GB799797A - An improved process for the manufacture of unsaturated ketones - Google Patents
An improved process for the manufacture of unsaturated ketonesInfo
- Publication number
- GB799797A GB799797A GB11631/56A GB1163156A GB799797A GB 799797 A GB799797 A GB 799797A GB 11631/56 A GB11631/56 A GB 11631/56A GB 1163156 A GB1163156 A GB 1163156A GB 799797 A GB799797 A GB 799797A
- Authority
- GB
- United Kingdom
- Prior art keywords
- methyl
- acetoacetate
- dimethyl
- allyl acetoacetate
- heptene
- 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
- C07C403/02—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 containing only carbon and hydrogen atoms
-
- 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
- C07C403/06—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 singly-bound oxygen atoms
- C07C403/12—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 singly-bound oxygen atoms by esterified hydroxy groups
-
- 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
- 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
- C07C45/61—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
- C07C45/673—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 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
- C07C45/61—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
- C07C45/673—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 by change of size of the carbon skeleton
- C07C45/676—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 by change of size of the carbon skeleton by elimination of carboxyl groups
-
- 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
- C11B9/0034—Essential oils; Perfumes compounds containing an alicyclic ring not condensed with another ring the ring containing six carbon atoms
-
- 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
- C07C2601/14—The ring being saturated
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Unsaturated ketones having the general formula <FORM:0799797/IV (b)/1> wherein R1 represents an acyclic or cyclic alkenyl (including acyclic alkapolenyl) or alkyl radical or phenyl and R2 represents an alkyl radical having up to 4 carbon atoms, or R1 and R2 together with their shared carbon atom represent cyclohexylidene, and R3 represents hydrogen or an alkyl radical containing up to 4 carbon atoms, are prepared by eliminating the elements of CO2 from acetoacetic esters having the general formula <FORM:0799797/IV (b)/2> in which the R's are as defined above, by heating the esters in the presence of an aluminium trialkoxide containing up to 4 carbon atoms in each alkyl radical. The process may be effected by heating the reaction mixture with agitation at a sufficiently high temperature to cause a steady evolution of CO2. The aluminium trialkoxide is preferably used in amounts of about 8-25 millimoles. per mol. of acetoacetic ester. An inert solvent may be present. Examples describe the conversion of (1), (6) and (7) 1,1-dimethyl-allylacetoacetate to 6-methyl-heptene-5 - one - 2, (2) 1,1,2 - trimethyl - allyl acetoacetate to 5,6 - dimethyl - heptene - 5 - one - 2, (3) 1 - methyl - 1 - isobutyl - allyl acetoacetate to 6,8 - dimethyl - nonene - 5 - one - 2, (4) 1-methyl - 1 - (41 - methyl - pentene - 31 - yl)-allyl acetoacetate to 6,10 - dimethyl - hendecadiene-5,9 - one - 2, (5) 1 - methyl - 1(41, 81 - dimethyl - nonyl)-allyl acetoacetate to 6,10,14-trimethyl-pentadecene - 5 - one - 2, (8) 1 - methyl - 1 -phenyl-allyl acetoacetate to 6-phenyl-heptene-5-one-2, (9) 1-vinyl cyclohexyl acetoacetate to 5 - cyclohexylidene - pentanone - 2, (10) 3,7,9-trimethyl - decadiene - 1,6 - yl - 3 acetoacetate to 6,10,12 - trimethyl - tridecadiene - 5,9 - one-2 and (11) 6-cyclohexylidene-3-methyl-hexene-1-yl-3 acetoacetate to 9-cyclohexylidene-6-methyl-nonene-5-one-2, by heating the specified acetoacetate with aluminium tri-isoproxide, ethoxide or butoxide at temperatures ranging from 120 DEG to 175 DEG C. The product is purified by fractional distillation and/or washing with acid or alkaline washes. 1,1-Diethyl allyl acetoacetate, 1-methyl - 1 - ethyl - allyl acetoacetate, 1-methyl-1 - (41, 61 - dimethyl - heptene - 3 - yl - allyl acetoacetate and 1-methyl-1-(41, 81-dimethyl-nonadiene-3,7-yl) allyl acetoacetate are other specified acetoacetic reagents and a table lists additional values for the R's in the above ester formula. Aluminium tri-methoxide and -isobutoxide are further specified alkoxides. The acetoacetates used as starting materials in the examples are prepared by reacting diketene with appropriate carbinols in petroleum ether solution in the presence of pyridine and acetic acid at 25-30 DEG C. followed by a specified working up to isolate the resulting acetoacetates. Specifications 702,647, 725,621, 737,512, 785,086 and 787,350, [Group XL (c)], are referred to.
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US50252655A | 1955-04-19 | 1955-04-19 |
Publications (1)
Publication Number | Publication Date |
---|---|
GB799797A true GB799797A (en) | 1958-08-13 |
Family
ID=23998229
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
GB11631/56A Expired GB799797A (en) | 1955-04-19 | 1956-04-17 | An improved process for the manufacture of unsaturated ketones |
Country Status (4)
Country | Link |
---|---|
BE (1) | BE547084A (en) |
DE (1) | DE1053498B (en) |
FR (1) | FR1205812A (en) |
GB (1) | GB799797A (en) |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE2928944A1 (en) * | 1979-07-18 | 1981-02-12 | Basf Ag | IMPROVED METHOD FOR PRODUCING HIGHER UNSATURATED KETONES |
DE19647117A1 (en) * | 1996-11-14 | 1998-05-28 | Basf Ag | Process for the production of gamma, delta-unsaturated ketones by Caroll reaction in cyclic carbonates or gamma-lactones as solvents |
DE10123066A1 (en) | 2001-05-11 | 2002-11-14 | Basf Ag | Process for the production of higher alpha, beta-unsaturated alcohols |
Family Cites Families (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2638484A (en) * | 1951-06-05 | 1953-05-12 | Hoffmann La Roche | Preparation of an octenone |
US2662920A (en) * | 1952-06-10 | 1953-12-15 | Hoffmann La Roche | Process for preparing 2, 3-dimethylheptene-2-one-6 |
FR1079408A (en) * | 1952-06-10 | 1954-11-30 | Hoffmann La Roche | Process for the preparation of unsaturated ketones |
-
1956
- 1956-04-16 DE DEH26778A patent/DE1053498B/en active Pending
- 1956-04-17 GB GB11631/56A patent/GB799797A/en not_active Expired
- 1956-04-17 BE BE547084D patent/BE547084A/xx unknown
- 1956-04-18 FR FR1205812D patent/FR1205812A/en not_active Expired
Also Published As
Publication number | Publication date |
---|---|
FR1205812A (en) | 1960-02-04 |
DE1053498B (en) | 1959-03-26 |
BE547084A (en) | 1956-10-17 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
SAREL et al. | Organic carbonates. IV. 1a, b, c factors affecting formation of homologous cyclic carbonates | |
US2824121A (en) | Process for preparation of oxy alkylidene compounds | |
US2000252A (en) | Production of acetals | |
US2839579A (en) | Process for the production of ketones | |
US2868786A (en) | Esters of phenyl acetic acids and a process of making same | |
GB799797A (en) | An improved process for the manufacture of unsaturated ketones | |
US2763665A (en) | Process for the manufacture of levulinic acid esters | |
US3227736A (en) | Production of alpha-fluorocarboxylic acids and esters | |
US2934560A (en) | Cyclic alcohols and esters and preparation thereof | |
US2905690A (en) | Vinylation of oxazolidinones | |
GB911290A (en) | Process for the production of esters and carboxylates of alkyl boric acids | |
US2453677A (en) | Alkamine esters of pyrrole-3, 4-dicarboxylic acids | |
US2673212A (en) | Process for preparing beta-methyl glutaconic acid esters from alkyl isodehydroacetates | |
US2433645A (en) | Plasticizers | |
US2719855A (en) | Steroid alkali-metal enolates | |
DE974764C (en) | Process for the preparation of monomeric organosilicon compounds | |
US2348159A (en) | Production of acyclic condensation products of acetylene | |
US2877245A (en) | Process of preparing beta, beta, beta-tris (hydroxymethyl) methyl amides | |
GB733448A (en) | Steroid alkali-metal enolates | |
GB1103415A (en) | Process for the manufacture of acetoacetic acid methyl ester and acetoacetic acid ethyl ester | |
GB831837A (en) | New esters of hyponitrous acid and their preparation | |
GB733884A (en) | Unsaturated keto-esters and the manufacture thereof | |
US2826603A (en) | Process for preparing 3, 3 dichloro-2-methallyl substituted malonates | |
US2617821A (en) | Method for preparing formic esters | |
GB782316A (en) | Unsaturated compounds and the manufacture thereof |