CA1287838C - Process for the preparation of unsaturated carboxylate esters - Google Patents
Process for the preparation of unsaturated carboxylate estersInfo
- Publication number
- CA1287838C CA1287838C CA000517354A CA517354A CA1287838C CA 1287838 C CA1287838 C CA 1287838C CA 000517354 A CA000517354 A CA 000517354A CA 517354 A CA517354 A CA 517354A CA 1287838 C CA1287838 C CA 1287838C
- Authority
- CA
- Canada
- Prior art keywords
- acid
- ketone
- palladium
- carbon atoms
- promoter
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/36—Preparation of carboxylic acid esters by reaction with carbon monoxide or formates
- C07C67/38—Preparation of carboxylic acid esters by reaction with carbon monoxide or formates by addition to an unsaturated carbon-to-carbon bond
Abstract
A B S T R A C T
PROCESS FOR THE PREPARATION OF UNSATURATED CARBOXYLATE ESTERS
Process for the preparation of carboxylate esters of alpha-ethylenically unsaturated alcohols by reacting an ethylenically unsaturated compound with carbon monoxide and an enolizable ketone in the presence of a catalytic system rormed by combining a palladium catalyst, a triarvlphosphine and a protonic acid having a PKa below 1.5, except hvdrohalogenic acids and carboxylic acids.
PROCESS FOR THE PREPARATION OF UNSATURATED CARBOXYLATE ESTERS
Process for the preparation of carboxylate esters of alpha-ethylenically unsaturated alcohols by reacting an ethylenically unsaturated compound with carbon monoxide and an enolizable ketone in the presence of a catalytic system rormed by combining a palladium catalyst, a triarvlphosphine and a protonic acid having a PKa below 1.5, except hvdrohalogenic acids and carboxylic acids.
Description
3~
~1- 632~3~269~
PROCESS FOR TH~ PREPARATION 0~ UNSATURATED CARBOXYLATE ESTERS
The inventlon relates to a process for the preparation o~ carboxylate esters of alpha-ethylenically unsaturated alcohols.
Carboxylate esters of alpha-eth~lenically unsaturated alcohols can be polymerized to yield polyvinyl-type polymers. It has now surprisingly been found ~hat such carboxylate esters can be prepared with high selectivity and acceptable yield using relatively simple starting compounds~
The invention, therefore, provides a process for the preparation of carboxylate esters of alpha-ethylenically unsaturated alcohols, which process comprises causing an ethylenically unsaturated compound to react with carbon monoxide and an enolizable ketone in the presence of a catalytic system forméd by combining:-a) a palladium catalyst, b) a phosphine having the general formula (I) Rl p~R2 R3 (I) in which R1, R2 and R3 each individually represent an aryl group which is unsubstituted or i~ substi~uted by a substi~uent that doe~ not interfere with the course of the reaction, and c) a protonic acid having a PKa below 1.5 as a promoter (measured at 18C in aqueous solution)j except hydrohalogenic acids and carboxylic acids.
. ~
.
.' . :
-1~- 63293-2G96 The reaction may schematically be represented by means of the following e~uation: `
C - C -~ co -~ - c ~ c - c - -- I I o *
OH
. ,;
.;
.
~X~ 38 in which the hydroxy compound represents the enolized fqrm of a ketone having the structure:
-- C -- C -- C --~1 0 ,.
The two carbon atoms marked with an asterisk are the same carbon atoms.
The ethylenically unsaturated compound may be an optionally substituted alkene or an optionally substituted cycloalkene, preferably having in the range of from 2 to 30, in particular 2 to 20 and, more particularly, 2 to 10 carbon atoms per molecule, and preferably I to 3 carbon-carbon double bonds per molecule. Very good results have been obtained with ethylene. The~alkene or cycloalkene may be substituted, for instance with one or more halogen atoms, or cyano, ester, alkoxy or aryl groups. Examples of suitable ethylenically unsaturated compounds are propene, 1-butene, 2-butene, isobutene, the isomeric pentenes, hexenes, heptenes, octenes and d~decenes, 1~5-cyclooctadiene, cyclododecene, 1,5,9-cyclododecatriene, methyl acrylate, ethyl acrylate~ methyl methacrylate, acrylonitrile, acrylamide, N,N-dimethylacrylamide, vinyl chloride, allyl chloride, methyl allyl ether and styrene.
The enolizable ketone should have a hydrogen atom bound to a carbon atom ad~acent to the carbonyl group. A wide variety o~
enolizable ketones may be used. The enolizable ketone may have optionally substituted alkyl, optionally substituted cycloalkyl or optionally substituted aryl groups bound to the carbonyl group.
Preference is given to alkanones, two optionally substituted alkyl groups being bound to the carbonyI group; the optionally substituted alkanones suitably have in the range of from 3 to 30 carbon atoms per moIecule. Particularly preferred are methyl alkyl ketones having in the range of from 3 to 30 carbon atoms per molecule; among the latter ketones those havlng 3 or 4 carbon atoms .~
:::
....
.. ;~ '' :. '~ ,: ' ., ., . " ~,, . ' "- : . .'' ~
-, ~2~3713~ :
per molecule are preferred. Enolizable alkyl phenyl ke~ones are also very suitable, particularly those in which the alkyl group has in the range of from 1 to 10 carbon atoms. Very good results have been obtained with acetophenone. Other examples of suitable enolizable ketones are methyl butyl ketone, methyl isobutyl ketone, diheptyl ketone, dioctyl ketone, 3-butylheptyl ethyl ketone, methyl cyclohexyl ketone and ethyl phenyl ketone.
Enolizable ketones which are symmetric with respect to the carbonyl group yield one carboxylate ester. Enolizable ketones which are not symmetric with respect to the carbonyl group and in which ketones the two carbon atoms bound to the carbonyl group each carry a hydrogen atom yield two different carboxylate esters of the same carboxylic acid, two different enolized forms being possible.
Both homdgeneous and heterogeneous palladium catalysts may be used in the process according to the invention. Homogeneous catalysts are preferred. The palladium catalyst preferably contains a compound of divalent palladium. Suitable homogeneous catalysts are the salts of palladium with, for example, nitric acid, sulphuric acid or, particularly, alkanoic acids; among the alkanoic acids those having not more than 12 carbon atoms per molecule are preferred. Very good results have been obtained with palladium acetate. Moreover, palladium complexes may be used, for instance palladium acetylacetonate, tetrakistriphenylphosphinepalladium, bis-tri-o-toLylphosphinepalladium acetate or bis-triphenylphos-phinepalladium sulphate. Palladium on charcoal and palladium bonded to an ion exchanger - for instance an ion exchanger comprising sulphonic acid groups - are examples of suitable heterogeneous catalysts.
It was found that when at least 5 mol of the phosphine having the general formula (I) are used per gram atom of palladium, a considerable increase in the reaction rate is obtained. Preferably at least 20 moI of the phosphine having the general formula (I) are used per gram atom of palladium. In general, more than 500 mol phosphine per gram atom of palladium need not be used. Usually, in the range of from 10 to 150 mol phosphine per gram atom of ' -' ' ' ' .- -' ~ . ' :
,, ' ' '. ; '' ,. ' '. . ' . ' ~' , ' . . , . , ~
: . , : ,: . . . .
~z~7~3~
palladium are used. If the palladium catalyst already contains phosphine, thi~s should be taken into account when calculating the amount of phosphine to be used.
The protonic acid having a pK below 1.5 preferably has a non-coordinating anion, by which is meant that little or no covalen~ interaction takes place between the palladium and the anion (cf. British patent application No. 2,05~,074). Typical examples of such anions are PF6 , SbF6 , BF4 and C104 . Preferred acids are sulphonic acids and acids that can be formed, possibly in ]O situ, by interacting a Lewis acid such as, for example BF3J AsF5,SbF5, PF5, TaF5 or NbF5 with a Broensted acid such as, for example, a hydrogen halide, in particular HF, or fluorosulphonic acid, orthophosphoric acid or sulphuric acid. Specific examples of acids of the latter type are fluorosilicic acid, H~F4, ~lPF6 and ~SbE6.
Examples of usable sulphonic acids are fluorosulphonic acid and chlorosulphonic acid and the hereinafter specified sulphonic acids.
A preferred group of non-carboxylic protonic acids having a pK below l.S are those having the general formula (II): ~
O "
R - b - O - H (II) wherein Z represents sulphur or chlorlne and, if Z is chlorine, R4 represents oxygen and, if Z is sulphur, R4 represents an OH group or an optionally substituted hydrocarbon group.
When the hereinbefore-stated acids of the general formula (II) are used in the process according to the invention, the anions thereof can be considered to be non-coordinating.
The optionally substituted hydrocarbon group represented by R4 is preferably an alkyl, aryl, aralkyl or alkaryl group having 1 to 30, in particular 1 to 14, carbon atoms. The hydrocarbon group may be substituted for example with halogen atoms, in particular fluorine atoms. Examples of suitable acids of the general formu]a (II~ are perchloric acid, sulphuric acid, .'. '': , : :' , -.
- . , , -: ., , , , ::. ..
1~8~338 2-hydroxyprop~ne-2-sulphonic acid, benzenesulphonic acid, 1-naphthalenesulphonic acid, 2-naphthalenesulphonic acid, p-toluenesulphonic acid and triEluoromethanest1lphonic acid, p-toluenesulphonic acid belng the most preferred.
The optionally substituted aryl groups R1, R2 and R3 in the general formula (I~ preferably contain not more than 18, and in particular in the range of from 6 to 1~s carbon atoms. Examples of suitable aryl groups are naphthyl groups and, in particular, phenyl groups. Suitable substituents on the aryl groups are halogen atoms and alkyl, aryl, alkoxy, trihalomethyl, cyano, dialkylamino and alkanoyloxy groups. Examples of suitable phosphines are tri(p-tolyl)phosphine, tri(p-methoxyphenyl)phosphine and, in particular, triphenylphosphine.
The number of equivalents of the phosphine having the general formula (I) which is used per equivalent of non-carboxylic protonic acid having a pK below 1.5 is not critical and may vary within wide limits. This number is suitably in the range of from 0.5 to 50. The quantity of palladium catalyst is not critical and `
may vary within wide lirnits. Preference is given to the use of quantities in the range between 10 5 and 10 gram atom palladium per mol of ethylenically unsaturated compound.
A separate solvent is not essential in the process according to the invention, and often a large excess of one of the reactants, usually the enolizable ketone, may form a convenient liquid phase.
However, it may in some cases be desirable to use a separate solvent and any inert solvent may be used. A suitable solvent may for example, be selected from aromatic hydrocarbons, fo~ example benzene, toluene, ethylbenzene and the three xylenes; sulphoxides, for example dimethyl sulphoxide and diethyl sulphoxide; sulphones, for example diisopropyl sulphone and tetrahydrothiophene 1,1-dioxide( also referred to as "sulfolane") and ethers, for example anisole, 2,5,8-trioxanonane (also referred to as "diglyme"), diphenyl ether and diisopropyl ether.
In the process according to the invention the carbon monoxide may be used pure -r diluted with an lnert gas, such as nitrogen, ~ , :
,~ , !37838 noble gases ~r carbon dioxide. Cenerally, the pres~nce of more than 10% by volume of hydrogen is undesirable, since under the reaction conditions it may cause hydrogenation of carbon-carbon double bonds. Preference is given ~o the use of pure carbon monoxide or a carbon monoxide-containing gas which contains less than 5% by volume of hydrogen.
The process according to the invention permits the use of very mild reaction conditions. Temperatures in the range of from 50 C
to 200 C, especially 100 C to 150 C, are generally suitable. The pressure may vary over a wide range. Generally, a pressure in the range of from 1 to 100 bar is suitable, with pressures of from 5 to 50 bar being preferred. ~ressures higher than 100 bar may be used, but are usually economically unattractive.
The molar ratio of the ethylenically unsaturated compound to the enolizable ketone is not critical and may vary within wide limits. The molar ratio carbon-carbon double bonds to enolizable ketone may lie, for instance, between 0.1:1 and 10:1.
The process according to the invention may be carried out batchwise, continuously or semi-continuously.
The following examples further illustrate the invention. The selectivity to a certain compound, expressed in a percentage, is defined as 100 a/b, in which "a" is the amount of ketone that has been converted into that certain compound and "b" is the total amount of ketone that has been converted.
_ample I
A 250-ml magnetically stirred Hastelloy C autoclave ("~lastelloy" is a trade name~ was charged with o-xylene (50 ml), methyl ethyl ketone (20 ml), palladium acetate (0.2 mmol), tri-phenylphosphine (10 mmol) and p-toluenesulphonic acid (2 mmol). The autoclave was flushed with carbon monoxide, filled with carbon monoxide and ethylene until partial pressures thereof of 20 bar -each were obtained and heated to a temperature of 110 C. After a reaction time of 5 h at this temperature the contents of the autoclave were ana]ysed by means o~f gas-liquid chromatography. The conversion of methyl ethyl ketone wa~s 30 %, with a total .
... .
. ..
.. . . . . . .
~z~7133~3 selectivity to l-ethylvinyl propionate and l-methylallyl propionate of 95 %; the former and the latter propionate were obtained in a molar ratio of 2.3.
Example 2 The experiment of Example 1 was repeated with the difference that 20 ml of methyl ethyl ketone were replaced with 20 ml of acetone. The conversion of acetone was 26%, with a selectivity to isopropyl propionate of 95%.
Example 3 The experiment of Example 1 was repeated with the difference that 20 ml of methyl ethyl ketone were replaced with 20 ml of acetophenone. The conversion of acetophenone was 15 %, with a selectivity to l-phenylvinyl propionate of 95~.
Example 4 ~n experiment was carried out in the manner of Example 1, using o-xylene(50 ml), acetophenone (20 ml), palladium acetate ~0.2 mmol), trlphenylphosphine (20 mmo]) and p-toluenesulphonic acid (5 mmol). After a reaction time of 2.5 h at 100 C the conversion of acetophenone was 15%, with a selectivity to l~phenylvinyl propionate of 95%.
Example 5 The experiment of Example 4 was repeated with the difference that 10 mmol instead of 5 mmol of p-toluenesulphonic acid were used and that the reaction was carried out for 3.5 h at 115 C. The conversion of acetophenone was 23%, with a selectivity to l-phenylvinyl propionate of 95%.
Example 6 . .
An experiment was carried out in the manner of Example 1, using o-xylene (50 ml), acetophenone (20 ml~, palladium acetate (0.2 mmol), triphenylphosphine (30 mmol) and p-toluenesulphonic acid (10 mmol). The partial pressures of ethylene and carbon monoxide were 30 bar each. After a reaction time of 5 h at 125 C
the conversion of acetophenone was 30%, with a selectivity to l-phenylvinyl propionate of 95%.~
, .
:
... ~1' ~ '~
.. . .
, ' ' ,( . . . ' . ' .: ' ' - , .:: ' -~2137~
Example 7 .
An experiment was carried O~lt in the manner of Exa~ple 1 uslng o xylene (50 ml), acetophenone (20 ml), palladiùm aceta~
(0.1 mmol), triphenylphosphlne (50 mmol) and p-toluenesulphonic S acid (15 mmol). The partial pressures of ethylene and carbon monoxide were 30 bar each. After a reaction time of 5 h at 125 C
the conversion of acetophenone was 33%, with a selectivity to l-phenylvinyl propionate of 95%.
Exampl _8 ~0 ~n experiment was carried out in the manner of Example 1, using o-xylene ~50 ml), acetophenone (20 ml), palladium acetate (0.1 mmol), triphenylphosphine (30 mmol), p-toluenesulphonic acid (lO mmol) and propionic acid (2 ml). The partial pressures of ethylene and'carbon monoxide were 30 bar each. After a reaction time of 5 h at 125 C the conversion of acetophenone was 25%, with a selectivity to l-phenylvinyl propionate of 95%. Propionic acid was converted into propionic anhydride with a yield of 90%.
Example 9 An experiment was carried out in the manner of Example 1, using o-xylene (50 ml), acetophenone (20 ml), palladium acetate (0.1 mmol), triphenylphosphine (50 mmol) and methanesulphonic acid (15 mmol). The partial pressures of ethylene and carbon monoxide were 30 bar each. After a reaction time of 5 h at 125 C the conversion of acetophenone was 22%, with a selectivity to l-phenyl-vinyl propionate of 95%.
Example 10 The experiment of Example 9 was repeated with the dlfference that 15 mmol of methanesulphonic acid were replaced with lS mmol of mesitylenesulphonic acid. The conversion of acetophenone was 14~, with a selectivity to l-phenylvinyl propionate of 95%.
Example 11 ~
An experiment~was carried out in the manner of Example 1, using diglyme ~50 ml), acetophenone (20 ml), palladium acetate (0.1 mmol), triphenylphosphine (50 mmol) and p-toluenesulphonic -~
acid (15 mmol). The partial pressures of ethylene and carbon monoxide were 30 bar each. After a reaction ~ime of 5 h at 125 C -~
~ '~
~ . .
33~
the conversion of acetophenone was 30%, with a selectlvity to l-phenylvinyl propionate of more than 95%.
Example 12 An experiment was carried out in the manner of Example 1, S using diglyme (50 ml), acetophenone (20 ml), palladium acetate (0.1 mmol), tri(m-chlorophenyl)phosphine t20 mmol) and p-toluene-sulphonic acid (5 mmol). The partial pressures of ethylene and carbon monoxide were 30 bar each. After a reaction time of 3 h at 125 C the conversion of acetophenone was 8%~ with a selectivity to l-phenylvinyl propionate of more than 95%.
~xample 13 The experiment of Example 11 was repeated with the difference that the partial pressures of ethylene and carbon monoxide were 20 and 40 bar, respectively. The conversion of acetophenone was 25%, with a selectivity to l-phenylvinyl propionate of 95%.
Example 14 The experiment of Example 11 was repeated with the difference that the partial pressures of ethylene and carbon monoxide were 40 and 20 bar, respectlvely. The conversion of acetophenone was 25%, with a selectivity to l-phenylvinyl propionate of 95%.
Example 15 The experiment of Example 11 was repeated with the difference that 50 ml instead of 20 ml o~ acetophenone were used and that no diglyme was present. The conversion of acetophenone was 1~%, with a selectivity to l-phenylvinyl propionate of 95%.
Comparative Experiment A
The experiment described in Example 1 was repeated with the difference that p toluenesulphonic acid (2 mmol) was replaced with ben~enephosphonic acid (pK - 1.5, 2 mmol). The conversion of the ketone was below 5% and propionate could not be detected in the reaction mixture.
Comparative Experiment B
The experiment described in Example 1 was repeated with the d~flerence that p-toluenesu pùonic aci (2 mmol) was replaced with ~ .
' :, , : : , ., - , . , ~287~
2,6-dichlorobenzoic acid ~P~a = 1.5, 2 mmol). The conversion of ketone was below 5% and propionate could not be detected in the reaction mix~ure. -:
: :
, -. , .. . , , :, ,: , :
~1- 632~3~269~
PROCESS FOR TH~ PREPARATION 0~ UNSATURATED CARBOXYLATE ESTERS
The inventlon relates to a process for the preparation o~ carboxylate esters of alpha-ethylenically unsaturated alcohols.
Carboxylate esters of alpha-eth~lenically unsaturated alcohols can be polymerized to yield polyvinyl-type polymers. It has now surprisingly been found ~hat such carboxylate esters can be prepared with high selectivity and acceptable yield using relatively simple starting compounds~
The invention, therefore, provides a process for the preparation of carboxylate esters of alpha-ethylenically unsaturated alcohols, which process comprises causing an ethylenically unsaturated compound to react with carbon monoxide and an enolizable ketone in the presence of a catalytic system forméd by combining:-a) a palladium catalyst, b) a phosphine having the general formula (I) Rl p~R2 R3 (I) in which R1, R2 and R3 each individually represent an aryl group which is unsubstituted or i~ substi~uted by a substi~uent that doe~ not interfere with the course of the reaction, and c) a protonic acid having a PKa below 1.5 as a promoter (measured at 18C in aqueous solution)j except hydrohalogenic acids and carboxylic acids.
. ~
.
.' . :
-1~- 63293-2G96 The reaction may schematically be represented by means of the following e~uation: `
C - C -~ co -~ - c ~ c - c - -- I I o *
OH
. ,;
.;
.
~X~ 38 in which the hydroxy compound represents the enolized fqrm of a ketone having the structure:
-- C -- C -- C --~1 0 ,.
The two carbon atoms marked with an asterisk are the same carbon atoms.
The ethylenically unsaturated compound may be an optionally substituted alkene or an optionally substituted cycloalkene, preferably having in the range of from 2 to 30, in particular 2 to 20 and, more particularly, 2 to 10 carbon atoms per molecule, and preferably I to 3 carbon-carbon double bonds per molecule. Very good results have been obtained with ethylene. The~alkene or cycloalkene may be substituted, for instance with one or more halogen atoms, or cyano, ester, alkoxy or aryl groups. Examples of suitable ethylenically unsaturated compounds are propene, 1-butene, 2-butene, isobutene, the isomeric pentenes, hexenes, heptenes, octenes and d~decenes, 1~5-cyclooctadiene, cyclododecene, 1,5,9-cyclododecatriene, methyl acrylate, ethyl acrylate~ methyl methacrylate, acrylonitrile, acrylamide, N,N-dimethylacrylamide, vinyl chloride, allyl chloride, methyl allyl ether and styrene.
The enolizable ketone should have a hydrogen atom bound to a carbon atom ad~acent to the carbonyl group. A wide variety o~
enolizable ketones may be used. The enolizable ketone may have optionally substituted alkyl, optionally substituted cycloalkyl or optionally substituted aryl groups bound to the carbonyl group.
Preference is given to alkanones, two optionally substituted alkyl groups being bound to the carbonyI group; the optionally substituted alkanones suitably have in the range of from 3 to 30 carbon atoms per moIecule. Particularly preferred are methyl alkyl ketones having in the range of from 3 to 30 carbon atoms per molecule; among the latter ketones those havlng 3 or 4 carbon atoms .~
:::
....
.. ;~ '' :. '~ ,: ' ., ., . " ~,, . ' "- : . .'' ~
-, ~2~3713~ :
per molecule are preferred. Enolizable alkyl phenyl ke~ones are also very suitable, particularly those in which the alkyl group has in the range of from 1 to 10 carbon atoms. Very good results have been obtained with acetophenone. Other examples of suitable enolizable ketones are methyl butyl ketone, methyl isobutyl ketone, diheptyl ketone, dioctyl ketone, 3-butylheptyl ethyl ketone, methyl cyclohexyl ketone and ethyl phenyl ketone.
Enolizable ketones which are symmetric with respect to the carbonyl group yield one carboxylate ester. Enolizable ketones which are not symmetric with respect to the carbonyl group and in which ketones the two carbon atoms bound to the carbonyl group each carry a hydrogen atom yield two different carboxylate esters of the same carboxylic acid, two different enolized forms being possible.
Both homdgeneous and heterogeneous palladium catalysts may be used in the process according to the invention. Homogeneous catalysts are preferred. The palladium catalyst preferably contains a compound of divalent palladium. Suitable homogeneous catalysts are the salts of palladium with, for example, nitric acid, sulphuric acid or, particularly, alkanoic acids; among the alkanoic acids those having not more than 12 carbon atoms per molecule are preferred. Very good results have been obtained with palladium acetate. Moreover, palladium complexes may be used, for instance palladium acetylacetonate, tetrakistriphenylphosphinepalladium, bis-tri-o-toLylphosphinepalladium acetate or bis-triphenylphos-phinepalladium sulphate. Palladium on charcoal and palladium bonded to an ion exchanger - for instance an ion exchanger comprising sulphonic acid groups - are examples of suitable heterogeneous catalysts.
It was found that when at least 5 mol of the phosphine having the general formula (I) are used per gram atom of palladium, a considerable increase in the reaction rate is obtained. Preferably at least 20 moI of the phosphine having the general formula (I) are used per gram atom of palladium. In general, more than 500 mol phosphine per gram atom of palladium need not be used. Usually, in the range of from 10 to 150 mol phosphine per gram atom of ' -' ' ' ' .- -' ~ . ' :
,, ' ' '. ; '' ,. ' '. . ' . ' ~' , ' . . , . , ~
: . , : ,: . . . .
~z~7~3~
palladium are used. If the palladium catalyst already contains phosphine, thi~s should be taken into account when calculating the amount of phosphine to be used.
The protonic acid having a pK below 1.5 preferably has a non-coordinating anion, by which is meant that little or no covalen~ interaction takes place between the palladium and the anion (cf. British patent application No. 2,05~,074). Typical examples of such anions are PF6 , SbF6 , BF4 and C104 . Preferred acids are sulphonic acids and acids that can be formed, possibly in ]O situ, by interacting a Lewis acid such as, for example BF3J AsF5,SbF5, PF5, TaF5 or NbF5 with a Broensted acid such as, for example, a hydrogen halide, in particular HF, or fluorosulphonic acid, orthophosphoric acid or sulphuric acid. Specific examples of acids of the latter type are fluorosilicic acid, H~F4, ~lPF6 and ~SbE6.
Examples of usable sulphonic acids are fluorosulphonic acid and chlorosulphonic acid and the hereinafter specified sulphonic acids.
A preferred group of non-carboxylic protonic acids having a pK below l.S are those having the general formula (II): ~
O "
R - b - O - H (II) wherein Z represents sulphur or chlorlne and, if Z is chlorine, R4 represents oxygen and, if Z is sulphur, R4 represents an OH group or an optionally substituted hydrocarbon group.
When the hereinbefore-stated acids of the general formula (II) are used in the process according to the invention, the anions thereof can be considered to be non-coordinating.
The optionally substituted hydrocarbon group represented by R4 is preferably an alkyl, aryl, aralkyl or alkaryl group having 1 to 30, in particular 1 to 14, carbon atoms. The hydrocarbon group may be substituted for example with halogen atoms, in particular fluorine atoms. Examples of suitable acids of the general formu]a (II~ are perchloric acid, sulphuric acid, .'. '': , : :' , -.
- . , , -: ., , , , ::. ..
1~8~338 2-hydroxyprop~ne-2-sulphonic acid, benzenesulphonic acid, 1-naphthalenesulphonic acid, 2-naphthalenesulphonic acid, p-toluenesulphonic acid and triEluoromethanest1lphonic acid, p-toluenesulphonic acid belng the most preferred.
The optionally substituted aryl groups R1, R2 and R3 in the general formula (I~ preferably contain not more than 18, and in particular in the range of from 6 to 1~s carbon atoms. Examples of suitable aryl groups are naphthyl groups and, in particular, phenyl groups. Suitable substituents on the aryl groups are halogen atoms and alkyl, aryl, alkoxy, trihalomethyl, cyano, dialkylamino and alkanoyloxy groups. Examples of suitable phosphines are tri(p-tolyl)phosphine, tri(p-methoxyphenyl)phosphine and, in particular, triphenylphosphine.
The number of equivalents of the phosphine having the general formula (I) which is used per equivalent of non-carboxylic protonic acid having a pK below 1.5 is not critical and may vary within wide limits. This number is suitably in the range of from 0.5 to 50. The quantity of palladium catalyst is not critical and `
may vary within wide lirnits. Preference is given to the use of quantities in the range between 10 5 and 10 gram atom palladium per mol of ethylenically unsaturated compound.
A separate solvent is not essential in the process according to the invention, and often a large excess of one of the reactants, usually the enolizable ketone, may form a convenient liquid phase.
However, it may in some cases be desirable to use a separate solvent and any inert solvent may be used. A suitable solvent may for example, be selected from aromatic hydrocarbons, fo~ example benzene, toluene, ethylbenzene and the three xylenes; sulphoxides, for example dimethyl sulphoxide and diethyl sulphoxide; sulphones, for example diisopropyl sulphone and tetrahydrothiophene 1,1-dioxide( also referred to as "sulfolane") and ethers, for example anisole, 2,5,8-trioxanonane (also referred to as "diglyme"), diphenyl ether and diisopropyl ether.
In the process according to the invention the carbon monoxide may be used pure -r diluted with an lnert gas, such as nitrogen, ~ , :
,~ , !37838 noble gases ~r carbon dioxide. Cenerally, the pres~nce of more than 10% by volume of hydrogen is undesirable, since under the reaction conditions it may cause hydrogenation of carbon-carbon double bonds. Preference is given ~o the use of pure carbon monoxide or a carbon monoxide-containing gas which contains less than 5% by volume of hydrogen.
The process according to the invention permits the use of very mild reaction conditions. Temperatures in the range of from 50 C
to 200 C, especially 100 C to 150 C, are generally suitable. The pressure may vary over a wide range. Generally, a pressure in the range of from 1 to 100 bar is suitable, with pressures of from 5 to 50 bar being preferred. ~ressures higher than 100 bar may be used, but are usually economically unattractive.
The molar ratio of the ethylenically unsaturated compound to the enolizable ketone is not critical and may vary within wide limits. The molar ratio carbon-carbon double bonds to enolizable ketone may lie, for instance, between 0.1:1 and 10:1.
The process according to the invention may be carried out batchwise, continuously or semi-continuously.
The following examples further illustrate the invention. The selectivity to a certain compound, expressed in a percentage, is defined as 100 a/b, in which "a" is the amount of ketone that has been converted into that certain compound and "b" is the total amount of ketone that has been converted.
_ample I
A 250-ml magnetically stirred Hastelloy C autoclave ("~lastelloy" is a trade name~ was charged with o-xylene (50 ml), methyl ethyl ketone (20 ml), palladium acetate (0.2 mmol), tri-phenylphosphine (10 mmol) and p-toluenesulphonic acid (2 mmol). The autoclave was flushed with carbon monoxide, filled with carbon monoxide and ethylene until partial pressures thereof of 20 bar -each were obtained and heated to a temperature of 110 C. After a reaction time of 5 h at this temperature the contents of the autoclave were ana]ysed by means o~f gas-liquid chromatography. The conversion of methyl ethyl ketone wa~s 30 %, with a total .
... .
. ..
.. . . . . . .
~z~7133~3 selectivity to l-ethylvinyl propionate and l-methylallyl propionate of 95 %; the former and the latter propionate were obtained in a molar ratio of 2.3.
Example 2 The experiment of Example 1 was repeated with the difference that 20 ml of methyl ethyl ketone were replaced with 20 ml of acetone. The conversion of acetone was 26%, with a selectivity to isopropyl propionate of 95%.
Example 3 The experiment of Example 1 was repeated with the difference that 20 ml of methyl ethyl ketone were replaced with 20 ml of acetophenone. The conversion of acetophenone was 15 %, with a selectivity to l-phenylvinyl propionate of 95~.
Example 4 ~n experiment was carried out in the manner of Example 1, using o-xylene(50 ml), acetophenone (20 ml), palladium acetate ~0.2 mmol), trlphenylphosphine (20 mmo]) and p-toluenesulphonic acid (5 mmol). After a reaction time of 2.5 h at 100 C the conversion of acetophenone was 15%, with a selectivity to l~phenylvinyl propionate of 95%.
Example 5 The experiment of Example 4 was repeated with the difference that 10 mmol instead of 5 mmol of p-toluenesulphonic acid were used and that the reaction was carried out for 3.5 h at 115 C. The conversion of acetophenone was 23%, with a selectivity to l-phenylvinyl propionate of 95%.
Example 6 . .
An experiment was carried out in the manner of Example 1, using o-xylene (50 ml), acetophenone (20 ml~, palladium acetate (0.2 mmol), triphenylphosphine (30 mmol) and p-toluenesulphonic acid (10 mmol). The partial pressures of ethylene and carbon monoxide were 30 bar each. After a reaction time of 5 h at 125 C
the conversion of acetophenone was 30%, with a selectivity to l-phenylvinyl propionate of 95%.~
, .
:
... ~1' ~ '~
.. . .
, ' ' ,( . . . ' . ' .: ' ' - , .:: ' -~2137~
Example 7 .
An experiment was carried O~lt in the manner of Exa~ple 1 uslng o xylene (50 ml), acetophenone (20 ml), palladiùm aceta~
(0.1 mmol), triphenylphosphlne (50 mmol) and p-toluenesulphonic S acid (15 mmol). The partial pressures of ethylene and carbon monoxide were 30 bar each. After a reaction time of 5 h at 125 C
the conversion of acetophenone was 33%, with a selectivity to l-phenylvinyl propionate of 95%.
Exampl _8 ~0 ~n experiment was carried out in the manner of Example 1, using o-xylene ~50 ml), acetophenone (20 ml), palladium acetate (0.1 mmol), triphenylphosphine (30 mmol), p-toluenesulphonic acid (lO mmol) and propionic acid (2 ml). The partial pressures of ethylene and'carbon monoxide were 30 bar each. After a reaction time of 5 h at 125 C the conversion of acetophenone was 25%, with a selectivity to l-phenylvinyl propionate of 95%. Propionic acid was converted into propionic anhydride with a yield of 90%.
Example 9 An experiment was carried out in the manner of Example 1, using o-xylene (50 ml), acetophenone (20 ml), palladium acetate (0.1 mmol), triphenylphosphine (50 mmol) and methanesulphonic acid (15 mmol). The partial pressures of ethylene and carbon monoxide were 30 bar each. After a reaction time of 5 h at 125 C the conversion of acetophenone was 22%, with a selectivity to l-phenyl-vinyl propionate of 95%.
Example 10 The experiment of Example 9 was repeated with the dlfference that 15 mmol of methanesulphonic acid were replaced with lS mmol of mesitylenesulphonic acid. The conversion of acetophenone was 14~, with a selectivity to l-phenylvinyl propionate of 95%.
Example 11 ~
An experiment~was carried out in the manner of Example 1, using diglyme ~50 ml), acetophenone (20 ml), palladium acetate (0.1 mmol), triphenylphosphine (50 mmol) and p-toluenesulphonic -~
acid (15 mmol). The partial pressures of ethylene and carbon monoxide were 30 bar each. After a reaction ~ime of 5 h at 125 C -~
~ '~
~ . .
33~
the conversion of acetophenone was 30%, with a selectlvity to l-phenylvinyl propionate of more than 95%.
Example 12 An experiment was carried out in the manner of Example 1, S using diglyme (50 ml), acetophenone (20 ml), palladium acetate (0.1 mmol), tri(m-chlorophenyl)phosphine t20 mmol) and p-toluene-sulphonic acid (5 mmol). The partial pressures of ethylene and carbon monoxide were 30 bar each. After a reaction time of 3 h at 125 C the conversion of acetophenone was 8%~ with a selectivity to l-phenylvinyl propionate of more than 95%.
~xample 13 The experiment of Example 11 was repeated with the difference that the partial pressures of ethylene and carbon monoxide were 20 and 40 bar, respectively. The conversion of acetophenone was 25%, with a selectivity to l-phenylvinyl propionate of 95%.
Example 14 The experiment of Example 11 was repeated with the difference that the partial pressures of ethylene and carbon monoxide were 40 and 20 bar, respectlvely. The conversion of acetophenone was 25%, with a selectivity to l-phenylvinyl propionate of 95%.
Example 15 The experiment of Example 11 was repeated with the difference that 50 ml instead of 20 ml o~ acetophenone were used and that no diglyme was present. The conversion of acetophenone was 1~%, with a selectivity to l-phenylvinyl propionate of 95%.
Comparative Experiment A
The experiment described in Example 1 was repeated with the difference that p toluenesulphonic acid (2 mmol) was replaced with ben~enephosphonic acid (pK - 1.5, 2 mmol). The conversion of the ketone was below 5% and propionate could not be detected in the reaction mixture.
Comparative Experiment B
The experiment described in Example 1 was repeated with the d~flerence that p-toluenesu pùonic aci (2 mmol) was replaced with ~ .
' :, , : : , ., - , . , ~287~
2,6-dichlorobenzoic acid ~P~a = 1.5, 2 mmol). The conversion of ketone was below 5% and propionate could not be detected in the reaction mix~ure. -:
: :
, -. , .. . , , :, ,: , :
Claims (21)
1. A process for the preparation of carboxylate esters of alphaethylenically unsaturated alcohols, which process comprises causing an ethylenically unsaturated compound to react with carbon monoxide and an enolizable ketone in the presence of a catalytic system formed by combining:-(a) a palladium catalyst, (b) a phosphine having the general formula (I) (I) in which R1, R2 and R3 each individually represent an aryl group which is unsubstituted or is substituted by a substituent that does not interfere with the course of the reaction, and (c) a protonic acid having a PKa below 1.5 as a promoter (measured at 18°C in aqueous solution), except hydrohalogenic acids and carboxylic acids.
2. A process as claimed in claim 1, in which the ethylenically unsaturated compound is an optionally substituted alkene having in the range of from 2 to 30 carbon atoms per molecule.
3. A process as claimed in claim 2, in which the optionally substituted alkene has in the range of from 2 to 10 carbon atoms per molecule.
4. A process as claimed in claim 3, in which the alkene is ethylene.
5. A process as claimed in claim 1, 2 or 3, in which an optionally substituted alkanone having in the range of from 3 to 30 carbon atoms per molecule is used as enolizable ketone.
6. A process as claimed in claim 5, in which methyl alkyl ketone is used as enolizable ketone.
7. A process as claimed in claim 1, 2 or 3, in which an alkanone that has 3 or 4 carbon atoms per molecule is used as enolizable ketone.
8. A process as claimed in claim 1, 2 or 3, in which an alkyl phenyl ketone is used as enolizable ketone.
9. A process as claimed in claim 8, in which acetophenone is used as enolizable ketone.
10. A process as claimed in claim 1, 2 or 3, in which the palladium catalyst contains a compound of divalent palladium.
11. A process as claimed in claim 1, 2 or 3, in which the palladium catalyst is a palladium alkanoate.
12 12. A process as claimed in claim 1, 2 or 3, in which the palladium catalyst is palladium acetate.
13. A process as claimed in claim 1, 2 or 3, in which at least 5 mol of the phosphine having the general formula (I) are used per gram atom of palladium.
14. A process as claimed in claim 1, 2 or 3, in which an acid with a non-coordinating anion is used as promoter.
15. A process as claimed in claim 1, 2 or 3, in which a sulphonic acid or an acid that can be formed by interaction of a Lewis acid with a Broensted acid is used as promoter.
16. A process as claimed in claim 1, 2 or 3, in which an acid having the general formula (II) (II) in which Z represents a sulphur or a chlorine atom, and, if Z
represents a chlorine atom, R4 represents an oxygen atom, and, if Z represents a sulphur atom, R4 represents an OH group or an optionally substituted hydrocarbyl group, is used as a promoter.
represents a chlorine atom, R4 represents an oxygen atom, and, if Z represents a sulphur atom, R4 represents an OH group or an optionally substituted hydrocarbyl group, is used as a promoter.
17. A process as claimed in claim 1, 2 or 3, in which an acid having the general formula R4 - SO3H, in which R4 is an alkyl, aryl, aralkyl or alkaryl group having not more than 30 carbon atoms, is used as a promoter.
18. A process as claimed in claim 1, 2 or 3, in which p-toluenesulphonic acid is used as a promoter.
19. A process as claimed in claim 1, 2 or 3, in which the aryl groups represented by the groups R1, R2 and R3 in formula (I) have in the range of from 6 to 14 carbon atoms.
20. A process as claimed in claim 1, 2 or 3, in which the aryl groups represented by the groups R1, R2 and R3 are phenyl groups.
21. A process as claimed in claim 1, 2 or 3, which is carried out at a temperature in the range of from 50 °C to 200 °C.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB858523859A GB8523859D0 (en) | 1985-09-27 | 1985-09-27 | Unsaturated carboxylate esters |
| GB8523859 | 1985-09-27 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1287838C true CA1287838C (en) | 1991-08-20 |
Family
ID=10585812
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000517354A Expired CA1287838C (en) | 1985-09-27 | 1986-09-03 | Process for the preparation of unsaturated carboxylate esters |
Country Status (7)
| Country | Link |
|---|---|
| US (1) | US4670582A (en) |
| EP (1) | EP0218282B1 (en) |
| JP (1) | JPH0717572B2 (en) |
| CA (1) | CA1287838C (en) |
| DE (1) | DE3660958D1 (en) |
| ES (1) | ES2001439A6 (en) |
| GB (1) | GB8523859D0 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0319083A3 (en) * | 1987-11-30 | 1990-11-07 | Shell Internationale Researchmaatschappij B.V. | Polyketone polymer preparation |
| GB9026211D0 (en) * | 1990-12-03 | 1991-01-16 | Shell Int Research | Carbonylation process |
| US6489506B2 (en) * | 1997-03-19 | 2002-12-03 | Lucite International Uk Limited | Process for the palladium and phosphine ligand catalyzed carbonylation of ethylene |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1051627A (en) * | 1961-12-29 | |||
| US3349119A (en) * | 1965-02-19 | 1967-10-24 | Union Oil Co | Oxidative carbonylation of olefins in the presence of inorganic acid anhydrides |
| US3641074A (en) * | 1969-02-25 | 1972-02-08 | Union Oil Co | Carbonylation of olefins |
| US3652655A (en) * | 1969-10-10 | 1972-03-28 | Union Oil Co | Preparation of esters of unsaturated carboxylic acids |
| US3660439A (en) * | 1970-03-20 | 1972-05-02 | Ethyl Corp | Catalytic preparation of carboxylic acid esters from olefins alcohols and carbon monoxide in the presence of ketone promoter |
| GB1411396A (en) * | 1971-12-28 | 1975-10-22 | Lion Fat Oil Co Ltd | Method of preparing esters of carboxylic acids |
| JPS5210213A (en) * | 1975-07-10 | 1977-01-26 | Idemitsu Kosan Co Ltd | Process for preparation of unsaturated carbonyl compounds |
| US4414409A (en) * | 1981-12-21 | 1983-11-08 | E. I. Du Pont De Nemours & Company | Palladium sulfonate catalyst systems for carbonylation of olefins |
-
1985
- 1985-09-27 GB GB858523859A patent/GB8523859D0/en active Pending
-
1986
- 1986-08-15 US US06/896,681 patent/US4670582A/en not_active Expired - Lifetime
- 1986-09-03 CA CA000517354A patent/CA1287838C/en not_active Expired
- 1986-09-12 DE DE8686201573T patent/DE3660958D1/en not_active Expired
- 1986-09-12 EP EP86201573A patent/EP0218282B1/en not_active Expired
- 1986-09-25 JP JP61225093A patent/JPH0717572B2/en not_active Expired - Lifetime
- 1986-09-25 ES ES8602154A patent/ES2001439A6/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6272648A (en) | 1987-04-03 |
| JPH0717572B2 (en) | 1995-03-01 |
| US4670582A (en) | 1987-06-02 |
| EP0218282B1 (en) | 1988-10-19 |
| DE3660958D1 (en) | 1988-11-24 |
| EP0218282A1 (en) | 1987-04-15 |
| ES2001439A6 (en) | 1988-05-16 |
| GB8523859D0 (en) | 1985-10-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP0186228B1 (en) | Process for the carbonylation of acetylenically unsaturated compounds | |
| EP0227160B1 (en) | Process for the carbonylation of ethylenically unsaturated compounds | |
| KR100220824B1 (en) | Carbonylation of olefins | |
| CA1263122A (en) | Process for the carbonylation of allenically unsaturated compounds | |
| US5149868A (en) | Carbonylation process | |
| US4861912A (en) | Process for the preparation of a diester of adipic acid | |
| JP3108490B2 (en) | Carbonylation method and catalyst composition | |
| EP0291117B1 (en) | Process for the preparation of carboxylic acids or of esters thereof | |
| CA1287838C (en) | Process for the preparation of unsaturated carboxylate esters | |
| EP0198521B1 (en) | Preparation of carboxylic di-esters or acids | |
| US4849542A (en) | Process for the preparation of oxo-alkanedioic acids or diesters thereof | |
| EP0218283B1 (en) | Process for the preparation of esters of alpha-ethylenically unsaturated alcohols and alpha-ethylenically unsaturated carboxylic acids | |
| US4730080A (en) | Process for the preparation of diesters of alkanedioic acids | |
| US4431839A (en) | Toluic acid | |
| KR20000075730A (en) | Process to prepare a pentenoic acid derivative | |
| CA1253877A (en) | Process for the preparation of carboxylic acid esters of hydroxy sulfonates | |
| CA1334674C (en) | Process for the preparation of carboxylic acids or esters thereof | |
| EP0096905B1 (en) | Process for the preparation of glycol aldehyde | |
| EP1572609B1 (en) | Process for the hydroformylation of ethylenically unsaturated compounds in the presence of an acid and a mono tert-phosphine | |
| US4463103A (en) | Toluic acid | |
| US6049005A (en) | Process to prepare a pentenoic acid anhydride | |
| GB2238538A (en) | Preparation of alcohols |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MKLA | Lapsed |