulae (III), (II) and (I) and, if appropriate, less than or equal to the boiling point of the solvent used.
22. A process according to claim 21, in which the reaction temperature is between 70 and 180°C.
23. A process according to claim 21 in which the reaction is carried out in the absence of a solvent and the reaction temperature is between 80 and 120°C.
24. A process according to claim 21 in which the reaction is carried out in the presence of a solvent and the reaction temperature is between 80 and 150°C.
CLAIMS SUPPORTED BY THE SUPPLEMENTARY DISCLOSURE
CLAIMS SUPPORTED BY THE SUPPLEMENTARY DISCLOSURE
25. A process according to Claim 1 in which, in general formulae (I) and (II), A is hydrogen, B is chlorine, C is hydrogen, D 13 trifluoromethyl, E is hydrogen, W is a -C(H)-group, X in general formula (II) is chlorine, and R3 in formulae (I) and (III) is methyl.
26. A process according to Claim 25 in which the halogenating agent is phosphoryl chloride.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR8308338 | 1983-05-17 | ||
| FR8308338A FR2546165B1 (en) | 1983-05-17 | 1983-05-17 | PROCESS FOR THE PREPARATION OF SULFONAMIDE GROUP PHENOXYBENZOIC ACIDS |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1230593A true CA1230593A (en) | 1987-12-22 |
Family
ID=9289009
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000454361A Expired CA1230593A (en) | 1983-05-17 | 1984-05-15 | Process for the preparation of aryloxybenzoic acids containing a sulphonamide group |
Country Status (6)
| Country | Link |
|---|---|
| BR (1) | BR8402323A (en) |
| CA (1) | CA1230593A (en) |
| FR (1) | FR2546165B1 (en) |
| GB (1) | GB2140417B (en) |
| HU (1) | HU194539B (en) |
| IL (1) | IL71637A (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4945113A (en) * | 1989-09-29 | 1990-07-31 | Uniroyal Chemical Company, Inc. | herbicidal sulfonamide derivatives |
| GB9930369D0 (en) * | 1999-12-22 | 2000-02-09 | Zeneca Ltd | Chemical process |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0003416B1 (en) * | 1978-01-19 | 1981-08-26 | Imperial Chemical Industries Plc | Diphenyl ether compounds useful as herbicides; methods of using them, processes for preparing them, and herbicidal compositions containing them |
-
1983
- 1983-05-17 FR FR8308338A patent/FR2546165B1/en not_active Expired
-
1984
- 1984-04-25 IL IL71637A patent/IL71637A/en unknown
- 1984-05-15 CA CA000454361A patent/CA1230593A/en not_active Expired
- 1984-05-16 HU HU841891A patent/HU194539B/en not_active IP Right Cessation
- 1984-05-16 BR BR8402323A patent/BR8402323A/en unknown
- 1984-05-16 GB GB08412495A patent/GB2140417B/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| IL71637A (en) | 1987-08-31 |
| GB8412495D0 (en) | 1984-06-20 |
| GB2140417B (en) | 1986-12-17 |
| IL71637A0 (en) | 1984-07-31 |
| BR8402323A (en) | 1984-12-26 |
| GB2140417A (en) | 1984-11-28 |
| FR2546165B1 (en) | 1985-12-06 |
| FR2546165A1 (en) | 1984-11-23 |
| HUT34155A (en) | 1985-02-28 |
| HU194539B (en) | 1988-02-29 |
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