CA1076136A - Process for the preparation of 5-oxohexanoic acid and its derivatives - Google Patents
Process for the preparation of 5-oxohexanoic acid and its derivativesInfo
- Publication number
- CA1076136A CA1076136A CA260,943A CA260943A CA1076136A CA 1076136 A CA1076136 A CA 1076136A CA 260943 A CA260943 A CA 260943A CA 1076136 A CA1076136 A CA 1076136A
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- acetone
- acrylic acid
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C255/00—Carboxylic acid nitriles
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C59/00—Compounds having carboxyl groups bound to acyclic carbon atoms and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups
- C07C59/185—Saturated compounds having only one carboxyl group and containing keto groups
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/582—Recycling of unreacted starting or intermediate materials
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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
Abstract of the Disclosure Process for the preparation of 5-oxo-hexanoic acid, its nitrile and its esters by reacting acetone with acrylic acid, its nitrile or its esters in the presence of mesityl oxide.
Description
1076~36 It is known that 5-oxo-hexanoic acid and derivatives thereof, for example 5-oxo-hexane nitrile and 5-oxo-hexanoic acid alkyl esters may be prepared by the addition of acetone to acrylic acid or acrylic acid derivatives catalyzed by amines, known als Michael aadition.
It is further known that the aforesaid 5-oxo-hexanoic acid and derivatives thereoE may be converted into valuable resorci-nols by cyclization and subsequent dehydrogenation, which resorcinols may be used as starting components in the prepara-tion of plastics, caoutchouc and wood glue, as coupling ~`~ components in diazotation processes or as antiseptic agents.
; In said process for preparing 5-oxo-hexanoic acid and ~; derivatives thereof, there are formed various by-products besides the desired reaction products, inter alia mesityl oxide, which may be found for example in an amount of even up . , to 50~, calculated on converted acetone, when 5-oxo-hexa-noic acid is prepared from acetone and acr~lic acid. This signifies a considerable disadvantage of the described process.
Although it is know from the literature that mesityl oxide may be hydrolyzed under the action oE basic catalysts to acetone, this method has the substantial disadvantage that mesityl oxide must first be separated from the reaation mixture and then be split into acetone in a separate operation.
It has now been found that in the aforesaid reaction of acetone with acrylic acid or an acrylic acid derivative to ~ yield 5-oxo-hexanoic acid or a 5-oxo-hexanoic acid derivative ; a formation of mesityl oxide no longer takes place once a "
-: 2 ~
~ -. -.; . .;, ... - .,. . - . . , . ; ., .. . - . , . - :,, -, ....... . ., . ~
, , . , . , , -, . : , . , . ' .... :'. ,: . ' : . ' '~ , ' ' ': ' '' . ' , ' " ', ' '' .:, ' ,' ' . ,; " , ' ',' ' ' ~ ,,, ''. ~
~`
i ~ 1076i36 certain concentration of mesityl oxide is attained in the reaction mixturs. The mesit~l oxide concentration required for this-purpose may be attained for example by adding an .~
adequate quantity of mesityl oxide to the mixture of reac-tants. ~en performing the reaction continuously mesityi oxide may either be added to the starting components as such or it may be formed during the reaction from acetone- In $his pro-cess mPsityl o~ide is advantageously recycled continuously, especially together with the unreacted portions of acetone and acrylic acid component after having separated the reaction mixture by distillation.
The present invention provides a process for the pre-paration of 5-oxo-hexanoic acid and derivatives thereof of the general formula (I) 3 2 CH2 CH2 (I) ' whsrein the radical R is carboxyl, alkoxycarbonyl containing alkoxy groups having up to 12 oarbon atoms)or carbonitrile, by reaction of acetone with an acrylic acid compound of the formula (II) ~ Cll2 = CH - R (II) : :
whe~ein R has the meaning indicated in formula I, at elevated ;~ temporature with the addition of basic ca1;alysts1 whish com-prises performing the reaction in tho presence of from 2 to 8% by weight of m~sityl oxid~ calculated on the reaction mixture.
Suitable alkyl substituents in the alkoxycarbonyl radi-, ~ 3 ~
::
.: - . .. ~ -, .. . . . . .. .. . .. . . . . .. . . .
,: , . . , . , .. .. , ,. . , ,, . . ., . , . . . , .: .
. :: . . ,, ,. ,.,. ,: ., ,............ , , :: .. ., ~ . ,: : :, .
:, ,.,. ' ' ~ '' .,, ''. ::: :,: :: . ' . ': ' '..... ,::
~-` 107613~; ~
cals are straight chain, branched or cyclic alkyl groups having up to 12 carbon atoms which may be substituted, for example methyl, ethyl, propyl, isopropyl, butyl, pentyl, hexyl, isooctyl, :-dodecyl or cyclohexyl. Alkyl groups having from 1 to 6, expecially from 1 to 3 carbon atoms are preferred. ~ :
Examples of suitable acrylic components of formula II are :
acrylic acid, acrylonitrile, acrylic acid methyl ester, acrylic acid ethyl ester, acrylic acid isobutyl ester, acrylic acid hexyl ester, acrylic acid dodecyl ester or acrylic acid cyclo- .
hexyl ester. ~:
Suitable catalysts are for example, primary amines, amino-alcohols, aminocarboxylic acids, and the Schiff's bases formed - by these amino compounds with acetone as well as N-substituted ~-aminopropionates, which may be formed by addition of primary amines and acrylic acid esters. Examples are methylamine, ethylamlne, n-propylamine, isopropylamine, n-butylamine, isobutyl-: amine, secondary butylamine, tertiary butylamine, isoamylamine, ethylenediamine, amylamine, tetramethylene-diamine, cyclopentyl-amine, cyclohexylamine, benzylamine, aminoethanol, ~-aminopro-pionic acid, ~-aminocaproic acid or the Schiff's bases derived from acetone and the aforesaid amines or the N-substituted -aminopropionates from said amines and the acrylic acid esters used.
The catalysts are generally used in an amount of from about 0.01 to about 0.2 mol per mol of acrylic component of the ~ormula II. : .
The starting components may be reacted discontinuously or continuously at a temperature in the range of from about 150 to 29 about 250C, preferably in the range of from 200 to 240C.
: 4 ~:
: : . .... . .... . . . .
... . . , . . , . : ., . , , , , :
., , - ,.,- , . . , ., ~ ' . ,: . ' The mesityl oxide concentration in the reaction mixture according to the invention may vary within a certain limit and is approximately in the range of from 2 to 8% by weight, preferably 4 to 5% by weight.
The ratio of acetone and acrylic acid or derivatives thereof in the reaction mixture may vary within wide limits and is generally in the range of from 1:1 to 20:1, preferably from 3:1 to 8:1.
When using a compound other than acrylic acid as starting component of formula II, for example acrylonitrile or an acrylic acld ester, an acid is advantageously added to the reaction mixture in an amount of from about 0.1 to 0.5% by weight, calculated on the reaction mixture. Mineral acids may be used as well as organic acids. Suitable acids are for example benzoic acid, acetic acid or propionic acid.
The addition of polymerization inhibitors is generally advantageous; those conventionally used for acrylic compounds, for example hydroquinone, are used preferably.
The reaction pressure is not critical. Preferred is the range from atmospheric pressure to a pressure of about 50 ~: .
atmospheres. When carrying out the reaction in the liquid phase it is preferably operated under the vapor pressure corresponding ~ to the reaction temperature. It is also possible to operate j,~: :
,~ in the gaseous phase.
, . . . .
The process may be performed with the use of a solvent or ~ ~:
without. Suitable solvents are for example acetonitrile, tetrahydrofurane or benzene.
The acrylic component of formula II may be reacted completely 29 or partially. The conversion should not be higher than 90%
- 5 - ~;
:'' ... . .. . . .
, . , ... .... , , . .. .,.. , ,, . ,. , ~:
~076136 ..:
preferably, as otherwise secondary reactions could occur owing to the long reaction times and the elevated reaction temperatures ~-which may be necessary for a conversion of more than 90%. ~ -The fraction obtained in the separation of the reaction products by distillation substantially containing unreacted starting products, mesityl oxide and the catalyst may be reused in the reaction.
The process according to the invention may be performed as ~follows when working discontinuously: The reaction components, mesityl oxide included, are mixed with one another at room temperature, introduced into a reactor, for example an autoclave or a bomb tube and heated to the desired reaction temperature for a certain reaction time, for example for about 30 to 60 minutes. The reaction mixture is then cooled to room temperature ~ and worked up.
When working continuously the process may be carried out in the following manner: A mixture A of reactants, comprising .
acetone, acrylic acid, a polymerization inhibitor and optionally ;~ mesityl oxide or comprising acetone, acrylonitrile or acrylic 20~ acid ester, an acid such as benzoic acid, a polymerization ~ inhibitor and optionally mesityl oxide is passed by means of ; dosing pumps while vigorously stirring together with a mixture B of reactants, comprising acetone and isopropylamine through a reaction tube of an inner width of about 8 mm and a length of about 50 m heated to the desired reaction temperature.
After the desired residence time in the reaction tube, of about 30 minutes for example the reaction mixture is cooled to room 28 temperature and separated by distillation to yield a head ..
. . ,.. .. , . ~ . : . . .
' ' ' ''". ` ' ' " ', '` ' . ' ' , , ` " ' `~ , ' . . '~ ' ',' '~' ' ' :i........... , ,:,,, ., :, . . . . .. .. .
. , . . . . , . , ~,, , 1~76136 product substantially comprising acetone, acrylic acid component, mesityl oxide and the catalyst and a bottom product comprising substantially the desired reaction product of the formula I and high boiling by-products if any. The head product containing mesityl oxide is recycled to the starting mixture A.
The products of the present invention of the formula I
may be isolated from the bottom product, for example by distillation in vacuo and/or crystallization or extraction in a -pure form and with high yields, calculated on the converted starting components. As no further mesityl oxide formation from acetone takes place in the process according to the invention involving the presence of mesityl oxide, there are obtained unexpectedly high yields of the products of formula I, calculated on converted acetone. This signifies a considerable technical progress.
The following examples illustrate the invention:
: ~ :
C O M P A R A T I V E E X A M P L E 1:
3.04 kg of a mixture A comprising 73.9% by weight of acetone, 1.0% by weight of water, 25.0% by weight of acrylic acid and 0.1%
20 ; by weight of hydroquinone and 0.24 kg of a second mixture B
comprising 86.1% by weight of acetone and 13.9% by weight of isopropylamine were mixed with one another at room temperature and pumped through a reaction tube of about 8 mm width and a -volume of about 2 liters heated to 230C and cooled thereafter to 20C. According to the ~aschromatographic analysis the reaction product had the following composition: 61.6% by weight of acetone, 10.1~ by weight of acrylic acid, 16.4% by weight of 28 5-oxo-hexanoic acid, 5.8% by weight of mesityl oxide and 0.5 1~6136 by weight of 4-acetylheptanedioic acid.
The conversion, calculated on acrylic acid, was 57.2% and, calculated on acetone, 15.6%.
The yield of 5-oxo-hexanoic acid, calculated on converted acrylic acid, was 68.1% and, calculated on converted acetone, 47.7%.
The formation of mesityl oxide, calculated on converted acetone, was 52.3%.
E X A M P L E 1:
The example was carried out under the same reaction condi-tions as in Comparative Example 1, except that the starting mixture A contained additionally mesityl oxide. The composition of mixture A was as follows: 70.4% by weight of acetone, 5.4%
~ ~by weight of mesityl oxide, 23.1% by weight of acrylic acid, ; 15 ~ 1.0% by weight of water and 0.1~ by weight of hydroquinone. The composition of mixture B was the same as in Com- -: : ' : ' :'', :~: .
: ~ ' ' .
' ~ ' .
' , '';
;~ - 8 . - . , .
,, :, ' ,: ' ~ ' ,'' , , . ~
: . . .
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.
I-IO~.S_~_2 Ll 6 ~7f~
parative ~xalnple 1. The reaction product had the following compositioll: 63~3~ by weight of acetone, 12.7~ by weight of acrylic acid, 13.~oby weight of 5-oxo-hexanoic acid, 5.7~0 b-y weight o* mesityl oxide a~d 0.7~ by weight of 4-acetyl-heptanedioic acid.
The conversion, calculated on acrylic acid, was 48.1 and, calculated on acetone, 8.2~.
The yield of 5-oxo-hexanoic acid, calculated on con-verted acrylic acid, was 66~4~o and, calculated on converted acetone, 96.2~.
The formation of nnesityl oxide, calculated on converted . .
acetone, was only 3.8~.
C-0 M P A R ~_T I V E E X A M P L E 2-3157 g of a mixture comprising 79.2% by weight of acetone ~. - - / . . .:
1~ 19.8~ by weight of acrylic acid, 1.0~ by weight of isopropyl~
amine and 0.05% by weight of hydroquinolle were heated to 230 C Por a psriod of 1 hour in a S liter autoclave and cooled subsequently. The composition of the reaction product (3085 g) :.: :: .
was as follows: 70.5% by weight of acetone, 6.7% by weight of ~ ~ -acrylic acid, 3-5% by weight of mesityl oxide, 12.8~ by weight of 5-oxo-hexanoic acid and 0.9% by weight of 4-acetylheptane-~
~, :
~ dioic acid.
. . .
The conyersion, calcu:Lated on acrylic acid, was 65.65' and, calculated on aoetone, 13.09~.
The yiold Or 5-oxo-hexanoic acid, calculated on con-verted acrylic acid, was 68~1~o and, calculated on converted acetone, 55,9~o.
The formatlon of n1esityl oxide, calculated on convertad 29 acetone, was 1l0~5~o~
' . ". ' . ., , , i" ,, ;, ,','. . ,., ,: , . :, , . .::::,; " . ,: , ", ,: , E X A M P L E 2: -The example was performed under the same reaction conditions as Comparative Example 2, except that the starting mixture contained additionally mesityl oxide. The mixture (3157 g) had the following composition: 74.6% by weight of acetone, 19.8%
by weight of acrylic acid, 4.5% by weight of mesityl oxide~ 1.0% ~ -by weight of isopropylamine and 0.05% by weight of hydroquinone.
The composition of the reaction product (3145 g) was as follows:
65.8% by weight of acetone, 7.4% by weight of acrylic acid, 4.8% by weight of mesityl oxide, 14.6% by weight of 5-oxo-hexanoic acid and 1.2% by weight of 4-acetylheptanedioic acid.
The conversion, calculated on acrylic acid, was 62.0% and, ~ calculated on acetone, 9.3%.
; The yield of 5-oxo-hexanoic acid, calculated on converted acrylic acid, was 66.8% and, calculated on acetone, 95%.
The formation of mesityl oxide, calculated on converted acetone, was only 4.8%.
4.0 g of a mixture of 80.1 % by weight of acetone, 18.6%
~ 20 by weight of acrylic acid methyl ester, 1.0% by weight of iso-; ~ ~ propylamine, 0.2% by weight of benzoic acid and 0.05% by weight of hydroquinone were heated to 230C for 30 minutes in a bomb tube having a capacity of 6 cm3 and immediately cooled to 20C
thereafter. The reaction product had the following composition:
67.4% by weight of acetone, 5.6% by weight of acrylic acid methyl ester, 0.8% by weight of mesityl oxide, 15.6% by weight of 5-oxo-hexanoic acid methyl ester and 2.0% by weight of 4-acetylheptanedioic acid dimethyl ester.
. ., . - -. .. . , . ~ . .
- . - , .
,, . .: . ' . :
. " , ~. .,,, , , ; , ... , . -. .
.......
~ . '. ' ' ;"
107~:;136 The conversion, calculated on acrylic acid methyl ester, was 69.1% and, calculated on acetone, 14.4%.
The yield of 5-oxo-hexanoic acid methylester, calculated on converted acrylic acid methyl ester, was 79.3% and, calculated on converted acetone, 81.2%.
The formation of mesityl oxide, calculated on converted acetone, was 12.2%.
E X A M P L E 3:
The example was carried out under the same conditions as Comparative Example 3, except that the starting mixture contained additionally mesityl oxide. The mixture (4.0 g) had the follow-ng composition: 74.6~ by weight o acetone, 5.5% by weight of mesityl oxide, 18.6% by weight of acrylic acid methyl ester, 1.0%
, by weight of isopropylamine, 0.2% by weight of benzoic acid and lS~ 0.05% by weight o hydroquinone. The reaction product had the following composition: 75.0% by weight of acetone, 9.4% by weight of acrylic acid methyl ester, 5.5% by weight o mesityl -oxide, 8.0% by weight of 5-oxo-hexanoic acid methyl ester and - ;
0.9% by weight of 4-acetylheptanedioic acid dimethyl ester.
20 ~ The conversion, calculated on acrylic acid methyl ester, was 47.2% and, calculated on acetone, 3.1%.
~ ~ The yield of 5-oxo-hexanoic acid methyl ester, calculated ;~ on converted acrylic acid methyl ester, was 77% and calculated on converted acetone, 92.9%.
~25 A urther ormation o mesityl oxide could not be observed.
~: :, ' ' ' : . ~. . .
''' ' '"' '. ,' "" '"' ~,', '','."'' ' ' . " ' '," ',."''' ",,' '" '' ' '; '~'', ' ~"' ' .. . .. . . .
It is further known that the aforesaid 5-oxo-hexanoic acid and derivatives thereoE may be converted into valuable resorci-nols by cyclization and subsequent dehydrogenation, which resorcinols may be used as starting components in the prepara-tion of plastics, caoutchouc and wood glue, as coupling ~`~ components in diazotation processes or as antiseptic agents.
; In said process for preparing 5-oxo-hexanoic acid and ~; derivatives thereof, there are formed various by-products besides the desired reaction products, inter alia mesityl oxide, which may be found for example in an amount of even up . , to 50~, calculated on converted acetone, when 5-oxo-hexa-noic acid is prepared from acetone and acr~lic acid. This signifies a considerable disadvantage of the described process.
Although it is know from the literature that mesityl oxide may be hydrolyzed under the action oE basic catalysts to acetone, this method has the substantial disadvantage that mesityl oxide must first be separated from the reaation mixture and then be split into acetone in a separate operation.
It has now been found that in the aforesaid reaction of acetone with acrylic acid or an acrylic acid derivative to ~ yield 5-oxo-hexanoic acid or a 5-oxo-hexanoic acid derivative ; a formation of mesityl oxide no longer takes place once a "
-: 2 ~
~ -. -.; . .;, ... - .,. . - . . , . ; ., .. . - . , . - :,, -, ....... . ., . ~
, , . , . , , -, . : , . , . ' .... :'. ,: . ' : . ' '~ , ' ' ': ' '' . ' , ' " ', ' '' .:, ' ,' ' . ,; " , ' ',' ' ' ~ ,,, ''. ~
~`
i ~ 1076i36 certain concentration of mesityl oxide is attained in the reaction mixturs. The mesit~l oxide concentration required for this-purpose may be attained for example by adding an .~
adequate quantity of mesityl oxide to the mixture of reac-tants. ~en performing the reaction continuously mesityi oxide may either be added to the starting components as such or it may be formed during the reaction from acetone- In $his pro-cess mPsityl o~ide is advantageously recycled continuously, especially together with the unreacted portions of acetone and acrylic acid component after having separated the reaction mixture by distillation.
The present invention provides a process for the pre-paration of 5-oxo-hexanoic acid and derivatives thereof of the general formula (I) 3 2 CH2 CH2 (I) ' whsrein the radical R is carboxyl, alkoxycarbonyl containing alkoxy groups having up to 12 oarbon atoms)or carbonitrile, by reaction of acetone with an acrylic acid compound of the formula (II) ~ Cll2 = CH - R (II) : :
whe~ein R has the meaning indicated in formula I, at elevated ;~ temporature with the addition of basic ca1;alysts1 whish com-prises performing the reaction in tho presence of from 2 to 8% by weight of m~sityl oxid~ calculated on the reaction mixture.
Suitable alkyl substituents in the alkoxycarbonyl radi-, ~ 3 ~
::
.: - . .. ~ -, .. . . . . .. .. . .. . . . . .. . . .
,: , . . , . , .. .. , ,. . , ,, . . ., . , . . . , .: .
. :: . . ,, ,. ,.,. ,: ., ,............ , , :: .. ., ~ . ,: : :, .
:, ,.,. ' ' ~ '' .,, ''. ::: :,: :: . ' . ': ' '..... ,::
~-` 107613~; ~
cals are straight chain, branched or cyclic alkyl groups having up to 12 carbon atoms which may be substituted, for example methyl, ethyl, propyl, isopropyl, butyl, pentyl, hexyl, isooctyl, :-dodecyl or cyclohexyl. Alkyl groups having from 1 to 6, expecially from 1 to 3 carbon atoms are preferred. ~ :
Examples of suitable acrylic components of formula II are :
acrylic acid, acrylonitrile, acrylic acid methyl ester, acrylic acid ethyl ester, acrylic acid isobutyl ester, acrylic acid hexyl ester, acrylic acid dodecyl ester or acrylic acid cyclo- .
hexyl ester. ~:
Suitable catalysts are for example, primary amines, amino-alcohols, aminocarboxylic acids, and the Schiff's bases formed - by these amino compounds with acetone as well as N-substituted ~-aminopropionates, which may be formed by addition of primary amines and acrylic acid esters. Examples are methylamine, ethylamlne, n-propylamine, isopropylamine, n-butylamine, isobutyl-: amine, secondary butylamine, tertiary butylamine, isoamylamine, ethylenediamine, amylamine, tetramethylene-diamine, cyclopentyl-amine, cyclohexylamine, benzylamine, aminoethanol, ~-aminopro-pionic acid, ~-aminocaproic acid or the Schiff's bases derived from acetone and the aforesaid amines or the N-substituted -aminopropionates from said amines and the acrylic acid esters used.
The catalysts are generally used in an amount of from about 0.01 to about 0.2 mol per mol of acrylic component of the ~ormula II. : .
The starting components may be reacted discontinuously or continuously at a temperature in the range of from about 150 to 29 about 250C, preferably in the range of from 200 to 240C.
: 4 ~:
: : . .... . .... . . . .
... . . , . . , . : ., . , , , , :
., , - ,.,- , . . , ., ~ ' . ,: . ' The mesityl oxide concentration in the reaction mixture according to the invention may vary within a certain limit and is approximately in the range of from 2 to 8% by weight, preferably 4 to 5% by weight.
The ratio of acetone and acrylic acid or derivatives thereof in the reaction mixture may vary within wide limits and is generally in the range of from 1:1 to 20:1, preferably from 3:1 to 8:1.
When using a compound other than acrylic acid as starting component of formula II, for example acrylonitrile or an acrylic acld ester, an acid is advantageously added to the reaction mixture in an amount of from about 0.1 to 0.5% by weight, calculated on the reaction mixture. Mineral acids may be used as well as organic acids. Suitable acids are for example benzoic acid, acetic acid or propionic acid.
The addition of polymerization inhibitors is generally advantageous; those conventionally used for acrylic compounds, for example hydroquinone, are used preferably.
The reaction pressure is not critical. Preferred is the range from atmospheric pressure to a pressure of about 50 ~: .
atmospheres. When carrying out the reaction in the liquid phase it is preferably operated under the vapor pressure corresponding ~ to the reaction temperature. It is also possible to operate j,~: :
,~ in the gaseous phase.
, . . . .
The process may be performed with the use of a solvent or ~ ~:
without. Suitable solvents are for example acetonitrile, tetrahydrofurane or benzene.
The acrylic component of formula II may be reacted completely 29 or partially. The conversion should not be higher than 90%
- 5 - ~;
:'' ... . .. . . .
, . , ... .... , , . .. .,.. , ,, . ,. , ~:
~076136 ..:
preferably, as otherwise secondary reactions could occur owing to the long reaction times and the elevated reaction temperatures ~-which may be necessary for a conversion of more than 90%. ~ -The fraction obtained in the separation of the reaction products by distillation substantially containing unreacted starting products, mesityl oxide and the catalyst may be reused in the reaction.
The process according to the invention may be performed as ~follows when working discontinuously: The reaction components, mesityl oxide included, are mixed with one another at room temperature, introduced into a reactor, for example an autoclave or a bomb tube and heated to the desired reaction temperature for a certain reaction time, for example for about 30 to 60 minutes. The reaction mixture is then cooled to room temperature ~ and worked up.
When working continuously the process may be carried out in the following manner: A mixture A of reactants, comprising .
acetone, acrylic acid, a polymerization inhibitor and optionally ;~ mesityl oxide or comprising acetone, acrylonitrile or acrylic 20~ acid ester, an acid such as benzoic acid, a polymerization ~ inhibitor and optionally mesityl oxide is passed by means of ; dosing pumps while vigorously stirring together with a mixture B of reactants, comprising acetone and isopropylamine through a reaction tube of an inner width of about 8 mm and a length of about 50 m heated to the desired reaction temperature.
After the desired residence time in the reaction tube, of about 30 minutes for example the reaction mixture is cooled to room 28 temperature and separated by distillation to yield a head ..
. . ,.. .. , . ~ . : . . .
' ' ' ''". ` ' ' " ', '` ' . ' ' , , ` " ' `~ , ' . . '~ ' ',' '~' ' ' :i........... , ,:,,, ., :, . . . . .. .. .
. , . . . . , . , ~,, , 1~76136 product substantially comprising acetone, acrylic acid component, mesityl oxide and the catalyst and a bottom product comprising substantially the desired reaction product of the formula I and high boiling by-products if any. The head product containing mesityl oxide is recycled to the starting mixture A.
The products of the present invention of the formula I
may be isolated from the bottom product, for example by distillation in vacuo and/or crystallization or extraction in a -pure form and with high yields, calculated on the converted starting components. As no further mesityl oxide formation from acetone takes place in the process according to the invention involving the presence of mesityl oxide, there are obtained unexpectedly high yields of the products of formula I, calculated on converted acetone. This signifies a considerable technical progress.
The following examples illustrate the invention:
: ~ :
C O M P A R A T I V E E X A M P L E 1:
3.04 kg of a mixture A comprising 73.9% by weight of acetone, 1.0% by weight of water, 25.0% by weight of acrylic acid and 0.1%
20 ; by weight of hydroquinone and 0.24 kg of a second mixture B
comprising 86.1% by weight of acetone and 13.9% by weight of isopropylamine were mixed with one another at room temperature and pumped through a reaction tube of about 8 mm width and a -volume of about 2 liters heated to 230C and cooled thereafter to 20C. According to the ~aschromatographic analysis the reaction product had the following composition: 61.6% by weight of acetone, 10.1~ by weight of acrylic acid, 16.4% by weight of 28 5-oxo-hexanoic acid, 5.8% by weight of mesityl oxide and 0.5 1~6136 by weight of 4-acetylheptanedioic acid.
The conversion, calculated on acrylic acid, was 57.2% and, calculated on acetone, 15.6%.
The yield of 5-oxo-hexanoic acid, calculated on converted acrylic acid, was 68.1% and, calculated on converted acetone, 47.7%.
The formation of mesityl oxide, calculated on converted acetone, was 52.3%.
E X A M P L E 1:
The example was carried out under the same reaction condi-tions as in Comparative Example 1, except that the starting mixture A contained additionally mesityl oxide. The composition of mixture A was as follows: 70.4% by weight of acetone, 5.4%
~ ~by weight of mesityl oxide, 23.1% by weight of acrylic acid, ; 15 ~ 1.0% by weight of water and 0.1~ by weight of hydroquinone. The composition of mixture B was the same as in Com- -: : ' : ' :'', :~: .
: ~ ' ' .
' ~ ' .
' , '';
;~ - 8 . - . , .
,, :, ' ,: ' ~ ' ,'' , , . ~
: . . .
- . - , , , ... . .
.
I-IO~.S_~_2 Ll 6 ~7f~
parative ~xalnple 1. The reaction product had the following compositioll: 63~3~ by weight of acetone, 12.7~ by weight of acrylic acid, 13.~oby weight of 5-oxo-hexanoic acid, 5.7~0 b-y weight o* mesityl oxide a~d 0.7~ by weight of 4-acetyl-heptanedioic acid.
The conversion, calculated on acrylic acid, was 48.1 and, calculated on acetone, 8.2~.
The yield of 5-oxo-hexanoic acid, calculated on con-verted acrylic acid, was 66~4~o and, calculated on converted acetone, 96.2~.
The formation of nnesityl oxide, calculated on converted . .
acetone, was only 3.8~.
C-0 M P A R ~_T I V E E X A M P L E 2-3157 g of a mixture comprising 79.2% by weight of acetone ~. - - / . . .:
1~ 19.8~ by weight of acrylic acid, 1.0~ by weight of isopropyl~
amine and 0.05% by weight of hydroquinolle were heated to 230 C Por a psriod of 1 hour in a S liter autoclave and cooled subsequently. The composition of the reaction product (3085 g) :.: :: .
was as follows: 70.5% by weight of acetone, 6.7% by weight of ~ ~ -acrylic acid, 3-5% by weight of mesityl oxide, 12.8~ by weight of 5-oxo-hexanoic acid and 0.9% by weight of 4-acetylheptane-~
~, :
~ dioic acid.
. . .
The conyersion, calcu:Lated on acrylic acid, was 65.65' and, calculated on aoetone, 13.09~.
The yiold Or 5-oxo-hexanoic acid, calculated on con-verted acrylic acid, was 68~1~o and, calculated on converted acetone, 55,9~o.
The formatlon of n1esityl oxide, calculated on convertad 29 acetone, was 1l0~5~o~
' . ". ' . ., , , i" ,, ;, ,','. . ,., ,: , . :, , . .::::,; " . ,: , ", ,: , E X A M P L E 2: -The example was performed under the same reaction conditions as Comparative Example 2, except that the starting mixture contained additionally mesityl oxide. The mixture (3157 g) had the following composition: 74.6% by weight of acetone, 19.8%
by weight of acrylic acid, 4.5% by weight of mesityl oxide~ 1.0% ~ -by weight of isopropylamine and 0.05% by weight of hydroquinone.
The composition of the reaction product (3145 g) was as follows:
65.8% by weight of acetone, 7.4% by weight of acrylic acid, 4.8% by weight of mesityl oxide, 14.6% by weight of 5-oxo-hexanoic acid and 1.2% by weight of 4-acetylheptanedioic acid.
The conversion, calculated on acrylic acid, was 62.0% and, ~ calculated on acetone, 9.3%.
; The yield of 5-oxo-hexanoic acid, calculated on converted acrylic acid, was 66.8% and, calculated on acetone, 95%.
The formation of mesityl oxide, calculated on converted acetone, was only 4.8%.
4.0 g of a mixture of 80.1 % by weight of acetone, 18.6%
~ 20 by weight of acrylic acid methyl ester, 1.0% by weight of iso-; ~ ~ propylamine, 0.2% by weight of benzoic acid and 0.05% by weight of hydroquinone were heated to 230C for 30 minutes in a bomb tube having a capacity of 6 cm3 and immediately cooled to 20C
thereafter. The reaction product had the following composition:
67.4% by weight of acetone, 5.6% by weight of acrylic acid methyl ester, 0.8% by weight of mesityl oxide, 15.6% by weight of 5-oxo-hexanoic acid methyl ester and 2.0% by weight of 4-acetylheptanedioic acid dimethyl ester.
. ., . - -. .. . , . ~ . .
- . - , .
,, . .: . ' . :
. " , ~. .,,, , , ; , ... , . -. .
.......
~ . '. ' ' ;"
107~:;136 The conversion, calculated on acrylic acid methyl ester, was 69.1% and, calculated on acetone, 14.4%.
The yield of 5-oxo-hexanoic acid methylester, calculated on converted acrylic acid methyl ester, was 79.3% and, calculated on converted acetone, 81.2%.
The formation of mesityl oxide, calculated on converted acetone, was 12.2%.
E X A M P L E 3:
The example was carried out under the same conditions as Comparative Example 3, except that the starting mixture contained additionally mesityl oxide. The mixture (4.0 g) had the follow-ng composition: 74.6~ by weight o acetone, 5.5% by weight of mesityl oxide, 18.6% by weight of acrylic acid methyl ester, 1.0%
, by weight of isopropylamine, 0.2% by weight of benzoic acid and lS~ 0.05% by weight o hydroquinone. The reaction product had the following composition: 75.0% by weight of acetone, 9.4% by weight of acrylic acid methyl ester, 5.5% by weight o mesityl -oxide, 8.0% by weight of 5-oxo-hexanoic acid methyl ester and - ;
0.9% by weight of 4-acetylheptanedioic acid dimethyl ester.
20 ~ The conversion, calculated on acrylic acid methyl ester, was 47.2% and, calculated on acetone, 3.1%.
~ ~ The yield of 5-oxo-hexanoic acid methyl ester, calculated ;~ on converted acrylic acid methyl ester, was 77% and calculated on converted acetone, 92.9%.
~25 A urther ormation o mesityl oxide could not be observed.
~: :, ' ' ' : . ~. . .
''' ' '"' '. ,' "" '"' ~,', '','."'' ' ' . " ' '," ',."''' ",,' '" '' ' '; '~'', ' ~"' ' .. . .. . . .
Claims (9)
PROPERTY OF PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A process for the preparation of 5-oxo-hexanoic acid or of a derivative thereof of the general formula (I) CH3 - CO - CH2 - CH2 - CH2 - R (I) wherein R represents carboxyl, alkoxycarbonyl containing alkoxy groups having up to 12 carbon atoms or carbonitrile, in which acetone is reacted with an acrylic acid compound of the formula (II) CH2 = CH - R (II) wherein R is as defined above, at an elevated temperature in the presence of a basic catalyst and the reaction is carried out in the presence of from 2 to 8% by weight of mesityl oxide, calcu-lated on the reaction mixture.
2. A process as claimed in claim 1 in which the reaction is carried out in the presence of from 4 to 6% by weight of mesityl oxide, calculated on the reaction mixture.
3. A process as claimed in claim 1 in which the catalyst is selected from the group of primary amines, aminoalcohols, amino-carboxylic acids, the Schiff bases thereof with acetone and N-substituted .beta.-aminopropionates formed by the addition of primary amines and acrylic acid esters.
4. A process as claimed in claim 1, claim 2 or claim 3 in which the catalyst is used in an amount of from about 0.01 to 0.2 mol per mol of the compound of the formula II.
5. A process as claimed in claim 1, claim 2 or claim 3 in which the reaction is carried out continuously.
6. A process as claimed in claim 1, claim 2 or claim 3 in which the reaction is carried out discontinuously.
7. A process as claimed in claim 1, claim 2 or claim 3 in which the reaction is carried out at a temperature in the range of from 150 to 250°C.
8. A process as claimed in claim 1, claim 2 or claim 3 in which the reaction is carried out at a temperature in the range of from 200 to 240°C.
9. A process as claimed in claim 1, claim 2 or claim 3 in which the ratio of acetone to the compound of the formula (II) is in the range of from 1:1 to 20:1.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE2540972A DE2540972C3 (en) | 1975-09-13 | 1975-09-13 | Process for the preparation of 5-oxohexanoic acid and its derivatives |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1076136A true CA1076136A (en) | 1980-04-22 |
Family
ID=5956448
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA260,943A Expired CA1076136A (en) | 1975-09-13 | 1976-09-10 | Process for the preparation of 5-oxohexanoic acid and its derivatives |
Country Status (12)
| Country | Link |
|---|---|
| JP (1) | JPS5236624A (en) |
| BE (1) | BE846141A (en) |
| BR (1) | BR7606039A (en) |
| CA (1) | CA1076136A (en) |
| CH (1) | CH605559A5 (en) |
| DE (1) | DE2540972C3 (en) |
| FR (1) | FR2323673A1 (en) |
| GB (1) | GB1554310A (en) |
| IT (1) | IT1070590B (en) |
| MX (1) | MX144675A (en) |
| NL (1) | NL7609962A (en) |
| ZA (1) | ZA765386B (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NL7609478A (en) * | 1976-08-26 | 1978-02-28 | Stamicarbon | PROCESS FOR THE PREPARATION OF 4-OXOCAPRONI TRIL. |
| NL7800982A (en) * | 1978-01-27 | 1979-07-31 | Stamicarbon | PROCESS FOR PREPARING THE METHYL ESTER 4-OXOPENTANE-1-CARBONIC ACID. |
| NL7808605A (en) * | 1978-08-19 | 1980-02-21 | Stamicarbon | PROCESS FOR THE PREPARATION OF DELTA KETO ACIDS AND THEIR DERIVATIVES. |
| DE2952044A1 (en) * | 1979-12-22 | 1981-07-02 | Hoechst Ag, 6230 Frankfurt | METHOD FOR PRODUCING 5-OXOALKANIC ACIDS |
| JPS56102609A (en) * | 1980-01-19 | 1981-08-17 | Matsushita Electric Ind Co Ltd | Gas combustion control device |
| CA1212382A (en) * | 1982-04-26 | 1986-10-07 | Koppers Company, Inc. | Liquid-phase preparation of delta-keto carboxylic acid esters utilizing liquid-phase insoluble catalyst |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2820805A (en) * | 1954-07-02 | 1958-01-21 | Polak & Schwarz C Essencefabri | Process of preparing keto acids |
-
1975
- 1975-09-13 DE DE2540972A patent/DE2540972C3/en not_active Expired
-
1976
- 1976-09-08 NL NL7609962A patent/NL7609962A/en not_active Application Discontinuation
- 1976-09-09 ZA ZA765386A patent/ZA765386B/en unknown
- 1976-09-10 CH CH1156576A patent/CH605559A5/xx not_active IP Right Cessation
- 1976-09-10 JP JP51107964A patent/JPS5236624A/en active Pending
- 1976-09-10 CA CA260,943A patent/CA1076136A/en not_active Expired
- 1976-09-10 IT IT27119/76A patent/IT1070590B/en active
- 1976-09-13 BE BE170586A patent/BE846141A/en not_active IP Right Cessation
- 1976-09-13 MX MX166288A patent/MX144675A/en unknown
- 1976-09-13 GB GB37902/76A patent/GB1554310A/en not_active Expired
- 1976-09-13 FR FR7627453A patent/FR2323673A1/en active Granted
- 1976-09-13 BR BR7606039A patent/BR7606039A/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| IT1070590B (en) | 1985-03-29 |
| ZA765386B (en) | 1977-08-31 |
| BR7606039A (en) | 1977-08-23 |
| MX144675A (en) | 1981-11-10 |
| BE846141A (en) | 1977-03-14 |
| FR2323673A1 (en) | 1977-04-08 |
| JPS5236624A (en) | 1977-03-22 |
| DE2540972A1 (en) | 1977-03-17 |
| NL7609962A (en) | 1977-03-15 |
| DE2540972B2 (en) | 1978-07-27 |
| FR2323673B1 (en) | 1980-05-23 |
| CH605559A5 (en) | 1978-09-29 |
| DE2540972C3 (en) | 1979-03-22 |
| GB1554310A (en) | 1979-10-17 |
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