US4529808A
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Bi-solvent system for the hydroformylation of allyl alcohol using a rhodium catalyst
Assignee: Huntsman Corp
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Filing: 1984-02-02
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Granted: 1985-07-16
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Expires: 2004-02-02
Abstract
Abstract A process is disclosed for preparing products such as 2-hydroxytetrahydrofuran which comprises contacting unsaturated compounds such as allyl alcohol with carbon monoxide and hydrogen in the presence of a rhodium carbonyl catalyst and a bi-solvent system. The bi-solvent system includes an aromatic solvent and an amide solvent and may be materials such as p-xylene and acetamide. Such a system provides for easy catalyst recovery since the rhodium catalyst is selectively soluble in the p-xylene whereas the desired product is conversely selectively soluble in the acetamide phase.
Inventors
- 👤 Jiang-Jen Lin
- 👤 John F. Knifton
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-11-09 16:44
CPC Classifications
C; C07; C07D; C07D307/00; C07D307/02; C07D307/04; C07D307/18; C07D307/20
Claims Analysis
Total Claims: 18
Claim 1
Independent Claim
93 words
A process for preparing 2-hydroxytetrahydrofuran which comprises hydroformylating allyl alcohol by reaction with carbon monoxide and hydrogen in the presence of a rhodium carbonyl catalyst and a bi-solvent system comprising an aromatic hydrocarbon solvent and an amide solvent having the formula ##STR2## where R is hydrogen or a lower alkyl group of one to four carbon atoms and where the weight ratio of aromatic hydrocarbon solvent to amide solvent is in the range of 1:5 to 5:1, in a reaction mixture where after the reaction, the mixture separates into two immiscible liquid phases.
Claim 2
Dependent Claim
93 words
A process for preparing 2-hydroxytetrahydrofuran which comprises hydroformylating allyl alcohol by reaction with carbon monoxide and hydrogen in the presence of a rhodium carbonyl catalyst and a bi-solvent system comprising an aromatic hydrocarbon solvent and an amide solvent having the formula ##STR2## where R is hydrogen or a lower alkyl group of one to four carbon atoms and where the weight ratio of aromatic hydrocarbon solvent to amide solvent is in the range of 1:5 to 5:1, in a reaction mixture where after the reaction, the mixture separates into two immiscible liquid phases.
Claim 3
Dependent Claim
56 words
The process of claim 1 in which after the reaction the mixture separates into two liquid phases, an aromatic-rich phase and an amide-rich phase, where at least 90 wt. % of the rhodium catalyst is present in the aromatic phase and at least 90 wt. % of the 2-hydroxytetrahydrofuran product is present in the amide phase.
Claim 4
Dependent Claim
37 words
The process of claim 1 in which the reaction is conducted at a temperature in the range of from about 50 to 120° C. and at a pressure in the range from about 500 to 1,500 psi.
Claim 5
Dependent Claim
18 words
The process of claim 1 in which the catalyst is a rhodium carbonyl-triphenylphosphine complex together with excess triphenylphosphine.
Claim 6
Dependent Claim
12 words
The process of claim 1 in which the aromatic solvent is p-xylene.
Claim 7
Dependent Claim
20 words
The process of claim 1 in which the amide solvent is selected from the group consisting of formamide and acetamide.
Claim 8
Dependent Claim
14 words
The process of claim 1 in which the rhodium carbonyl catalyst is hydridocarbonyltris(triphenylphosphine) rhodium(I).
Claim 9
Dependent Claim
76 words
A process for preparing 2-hydroxytetrahydrofuran which comprises hydroformylating allyl alcohol by reaction with carbon monoxide and hydrogen in the presence of a rhodium carbonyl-triphenylphosphine complex catalyst and a bi-solvent system comprising p-xylene and an amide selected from the group consisting of formamide and acetamide, where the weight ratio of p-xylene to amide is in the range of 1:5 to 5:1, in a reaction mixture where after the reaction, the mixture separates into two immiscible liquid phases.
Claim 10
Dependent Claim
76 words
A process for preparing 2-hydroxytetrahydrofuran which comprises hydroformylating allyl alcohol by reaction with carbon monoxide and hydrogen in the presence of a rhodium carbonyl-triphenylphosphine complex catalyst and a bi-solvent system comprising p-xylene and an amide selected from the group consisting of formamide and acetamide, where the weight ratio of p-xylene to amide is in the range of 1:5 to 5:1, in a reaction mixture where after the reaction, the mixture separates into two immiscible liquid phases.
Claim 11
Dependent Claim
41 words
The process of claim 8 in which upon separation, at least 90 wt. % of the rhodium catalyst is present in the p-xylene rich phase and at least 90 wt. % of the 2-hydroxytetrahydrofuran product is present in the amide-rich phase.
Claim 12
Dependent Claim
37 words
The process of claim 8 in which the reaction is conducted at a temperature in the range of from about 50 to 120° C. and at a pressure in the range from about 500 to 1,500 psi.
Claim 13
Dependent Claim
14 words
The process of claim 8 in which the rhodium carbonyl-triphenylphosphine complex is hydridocarbonyltris(triphenylphosphine)rhodium (I).
Claim 14
Dependent Claim
19 words
The process of claim 8 in which the two solvents are present in approximately equal amounts based on weight.
Claim 15
Dependent Claim
122 words
A process for preparing 2-hydroxytetrahydrofuran which comprises hydroformylating allyl alcohol by reaction with carbon monoxide and hydrogen in the presence of a rhodium carbonyl-triphenylphosphine complex catalyst and a bi-solvent system comprisng p-xylene and an amide selected from the group consisting of formamide and acetamide, where the weight ratio of p-xylene to amide is about 1:1, in a reaction mixture where, after the reaction, the mixture separates into two liquid phases, a p-xylene phase and an amide phase where at least 90 wt. % of the rhodium catalyst is present in the p-xylene phase and at least 90 wt. % of the 2-hydroxytetrahydrofuran is present in the amide phase, allyl alcohol conversion being at least 90% and 2-hydroxytetrahydrofuran selectivity being at least 90%.
Claim 16
Dependent Claim
122 words
A process for preparing 2-hydroxytetrahydrofuran which comprises hydroformylating allyl alcohol by reaction with carbon monoxide and hydrogen in the presence of a rhodium carbonyl-triphenylphosphine complex catalyst and a bi-solvent system comprisng p-xylene and an amide selected from the group consisting of formamide and acetamide, where the weight ratio of p-xylene to amide is about 1:1, in a reaction mixture where, after the reaction, the mixture separates into two liquid phases, a p-xylene phase and an amide phase where at least 90 wt. % of the rhodium catalyst is present in the p-xylene phase and at least 90 wt. % of the 2-hydroxytetrahydrofuran is present in the amide phase, allyl alcohol conversion being at least 90% and 2-hydroxytetrahydrofuran selectivity being at least 90%.
Claim 17
Dependent Claim
38 words
The process of claim 13 in which the reaction is conducted at a temperature in the range of from about 50° to 120° C. and at a pressure in the range of from about 500 to 1,500 psi.
Claim 18
Dependent Claim
13 words
The process of claim 13 in which the rhodium carbonyltriphenylphosphine complex is hydridocarbonyltris(triphenylphosphine)rhodium(I).
References Cited (Backward Citations)
US4139542A
Cited
US4356125A
Cited
USPTO Annuity & Maintenance Windows
| Annuity Stage | Window Opens | Payment Deadline | Surcharge Period Until | Estimated Fee | Status |
|---|---|---|---|---|---|
| 3.5 Years (Year 4) | 1988-07-15 | 1989-01-14 | 1989-07-16 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1992-07-15 | 1993-01-14 | 1993-07-16 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1996-07-15 | 1997-01-14 | 1997-07-16 | $7700.00 | Window Closed / Lapsed |