CA1094103A - 2-cyanohexanoic acid derivatives - Google Patents
2-cyanohexanoic acid derivativesInfo
- Publication number
- CA1094103A CA1094103A CA278,776A CA278776A CA1094103A CA 1094103 A CA1094103 A CA 1094103A CA 278776 A CA278776 A CA 278776A CA 1094103 A CA1094103 A CA 1094103A
- Authority
- CA
- Canada
- Prior art keywords
- general formula
- process according
- compound
- catalyst
- chloride
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C255/00—Carboxylic acid nitriles
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
A B S T R A C T
2-Cyanohexanoic acid derivatives having the general formula:
2-Cyanohexanoic acid derivatives having the general formula:
Description
This invention relates to 2-cyanohexanoic acid derivatives which are useful intermediates in the preparation of insecticidally-active com-pounds.
Accordingly the invention provides 2-cyanohexanoic acid derivatives of the general formula:
X Y
~ C ~" CH - CH2 - CHal2 (I) R CHC(O)OH
C~
wherein X and Y each represent a chlorine or bromine atom, Hal represents a fluorine, chlorine or bromine atom and Rl and R2 each independently represent an alkyl group of one to four carbon atoms or a salt thereof, preferably an alkali metal or ammonium salt.
A particularly preferred novel compound is ~,6,6,6-tetrachloro-2-cyano-3,3-dimethylhexanoic acid, together with its alkali metal and ammonium salts. These compounds are useful intermediates in the preparation of 2-(2,2-dichlorovinyl)-3,3-dimethylcyclopropar.ecarboxylic acid, certain esters of which possess insecticidal activity.
The invention also relates to a process for the preparation of the
Accordingly the invention provides 2-cyanohexanoic acid derivatives of the general formula:
X Y
~ C ~" CH - CH2 - CHal2 (I) R CHC(O)OH
C~
wherein X and Y each represent a chlorine or bromine atom, Hal represents a fluorine, chlorine or bromine atom and Rl and R2 each independently represent an alkyl group of one to four carbon atoms or a salt thereof, preferably an alkali metal or ammonium salt.
A particularly preferred novel compound is ~,6,6,6-tetrachloro-2-cyano-3,3-dimethylhexanoic acid, together with its alkali metal and ammonium salts. These compounds are useful intermediates in the preparation of 2-(2,2-dichlorovinyl)-3,3-dimethylcyclopropar.ecarboxylic acid, certain esters of which possess insecticidal activity.
The invention also relates to a process for the preparation of the
2-cyanohexanoic acid derivatives of the general formula I, which comprises reacting a pentenoic acid compound of the general formula:
R / CH = CH2 C (II) R2 / CHC(O)OH
C~
wherein R and R have the same meaning as in the general formula I, with a tetrahalomethane compound of the general formula CHal2XY (III) wherein Hal, X and Y have the same meaning as in the general formula I, in the presence of a catalyst, preferably a compound of copper or iron, and a solvent capable of dissolving the reactants and the catalyst.
4~ql3 Rl and R2 in the general formula II preferably represent methyl groups. Carbon tetrachloride is the preferred compound of the general for-mula III.
Suitable solvents for the reaction are polar solvents, for example, acetonitrile, methylene chloride, benzene and tetrahalomethane compounds of the general formula III; in order to use te-trahalomethane compound as a sol-vent in the process according to the invention it will have to be used in excess over the amount required as reactant. Mixtures of solvents may also be used.
Examples of suitable catalysts are ferric, cupric or ruthenium chloride, naphthenate, stearate or acetylace-tonate. Very good results have been obtained with ferric or cupric chloride.
The process is preferably conducted in the presence of a solubil-izer for the catalyst and/or reducing agent. Examples of compounds which enhance the solubility of the ca-talyst in the solvent are alkylammonium halides, for example diethylammonium chloride, di-n-butylammonium bromide, diethylpropylammonium chloride and trioctylammonium chloride. Examples of reducing agents are benzoin, hydroquinone, aldehydes, stannous chloride and alkali metal sulphites.
The molar ratios of solubilizer to compound of the general formula II and of catalyst to compound of the general formula II may vary within wide limits. ~ery good yields of compounds of the general formula I are usually obtained when these molar ratios are between 0.001 and 0.2.
An attractive fea-ture of theprocess according to the inven-tion is that the carboxylic acids of the general formulae I and II do not undergo de-carboxylation reactions to any appreciable extent.
The following Examples further illustrate the invention.
EXAMPLE I
A 250 ml glass autoclave was charged with 0.3 mol of 2-cyano-3,3-dimethyl_4-pentenoic acid, 0.9 mol of carbon tetrachloride, o.6 mol of acetonitrile, 0.03 mol of ferric chloride, 6H2o, 0.03 mol of benzoin and 0.018 mol oP diethylammonium chloride. The contents of the au-toclave were stirred with a turbine stirrer (620 revolutions per minute), first for two hours at 105 C and then for 18 hours at 75C. Subsequently, the con-tents of the flask were cooled to 22 C, 150 ml of diethyl ether was added and the so-lution formed was washed four times with 50 ml portions of lO~w aqueous hy-drochlorie acid to remove most of the iron salt. Then, the organic phase was contacted with a 50 ml bed of grains of silica gel for further removal of iron salt. The organic phase thus obtained was boiled down at 30C and 12 mm Hg. The NMR spec-trum of the residue showed that no starting acid and no deearboxylation produets were present. The yield of 4,6,6,6-tetrachloro-2-e~ano-3,3-dimethylhexanoic acid was more than 85%, calcula-ted on starting acid.
The NMR spectrum of the product acid measured at 60 MHz in deutero-chloroform solution showed the following absorptions relative to a tetra-methylsilane standard. On the basis of -the spectrum it was established that the acid consisted of two geometric isomers, configuration 1 and configura-tion 2.
~, ppm2 _ configuration CH2 lH doublet 3.42 3.18 CH2 lH single-t 4.23 4.33 CHCl lH quarte-t 4.57 4.90 HCCN lH doublet 3.58 3.58 CH3 3H singlet 1.40 1.40 CH3 3X singlet 1.53 1.53 COOH lH singlet 8.92 8.92 EXAMPLE II
The experiment of Example I was repeated, but 0.1 mol o-P 2-cyano-303,3-dimethyl_4-pentenoic acid, 0.01 mol of ferric chloride 6 H20, 0.01 mol of benzoin and 0. oo6 mol of diethylammonium chloride were used. The contents of the autoclave were stirred ~or 20 hours at 98 C. The yield of 4,6,6,6-tetrachloro-2-cyano-3,3-dimethylhexanoic acid was more than 90%, calculated ., on starting acid.
_ 4a -,
R / CH = CH2 C (II) R2 / CHC(O)OH
C~
wherein R and R have the same meaning as in the general formula I, with a tetrahalomethane compound of the general formula CHal2XY (III) wherein Hal, X and Y have the same meaning as in the general formula I, in the presence of a catalyst, preferably a compound of copper or iron, and a solvent capable of dissolving the reactants and the catalyst.
4~ql3 Rl and R2 in the general formula II preferably represent methyl groups. Carbon tetrachloride is the preferred compound of the general for-mula III.
Suitable solvents for the reaction are polar solvents, for example, acetonitrile, methylene chloride, benzene and tetrahalomethane compounds of the general formula III; in order to use te-trahalomethane compound as a sol-vent in the process according to the invention it will have to be used in excess over the amount required as reactant. Mixtures of solvents may also be used.
Examples of suitable catalysts are ferric, cupric or ruthenium chloride, naphthenate, stearate or acetylace-tonate. Very good results have been obtained with ferric or cupric chloride.
The process is preferably conducted in the presence of a solubil-izer for the catalyst and/or reducing agent. Examples of compounds which enhance the solubility of the ca-talyst in the solvent are alkylammonium halides, for example diethylammonium chloride, di-n-butylammonium bromide, diethylpropylammonium chloride and trioctylammonium chloride. Examples of reducing agents are benzoin, hydroquinone, aldehydes, stannous chloride and alkali metal sulphites.
The molar ratios of solubilizer to compound of the general formula II and of catalyst to compound of the general formula II may vary within wide limits. ~ery good yields of compounds of the general formula I are usually obtained when these molar ratios are between 0.001 and 0.2.
An attractive fea-ture of theprocess according to the inven-tion is that the carboxylic acids of the general formulae I and II do not undergo de-carboxylation reactions to any appreciable extent.
The following Examples further illustrate the invention.
EXAMPLE I
A 250 ml glass autoclave was charged with 0.3 mol of 2-cyano-3,3-dimethyl_4-pentenoic acid, 0.9 mol of carbon tetrachloride, o.6 mol of acetonitrile, 0.03 mol of ferric chloride, 6H2o, 0.03 mol of benzoin and 0.018 mol oP diethylammonium chloride. The contents of the au-toclave were stirred with a turbine stirrer (620 revolutions per minute), first for two hours at 105 C and then for 18 hours at 75C. Subsequently, the con-tents of the flask were cooled to 22 C, 150 ml of diethyl ether was added and the so-lution formed was washed four times with 50 ml portions of lO~w aqueous hy-drochlorie acid to remove most of the iron salt. Then, the organic phase was contacted with a 50 ml bed of grains of silica gel for further removal of iron salt. The organic phase thus obtained was boiled down at 30C and 12 mm Hg. The NMR spec-trum of the residue showed that no starting acid and no deearboxylation produets were present. The yield of 4,6,6,6-tetrachloro-2-e~ano-3,3-dimethylhexanoic acid was more than 85%, calcula-ted on starting acid.
The NMR spectrum of the product acid measured at 60 MHz in deutero-chloroform solution showed the following absorptions relative to a tetra-methylsilane standard. On the basis of -the spectrum it was established that the acid consisted of two geometric isomers, configuration 1 and configura-tion 2.
~, ppm2 _ configuration CH2 lH doublet 3.42 3.18 CH2 lH single-t 4.23 4.33 CHCl lH quarte-t 4.57 4.90 HCCN lH doublet 3.58 3.58 CH3 3H singlet 1.40 1.40 CH3 3X singlet 1.53 1.53 COOH lH singlet 8.92 8.92 EXAMPLE II
The experiment of Example I was repeated, but 0.1 mol o-P 2-cyano-303,3-dimethyl_4-pentenoic acid, 0.01 mol of ferric chloride 6 H20, 0.01 mol of benzoin and 0. oo6 mol of diethylammonium chloride were used. The contents of the autoclave were stirred ~or 20 hours at 98 C. The yield of 4,6,6,6-tetrachloro-2-cyano-3,3-dimethylhexanoic acid was more than 90%, calculated ., on starting acid.
_ 4a -,
Claims (11)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. 2-Cyanohexanoic acid derivatives having the general formula:
(I) wherein X and Y each represent a chlorine or bromine atom, Hal represents a fluorine, chlorine or bromine atom and R1 and R2 each independently represent an alkyl group of one to four carbon atoms, or a salt thereof.
(I) wherein X and Y each represent a chlorine or bromine atom, Hal represents a fluorine, chlorine or bromine atom and R1 and R2 each independently represent an alkyl group of one to four carbon atoms, or a salt thereof.
2. The compound 4,6,6,6-tetrachloro-2-cyano-3,3-dimethylhexanoic acid and its alkali metal and ammonium salts.
3. A process for the preparation of 2-cyanohexanoic acid derivatives of the general formula I, which comprises reacting a pentenoic acid compound of the general formula:
(II) wherein R1 and R2 have the same meaning as in the general formula I, with a tetrahalomethane compound of the general formula:
CHal2XY (III) wherein Hal, X and Y have the same meaning as in the general formula I, in the presence of a catalyst and in an inert solvent capable of dissolving the reactants and the catalyst.
(II) wherein R1 and R2 have the same meaning as in the general formula I, with a tetrahalomethane compound of the general formula:
CHal2XY (III) wherein Hal, X and Y have the same meaning as in the general formula I, in the presence of a catalyst and in an inert solvent capable of dissolving the reactants and the catalyst.
4. A process according to claim 3 wherein the tetrahalomethane compound of general formula III is carbon tetrachloride.
5. A process according to claim 3 wherein the solvent is a polar solvent.
6. A process according to claim 5 wherein the polar solvent is acetonitrile, methylene chloride, benzene, or a tetrahalomethane compound of general formula III.
7. A process according to claim 3, 4 or 5 wherein the catalyst is ferric, cupric or ruthenium chloride, naphthenate, stearate or acetyl-acetonate.
8. A process according to claim 3, 4 or 5 wherein the catalyst is ferric or cupric chloride.
9. A process according to claim 3 wherein the reaction is carried out in the presence of a solubilizer for the catalyst and/or a reducing agent.
10. A process according to claim 9 wherein the solubilizer is an alkylammonium halide.
11. A process according to claim 9 wherein the reducing agent is benzoin, hydroquinone, an aldehyde, stannous chloride or an alkali metal sulphite.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GB28262/76 | 1976-07-07 | ||
GB2826276A GB1580204A (en) | 1976-07-07 | 1976-07-07 | 2-cyanohexanoic acid derivatives |
Publications (1)
Publication Number | Publication Date |
---|---|
CA1094103A true CA1094103A (en) | 1981-01-20 |
Family
ID=10272872
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CA278,776A Expired CA1094103A (en) | 1976-07-07 | 1977-05-19 | 2-cyanohexanoic acid derivatives |
Country Status (12)
Country | Link |
---|---|
JP (1) | JPS537622A (en) |
BE (1) | BE856490A (en) |
BR (1) | BR7704406A (en) |
CA (1) | CA1094103A (en) |
CH (1) | CH628878A5 (en) |
DE (1) | DE2730359A1 (en) |
DK (1) | DK159265C (en) |
FR (1) | FR2357534A1 (en) |
GB (1) | GB1580204A (en) |
IT (1) | IT1081510B (en) |
MX (1) | MX4912E (en) |
NL (1) | NL7707416A (en) |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CA1115730A (en) * | 1978-02-20 | 1982-01-05 | Roger A. Sheldon | Preparation of 2-cyanohexanoic acid derivatives and the derivatives prepared by the process |
JP4958428B2 (en) * | 2005-11-25 | 2012-06-20 | Fdkエナジー株式会社 | Alkaline battery |
Family Cites Families (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
IN142702B (en) * | 1974-09-10 | 1977-08-20 | Sagami Chem Res | |
JPS5159839A (en) * | 1974-10-23 | 1976-05-25 | Sankyo Co | SHIKUROPUROPANKARUBONSANJUDOTAINO SEIZOHO |
LU73349A1 (en) * | 1975-09-08 | 1976-04-13 |
-
1976
- 1976-07-07 GB GB2826276A patent/GB1580204A/en not_active Expired
-
1977
- 1977-05-19 CA CA278,776A patent/CA1094103A/en not_active Expired
- 1977-07-05 DE DE19772730359 patent/DE2730359A1/en not_active Withdrawn
- 1977-07-05 MX MX587477U patent/MX4912E/en unknown
- 1977-07-05 JP JP7957777A patent/JPS537622A/en active Granted
- 1977-07-05 DK DK302577A patent/DK159265C/en not_active IP Right Cessation
- 1977-07-05 FR FR7720605A patent/FR2357534A1/en active Granted
- 1977-07-05 IT IT2541077A patent/IT1081510B/en active
- 1977-07-05 CH CH825077A patent/CH628878A5/en not_active IP Right Cessation
- 1977-07-05 BR BR7704406A patent/BR7704406A/en unknown
- 1977-07-05 NL NL7707416A patent/NL7707416A/en not_active Application Discontinuation
- 1977-07-05 BE BE179092A patent/BE856490A/en not_active IP Right Cessation
Also Published As
Publication number | Publication date |
---|---|
DK302577A (en) | 1978-01-08 |
DK159265B (en) | 1990-09-24 |
BR7704406A (en) | 1978-05-02 |
BE856490A (en) | 1978-01-05 |
JPS537622A (en) | 1978-01-24 |
GB1580204A (en) | 1980-11-26 |
FR2357534B1 (en) | 1978-11-03 |
DE2730359A1 (en) | 1978-01-12 |
MX4912E (en) | 1983-01-03 |
JPS616814B2 (en) | 1986-03-01 |
NL7707416A (en) | 1978-01-10 |
DK159265C (en) | 1991-02-18 |
FR2357534A1 (en) | 1978-02-03 |
IT1081510B (en) | 1985-05-21 |
CH628878A5 (en) | 1982-03-31 |
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Legal Events
Date | Code | Title | Description |
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