US4138420A
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Hydroformylation catalysts
Assignee: Celanese Corp
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Filing: 1977-09-23
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Granted: 1979-02-06
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Expires: 1997-09-23
Abstract
Abstract An organo metallic complex catalyst, useful in the hydroformylation of an olefin, e.g., an alkene, to yield an aldehyde product in which the normal aldehyde isomer predominates over branch-chain isomers, which has the structure: ##STR1## wherein capital M is a Group VIII metal (preferably rhodium); Q is phosphorus, arsenic, or antimony (preferably phosphorus); and R is phenyl or a lower alkyl group. In the process employing the new catalytic complex it is not necessary to employ an excess of any ligand, and moderate reaction conditions are adequate. The catalyst can be prepared ex situ or in situ from a suitable source of rhodium or the Group VIII metal and a suitable derivative of ferrocene.
Inventors
- 👤 Jerry D. Unruh
- 👤 William J. Wells, III
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-11-02 12:10
CPC Classifications
C; C07; C07C; C07C45/00; C07C45/49; C07C45/50; B; B01; B01J; B01J31/00; B01J31/16; B01J31/20; B01J31/24; B01J31/2404; B01J31/2409; B01J2231/00; B01J2231/30; B01J2231/32; B01J2231/321; B01J2531/00; B01J2531/80; B01J2531/82; B01J2531/822; B01J31/18; B01J31/1895
Claims Analysis
Total Claims: 27
Claim 1
Independent Claim
26 words
A complex having the structure ##STR8## wherein M is a Group VIII metal; Q is P, As, or Sb; and R is phenyl or lower alkyl.
Claim 2
Dependent Claim
26 words
A complex having the structure ##STR8## wherein M is a Group VIII metal; Q is P, As, or Sb; and R is phenyl or lower alkyl.
Claim 3
Dependent Claim
9 words
The complex of claim 1 wherein M is rhodium.
Claim 4
Dependent Claim
9 words
The complex of claim 2 wherein Q is phosphorus.
Claim 5
Dependent Claim
9 words
The complex of claim 3 wherein R is phenyl.
Claim 6
Dependent Claim
100 words
A process for forming a complex useful in catalyzing olefinhydroformylation reactions, which process comprises: reacting 1/2 mole of a disubstituted ferrocene of the formula ##STR9## wherein Q is P, As, or Sb and R is phenyl or lower alkyl with one mole of an interemediate complex of the formula ##STR10## wherein M is a Group VIII metal and Q and R are as defined above, said reaction being conducted in the liquid phase and in the presence of a chloride scavenger in an amount at least equivalent to the chloride content of said intermediate complex, together with a hydride source.
Claim 7
Dependent Claim
100 words
A process for forming a complex useful in catalyzing olefinhydroformylation reactions, which process comprises: reacting 1/2 mole of a disubstituted ferrocene of the formula ##STR9## wherein Q is P, As, or Sb and R is phenyl or lower alkyl with one mole of an interemediate complex of the formula ##STR10## wherein M is a Group VIII metal and Q and R are as defined above, said reaction being conducted in the liquid phase and in the presence of a chloride scavenger in an amount at least equivalent to the chloride content of said intermediate complex, together with a hydride source.
Claim 8
Dependent Claim
15 words
The process of claim 5 wherein M is rhodium and the hydride source is hydrogen.
Claim 9
Dependent Claim
9 words
The process of claim 6 wherein Q is phosphorus.
Claim 10
Dependent Claim
9 words
The process of claim 7 wherein R is phenyl.
Claim 11
Dependent Claim
69 words
A process for forming a complex useful in catalyzing olefin-hydroformylation reactions, which process comprises: reacting 1/2 mole of a disubstituted ferrocene of the formula ##STR11## wherein Q is P, As, or Sb and R is phenyl or lower alkyl in the liquid phase with one mole of an intermediate complex of the formula ##STR12## wherein M is a Group VIII metal and Q and R are as defined above.
Claim 12
Dependent Claim
69 words
A process for forming a complex useful in catalyzing olefin-hydroformylation reactions, which process comprises: reacting 1/2 mole of a disubstituted ferrocene of the formula ##STR11## wherein Q is P, As, or Sb and R is phenyl or lower alkyl in the liquid phase with one mole of an intermediate complex of the formula ##STR12## wherein M is a Group VIII metal and Q and R are as defined above.
Claim 13
Dependent Claim
9 words
The process of claim 9 wherein M is rhodium.
Claim 14
Dependent Claim
9 words
The process of claim 10 wherein Q is phorphorus.
Claim 15
Dependent Claim
9 words
The process of claim 11 wherein R is phenyl.
Claim 16
Dependent Claim
52 words
A process for forming a complex of the formula ##STR13## wherein M is rhodium, Q is phorphorus, and R is phenyl, said complex being useful as a component of hydroformylation catalysts, which process comprises: reacting 1/2 mole of [Rh(CO) 2 Cl] 2 with one mole of 1,1'-bis(diphenylphosphino) ferrocene in the liquid phase.
Claim 17
Dependent Claim
52 words
A process for forming a complex of the formula ##STR13## wherein M is rhodium, Q is phorphorus, and R is phenyl, said complex being useful as a component of hydroformylation catalysts, which process comprises: reacting 1/2 mole of [Rh(CO) 2 Cl] 2 with one mole of 1,1'-bis(diphenylphosphino) ferrocene in the liquid phase.
Claim 18
Dependent Claim
82 words
A process for forming a complex of the formula ##STR14## wherein M is rhodium, Q is phosphorus, and R is phenyl, said complex being useful as a hydroformylation catalyst and also as a component of other hydroformylation catalysts, which process comprises: reacting one mole of triphenylphosphine in the liquid phase with one mole of a complex of the formula ##STR15## wherein M is rhodium, Q is phosphorus, and R is phenyl, in the presence of a hydride source and a chloride-scavenging cation.
Claim 19
Dependent Claim
82 words
A process for forming a complex of the formula ##STR14## wherein M is rhodium, Q is phosphorus, and R is phenyl, said complex being useful as a hydroformylation catalyst and also as a component of other hydroformylation catalysts, which process comprises: reacting one mole of triphenylphosphine in the liquid phase with one mole of a complex of the formula ##STR15## wherein M is rhodium, Q is phosphorus, and R is phenyl, in the presence of a hydride source and a chloride-scavenging cation.
Claim 20
Dependent Claim
30 words
The process of claim 14 wherein the hydride source and the chloride-scavenging cation are both introduced into the reaction zone in the form of a borohydride of an alkaline-reacting cation.
Claim 21
Dependent Claim
46 words
A process for forming a complex useful in catalyzing hydroformylation reactions, which process comprises: reacting 1.5 moles of a compound of the formula ##STR16## wherein Q is phorphorus and R is phenyl or lower alkyl, in the liquid phase, with one mole of hydridocarbonyltris(triphenylphosphine) rhodium (I).
Claim 22
Dependent Claim
46 words
A process for forming a complex useful in catalyzing hydroformylation reactions, which process comprises: reacting 1.5 moles of a compound of the formula ##STR16## wherein Q is phorphorus and R is phenyl or lower alkyl, in the liquid phase, with one mole of hydridocarbonyltris(triphenylphosphine) rhodium (I).
Claim 23
Dependent Claim
9 words
The process of claim 16 wherein R is phenyl.
Claim 24
Dependent Claim
142 words
A process for forming a complex useful in catalyzing hydroformylation reactions, which process comprises: converting a rhodium source to a corresponding rhodium carbonyl derivative by reacting said rhodium source with carbon monoxide, and reacting said rhodium carbonyl derivative in the liquid phase with a disubstituted ferrocene of the formula ##STR17## wherein Q is P, As, or Sb and R is phenyl or lower alkyl, in a proportion of at least 1.5 moles of said disubstituted ferrocene per atom of rhodium contained in said rhodium carbonyl derivative, said reaction being conducted in the presence of a hydrogen source as necessary to convert said carbonyl derivative to a hydrido derivative thereof and also in the presence of a halide scavenger as necessary to neutralize halogen acid liberated during reaction of said hydrogen source with said carbonyl derivative when said carbonyl derivative contains halide moiety.
Claim 25
Dependent Claim
142 words
A process for forming a complex useful in catalyzing hydroformylation reactions, which process comprises: converting a rhodium source to a corresponding rhodium carbonyl derivative by reacting said rhodium source with carbon monoxide, and reacting said rhodium carbonyl derivative in the liquid phase with a disubstituted ferrocene of the formula ##STR17## wherein Q is P, As, or Sb and R is phenyl or lower alkyl, in a proportion of at least 1.5 moles of said disubstituted ferrocene per atom of rhodium contained in said rhodium carbonyl derivative, said reaction being conducted in the presence of a hydrogen source as necessary to convert said carbonyl derivative to a hydrido derivative thereof and also in the presence of a halide scavenger as necessary to neutralize halogen acid liberated during reaction of said hydrogen source with said carbonyl derivative when said carbonyl derivative contains halide moiety.
Claim 26
Dependent Claim
9 words
The process of claim 18 wherein Q is phosphorus.
Claim 27
Dependent Claim
9 words
The process of claim 19 wherein R is phenyl.
References Cited (Backward Citations)
US3320293A
Cited
USPTO Annuity & Maintenance Windows
| Annuity Stage | Window Opens | Payment Deadline | Surcharge Period Until | Estimated Fee | Status |
|---|---|---|---|---|---|
| 3.5 Years (Year 4) | 1982-02-05 | 1982-08-07 | 1983-02-06 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1986-02-05 | 1986-08-07 | 1987-02-06 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1990-02-05 | 1990-08-07 | 1991-02-06 | $7700.00 | Window Closed / Lapsed |