US4171450A
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US
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Preparation of unsaturated diesters by catalytic oxidative carbonylation of diolefins
Assignee: Atlantic Richfield Co
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Filing: 1977-06-22
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Granted: 1979-10-16
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Expires: 1997-06-22
Abstract
Abstract A process for the preparation of an unsaturated diester having the formula <IMAGE> wherein R is an alkyl group of from 1 to 8 carbon atoms or an aralkyl group containing 6 carbon atoms in the ring and from 1 to 4 carbon atoms in the alkyl substituent, and R1 to R4 is hydrogen, a halogen, an alkyl group of from 1 to 4 carbon atoms or an aryl group containing 6 carbon atoms in the ring, by reacting carbon monoxide and oxygen with a diolefin having the formula <IMAGE> wherein R1 to R4 which may be the same or different is as hereinabove described, in the presence of a catalytic amount of a platinum group metal compound, a copper for iron oxidant salt compound and a stoichiometric amount of a dehydrating agent.
Inventors
- 👤 Haven S. Kesling, Jr.
- 👤 Lee R. Zehner
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-11-09 21:37
CPC Classifications
C; C07; C07C; C07C69/00; C07C69/52
Claims Analysis
Total Claims: 30
Claim 1
Independent Claim
212 words
A process for the preparation of an unsaturated diester having the formula ##STR11## wherein R is an alkyl group of from 1 to 4 carbon atoms or an aralkyl group containing 6 carbon atoms in the ring and from 1 to 4 carbon atoms in the alkyl substituent and R 1 , R 2 , R 3 and R 4 is hydrogen, a halogen, an alkyl group of from 1 to 4 carbon atoms or an aryl group containing 6 carbon atoms in the ring, which consists essentially of reacting a diolefin having the formula ##STR12## wherein R 1 , R 2 , R 3 and R 4 which may be the same or different are as above described, with a mixture of carbon monoxide and oxygen and at least a stoichiometric amount of a dehydrating agent selected from acetals, ketals, carboxylic ortho esters, trialkylorthoborates or dialkoxycycloalkanes, at a pressure of between about 15 psig and 5000 psig and at a temperature in the range of about 25° C. to 200° C. in the presence of an effective amount of a catalytic mixture of a platinum group metal compound or mixtures thereof and a copper (I), copper (II), iron (II) or iron (III) oxidant salt compound and recovering the desired unsaturated diester.
Claim 2
Dependent Claim
212 words
A process for the preparation of an unsaturated diester having the formula ##STR11## wherein R is an alkyl group of from 1 to 4 carbon atoms or an aralkyl group containing 6 carbon atoms in the ring and from 1 to 4 carbon atoms in the alkyl substituent and R 1 , R 2 , R 3 and R 4 is hydrogen, a halogen, an alkyl group of from 1 to 4 carbon atoms or an aryl group containing 6 carbon atoms in the ring, which consists essentially of reacting a diolefin having the formula ##STR12## wherein R 1 , R 2 , R 3 and R 4 which may be the same or different are as above described, with a mixture of carbon monoxide and oxygen and at least a stoichiometric amount of a dehydrating agent selected from acetals, ketals, carboxylic ortho esters, trialkylorthoborates or dialkoxycycloalkanes, at a pressure of between about 15 psig and 5000 psig and at a temperature in the range of about 25° C. to 200° C. in the presence of an effective amount of a catalytic mixture of a platinum group metal compound or mixtures thereof and a copper (I), copper (II), iron (II) or iron (III) oxidant salt compound and recovering the desired unsaturated diester.
Claim 3
Dependent Claim
23 words
A process according to claim 1 wherein the diolefin is selected from the group consisting of 1,3-butadiene, isoprene, chloroprene, 1,3-pentadiene, 2,3-diethylbutadiene, and 1,4-diphenylbutadiene.
Claim 4
Dependent Claim
11 words
A process according to claim 2 wherein the diolefin is 1,3-butadiene.
Claim 5
Dependent Claim
28 words
A process according to claim 1 wherein the dehydrating agent is selected from the group consisting of 1,1-dimethoxycyclohexane, trimethylorthoformate, 2,2-dimethoxypropane, trimethylorthoborate, 1,1-dimethoxyethane, 1,1-diethoxypropane, 2,2-dimethoxybutane, 1,1-dibutoxycyclohexane, 1,1-diethoxyhexane, and triethylorthoformate.
Claim 6
Dependent Claim
12 words
A process according to claim 4 wherein the dehydrating agent is 1,1-dimethoxycyclohexane.
Claim 7
Dependent Claim
17 words
A process according to claim 1 wherein the pressure is between about 500 psig and 1800 psig.
Claim 8
Dependent Claim
21 words
A process according to claim 1 wherein the temperature is in the range of from about 80° C. to 150° C.
Claim 9
Dependent Claim
36 words
A process according to claim 1 wherein the platinum group metal compound is selected from the group consisting of palladium, ruthenium, rhodium, and platinum, halides, cyanates, sulfates, nitrates, oxides, oxalates, acetates, and trifluoroacetates or mixtures thereof.
Claim 10
Dependent Claim
45 words
A process according to claim 8 wherein the platinum group metal compound is selected from palladium (II) chloride, palladium (II) bromide, platinum (II) chloride, rhodium (III) chloride, ruthenium (III) chloride, palladium (II) acetate, palladium (II) sulfate, palladium (II) nitrate, palladium (II) cyanide, or palladium metal.
Claim 11
Dependent Claim
16 words
A process according to claim 9 wherein the platinum group metal compound is palladium (II) chloride.
Claim 12
Dependent Claim
16 words
A process according to claim 9 wherein the platinum group metal compound is palladium (II) bromide.
Claim 13
Dependent Claim
35 words
A process according to claim 1 wherein the oxidant salt compound is selected from the group consisting of copper (I), copper (II), iron (II) and iron (III) halides, sulfates, trifluoroacetates, oxalates, naphthenates, nitrates and acetates.
Claim 14
Dependent Claim
46 words
A process according to claim 12 wherein the oxidant salt compound is selected from the group consisting of copper (II) chloride, copper (II) bromide, iron (II) chloride, iron (III) chloride, copper (II) sulfate, copper (II) nitrate, copper (II) acetate, copper (I) chloride and copper (I) bromide.
Claim 15
Dependent Claim
15 words
A process according to claim 13 wherein the oxidant salt compound is copper (II) chloride.
Claim 16
Dependent Claim
15 words
A process according to claim 13 wherein the oxidant salt compound is copper (II) bromide.
Claim 17
Dependent Claim
15 words
A process according to claim 13 wherein the oxidant salt compound is iron (III) chloride.
Claim 18
Dependent Claim
44 words
A process according to claim 1 wherein the reaction is carried out in the presence of an organic mono- or poly-dentate ligand or coordination complex compound selected from the group consisting of alkyl, aryl, and halogen substituted phosphines, arsines, stibines, and alkali metal salts.
Claim 19
Dependent Claim
15 words
A process according to claim 17 wherein the ligand or coordination complex is lithium chloride.
Claim 20
Dependent Claim
15 words
A process according to claim 17 wherein the ligand or coordination complex is lithium bromide.
Claim 21
Dependent Claim
20 words
A process according to claim 17 wherein the ligand or coordination complex is potassium chloride, potassium bromide, or sodium chloride.
Claim 22
Dependent Claim
59 words
A process according to claim 1 wherein the reaction is carried out in the presence of a catalytic amount of from 0 to 20 weight percent based on the diolefin employed of a monohydric saturated aliphatic, alicyclic or aralkyl alcohol containing from 1 to 20 carbon atoms which may contain other substituents which would not interfere with the reaction.
Claim 23
Dependent Claim
26 words
A process according to claim 21 wherein the alcohol is employed in a catalytic amount of from 0.5 to 10 weight percent of the diolefin employed.
Claim 24
Dependent Claim
21 words
A process according to claim 21 wherein the alcohol is an unsubstituted aliphatic alcohol containing from 1 to 8 carbon atoms.
Claim 25
Dependent Claim
12 words
A process according to claim 23 wherein the alcohol is methyl alcohol.
Claim 26
Dependent Claim
12 words
A process according to claim 23 wherein the alcohol is ethyl alcohol.
Claim 27
Dependent Claim
85 words
A process for the preparation of dimethylhex-3-endioate which consists essentially of reacting 1,3-butadiene with a mixture of carbon monoxide and oxygen and a stoichiometric quantity of a dehydrating agent selected from acetals, ketals, carboxylic ortho esters, trialkylorthoborates or dialkoxycycloalkanes, at a pressure of between about 500 psig and 1800 psig and at a temperature in the range of from about 80° C. to 150° C. in the presence of an effective amount of a palladium metal salt compound and a copper (II) oxidant salt compound.
Claim 28
Dependent Claim
85 words
A process for the preparation of dimethylhex-3-endioate which consists essentially of reacting 1,3-butadiene with a mixture of carbon monoxide and oxygen and a stoichiometric quantity of a dehydrating agent selected from acetals, ketals, carboxylic ortho esters, trialkylorthoborates or dialkoxycycloalkanes, at a pressure of between about 500 psig and 1800 psig and at a temperature in the range of from about 80° C. to 150° C. in the presence of an effective amount of a palladium metal salt compound and a copper (II) oxidant salt compound.
Claim 29
Dependent Claim
32 words
A process according to claim 26 wherein the dehydrating agent is dimethoxycyclohexane, the palladium metal salt compound is palladium (II) chloride, and the copper (II) oxidant salt compound is copper (II) chloride.
Claim 30
Dependent Claim
41 words
A process according to claim 27 wherein the reaction is carried out in the presence of a catalytic amount of lithium chloride and a catalytic amount of from 0.5 to 10 weight percent based on the 1,3-butadiene employed of methyl alcohol.
References Cited (Backward Citations)
US3397226A
Cited
US3952034A
Cited
USPTO Annuity & Maintenance Windows
| Annuity Stage | Window Opens | Payment Deadline | Surcharge Period Until | Estimated Fee | Status |
|---|---|---|---|---|---|
| 3.5 Years (Year 4) | 1982-10-15 | 1983-04-16 | 1983-10-16 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1986-10-15 | 1987-04-16 | 1987-10-16 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1990-10-15 | 1991-04-16 | 1991-10-16 | $7700.00 | Window Closed / Lapsed |