GB790612A - Novel unsaturated aldehydes and a process for the manufacture thereof - Google Patents

Novel unsaturated aldehydes and a process for the manufacture thereof

Info

Publication number
GB790612A
GB790612A GB23536/55A GB2353655A GB790612A GB 790612 A GB790612 A GB 790612A GB 23536/55 A GB23536/55 A GB 23536/55A GB 2353655 A GB2353655 A GB 2353655A GB 790612 A GB790612 A GB 790612A
Authority
GB
United Kingdom
Prior art keywords
trimethyl
methyl
acid
condensing
resulting
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
GB23536/55A
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 GB790612A publication Critical patent/GB790612A/en
Expired legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C43/00—Ethers; Compounds having groups, groups or groups
    • C07C43/30—Compounds having groups
    • C07C43/303—Compounds having groups having acetal carbon atoms bound to acyclic carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
    • C07C41/48—Preparation of compounds having groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
    • C07C41/48—Preparation of compounds having groups
    • C07C41/50—Preparation of compounds having groups by reactions producing groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C43/00—Ethers; Compounds having groups, groups or groups
    • C07C43/30—Compounds having 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
    • C07C45/51—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition
    • C07C45/511—Preparation 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
    • C07C45/515—Preparation 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
    • 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
    • C07C45/56—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds from heterocyclic compounds
    • C07C45/57—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds from heterocyclic compounds with oxygen as the only heteroatom
    • C07C45/59—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds from heterocyclic compounds with oxygen as the only heteroatom in five-membered rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C47/00—Compounds having —CHO groups
    • C07C47/20—Unsaturated compounds having —CHO groups bound to acyclic carbon atoms
    • C07C47/21—Unsaturated compounds having —CHO 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

The invention comprises aldehydes having the general formula: <FORM:0790612/IV (b)/1> in which R stands for (2,6,6-trimethyl-cyclohexylidene) - methyl or [2,6,6 - trimethyl-cyclohexen - (2) - ylidene] - methyl or [2,6,6-trimethyl - cyclohexadien - (1,3) - yl] - methyl. Such compounds are prepared by a process comprising acetylizing iso- or retrodehydro- or b -dehydro-C14-aldehyde in a known manner, condensing the resulting iso- or retrodehydro or b -dehydro-C14-acetal with a vinyl alkyl ether in the presence of an acidic condensing agent and treating the isoretrodehydro or b -dehydro-C16-ether-acetal so obtained with an aqueous acidic agent. The iso-, retrodehydro- and b -dehydro-C14 aldehydes employed as starting materials are respectively compounds of the general formula: <FORM:0790612/IV (b)/2> wherein R stands for (2,6,6-trimethyl-cyclohexylidene) - methyl, [2,6,6 - trimethyl-cyclohexen - (2) - ylidene] - methyl and [2,6,6 - trimethyl - cyclohexadiene - (1,3) - yl] - methyl. The iso-, retrodehydro and b -dehydro-C14-acetals are compounds of the formula: <FORM:0790612/IV (b)/3> wherein R has the above meaning and R1 is the characterizing group of the ester radical of the acetylizing agent. The iso-, retrodehydro- and b -dehydro-C16-ether acetals are compounds of the formula: <FORM:0790612/IV (b)/4> wherein R and R1 have the above meanings and O-R11 is an ether group derived from the vinyl alkyl ether used. The acetalization in the first step may be carried out by means of an ester of an orthocarboxylic acid, e.g. a triester of an aliphatic orthocarboxylic acid with an aliphatic alcohol, e.g. methyl, ethyl or butyl orthoformate, in the presence of an acid condensation agent, e.g. boron trifluoride etherate, zinc chloride, ammonium nitrate, phosphoric acid or p-toluene-sulphonic acid. In the second step vinyl methyl, ethyl or butyl ether may be employed in the presence of boron trifluoride etherate, zinc chloride, titanium tetrachloride, aluminium trichloride, ferric chloride or tin tetrachloride. The third step is carried out in the present e.g. of aqueous p-toluene-sulphonic, acetic, propionic, oxalic, sulphuric or phosphoric acid or water-soluble salts having an acid reaction, e.g. zinc chloride or sodium bisulphate. Preferably oxygen is excluded and an antioxidant, e.g. hydroquinone, is added. Water is preferably removed continuously during the hydrolysis and a water-miscible solvent, e.g. dioxane, tetrahydrofuran, ethylene glycol or dimethyl ether may be added to the hydrolysis mixture. Examples are furnished. The iso-C14-aldehyde is obtained by condensing 2,6,6 - trimethyl - cyclohexanone - (1) with ethoxy - acetylene, treating the product with acid, acetalizing the resulting [2,6,6-trimethyl-cyclohexyl - idene] - acetaldehyde, condensing the resulting acetal with a propenyl ether and treating the condensation product with an acid in accordance with the process of Specification 789,693 or by condensing 2,6,6-trimethyl-cyclohexanone-(1) with 1-methoxy-2-methyl-2-hydroxy-butine-(3), partially hydrogenating the resulting acetylenic glycol, dehydrating the ethylenic glycol so obtained and treating the dehydration product with an acid. The retrodehydro-C14-aldehyde is obtained by partially hydrogenating the ethoxy-(acetylenic carbinol) obtained by condensing [2,6,6-trimethyl-cyclohexen-(2)-one-(1)] with ethoxy acetylene, treating the product with acid, acetylizing the resulting [2,6,6-trimethyl-cyclohexen-(2)-ylidene]-acetaldehyde, condensing the resulting acetal with propenyl ether and treating the product with an acid in accordance with the process of Specification 789,693 or alternatively by condensing b -ionone in a glycide-ester reaction with ethyl chloro-acetate, saponifying the resulting glycide ester with alkali, brominating, the 4 - [21,61,61 - trimethyl - cyclohexen - (11)-yl] - 2 - methyl - buten - (2) - al - (1) with N-bromosuccinimide and splitting off hydrogen bromide from the bromination product by mears of quinoline in accordance with the process of Specification 790,611. The b -dehydro-C14-aldehyde is obtained by condensing the retrodehydro - C14 - aldehyde with isopropenyl-acetate in the presence of an acidic agent and hydrolysing the resulting 4-[21,61,61-trimethyl - cyclohexadien - (11,31) - yl] - 2-methyl - 1 - acetoxy - butadiene - (1,3) - under mild conditions in accordance with the process of Specification 775,060.
GB23536/55A 1954-08-16 1955-08-16 Novel unsaturated aldehydes and a process for the manufacture thereof Expired GB790612A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CH790612X 1954-08-16

Publications (1)

Publication Number Publication Date
GB790612A true GB790612A (en) 1958-02-12

Family

ID=4536950

Family Applications (1)

Application Number Title Priority Date Filing Date
GB23536/55A Expired GB790612A (en) 1954-08-16 1955-08-16 Novel unsaturated aldehydes and a process for the manufacture thereof

Country Status (1)

Country Link
GB (1) GB790612A (en)

Similar Documents

Publication Publication Date Title
US2359208A (en) beta-substituted-delta alpha,beta-gamma-butyrolactones and beta-substituted-beta-hydroxy-gamma-butyrolactones and the methods of preparing them
US2615922A (en) Synthesis of vitamin a and intermediates therefor
GB790612A (en) Novel unsaturated aldehydes and a process for the manufacture thereof
GB629695A (en) Improvements in or relating to a process for preparing high viscosity polyvinyl alcohol and the high polyvinyl alcohol resulting from said process
GB789693A (en) Unsaturated aldehydes, acetals and ether acetals and a process for the manufacture thereof
GB756896A (en) Polyene dialdehydes and process for the manufacture thereof
GB768172A (en) Dialkoxy derivatives of bis-acetals of an unsaturated dial and their preparation and conversion into a trienic dial
GB790613A (en) Novel unsaturated aldehydes and a process for the manufacture thereof
GB935006A (en) Improvements in or relating to isoprene derivatives of trimethyl cyclohexene
US2779792A (en) Hoxchsxchxo
GB802567A (en) Novel polyene aldehydes and a process for the manufacture thereof
GB651653A (en) Improvements in or relating to marihuana-like compounds
US2876239A (en) Production of polymeric compositions and derivatives thereof
US2532137A (en) Diphenyl-t-6-hydroxydehydroabietinol
US2819314A (en) Production of vitamin a and related compounds
GB636323A (en) Polymerization of alpha-haloacrylic compounds
US2744142A (en) Reduction process
GB654771A (en) Production of ethers of 1,4-butane diol
GB827046A (en) Novel diethers and a process for the manufacture thereof
GB671713A (en) Improvements in or relating to acetals of hydroxyl polymers
GB802136A (en) Synthesis of carotenoids and novel substances usable therein
US2412012A (en) Acetals
GB753552A (en) A polyene aldehyde and the manufacture thereof
GB589350A (en) Improvements in or relating to the manufacture of acetylenic alcohols
GB802568A (en) Polyene aldehydes and a process for the manufacture thereof