GB865478A - A process for the manufacture of unsaturated ketones - Google Patents

A process for the manufacture of unsaturated ketones

Info

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
Application number
GB26420/59A
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
F Hoffmann La Roche AG
Original Assignee
F Hoffmann La Roche AG
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by F Hoffmann La Roche AG filed Critical F Hoffmann La Roche AG
Publication of GB865478A publication Critical patent/GB865478A/en
Expired legal-status Critical Current

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/61Preparation 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
    • C07C45/67Preparation 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
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/51Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition
    • C07C45/511Preparation 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
    • C07C45/513Preparation 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
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/51Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition
    • C07C45/511Preparation 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
    • C07C45/515Preparation 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
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C49/00Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
    • C07C49/20Unsaturated compounds containing keto groups bound to acyclic carbon atoms
    • C07C49/203Unsaturated 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.
GB26420/59A 1958-08-01 1959-07-31 A process for the manufacture of unsaturated ketones Expired GB865478A (en)

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)

* Cited by examiner, † Cited by third party
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

Cited By (6)

* Cited by examiner, † Cited by third party
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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