GB802568A - Polyene aldehydes and a process for the manufacture thereof - Google Patents
Polyene aldehydes and a process for the manufacture thereofInfo
- Publication number
- GB802568A GB802568A GB20989/56A GB2098956A GB802568A GB 802568 A GB802568 A GB 802568A GB 20989/56 A GB20989/56 A GB 20989/56A GB 2098956 A GB2098956 A GB 2098956A GB 802568 A GB802568 A GB 802568A
- Authority
- GB
- United Kingdom
- Prior art keywords
- trimethyl
- cyclohexen
- acetal
- dimethyl
- ether
- 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
- C07C403/14—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 doubly-bound oxygen atoms
-
- 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
- C07C2601/14—The ring being saturated
-
- 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
8 - Substituted - 2,6 - dimethyloctatrien - (2,4,6)-al-(1)s in which the 8-substituent (R) is a 21,61,61 - trimethyl - cyclohexylidene or a 21,61,61 - trimethyl - cyclohexen - (21) - ylidene, or a 21,61,61 - trimethyl - cyclohexen - (1) - y radical, which contains an oxo, hydroxy or esterified hydroxy group in the 41-position, are prepared. The process comprises acetalizing a 6 - substituted - 4 - methyl - hexadiene - (2,4)-al-(1) of general formula <FORM:0802568/IV (b)/1> condensing the resulting 1-acetal with a propenyl ether in the presence of an acidic condensing agent and treating the resulting 3-ether-1-acetal with an acid in order to hydrolyse the acetal group and split off the elements of an alcohol from 2,3-position. The acetalization step may be carried out using an aliphatic orthocarboxylic acid ester, e.g. methyl, ethyl or butyl esters of orthoformic acid, in the presence of an alcohol, boron trifluoride etherate, zinc chloride, phosphoric acid and/or p-toluene sulphonic acid and the starting material as defined. The resulting acetals, viz. 6[21,61,61 - trimethyl - cyclohexen - (11) - yl]-4 - methyl - hexadiene - (2,4) - acetal - (1)s, 6 - [21,61,61 - trimethyl - cyclohexylidene] - 4 - methyl - hexadiene - (2,4) - acetal - (1)s, 6 - [21,61,61 - trimethyl - cyclohexen - (21 - ylidene]-4 - methyl - hexadiene - (2,4) - acetal - (1)s containing an oxo, hydroxy, or esterified hydroxy group in 41-position are then condensed with a propenyl ether in the presence of e.g. boron trifluoride etherate, zinc chloride, titanium tetrachloride, aluminium chloride, ferric chloride or tin tetrachloride. Suitable propenyl ethers are methyl ether or butyl propenyl ethers. The reaction is preferably carried out between 0 DEG and 50 DEG C. with approximately molar proportions of the reactants. The 3-ether-1-acetals, viz. 8 - [21,61,61 - trimethyl cyclohexen - (11)-yl], 2 - 6 - dimethyl - 3 - alkoxy - octadiene - (4,6)-acetal-(1)s and the corresponding cyclohexylidene, and cyclohexyl-21-ylidene compounds containing an oxo, hydroxy, or esterified hydroxy group in 41-position, are then hydrolysed, preferably in the presence of e.g. p-toluene sulphonic acid, acetic acid, propionic acid, zinc chloride, or sodium hydrogen sulphate, and also with the addition of an anti-oxidant, e.g. hydroquinone, and in the absence of oxygen. A solvent, e.g. dioxan, tetrahydrofuran, or ethylene glycol dimethyl ether may also be present. The hydrolysis is preferably carried out by heating the 3-ether-1-acetals with acetic acid containing an alkali metal acetate, and a little water at about 100 DEG C. in a carbon dioxide atmosphere. The product may be purified by distillation or chromatographed on an aluminium oxide column. The temperature should be kept below 120 DEG C. throughout the process. Examples are given of the preparation of (1) 8-[21,61,61-trimethyl - 41 - acetoxy-cyclohexylidene] - 2,6 - dimethyl - octatrien - (2,4,6) - al - (1); (2) 8[21,61,61 - trimethyl - 41 - oxo - cyclohexylidene] - 2,6 - dimethyl - octatrien - (2,4,6) - al - (1); (3) 8 - [21,61,61 - trimethyl - 41 - oxo - cyclohexen - (21) - ylidene]-2,6 - dimethyl - octatrien - (2,4,6) - al - (1); (4) 8 - [21,61,61 - trimethyl - 41 - acetoxy - cyclohexen - (11) - yl] - 2,6 - dimethyl - octatrien - (2,4,6) - al - (1); (5) 8 - [21,61,61 - trimethyl - 41-acetoxy - cyclohexen - (21) - ylidene] - 2,6 - dimethyl - octatrien (2,4,6) - al - (1). Specification 802,567 is referred to.
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CH802568X | 1955-07-06 |
Publications (1)
Publication Number | Publication Date |
---|---|
GB802568A true GB802568A (en) | 1958-10-08 |
Family
ID=4537765
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
GB20989/56A Expired GB802568A (en) | 1955-07-06 | 1956-07-06 | Polyene aldehydes and a process for the manufacture thereof |
Country Status (1)
Country | Link |
---|---|
GB (1) | GB802568A (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4058536A (en) * | 1971-11-17 | 1977-11-15 | Basf Aktiengesellschaft | Production of high molecular weight α,β-unsaturated aldehydes |
-
1956
- 1956-07-06 GB GB20989/56A patent/GB802568A/en not_active Expired
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4058536A (en) * | 1971-11-17 | 1977-11-15 | Basf Aktiengesellschaft | Production of high molecular weight α,β-unsaturated aldehydes |
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