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GB859897A - Novel unsaturated acids and esters thereof and a process for the manufacture and conversion of same - Google Patents

Novel unsaturated acids and esters thereof and a process for the manufacture and conversion of same

Info

Publication number
GB859897A
GB859897A GB21618/58A GB2161858A GB859897A GB 859897 A GB859897 A GB 859897A GB 21618/58 A GB21618/58 A GB 21618/58A GB 2161858 A GB2161858 A GB 2161858A GB 859897 A GB859897 A GB 859897A
Authority
GB
United Kingdom
Prior art keywords
acid
esters
linoleic
oic
acids
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
GB21618/58A
Inventor
John Mervyn Osborn
Peter George Philpott
James Charles Wickens
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
Priority to GB21618/58A priority Critical patent/GB859897A/en
Priority to CH379864A priority patent/CH390239A/en
Priority to CH7472459A priority patent/CH383353A/en
Priority to CH506664A priority patent/CH414595A/en
Priority to CH506864A priority patent/CH396879A/en
Priority to CH7472559A priority patent/CH383354A/en
Priority to CH506764A priority patent/CH412860A/en
Priority to DEH36731A priority patent/DE1174770B/en
Priority to US823844A priority patent/US3033884A/en
Priority to NL240875A priority patent/NL108652C/xx
Priority to ES0250537A priority patent/ES250537A1/en
Priority to ES0250536A priority patent/ES250536A1/en
Priority to DK241659AA priority patent/DK116053B/en
Priority to DK241559AA priority patent/DK113710B/en
Priority to FR836201A priority patent/FR219M/en
Priority to FR836200A priority patent/FR218M/en
Publication of GB859897A publication Critical patent/GB859897A/en
Priority to SE12890/61A priority patent/SE309980B/xx
Expired legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C57/00—Unsaturated compounds having carboxyl groups bound to acyclic carbon atoms
    • C07C57/18—Unsaturated compounds having carboxyl groups bound to acyclic carbon atoms with only carbon-to-carbon triple bonds as unsaturation
    • 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
    • C07C29/09—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis
    • C07C29/12—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis of esters of mineral acids
    • C07C29/124—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis of esters of mineral acids of halides
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/347—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups
    • C07C51/353—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups by isomerisation; by change of size of the carbon skeleton

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The invention comprises acetylenically unsaturated acids and esters of general formula: <FORM:0859897/IV(b)/1> where c is an integer from 2 to 5 and d an integer from 0 to 8, but where c is 2, d is other than 6 and the corresponding ethylencially unsaturated acids or esters other than linoleic, homolinoleic, y-linoleic, and arachidonic acids and those compounds in which c and d are 2 and 8, 3 and 5, 4 and 6, 4 and 4, and 5 and 1, and a process for the preparation thereof which comprises condensing a halogen compound of general formula: CH3-(CH2)4-(C­CH2)s-X with an acid or ester of formula <FORM:0859897/IV(b)/2> group, s and t being integers from 0 to 4 but totalling 4, and X being a chlorine, bromine or iodine atom, in a Grignard reaction, in th presence of a copper or cuprous salt, hydrolysing the adamantyl group if present esterifying if desired, or selectively hydrogenating to the ethylenically unsaturated acid or alkyl ester. Specified compounds are 1-ethyloxy-carbonyloctadecadiyne-(9, 12), and -nonadecadiyne-(10, 13), 1-methoxycarbonyl-octadecatriyne -(6, 9, 12), docosapentayn- (4, 7, 10, 13, 16)-oic acid, octadecatriyne- (6, 9, 12)-oic-(1) acid, eicosatetrayn -(5, 8, 11, 14)-oic-(1) acid, and examples describe, their preparation and hydrogenation to the ethylenically unsaturated compounds such as linoleic, homolinoleic, y-linoleic, docosapentaen- (4, 7, 10, 13, 16)-oic, and arachidonic acids and esters. The acetylenic halogeno compounds are prepared in repeated stages from pentyl bromide by condensing with a dimagnesium bromide derivative of propargyl alcohol in the presence of cuprous chloride and brominating the resulting octyn-(2)-ol-(1) with phosphorus tribromide to form octyn-(2)-yl bromide. The 1-bromo-octyne -(2) may also be prepared by reacting acetylene with amyl bromide in loquid ammonia and condensing the resulting heptyne- (1) with formaldehyde in a Grignard reaction and hydrolysing the resulting magnesium bromide derivative of octyn-(2)-ol-1. The acetylenic acids are prepared by the condensation of an acid of general formula: <FORM:0859897/IV(b)/3> with propargyl halide in a Grignard reaction with copper or a cuprous salt; and the adamantyl hindered esters are prepared in stages from a nitrile of general formula: CH ­ C-CH2-(CH2)b-C ­ N byconverting into an imino ether hydrochloride with ethanol and hydrogen chloride, and reacting with ethanol and ether to yield ortho-ester which is reacted with cis 1, 3, 5-trihydroxycyclohexane in the presence of boron trifluoride etherate to give the hindered ortho ester which is condensed if necessary with propargyl halide in a Grignard reaction until the required chain length is obtained. The hydrogenation to the ethylenically unsaturated compounds is preferably by lead inhibited palladium catalysts. Specification 859,898 is referred to.
GB21618/58A 1958-07-05 1958-07-05 Novel unsaturated acids and esters thereof and a process for the manufacture and conversion of same Expired GB859897A (en)

Priority Applications (17)

Application Number Priority Date Filing Date Title
GB21618/58A GB859897A (en) 1958-07-05 1958-07-05 Novel unsaturated acids and esters thereof and a process for the manufacture and conversion of same
CH379864A CH390239A (en) 1958-07-05 1959-06-22 Process for the preparation of unsaturated aliphatic carboxylic acids
CH7472459A CH383353A (en) 1958-07-05 1959-06-22 Process for the preparation of unsaturated aliphatic alcohols
CH506664A CH414595A (en) 1958-07-05 1959-06-22 Process for the preparation of esters of unsaturated aliphatic carboxylic acids
CH506864A CH396879A (en) 1958-07-05 1959-06-22 Process for the production of unsaturated aliphatic acids
CH7472559A CH383354A (en) 1958-07-05 1959-06-22 Process for the production of unsaturated aliphatic acids
CH506764A CH412860A (en) 1958-07-05 1959-06-22 Process for the preparation of esters of unsaturated aliphatic carboxylic acids
DEH36731A DE1174770B (en) 1958-07-05 1959-06-24 Process for the preparation of polyincarboxylic acids and their esters
US823844A US3033884A (en) 1958-07-05 1959-06-30 Unsaturated aliphatic compounds and process for the manufacture thereof
NL240875A NL108652C (en) 1958-07-05 1959-07-03
ES0250537A ES250537A1 (en) 1958-07-05 1959-07-04 Procedure for the preparation of unsaturated aliphatic compounds (Machine-translation by Google Translate, not legally binding)
ES0250536A ES250536A1 (en) 1958-07-05 1959-07-04 Unsaturated aliphatic compounds and process for the manufacture thereof
DK241659AA DK116053B (en) 1958-07-05 1959-07-06 Process for the preparation of unsaturated aliphatic alcohols.
DK241559AA DK113710B (en) 1958-07-05 1959-07-06 Process for the preparation of unsaturated aliphatic carboxylic acids.
FR836201A FR219M (en) 1958-07-05 1960-08-19 New unsaturated aliphatic compounds.
FR836200A FR218M (en) 1958-07-05 1960-08-19 Unsaturated aliphatic compounds.
SE12890/61A SE309980B (en) 1958-07-05 1961-12-22

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
GB21618/58A GB859897A (en) 1958-07-05 1958-07-05 Novel unsaturated acids and esters thereof and a process for the manufacture and conversion of same
GB3994058 1958-12-11
GB179559 1959-01-17
GB420659 1959-02-06

Publications (1)

Publication Number Publication Date
GB859897A true GB859897A (en) 1961-01-25

Family

ID=27447176

Family Applications (1)

Application Number Title Priority Date Filing Date
GB21618/58A Expired GB859897A (en) 1958-07-05 1958-07-05 Novel unsaturated acids and esters thereof and a process for the manufacture and conversion of same

Country Status (5)

Country Link
US (1) US3033884A (en)
CH (2) CH412860A (en)
DE (1) DE1174770B (en)
ES (1) ES250536A1 (en)
GB (1) GB859897A (en)

Families Citing this family (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3299111A (en) * 1963-01-02 1967-01-17 Diamond Alkali Co Unsaturated acids derived from polyacetylenic compounds
US3235577A (en) * 1963-01-04 1966-02-15 Diamond Alkali Co Polyacetylenic carboxylic acids and the ester and amide derivatives thereof
US3450821A (en) * 1967-03-02 1969-06-17 Hoffmann La Roche Stable compositions containing eicosatetrayn - (5,8,11,14) - oic-(1) acid and derivatives thereof
GB1370021A (en) * 1971-03-25 1974-10-09 Unilever Ltd Process for preparing usaturated carboxylic acids
NL7405325A (en) * 1973-04-25 1974-10-29
US4026911A (en) * 1976-02-23 1977-05-31 Miles Laboratories, Inc. Process for the preparation of ketoalkynoic acids and use of the process in an improved synthesis of 2-(substituted)-cyclo-pentane-1,3,4-triones
US4190669A (en) * 1976-03-08 1980-02-26 The Regents Of The University Of Michigan Method for treating psoriasis
US4181725A (en) * 1977-05-02 1980-01-01 The Regents Of The University Of Michigan Method for alleviating psoriasis
AU3532978A (en) * 1977-05-02 1979-10-25 Michigan The Regents Of The Un Treating psoriasis
JPS56145232A (en) * 1980-04-14 1981-11-11 Shin Etsu Chem Co Ltd Preparation of cis-6-nonene-1-chloride
FR2609026B1 (en) * 1986-12-31 1989-03-31 Cird AMIDES OF EICOSATETRAYNOIC ACID AND THEIR APPLICATION IN PHARMACY AND COSMETICS
US5268494A (en) * 1988-05-10 1993-12-07 Centre International De Recherches Dermatologiques C.I.R.D. Sulphur-containing eicosanoides and their application in pharmacy and in cosmetics
FR2631339B1 (en) * 1988-05-10 1990-11-16 Cird NOVEL SULFID EICOSANOIDES AND THEIR APPLICATION IN PHARMACY AND COSMETICS

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2783258A (en) * 1951-11-08 1957-02-26 Pfizer & Co C Unsaturated organic compounds and their preparation
US2789993A (en) * 1953-12-22 1957-04-23 Union Chimique Belge Sa Process for the extraction of isanic acid from vegetable oils

Also Published As

Publication number Publication date
CH412860A (en) 1966-05-15
ES250536A1 (en) 1960-01-16
US3033884A (en) 1962-05-08
CH414595A (en) 1966-06-15
DE1174770B (en) 1964-07-30

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