GB2265373A - Halogenophenoxy compounds - Google Patents

Halogenophenoxy compounds Download PDF

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GB2265373A
GB2265373A GB9305508A GB9305508A GB2265373A GB 2265373 A GB2265373 A GB 2265373A GB 9305508 A GB9305508 A GB 9305508A GB 9305508 A GB9305508 A GB 9305508A GB 2265373 A GB2265373 A GB 2265373A
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lower alkyl
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alkyl group
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Tomokazu Hino
Kenji Tsubata
Hiroshi Hamaguchi
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Nihon Nohyaku Co Ltd
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Nihon Nohyaku Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
    • C07D295/16—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms acylated on ring nitrogen atoms
    • C07D295/18—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms acylated on ring nitrogen atoms by radicals derived from carboxylic acids, or sulfur or nitrogen analogues thereof
    • C07D295/182—Radicals derived from carboxylic acids
    • C07D295/185—Radicals derived from carboxylic acids from aliphatic carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B39/00—Halogenation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C231/00—Preparation of carboxylic acid amides
    • C07C231/12—Preparation of carboxylic acid amides by reactions not involving the formation of carboxamide groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C235/00—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms
    • C07C235/02—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms having carbon atoms of carboxamide groups bound to acyclic carbon atoms and singly-bound oxygen atoms bound to the same carbon skeleton
    • C07C235/04—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms having carbon atoms of carboxamide groups bound to acyclic carbon atoms and singly-bound oxygen atoms bound to the same carbon skeleton the carbon skeleton being acyclic and saturated
    • C07C235/18—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms having carbon atoms of carboxamide groups bound to acyclic carbon atoms and singly-bound oxygen atoms bound to the same carbon skeleton the carbon skeleton being acyclic and saturated having at least one of the singly-bound oxygen atoms further bound to a carbon atom of a six-membered aromatic ring, e.g. phenoxyacetamides
    • C07C235/20—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms having carbon atoms of carboxamide groups bound to acyclic carbon atoms and singly-bound oxygen atoms bound to the same carbon skeleton the carbon skeleton being acyclic and saturated having at least one of the singly-bound oxygen atoms further bound to a carbon atom of a six-membered aromatic ring, e.g. phenoxyacetamides having the nitrogen atoms of the carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C235/00—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms
    • C07C235/02—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms having carbon atoms of carboxamide groups bound to acyclic carbon atoms and singly-bound oxygen atoms bound to the same carbon skeleton
    • C07C235/04—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms having carbon atoms of carboxamide groups bound to acyclic carbon atoms and singly-bound oxygen atoms bound to the same carbon skeleton the carbon skeleton being acyclic and saturated
    • C07C235/18—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms having carbon atoms of carboxamide groups bound to acyclic carbon atoms and singly-bound oxygen atoms bound to the same carbon skeleton the carbon skeleton being acyclic and saturated having at least one of the singly-bound oxygen atoms further bound to a carbon atom of a six-membered aromatic ring, e.g. phenoxyacetamides
    • C07C235/24—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms having carbon atoms of carboxamide groups bound to acyclic carbon atoms and singly-bound oxygen atoms bound to the same carbon skeleton the carbon skeleton being acyclic and saturated having at least one of the singly-bound oxygen atoms further bound to a carbon atom of a six-membered aromatic ring, e.g. phenoxyacetamides having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a six-membered aromatic ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C253/00—Preparation of carboxylic acid nitriles
    • C07C253/30—Preparation of carboxylic acid nitriles by reactions not involving the formation of cyano groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C255/00—Carboxylic acid nitriles
    • C07C255/01—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms
    • C07C255/16—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms containing cyano groups and singly-bound oxygen atoms bound to the same carbon atom of an acyclic carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C255/00—Carboxylic acid nitriles
    • C07C255/49—Carboxylic acid nitriles having cyano groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton
    • C07C255/58—Carboxylic acid nitriles having cyano groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton containing cyano groups and singly-bound nitrogen atoms, not being further bound to other hetero atoms, bound to the carbon skeleton
    • C07C255/60—Carboxylic acid nitriles having cyano groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton containing cyano groups and singly-bound nitrogen atoms, not being further bound to other hetero atoms, bound to the carbon skeleton at least one of the singly-bound nitrogen atoms being acylated
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C327/00—Thiocarboxylic acids
    • C07C327/38—Amides of thiocarboxylic acids
    • C07C327/40—Amides of thiocarboxylic acids having carbon atoms of thiocarboxamide groups bound to hydrogen atoms or to acyclic carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/347—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups
    • C07C51/363—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups by introduction of halogen; by substitution of halogen atoms by other halogen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
    • C07C67/307—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by introduction of halogen; by substitution of halogen atoms by other halogen atoms

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Abstract

A process for producing a halogenophenoxyfatty acid derivative represented by the formula (I): <IMAGE> (wherein R, R<1>, R<2>, X and Y are as defined in the specification) which comprises selectively halogenating a phenoxyfatty acid represented by the following formula (II) in the presence of a halogenating agent: <IMAGE> (wherein R, R<1>, R<2> and X are as defined in the specification). The present invention further provides novel halogenophenoxyfatty acid derivatives represented by the formula (I'): <IMAGE> wherein R', R<1>', R<2>', X' and Y' are as defined in the specification.

Description

BACKGROUND OF THE INVENTION Field of the Invention The present invention relates to a process for producing halogenophenoxyfatty acid derivatives represented by the formula (I):
[wherein.R represents a cyano group, -CON(R3)R4 (wherein R3 and R4 which may be identical or different each represents a hydrogen atom, a lower alkyl group, a phenyl group, a phenyl group having 1 to 5 substituents which may be identical or different and are selected from halogen atom, nitro group, cyano group, lower alkyl group, lower haloalkyl group, lower alkoxy group, lower haloalkoxy group, lower alkylthio group and lower haloalkylthio group, a benzyl group or a benzyl group having 1 to 5 substituents which may be identical or different and are selected from lower alkyl group, lower haloalkyl group, lower alkoxy group, lower haloalkoxy group, lower alkylthio group and lower haloalkylthio group and R3 and R4 may together represent an alkylene group) or -COAR5 (wherein R5 represents a hydrogen atom, a lower alkyl group, a phenyl group, a phenyl group having 1 to 5 substituents which may be identical or different and are selected from halogen atom, nitro group, cyano group, lower alkyl group, lower haloalkyl group, lower alkoxy group, lower haloalkoxy group, lower alkylthio group and lower haloalkylthio group, a benzyl group or a benzyl group having 1 to 5 substituents which may be identical or different and are selected from lower alkyl group, lower haloalkyl group, lower alkoxy group, lower haloalkoxy group, lower alkylthio group and lower haloalkylthio group and A represents an oxygen atom or a sulfur atom), R1 and R2.which may be identical or different each represents a hydrogen atom or a lower alkyl group, X represents a halogen atom or a lower alkyl group and Y represents a halogen atom] and further relates to a part of halogenophenoxyfatty acid derivatives obtained by said process.
The term "lower" alkyl group or the like in the present specification denotes a group having one to six carbon atoms.
In general, halogenophenoxyfatty acid derivatives are produced by halogenating monohalogenophenols to obtain dihalogenophenols and then preparing halogenophenoxyfatty acid derivatives from the resulting dihalogenophenols. Said dihalogenophenols are prepared by the processes disclosed in Japanese Patent Kokai (Laid-Open) Nos. 60-193939, 62-223140 and 3-99033 and Japanese Patent Kokoku (Post Exam. Publ.) No. 3-22377.
However, these processes involve the possibility of producing the toxic dioxines as by-products.
Besides, it is necessary to use hydrogen peroxide in the process of Japanese Patent Kokai (Laid-Open) No. 62223140, nitrogen-containing bases in the process of Japanese Patent Kokoku (Post Exam. Publ.) No. 3-22377 and water and two phase system in the process of Japanese Patent Kokai (Laid-Open) No. 3-99033 in addition to the chlorinating agents Furthermore, as a process for producing halogenophenoxyfatty acid derivatives by halogenating monohalogenophenoxyfatty acid derivatives, it was reported to carry out the halogenation using halogenating agents and catalysts such as iodine and iron [J.O.C., 426 (1946)]. However, this process has the problem in after-treatment of the used catalysts.
SUMMARY OF THE INVENTION The inventors have made intensive research in order to develop a novel process for producing halogenophenoxyfatty acid derivatives in a high yield without using catalysts. As a result, the present invention has been accomplished.
The halogenophenoxyfatty acid derivatives represented by the formula (I) which are produced by the process of the present invention are useful as intermediates for pharmaceuticals, agricultural chemicals and chemical products and some of them which are represented by the following formula (I') are novel compounds which have not yet been mentioned in literature.
[wherein R' represents a cyano group or -CON(R3')R4' (wherein R3' and R4' which may be identical or different each represents a hydrogen atom, a lower alkyl group, a phenyl group, a phenyl group having 1 to 5 substituents which may be identical or different and are selected from halogen atom, nitro group, cyano group, lower alkyl group, lower haloalkyl group, lower alkoxy group, lower haloalkoxy group, lower alkylthio group and lower haloalkylthio group, a benzyl group or a benzyl group having 1 to 5 substituents which may be identical or different and are selected from lower alkyl group, lower haloalkyl group, lower alkoxy group, lower haloalkoxy group, lower alkylthio group and lower haloalkylthio group), R1' and R2' which may be identical or different each represents a hydrogen atom or a lower alkyl group, X' represents a fluorine atom, an iodine atom, a bromine atom or a lower alkyl group and Y' represents a halogen atom, with a proviso that R' does not represent a cyano group when R1' and R2, represent hydrogen atom, X' represents a fluorine atom and Y' represents a chlorine atom].
DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS The halogenophenoxyfatty acid derivatives of the present invention can be produced, for example, by the process as illustrated below.
(wherein R, R1, R2, X and Y are as defined above).
The objective halogenophenoxyfatty acid derivatives can be selectively produced by halogenating the phenoxyfatty acids represented by the formula (II) with halogenating agents in the presence of inert solvents.
The inert solvents used in the present invention may be any of those which do not considerably hinder the progress of the above reaction. Examples of the solvents are halogenated hydrocarbons such as methylene chloride, chloroform, carbon tetrachloride and perchloroethylene, carboxylic acids such as formic acid, acetic acid and propionic acid, aromatic hydrocarbons such as nitrobenzene, chlorobenzene, dichlorobenzene and trichlorobenzene, esters such as ethyl acetate, nitriles such as acetonitrile and benzonitrile, amides such as dimethylformamide and dimethylacetamide, sulfolane, dimethyl sulfone, dimethyl sulfoxide, 1,3-dimethyl-2imidazolidinone, and water. These inert solvents may be used each alone or in combination.
As the halogenating agents, there may be used, for example, chlorine, bromine, iodine, hydrochloric acid-hydrogen peroxide, sulfuryl chloride, phosphorus pentachloride, N,N-dichlorourea, N-chlorosuccinimide, Nbromosuccinimide, hypohalogenous acid t-butyl esters, trichloroisocyanuric acid and trichloromethanesulfonylhalogenides. The amount of the halogenating agent can be optionally selected from the range of from 0.1 mol to an excess mol per mol of the phenoxyfatty acids represented by the formula (II).
If necessary, organic bases, inorganic bases or organic salts can be used in the process of the present invention. Examples of the organic bases are amines such as triethylamine and pyridine, examples of the inorganic bases are alkali metal or alkaline earth metal hydroxides such as sodium hydroxide, potassium hydroxide, calcium hydroxide and barium hydroxide and alkali metal or alkaline earth metal carbonates such as sodium carbonate, potassium carbonate and calcium carbonate, and examples of the organic salts are alkali metal or alkaline earth metal salts of organic acids such as sodium acetate, potassium acetate, calcium acetate and sodium benzoate and ammonium acetate.
The amount of them can be optionally selected from the range of from 0.1 mol to an excess mol per mol of the phenoxyfatty acids represented by the formula (II).
The reaction temperature can be optionally selected from the range of from -200C to the boiling point of the inert solvents used.
The reaction time depends on the reaction temperature and the reaction scale, but can be selected from the range of several minutes to 48 hours.
After completion of the reaction, the reaction mixture containing the objective products is isolated by usual methods such as extraction with solvents and, if necessary, is purified by column chromatography, recrystallization, distillation or the like whereby the halogenophenoxyfatty acid derivatives represented by the formula (I) or (I') can be produced.
Representative examples of the halogenophenoxyfatty acid derivatives represented by the formula (I') which are novel compounds are shown in Table 1.
Table 1
No. X' Y' R1, R2, R' Yield Property (%) X' ~ R1' R2' R Yield 2lorty (m.p./0C) I 1 F C1 H H CONH2 90.4 148.3 2 F C1 H H CONHCH3 92.0 87.9-88.1 3 F C1 H H CONHC2H5 75.6 66.8-67.0 4 F C1 H H CONHC3H7-i 81.5 117.1 5 F C1 H H CON(CH3)2 74.7 79.8-81.7 Cl 6 F C1 H H CONH 9 81.6 151.6-152.5 CONH- 'C1 7 F C1 H H CON 2 1 84.7 103.6 8 F C1 CH3 H CN 80.6 Oil 9 CH3 C1 C1 H CONH2 70.2 Oil NMR data of the compounds in the above Table 1 which are shown to be oil in the column of "property" are shown in Table 2.
Table 2
No. 1H-NHR(CDC13, ppm) 8 1.63 (3H, d), 4.97 (1H, m), 6.99 (111, m), 7.08 (1H, d. d), 7.17 (1H, d. d).
9 2.27 (3H, s), 4.49 (2H, s), 5.64 (1H, br), 6.79 (1H, br), 6.80 (111, d), 7.02 (1H, d. d), 7.20 (111, d).
The present invention is illustrated by the following nonlimiting typical examples.
Example 1 Preparation of 2-chloro-4-fluorophenoxyaceto nitrile (compound No. 25)
1.51 g (0.01 mol) of 4-fluorophenoxyacetonitrile and 0.82 g (0.01 mol) of sodium acetate were dissolved in a mixed solvent comprising 7 ml of acetic acid and 3 ml of water and chlorine gas was introduced into the solution at a rate of 12.3 ml/min for 60 minutes at 500C with stirring.
After termination of the reaction, to the reaction mixture was added 3 ml of a 10% aqueous sodium thiosulfate solution and the solvent was distilled off under reduced pressure. To the resulting residue was added 20 ml of a 10% aqueous sodium hydrogencarbonate solution and the objective product was extracted with ethyl acetate (30 ml x 2).
The organic layer was dried over anhydrous sodium sulfate and concentrated under reduced pressure.
The resulting concentrate was distilled to obtain 1.54 g of 2-chloro-4-fluorophenoxyacetonitrile.
This compound was known compound and had the same melting point and NMR as those mentioned in literature.
Yield: 83.0% Example 2 Preparation of 2,4-dichlorophenoxyacetamide (compound No. 10)
1.86 g (0.01 mol) of 4-chlorophenoxyacetamide was dissolved in 11 ml of acetic acid with heating at 500C and chlorine gas was introduced thereinto at that temperature for 50 minutes at a rate of 12.3 ml/mine After termination of the reaction, to the reaction mixture was added 3 ml of a 10% aqueous sodium thiosulfate solution and the solvent was distilled off under reduced pressure. To the residue was added 20 ml of a 10% aqueous sodium hydrogencarbonate solution and the objective product was extracted with ethyl acetate (30 ml x 2).
The organic layer was dried over anhydrous sodium sulfate and concentrated under reduced pressure.
The resulting crystal was washed with n-hexane to obtain 2.02 g of the objective 2,4-dichlorophenoxyacetamide.
Yield: 92.0% This compound was known compound and had the same melting point and NMR as those mentioned in literature.
Example 3 Preparation of 2,4-dichlorophenoxyacetic acid (compound No. 17)
1.87 g (0.01 mol) of 4-chlorophenoxyacetic acid was added to 10 ml of dimethylformamide and chlorine gas was introduced thereinto at 500C for 45 minutes at a rate of 12.3 ml/min with stirring.
After termination of the reaction, to the reaction mixture was added 3 ml of a 10% aqueous sodium thiosulfate solution and the solvent was distilled off under reduced pressure. To the residue was added 20 ml of a 10% aqueous sodium hydrogencarbonate solution and the objective product was extracted with ethyl acetate (30 ml x 2).
The organic layer was dried over anhydrous sodium sulfate and concentrated under reduced pressure.
The resulting crystal was washed with n-hexane to obtain 2.07 g of the objective 2,4-dichlorophenoxyacetic acid.
Yield: 93.6% This compound was known compound and had the same melting point and NMR as those mentioned in literature.
Table 3 shows typical examples of the halogenophenoxyfatty acid derivatives represented by the formula (I) which were prepared in the same manner as in Examples 1-3.
Since the compounds shown in Table 3 are known compounds, they were identified by the identity of their melting point, NMR and IR with those mentioned in literature.
Table 3
No. X Y' R1, R21 R' Yield (%) 10 C1 C1 H H CONH2 92.0 11 C1 C1 H H CONHCH3 94.4 12 C1 C1 H H CONHC2H5 93.3 13 C1 C1 H H CONHC3H7-i 87.5 14 C1 C1 H H CON(CH3)2 77.4 Cl 15 Cl Cl H H CONH ss C1 81.7 15 C1 C1 H H CONH'I 16 C1 C1 H H CON 2 1 96.2 17 C1 C1 H H COOH 93.6 18 C1 C1 H H COOCH3 81.5 19 C1 C1 H H COOC2H5 83.6 20 C1 C1 H H COOC3H7-i 87.1 21 F C1 H H COOH 80.6 22 F C1 H H COOCH3 84.2 23 F C1 H H COOC2H5 76.3 24 F C1 H H COOC3H7-i 80.9 25 F C1 H H CN 83.0 26 C1 C1 CH3 H COOH 82.0 27 C1 C1 CH3 H CONH2 88.9 28 C1 C1 CH3 H CON O 74.5 29 C1 C1 CH3 H COOCH3 81.5 The halogenophenoxyfatty acid derivatives represented by the formula (I) are important especially as intermediates in preparation of the herbicides disclosed in Japanese Patent Kokai (Laid-open) No. 3163063. The typidal herbicides which are final products can be prepared, for example, by the process as illustrated below.
(wherein R, R1, R2, X and Y are as defined above, R3" denotes a lower alkoxyl group, R4" denotes a lower alkyl group or a lower haloalkyl group, R5" denotes a lower alkyl group or a lower haloalkyl group and Hal denotes a halogen atom.)

Claims (4)

  1. WHAT IS CLAIMED IS: A A process for producing a halogenophenoxyfatty acid derivative represented by the formula (I):
    [wherein R represents a cyano group, -CON(R3)R4 (wherein R3 and R4 which may be identical or different each represents a hydrogen atom, a lower alkyl group, a phenyl group, a phenyl group having 1 to 5 substituents which may be identical or different and are selected from halogen atom, nitro group, cyano group, lower alkyl group, lower haloalkyl group, lower alkoxy group, lower haloalkoxy group, lower alkylthio group and lower haloalkylthio group, a benzyl group or a benzyl group having 1 to 5 substituents which may be identical or different and are selected from lower alkyl group, lower haloalkyl group, lower alkoxy group, lower haloalkoxy group, lower alkylthio group and lower haloalkylthio group and R3 and R4 may together represent an alkylene group) or -COAR5 (wherein R5 represents a hydrogen atom, a lower alkyl group, a phenyl group, a phenyl group having 1 to 5 substituents which may be identical or different and are selected from halogen atom, nitro group, cyano group, lower alkyl group, lower haloalkyl group, lower alkoxy group, lower haloalkoxy group, lower alkylthio group and lower haloalkylthio group, a benzyl group or a benzyl group having 1 to 5 substituents which may be identical or different and are selected from lower alkyl group, lower haloalkyl group, lower alkoxy group, lower haloalkoxy group, lower alkylthio group and lower haloalkylthio group and A represents an oxygen atom or a sulfur atom) r R1 and R2 which may be identical or different each represents a hydrogen atom or a lower alkyl group, and X represents a halogen atom or a lower alkyl group and Y represents a halogen atom] which comprises selectively halogenating a phenoxyfatty acid represented by the following formula (II) in the presence of a halogenating agent:
    (wherein R, R1, R2 and X are as defined above).
  2. 2. A process according to claim 1 wherein the.
    halogenating agent is a chlorinating agent.
  3. 3. A halogenophenoxyfatty acid derivative represented by the formula (I'):
    wherein R' represents a cyano group or -CON(R3')R4' (wherein R3' and R4' which may be identical or different each represents a hydrogen atom, a lower alkyl group, a phenyl group, a phenyl group having 1 to 5 substituents which may be identical or different and are selected from halogen atom, nitro group, cyano group, lower alkyl group, lower haloalkyl group, lower alkoxy group, lower haloalkoxy group, lower alkylthio group and lower haloalkylthio group, a benzyl group or a benzyl group having 1 to 5 substituents which may be identical or different and are selected from lower alkyl group, lower haloalkyl group, lower alkoxy group, lower haloalkoxy group, lower alkylthio group and lower haloalkylthio group), R1' and R2' which may be identical or different each represents a hydrogen atom or a lower alkyl group, Xg represents a fluorine atom, an iodine atom, a bromine atom or a lower alkyl group and Y' represents a halogen atom, with a proviso that R' does not represent a cyano group when R11 and R21 represent hydrogen atom, X' represents a fluorine atom and Y' represents a chlorine atom].
  4. 4. A halogenophenoxyfatty acid derivative according to claim 3 wherein in the formula (I'), R' represents a cyano group or -CON(R3')R4' (wherein R3' and R4' which may be identical or different each represents a hydrogen atom, a lower alkyl group, a phenyl group or a phenyl group substituted with 1 to 5 halogen atoms which may be identical or different and R3' and R4' may together represent an alkylene group), R1' represents a hydrogen atom or a lower alkyl group, R2' represents a hydrogen atom, X' represents a fluorine atom or a lower alkyl group and Y' represents a chlorine atom.
GB9305508A 1992-03-26 1993-03-17 Process for producing halogenophenoxy fatty acid derivatives by selective halogenation and halogenophenoxy fatty acid derivatives Expired - Fee Related GB2265373B (en)

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* Cited by examiner, † Cited by third party
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US7045652B2 (en) * 2002-07-03 2006-05-16 Pfizer Inc Processes for preparing substituted aryl boronic acids
WO2014025749A2 (en) * 2012-08-06 2014-02-13 Sirga Advanced Biopharma, Inc. Small molecule inhibitors of viral protein interactions with human t-rna

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IL33089A (en) * 1968-10-02 1974-05-16 Pepro Herbicidal compositions containing phenoxyalkyl amides
IN146297B (en) * 1976-07-30 1979-04-14 Stauffer Chemical Co
GB2108498B (en) * 1981-10-20 1985-11-06 Ube Industries Phenoxyalkylamide derivative, process for preparing the same, herbicidal composition containing the same and method for controlling weeds by the use of the same
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ITTO930201A0 (en) 1993-03-25
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AU3537793A (en) 1993-09-30
ES2059275B1 (en) 1997-08-01
CA2091864A1 (en) 1993-09-27
TW412514B (en) 2000-11-21
DE4309365C2 (en) 1995-10-19
FR2689125B1 (en) 1996-10-18
CN1078232A (en) 1993-11-10
KR950014225B1 (en) 1995-11-23
FR2689125A1 (en) 1993-10-01
ES2059275A1 (en) 1994-11-01
DE4309365A1 (en) 1993-11-04
CA2091864C (en) 1999-09-07
GB9305508D0 (en) 1993-05-05
CH685053A5 (en) 1995-03-15
KR930019610A (en) 1993-10-18
IT1260629B (en) 1996-04-22
CN1043228C (en) 1999-05-05
GB2265373B (en) 1995-11-22

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