US4281173A
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US
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Preparation of unsaturated diesters by catalytic oxidative carbonylation of diolefins
Assignee: Lyondell Chemical Technology LP
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Filing: 1979-12-03
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Granted: 1981-07-28
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Expires: 1999-12-03
Abstract
Abstract A process for the preparation of an unsaturated diester having the formula ##STR1## wherein R is alkyl having 1 to 8 carbon atoms or aralkyl having 6 carbon atoms in the ring and from 1 to 4 carbon atoms in the alkyl moiety, and R 1 , R 2 , R 3 and R 4 are the same or different and are each hydrogen, halogen, alkyl having 1 to 4 carbon atoms or aryl having 6 carbon atoms in the ring, by reacting carbon monoxide and oxygen with a diolefin having the formula ##STR2## wherein R 1 , R 2 , R 3 and R 4 are as aforesaid, in the presence of a catalytic amount of a platinum group metal compound, a copper or iron oxidant salt compound, a soluble vanadium salt and a stoichiometric amount of a dehydrating agent. Optionally, an anhydrous-halogen containing acid may be included. Alternatively, a ligand or coordination complex compound of the metal salt compound, and catalytic quantities of an alcohol may be employed.
Inventors
- 👤 Haven S. Kesling, Jr.
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-11-08 20:18
CPC Classifications
C; C07; C07C; C07C69/00; C07C69/52; C07C69/593
Claims Analysis
Total Claims: 12
Claim 1
Independent Claim
227 words
In the process for preparing an unsaturated diester having the formula ##STR11## wherein R is alkyl having 1 to 8 carbon atoms or aralkyl having 6 carbon atoms in the ring and 1 to 4 carbon atoms in the alkyl moiety and R 1 , R 2 , R 3 and R 4 are the same or different and are each hydrogen, halogen, alkyl having 1 to 4 carbon atoms or aryl having 6 carbon atoms in the ring by reacting a diolefin having the formula ##STR12## wherein R 1 , R 2 , R 3 , and R 4 are as aforesaid, with a mixture of carbon monoxide and oxygen and a stoichiometric amount of a dehydrating agent selected from the group consisting of acetals, ketals, carboxylic ortho esters, trialkylorthoborates and dialkoxycycloalkanes, at a pressure of from about 15 psig to 5,000 psig and at a temperature of about 25° to 200° C. in the presence of an effective amount of a catalytic mixture of (1) a platinum group metal compound or mixtures thereof and (2) a copper (I), copper (II), iron (II) or iron (III) oxidant salt compound and recovering the desired unsaturated diester, the improvement comprising carrying out said reaction in the presence of from 0.3 to 3 weight percent of a vanadium salt which is soluble in the reaction mixture under reaction conditions.
Claim 2
Dependent Claim
227 words
In the process for preparing an unsaturated diester having the formula ##STR11## wherein R is alkyl having 1 to 8 carbon atoms or aralkyl having 6 carbon atoms in the ring and 1 to 4 carbon atoms in the alkyl moiety and R 1 , R 2 , R 3 and R 4 are the same or different and are each hydrogen, halogen, alkyl having 1 to 4 carbon atoms or aryl having 6 carbon atoms in the ring by reacting a diolefin having the formula ##STR12## wherein R 1 , R 2 , R 3 , and R 4 are as aforesaid, with a mixture of carbon monoxide and oxygen and a stoichiometric amount of a dehydrating agent selected from the group consisting of acetals, ketals, carboxylic ortho esters, trialkylorthoborates and dialkoxycycloalkanes, at a pressure of from about 15 psig to 5,000 psig and at a temperature of about 25° to 200° C. in the presence of an effective amount of a catalytic mixture of (1) a platinum group metal compound or mixtures thereof and (2) a copper (I), copper (II), iron (II) or iron (III) oxidant salt compound and recovering the desired unsaturated diester, the improvement comprising carrying out said reaction in the presence of from 0.3 to 3 weight percent of a vanadium salt which is soluble in the reaction mixture under reaction conditions.
Claim 3
Dependent Claim
40 words
The process of claim 1 wherein said reaction is also carried out in the presence of an anhydrous halogen-containing acid selected from the group consisting of hydrochloric, hydrobromic and hydroiodic acid at a concentration of from 0.01 to 1 mole/liter.
Claim 4
Dependent Claim
11 words
The process of claim 2 wherein said acid is hydrochloric acid.
Claim 5
Dependent Claim
19 words
The process of claim 3 wherein said hydrochloric acid is generated in situ by the thermal disassociation of 1-chloro-1-methoxycyclohexane.
Claim 6
Dependent Claim
19 words
The process of claim 1 wherein said soluble vanadium salt is a chloride, bromide or iodide of vanadium (III).
Claim 7
Dependent Claim
46 words
The process of claim 1 wherein the reaction is carried out in the presence of a catalytic amount 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 8
Dependent Claim
43 words
The process of 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 9
Dependent Claim
103 words
In the process of preparing dimethylhex-3-endioate by reacting 1,3-butadiene with a mixture of carbon monoxide and oxygen and a stoichiometric quantity of a dehydrating agent selected from the group consisting of acetals, ketals, carboxylic ortho esters, trialkylorthoborates and dialkoxycycloalkanes, at a pressure of between about 500 psig and 1800 psig and at a temperature of from about 80° to 150° C. in the presence of an effective amount of a palladium metal salt compound and a copper (II) oxidant salt compound, the improvement comprising carrying out said reaction in the presence of from 0.3 to 3 weight percent of a soluble vanadium salt.
Claim 10
Dependent Claim
103 words
In the process of preparing dimethylhex-3-endioate by reacting 1,3-butadiene with a mixture of carbon monoxide and oxygen and a stoichiometric quantity of a dehydrating agent selected from the group consisting of acetals, ketals, carboxylic ortho esters, trialkylorthoborates and dialkoxycycloalkanes, at a pressure of between about 500 psig and 1800 psig and at a temperature of from about 80° to 150° C. in the presence of an effective amount of a palladium metal salt compound and a copper (II) oxidant salt compound, the improvement comprising carrying out said reaction in the presence of from 0.3 to 3 weight percent of a soluble vanadium salt.
Claim 11
Dependent Claim
40 words
The process of claim 8 wherein said reaction is also carried out in the presence of an anhydrous halogen-containing acid selected from the group consisting of hydrochloric, hydrobromic and hydroiodic acid at a concentration of from 0.01 to 1 mole/liter.
Claim 12
Dependent Claim
11 words
The process of claim 1 wherein said dehydrating agent is 1,1-dimethoxycyclohexane.
References Cited (Backward Citations)
US4039572A
Cited
US4171450A
Cited
USPTO Annuity & Maintenance Windows
| Annuity Stage | Window Opens | Payment Deadline | Surcharge Period Until | Estimated Fee | Status |
|---|---|---|---|---|---|
| 3.5 Years (Year 4) | 1984-07-27 | 1985-01-26 | 1985-07-28 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1988-07-27 | 1989-01-26 | 1989-07-28 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1992-07-27 | 1993-01-26 | 1993-07-28 | $7700.00 | Window Closed / Lapsed |