CA1123007A - Preparation of esters - Google Patents
Preparation of estersInfo
- Publication number
- CA1123007A CA1123007A CA279,044A CA279044A CA1123007A CA 1123007 A CA1123007 A CA 1123007A CA 279044 A CA279044 A CA 279044A CA 1123007 A CA1123007 A CA 1123007A
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- general formula
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- atom
- alkali metal
- hydrocarbon
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C255/00—Carboxylic acid nitriles
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- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
ABSTRACT
A process for the preparation of an ester of cyanoacetic acid hav-ing the following general formula:
(I) (wherein R represents an aliphatic or cycloaliphatic hydrocarbyl group), which comprises reacting an alkali metal carboxylate of general formula:
(II) (wherein M represents an alkali metal atom) with a hydrocarbyl halide of general formula:
R - Hal (III) (wherein R has the meaning hereinbefore defined and Hal is a halogen atom :
having an atomic number of at least 17) in the presence of a phase transfer catalyst and an organic solvent. Esters of cyanoacetic acid are valuable chemical intermediates, especially in the preparation of pesticides such as esters of 2-(2,2-dichlorovinyl)-cyclopropanecarboxylic acids.
A process for the preparation of an ester of cyanoacetic acid hav-ing the following general formula:
(I) (wherein R represents an aliphatic or cycloaliphatic hydrocarbyl group), which comprises reacting an alkali metal carboxylate of general formula:
(II) (wherein M represents an alkali metal atom) with a hydrocarbyl halide of general formula:
R - Hal (III) (wherein R has the meaning hereinbefore defined and Hal is a halogen atom :
having an atomic number of at least 17) in the presence of a phase transfer catalyst and an organic solvent. Esters of cyanoacetic acid are valuable chemical intermediates, especially in the preparation of pesticides such as esters of 2-(2,2-dichlorovinyl)-cyclopropanecarboxylic acids.
Description
~ ~3~37 This invention relates to a process for the preparation of an ester of cyanoacetic acid which is a valuable chemical intermediate, espe-cially in the preparation of pesticides such as esters of 2-(2,2-dichloro-vinyl)-cyclopropanecarboxylic acids.
The present invention provides a process for the preparation of an ester of cyanoacetic acid having the following general formula:
R - C = C - C - O - C - CH - CN
Il ~wherein R , R , R3, R and R each represent a hydrogen atom or an alkyl group of l to 4 carbon atoms), which comprises reacting an alkali metal carboxylate of general formula:
qO
(wherein M represents an alkali metal atom) with an alkyl halide of general formula:
R - l = C - C - Hal III
Il (wherein Rl, R2, R , R4 and R have the meanings herei.nbefore defined and Hal is a halogen atom having an atomic number of at least 17) at a tempera-ture in the range 20 to 100C and in the presence of an organic solvent and a quaternary onium salt phase transfer catalyst of the general formula:
~7 - X - R~ Y- IV
L l8 l wherein X represents a nitrogen, phosphorus or arsenic atom, R , R , R and R9 each an alkyl, aralkyl, alkaryl or aryl group and Y a monovalent ion, or a ternary sulphonium salt of the general formula:
RlO +
R - S - R Y V
wh r in R10 Rll d R12 h resents an alk~ ~1 group and Y a monovalent
The present invention provides a process for the preparation of an ester of cyanoacetic acid having the following general formula:
R - C = C - C - O - C - CH - CN
Il ~wherein R , R , R3, R and R each represent a hydrogen atom or an alkyl group of l to 4 carbon atoms), which comprises reacting an alkali metal carboxylate of general formula:
qO
(wherein M represents an alkali metal atom) with an alkyl halide of general formula:
R - l = C - C - Hal III
Il (wherein Rl, R2, R , R4 and R have the meanings herei.nbefore defined and Hal is a halogen atom having an atomic number of at least 17) at a tempera-ture in the range 20 to 100C and in the presence of an organic solvent and a quaternary onium salt phase transfer catalyst of the general formula:
~7 - X - R~ Y- IV
L l8 l wherein X represents a nitrogen, phosphorus or arsenic atom, R , R , R and R9 each an alkyl, aralkyl, alkaryl or aryl group and Y a monovalent ion, or a ternary sulphonium salt of the general formula:
RlO +
R - S - R Y V
wh r in R10 Rll d R12 h resents an alk~ ~1 group and Y a monovalent
- 2 -~.~ 2~
ion.
In the reaction of an alkali metal carboxylate of the general formula II with a halide of the general Eormula III in the presence of a phase transfer catalyst, an undesirable side-reaction may take place with the EormatioTI oE compouncls of the general formula:
R3 R4 R5 o R
2 ~
R - C = C - C - 0 - C - CH - CN
wherein R , R , R , R4 and R5 have the same meaning as in the general formula I; the latter reaction tends to occur at temperatures above 100C
and is clearly undesirable because it decreases the yield of the desired compounds of the general formula I. An attractive feature of the process according to the invention is that it allows the use of a relatively low reaction temperature, for example between 20 and 100C, and thereby avoids the production of substantial quantities of unwanted by-products; a low yield of by-product IV is particularly noticeable when the organic solvent is a halogenated hydrocarbon, especially a chlorinated hydrocarbon of 1 to 4 carbon atoms, e.g. tetrachlorome~hane, chloroform, dichloromethane and perchloroethylene, or an aromatic hydrocarbon especially an alkylbenzene, e.g. toluene or a xylene or mixture of xylenes. Carbon tetrachloride and xylene have shown excellent properties in this respect.
The halides of the general formula III may be primary, secondary or tertiary. Halides of the general formula III are generally stable and do not decompose at a temperature below 100C. Preferably R2, R3 and R4 in the general formula III, each represent a hydrogen atom or a methyl group and Rl and R represent hydrogen atoms. The preferred starting compound of the general formula III is l-chloro-3-methyl-2-butene.
In the alkali metal carboxylate of general formula II the alkali metal atom M may be lithium, sodium, potassium, rubidium or cesium but, for economic reasons, sodium or potassium are generally preferred. Very good results have been obtained with potassium cyanoacetate.
-s - 3 , ~ . .. ,-~
The pha~e transfer cataly3t may be an~ reagent ~hich i8 capable of aocel~ratingjinterphase reactions taking place in two-;?hase systems and may take the form of an onium salt, a macrocyolic polyether, or a ~urface-active agent.
~he phaae transfer catalyst may be an onium ~alt, particularly a quaternary onium salt of the general formula:-R6 I t ~7 - X - R~ ~ Y~
~8 J
wherein ~ represents a nitrogen, phosphorus or arsenic atom, R~, R7, R8 and R9 each an alkyl, aralkyl, alkaryl or aryl group and Y a monovalent ion, e.g. a halide such as chloride, bromide or iodide, or an alkyl~ulphate such as methylsulph2te or ethylsulphate or a sulphonium ~alt of the general formula:-1-- 10 - ' ¦R11 _ S _ R12 I y wherein R10, R11 and R12 each represent an ~lkyl group and Y a mono~alent isn, e.g. a halide such as chloride, bro~ide or iodide, or an alkyl~ulphate such a~ methyl~ulp~nate or ethylflulphate. Preferab~y the alkyl group~ contain 1 to 18 carbon atoms and the aralkyl and alkaryl groups contain up to 10 carbon atoms, the aryl gTOUp iB preferably phenyl.
Esamples of ~uitable onium ~alts are tetra-n~butylammonium bromide, tetra~n-butylammonium ¢hloride 9 methyltrioctyl-ammonium chloride, m~thyltri-(2-methylheptyl)ammonium c~loride, methyltri-2-methylphe~yl~ammonium chloride, tetramethyl-phosp~nium iodide, tetra-n-butylphosphonium bromide, ethyl-2-methylpentyl-2-methylundecylsulphonium ethyl~ulphate, ~eth~l-triphenylarsonium iodide, ethyl~2~mathylpsntadecyl-2-methyl-undecyl-sulphonium ethyls~lphate, methyldinonyl-aulphonium methylsulphate and n-hexadecyldimethyl~ulphonium iodide. V~ry good re~ults have been obtalned with quaternary a~onium compounds~
r~hs onium ~alt may be a hydroxide or a ~alt and oan be employed a~ the functional portion of a strongly-basic anion e~chang~ resin having a structural portion (poly~er matrix) and a funct~onal portion (ion-active group). Of ~pecial importance ~re polystyrene resins, such as copolymers of aromatic mono~inyl compounds and aromatic polyvinyl compo~nds, particularl~ styrene/divinylbenzene copolymers.
The functional portion i~ a quaternary ammonium, phosphonium or ar~onium group. Examples of ~trongly-ba~ic anion exchange resin~ which may be employed are tho~e derived from tri~ethyl-amine (such as thè producta known under the trade names of "Amberlite IRA-400", "Amberlite IRA-401", "Amberlite IRA-402", "~mberlite IRA~900", "Duolite A~101-D"~ "Duolite ES-111~, '1Dowex 1", "Dowex 11n, I'Dowex 21E" and "Ionac A-450n), and those deri~ed from dimethylethanol amine (such as the products known under the trade names of "Amberlite IRA-410N, "Amberlite IR~-911", "Dowex 2N, "Duolite A-102-D", "Ionac A-542" and ~Ionac A-550"). Very good results ha~e been obtained with tho~e derived from trimethylamine.
Other suitable phase tran~fer catalyst~ are maorocycl~c polyethers kno~n as "crown ether~". The~e compounds, together with their preparation, are described in the literature, for example in ~etrahedron ~etters No. 18(1972~ pages 1793-1796, and are commonly designated by reference to the total numbar of atom~ forming the mscrocyclic ring together with the number of o~ygen atoms in that ring. Thus the macrocyclic polyether whos2 formal chemical name i8 1, 4,7,10,13,16-hexao~acyclooctadecane i~ de~ignated as "18-crown-6~. Other axamples of ~uitable macrocyclic polyethers are 3,4-benzo-1,S 9 9,12,15,18,21-heptacxacyclotrico~-3-ene and3,~-ben~-1,6,9,12-tetra-o~acyclotetradec-3-ene. 18-Crown-6 i~ particularly ~uitable.
Other ~uitable pha~e transfer catalysts are ~urface-acti~'e agent~. A "surface-acti~e agent" i~ defined as in Eirk-Othmer, "Encyclopedia of Chemi¢al ~echnology", second edition, ~olume 19(1969) paga 508: "An organic compound that encompasses in the ~ame molecule two dis~imilar structural group~, one bei~g water soluble and one being water-insoluble".
The surface-active agent i8 preferably non-ionic1 such a~
fJL~
a poly~(alkyle~eoxy) derivative formed by reacting a higher alcohol, alkylphenol or fatty acid with ethylene oxide or propylene o~ide. Suitable alcohols, alkylphenols or fatty acidc contain an alkyl group of 8-20 carbon atoms and the nuMber of alkyleneo~y units is in the i~ange of 1-50. ~
particularly ~uitable non-ionic surfa¢e-active agent (referred to in the examplec a~ "Dobanol 91-6n) ic formed from a C6-C
n-alkanol mlxture and contain~ an average of ~i~ ethyleneo~y units. The non-ionic surface-active agent may be an alkyl-benzene containing a straight alkyl group. Suitable alkyl-benz~ne~ contain an alkyl group of B-20 carbon atom~0 ~he molar ratio o~ the phaae transfer catalyct to the halide of the general formula III can va~y within wide limits, but iB ~uitably ~rom 1:5 to 1:5,000 and preferably from 1:20 to 1:200. The molar ratio of the alkali metal carbo~ylate of the general formula II to the halide of the general formula III can also var~ within wide limits, but i8 euitably from 1:0.75 to 1:1, the equimolar ratio being preferred.
The proces~ may suitably be carried out by stirrin~ ths ctartin~ compounds, the onium sslt and the organic solvent for periods of ~p to five hours at temperatures from 20 to 1 00C .
~he compound of the general form~la I may be i~olated from the reaction mixture by washing it with wat~r to remove the simultaneously formed alkali metal halide, drying the wa~hed mixture and fractionatlng the dried mixture.
Compo~nd~ generated by the proce~s according to the in~ention and ha~ing the following general fonmula are novel compound~ and, accordingly repre~ent another feature of the pre~ent inventlon:-R2 _ C = C - ~ - O - C - C~[2 wherein each o~ R1, R , R , R4 and R5 independently repre~ent a hydrogen atom or a hydrocarbyl group, eOg~ an alkyl group -~ ~3~637 !
of 1 to 4 carbon A~oms such as a methyl group. An example of such a novel compound i~ 3 methyl-2-butenyl cyanoacetate.
The following examplec illu~trste the proce~ according to the invention and the novel compounds produced therefrom.
EXANPLES I to VI
A ves~el was char~ed with 25 mmol of potassi~m cyanoaoetate, 25 mmol of 1-chloro-3 meth~l-2-butene, tetra-n-butylammonium chloride and 25 ml of a solvent. The content~ of the ve~sel were stlrred for a certain period. The mixture fo~med was wa~hed twioe with 10 ml of water, the wa~hed mixt~re wa~ -dried in the presence of anhydrous magnesium sulphate, the magnesium sulphate was remo~ed by filtration and the filtrate was boiled down. ~nal~is by means of ga~-~quid chromatograph~
showed that the residue consi~ted of 3-methyl-2-butonyl cyanoacQtate (x mmole) and 3-methyl-2-butenyl 2-cyano-5-meth~l-4-he~enoate, e~pressed in ~, were calculated a~ x ~ 2y ~ 100 and ~2y 2~ x 100, respectively. ~he yield of 3-methyl-2-butenyl cyanoacetate, expressed in ~, was calculated as conversion of 1-~hloro-3-meth~1-2-butene x gelectivitY to_~-meth~1-100 ?-buten~l cyanoacetate Six e~periments were conducted in the manner described above. The table shows the solvent~ used, the amounts of tetra-n-butyl-ammonium ¢hlorids employed, calculated on 1-chloro-3-meth~1-2-butene, the tempexature~, the reaction times and the result~.
,, ~, ,, ~, ~l ~, ,, ~, ~, . ..
o ~ 0, ,, 2~ ,1 ,1 ~ I o a~ 0 ~ ~ ~ 1~
.qa~ l n 0 0 ~ h I
~ ~ P o 1 11 :~ I ~ 1 11 I ~1 1 11 I P~ 1 11 I ~ 1 11 Q~
I ~ ~1 11 ,~1 1 01 11 hl U~ 01 11 O Gl I Gl ~ ~ 0 U~ ~ ~ 11 ~PI~XI 11 ~-.QI h~l 11 h I I o 11 11 .,~ I I C~ I I
P ~1 11 ~ ,C I 1 1 11 o ~1 o a~l 11 ~1)1 G ~1 0 ~ C`l U~ ~ ~ !!
~1 ~31 0 G~ 0 CO O~
0 11 h 01 11 U~ ~1 o ~1 11 h 'qO h a I cu C~l ~ CO O
G el 0~ 1 ~ I 1~
C~ o~ I 1 11 ~3 ~ I 11 o ~- ~ o o u~ 11 E~ f~ I 11 a Il ,~
~0 ! 1~
P o~ I ~1 ~
ON~-O !, ~
~ a ~
E~ ~ hI ~ ¦~
IC~ 01 11 ~
0 ~0 ~ ~ 11 _I V C~
l ~ ~,1 ~t 11 h ,1 ,, I 'I '~3 O O I ~ 1 H ~ p t-l il Z; I H H H P N
ll ~L~ 2~
The ~MR ~pectrum of ~-methyl-2~butenyl cyanoacetate measured at 60 MHz in deuterochloroform ~olution ~ho~ed the following abaorption~ relative to a tetramethylsilane standard: 1 o ~ 1.7-1.B ppm (two doubletc, two CH3) b = 5. 37 pp~ (multiplet = CH) o ~ 4.67 ppm (doublet, CH20~
o = 3.53 ppm (singlet, CH2CN)
ion.
In the reaction of an alkali metal carboxylate of the general formula II with a halide of the general Eormula III in the presence of a phase transfer catalyst, an undesirable side-reaction may take place with the EormatioTI oE compouncls of the general formula:
R3 R4 R5 o R
2 ~
R - C = C - C - 0 - C - CH - CN
wherein R , R , R , R4 and R5 have the same meaning as in the general formula I; the latter reaction tends to occur at temperatures above 100C
and is clearly undesirable because it decreases the yield of the desired compounds of the general formula I. An attractive feature of the process according to the invention is that it allows the use of a relatively low reaction temperature, for example between 20 and 100C, and thereby avoids the production of substantial quantities of unwanted by-products; a low yield of by-product IV is particularly noticeable when the organic solvent is a halogenated hydrocarbon, especially a chlorinated hydrocarbon of 1 to 4 carbon atoms, e.g. tetrachlorome~hane, chloroform, dichloromethane and perchloroethylene, or an aromatic hydrocarbon especially an alkylbenzene, e.g. toluene or a xylene or mixture of xylenes. Carbon tetrachloride and xylene have shown excellent properties in this respect.
The halides of the general formula III may be primary, secondary or tertiary. Halides of the general formula III are generally stable and do not decompose at a temperature below 100C. Preferably R2, R3 and R4 in the general formula III, each represent a hydrogen atom or a methyl group and Rl and R represent hydrogen atoms. The preferred starting compound of the general formula III is l-chloro-3-methyl-2-butene.
In the alkali metal carboxylate of general formula II the alkali metal atom M may be lithium, sodium, potassium, rubidium or cesium but, for economic reasons, sodium or potassium are generally preferred. Very good results have been obtained with potassium cyanoacetate.
-s - 3 , ~ . .. ,-~
The pha~e transfer cataly3t may be an~ reagent ~hich i8 capable of aocel~ratingjinterphase reactions taking place in two-;?hase systems and may take the form of an onium salt, a macrocyolic polyether, or a ~urface-active agent.
~he phaae transfer catalyst may be an onium ~alt, particularly a quaternary onium salt of the general formula:-R6 I t ~7 - X - R~ ~ Y~
~8 J
wherein ~ represents a nitrogen, phosphorus or arsenic atom, R~, R7, R8 and R9 each an alkyl, aralkyl, alkaryl or aryl group and Y a monovalent ion, e.g. a halide such as chloride, bromide or iodide, or an alkyl~ulphate such as methylsulph2te or ethylsulphate or a sulphonium ~alt of the general formula:-1-- 10 - ' ¦R11 _ S _ R12 I y wherein R10, R11 and R12 each represent an ~lkyl group and Y a mono~alent isn, e.g. a halide such as chloride, bro~ide or iodide, or an alkyl~ulphate such a~ methyl~ulp~nate or ethylflulphate. Preferab~y the alkyl group~ contain 1 to 18 carbon atoms and the aralkyl and alkaryl groups contain up to 10 carbon atoms, the aryl gTOUp iB preferably phenyl.
Esamples of ~uitable onium ~alts are tetra-n~butylammonium bromide, tetra~n-butylammonium ¢hloride 9 methyltrioctyl-ammonium chloride, m~thyltri-(2-methylheptyl)ammonium c~loride, methyltri-2-methylphe~yl~ammonium chloride, tetramethyl-phosp~nium iodide, tetra-n-butylphosphonium bromide, ethyl-2-methylpentyl-2-methylundecylsulphonium ethyl~ulphate, ~eth~l-triphenylarsonium iodide, ethyl~2~mathylpsntadecyl-2-methyl-undecyl-sulphonium ethyls~lphate, methyldinonyl-aulphonium methylsulphate and n-hexadecyldimethyl~ulphonium iodide. V~ry good re~ults have been obtalned with quaternary a~onium compounds~
r~hs onium ~alt may be a hydroxide or a ~alt and oan be employed a~ the functional portion of a strongly-basic anion e~chang~ resin having a structural portion (poly~er matrix) and a funct~onal portion (ion-active group). Of ~pecial importance ~re polystyrene resins, such as copolymers of aromatic mono~inyl compounds and aromatic polyvinyl compo~nds, particularl~ styrene/divinylbenzene copolymers.
The functional portion i~ a quaternary ammonium, phosphonium or ar~onium group. Examples of ~trongly-ba~ic anion exchange resin~ which may be employed are tho~e derived from tri~ethyl-amine (such as thè producta known under the trade names of "Amberlite IRA-400", "Amberlite IRA-401", "Amberlite IRA-402", "~mberlite IRA~900", "Duolite A~101-D"~ "Duolite ES-111~, '1Dowex 1", "Dowex 11n, I'Dowex 21E" and "Ionac A-450n), and those deri~ed from dimethylethanol amine (such as the products known under the trade names of "Amberlite IRA-410N, "Amberlite IR~-911", "Dowex 2N, "Duolite A-102-D", "Ionac A-542" and ~Ionac A-550"). Very good results ha~e been obtained with tho~e derived from trimethylamine.
Other suitable phase tran~fer catalyst~ are maorocycl~c polyethers kno~n as "crown ether~". The~e compounds, together with their preparation, are described in the literature, for example in ~etrahedron ~etters No. 18(1972~ pages 1793-1796, and are commonly designated by reference to the total numbar of atom~ forming the mscrocyclic ring together with the number of o~ygen atoms in that ring. Thus the macrocyclic polyether whos2 formal chemical name i8 1, 4,7,10,13,16-hexao~acyclooctadecane i~ de~ignated as "18-crown-6~. Other axamples of ~uitable macrocyclic polyethers are 3,4-benzo-1,S 9 9,12,15,18,21-heptacxacyclotrico~-3-ene and3,~-ben~-1,6,9,12-tetra-o~acyclotetradec-3-ene. 18-Crown-6 i~ particularly ~uitable.
Other ~uitable pha~e transfer catalysts are ~urface-acti~'e agent~. A "surface-acti~e agent" i~ defined as in Eirk-Othmer, "Encyclopedia of Chemi¢al ~echnology", second edition, ~olume 19(1969) paga 508: "An organic compound that encompasses in the ~ame molecule two dis~imilar structural group~, one bei~g water soluble and one being water-insoluble".
The surface-active agent i8 preferably non-ionic1 such a~
fJL~
a poly~(alkyle~eoxy) derivative formed by reacting a higher alcohol, alkylphenol or fatty acid with ethylene oxide or propylene o~ide. Suitable alcohols, alkylphenols or fatty acidc contain an alkyl group of 8-20 carbon atoms and the nuMber of alkyleneo~y units is in the i~ange of 1-50. ~
particularly ~uitable non-ionic surfa¢e-active agent (referred to in the examplec a~ "Dobanol 91-6n) ic formed from a C6-C
n-alkanol mlxture and contain~ an average of ~i~ ethyleneo~y units. The non-ionic surface-active agent may be an alkyl-benzene containing a straight alkyl group. Suitable alkyl-benz~ne~ contain an alkyl group of B-20 carbon atom~0 ~he molar ratio o~ the phaae transfer catalyct to the halide of the general formula III can va~y within wide limits, but iB ~uitably ~rom 1:5 to 1:5,000 and preferably from 1:20 to 1:200. The molar ratio of the alkali metal carbo~ylate of the general formula II to the halide of the general formula III can also var~ within wide limits, but i8 euitably from 1:0.75 to 1:1, the equimolar ratio being preferred.
The proces~ may suitably be carried out by stirrin~ ths ctartin~ compounds, the onium sslt and the organic solvent for periods of ~p to five hours at temperatures from 20 to 1 00C .
~he compound of the general form~la I may be i~olated from the reaction mixture by washing it with wat~r to remove the simultaneously formed alkali metal halide, drying the wa~hed mixture and fractionatlng the dried mixture.
Compo~nd~ generated by the proce~s according to the in~ention and ha~ing the following general fonmula are novel compound~ and, accordingly repre~ent another feature of the pre~ent inventlon:-R2 _ C = C - ~ - O - C - C~[2 wherein each o~ R1, R , R , R4 and R5 independently repre~ent a hydrogen atom or a hydrocarbyl group, eOg~ an alkyl group -~ ~3~637 !
of 1 to 4 carbon A~oms such as a methyl group. An example of such a novel compound i~ 3 methyl-2-butenyl cyanoacetate.
The following examplec illu~trste the proce~ according to the invention and the novel compounds produced therefrom.
EXANPLES I to VI
A ves~el was char~ed with 25 mmol of potassi~m cyanoaoetate, 25 mmol of 1-chloro-3 meth~l-2-butene, tetra-n-butylammonium chloride and 25 ml of a solvent. The content~ of the ve~sel were stlrred for a certain period. The mixture fo~med was wa~hed twioe with 10 ml of water, the wa~hed mixt~re wa~ -dried in the presence of anhydrous magnesium sulphate, the magnesium sulphate was remo~ed by filtration and the filtrate was boiled down. ~nal~is by means of ga~-~quid chromatograph~
showed that the residue consi~ted of 3-methyl-2-butonyl cyanoacQtate (x mmole) and 3-methyl-2-butenyl 2-cyano-5-meth~l-4-he~enoate, e~pressed in ~, were calculated a~ x ~ 2y ~ 100 and ~2y 2~ x 100, respectively. ~he yield of 3-methyl-2-butenyl cyanoacetate, expressed in ~, was calculated as conversion of 1-~hloro-3-meth~1-2-butene x gelectivitY to_~-meth~1-100 ?-buten~l cyanoacetate Six e~periments were conducted in the manner described above. The table shows the solvent~ used, the amounts of tetra-n-butyl-ammonium ¢hlorids employed, calculated on 1-chloro-3-meth~1-2-butene, the tempexature~, the reaction times and the result~.
,, ~, ,, ~, ~l ~, ,, ~, ~, . ..
o ~ 0, ,, 2~ ,1 ,1 ~ I o a~ 0 ~ ~ ~ 1~
.qa~ l n 0 0 ~ h I
~ ~ P o 1 11 :~ I ~ 1 11 I ~1 1 11 I P~ 1 11 I ~ 1 11 Q~
I ~ ~1 11 ,~1 1 01 11 hl U~ 01 11 O Gl I Gl ~ ~ 0 U~ ~ ~ 11 ~PI~XI 11 ~-.QI h~l 11 h I I o 11 11 .,~ I I C~ I I
P ~1 11 ~ ,C I 1 1 11 o ~1 o a~l 11 ~1)1 G ~1 0 ~ C`l U~ ~ ~ !!
~1 ~31 0 G~ 0 CO O~
0 11 h 01 11 U~ ~1 o ~1 11 h 'qO h a I cu C~l ~ CO O
G el 0~ 1 ~ I 1~
C~ o~ I 1 11 ~3 ~ I 11 o ~- ~ o o u~ 11 E~ f~ I 11 a Il ,~
~0 ! 1~
P o~ I ~1 ~
ON~-O !, ~
~ a ~
E~ ~ hI ~ ¦~
IC~ 01 11 ~
0 ~0 ~ ~ 11 _I V C~
l ~ ~,1 ~t 11 h ,1 ,, I 'I '~3 O O I ~ 1 H ~ p t-l il Z; I H H H P N
ll ~L~ 2~
The ~MR ~pectrum of ~-methyl-2~butenyl cyanoacetate measured at 60 MHz in deuterochloroform ~olution ~ho~ed the following abaorption~ relative to a tetramethylsilane standard: 1 o ~ 1.7-1.B ppm (two doubletc, two CH3) b = 5. 37 pp~ (multiplet = CH) o ~ 4.67 ppm (doublet, CH20~
o = 3.53 ppm (singlet, CH2CN)
Claims (9)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A process for the preparation of an ester of cyanoacetic acid having the following general formula:- ( I ) (wherein R1 , R2, R3, R4 and R5 each represent a hydrogen atom or an alkyl group of 1 to 4 carbon atoms), which comprises reacting an alkali metal carboxylate of general formula:
(II) (wherein M represents an alkali metal atom) with an alkyl halide of general formula:- (III) (wherein R1, R2, R3, R4 and R5 have the meanings hereinbefore defined and Hal is a halogen atom having an atomic number of at least 17) at a temperature in the range 20 to 100°C
and in the presence of an organic solvent and a quaternary onium salt phase transfer catalyst of the general formula:-(IV) wherein X represents a nitrogen, phosphorus or arsenic atom, R6, R7, R8 and R9 each an alkyl, aralkyl, alkaryl or aryl group and Y a monovalent ion, or a ternary sulphonium salt of the general formula:
(V) wherein R10, R11 and R12 each represents an alkyl group and Y a monovalent ion.
(II) (wherein M represents an alkali metal atom) with an alkyl halide of general formula:- (III) (wherein R1, R2, R3, R4 and R5 have the meanings hereinbefore defined and Hal is a halogen atom having an atomic number of at least 17) at a temperature in the range 20 to 100°C
and in the presence of an organic solvent and a quaternary onium salt phase transfer catalyst of the general formula:-(IV) wherein X represents a nitrogen, phosphorus or arsenic atom, R6, R7, R8 and R9 each an alkyl, aralkyl, alkaryl or aryl group and Y a monovalent ion, or a ternary sulphonium salt of the general formula:
(V) wherein R10, R11 and R12 each represents an alkyl group and Y a monovalent ion.
2. A process according to claim 1 wherein the onium salt is a quaternary ammonium salt.
3. A process according to claim 2 wherein the quaternary ammonium salt is tetra-butyl-ammonium chloride.
4. A process according to claim 1 wherein the organic solvent is a halo-genated hydrocarbon or an aromatic hydrocarbon.
5. A process according to claim 4 wherein the halogenated hydrocarbon is a chlorinated hydrocarbon containing 1 to 4 carbon atoms.
6. A process according to claim 5 wherein the chlorinated hydrocarbon is carbon tetrachloride.
7. A process according to claim 4 wherein the aromatic hydrocarbon is xylene.
8. A process according to claim 1 wherein R2, R3 and R4 represent hydrogen or a methyl group and R1 and R5 represent hydrogen atoms.
9. 3-Methyl-2-butenyl cyanoacetate.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB2826176A GB1580533A (en) | 1976-07-07 | 1976-07-07 | Cyanoacetic acid esters |
| GB28261/76 | 1976-07-07 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1123007A true CA1123007A (en) | 1982-05-04 |
Family
ID=10272858
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA279,044A Expired CA1123007A (en) | 1976-07-07 | 1977-05-24 | Preparation of esters |
Country Status (12)
| Country | Link |
|---|---|
| JP (1) | JPS537621A (en) |
| BE (1) | BE856489A (en) |
| BR (1) | BR7704405A (en) |
| CA (1) | CA1123007A (en) |
| CH (1) | CH628879A5 (en) |
| DE (1) | DE2730332A1 (en) |
| DK (1) | DK156954C (en) |
| FR (1) | FR2357533A1 (en) |
| GB (1) | GB1580533A (en) |
| IT (1) | IT1143740B (en) |
| MX (1) | MX4913E (en) |
| NL (1) | NL188638C (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2471973A1 (en) | 1979-12-20 | 1981-06-26 | Rhone Poulenc Ind | PROCESS FOR THE PREPARATION OF ALKYL CYANOACETATES |
| JPS5954767U (en) * | 1982-10-01 | 1984-04-10 | トヨタ自動車株式会社 | Igniter for automobile engine |
-
1976
- 1976-07-07 GB GB2826176A patent/GB1580533A/en not_active Expired
-
1977
- 1977-05-24 CA CA279,044A patent/CA1123007A/en not_active Expired
- 1977-07-05 DK DK302677A patent/DK156954C/en not_active IP Right Cessation
- 1977-07-05 CH CH825177A patent/CH628879A5/en not_active IP Right Cessation
- 1977-07-05 NL NL7707417A patent/NL188638C/en not_active IP Right Cessation
- 1977-07-05 BE BE179091A patent/BE856489A/en not_active IP Right Cessation
- 1977-07-05 BR BR7704405A patent/BR7704405A/en unknown
- 1977-07-05 FR FR7720604A patent/FR2357533A1/en active Granted
- 1977-07-05 DE DE19772730332 patent/DE2730332A1/en not_active Withdrawn
- 1977-07-05 MX MX587577U patent/MX4913E/en unknown
- 1977-07-05 JP JP7957677A patent/JPS537621A/en active Granted
- 1977-07-05 IT IT2540977A patent/IT1143740B/en active
Also Published As
| Publication number | Publication date |
|---|---|
| GB1580533A (en) | 1980-12-03 |
| JPS618823B2 (en) | 1986-03-18 |
| BR7704405A (en) | 1978-05-02 |
| DK302677A (en) | 1978-01-08 |
| DK156954C (en) | 1990-02-26 |
| NL188638C (en) | 1992-08-17 |
| DK156954B (en) | 1989-10-23 |
| NL188638B (en) | 1992-03-16 |
| FR2357533B1 (en) | 1981-01-09 |
| JPS537621A (en) | 1978-01-24 |
| DE2730332A1 (en) | 1978-01-12 |
| MX4913E (en) | 1983-01-03 |
| NL7707417A (en) | 1978-01-10 |
| IT1143740B (en) | 1986-10-22 |
| BE856489A (en) | 1978-01-05 |
| CH628879A5 (en) | 1982-03-31 |
| FR2357533A1 (en) | 1978-02-03 |
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