CA1152527A - Process for the manufacture of 5 - oxoalkanoic acids, their esters and their nitrils - Google Patents
Process for the manufacture of 5 - oxoalkanoic acids, their esters and their nitrilsInfo
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- CA1152527A CA1152527A CA000342369A CA342369A CA1152527A CA 1152527 A CA1152527 A CA 1152527A CA 000342369 A CA000342369 A CA 000342369A CA 342369 A CA342369 A CA 342369A CA 1152527 A CA1152527 A CA 1152527A
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- 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
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/347—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups
- C07C51/373—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups by introduction of functional groups containing oxygen only in doubly bound form
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- Chemical Kinetics & Catalysis (AREA)
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- Oil, Petroleum & Natural Gas (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 manufacture of 5-oxoalkanoic acids, their esters or nitrils, by reaction of a ketone containing at least one .alpha.-hydrogen atom, at elevated temperature, with an .alpha.,.beta.-unsaturated acid, its ester or nitril, in the liquid phase, in the presence of at least one compound selected from the group consisting of: primary amines, primary aminoalcohols, primary aminocarboxylic acids, Schiff's bases of primary amines and the ketone used, and, if .alpha.,.beta.-unsaturated carboxylic acid eaters are reacted, the .beta.,aminopropionates formed from the latter esters and primary amines, which comprises conducting the reaction under a pressure above the vapor pressure of the reaction mixture and below 500 bars.
Process for the manufacture of 5-oxoalkanoic acids, their esters or nitrils, by reaction of a ketone containing at least one .alpha.-hydrogen atom, at elevated temperature, with an .alpha.,.beta.-unsaturated acid, its ester or nitril, in the liquid phase, in the presence of at least one compound selected from the group consisting of: primary amines, primary aminoalcohols, primary aminocarboxylic acids, Schiff's bases of primary amines and the ketone used, and, if .alpha.,.beta.-unsaturated carboxylic acid eaters are reacted, the .beta.,aminopropionates formed from the latter esters and primary amines, which comprises conducting the reaction under a pressure above the vapor pressure of the reaction mixture and below 500 bars.
Description
5~Z7
- 2 - HOE 78/F 2~1 The present invention relal;es to a process Ior the ma-nufacture of 5-oxoalkanoic acids, their esters and their nitrils.
It is known to obtain 5-oxoalkanoic acids by amine-catalyzed addition of a ketone containing at least one hydrogen atom in ~-position with regard to the keto group, to an ~,B-unsaturated acid (cf. DE-OS 2 348 536). 5-oxo-alkanoic acid esters (cf. DE-OS 2 325 160) or 5-oxoalkane nitrils (cf. DE-OS 2 329 923) may be prepared analogously from the corresponding ~,R-unsaturated carboxylic acid esters or nitrils.
The 5-oxoalkanoic acids and their esters are valuable starting products for resorcinols, these latter being used in rubber and glue industries or as antiseptics. The 5-oxo-alkane nitrils may be converted into the 5-oxoalkanoic acids or 5-oxoalkanoic acid esters. They are furthermore starting substances for Oc-picolines~ which latter may be used for the manufacture of vinylpyridines (comonomers in the copolymerization using butadiene, styrene or acryloni-tril).
An substantial disadvantage of the aforesaid processes resides in their moderate productivity.
It was, consequently, a need to increase the space-- time yield in the above-described processes without impair-ing their selectivity.
A process for the manufacture of 5-oxoalkanoic acids, their esters or nitrils has now been found by reaction of a ketone containing at least one oC-hydrogen atom, at ele-vated temperature, with an ~ unsaturated acid, its ester 29 or nitril, in the liquid phase, in the presence of at least ,:
' ~':
~52527 _ 3 _ HOE 78/F 281 one compound selected from the group conslsting of:
primary amines, primary aminoalcohols, primary aminocarb-oxylic acid, Schiff's bases of primary amines and the ke-tone used, and if, ~,~-unsaturated carboxylic acid esters are reacted, the ~-aminopropionates formed from the latter esters and primary amines, which comprises conducting the reaction under a pressure above the vapor pressure of the reaction mixture and below 500 bars, a pressure below 280 bars, especially below 200 bars, being preferred.
In the prior art publ1cations DE-OS 2 348 536, DE-OS
2 325 160, DE-OS 2 329 923 it had been stated that the pressure was not critical, operation being generally per-formed under a pressure from atmospheric pressure to 50 atmospheres, preferably under the vapor pressure corres-ponding to the reaction temperature. DE-OS 2 246 284, DE-OS 2 355 859 and DE-OS 2 738 388 disclosed that the pressure should be chosen only as high as to make sure that the reaction mixture be present as a liquid.
It was, consequently, very surprising that the space-time yield could be significantly increased by increasing the pressure above the vapor pressure of the reactants corresponding to the reaotion temperature, although it had to be expected that a pressure increase in a liquid phase reaction would have no influence on the space-time yield.
The most favorable reaction temperature depends on the nature and on the quantity of the ketone used, of the ~ -unsaturated compound used and of the catalyst used. Gene-rally operation is carried out at a temperature between 29 100 and 250C, preferably between 150C and the critical .
, ^~5'~527 temperature of the reactants used.
A pressure increase above the vapor pressure (corres-ponding to the chosen reaction temperature) of the reac-tants may be brought about by the liquid pressure which establishes when the reactor used for the reaction is charged with the reaction components at room temperature at least to such a degree that the gaseous phase vanishes on heating to the reaotion temperature. A further appro-priate method, in particular with ketones of rather high boiling point ti.e. those having more than 6 carbon atoms) is to press into the reactor an inert gas such as N2 or argon under a pressure surpassing the vapor pressure of the reaction components.
Suitable ketones for the reaction include acetone, methylethylketone, diethylketone, methylpropylketone, methylisopropylketone, methylbutylketone, cyclopentanone, cyclohexanone and benzylmethylketone.
Examples of ~,~-unsaturated compounds are acrylic acid, methacrylic acid, crotonic acid, maleio acid, fumaric acid and itaconic acid, and the corresponding nitrils and alkyl ester thereof having up to 12, preferably up to 6, carbon atoms in the alkyl moiety.
Suitable catalysts are for example: methylamine, ethyl-amine, n-propylamine, isopropylamine, n-butylamine, isobu-tylamine, sec. butylamine, tert. butylamine, amylamine, iso-amylamine, ethylene diamine, tetramethylene diamine, cyclo-hexylamine, cyclopentylamine, benzylamine, aniline, o-, m-, p-toluidine, -aminocaProic acid, aminoethanol, Schiff's 29 bases obtained from the ketones used as starting products -::
,: ~' ... . .
~52527 _ 5 _ HOE 78/F 281 and the said primary a~ines, N-substituted ~-aminopropio-nates formed from the said amines in case that ~,~-unsatu-rated carboxylic acid esters are used.
Catalysts whose boiling points are below that of the 5-oxo compounds formed are used preferably. Upon distil-lation the reaction mixture obtained in the process accord-ing to the invention yields a first fraction containing un-reacted ketone, unreacted ~R-unsaturated compound and the catalyst, a second (and main) fraction containing substan-tially the desired oxo compound and third a residue consist-ing of compounds as obtained by addition of two molecules of unsaturated compound to one ketone molecule. The first fraction can be reused in another test without further treatment or, in the case of a continuous mode of operat-ing, by recycled to the reactor.
The quantity of catalyst is generally in the range offrom 0.01 to 0.4 mol per mol of ~,~-unsaturated compound.
When an d~-unsaturated carboxylic acid ester or an oG~R-unsaturated nitril is used as starting component, it is advisable to add an acid compound to improve the se-lectivity, generally in an amount of from approximately 0.01 to 2 weight %, preferably from 0.1 to 0.5 weight ~, referred to the reaction mixture, it being possible to use organic acids as well as inorganic acids. Examples thereof are: acrylic acid, methacrylic acid, crotonic acid, benzoic acid, 2-nitrobenzoic acid, 4-nitrobenzoic acid, hexanoic acid, p-toluene sulfonic acid, 4-methoxy-benzoic acid, acetic acid, propionic acid, ethylhexanoic 29 acid, boric acid, hydrochloric acid, sulfuric acid and ' ; .' -, ~: ., '.
phosphoric acid. It is particularly advisable in the case of the reaction of a ketore with an unsaturated ester, to use as the additive the unsaturated acid corresponding to the ester.
The ratio of ketone to ~ ~-unsaturated compound is generally from 1:2 to 20:1, preferably from 3:1 to 8:1.
The reaction can be conducted with or without the use of solvents or diluents.
Suitably a polymerization inhibitor such as hydroqui-none, hydroquinone monomethyl ester or phenothiazine is added.
- When operating in discontinuous manner, the process according to the invention may be carried out in the following manner:
The reaction components are mixed with one another at room temperature and charged subsequently into a reactor such as an autoclave or a bomb tube and heated for a certain period of time to the desired reaction temperature. Thereafter :
the reaction mixture is rapidly cooled, analyzed and worked up by distillation.
When operating in continuous manner, the following pro-cedure has proved advantageous: A mixture consisting for example of acetone, methylaorylate , polymerization inhibi-t-or, an acid such as acrylic acid, and isopropylamine, is thoroughly mixed and subsequently pumped through a reaction tube heated to the desired reaction temperature, by means of a metering pump. At the outlet this reaction tube is provided with an automatic level ard pressure control. The 29 desired reaction pressure is set up by superposition with .
: ~ ' .. ..
~5;25;~7 an inert gas.
The fo lowing examples illustrate the invention in greater detail.
Manufacture of 5-oxohexanoic acid methyl ester (OHM) E X A M P L E 1:
.
A bomb tube of 30 ml volume is charged with 15, 18, 23 and 27.5 ml, respectively, of the below-indicated starting mixture and submerged into an oilbath 220C hot for 30 minutes. Thereaftèr the contents are cooled and analyzed.
- The test conditions and the results are summarized in Table 1.
The abbreviations used in this Example and in the following Examples are defined as follows:
STY (g/l-h) = space-time yield (gram per liter of reactor ~olume and per hour) Sel/X = mol of final product per mol of consumed starting product X(mol ~) Ac = acetone 20 MEK = methylethyl ketone IPA = isopropylamine MAC = methacrylate AA = acrylic acid HQ = hydroquinone 25 reactor = part of the reactor volume which has been charge charged with starting mixture at room tempe-rature.
Starting mixture Ac MAC IPA H20 AA HQ
(weight %) 72.0 23.0 2.2 2.5 0.2 0.05 : : ~
- ~ ~
~152527 - 8 - HOE 78tF 281 Table 1:
Test Reactor Pressure Product comp.OHM
charge (weight g) (vol. ~) (g~ (bar) Sel/ Sel/ STY
Ac MAC OHM MAC Ac ________________~_____________ _______ __________. _________ 1 A 50 12 40 67.6 16.4 7.9 72 73 63 1 B 60 14.4 40 67.7 16.5 8.2 75 76 79 1 C 77 18.4 60 65.4 12.4 13.4 82 82 167 1 D 92 22.0 250 62.4 9.0 18.6 79 79 273 Tests 1 A and 1 B are comparative tests. In this case the reaction pressure corresponds to the vapor pres-sure of the reaction mixture. An increase of the reactor charge from 50 % (Test 1 A) to 77 % (Test 1 C) or to 92 %
(Test 1 D) gi~es rise to an increase of the pressure in the reactor from 40 bars (1 A) to 60 bars (1 C) or to 250 bars t1 D). The pressure increase from 40 to 250 bars brings about an increase of the OHM space-time yield to
It is known to obtain 5-oxoalkanoic acids by amine-catalyzed addition of a ketone containing at least one hydrogen atom in ~-position with regard to the keto group, to an ~,B-unsaturated acid (cf. DE-OS 2 348 536). 5-oxo-alkanoic acid esters (cf. DE-OS 2 325 160) or 5-oxoalkane nitrils (cf. DE-OS 2 329 923) may be prepared analogously from the corresponding ~,R-unsaturated carboxylic acid esters or nitrils.
The 5-oxoalkanoic acids and their esters are valuable starting products for resorcinols, these latter being used in rubber and glue industries or as antiseptics. The 5-oxo-alkane nitrils may be converted into the 5-oxoalkanoic acids or 5-oxoalkanoic acid esters. They are furthermore starting substances for Oc-picolines~ which latter may be used for the manufacture of vinylpyridines (comonomers in the copolymerization using butadiene, styrene or acryloni-tril).
An substantial disadvantage of the aforesaid processes resides in their moderate productivity.
It was, consequently, a need to increase the space-- time yield in the above-described processes without impair-ing their selectivity.
A process for the manufacture of 5-oxoalkanoic acids, their esters or nitrils has now been found by reaction of a ketone containing at least one oC-hydrogen atom, at ele-vated temperature, with an ~ unsaturated acid, its ester 29 or nitril, in the liquid phase, in the presence of at least ,:
' ~':
~52527 _ 3 _ HOE 78/F 281 one compound selected from the group conslsting of:
primary amines, primary aminoalcohols, primary aminocarb-oxylic acid, Schiff's bases of primary amines and the ke-tone used, and if, ~,~-unsaturated carboxylic acid esters are reacted, the ~-aminopropionates formed from the latter esters and primary amines, which comprises conducting the reaction under a pressure above the vapor pressure of the reaction mixture and below 500 bars, a pressure below 280 bars, especially below 200 bars, being preferred.
In the prior art publ1cations DE-OS 2 348 536, DE-OS
2 325 160, DE-OS 2 329 923 it had been stated that the pressure was not critical, operation being generally per-formed under a pressure from atmospheric pressure to 50 atmospheres, preferably under the vapor pressure corres-ponding to the reaction temperature. DE-OS 2 246 284, DE-OS 2 355 859 and DE-OS 2 738 388 disclosed that the pressure should be chosen only as high as to make sure that the reaction mixture be present as a liquid.
It was, consequently, very surprising that the space-time yield could be significantly increased by increasing the pressure above the vapor pressure of the reactants corresponding to the reaotion temperature, although it had to be expected that a pressure increase in a liquid phase reaction would have no influence on the space-time yield.
The most favorable reaction temperature depends on the nature and on the quantity of the ketone used, of the ~ -unsaturated compound used and of the catalyst used. Gene-rally operation is carried out at a temperature between 29 100 and 250C, preferably between 150C and the critical .
, ^~5'~527 temperature of the reactants used.
A pressure increase above the vapor pressure (corres-ponding to the chosen reaction temperature) of the reac-tants may be brought about by the liquid pressure which establishes when the reactor used for the reaction is charged with the reaction components at room temperature at least to such a degree that the gaseous phase vanishes on heating to the reaotion temperature. A further appro-priate method, in particular with ketones of rather high boiling point ti.e. those having more than 6 carbon atoms) is to press into the reactor an inert gas such as N2 or argon under a pressure surpassing the vapor pressure of the reaction components.
Suitable ketones for the reaction include acetone, methylethylketone, diethylketone, methylpropylketone, methylisopropylketone, methylbutylketone, cyclopentanone, cyclohexanone and benzylmethylketone.
Examples of ~,~-unsaturated compounds are acrylic acid, methacrylic acid, crotonic acid, maleio acid, fumaric acid and itaconic acid, and the corresponding nitrils and alkyl ester thereof having up to 12, preferably up to 6, carbon atoms in the alkyl moiety.
Suitable catalysts are for example: methylamine, ethyl-amine, n-propylamine, isopropylamine, n-butylamine, isobu-tylamine, sec. butylamine, tert. butylamine, amylamine, iso-amylamine, ethylene diamine, tetramethylene diamine, cyclo-hexylamine, cyclopentylamine, benzylamine, aniline, o-, m-, p-toluidine, -aminocaProic acid, aminoethanol, Schiff's 29 bases obtained from the ketones used as starting products -::
,: ~' ... . .
~52527 _ 5 _ HOE 78/F 281 and the said primary a~ines, N-substituted ~-aminopropio-nates formed from the said amines in case that ~,~-unsatu-rated carboxylic acid esters are used.
Catalysts whose boiling points are below that of the 5-oxo compounds formed are used preferably. Upon distil-lation the reaction mixture obtained in the process accord-ing to the invention yields a first fraction containing un-reacted ketone, unreacted ~R-unsaturated compound and the catalyst, a second (and main) fraction containing substan-tially the desired oxo compound and third a residue consist-ing of compounds as obtained by addition of two molecules of unsaturated compound to one ketone molecule. The first fraction can be reused in another test without further treatment or, in the case of a continuous mode of operat-ing, by recycled to the reactor.
The quantity of catalyst is generally in the range offrom 0.01 to 0.4 mol per mol of ~,~-unsaturated compound.
When an d~-unsaturated carboxylic acid ester or an oG~R-unsaturated nitril is used as starting component, it is advisable to add an acid compound to improve the se-lectivity, generally in an amount of from approximately 0.01 to 2 weight %, preferably from 0.1 to 0.5 weight ~, referred to the reaction mixture, it being possible to use organic acids as well as inorganic acids. Examples thereof are: acrylic acid, methacrylic acid, crotonic acid, benzoic acid, 2-nitrobenzoic acid, 4-nitrobenzoic acid, hexanoic acid, p-toluene sulfonic acid, 4-methoxy-benzoic acid, acetic acid, propionic acid, ethylhexanoic 29 acid, boric acid, hydrochloric acid, sulfuric acid and ' ; .' -, ~: ., '.
phosphoric acid. It is particularly advisable in the case of the reaction of a ketore with an unsaturated ester, to use as the additive the unsaturated acid corresponding to the ester.
The ratio of ketone to ~ ~-unsaturated compound is generally from 1:2 to 20:1, preferably from 3:1 to 8:1.
The reaction can be conducted with or without the use of solvents or diluents.
Suitably a polymerization inhibitor such as hydroqui-none, hydroquinone monomethyl ester or phenothiazine is added.
- When operating in discontinuous manner, the process according to the invention may be carried out in the following manner:
The reaction components are mixed with one another at room temperature and charged subsequently into a reactor such as an autoclave or a bomb tube and heated for a certain period of time to the desired reaction temperature. Thereafter :
the reaction mixture is rapidly cooled, analyzed and worked up by distillation.
When operating in continuous manner, the following pro-cedure has proved advantageous: A mixture consisting for example of acetone, methylaorylate , polymerization inhibi-t-or, an acid such as acrylic acid, and isopropylamine, is thoroughly mixed and subsequently pumped through a reaction tube heated to the desired reaction temperature, by means of a metering pump. At the outlet this reaction tube is provided with an automatic level ard pressure control. The 29 desired reaction pressure is set up by superposition with .
: ~ ' .. ..
~5;25;~7 an inert gas.
The fo lowing examples illustrate the invention in greater detail.
Manufacture of 5-oxohexanoic acid methyl ester (OHM) E X A M P L E 1:
.
A bomb tube of 30 ml volume is charged with 15, 18, 23 and 27.5 ml, respectively, of the below-indicated starting mixture and submerged into an oilbath 220C hot for 30 minutes. Thereaftèr the contents are cooled and analyzed.
- The test conditions and the results are summarized in Table 1.
The abbreviations used in this Example and in the following Examples are defined as follows:
STY (g/l-h) = space-time yield (gram per liter of reactor ~olume and per hour) Sel/X = mol of final product per mol of consumed starting product X(mol ~) Ac = acetone 20 MEK = methylethyl ketone IPA = isopropylamine MAC = methacrylate AA = acrylic acid HQ = hydroquinone 25 reactor = part of the reactor volume which has been charge charged with starting mixture at room tempe-rature.
Starting mixture Ac MAC IPA H20 AA HQ
(weight %) 72.0 23.0 2.2 2.5 0.2 0.05 : : ~
- ~ ~
~152527 - 8 - HOE 78tF 281 Table 1:
Test Reactor Pressure Product comp.OHM
charge (weight g) (vol. ~) (g~ (bar) Sel/ Sel/ STY
Ac MAC OHM MAC Ac ________________~_____________ _______ __________. _________ 1 A 50 12 40 67.6 16.4 7.9 72 73 63 1 B 60 14.4 40 67.7 16.5 8.2 75 76 79 1 C 77 18.4 60 65.4 12.4 13.4 82 82 167 1 D 92 22.0 250 62.4 9.0 18.6 79 79 273 Tests 1 A and 1 B are comparative tests. In this case the reaction pressure corresponds to the vapor pres-sure of the reaction mixture. An increase of the reactor charge from 50 % (Test 1 A) to 77 % (Test 1 C) or to 92 %
(Test 1 D) gi~es rise to an increase of the pressure in the reactor from 40 bars (1 A) to 60 bars (1 C) or to 250 bars t1 D). The pressure increase from 40 to 250 bars brings about an increase of the OHM space-time yield to
3.5 times the original one (79 to 274 g/l~h).
E X A M P L E 2:
An autoclave of 110 ml volume is charged to 50, 70, 80 and 90 %, respectively, with a starting mixture of the be-low-indicated composition and the contents are heated for 45 minutes to 230C. Thereafter they are immediately cool-ed and analyzed. Table 2 indicates the test conditions and the test results.
- :
;
-;Z52t7 ` - g - HOE 78/F 281 Starting mixture Ac MAC IPA BA H20 HQ
(weight ~) 75.8 20.0 1.0 0.1 3.0 0.05 BA = benzoic acid.
Table 2:
Test Reactor Pressure Product comp. OHM
charge (weight %) (vol. g) (g) (bar) Sel/ Sel/ STY
Ac MAC OHM MAC Ac 2 A 50 44 45 70.9 13.1 9.3 81 77 50 2 B 70 61.6 76 69.5 10.6 12.4 79 79 83 2 C 80 7.4 170 68.2 8.316.3 83 86 139 2 D 9 79.2 250 64.9 4.221.2 80 78 203 Test 2 A is a comparative test carried out at the va-por pressure of the reaction mixture.
The increase of the reactor pressure from 45 bars (Test 2 A) to 250 bars (Test 2 D) causes an improvement of the space-time yield of OHM to the 4-fold original level.
E X A M P L E 3:
A flow tube of 3.2 liters volume being provided at one end with a level and pressure control is heated to 230C.
Thereafter 3500 g of the starting mixture of the c~mposi-tion shown below, per hour, are pumped through the reaction tube. The vapor pressure is 45 bars. The reaction product is collected at the end of the reactor and analyzed. The results are s~nmarized in Table 3.
~-5~527 Test 3 B
The reactor pressure is raised to 60 bars by means of superposition with an inert gas, the rest of the procedure being the same of in Comparative Test 3 A. The results are summarized in Table 3.
Starting mixture Ac MAC IPA H20 AA
(weight ~) 80 15 3 2 0.1 Table 3: -Test Pressure Product comp. STY of OHM
(weight %) tbar) Ac MAC OHM
___________________________________________________ - 3 A 45 71.1 4.2 13.4 147 3 B 60 67.0 1.1 17.9 196 The increase of the reaction pressure from 45 to 60 bars brings about an increase of the space-time yield from 147 g/l-h to 196 gtl h, in this case of continuous opera-tion.
Manufacture of 5-oxohexane nitril ~OHN) E X A M P E E 4:
To an autoclave of 110 ml volume which is provided with a manometer there are fed 66 ml, 77 ml or 99 ml, respectively (60, 70 or 90 volume %, respectively) of the below-indicated starting mixture and the contents are heated to 230C for 45 minutes, subsequently cooled and .- ' ~
~ ~-:
:-: ':
analyzed. The ~est conditions and the results are summa-rized in Table 4.
Starting mixture IPA Ac AN H20 AA HQ
(weight g) 0.9 81.0 15.7 2.3 0.1 0.05 AN = acrylonitril Table 4:
Test Pressure Reactor Product comp. OHN
charge (weight %) (bar) (ml) (g) Ac AN OHN Sel/ Sel/ STY
AN Ac
E X A M P L E 2:
An autoclave of 110 ml volume is charged to 50, 70, 80 and 90 %, respectively, with a starting mixture of the be-low-indicated composition and the contents are heated for 45 minutes to 230C. Thereafter they are immediately cool-ed and analyzed. Table 2 indicates the test conditions and the test results.
- :
;
-;Z52t7 ` - g - HOE 78/F 281 Starting mixture Ac MAC IPA BA H20 HQ
(weight ~) 75.8 20.0 1.0 0.1 3.0 0.05 BA = benzoic acid.
Table 2:
Test Reactor Pressure Product comp. OHM
charge (weight %) (vol. g) (g) (bar) Sel/ Sel/ STY
Ac MAC OHM MAC Ac 2 A 50 44 45 70.9 13.1 9.3 81 77 50 2 B 70 61.6 76 69.5 10.6 12.4 79 79 83 2 C 80 7.4 170 68.2 8.316.3 83 86 139 2 D 9 79.2 250 64.9 4.221.2 80 78 203 Test 2 A is a comparative test carried out at the va-por pressure of the reaction mixture.
The increase of the reactor pressure from 45 bars (Test 2 A) to 250 bars (Test 2 D) causes an improvement of the space-time yield of OHM to the 4-fold original level.
E X A M P L E 3:
A flow tube of 3.2 liters volume being provided at one end with a level and pressure control is heated to 230C.
Thereafter 3500 g of the starting mixture of the c~mposi-tion shown below, per hour, are pumped through the reaction tube. The vapor pressure is 45 bars. The reaction product is collected at the end of the reactor and analyzed. The results are s~nmarized in Table 3.
~-5~527 Test 3 B
The reactor pressure is raised to 60 bars by means of superposition with an inert gas, the rest of the procedure being the same of in Comparative Test 3 A. The results are summarized in Table 3.
Starting mixture Ac MAC IPA H20 AA
(weight ~) 80 15 3 2 0.1 Table 3: -Test Pressure Product comp. STY of OHM
(weight %) tbar) Ac MAC OHM
___________________________________________________ - 3 A 45 71.1 4.2 13.4 147 3 B 60 67.0 1.1 17.9 196 The increase of the reaction pressure from 45 to 60 bars brings about an increase of the space-time yield from 147 g/l-h to 196 gtl h, in this case of continuous opera-tion.
Manufacture of 5-oxohexane nitril ~OHN) E X A M P E E 4:
To an autoclave of 110 ml volume which is provided with a manometer there are fed 66 ml, 77 ml or 99 ml, respectively (60, 70 or 90 volume %, respectively) of the below-indicated starting mixture and the contents are heated to 230C for 45 minutes, subsequently cooled and .- ' ~
~ ~-:
:-: ':
analyzed. The ~est conditions and the results are summa-rized in Table 4.
Starting mixture IPA Ac AN H20 AA HQ
(weight g) 0.9 81.0 15.7 2.3 0.1 0.05 AN = acrylonitril Table 4:
Test Pressure Reactor Product comp. OHN
charge (weight %) (bar) (ml) (g) Ac AN OHN Sel/ Sel/ STY
AN Ac
4 A44 66 52 72.8 8.4 12.2 80 78 77 4 B60 77 60 71.6 7.3 14.3 82 80 104 4 C280 99 78 68.4 4.7 19.1 83 79 181 A pressure increase of 44 bars in Comparative Test 4 A (vapor pressure of the starting mixture at 230C) to 280 bars (Test 4 C) brir.gs about a 2.4 fold increase of the space-time yield.
Manufacture of 5-oxohexanoic acid (OHS) E X A M P L E 5:
- Three bomb tubes of 30 ml volume each are charged with 18 ml, 24 ml and 27 respectively, of the starting mixture indicated below and submerged togehter into an oilbath heated to 230C for 30 minutes. The contents are subsequently cooled and analyzed. The test condiiions and results are summarized in Table 5.
`~ :
, ~ ., .
~52~2~7 - 12 - HOE 78~F 281 Starting mixture Ac AA IPQ MO H20 HQ
(weight ~) 68.9 24.0 1.0 5.0 1.0 0.05 MO = mesityl oxide Table 5:
Test Reactor Pressure Product comp. OHS
charge (weight %) (vol.%) (g) (bar) Ac AA MO OHS Sel/ Sel/ STY
AA Ac -
Manufacture of 5-oxohexanoic acid (OHS) E X A M P L E 5:
- Three bomb tubes of 30 ml volume each are charged with 18 ml, 24 ml and 27 respectively, of the starting mixture indicated below and submerged togehter into an oilbath heated to 230C for 30 minutes. The contents are subsequently cooled and analyzed. The test condiiions and results are summarized in Table 5.
`~ :
, ~ ., .
~52~2~7 - 12 - HOE 78~F 281 Starting mixture Ac AA IPQ MO H20 HQ
(weight ~) 68.9 24.0 1.0 5.0 1.0 0.05 MO = mesityl oxide Table 5:
Test Reactor Pressure Product comp. OHS
charge (weight %) (vol.%) (g) (bar) Ac AA MO OHS Sel/ Sel/ STY
AA Ac -
5 A 60 15.740 63.4 16.1 5.4 9.7 68 79 102 5 B 80 20.9130 61.4 13.9 5~5 13.1 72 78 183 5 C 90 23.5250 59.7 11.6 5.6 17.1 76 83 268 An increase of the reaction pressure from 40 bars (Comparative Test 5 A) to 250 bars ~Test 5 C) brings about a 2.6-fold increase of the space-time yield of OHS with simultaneous improvement of the selectivity of OHS, rela-tive to AA and acetone.
Manufacture of 5-oxohexanoic acid n-butyl ester (OHB) E X A M P L E 6:
Two bomb tubes of 30 ml volume each are charged with 18 and 27 ml, respectively, of the starting mixture indi-cated below and heated simulatneously to 230C for 30 minu-tes. Thereafter the contents are cooled and analyzed. The test conditions and results are summarized in Table 6.
Starting mixture Ac BAC H20 AA IPA HQ
(weight %) 71.4 22.0 2.5 0.12 1.0 0.05 BAC = n-butylacrylate ~ ... . . . : ~
:
:
- 13 - ~ HOE ?8/F 281 Table 6:
Test Pressure Reactor Product comp. OHB
charge (we1ght ~) (bar) (vol.~) (g) Ac BAC OHB Sel/ Sel~ STY
BAC Ac
Manufacture of 5-oxohexanoic acid n-butyl ester (OHB) E X A M P L E 6:
Two bomb tubes of 30 ml volume each are charged with 18 and 27 ml, respectively, of the starting mixture indi-cated below and heated simulatneously to 230C for 30 minu-tes. Thereafter the contents are cooled and analyzed. The test conditions and results are summarized in Table 6.
Starting mixture Ac BAC H20 AA IPA HQ
(weight %) 71.4 22.0 2.5 0.12 1.0 0.05 BAC = n-butylacrylate ~ ... . . . : ~
:
:
- 13 - ~ HOE ?8/F 281 Table 6:
Test Pressure Reactor Product comp. OHB
charge (we1ght ~) (bar) (vol.~) (g) Ac BAC OHB Sel/ Sel~ STY
BAC Ac
6 A40 60 14.1 67.2 13.5 10.8 87 80 102 6 B260 90 21.2 64.5 8.o 18.3 90 83 259 A pressure increase from 40 bars (Comparative Test 6 A) to 260 bars (Test 6 B) brings about a 2.5-fold increase of the space-time yield of OHB.
Manufacture of 5-oxohexanoic acid ethylhexyl ester (OHEH) E X A M P L E 7:
An autoclave of 110 ml volume is charged with a start-ing mixture of the composition shown below until a volume of 60 or 90 %, respectively, is occupied and the contents are heated to 230C for 30 minutes, immediately cooled and subsequently analyzed.
The test conditions and the results are summarized in Table 7.
Starting mixture Ac EHAC IPA H2O AA HQ
(weight %) 74.4 22.0 1.5 2.0 0.1 0.05 EHAC = 2-ethylhexylacrylate .
;252~7 Table 7:
Test Reactor Pressure Product comp. OHEH
charge (weight %) (vol.~) (g) (bar) Ac EHAC OHEH Sel/ Sel/ STY
EHAC Ac
Manufacture of 5-oxohexanoic acid ethylhexyl ester (OHEH) E X A M P L E 7:
An autoclave of 110 ml volume is charged with a start-ing mixture of the composition shown below until a volume of 60 or 90 %, respectively, is occupied and the contents are heated to 230C for 30 minutes, immediately cooled and subsequently analyzed.
The test conditions and the results are summarized in Table 7.
Starting mixture Ac EHAC IPA H2O AA HQ
(weight %) 74.4 22.0 1.5 2.0 0.1 0.05 EHAC = 2-ethylhexylacrylate .
;252~7 Table 7:
Test Reactor Pressure Product comp. OHEH
charge (weight %) (vol.~) (g) (bar) Ac EHAC OHEH Sel/ Sel/ STY
EHAC Ac
7 A 60 53.4 41 68.9 5 18.6 83 82 180 7 B 90 79.8 266 68.2 2.1 22.2 85 86 322 Bp. of OHEH: 130C (under 7 mbars) - By increasing the pressure from 41 to 266 bars, the space-time yield is improved from 180 to 322 g/l'h.
Manufacture of acetonylsuccinic acid ester (AcBE) E X A M P L E 8:
An autoclave of 110 ml volume is charged with the starting mixture of the composition shown below until 60 or 90 %, respecti~ely, of its volume is occupied and the contents are heated to 200C for 30 minutes. The contents are cooled immediately and analyzed subsequently. The test conditions and results are summarized in Table 8.
Starting mixture Ac MDME IPA HQ BA
(weight %) 78.7 20.0 1.0 0.1 0.2 MDME = maleic acid dimethyl ester Table 8:
Test Reactor Pressure Product comp. AcBE
charge (weight %) (vol.%) (g) (bar) Ac FDME AcBE Sel/ Sel/ STY
MDME Ac -
Manufacture of acetonylsuccinic acid ester (AcBE) E X A M P L E 8:
An autoclave of 110 ml volume is charged with the starting mixture of the composition shown below until 60 or 90 %, respecti~ely, of its volume is occupied and the contents are heated to 200C for 30 minutes. The contents are cooled immediately and analyzed subsequently. The test conditions and results are summarized in Table 8.
Starting mixture Ac MDME IPA HQ BA
(weight %) 78.7 20.0 1.0 0.1 0.2 MDME = maleic acid dimethyl ester Table 8:
Test Reactor Pressure Product comp. AcBE
charge (weight %) (vol.%) (g) (bar) Ac FDME AcBE Sel/ Sel/ STY
MDME Ac -
8 A 60 54.428 74.411.4 8.7 72 7586 8 B 90 83.1180 73.99.5 11.6 79 70175 :,,- , FDME = fumario acid dimethyl ester (isomerization takes place under the reaction conditions) AcBE = acetonylsuccinic acid dimethyl ester H3CCOCH2CH - COOCH3 Bp3 = 122 to 123C
A pressure increase above the vapor pressure of the reaction mixture of 28 bars (Comparative Test 8 A) to 180 bars (Test 8 B) brings about an increase of the space-time yield of AcBE from 86 to 175 g/l-h.
Manufacture of 4-methyl-5-oxohexanoic acid methyl ester (MOHM) and 5-oxoheptanoic acid methyl ester (OHPM) E X A M P L E 9:
An autoclave of 110 ml volume is charged with the starting mixture having the composition shown below until 60 or 90 ~, respectively~of its volume is occupied and the contents are heated to 230C for 30 minutes. Thereafter the contents are cooled and analyzed. The test conditions and results are summarized in Table 9. .
Starting mixture MEK MAC IPA AA HQ
tweight ~) 78.3 20.0 1.5 0.1 0.05 Table 9:
Test Reactor Pressure Product comp. MOHM + OHPM
charge (weight %) (vol.~) (g) (bar) MEK MAC MOHM OHPM Sel/ Sel/ STY
MAC MEK
A pressure increase above the vapor pressure of the reaction mixture of 28 bars (Comparative Test 8 A) to 180 bars (Test 8 B) brings about an increase of the space-time yield of AcBE from 86 to 175 g/l-h.
Manufacture of 4-methyl-5-oxohexanoic acid methyl ester (MOHM) and 5-oxoheptanoic acid methyl ester (OHPM) E X A M P L E 9:
An autoclave of 110 ml volume is charged with the starting mixture having the composition shown below until 60 or 90 ~, respectively~of its volume is occupied and the contents are heated to 230C for 30 minutes. Thereafter the contents are cooled and analyzed. The test conditions and results are summarized in Table 9. .
Starting mixture MEK MAC IPA AA HQ
tweight ~) 78.3 20.0 1.5 0.1 0.05 Table 9:
Test Reactor Pressure Product comp. MOHM + OHPM
charge (weight %) (vol.~) (g) (bar) MEK MAC MOHM OHPM Sel/ Sel/ STY
MAC MEK
9 A 60 53.5 30 68.3 8 14.7 3.0 80 78 172 9 B 90 80.8 180 63.5 2.8 22.0 4.5 84 81 390 , .
- - ~
- ~ ` , , :
~2S;~
- 16 - HOE 78/F_281 A pressure increase above the vapor pressure (30 bars) of the reaciion mixture, to 180 bars, brings about an im-provement of the space-time yield from 172 to 390 g/l-h.
Manu~acture of 3(-2-oxocyclohexyl)-propanoic acid methyl ester (OCPM) E X A M P L E 10:
In the first test (10 A) an autoclave of 110 ml is charged with a starting mixture of the composition indi-cated below `until 90 % of its volume is occupied and the autoclave is heated to 180C for 30 minutes. Thereafter the contents are rapidly cooled and analyzed. In the se-cond test (10 B) N2 is added prior to heating until a pres-sure of 150 bars is reached, the rest of the procedure being identical to that of Test 10 A. The test conditions and results are summarized in Table 10.
Starting mixture cyclohexanone MAC IPA BA HQ
(weight ~) 63.0 36.0 0.6 0.2 0.2 Table 10:
Test Reactor Pressure Product comp. OCPM
charge (weight %) (vol.%) (g) (bar) CHO MAC OCPM Sel/ Sel/ STY
MAC CHO
- - ~
- ~ ` , , :
~2S;~
- 16 - HOE 78/F_281 A pressure increase above the vapor pressure (30 bars) of the reaciion mixture, to 180 bars, brings about an im-provement of the space-time yield from 172 to 390 g/l-h.
Manu~acture of 3(-2-oxocyclohexyl)-propanoic acid methyl ester (OCPM) E X A M P L E 10:
In the first test (10 A) an autoclave of 110 ml is charged with a starting mixture of the composition indi-cated below `until 90 % of its volume is occupied and the autoclave is heated to 180C for 30 minutes. Thereafter the contents are rapidly cooled and analyzed. In the se-cond test (10 B) N2 is added prior to heating until a pres-sure of 150 bars is reached, the rest of the procedure being identical to that of Test 10 A. The test conditions and results are summarized in Table 10.
Starting mixture cyclohexanone MAC IPA BA HQ
(weight ~) 63.0 36.0 0.6 0.2 0.2 Table 10:
Test Reactor Pressure Product comp. OCPM
charge (weight %) (vol.%) (g) (bar) CHO MAC OCPM Sel/ Sel/ STY
MAC CHO
10 A 90 92.5 6 51.5 24.7 20.0 83 90 336 10 B 90 92.5 280 47.4 21.1 26.8 84 92 450 CHO = cyclohexanone It can be seen from this Example that with a ketone of rather high boiling point such as cyclohexanone an improvement of the space-time yield is reached on pressing into the reactor nitrogen.
. ,~ .
,
. ,~ .
,
Claims (9)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A process for the preparation of a 5-oxoalkanoic acid, an ester or a nitril thereof in which a ketone containing at least one .alpha.-hydrogen atom is reacted at an elevated temperature under a pressure above the vapor pressure of the reaction mixture and below 500 bars, with an .alpha.,.beta.-unsaturated acid, an ester or a nitril thereof, in the liquid phase, in the presence of at least one compound selected from the group consisting of: primary amines, primary aminoalcohols, primary aminocarboxylic acids, Schiff's bases of primary amines and the ketone used, and, if an .alpha.,.beta.-unsaturated carboxylic acid ester is reacted, the .beta.-amino-propionates formed from the latter esters and primary amines.
2. A process as claimed in claim 1, in which the pressure is produced by charging the reactor used for the reaction, at room temperature, at least to such a degree with the starting material that the gaseous phase vanishes on heating to the reac-tion temperature.
3. A process as claimed in claim 1, in which the pressure is produced by pressing into the reactor used for the reaction an inert gas under a pressure exceeding the vapour pressure of the reaction components.
4. A process as claimed in claim 1, claim 2 or claim 3, in which the reaction is carried out under a pressure below 280 bars.
5. A process as claimed in claim 1, claim 2 or claim 3, in which the reaction is carried out under a pressure below 200 bars.
6. A process as claimed in claim 1, claim 2 or claim 3, in which the ketone is selected from the group consisting of acetone, methylethylketone, diethylketone, methylpropylketone, methylisopropylketone, methylbutylketone, cyclopentanone, cyclohexanone and benzylmethylketone.
7. A process as claimed in claim 1, claim 2 or claim 3, in which the .alpha.,.beta.-unsaturated acid is selected from the group consisting of acrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid and itaconic acid.
8. A process as claimed in claim 1, claim 2 or claim 3, in which the catalyst is present in an amount in the range of from 0.01 to 0.4 mol per mol of .alpha.,.beta.-unsaturated compound.
9. A process as claimed in claim 1, claim 2 or claim 3, in which a polymerization inhibitor is present during the reaction.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19782855195 DE2855195A1 (en) | 1978-12-21 | 1978-12-21 | METHOD FOR PRODUCING 5-OXOALKANIC ACIDS, THEIR ESTERS AND NITRILES |
| DEP2855195.3 | 1978-12-21 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1152527A true CA1152527A (en) | 1983-08-23 |
Family
ID=6057834
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000342369A Expired CA1152527A (en) | 1978-12-21 | 1979-12-20 | Process for the manufacture of 5 - oxoalkanoic acids, their esters and their nitrils |
Country Status (6)
| Country | Link |
|---|---|
| EP (1) | EP0013254B1 (en) |
| JP (1) | JPS5587742A (en) |
| BR (1) | BR7908376A (en) |
| CA (1) | CA1152527A (en) |
| DE (2) | DE2855195A1 (en) |
| ZA (1) | ZA796942B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3142423A1 (en) * | 1981-10-26 | 1983-05-05 | Hoechst Ag, 6230 Frankfurt | "METHOD FOR PRODUCING ESTERS OR NITRILES OF 5-OXOALKANIC ACIDS" |
| 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 |
|---|---|---|---|---|
| JPS53124219A (en) * | 1977-04-05 | 1978-10-30 | Mitsui Petrochem Ind Ltd | Preparation of derivative of 5-oxocarboxylic acid |
-
1978
- 1978-12-21 DE DE19782855195 patent/DE2855195A1/en not_active Withdrawn
-
1979
- 1979-12-14 DE DE7979710015T patent/DE2963517D1/en not_active Expired
- 1979-12-14 EP EP79710015A patent/EP0013254B1/en not_active Expired
- 1979-12-20 ZA ZA00796942A patent/ZA796942B/en unknown
- 1979-12-20 JP JP16492279A patent/JPS5587742A/en active Pending
- 1979-12-20 CA CA000342369A patent/CA1152527A/en not_active Expired
- 1979-12-20 BR BR7908376A patent/BR7908376A/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| EP0013254A2 (en) | 1980-07-09 |
| DE2855195A1 (en) | 1980-07-17 |
| EP0013254B1 (en) | 1982-08-04 |
| JPS5587742A (en) | 1980-07-02 |
| EP0013254A3 (en) | 1980-07-23 |
| DE2963517D1 (en) | 1982-09-30 |
| BR7908376A (en) | 1980-09-23 |
| ZA796942B (en) | 1980-12-31 |
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| MKEX | Expiry |