GB774462A - Novel unsaturated esters ethers and aldehydes and a process for the manufacture thereof - Google Patents

Novel unsaturated esters ethers and aldehydes and a process for the manufacture thereof

Info

Publication number
GB774462A
GB774462A GB20261/55A GB2026155A GB774462A GB 774462 A GB774462 A GB 774462A GB 20261/55 A GB20261/55 A GB 20261/55A GB 2026155 A GB2026155 A GB 2026155A GB 774462 A GB774462 A GB 774462A
Authority
GB
United Kingdom
Prior art keywords
cyclohexen
trimethyl
ether
methylmalonyl
dialdehyde
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
GB20261/55A
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 GB774462A publication Critical patent/GB774462A/en
Expired legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/02—Esters of acyclic saturated monocarboxylic acids having the carboxyl group bound to an acyclic carbon atom or to hydrogen
    • C07C69/12—Acetic acid esters
    • C07C69/14—Acetic acid esters of monohydroxylic compounds
    • C07C69/145—Acetic acid esters of monohydroxylic compounds of unsaturated alcohols
    • 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
    • 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
    • C07C33/00—Unsaturated compounds having hydroxy or O-metal groups bound to acyclic carbon atoms
    • C07C33/05—Alcohols containing rings other than six-membered aromatic rings
    • C07C33/14—Alcohols containing rings other than six-membered aromatic rings containing six-membered rings
    • 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
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/007—Esters of unsaturated alcohols having the esterified hydroxy group bound to an acyclic carbon atom
    • 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)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The invention comprises 1-esters and 1-ethers of 1,3,6-trihydroxy-2,6-dimethyl-8-[21, 61, 61-trimethyl - cyclohexen - 11 - yl] - octadien - 1,7 - yne - 4, 2,6 - dimethyl - 8 - [21,61,61 - trimethyl-cyclohexen - 21 - ylidene] - octadien - 2,6 - yn - 4 - al - 1, 2,6 - dimethyl - 8 - [21,61,61 - trimethyl-cyclohexen-21-ylidene]-octatriene-2,4,6-al-1 and a process of condensing 3-hydroxy-3-methyl-5-[21,61,61 - trimethyl - cyclohexen - 11 - yl] - penten - 4 - yne - 1 with an ester or ether of 3 - hydroxy - 2 - methyl - propen - 2 - al - 1 in an organo-alkali metal or Grignard reaction to produce said 1-esters and 1-ethers, and, if desired, converting the 1-ester or 1-ether to an aldehyde by treatment with an acid agent and selective hydrogenation of the product. The organo alkali-metal reaction may be effected using phenyl-lithium in diethyl ether or lithium amide or sodamide in liquid ammonia. The conversion of the 1-ester or 1-ether to the acetylenicaldehyde may be effected in aqueous acetone with sulphuric acid. The selective hydrogenation may be effected in the presence of a small quantity of quinoline and of a palladium lead catalyst. Starting compounds. 3-Hydroxy-3-methyl-5-[21,61,61 - trimethyl - cyclohexen - 11 - yl] - penten-4-yne-1 is obtained by condensing b -ionone with lithium acetylide in liquid ammonia; 3-hydroxy - 2 - methyl - propen - 2 - al - 1 is obtained by reacting the sodium salt methylmalonyl dialdehyde with an acid chloride in an inert water-free solvent or by reacting methylmalonyl dialdehyde with an alcohol at an elevated temperature; the sodium salt of methylmalonyl dialdehyde is obtained by condensing a propenyl ether with ortho-formic acid ethyl ester to form the tetraethyl acetal of methylmalonyl dialdehyde, which is subsequently hydrolysed and neutralised with caustic soda.
GB20261/55A 1954-07-16 1955-07-13 Novel unsaturated esters ethers and aldehydes and a process for the manufacture thereof Expired GB774462A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CH774462X 1954-07-16

Publications (1)

Publication Number Publication Date
GB774462A true GB774462A (en) 1957-05-08

Family

ID=4535697

Family Applications (1)

Application Number Title Priority Date Filing Date
GB20261/55A Expired GB774462A (en) 1954-07-16 1955-07-13 Novel unsaturated esters ethers and aldehydes and a process for the manufacture thereof

Country Status (1)

Country Link
GB (1) GB774462A (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3091631A (en) * 1957-10-18 1963-05-28 Hoffmann La Roche Production of acetylenic carotenoid aldehydes and acetal intermediates therefor
US4092366A (en) * 1975-04-10 1978-05-30 Scm Corporation Synthesis of Vitamin A, intermediates and conversion thereof to Vitamin A

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3091631A (en) * 1957-10-18 1963-05-28 Hoffmann La Roche Production of acetylenic carotenoid aldehydes and acetal intermediates therefor
US4092366A (en) * 1975-04-10 1978-05-30 Scm Corporation Synthesis of Vitamin A, intermediates and conversion thereof to Vitamin A

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