GB722911A - Polyene syntheses and compounds prepared thereby - Google Patents
Polyene syntheses and compounds prepared therebyInfo
- Publication number
- GB722911A GB722911A GB27627/51A GB2762751A GB722911A GB 722911 A GB722911 A GB 722911A GB 27627/51 A GB27627/51 A GB 27627/51A GB 2762751 A GB2762751 A GB 2762751A GB 722911 A GB722911 A GB 722911A
- Authority
- GB
- United Kingdom
- Prior art keywords
- ester
- yne
- hydroxy
- methyl
- cyclohexen
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention comprises esters of 3-methyl-3-hydroxy - 5 - (2,6,6 - trimethylcyclohexen - 1 - yl) - penta - 4 - yne - oic acid and the preparation thereof, in a process for the synthesis of Vitamin A which includes subjecting a ketone of the type <FORM:0722911/IV (b)/1> wherein R is a hydrocarbon group, to a Reformatsky reaction effective to form a b -hydroxy ester and dehydrating the b -hydroxy ester to an unsaturated ester, by subjecting a ketone of the formula <FORM:0722911/IV (b)/2> wherein n is 1 or 0 to a Reformatsky reaction effective to form a b -hydroxy ester having an acetylenic bond between the b -hydroxy group and the terminal ring. Vitamin A ester is obtained by subjecting the butyryl ketone, 4-(2,6,6 - trimethyl cyclohexen - 1 - yl) but - 3 - yne-2-one, to a Reformatsky reaction with a haloacetate and thereby converting said butynyl ketone to the b -hydroxy ester, 3-methyl-3-hydroxy - 5 - (2,6,6 - trimethyl cyclohexen - 1 - yl) - penta - 4 - yne - oic ester; dehydrating said b -hydroxy ester to the a ,b -unsaturated ester, 3 - methyl - 5 - (2,6,6 - trimethyl cyclohexen - 1 - yl) - penta - 2 - ene - 4 - yne - oic ester; reducing said a ,b -unsaturated ester to the primary alcohol, 3-methyl-5-(2,6,6-trimethyl-cyclohexen - 1 - yl) - penta - 2 - ene - 4 - yne - 1 - ol, oxidizing said primary alcohol with acetone and a metal alkoxide to the ketone, 6-methyl-8-(2,6,6 - trimethyl cyclohexen - 1 - yl) - octa - 3,5 - diene-7-yne-2-one; subjecting the last said ketone to a Reformatsky reaction with a haloacetate and thereby forming a b -hydroxy ester 3,7 - dimethyl - 3 - hydroxy - 9 - (2,6,6 - trimethyl cyclohexen - 1 - yl) - nona - 4,6 - diene - 8-yne-oic ester; dehydrating the last said b -hydroxy ester to the a ,b -unsaturated ester, 3,7 - dimethyl - 9 - (2,6,6 - trimethyl cyclohexen - 1 - yl) - nona - 2,4,6 - triene - 8 - yne - oic ester; and hydrogenating the last said a ,b -unsaturated ester to Vitamin A ester. Alternatively 3,7 - dimethyl - 9 - (2,6,6 - trimethyl cyclohexen - 1 - yl) - nona - 2,4,6 - triene - 8 - yne - oic acid is obtained by oxidizing primary alcohol 3-methyl-5 - (2,6,6 - trimethyl cyclohexen - 1 - yl) - penta - 2 - ene - 4 - yne - 1 - ol to the aldehyde, 3 - methyl - 5 - (2,6,6 - trimethyl cyclohexen - 1 - yl)-penta-2-ene-4-1-ol; condensing said aldehyde with b -methyl glutaconic acid diester and acidifying the product of said condensing and thereby forming the diacid 4-carboxy-3,7-di-methyl - 9 - (2,6,6 - trimethyl cyclohexen - 1 - yl)-nona - 2,4,6 - triene - 8 - yne - oic acid and then decarboxylating said diacid to the monoacid. Said monoacid, 3,7-dimethyl-4-(2,6,6-trimethyl cyclohexen - 1 - yl) - nona - 2,4,6 - triene - 8 - yne-oic acid may be reduced to the corresponding alcohol which may be converted by hydrogenation to Vitamin A alcohol.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US722911XA | 1950-11-25 | 1950-11-25 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| GB722911A true GB722911A (en) | 1955-02-02 |
Family
ID=22106687
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB27627/51A Expired GB722911A (en) | 1950-11-25 | 1951-11-26 | Polyene syntheses and compounds prepared thereby |
Country Status (1)
| Country | Link |
|---|---|
| GB (1) | GB722911A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0010208A1 (en) * | 1978-10-07 | 1980-04-30 | BASF Aktiengesellschaft | Pharmaceutical composition containing all-E- or 13-Z-7,8-dehydro-retinoic acid and process for its preparation |
-
1951
- 1951-11-26 GB GB27627/51A patent/GB722911A/en not_active Expired
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0010208A1 (en) * | 1978-10-07 | 1980-04-30 | BASF Aktiengesellschaft | Pharmaceutical composition containing all-E- or 13-Z-7,8-dehydro-retinoic acid and process for its preparation |
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