CA1086329A - Unsaturated carboxylic acids - Google Patents
Unsaturated carboxylic acidsInfo
- Publication number
- CA1086329A CA1086329A CA261,226A CA261226A CA1086329A CA 1086329 A CA1086329 A CA 1086329A CA 261226 A CA261226 A CA 261226A CA 1086329 A CA1086329 A CA 1086329A
- Authority
- CA
- Canada
- Prior art keywords
- salt
- acid
- unsaturated carboxylic
- carboxylic acids
- formula
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
A B S T R A C T
Unsaturated carboxylic acids of formula:-
Unsaturated carboxylic acids of formula:-
Description
This invention relates to novel unsaturated carboxylic - acids which are valuable chemical intermediates and to a process for their preparation.
Accordingly the invention provides an unsaturated carboxylic acid of formula:~
Rl HOOC ~ CH - IC - CH CH2 I
X R
in which X represents a cyano group or an alkoxycarbonyl group, preferably of up to 6 carbon atoms; and Rl and R2 each represents an alkyl group, preferably of 1 to 4 carbon atoms, for example -methyl, or a salt of such an acid.
Particularly preferred unsaturated carboxylic acids are
Accordingly the invention provides an unsaturated carboxylic acid of formula:~
Rl HOOC ~ CH - IC - CH CH2 I
X R
in which X represents a cyano group or an alkoxycarbonyl group, preferably of up to 6 carbon atoms; and Rl and R2 each represents an alkyl group, preferably of 1 to 4 carbon atoms, for example -methyl, or a salt of such an acid.
Particularly preferred unsaturated carboxylic acids are
2-cyano-3,3-dimethyl-4-pentenoic acid, and 2-ethoxycarbonyl-3,3-dimethyl-4~pentenoic acid, together with their alkali metal salts, in particular the sodium salts.
The unsaturated carboxylic acids of formula I may -be prepared by a process which comprises thermally rearranging an enolate salt of an ester of formula:-11 ' ~
Cl = CH - CH20C - CH2X II
and liberating the acid from the salt thus formed by acidification.
, !
, . ~
1~863Zg `; - 3 -, The enolate salt is preferably an alkali or alkaline earth metal salt which may be formed by reacting the ester with the metal itself or a basic compound thereof for example a hydride. Particularly preferred is the sodium salt which may be formed conveniently by the reaction of the ester with sodium hydride.
The thermal rearrangement is preferably carried out at a temperature o~ 100-150C. An inert diluent for example a liquid aromatic compound such as toluene, xylene or chlorobenzene may also be present.
;The product of the thermal rearrangement is a salt of the acid of formula I, from which the acid may be liberated by acidifcation with a strong mineral acid such as hydrochloric acid, preferably under aqueous `~
conditions.
As mentioned above the compounds of formula I
are of interest as intermediates, especially for the preparation of pesticides. Thus the 2-cyano-4-pentenoic acid derivatives may be used in the preparation of esters of 2(2,2-dichlorovinyl)cyclopropanecarboxylic acids which possess interesting insecticidal properties, cf published Netherlands patent application 7307130.
The invention is illustrated further in the following Examples. The NMR spectra were measured at 60 MHz in deuterochloroform solution; the absorptions are auoted relative to a tetramethylsilane standard.
:, . . . . -: ,., -., , . ~ ,.
..
EXAMPLE I
A solution of 3-methyl-2-butenyl cyanoacetate (30 g, 0.2 mol) in a mixture of xylenes (b.p. 137-143C, 50 ml) was added with stirring over a period of 15 minutes to a suspension of sodium hydride (5.0 g, 0.2 mol) in the xylene mixture tl50 ml). The suspension of the enolate salt formed was diluted to 500 ml with further ~-xylene mixture and then stirred at 130C for 2.5 hours.
The suspension was then cooled to 22C and extracted l~ith water (3 x 150 ml). The aqueous extract was acidified to pH 1 with aqueous hydrochloric acid and the precipitate formed was extracted with diethyl ether (3 x 150 ml).
The extracts were dried (Na2SO4) and the ether was removed ;
under reduced pressure to give the desired 2-cyano-3,3-dimethyl-4-pentenoic acid as a viscous oil in 86% yield.
The NMR spectrum of the compound showed the following -absorptions: ~ ;
= 1.30 ppm (singlet >C(CH3)2) = 3.41 ppm (singlet, ~CHCN) ~ = 5.17 ppm (double doublet, =CH2) = 5.95 ppm (double doublet, -CH=) ~ .= 10.1 ppm (singlet, -COOH) EXAMPLE II
The procedure of Example I was repeated using toluene as diluent, a reaction temperature of 110C, and a reaction time of 3 hours. The yield of acid was 80%.
,, .
.,.. ;.. ,., . ... .. , ",....... ., . ~
1~)863Z9 EXAMPLE III
The procedure of Example I was repeated using sodium metal instead of sodium hydride. The yield of acid was 40%.
EXAMPLE IV
The procedure of Example I was repeated using chloro-benzene as diluent, and a reaction time of one hour.
The yield of acid was 68%.
EXAMPLE V
The procedure of Example I was repeated using 3-methyl-2-bu- ;
tenyl ethyl malonate as starting material. The product , ' was 2-ethoxycarbonyI-3,3-dimethyl-4-pentenoic acid which was formed as a viscous oil in 40% yield.
The NMR spectrum of this compound showed the following absorptions~
= 6.05 ppm (double doublet, HC=) = 5.05 ppm (double doublet, =CH2) '' = 4.2 ppm (quartet, -CH2-0) ~ = 3.3 ppm (singlet, - C ~C00 ) ~ = 1.28 ppm (singlet cn triplet, three CH3 groups) ,-.
~' .
~'
The unsaturated carboxylic acids of formula I may -be prepared by a process which comprises thermally rearranging an enolate salt of an ester of formula:-11 ' ~
Cl = CH - CH20C - CH2X II
and liberating the acid from the salt thus formed by acidification.
, !
, . ~
1~863Zg `; - 3 -, The enolate salt is preferably an alkali or alkaline earth metal salt which may be formed by reacting the ester with the metal itself or a basic compound thereof for example a hydride. Particularly preferred is the sodium salt which may be formed conveniently by the reaction of the ester with sodium hydride.
The thermal rearrangement is preferably carried out at a temperature o~ 100-150C. An inert diluent for example a liquid aromatic compound such as toluene, xylene or chlorobenzene may also be present.
;The product of the thermal rearrangement is a salt of the acid of formula I, from which the acid may be liberated by acidifcation with a strong mineral acid such as hydrochloric acid, preferably under aqueous `~
conditions.
As mentioned above the compounds of formula I
are of interest as intermediates, especially for the preparation of pesticides. Thus the 2-cyano-4-pentenoic acid derivatives may be used in the preparation of esters of 2(2,2-dichlorovinyl)cyclopropanecarboxylic acids which possess interesting insecticidal properties, cf published Netherlands patent application 7307130.
The invention is illustrated further in the following Examples. The NMR spectra were measured at 60 MHz in deuterochloroform solution; the absorptions are auoted relative to a tetramethylsilane standard.
:, . . . . -: ,., -., , . ~ ,.
..
EXAMPLE I
A solution of 3-methyl-2-butenyl cyanoacetate (30 g, 0.2 mol) in a mixture of xylenes (b.p. 137-143C, 50 ml) was added with stirring over a period of 15 minutes to a suspension of sodium hydride (5.0 g, 0.2 mol) in the xylene mixture tl50 ml). The suspension of the enolate salt formed was diluted to 500 ml with further ~-xylene mixture and then stirred at 130C for 2.5 hours.
The suspension was then cooled to 22C and extracted l~ith water (3 x 150 ml). The aqueous extract was acidified to pH 1 with aqueous hydrochloric acid and the precipitate formed was extracted with diethyl ether (3 x 150 ml).
The extracts were dried (Na2SO4) and the ether was removed ;
under reduced pressure to give the desired 2-cyano-3,3-dimethyl-4-pentenoic acid as a viscous oil in 86% yield.
The NMR spectrum of the compound showed the following -absorptions: ~ ;
= 1.30 ppm (singlet >C(CH3)2) = 3.41 ppm (singlet, ~CHCN) ~ = 5.17 ppm (double doublet, =CH2) = 5.95 ppm (double doublet, -CH=) ~ .= 10.1 ppm (singlet, -COOH) EXAMPLE II
The procedure of Example I was repeated using toluene as diluent, a reaction temperature of 110C, and a reaction time of 3 hours. The yield of acid was 80%.
,, .
.,.. ;.. ,., . ... .. , ",....... ., . ~
1~)863Z9 EXAMPLE III
The procedure of Example I was repeated using sodium metal instead of sodium hydride. The yield of acid was 40%.
EXAMPLE IV
The procedure of Example I was repeated using chloro-benzene as diluent, and a reaction time of one hour.
The yield of acid was 68%.
EXAMPLE V
The procedure of Example I was repeated using 3-methyl-2-bu- ;
tenyl ethyl malonate as starting material. The product , ' was 2-ethoxycarbonyI-3,3-dimethyl-4-pentenoic acid which was formed as a viscous oil in 40% yield.
The NMR spectrum of this compound showed the following absorptions~
= 6.05 ppm (double doublet, HC=) = 5.05 ppm (double doublet, =CH2) '' = 4.2 ppm (quartet, -CH2-0) ~ = 3.3 ppm (singlet, - C ~C00 ) ~ = 1.28 ppm (singlet cn triplet, three CH3 groups) ,-.
~' .
~'
Claims (13)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. Unsaturated carboxylic acids of formula:- I
in which X represents a cyano group or an alkoxycarbonyl group; and Rl and R2 each represents an alkyl group, or a salt of such an acid.
in which X represents a cyano group or an alkoxycarbonyl group; and Rl and R2 each represents an alkyl group, or a salt of such an acid.
2. Unsaturated carboxylic acids as claimed in claim 1 in which X
represents a cyano group or an alkoxycarbonyl group of up to 6 carbon atoms;
and R1 and R2 each represents an alkyl group of 1 to 4 carbon atoms.
represents a cyano group or an alkoxycarbonyl group of up to 6 carbon atoms;
and R1 and R2 each represents an alkyl group of 1 to 4 carbon atoms.
3. 2-Cyano-3,3-dimethyl-4-pentenoic acid, or the sodium salt thereof.
4. 2-Ethoxycarbonyl-3,3-dimethyl-4-pentenoic acid, or the sodium salt thereof.
5. A process for the preparation of unsaturated carboxylic acids as claimed in claim 1 which comprises thermally rearranging an enolate salt of an ester of formula:- II
and liberating the acid from the salt thus formed by acidification.
and liberating the acid from the salt thus formed by acidification.
6. A process as claimed in claim 5 in which the enolate salt is the sodium salt.
7. A process as claimed in claim 5 in which the thermal rearrangement is carried out at 100° to 150°C.
8. A process as claimed in claim 5, 6 or 7 in which the thermal rearrangement is carried out in the presence of a liquid aromatic compound.
9. An unsaturated carboxylic acid of formula;- I
in which X represents a cyano group or an alkoxycarbonyl group of up to 6 carbon atoms; and R1 and R2 each represents an alkyl group of 1 to 4 carbon atoms, or a salt of such an acid.
in which X represents a cyano group or an alkoxycarbonyl group of up to 6 carbon atoms; and R1 and R2 each represents an alkyl group of 1 to 4 carbon atoms, or a salt of such an acid.
10. A process for the preparation of an unsaturated carboxylic acid as claimed in claim 9 which comprises thermally rearranging an enolate salt of an ester of formula:- II
and liberating the acid from the salt thus formed by acidification.
and liberating the acid from the salt thus formed by acidification.
11. A process as claimed in claim 10 in which the enolate salt is the sodium salt.
12. A process as claimed in claim 10 in which the thermal rearrangement is carried out at 100° to 150°C.
13. A process as claimed in claim 10, 11 or 12 in which the thermal rearrangement is carried out in the presence of a liquid aromatic compound.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB45155/75 | 1975-10-31 | ||
| GB45155/75A GB1556999A (en) | 1975-10-31 | 1975-10-31 | Unsaturated carboxylic acids |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1086329A true CA1086329A (en) | 1980-09-23 |
Family
ID=10436104
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA261,226A Expired CA1086329A (en) | 1975-10-31 | 1976-09-14 | Unsaturated carboxylic acids |
Country Status (19)
| Country | Link |
|---|---|
| JP (1) | JPS602296B2 (en) |
| AU (1) | AU502376B2 (en) |
| BR (1) | BR7607252A (en) |
| CA (1) | CA1086329A (en) |
| CH (1) | CH624380A5 (en) |
| DD (1) | DD127238A5 (en) |
| DE (1) | DE2649711C2 (en) |
| DK (1) | DK155001C (en) |
| ES (1) | ES452860A1 (en) |
| FR (1) | FR2329649A1 (en) |
| GB (1) | GB1556999A (en) |
| IL (1) | IL50795A (en) |
| IT (1) | IT1075871B (en) |
| MX (1) | MX3822E (en) |
| NL (1) | NL187205C (en) |
| SE (1) | SE7612068L (en) |
| SU (1) | SU668591A3 (en) |
| TR (1) | TR19157A (en) |
| ZA (1) | ZA766490B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA1128958A (en) * | 1977-09-19 | 1982-08-03 | Johannes L.M. Syrier | Preparation of an alkenyl cyanoacetate |
| CA1182469A (en) * | 1981-12-11 | 1985-02-12 | William D. Emmons | Esters of michael addition homopolymers of acrylic acid |
| IL111484A (en) * | 1993-11-03 | 2001-06-14 | Commw Scient Ind Res Org | Polymerization process using allylic chain transfer agents for molecular weight control, the polymers obtained thereby and certain novel allylic compounds |
| AU688403B2 (en) * | 1993-11-03 | 1998-03-12 | Commonwealth Scientific And Industrial Research Organisation | Allylic chain transfer agents |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2326077C2 (en) * | 1972-05-25 | 1985-12-12 | National Research Development Corp., London | Unsaturated cyclopropanecarboxylic acids and their derivatives, their preparation and insecticides containing them |
-
1975
- 1975-10-31 GB GB45155/75A patent/GB1556999A/en not_active Expired
-
1976
- 1976-09-14 CA CA261,226A patent/CA1086329A/en not_active Expired
- 1976-10-27 TR TR19157A patent/TR19157A/en unknown
- 1976-10-28 NL NLAANVRAGE7611939,A patent/NL187205C/en not_active IP Right Cessation
- 1976-10-29 IL IL50795A patent/IL50795A/en unknown
- 1976-10-29 FR FR7632778A patent/FR2329649A1/en active Granted
- 1976-10-29 ES ES452860A patent/ES452860A1/en not_active Expired
- 1976-10-29 BR BR7607252A patent/BR7607252A/en unknown
- 1976-10-29 SU SU762415403A patent/SU668591A3/en active
- 1976-10-29 DK DK492576A patent/DK155001C/en not_active IP Right Cessation
- 1976-10-29 AU AU19145/76A patent/AU502376B2/en not_active Expired
- 1976-10-29 SE SE7612068A patent/SE7612068L/en unknown
- 1976-10-29 MX MX765034U patent/MX3822E/en unknown
- 1976-10-29 ZA ZA766490A patent/ZA766490B/en unknown
- 1976-10-29 DD DD195534A patent/DD127238A5/xx unknown
- 1976-10-29 CH CH1370076A patent/CH624380A5/en not_active IP Right Cessation
- 1976-10-29 DE DE2649711A patent/DE2649711C2/en not_active Expired
- 1976-10-29 IT IT28901/76A patent/IT1075871B/en active
- 1976-10-29 JP JP51129567A patent/JPS602296B2/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| GB1556999A (en) | 1979-12-05 |
| NL187205C (en) | 1991-07-01 |
| JPS602296B2 (en) | 1985-01-21 |
| IL50795A0 (en) | 1976-12-31 |
| DE2649711C2 (en) | 1985-01-10 |
| DE2649711A1 (en) | 1977-05-05 |
| IL50795A (en) | 1980-02-29 |
| TR19157A (en) | 1978-06-01 |
| DK155001B (en) | 1989-01-23 |
| NL187205B (en) | 1991-02-01 |
| DD127238A5 (en) | 1977-09-14 |
| AU1914576A (en) | 1978-05-04 |
| BR7607252A (en) | 1977-09-13 |
| AU502376B2 (en) | 1979-07-26 |
| JPS5257118A (en) | 1977-05-11 |
| CH624380A5 (en) | 1981-07-31 |
| MX3822E (en) | 1981-07-31 |
| FR2329649A1 (en) | 1977-05-27 |
| ZA766490B (en) | 1977-10-26 |
| SE7612068L (en) | 1977-05-01 |
| ES452860A1 (en) | 1977-10-16 |
| IT1075871B (en) | 1985-04-22 |
| FR2329649B1 (en) | 1979-09-21 |
| SU668591A3 (en) | 1979-06-15 |
| NL7611939A (en) | 1977-05-03 |
| DK155001C (en) | 1989-06-05 |
| DK492576A (en) | 1977-05-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR100758620B1 (en) | 4-Alkoxy cyclohexane-1 amino carboxylic acid esters and method for the production thereof | |
| CA1086329A (en) | Unsaturated carboxylic acids | |
| SU797570A3 (en) | Method of preparing cyclohexane carboxylic acid derivatives | |
| JPH10507167A (en) | Substituted biphenyl oxazoline | |
| US5942623A (en) | Process for the preparation of 2-(pyrid-2-yloxymethyl)phenylacetates as pesticide intermediates | |
| US6657074B1 (en) | Process for the preparation of acylated 1,3-dicarbonyl compounds | |
| US4359428A (en) | Preparation of fluorinated anthranilic acid and anthranilonitrile | |
| EP0007652B1 (en) | Derivatives of 3-azabicyclo(3.1.0)hexane and a process for their preparation | |
| US4259263A (en) | Halogenated hydrocarbons and a method for their preparation | |
| US4537901A (en) | Insecticidal carbamates | |
| CN115466208B (en) | Method for purifying spirotetramat cis-intermediate | |
| US4446077A (en) | Substituted-cyclopropyl sulfones | |
| DD255730A5 (en) | PROCESS FOR THE PREPARATION OF NEW ARYLOXY-PHENOXYACYL-MALONSAEUREESTER DERIVATIVES | |
| US4211720A (en) | Preparation of cyano-substituted cyclopropane derivatives | |
| US3988328A (en) | 5-Amino-2,3,7,8-tetrathiaalkane-1,9-dioic acids, esters and salts | |
| US5068343A (en) | 4-substituted 5-chloro-2-hydrazinothiazoles | |
| US4469891A (en) | Substituted-cyclopropyl sulfones | |
| US4377531A (en) | Method for the alkylation of phenylacetonitriles | |
| JPS6344746B2 (en) | ||
| JP2932207B2 (en) | Phenoxyacetic acid derivative and plant growth regulator containing the same as active ingredient | |
| US4792606A (en) | Process for the preparation of dimeric aromatic acyl cyanides | |
| RU1679761C (en) | 1s,3r - 2,2 - dimethyl -3(2-methyl -2- oxypropyl) -cyclopropanecarbonitrile as intermediate compound in synthesis of pyrethroid insecticide of deltametrine and method for production of intermediate compound | |
| RU2053225C1 (en) | Method for production of n,n-di(cyclohexyl)amine of sorbic acid | |
| JP3280977B2 (en) | Method for producing chlorine-substituted olefin compound | |
| KR790001357B1 (en) | Process for the preparation of new nitrodiphenyl ethers |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MKEX | Expiry |