GB865478A - A process for the manufacture of unsaturated ketones - Google Patents
A process for the manufacture of unsaturated ketonesInfo
- Publication number
- GB865478A GB865478A GB26420/59A GB2642059A GB865478A GB 865478 A GB865478 A GB 865478A GB 26420/59 A GB26420/59 A GB 26420/59A GB 2642059 A GB2642059 A GB 2642059A GB 865478 A GB865478 A GB 865478A
- Authority
- GB
- United Kingdom
- Prior art keywords
- isomerisation
- pseudo
- methyl
- general formula
- ketone
- 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
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
- C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/51—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition
- C07C45/511—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition involving transformation of singly bound oxygen functional groups to >C = O groups
- C07C45/513—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition involving transformation of singly bound oxygen functional groups to >C = O groups the singly bound functional group being an etherified hydroxyl group
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/51—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition
- C07C45/511—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition involving transformation of singly bound oxygen functional groups to >C = O groups
- C07C45/515—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition involving transformation of singly bound oxygen functional groups to >C = O groups the singly bound functional group being an acetalised, ketalised hemi-acetalised, or hemi-ketalised hydroxyl group
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
- C07C49/20—Unsaturated compounds containing keto groups bound to acyclic carbon atoms
- C07C49/203—Unsaturated compounds containing keto groups bound to acyclic carbon atoms with only carbon-to-carbon double bonds as unsaturation
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Unsaturated ketones of the general formula: <FORM:0865478/IV (b)/1> where R1 represents hydrogen or a C1-6 alkyl or alkenyl radical and R2 represents a C1-6 alkyl radical or R1 and R2 together represent a polymethylene bridge, and R4 and R5 each represent an acyclic or cyclic hydrocarbon group, including alkyl, alkenyl, cycloaliphatic, aromatic and araliphatic groups, or together form a polymethylene bridge, R4 and R5 optionally bearing substituents, such as alkyl or alkoxy groups, which are inert under the hereinafter specified reaction conditions are prepared by reacting a ketal of the general formula: <FORM:0865478/IV (b)/2> or an enol ether of the general formula: <FORM:0865478/IV (b)/3> R3 representing a C1-6 alkyl group, with a 1, 1-disubstituted propargyl alcohol of the general formula: <FORM:0865478/IV (b)/4> in the presence of a catalytic amount of an acidic condensing agent which may be a strong mineral or organic acid, an acid-reacting salt or a Lewis acid, many examples being given. The reaction is suitably carried out in a solvent, for example a hydrocarbon solvent and a part of this solvent may be distilled off to remove alcohol formed in the reaction. Alternatively, the enol-ether reactant may be used in excess to bind the liberated alcohol. The resulting allene-type ketone may be isomerised to a ketone of the general formula: <FORM:0865478/IV (b)/5> by treatment with acidic or basic agents or by the influence of heat, for example by heating at about 100 DEG -180 DEG C. alone or with an acid such as acetic acid or by treatment with a dilute solution of alkali or alkaline earth metal hydroxide, preferably dilute methanolic NaOH at, for example, room temperature. If desired, the condensation step yielding the allene-type ketone may be so carried out that extensive isomerisation is also effected, namely by use of a lengthy heating period and larger amounts of the acidic condensing agent; the isomerisation is facititated by the addition of copper powder or a copper salt e.g. cupric acetate. The reactions are preferably carried out under an inert atmosphere and anti-oxidants such as hydroquinone or butoxy anisole may be present. The unsaturated ketones may be purified by partition between petroleum ether and aqueous methanol. The ketones may cyclise after the reaction or isomerisation steps to give a - and b -ionone type ketones (see Specification 865,479). Examples describe the preparation of (1) 4:7-dimethyl-octadien-4, 6-one-3, by the one step method; (2) 6:10-dimethyl-undecatrien-4, 5, 9-one-2 and its isomerisation to pseudo ionone; (3) 4:7:11-trimethyl-dodecatrien-5, 6, 10-one-3; (4) 3-allyl-6, 10-dimethyl undecatrien-4, 5, 9-one-2 and its isomerisation to 3-allyl-6, 10-dimethylundecatrien-3, 5, 9-one-2; (5) 6:9:10-trimethylundecatrien-4, 5, 9-one-2, acetone diethyl ketal being used to form isopropenyl ether in situ, and isomerisation of the allenic ketone to pseudo-irone;(6) (9) and (12) 3:6:10-trimethyl -undecatrien-4, 5, 9-one-2 and its isomerisation to iso methyl-pseudo-ionone; (7) 4-methyl-6-cyclohexylidene-hexene-5-one-3 and its isomerisation to 4-methyl-6-cyclohexylidene-hexene-4-one-3; (8) 1-[21-oxo-cyclohexylidene]-3, 6, 7-trimethyl-octadiene-2, 6 by the one step method; (10) iso ethyl-pseudo irone and (11) iso-methyl pseudoionone by the one step method; (13) a mixture of 4:7:10:11-tetramethyl-dodecatrien-5, 6, 10-one-3 and 4:7:10:11-tetramethyl-dodecatrien-4, 6, 10-one-3 by the one step method; (14) and (15) a mixture of 3:6:9:10-tetramethyl-undecatrien4, 5, 9-one-2 and iso methyl-pseudo irone, which mixture on further heating is converted wholly to iso methyl pseudo inone. Numerous other propargyl alcohols, ketals and enol-ethers are specified. Enol-ethers of the above type are prepared by acidic pyrolysis of the corresponding ketals in the presence of for example potassium bisulphate, or a mixture of acetic anhydride and pyridine. Hexene-5-one-2 diethyl ketal is prepared by reacting the ketone with ortho-formic ester and boron-trifluoride etherate.
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CH865478X | 1958-08-01 |
Publications (1)
Publication Number | Publication Date |
---|---|
GB865478A true GB865478A (en) | 1961-04-19 |
Family
ID=4543587
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
GB26420/59A Expired GB865478A (en) | 1958-08-01 | 1959-07-31 | A process for the manufacture of unsaturated ketones |
Country Status (1)
Country | Link |
---|---|
GB (1) | GB865478A (en) |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE1193490B (en) * | 1962-07-11 | 1965-05-26 | Hoffmann La Roche | Process for the production of gamma, delta-unsaturated aldehydes or ketones |
WO2005070857A1 (en) * | 2004-01-21 | 2005-08-04 | Basf Aktiengesellschaft | Method for the destillative production of pure isopropenyl ethers |
CN100361948C (en) * | 2005-12-30 | 2008-01-16 | 贵州黄果树烟草集团公司 | Synthesis of ketone-substituted alpha-ionone, ketone-substituted beta-ionone, ether and ester derivative by one-step method |
WO2008092655A1 (en) * | 2007-01-30 | 2008-08-07 | Dsm Ip Assets B.V. | Process for preparing dienones |
CN111807941A (en) * | 2020-07-31 | 2020-10-23 | 武汉理工大学 | Method for synthesizing alpha-diketone compound by catalyzing with metal salt |
-
1959
- 1959-07-31 GB GB26420/59A patent/GB865478A/en not_active Expired
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE1193490B (en) * | 1962-07-11 | 1965-05-26 | Hoffmann La Roche | Process for the production of gamma, delta-unsaturated aldehydes or ketones |
WO2005070857A1 (en) * | 2004-01-21 | 2005-08-04 | Basf Aktiengesellschaft | Method for the destillative production of pure isopropenyl ethers |
CN100361948C (en) * | 2005-12-30 | 2008-01-16 | 贵州黄果树烟草集团公司 | Synthesis of ketone-substituted alpha-ionone, ketone-substituted beta-ionone, ether and ester derivative by one-step method |
WO2008092655A1 (en) * | 2007-01-30 | 2008-08-07 | Dsm Ip Assets B.V. | Process for preparing dienones |
CN111807941A (en) * | 2020-07-31 | 2020-10-23 | 武汉理工大学 | Method for synthesizing alpha-diketone compound by catalyzing with metal salt |
CN111807941B (en) * | 2020-07-31 | 2022-07-05 | 武汉理工大学 | Method for synthesizing alpha-diketone compound by catalyzing with metal salt |
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