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Patent US4238419A successfully refreshed from Google Patents.
US4238419A
Expired / Lapsed
US
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Hydroformylation of olefinic compounds
Assignee: Kuraray Co Ltd
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Filing: 1979-06-04
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Granted: 1980-12-09
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Expires: 1999-06-04
Abstract
Abstract Rhodium catalyzed hydroformylation of olefinic compounds is essentially effected in the presence of a secondary phosphine oxide of the general formula (I) in an amount of at least one mole per gram atom of rhodium, which supresses the thermal degradation of the rhodium catalyst in the hydroformylation stage as well as in the distillation of the reaction products: ##STR1## wherein, in the formula (I), R 1 and R 2 are the same or different, substituted or unsubstituted hydrocarbon residues containing not more than 20 carbon atoms. The phosphine oxide of the general formula (I) maintains the catalytic activity over a prolonged period of time and prevents essentially metallic rhodium from sticking to the vessel during distillation of the reaction products from the reaction mixture, and consequently makes recycle of the catalyst easier and enables lowering the hydroformylation pressure.
Inventors
- 👤 Mitsuo Matsumoto
- 👤 Masuhiko Tamura
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-11-08 20:07
CPC Classifications
C; C07; C07D; C07D309/00; C07D309/02; C07D309/08; C07D309/10; C07C; C07C45/00; C07C45/49; C07C45/50; Y; Y02; Y02P; Y02P20/00; Y02P20/50; Y02P20/584
Claims Analysis
Total Claims: 16
Claim 1
Independent Claim
91 words
A process for hydroformylating an olefinic compound to obtain an aldehyde having an additional carbon atom, which process comprises contacting said olefinic compound with carbon monoxide and hydrogen in the presence of a rhodium catalyst and in the presence of an added secondary phosphine oxide having the formula (I) in an ##STR26## amount of at least one mole per gram atom of rhodium, wherein R 1 and R 2 are the same or different and each is a substituted or unsubstituted hydrocarbon residue containing not more than about 20 carbon atoms.
Claim 2
Dependent Claim
91 words
A process for hydroformylating an olefinic compound to obtain an aldehyde having an additional carbon atom, which process comprises contacting said olefinic compound with carbon monoxide and hydrogen in the presence of a rhodium catalyst and in the presence of an added secondary phosphine oxide having the formula (I) in an ##STR26## amount of at least one mole per gram atom of rhodium, wherein R 1 and R 2 are the same or different and each is a substituted or unsubstituted hydrocarbon residue containing not more than about 20 carbon atoms.
Claim 3
Dependent Claim
70 words
A process as claimed in claim 1, wherein the residues R 1 and R 2 in the secondary phosphine oxide of formula (I) are each selected from the group consisting of saturated aliphatic hydrocarbon residues, aromatic hydrocarbon residues and alicyclic hydrocarbon residues, with and without one or more substituents selected in turn from the group consisting of heteroatoms and heteroatom-containing groups comprising the fluorine atom, lower alkoxy, hydroxyl and amino.
Claim 4
Dependent Claim
28 words
A process as claimed in claim 1, wherein said secondary phosphine oxide of formula (I) is added in an amount of 1-500 moles per gram atom of rhodium.
Claim 5
Dependent Claim
25 words
A process as claimed in claim 3, wherein said secondary phosphine oxide is added in an amount of 2.5-100 moles per gram atom of rhodium.
Claim 6
Dependent Claim
105 words
A process as claimed in claim 1, wherein an organophosphorus compound having the formula (II) ##STR27## is added as a presursor of said secondary phosphine oxide of formula (I) in an amount of 1-500 moles per gram atom of rhodium, wherein, in formula (II), R 1 and R 2 are the same or different and each is a substituted or an unsubstituted hydrocarbon residue containing not more than about 20 carbon atoms, R 3 is a hydrogen atom or a hydrocarbon residue containing not more than about 20 carbon atoms and R 4 is a hydrocarbon residue containing not more than about 20 carbon atoms.
Claim 7
Dependent Claim
27 words
A process as claimed in claim 5, wherein said organophosphorus compound of formula (II) is added in an amount of 2.5-100 moles per gram atom of rhodium.
Claim 8
Dependent Claim
17 words
A process as claimed in claim 1, wherein said olefinic compound has a CH 2 ═CH-- group.
Claim 9
Dependent Claim
43 words
A process as claimed in claim 7, wherein a trisubstituted phosphine is added to the reaction system in combination with said secondary phosphine oxide of formula (I) to a concentration of said trisubstituted phosphine in the reaction system of 10-500 millimoles per liter.
Claim 10
Dependent Claim
104 words
A process as claimed in claim 8, wherein a diphosphinoalkane having the formula (V) ##STR28## is added to the reaction system in combination with said secondary phosphine oxide and with said trisubstituted phosphine, in an amount of 0.20-2.5 moles per gram atom of rhodium, wherein, in formula (V), R 6 and R 7 are each aromatic hydrocarbon residues, R 8 and R 9 are each aromatic hydrocarbon residues or saturated hydrocarbon residues containing one or more carbon atoms and Z is an alkylene radical whose main straight chain contains 2-5 carbon atoms and which may be substituted with one or more lower alkyl groups.
Claim 11
Dependent Claim
22 words
A process as claimed in claim 7, wherein the reaction pressure is in the range of atmospheric pressure to about 30 atmospheres.
Claim 12
Dependent Claim
29 words
A process as claimed in claim 1, wherein the concentration of said rhodium catalyst as calculated as metallic rhodium is in the range of 0.01-10 milligram atom per liter.
Claim 13
Dependent Claim
14 words
A process as claimed in claim 1, wherein the reaction temperature is 50°-150° C.
Claim 14
Dependent Claim
30 words
A process as claimed in claim 1, wherein the partial pressure ratio of hydrogen to carbon monoxide is in the range of 1/2 to 5/1 on the feed gas basis.
Claim 15
Dependent Claim
22 words
A process as claimed in claim 1, wherein the reaction pressure is in the range of atmospheric pressure to about 300 atmospheres.
Claim 16
Dependent Claim
47 words
A process as claimed in claim 1, wherein there is obtained a reaction mixture comprising the aldehyde reaction product and unreacted starting material containing the catalyst; the reaction mixture is separated by distillation; and the catalyst-containing material is reused by recycling it directly to the reaction site.
References Cited (Backward Citations)
USPTO Annuity & Maintenance Windows
| Annuity Stage | Window Opens | Payment Deadline | Surcharge Period Until | Estimated Fee | Status |
|---|---|---|---|---|---|
| 3.5 Years (Year 4) | 1983-12-09 | 1984-06-09 | 1984-12-09 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1987-12-09 | 1988-06-09 | 1988-12-09 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1991-12-09 | 1992-06-09 | 1992-12-09 | $7700.00 | Window Closed / Lapsed |