GB935412A - Production of ionine compounds - Google Patents
Production of ionine compoundsInfo
- Publication number
- GB935412A GB935412A GB9092/62A GB909262A GB935412A GB 935412 A GB935412 A GB 935412A GB 9092/62 A GB9092/62 A GB 9092/62A GB 909262 A GB909262 A GB 909262A GB 935412 A GB935412 A GB 935412A
- Authority
- GB
- United Kingdom
- Prior art keywords
- reaction
- methoxy
- alcohol
- yield
- effected
- 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
- C07C403/16—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 not being part of —CHO 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
Ionone compounds of the formulae <FORM:0935412/IV(a)/1> in which R1 is hydrogen or a methyl group, are prepared by a four-stage process in which (1) an unsaturated ketone of the formula <FORM:0935412/IV(a)/2> is ethinylated to yield an unsaturated ethinyl carbinol of the formula <FORM:0935412/IV(a)/3> (2) the ethinyl carbinol is treated with aliphatic, cycloaliphatic or araliphatic alcohol to yield a product of the formula <FORM:0935412/IV(a)/4> in which R2 is an aliphatic, cycloaliphatic or araliphatic radical, which (3) is reacted with an acetoacetio ester or with diketene to yield, after decarboxylation, a product of either of the formula <FORM:0935412/IV(a)/5> which (4) is then cyclicized to yield products of the first two formulae above. Reaction (1) may be effected with acetylene at a temperature between -60 and +120 DEG C. at atmospheric or raised pressure in the presence of a basic catalyst and optionally in a solvent, a number of catalysts and solvents being specified. Reaction (2) may be carried out at 0-120 DEG C. under acidic conditions, preferably in an excess of the alcohol. Specified alcohols for use in the reaction are methanol, ethanol, n- or iso-propyl, n- or iso-butyl alcohol, n- or iso-amyl alcohol, hexanol, allyl alcohol, crotyl alcohol, hexanediol-1,6, butanetriol-1,2,4-, glycol, methyl glycol, butyl glycol, glycerol, trimethylolpropane, cyclopentanol, cyclohexanol, benzyl alcohol and b -phenylethyl alcohol. Reaction (3) may be effected at 0-30 DEG C. and the decarboxylation of the intermediately formed acetoacetic ester may be effected in the liquid phase at 150-250 DEG C. Acid or alkaline substances and an inert solvent may be present during the decarboxylation, a number of acid or alkaline substances and inert solvents being specified. Alternatively, the decarboxylation may be effected in the vapour phase at 300-500 DEG C. The mixed isomers of the last two formulae above may be used as such or may be separated by distillation or by chromatography. Reaction (4) may be effected at a temperature of -80 to +80 DEG C. in an acid medium in the presence of a solvent, a number of acid media and solvents being specified. The reaction sequences may be modified by interchanging stages (1) and (2). The final products, and also the intermediates of the last three formulae above, are useful as perfumes. In examples of reactions (1) and (2), (a) 2-methylheptene-2-one-6 yields, successively, 2-methoxy-2-methylheptanone-6 and 2-methoxy-2,6-dimethyloctine-7-ol-6; (b) 2,6-dimethyloctene-2-ine-7-ol-6 yields 2-methoxy-2,6-dimethyloctine-7-ol-6. The corresponding 2-ethoxy, 2-n-butoxy, 2-(b -methoxyethoxy), 2-isopropoxy, 2-(b -hydroxyethoxy), 2-allyloxy and 2-(b -phenylethoxy) compounds are also described. In examples of reaction (3), 2,6-dimethyloctene-2-ine-7-ol-6 and methyl or ethyl acetoacetate or diketene yield a mixture of 2-methoxy-2,6-dimethylundecanediene- 6,7-one-10 and 2-methoxy-2,6-dimethylundecanediene-6,8-one-10, which may be fractionated. Mixtures of the corresponding 2-(b -hydroxyethoxy), 2-n-butoxy, 2-allyloxy and 2-(b -phenylethoxy) compounds are also described. In examples of reaction (4), (a) 2-methoxy-2,6-dimethyundecadiene-6,8-one-10 yields b -ionone, which is similarly obtainable from an isomeric mixture of 2-(b -hydroxyethoxy)-2,6-dimethylundecadiene-6,7-one-10 and 2-(b -hydroxyethoxy- 2,6-dimethylundecadiene-6,8-one-10; the corresponding isomers substituted with an allyloxy, a b -phenylethoxy, a b -methoxyethoxy or a butoxy group in the 2-position are similarly obtainable; (b) 2-methoxy- 2,3,6-trimethylundecadiene- 6,7-one-10 to yield b -irone.
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DEB61631A DE1137008B (en) | 1961-03-11 | 1961-03-11 | Process for the preparation of ionone compounds |
DEB61629A DE1182651B (en) | 1961-03-11 | 1961-03-11 | Process for the production of ethers with special fragrance properties |
DEB61632A DE1137432B (en) | 1961-03-11 | 1961-03-11 | Process for the production of unsaturated ketones with special fragrance properties |
DEB65434A DE1190933B (en) | 1962-01-08 | 1962-01-08 | Process for the preparation of ionone compounds |
Publications (1)
Publication Number | Publication Date |
---|---|
GB935412A true GB935412A (en) | 1963-08-28 |
Family
ID=27436603
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
GB9092/62A Expired GB935412A (en) | 1961-03-11 | 1962-03-09 | Production of ionine compounds |
Country Status (3)
Country | Link |
---|---|
BE (1) | BE614910A (en) |
CH (1) | CH410929A (en) |
GB (1) | GB935412A (en) |
-
1962
- 1962-03-09 CH CH285962A patent/CH410929A/en unknown
- 1962-03-09 BE BE614910A patent/BE614910A/en unknown
- 1962-03-09 GB GB9092/62A patent/GB935412A/en not_active Expired
Also Published As
Publication number | Publication date |
---|---|
BE614910A (en) | 1962-09-10 |
CH410929A (en) | 1966-04-15 |
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