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US3975446A
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Method for the preparation of unsaturated ketones
Assignee: Shin-Etsu Chemical Co Ltd
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Filing: 1974-06-25
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Granted: 1976-08-17
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Expires: 1994-06-25
Abstract
Abstract Unsaturated ketones represented by the general formula ##EQU1## are successfully synthesized with very good yield from corresponding unsaturated alcohols and diketene in a single-step process in which the esterification reaction and the decarboxylation reaction take place concurrently by the synergistic action of the catalyst system composed of a high-boiling amine and an aluminum trialkoxide.
Inventors
- 👤 Tetsuro Kitagaki
- 👤 Akira Yamamoto
- 👤 Toshinobu Ishihara
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-11-04 19:23
CPC Classifications
C; C07; C07C; C07C45/00; C07C45/61; C07C45/67; C07C45/673; C07C45/676
Claims Analysis
Total Claims: 14
Claim 1
Independent Claim
149 words
A method for the preparation of an unsaturated ketone represented by the general formula ##EQU2## where R 1 is a saturated or ethylenically unsaturated aliphatic cycloaliphatic or aromatic monovalent hydrocarbon group, R 2 is an alkyl group having from 1 to 6 carbon atoms, and R 3 is a hydrogen atom or an alkyl group having from 1 to 6 carbon atoms, which comprises subjecting an unsaturated alcohol represented by the general formula ##EQU3## where R 1 , R 2 and R 3 are as defined above, to a reaction with diketene at a temperature in the range from 135° to 170°C in the presence of a tertiary amine having the boiling point higher than 130°C and selected from the group consisting of quinoline, dimethylaniline, dimethylpyridine and ethylpyridine and an aluminum trialkoxide in which the alkoxy groups are lower alkoxy groups having from 1 to 4 of carbon atoms.
Claim 2
Independent Claim
149 words
A method for the preparation of an unsaturated ketone represented by the general formula ##EQU2## where R 1 is a saturated or ethylenically unsaturated aliphatic cycloaliphatic or aromatic monovalent hydrocarbon group, R 2 is an alkyl group having from 1 to 6 carbon atoms, and R 3 is a hydrogen atom or an alkyl group having from 1 to 6 carbon atoms, which comprises subjecting an unsaturated alcohol represented by the general formula ##EQU3## where R 1 , R 2 and R 3 are as defined above, to a reaction with diketene at a temperature in the range from 135° to 170°C in the presence of a tertiary amine having the boiling point higher than 130°C and selected from the group consisting of quinoline, dimethylaniline, dimethylpyridine and ethylpyridine and an aluminum trialkoxide in which the alkoxy groups are lower alkoxy groups having from 1 to 4 of carbon atoms.
Claim 3
Dependent Claim
27 words
The method for the preparation of an unsaturated ketone as claimed in claim 1, wherein said reaction is carried out in the presence of a diluent solvent.
Claim 4
Dependent Claim
29 words
The method for the preparation of an unsaturated ketone as claimed in claim 2, wherein said diluent solvent is an organic solvent having the boiling point higher than 150°C.
Claim 5
Dependent Claim
33 words
The method for the preparation of an unsaturated ketone as claimed in claim 2, wherein said diluent solvent is the same unsaturated ketone as the unsaturated ketone to be produced by said reaction.
Claim 6
Dependent Claim
35 words
The method for the preparaion of an unsaturated ketone as claimed in claim 1, wherein R 1 is selected from the class consisting of alkyl groups, cycloalkyl groups, alkenyl groups, cycloalkenyl groups and aryl groups.
Claim 7
Dependent Claim
33 words
The method for the preparation of an unsaturated ketone as claimed in claim 1, wherein said R 2 is selected from the class consisting of methyl, ethyl, propyl, butyl, pentyl and hexyl groups.
Claim 8
Dependent Claim
36 words
The method for the preparation of an unsaturated ketone as claimed in claim 1, wherein said R 3 is selected from the class consisting of hydrogen atom and methyl, ethyl, propyl, butyl, pentyl and hexyl groups.
Claim 9
Dependent Claim
36 words
The method for the preparation of an unsaturated ketone as claimed in claim 1, wherein said tertiary amine is employed in an amount of from 0.002 moles to 0.04 moles per mole of said unsaturated alcohol.
Claim 10
Dependent Claim
36 words
The method for the preparation of an unsaturated ketone as claimed in claim 1, wherein said aluminum trialkoxide is employed in an amount of from 0.01 mole to 0.03 mole per mole of said unsaturated alcohol.
Claim 11
Dependent Claim
38 words
The method for the preparation of an unsaturated ketone as claimed in claim 1, wherein said R 1 and R 2 are both methyl groups and said R 3 is either a methyl group or a hydrogen atom.
Claim 12
Dependent Claim
26 words
The method for the preparation of an unsaturated ketone as claimed in claim 1, wherein said unsaturated ketone is 6,10-dimethyl-5,9-undecadient-2-one and said unsaturated alcohol is 3,7-dimethyl-1,6-octadien-3-ol.
Claim 13
Dependent Claim
26 words
The method for the preparation of an unsaturated ketone as claimed in claim 1, wherein said unsaturated ketone is 6,10,14-trimethyl-5-pentadecen-2-one and said unsaturated alcohol is 3,7,11-trimethyl-1-dodecen-3-ol.
Claim 14
Dependent Claim
34 words
The method of claim 1 wherein R 1 is selected from the group consisting of methyl, ethyl, isobutyl, 4-methyl-pentyl, 3,4-dimethylpentyl, 4,8-dimethylnonyl, 4,7,8-trimethylnonyl, 3-pentenyl, 4-methyl-3-pentenyl, 4-methyl-3-hexenyl, 3,4-dimethyl-3-pentenyl, 4,6-dimethyl-3-heptenyl, 4,8-dimethyl-3,7-nonadienyl, cyclohexyl, cyclohexenyl, cyclohexylmethyl, phenyl, and tolyl.
References Cited (Backward Citations)
US2795617A
Cited
US2839579A
Cited
USPTO Annuity & Maintenance Windows
| Annuity Stage | Window Opens | Payment Deadline | Surcharge Period Until | Estimated Fee | Status |
|---|---|---|---|---|---|
| 3.5 Years (Year 4) | 1979-08-17 | 1980-02-16 | 1980-08-17 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1983-08-17 | 1984-02-16 | 1984-08-17 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1987-08-17 | 1988-02-16 | 1988-08-17 | $7700.00 | Window Closed / Lapsed |