CA2091864C - Process for producing halogenophenoxyfatty acid derivatives by selective halogenation and halogenophenoxyfatty acid derivatives - Google Patents
Process for producing halogenophenoxyfatty acid derivatives by selective halogenation and halogenophenoxyfatty acid derivativesInfo
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- 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
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- 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
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- 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
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- 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
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- 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
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- 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
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- 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
Disclosed are a process for producing a halogenophenoxyfatty acid derivative represented by the formula (I):
(see fig. I) [wherein R is CN, -CONR3R4 (in which R3 and R4 are H, alkyl, phenyl, benzyl or the like or together form alkylene) or -COAR5 (in which R5 is H, alkyl, phenyl, benzyl or the like and A is O or S), R1 and R2 are H or alkyl, X is halogen or alkyl and Y is halogen] which comprises selectively halogenating a phenoxyfatty acid represented by the following formula:
(see fig. II) with a halogenating agent; and a novel halogenophenoxyfatty acid derivative represented by the formula:
(see fig. III) [wherein R', R1', R2', X' and Y' have the meanings similar to R, R1, R2, X and Y]. The halogenophenoxyfatty acid derivative is useful as intermediate for producing herbicide or the like.
(see fig. I) [wherein R is CN, -CONR3R4 (in which R3 and R4 are H, alkyl, phenyl, benzyl or the like or together form alkylene) or -COAR5 (in which R5 is H, alkyl, phenyl, benzyl or the like and A is O or S), R1 and R2 are H or alkyl, X is halogen or alkyl and Y is halogen] which comprises selectively halogenating a phenoxyfatty acid represented by the following formula:
(see fig. II) with a halogenating agent; and a novel halogenophenoxyfatty acid derivative represented by the formula:
(see fig. III) [wherein R', R1', R2', X' and Y' have the meanings similar to R, R1, R2, X and Y]. The halogenophenoxyfatty acid derivative is useful as intermediate for producing herbicide or the like.
Description
Field o,f the Invention The present invention relates to a process for producing halogenophenoxyfatty acid derivatives represented by the formula (I):
Y
X O O-C-R (I) [wherein R represents a cyano group, -CON(R3)R4 (wherein R3 and R4 which may be identic<31 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 subst ituents which may be ide~nt ical 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 the process.
The term "lower" alkyl group or the like in the present specification denotes a grouip having one to six carbon atoms. The "alkylene" group in the present specification denotes such a group having 4 or 5 carbon atoms.
In general, halogenophenox:yfatty acid derivatives are produced by halogenating monohalogenophenols to obtain dihalogenophenols and then preparing' halogenophenoxyfatty acid derivatives from the resulting dihalogenophenols. The dihalogenophenols are prepared by th.e 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.
Y
X O O-C-R (I) [wherein R represents a cyano group, -CON(R3)R4 (wherein R3 and R4 which may be identic<31 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 subst ituents which may be ide~nt ical 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 the process.
The term "lower" alkyl group or the like in the present specification denotes a grouip having one to six carbon atoms. The "alkylene" group in the present specification denotes such a group having 4 or 5 carbon atoms.
In general, halogenophenox:yfatty acid derivatives are produced by halogenating monohalogenophenols to obtain dihalogenophenols and then preparing' halogenophenoxyfatty acid derivatives from the resulting dihalogenophenols. The dihalogenophenols are prepared by th.e 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.
1 However, these processes involve the possibil-ity 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. 62-223140, 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 halo~genation using halogenat-ing 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 halogeno-phenoxyfatty 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 novel compounds which have not yet been mentioned in literature.
The novel compounds are represented by the following formula (I'):
Y, 1' R
X' O O-C-R' 2~
R
[wherein R' represents a cyano group or -CON(R3~)R4~ (wherein R3~ and R4~ which may be identical or different each represent 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 sele~~ted from lower alkyl group, lower haloalkyl group, lower alkoxy group, lower haloalkoxy group, lower alkylthio group and lower haloalkylthio group or R3~ and R4~ 'together represent an alkylene group), R1~ and R2~ which may be identical or different each represent 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 the proviso [1] 'that R' does not represent a cyano group) when R1~ and R2~ each represent a hydrogen atom, X' represents a fluorine atom and Y' represents a chlorine atom, (2] that R' does not represent a cyano group, when R1~ and R2~ each represent a hydrogen atom and X' and Y' each represent a bromine atom and [~i] that R' does not represent -CONH2, when R1~ and R2~ each represent a hydrogen atom and X' and Y' each represent a fluorine atom.
DETAILED DESCRIPTION OF PREFERRED EbsBODIMENTS
The halogenophenoxyfatty acid derivatives of the present invention can be produced, f:or example, by the process as illustrated below.
R 1 haloge~ating R 1 X I -R - -~s X O O-C-R
R2 Rz (wherein R, R1, R2, X and Y are as defined above).
The objective halogenophenoxyfatty acid derivatives can be produced by selectively haloc~enating 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 20 918 8 ~
propionic acid, aromatic hydrocarbons such as nitrobenzene) chlorobenzene, dichlorobenzene and t:richlorobenzene, esters such as ethyl acetate, nitriles - 5a -1 such as acetonitrile and benzonitrile, amides such as dimethylformamide and dimethylacetamide, sulfolane, dimethyl sulfone, dimethyl sulfoxide, 1,3-dimethyl-2-imidazolidinone, 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, N-bromosuccinimide, hypohalogenous acid t-butyl esters, trichloroisocyanuric acid and trichloromethanesulfonyl-halogenides. The amount of the halogenating agent can be optionally selected from th.e range of from 0.1 mol to an excess mol per mol of the p~henoxyfatty 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 a.nd pyridine, examples of the inorganic bases are alkali metal or alkaline earth metal hydroxides such as sodium hydroxide, potassium hydroxide, calcium hydroxide a.nd barium hydroxide and alkali metal or alkaline earth metal carbonates such as sodium carbonate, potassium carbonate and calcium carbonate, and examples of they organic salts are alkali metal or alkaline earth metal salts of organic acids such as sodium acetate, potassium acetate, calcium acetate and sodium benzoate ar,~d ammonium acetate.
Besides, it is necessary to use hydrogen peroxide in the process of Japanese Patent Kokai (Laid-Open) No. 62-223140, 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 halo~genation using halogenat-ing 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 halogeno-phenoxyfatty 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 novel compounds which have not yet been mentioned in literature.
The novel compounds are represented by the following formula (I'):
Y, 1' R
X' O O-C-R' 2~
R
[wherein R' represents a cyano group or -CON(R3~)R4~ (wherein R3~ and R4~ which may be identical or different each represent 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 sele~~ted from lower alkyl group, lower haloalkyl group, lower alkoxy group, lower haloalkoxy group, lower alkylthio group and lower haloalkylthio group or R3~ and R4~ 'together represent an alkylene group), R1~ and R2~ which may be identical or different each represent 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 the proviso [1] 'that R' does not represent a cyano group) when R1~ and R2~ each represent a hydrogen atom, X' represents a fluorine atom and Y' represents a chlorine atom, (2] that R' does not represent a cyano group, when R1~ and R2~ each represent a hydrogen atom and X' and Y' each represent a bromine atom and [~i] that R' does not represent -CONH2, when R1~ and R2~ each represent a hydrogen atom and X' and Y' each represent a fluorine atom.
DETAILED DESCRIPTION OF PREFERRED EbsBODIMENTS
The halogenophenoxyfatty acid derivatives of the present invention can be produced, f:or example, by the process as illustrated below.
R 1 haloge~ating R 1 X I -R - -~s X O O-C-R
R2 Rz (wherein R, R1, R2, X and Y are as defined above).
The objective halogenophenoxyfatty acid derivatives can be produced by selectively haloc~enating 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 20 918 8 ~
propionic acid, aromatic hydrocarbons such as nitrobenzene) chlorobenzene, dichlorobenzene and t:richlorobenzene, esters such as ethyl acetate, nitriles - 5a -1 such as acetonitrile and benzonitrile, amides such as dimethylformamide and dimethylacetamide, sulfolane, dimethyl sulfone, dimethyl sulfoxide, 1,3-dimethyl-2-imidazolidinone, 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, N-bromosuccinimide, hypohalogenous acid t-butyl esters, trichloroisocyanuric acid and trichloromethanesulfonyl-halogenides. The amount of the halogenating agent can be optionally selected from th.e range of from 0.1 mol to an excess mol per mol of the p~henoxyfatty 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 a.nd pyridine, examples of the inorganic bases are alkali metal or alkaline earth metal hydroxides such as sodium hydroxide, potassium hydroxide, calcium hydroxide a.nd barium hydroxide and alkali metal or alkaline earth metal carbonates such as sodium carbonate, potassium carbonate and calcium carbonate, and examples of they organic salts are alkali metal or alkaline earth metal salts of organic acids such as sodium acetate, potassium acetate, calcium acetate and sodium benzoate ar,~d ammonium acetate.
1 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 -20°C 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.
Y' Rl X' O O-C-R~
R2' Table 1 No. X Y R1 RZ R
Yield Property (%) (mP/C) 1 F C1 H H CONHZ 90.4 148.3 2 F C1 H H CONHCH3 92.0 87.9-88.1 3 F C1 H H CONHCZH5 75.6 66.8-67.0 4 F C1 H H CONHC3H7-i 81.5 117.1 F C1 H H CON(CHg)2 74.7 79.8-81.7 Cl 6 F C1 H H 81.6 151.6-152.5 O ~' C1 CONH
The reaction temperature can be optionally selected from the range of from -20°C 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.
Y' Rl X' O O-C-R~
R2' Table 1 No. X Y R1 RZ R
Yield Property (%) (mP/C) 1 F C1 H H CONHZ 90.4 148.3 2 F C1 H H CONHCH3 92.0 87.9-88.1 3 F C1 H H CONHCZH5 75.6 66.8-67.0 4 F C1 H H CONHC3H7-i 81.5 117.1 F C1 H H CON(CHg)2 74.7 79.8-81.7 Cl 6 F C1 H H 81.6 151.6-152.5 O ~' C1 CONH
7 F C1 H H CON 84.7 103.6 8 F C1 CH3 H CN 80.6 Oil 9 CHg C1 C1 H CONHZ 70.2 Oil NMR data of the compounds in the above Table 1 which are shown to be oil in tlhe column of "property"
are shown in Table 2.
_ g __ Table 2 No. 1H-NHR(CDClg, ppm) 8 1.63(3H, d), 4.97 (1H, m), 6.99 (1H, 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 (1H, d), 7.02 (1H,d. d), 7.20 (1H, d).
1 The present invention is illustrated by the following nonlimiting typical examples.
Example 1 Preparation of 2-chloro-4-fluorophenoxyaceto-nitrile (compound No. 25) F O O-CHZCN -j- F O O-CHZCN
1.51 g (0.01 mol) of 4-fluorophenoxyaceto-nitrile 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 50°C with stirring.
After termination of the reaction, to the reaction mixture was added 3 m:l of a 10% aqueous sodium thiosulfate solution and the solvent was distilled off under reduced pressure. To the resulting residue was 1 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) C1 O O-CH2CINH2 C12 -~ C1 O 0-CH2CNH2 1.86 g (0.01 mol) of 4-chlorophenoxyacetamide was dissolved in 11 ml of acetic acid with heating at 50°C and chlorine gas was introduced thereinto at that temperature for 50 minutes at a rate of 12.3 ml/min.
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 tree residue was added 20 ml of a 10% aqueous sodium hydrogencarbonate solution and u. t X091864 1 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) Cl;~
C1 O O-CH2COH -~ Cl O O-CHZCOH
1.87 g (0.01 mol) o~f 4-chlorophenoxyacetic acid was added to 10 ml of di.methylformamide and chlorine gas was introduced t,hereinto at 50°C 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 t:he residue was added 20 ml of a 10% aqueous sodium hydrc>gencarbonate solution and - l:l -~0 918 6 4 1 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 witla those mentioned in literature.
X O - O-C-R ( I ) Tables 3 No. X' Y' Rl' RZ' R' Yield (%) 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 CONHC3H~-i 87.5 14 C1 Cl H H CON(CH3)2 77.4 C1 C1 H H CiJNH ~ C1 81 7 16 C1 C1 H H CON, I 96.2 V
17 Cl C1 H H CC~OH 93.6 18 C1 C1 H H C00CH3 81.5 19 C1 C1 H H COOC2H5 83.6 C1 C1 H H COOC3H~-i 87.1 21 F Cl H H COON 80.6 22 F C1 H H COOCH3 84.2 23 F C1 H H COOCZH5 76.3 24 F C1 H H COOC3H~-i 80.9 F C1 H H CN 83.0 26 Cl C1 CH3 H CO()H 82.0 27 C1 C1 CHg H CO1JH2 88.9 28 C1 C1 CH3 H CON 74.5 29 C1 C1 CHg H COOCH3 81.5 ._ X091864 1 The halogenophenoxyi°atty acid derivatives represented by the formula (I) are important especially as intermediates in preparation of the herbicides disclosed in Japanese Patent lCokai (Laid-open) No. 3-163063. The typical herbicides which are final products can be prepared, for example, by the process as illustrated below.
Y
Y R1 Bromina- R1 CH2=CHOC4H9-n tion I
X O O-C-R --~ X ~ O 0-C-R
Catalyst R2 Br R2 R3"O-C._OR3 ~~
X O O-C-R ~ X O 0-C-R
I Base CHgC RZ R3"-C-CH2C R2 II II II
O O O
Cyclyzation alkylation I
R-C-O OH
R2 Rq ~~
X X
Halogena-y O tion y O Hal ~ R1 NI \
N~ORS" N~OR5"
R-C-O I R-C-O
R2 R4,. R2 Rq ~~
~0 918 fi 4 1 (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 haloalltyl group and Hal denotes a halogen atom.)
are shown in Table 2.
_ g __ Table 2 No. 1H-NHR(CDClg, ppm) 8 1.63(3H, d), 4.97 (1H, m), 6.99 (1H, 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 (1H, d), 7.02 (1H,d. d), 7.20 (1H, d).
1 The present invention is illustrated by the following nonlimiting typical examples.
Example 1 Preparation of 2-chloro-4-fluorophenoxyaceto-nitrile (compound No. 25) F O O-CHZCN -j- F O O-CHZCN
1.51 g (0.01 mol) of 4-fluorophenoxyaceto-nitrile 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 50°C with stirring.
After termination of the reaction, to the reaction mixture was added 3 m:l of a 10% aqueous sodium thiosulfate solution and the solvent was distilled off under reduced pressure. To the resulting residue was 1 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) C1 O O-CH2CINH2 C12 -~ C1 O 0-CH2CNH2 1.86 g (0.01 mol) of 4-chlorophenoxyacetamide was dissolved in 11 ml of acetic acid with heating at 50°C and chlorine gas was introduced thereinto at that temperature for 50 minutes at a rate of 12.3 ml/min.
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 tree residue was added 20 ml of a 10% aqueous sodium hydrogencarbonate solution and u. t X091864 1 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) Cl;~
C1 O O-CH2COH -~ Cl O O-CHZCOH
1.87 g (0.01 mol) o~f 4-chlorophenoxyacetic acid was added to 10 ml of di.methylformamide and chlorine gas was introduced t,hereinto at 50°C 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 t:he residue was added 20 ml of a 10% aqueous sodium hydrc>gencarbonate solution and - l:l -~0 918 6 4 1 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 witla those mentioned in literature.
X O - O-C-R ( I ) Tables 3 No. X' Y' Rl' RZ' R' Yield (%) 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 CONHC3H~-i 87.5 14 C1 Cl H H CON(CH3)2 77.4 C1 C1 H H CiJNH ~ C1 81 7 16 C1 C1 H H CON, I 96.2 V
17 Cl C1 H H CC~OH 93.6 18 C1 C1 H H C00CH3 81.5 19 C1 C1 H H COOC2H5 83.6 C1 C1 H H COOC3H~-i 87.1 21 F Cl H H COON 80.6 22 F C1 H H COOCH3 84.2 23 F C1 H H COOCZH5 76.3 24 F C1 H H COOC3H~-i 80.9 F C1 H H CN 83.0 26 Cl C1 CH3 H CO()H 82.0 27 C1 C1 CHg H CO1JH2 88.9 28 C1 C1 CH3 H CON 74.5 29 C1 C1 CHg H COOCH3 81.5 ._ X091864 1 The halogenophenoxyi°atty acid derivatives represented by the formula (I) are important especially as intermediates in preparation of the herbicides disclosed in Japanese Patent lCokai (Laid-open) No. 3-163063. The typical herbicides which are final products can be prepared, for example, by the process as illustrated below.
Y
Y R1 Bromina- R1 CH2=CHOC4H9-n tion I
X O O-C-R --~ X ~ O 0-C-R
Catalyst R2 Br R2 R3"O-C._OR3 ~~
X O O-C-R ~ X O 0-C-R
I Base CHgC RZ R3"-C-CH2C R2 II II II
O O O
Cyclyzation alkylation I
R-C-O OH
R2 Rq ~~
X X
Halogena-y O tion y O Hal ~ R1 NI \
N~ORS" N~OR5"
R-C-O I R-C-O
R2 R4,. R2 Rq ~~
~0 918 fi 4 1 (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 haloalltyl group and Hal denotes a halogen atom.)
Claims (7)
1. 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 represent a hydrogen atom, a C1-C6 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, C1-C6 alkyl group, C1-C6 haloalkyl group, C1-C6 alkoxy group, C1-C6 haloalkoxy group, C1-C6 alkylthio group and C1-C6 haloalkylthio group, a benzyl group or a benzyl group having 1 to 5 substituents which may be identical or different and are selected from C1-C6 alkyl group, C1-C6 haloalkyl group, C1-C6 alkoxy group, C1-C6 haloalkoxy group, C1-C6 alkylthio group and C1-C6 haloalkylthio group or R3 and R4 together represent a C4-C5 alkylene group) or -COAR5 (wherein R5 represents a hydrogen atom, a C1-C6 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, C1-C6 alkyl group, C1-C6 haloalkyl group, C1-C6 alkoxy group, C1-C6 haloalkoxy group, C1-C6 alkylthio group and C1-C6 haloalkylthio group, a benzyl group or a benzyl group having 1 to 5 substituents which may be identical or different and are selected from C1-C6 alkyl group, C1-C6 haloalkyl group, C1-C6 alkoxy group, C1-C6 haloalkoxy group, C1-C6 alkylthio group and C1-C6 haloalkylthio group and A represents an oxygen atom or a sulfur atom), R1 and R2 which may be identical or different each represent a hydrogen atom or a C1-C6 alkyl group, and X
represents a halogen atom or a C1-C6 alkyl group and Y
represents a halogen atom], which comprises:
selectively halogenating a phenoxyfatty acid represented by the following formula:
(wherein R, R1, R2 and X are as defined above) with a halogenating agent in an inert solvent.
[wherein R represents a cyano group, -CON(R3)R4 (wherein R3 and R4 which may be identical or different each represent a hydrogen atom, a C1-C6 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, C1-C6 alkyl group, C1-C6 haloalkyl group, C1-C6 alkoxy group, C1-C6 haloalkoxy group, C1-C6 alkylthio group and C1-C6 haloalkylthio group, a benzyl group or a benzyl group having 1 to 5 substituents which may be identical or different and are selected from C1-C6 alkyl group, C1-C6 haloalkyl group, C1-C6 alkoxy group, C1-C6 haloalkoxy group, C1-C6 alkylthio group and C1-C6 haloalkylthio group or R3 and R4 together represent a C4-C5 alkylene group) or -COAR5 (wherein R5 represents a hydrogen atom, a C1-C6 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, C1-C6 alkyl group, C1-C6 haloalkyl group, C1-C6 alkoxy group, C1-C6 haloalkoxy group, C1-C6 alkylthio group and C1-C6 haloalkylthio group, a benzyl group or a benzyl group having 1 to 5 substituents which may be identical or different and are selected from C1-C6 alkyl group, C1-C6 haloalkyl group, C1-C6 alkoxy group, C1-C6 haloalkoxy group, C1-C6 alkylthio group and C1-C6 haloalkylthio group and A represents an oxygen atom or a sulfur atom), R1 and R2 which may be identical or different each represent a hydrogen atom or a C1-C6 alkyl group, and X
represents a halogen atom or a C1-C6 alkyl group and Y
represents a halogen atom], which comprises:
selectively halogenating a phenoxyfatty acid represented by the following formula:
(wherein R, R1, R2 and X are as defined above) with a halogenating agent in an inert solvent.
2. A process according to claim 1 wherein the halogenating agent is a chlorinating agent.
3. A halogenophenoxyfatty acid derivative represent 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 represent a hydrogen atom, a C1-C6 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, C1-C6 alkyl group, C1-C6 haloalkyl group, C1-C6 alkoxy group, C1-C6 haloalkoxy group, C1-C6 alkylthio group and C1-C6 haloalkylthio group, a benzyl group or a benzyl group having 1 to 5 substituents which may be identical or different and are selected from C1-C6 alkyl group, C1-C6 haloalkyl group, C1-C6 alkoxy group, C1-C6 haloalkoxy group, C1-C6 alkylthio group and C1-C6 haloalkylthio group or R3' and R4' together represent a C4-C5 alkylene group), R1' and R2' which may be identical or different each represent a hydrogen atom or a C1-C6 alkyl group, X' represents a fluorine atom, an iodine atom, a bromine atom or a C1-C6 alkyl group and Y' represents a halogen atom, with the proviso [1] that R' does not represent a cyano group) when R1' and R2' each represent a hydrogen atom, X' represents a fluorine atom and Y' represents a chlorine atom, [2] that R' does not represent a cyano group, when R1' and R2' each represent a hydrogen atom and X' and Y' each represent a bromine atom, and [3] that R' does not represent -CONH2, when R1' and R2' each represent a hydrogen atom and X' and Y' each represent a fluorine atom].
wherein R' represents a cyano group or -CON(R3')R4' (wherein R3' and R4' which may be identical or different each represent a hydrogen atom, a C1-C6 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, C1-C6 alkyl group, C1-C6 haloalkyl group, C1-C6 alkoxy group, C1-C6 haloalkoxy group, C1-C6 alkylthio group and C1-C6 haloalkylthio group, a benzyl group or a benzyl group having 1 to 5 substituents which may be identical or different and are selected from C1-C6 alkyl group, C1-C6 haloalkyl group, C1-C6 alkoxy group, C1-C6 haloalkoxy group, C1-C6 alkylthio group and C1-C6 haloalkylthio group or R3' and R4' together represent a C4-C5 alkylene group), R1' and R2' which may be identical or different each represent a hydrogen atom or a C1-C6 alkyl group, X' represents a fluorine atom, an iodine atom, a bromine atom or a C1-C6 alkyl group and Y' represents a halogen atom, with the proviso [1] that R' does not represent a cyano group) when R1' and R2' each represent a hydrogen atom, X' represents a fluorine atom and Y' represents a chlorine atom, [2] that R' does not represent a cyano group, when R1' and R2' each represent a hydrogen atom and X' and Y' each represent a bromine atom, and [3] that R' does not represent -CONH2, when R1' and R2' each represent a hydrogen atom and X' and Y' each represent a fluorine atom].
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 represent a hydrogen atom, a C1-C6 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' together represent a C4-C5 alkylene group), R1' represents a hydrogen atom or a C1-C6 alkyl group, R2' represents a hydrogen atom, X' represents a fluorine atom or a C1-C6 alkyl group and Y' represents a chlorine atom.
5. A process according to claim 2, wherein the chlorination is conducted using chlorine gas as the chlorinating agent in an inert solvent at a temperature of from -20°C to the boiling temperature of the solvent.
6. A process according to claim 2 or 5, wherein X is a chlorine or fluorine atom.
7. A halogenophenoxyfatty acid derivative according to claim 3, wherein in the formula (I'):
R' represents CONH 2, CONHCH3, CONHC2H5, CONHC3H.gamma.-i, CON(CH3)2, CN, R1' represents H or CH3;
R2' represents H;
X' represents F or CH3; and Y' represents Cl.
R' represents CONH 2, CONHCH3, CONHC2H5, CONHC3H.gamma.-i, CON(CH3)2, CN, R1' represents H or CH3;
R2' represents H;
X' represents F or CH3; and Y' represents Cl.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10041992 | 1992-03-26 | ||
| JP04-100419 | 1992-03-26 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CA2091864A1 CA2091864A1 (en) | 1993-09-27 |
| CA2091864C true CA2091864C (en) | 1999-09-07 |
Family
ID=14273463
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002091864A Expired - Fee Related CA2091864C (en) | 1992-03-26 | 1993-03-17 | Process for producing halogenophenoxyfatty acid derivatives by selective halogenation and halogenophenoxyfatty acid derivatives |
Country Status (11)
| Country | Link |
|---|---|
| KR (1) | KR950014225B1 (en) |
| CN (1) | CN1043228C (en) |
| AU (1) | AU644318B2 (en) |
| CA (1) | CA2091864C (en) |
| CH (1) | CH685053A5 (en) |
| DE (1) | DE4309365C2 (en) |
| ES (1) | ES2059275B1 (en) |
| FR (1) | FR2689125B1 (en) |
| GB (1) | GB2265373B (en) |
| IT (1) | IT1260629B (en) |
| TW (1) | TW412514B (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7045652B2 (en) * | 2002-07-03 | 2006-05-16 | Pfizer Inc | Processes for preparing substituted aryl boronic acids |
| CA2920331A1 (en) | 2012-08-06 | 2014-02-13 | Sirga Advanced Biopharma, Inc. | Small molecule inhibitors of viral protein interactions with human t-rna |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| JPS60193939A (en) * | 1984-03-13 | 1985-10-02 | Central Glass Co Ltd | Production of 2-chloro-4-fluorophenol |
| JPS62223140A (en) * | 1986-03-26 | 1987-10-01 | Nippon Kayaku Co Ltd | Production of 2-chloro-4-fluorophenol |
| JPH02229175A (en) * | 1989-03-02 | 1990-09-11 | Hokko Chem Ind Co Ltd | Cyclic acylhydroxylamine derivative and production thereof |
-
1993
- 1993-03-17 GB GB9305508A patent/GB2265373B/en not_active Expired - Fee Related
- 1993-03-17 CA CA002091864A patent/CA2091864C/en not_active Expired - Fee Related
- 1993-03-22 CH CH857/93A patent/CH685053A5/en not_active IP Right Cessation
- 1993-03-22 KR KR1019930004429A patent/KR950014225B1/en not_active IP Right Cessation
- 1993-03-23 AU AU35377/93A patent/AU644318B2/en not_active Ceased
- 1993-03-23 DE DE4309365A patent/DE4309365C2/en not_active Expired - Fee Related
- 1993-03-24 TW TW084105451A patent/TW412514B/en not_active IP Right Cessation
- 1993-03-25 CN CN93104506A patent/CN1043228C/en not_active Expired - Fee Related
- 1993-03-25 ES ES09300617A patent/ES2059275B1/en not_active Expired - Fee Related
- 1993-03-25 IT ITTO930201A patent/IT1260629B/en active IP Right Grant
- 1993-03-25 FR FR9303438A patent/FR2689125B1/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| IT1260629B (en) | 1996-04-22 |
| AU644318B2 (en) | 1993-12-02 |
| CN1078232A (en) | 1993-11-10 |
| CH685053A5 (en) | 1995-03-15 |
| GB2265373A (en) | 1993-09-29 |
| KR950014225B1 (en) | 1995-11-23 |
| CA2091864A1 (en) | 1993-09-27 |
| DE4309365A1 (en) | 1993-11-04 |
| ES2059275A1 (en) | 1994-11-01 |
| DE4309365C2 (en) | 1995-10-19 |
| ES2059275B1 (en) | 1997-08-01 |
| TW412514B (en) | 2000-11-21 |
| FR2689125B1 (en) | 1996-10-18 |
| ITTO930201A1 (en) | 1994-09-25 |
| ITTO930201A0 (en) | 1993-03-25 |
| GB9305508D0 (en) | 1993-05-05 |
| FR2689125A1 (en) | 1993-10-01 |
| CN1043228C (en) | 1999-05-05 |
| AU3537793A (en) | 1993-09-30 |
| GB2265373B (en) | 1995-11-22 |
| KR930019610A (en) | 1993-10-18 |
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