US4051174A
Expired / Lapsed
US
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Isomerization process
Assignee: Hoffmann La Roche Inc
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Filing: 1974-08-16
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Granted: 1977-09-27
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Expires: 1994-08-16
Abstract
Abstract A process for isomerizing vitamin A and derivatives thereof utilizing either palladium or a palladium containing compound as a catalyst.
Inventors
- 👤 Hansjorg Stoller
- 👤 Hans Peter Wagner
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-10-30 14:48
CPC Classifications
C; C07; C07C; C07C403/00; C07C403/06; C07C403/10; B; B01; B01J; B01J23/00; B01J23/38; B01J23/40; B01J23/44; B01J31/00; B01J31/16; B01J31/18; B01J31/1805; B01J31/22; B01J31/2282; B01J31/2295; C07C403/08; C07C403/12; C07C403/14; C07C403/20; B01J2231/00; B01J2231/50; B01J2231/52; B01J2531/00; B01J2531/80; B01J2531/82; B01J2531/824; C07B; C07B2200/00; C07B2200/09; C07C2601/00; C07C2601/12; C07C2601/16
Claims Analysis
Total Claims: 16
Claim 1
Independent Claim
151 words
A process for geometrically isomerizing an isomeric composition selected from the group consisting of 9-cis and 11-cis isomers of a compound of the formula: ##STR2## --COOR 2 , --CONHR 3 or --CON(R 3 ) 2 ; R is lower alkoxy or the two R's taken together form lower alkylenedioxy; R 1 is alkanoyl or aroyl; R 2 is alkyl, aryl or aralkyl; and R 3 is hydroxy, alkyl, aryl or aralkyl; mixtures thereof, or mixtures thereof with the all trans isomer of said compound comprising contacting at a temperature of from 0° C to 250° C, said composition in an inert solvent medium with a palladium compound catalyst where the palladium compound is other than palladium phthalocyanin or other than a palladium compound containing a cyanide ion and producing a geometric isomeric mixture of said composition from which the all trans isomer can be separated therefrom in pure form by crystallization.
Claim 2
Dependent Claim
151 words
A process for geometrically isomerizing an isomeric composition selected from the group consisting of 9-cis and 11-cis isomers of a compound of the formula: ##STR2## --COOR 2 , --CONHR 3 or --CON(R 3 ) 2 ; R is lower alkoxy or the two R's taken together form lower alkylenedioxy; R 1 is alkanoyl or aroyl; R 2 is alkyl, aryl or aralkyl; and R 3 is hydroxy, alkyl, aryl or aralkyl; mixtures thereof, or mixtures thereof with the all trans isomer of said compound comprising contacting at a temperature of from 0° C to 250° C, said composition in an inert solvent medium with a palladium compound catalyst where the palladium compound is other than palladium phthalocyanin or other than a palladium compound containing a cyanide ion and producing a geometric isomeric mixture of said composition from which the all trans isomer can be separated therefrom in pure form by crystallization.
Claim 3
Dependent Claim
19 words
A process of claim 1, wherein the isomerisation is carried out using Pd(O), Pd(II), or PD(IV) salts or complexes.
Claim 4
Dependent Claim
14 words
A process of claim 1, wherein the isomerisation is carried out using palladium oxide.
Claim 5
Dependent Claim
18 words
A process of claim 3, wherein the isomerisation is carried out using palladium oxide on a carrier material.
Claim 6
Dependent Claim
57 words
The process of claim 1, wherein the mixture contains from about 0% to about 15% by weight of 9-cis vitamin A acetate and from about 20% to about 40% by weight 11-cis vitamin A acetate and from about 40% to about 70% by weight all-tras vitamin A acetate based on the total weight of vitamin A acetate.
Claim 7
Dependent Claim
37 words
The process of claim 2, wherein the palladium compound is selected from the group consisting of a Pd(II) complex which contains a ligand selected from the group consisting of halogens, carboxylates, nitrite, nitrate, olefins, amines or nitriles.
Claim 8
Dependent Claim
17 words
The process of claim 6, wherein the Pd(II) complex contains alkadienes or alkatetraenes as the olefinic ligands.
Claim 9
Dependent Claim
21 words
The process of claim 7 wherein (1,5-cyclooctadiene)PdCl 2 , (1,5-cyclooctadiene)PdBr 2 , (1,5-cyclooctadiene)PdI 2 or (cyclooctatetraene)-PdBr 2 is the Pd(II) complex.
Claim 10
Dependent Claim
24 words
The process of claim 6 wherein (benzonitrile) 2 PdCl 2 , (acetonitrile) 2 PdCl 2 or (acetonitrile) 2 PdBr 2 is the Pd(II) complex.
Claim 11
Dependent Claim
29 words
The process of claim 1 wherein said palladium compound is a Pd(IV) composition selected from the group consisting of PdS 2 or (NH 4 ) 2 PdCl 6 .
Claim 12
Dependent Claim
21 words
The process of claim 1 wherein the isomerisation is carried out in a polar aprotic solvent or in a non-polar solvent.
Claim 13
Dependent Claim
17 words
The process according to claim 11 wherein the isomerisation is carried out with the addition of water.
Claim 14
Dependent Claim
22 words
The process of claim 1, wherein the isomerisation is carried out at a temperature of from 20° C. to about 80° C.
Claim 15
Dependent Claim
32 words
The process according to claim 1 wherein the catalyst is used in an amount of about 0.1 mol. % to about 100 mol. % based on the isomeric composition to be isomerised.
Claim 16
Dependent Claim
31 words
The process of claim 14 wherein the catalyst is used in an amount of about 1 mol. % to about 10 mol. % based on the isomeric composition to be isomerised.
References Cited (Backward Citations)
US2849507A
Cited
US3441623A
Cited
USPTO Annuity & Maintenance Windows
| Annuity Stage | Window Opens | Payment Deadline | Surcharge Period Until | Estimated Fee | Status |
|---|---|---|---|---|---|
| 3.5 Years (Year 4) | 1980-09-26 | 1981-03-28 | 1981-09-27 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1984-09-26 | 1985-03-28 | 1985-09-27 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1988-09-26 | 1989-03-28 | 1989-09-27 | $7700.00 | Window Closed / Lapsed |