GB762041A - Novel hydroxy-esters and the manufacture and conversion thereof - Google Patents

Novel hydroxy-esters and the manufacture and conversion thereof

Info

Publication number
GB762041A
GB762041A GB19867/54A GB1986754A GB762041A GB 762041 A GB762041 A GB 762041A GB 19867/54 A GB19867/54 A GB 19867/54A GB 1986754 A GB1986754 A GB 1986754A GB 762041 A GB762041 A GB 762041A
Authority
GB
United Kingdom
Prior art keywords
ester
methyl
trimethyl
cyclohexen
acid
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
GB19867/54A
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.)
Roche Products Ltd
Original Assignee
Roche Products Ltd
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 Roche Products Ltd filed Critical Roche Products Ltd
Publication of GB762041A publication Critical patent/GB762041A/en
Expired legal-status Critical Current

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
    • C07C403/14—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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C33/00—Unsaturated compounds having hydroxy or O-metal groups bound to acyclic carbon atoms
    • C07C33/02—Acyclic alcohols with carbon-to-carbon double bonds
    • C07C33/025—Acyclic alcohols with carbon-to-carbon double bonds with only one double bond
    • 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
    • C07C45/62—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 hydrogenation of carbon-to-carbon double or triple bonds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
    • C07C49/587—Unsaturated compounds containing a keto groups being part of a ring
    • C07C49/703—Unsaturated compounds containing a keto groups being part of a ring containing hydroxy groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B2200/00—Indexing scheme relating to specific properties of organic compounds
    • C07B2200/07—Optical isomers
    • 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
    • C07C2601/16—Systems containing only non-condensed rings with a six-membered ring the ring being unsaturated

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The invention comprises lower alkyl esters of 3 - hydroxy - 2,6 - dimethyl - 8 - [21.61.61 - tri-methyl - cyclohexene - (11) - yl] - octadien - (4,6)-oic-(1) acid. The lower alkyl groups are those containing from 1 to 4 carbon atoms. They may be prepared by a process comprising condensing 2 - methyl - 4 - [21.61.61 - trimethyl - cyclohexen - (11) - yl] - buten - (2) - ol(1) with a halogeno-acetic acid lower alkyl ester, either dehydrating the resulting 2.3-epoxy-4-methyl-6-[21.6.61 - trimethyl - cyclohexene - (1) - yl]-hexen - (4) - oic(1) acid ester or the corresponding 3-hydroxy ester by heating in a solvent in the presence of an acidic dehydrating agent and then reducing the lower alkyl ester of 4 - methyl - 6 - [21.61.61 - trimethyl - cyclohexen - (11) - yl] hexadien - (2.4) - oic - (1) acid with lithium aluminium hydride; or reducing the 2.3-epoxy- or 3-hydroxy compound with lithium aluminium hydride and then dehydrating the resulting 4-methyl-6-[21.61.61-trimethylcyclohexen - (11) - yl] - hexen - (4) - diol (1.3) by heating with an acidic dehydrating agent, after first esterifying the primary hydroxy group; oxidizing the resulting 4-methyl-6[21.61.61-trimethyl - cyclohexene - (1)1 - yl] - hexadien - (2.4)-ol-(1) so as to convert the hydroxy-methyl group to an aldehyde group and condensing the resulting 4 - methyl - 6 - [21.61.61 - trimethylcyclohexene - 11 - yl] - hexadien - (2.4) - al - (1) with an a -halogeno-propionic acid lower-alkyl ester. When the epoxy ester is formed in the first step it can, if desired, be converted into the hydroxy ester by heating it and reducing the resulting keto acid ester. The first step comprising the condensation of the aldehyde with a halogeno-acetic acid lower-alkyl ester may be brought about, for example, by using zinc or sodium or sodium methylate as condensing agent. Preferably the condensation is carried out as a Reformatsky reaction using a bromoacetic acid lower-alkyl ester. Alternatively the condensation may be carried out using a chloroacetic acid lower-alkyl ester and sodium methylate in which case the product is an epoxy ester. The dehydration step which follows may be carried out by heating the hydroxy ester in a solvent such as toluene or xylene in the presence of a p-toluene sulphonic acid. In the example a mixture of 2 - methyl - 4 - [21.61.61 - trimethylcyclohexen - (11) - yl] - buten - (2) - al - (1), bromo-acetic acid ethyl ester and ether is treated with zinc to give a mixture containing 3-hydroxy - 4 - methyl - 6 - [21.61.61 - trimethylcyclohexen - (11) - yl] - hexen - (4) - oic - (1) acid ethyl ester; this ester is heated in toluene solution with p-toluene-sulphonic acid to give 4-methyl - 6 - [21.61.61 - trimethyl - cyclohexen-(11) - yl] - hexadien - (2.4) - oic - (1) acid ethyl ester; this latter ester is dissolved in ether and treated with lithium aluminium hydride to give 4 - methyl - 6 - [21.61.61 - trimethyl - cyclohexen-(11) - yl] - hexadien - (2.4) - ol - (1); this alcohol is treated with manganese dioxide to give 4-methyl - [21.61.61 - trimethyl - cyclohexen - (11) - yl] - hexadien - (2.4) - al - (1); this aldehyde is treated with a -bromo-propionic acid ethyl ester dissolved in ether and zinc to give 2.6-dimethyl-3 - hydroxy - 8 - [21.61.61 - trimethyl - cyclohexen - (11) - yl] - octadien - (4.6) - oic - (1) acid ethyl ester; this ester is treated with p-toluene sulphonic acid to give 2.6-dimethyl-8-[21.61.61-trimethyl - cyclohexen - (11) - yl] - octatrien(2.4.6)-oic-(1) acid ethyl ester; a mixture of this ester and ether is treated with lithium aluminium hydride to give 2.6-dimethyl-8-[21.61.61-trimethyl - cyclohexen - (11) - yl] - octatrien(2.4.6) - ol - 1; and this alcohol is treated with manganese dioxide to convert it to 2.6-dimethyl8 - [21.61.61 - trimethyl - cyclohexen(11) - yl]-octatrien - (2.4.6) - al - (1). Specifications 744,113, 753,552, 753,635, 756,622, 762,067 and 762,068 are referred to.
GB19867/54A 1953-07-07 1954-07-07 Novel hydroxy-esters and the manufacture and conversion thereof Expired GB762041A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CH762041X 1953-07-07

Publications (1)

Publication Number Publication Date
GB762041A true GB762041A (en) 1956-11-21

Family

ID=4534755

Family Applications (1)

Application Number Title Priority Date Filing Date
GB19867/54A Expired GB762041A (en) 1953-07-07 1954-07-07 Novel hydroxy-esters and the manufacture and conversion thereof

Country Status (1)

Country Link
GB (1) GB762041A (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111333507A (en) * 2020-01-14 2020-06-26 赣南医学院 Synthesis method of β -hydroxy ester compound

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111333507A (en) * 2020-01-14 2020-06-26 赣南医学院 Synthesis method of β -hydroxy ester compound
CN111333507B (en) * 2020-01-14 2022-10-18 赣南医学院 Synthesis method of beta-hydroxy ester compound

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