GB793507A - Novel ketones and a process for the manufacture thereof - Google Patents

Novel ketones and a process for the manufacture thereof

Info

Publication number
GB793507A
GB793507A GB28121/56A GB2812156A GB793507A GB 793507 A GB793507 A GB 793507A GB 28121/56 A GB28121/56 A GB 28121/56A GB 2812156 A GB2812156 A GB 2812156A GB 793507 A GB793507 A GB 793507A
Authority
GB
United Kingdom
Prior art keywords
methyl
butanone
dimethyl
ethyl
acetoacetate
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
GB28121/56A
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 GB793507A publication Critical patent/GB793507A/en
Expired legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/36—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions with formation of hydroxy groups, which may occur via intermediates being derivatives of hydroxy, e.g. O-metal
    • C07C29/38—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions with formation of hydroxy groups, which may occur via intermediates being derivatives of hydroxy, e.g. O-metal by reaction with aldehydes or ketones
    • C07C29/42—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions with formation of hydroxy groups, which may occur via intermediates being derivatives of hydroxy, e.g. O-metal by reaction with aldehydes or ketones with compounds containing triple carbon-to-carbon bonds, e.g. with metal-alkynes
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11B—PRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
    • C11B9/00—Essential oils; Perfumes
    • C11B9/0026—Essential oils; Perfumes compounds containing an alicyclic ring not condensed with another ring
    • C11B9/003—Essential oils; Perfumes compounds containing an alicyclic ring not condensed with another ring the ring containing less than six carbon atoms

Abstract

The invention comprises ketones of the general formula <FORM:0793507/IV (b)/1> wherein each of the symbols R1, R2, R3 and R4 represents a hydrogen atom or an acyclic hydrocarbon radical containing less than eight carbon atoms, and the manufacture thereof by heating a mixture of an alcohol of the general formula <FORM:0793507/IV (b)/2> and its acetoacetate ester at a temperature of between about 130 DEG and 160 DEG C. Preferably, equal weights of the reaction components are heated together at a temperature between 150 DEG and 155 DEG C. until the evolution of carbon dioxide ceases. In Example (1), 4-[21-methyl-51 - isopropenylcyclopenten - (11) - yl] - butanone-(2) is prepared by heating equal weights of racemic 3,7 - dimethyl - octen - (6) - yn - (1)-ol-(3) and its acetoacetate ester. In a similar manner, 4 - [21, 51 - dimethyl - 51 - isopropenylcyclopenten - (11) - yl] - butanone - (2), 4 - [21-methyl - 51 - [buten - (211) - yl - (211)] - cyclopenten - (11) - yl] - butanone - (2), 4 - [21 - methyl - 51 - [411 - methyl - penten - (211) - yl-(211)] - cyclopenten - (11) - yl] - butanone - (2), 4 - [21 - methyl - 31 - ethyl - 51 - isopropenylcyclopenten - (11) - yl] - butanone - (2), 4 - [21-methyl - 31 - allyl - 51 - isopropenylcyclopenten-(11) - yl] - butanone - 2, 4 - [21 - methyl - 31 - propargyl - 51 - isopropenylcyclopenten - (11)-yl - (11)] - butanone - (2), 4 - [21 - methyl - 31-ethyl - 51 - [buten - (211) - yl - (211)] - cyclopenten-(11) - yl - (11)] - butanone - (2) and 4 - [21 - methyl - 31 - allyl - 51 - [buten - (211) - yl - (211)]-cyclopenten - (11) - yl - (11)] - butanone - (2) are obtained by heating respectively the acetoacetate esters of 3,6,7-trimethylocten-(6)-yn-(1) - ol - (3), 3,7 - dimethyl - nonen - (6) - yn-(1) - ol - (3), 3,7,9 - trimethyldecen - (6) - yn-(1) - ol - (3), 3,7 - dimethyl - 4 - ethylocten - (6)-yn - (1) - ol - (3), 3,7 - dimethyl - 4 - allylocten-(6) - yn - (1) - ol - (3), 3,7 - dimethyl - 4 - propargylocten - (6) - yn - (1) - ol - (3), 3,7 - dimethyl - 4 - ethylnonen - (6) - yn - (1) - ol - (3) and 3,7 - dimethyl - 4 - allylnonen - (6) - yn - (1) - ol - (3) with the corresponding parent alcohols. The products are characterized by conversion to the semicarbazone, phenylsemicarbazone and/or 2 : 4-dinitrophenylhydrazone. Starting materials. Alcohols of the second general formula above are obtained from ketones of the general formula <FORM:0793507/IV (b)/3> by the action of an alkali-metal acetylide and hydrolysis. Acetoacetate esters of these alcohols are obtained by condensing them with diketene. The preparation of the starting materials of the last seven examples is described in detail, including the following preliminary steps: The ketones of the foregoing general formula wherein R1 = methyl or isopropyl and R2 = R3 = R4 H are manufactured from 3-methyl-penten-(1)-ol-(3) and 3,5-dimethyl-hexen-(1)-ol-(3) respectively by treatment with concentrated hydrochloric acid to form respectively 1-chloro-3-methylpenten - (2) and 1 - chloro - 3,5 - dimethylhexene-(2), condensing these with ethyl sodio-acetoacetate and hydrolysing and decarboxylating the products. The ketones wherein R4 = ethyl, allyl or propargyl and R1 = R2 = R3 = H are obtained by the action of ethyl, allyl and propargyl bromides respectively on the sodio-derivative of 1,1-dimethylpropen-(2)-yl-(1) acetoacetate, followed by decarboxylation. The ketone wherein R1=methyl, R4= allyl and R2=R3=H is prepared similarly by condensing the sodio-derivative of 3-methyl-penten - (1) - yl - (3) acetoacetate with allyl bromide, followed by decarboxylation. The ketone wherein R1=methyl, R4=ethyl and R2=R3=H is prepared by condensing ethyl-methyl-vinyl-carbinol with diketene, condensing the sodio-derivative of the resulting acetoacetate ester with ethyl bromide and decarboxylating the product.
GB28121/56A 1955-09-19 1956-09-14 Novel ketones and a process for the manufacture thereof Expired GB793507A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US793507XA 1955-09-19 1955-09-19

Publications (1)

Publication Number Publication Date
GB793507A true GB793507A (en) 1958-04-16

Family

ID=22149979

Family Applications (1)

Application Number Title Priority Date Filing Date
GB28121/56A Expired GB793507A (en) 1955-09-19 1956-09-14 Novel ketones and a process for the manufacture thereof

Country Status (1)

Country Link
GB (1) GB793507A (en)

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