GB605772A - A process for the manufacture of pentaenes - Google Patents
A process for the manufacture of pentaenesInfo
- Publication number
- GB605772A GB605772A GB32725/46A GB3272546A GB605772A GB 605772 A GB605772 A GB 605772A GB 32725/46 A GB32725/46 A GB 32725/46A GB 3272546 A GB3272546 A GB 3272546A GB 605772 A GB605772 A GB 605772A
- Authority
- GB
- United Kingdom
- Prior art keywords
- methyl
- hydroxy
- trimethyl
- yne
- cyclohexene
- 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
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C403/00—Derivatives of cyclohexane or of a cyclohexene or of cyclohexadiene, having a side-chain containing an acyclic unsaturated part of at least four carbon atoms, this part being directly attached to the cyclohexane or cyclohexene or cyclohexadiene rings, e.g. vitamin A, beta-carotene, beta-ionone
- C07C403/06—Derivatives of cyclohexane or of a cyclohexene or of cyclohexadiene, having a side-chain containing an acyclic unsaturated part of at least four carbon atoms, this part being directly attached to the cyclohexane or cyclohexene or cyclohexadiene rings, e.g. vitamin A, beta-carotene, beta-ionone having side-chains substituted by singly-bound oxygen atoms
- C07C403/08—Derivatives of cyclohexane or of a cyclohexene or of cyclohexadiene, having a side-chain containing an acyclic unsaturated part of at least four carbon atoms, this part being directly attached to the cyclohexane or cyclohexene or cyclohexadiene rings, e.g. vitamin A, beta-carotene, beta-ionone having side-chains substituted by singly-bound oxygen atoms by hydroxy groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C403/00—Derivatives of cyclohexane or of a cyclohexene or of cyclohexadiene, having a side-chain containing an acyclic unsaturated part of at least four carbon atoms, this part being directly attached to the cyclohexane or cyclohexene or cyclohexadiene rings, e.g. vitamin A, beta-carotene, beta-ionone
- C07C403/06—Derivatives of cyclohexane or of a cyclohexene or of cyclohexadiene, having a side-chain containing an acyclic unsaturated part of at least four carbon atoms, this part being directly attached to the cyclohexane or cyclohexene or cyclohexadiene rings, e.g. vitamin A, beta-carotene, beta-ionone having side-chains substituted by singly-bound oxygen atoms
- C07C403/10—Derivatives of cyclohexane or of a cyclohexene or of cyclohexadiene, having a side-chain containing an acyclic unsaturated part of at least four carbon atoms, this part being directly attached to the cyclohexane or cyclohexene or cyclohexadiene rings, e.g. vitamin A, beta-carotene, beta-ionone having side-chains substituted by singly-bound oxygen atoms by etherified hydroxy groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C403/00—Derivatives of cyclohexane or of a cyclohexene or of cyclohexadiene, having a side-chain containing an acyclic unsaturated part of at least four carbon atoms, this part being directly attached to the cyclohexane or cyclohexene or cyclohexadiene rings, e.g. vitamin A, beta-carotene, beta-ionone
- C07C403/06—Derivatives of cyclohexane or of a cyclohexene or of cyclohexadiene, having a side-chain containing an acyclic unsaturated part of at least four carbon atoms, this part being directly attached to the cyclohexane or cyclohexene or cyclohexadiene rings, e.g. vitamin A, beta-carotene, beta-ionone having side-chains substituted by singly-bound oxygen atoms
- C07C403/12—Derivatives of cyclohexane or of a cyclohexene or of cyclohexadiene, having a side-chain containing an acyclic unsaturated part of at least four carbon atoms, this part being directly attached to the cyclohexane or cyclohexene or cyclohexadiene rings, e.g. vitamin A, beta-carotene, beta-ionone having side-chains substituted by singly-bound oxygen atoms by esterified hydroxy groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
- C07C2601/16—Systems containing only non-condensed rings with a six-membered ring the ring being unsaturated
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Pentaenes are obtained by heating, in order to split off acid, a compound of the general formula <FORM:0605772/IV(b)/1> (where R is an acyl, alkyl, aryl or aralkyl group and R1 is an acyl group), preferably in the presence of a basic agent, e.g. an alkali acetate or tertiary potassium amylate in tertiary amyl alcohol, or in an inert solvent in the presence of phthalic anhydride. The compound above is obtained by condensing 4-(21, 61, 61-trimethylcyclohexene - (11) - yl) - 2 - methyl - butene - (2) - al-(1) with a Grignard compound of 1-hydroxy-3 - methyl - pentene - (2) - yne - (4) or an ether thereof (both these starting materials being obtainable as described in Specification 605,208) and subjecting the 1-hydroxy-3 : 7-dimethyl-6-hydroxy - 9 - (21,61,61 - trimethyl - cyclohexenyl) - nonadiene-(2 : 7)-yne-(4) or the ether thereof thus formed to hydrogenation in the presence of a hydrogenation catalyst until 1 mol. of hydrogen has been added to the triple bond of of said ether or hydroxy compound, or (b) to esterification and allyl rearrangement by treating with an acylation agent, e.g. phthalic or acetic anhydride and by heating and subjecting the resulting ester to hydrogenation until one molecule of hydrogen has been added to the triple bond of said ester. Anti-oxidants, e.g. tocopherols, are preferably present during the synthesis. In examples: (1) 4-(21,61,61-trimethyl-cyclohexene-(11)-yl) -2-methyl-butene-2-al-(1) is condensed by means of ethyl magnesium bromide with 1 - methoxy - 3 - methyl - pentene - (2) - yne - (4) to produce 1 - methoxy - 3 : 4 - di - methyl - 6 - hydroxy - 9 - (21,61,61-trimethyl - cyclo - hexene - (11) - yl) - nonadiene - (2,7) - yne-(4) which is hydrogenated using palladised charcoal on which quinoline had been previously adsorbed to produce 1 - methoxy - 3 : 7 - dimethyl - 6 - hydroxy - 9 - (21,61,61 - trimethyl - cyclohexene - (1) - yl) - nonatriene - (2 : 4 : 7) which is refluxed in acetic anhydride with potassium acetate; a concentrate of Vitamin A methyl ether is obtained from the residue by chromatographic adsorption; (2) 1-methoxy-(3,7)-dimethyl-6-hydroxy-9-(21,61, 61-trimethyl-cyclohexene-(11)-yl)-nonotriene-(2 : 4 : 7) (obtained as in (1)) is refluxed with sodium acetate in acetic anhydride and the product boiled with potassium in tertiary amyl alcohol to produce Vitamin A methyl ether; (3) 1-methoxy-(3 : 7)-dimethyl-6-hydroxy-9-(21,61, 61-trimethyl-cyclohexene-(11)-yl)-nonadiene-(2 : 7)-yne-(4) (obtained as in (1)) is heated with potassium acetate in acetic anhydride and the product hydrogenated using palladised charcoal on which quinoline had been previously adsorbed as catalyst; the hydrogenated compound heated with potassium in tertiary amyl alcohol yields Vitamin A methyl ether; (4) as in (3) carrying out the acylation using benzoyl chloride instead of acetic anhydride; (5) 1-methoxy-3 : 7-dimethyl-6 - hydroxy - 9 - (21,61,61 - trimethyl - cyclohexene - (11)-yl)-nonatriene-(2 : 4 : 7) prepared as in (1)) is refluxed in xylene passing in dry phosgene to produce Vitamin A methyl ether; (6) 1-methoxy-3 : 7 - dimethyl - 6 - hydroxy - 9 - (21 : 61 : 61 - tri - methyl - cyclohexene - (11) - yl) - nonatriene - (2 : 4 : 7) (prepared as in (1)) in benzene is refluxed with phthalic anhydride in the presence of dl-a -tocophenol whilst introducing nitrogen to produce Vitamin A methyl ether; (7) 1 - butoxy - 3 - methyl - pentene - (2) - yne - (4) is condensed with 4 - (21,61,61 - trimethyl - cyclo - hexene - (11) - yl) - 2 - methyl - butene - 2 - al - (1) and hydrogenated as in (1) to produce 1-butoxy 3 : 7 - dimethyl - 6 - hydroxy - 9 - (21 : 61 : 61 - tri - (methyl-cyclohexene-(11)-yl)-nonatriene-2 : 4 : 7 which is treated with phthalic anhydride in benzene as in (6) to produce Vitamin A butyl ether. A sample furnished under Sect. 2 (5) was prepared by condensing 1-hydroxy-3-methyl-pentene-(2)-yne-(4) by means of ethyl magnesium bromide with 4-(2 : 61 : 61-trimethylcyclohexene-(11)-yl)-2-methyl-butene-(2) -al-(1) to produce 1 : 6 - dihydroxy - 3 : 7 - dimethyl - 9 - 2 : 61 : 61 - trimethyl - cyclohexene - (11) - yl) - nona - diene - (2 : 7) - yne - (4) which is treated in (1) above to produce Vitamin A acetate, which gave free Vitamin A when boiled with potassium.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GB32725/46A GB605772A (en) | 1945-11-05 | 1945-11-05 | A process for the manufacture of pentaenes |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GB32725/46A GB605772A (en) | 1945-11-05 | 1945-11-05 | A process for the manufacture of pentaenes |
Publications (1)
Publication Number | Publication Date |
---|---|
GB605772A true GB605772A (en) | 1948-07-29 |
Family
ID=10343085
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
GB32725/46A Expired GB605772A (en) | 1945-11-05 | 1945-11-05 | A process for the manufacture of pentaenes |
Country Status (1)
Country | Link |
---|---|
GB (1) | GB605772A (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE1005956B (en) * | 1954-12-22 | 1957-04-11 | Hoffmann La Roche | Process for the production of vitamin A or its esters |
-
1945
- 1945-11-05 GB GB32725/46A patent/GB605772A/en not_active Expired
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE1005956B (en) * | 1954-12-22 | 1957-04-11 | Hoffmann La Roche | Process for the production of vitamin A or its esters |
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