GB760078A - Production of derivatives of cyclo-octane having strong cholagogic activity - Google Patents

Production of derivatives of cyclo-octane having strong cholagogic activity

Info

Publication number
GB760078A
GB760078A GB23753/54A GB2375354A GB760078A GB 760078 A GB760078 A GB 760078A GB 23753/54 A GB23753/54 A GB 23753/54A GB 2375354 A GB2375354 A GB 2375354A GB 760078 A GB760078 A GB 760078A
Authority
GB
United Kingdom
Prior art keywords
cyclo
octenyl
acid
ester
ethyl
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
GB23753/54A
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.)
BASF SE
Original Assignee
BASF SE
Badische Anilin and Sodafabrik 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 BASF SE, Badische Anilin and Sodafabrik AG filed Critical BASF SE
Publication of GB760078A publication Critical patent/GB760078A/en
Expired legal-status Critical Current

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C61/00Compounds having carboxyl groups bound to carbon atoms of rings other than six-membered aromatic rings
    • C07C61/10Saturated compounds having a carboxyl group bound to a seven-to-twelve-membered ring

Abstract

A compound of the general formula <FORM:0760078/IV(b)/1> wherein two adjacent X's represent a double linkage and the remaining X represents hydrogen, R is an alkyl or alkenyl group, X is hydrogen and X2 is a carboxylic group is prepared by subjecting a compound of the above general formula wherein the X's and R have the meanings defined above, X1 is hydrogen or a carboxylic amide or ester group and X2 is a carboxylic ester, carboxylic amide or cyano group to a saponification treatment and, when X1 in the general formula of the starting materials is a carboxylic acid or ester group, effecting a partial decarboxylation during or after the saponification or at an intermediate stage thereof if it is effected stepwise. The invention also comprises the subjection of an ester, amide or nitrile of an acid of the general formula <FORM:0760078/IV(b)/2> where R has the above-defined meanings, to a saponification treatment and during this treatment or in any sequence splitting off water by known methods to form a double bond. The acids derived from either of the above processes may then be converted into salts with, for example, sodium hydroxide, magnesium carbonate, calcium carbonate, ammonia, diethylamine, ethanolamine, triethanolamine, morpholine, pyrrolidine, hexylamine or piperidine. The saponification is preferably carried out in alkaline solution in water or organic solvents at 80-200 DEG C. Reagents such as phosphorus tribromide, potassium bisulphate, acetic anhydride or para-toluene sulphonic acid may be used for the splitting off of water, or this can be achieved simultaneously with saponification under energetic conditions, e.g. with concentrated sulphuric acid. The unsaturated acids wherein the double bonds are attached to the C1 atom of the cyclo-octane ring are stated to be mixtures of isomers in which the double bond is either attached to a C2 atom of the ring or to the a -carbon atom of the side-chain. In examples: (1) D 1-cyclo-octenyl-ethyl-cyano-acetic acid ethyl ester is heated at 160-170 DEG C. with potassium hydroxide in alcohol and, after working-up the resulting solution, the product is vacuum distilled to give D 1-cyclo-octenylethyl-acetic acid; the corresponding D 1-cyclo-octenyl - methyl -, n - propyl, butyl and allyl-acetic acids are prepared similarly; (2) D 2-cyclo-octenyl-ethyl malonic acid diethyl ester is saponified with potassium hydroxide in aqueous alcohol at reflux temperature to give D 2-cyclo-octenyl-ethyl-malonic acid monoethyl ester which on heating in a slight vacuum at 180 DEG C. followed by high vacuum distillation yields D 2-cyclo-octenyl-ethyl-acetic acid ethyl ester which is then saponified to the free acid by refluxing with potassium hydroxide in aqueous methanol; the sodium, magnesium, calcium and zinc salts of the product are referred to; (3) (1-hydroxy-cyclo-octyl-(1)-)-ethyl acetic acid ethyl ester is heated with potassium bisulphate at 180 DEG C. to give D 1-cyclo-octenyl-ethyl-acetic acid ethyl ester which is saponified to the free acid with potassium hydroxide in methanol at reflux temperature; alternatively the ester can be converted to the amide and this saponified; and (4) D 1-cyclo-octenyl-propyl-acetonitrile with potassium hydroxide in aqueous methanol at 180 DEG C. gives D 1-cyclo-octenyl-propyl-acetic acid. The products have cholagogic activity. Starting materials. Cyclo-octenyl-alkyl- or alkenyl-malonic acid esters and -cyanoacetic acid esters are obtained by splitting off water from the hydroxycarboxylic acid esters obtainable by the Reformatski reaction between cyclo-octanone and a -bromo-fatty acid esters or by condensation of cyclo-octyl magnesium halides with functional derivatives of pyruvic acid or alpha-keto butyric acid. Esters, amides and nitriles of cyclo-octenyl-alkyl- or -alkenyl-malonic acids are obtained by condensing cyclo-octanone with functional derivatives of malonic acid and reacting the reaction products with alkyl or alkenyl halides, or with dimethyl or diethyl sulphate. In the examples, D 2-cyclo-octenyl-ethyl-malonic acid diethyl ester is prepared from 1,2-dibromo cyclo-octane and monoethyl-malonic acid diethyl ester, D 1-cyclo-octenyl-propylacetonitrile is prepared by hydrolysis and decarboxylation of D 1 - cyclo - octenyl - propyl - cyanoacetic acid ethyl ester, (1-hydroxy-cyclo-octyl - (1) - ) - ethyl - acetic acid ethyl ester is prepared from cyclo-octanone and a -bromo-butyric acid ethyl ester by the Reformatski reaction, and D 1-cyclo-octenyl-methyl- and ethyl-cyano-acetic acid ethyl esters are prepared from cyclo-octylidene-cyano-acetic acid ethyl ester and dimethyl or diethyl sulphate.
GB23753/54A 1953-08-28 1954-08-16 Production of derivatives of cyclo-octane having strong cholagogic activity Expired GB760078A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DE760078X 1953-08-28

Publications (1)

Publication Number Publication Date
GB760078A true GB760078A (en) 1956-10-31

Family

ID=6660838

Family Applications (1)

Application Number Title Priority Date Filing Date
GB23753/54A Expired GB760078A (en) 1953-08-28 1954-08-16 Production of derivatives of cyclo-octane having strong cholagogic activity

Country Status (1)

Country Link
GB (1) GB760078A (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3065134A (en) * 1958-02-19 1962-11-20 Lab Jacques Logeais Soc D Expl Choleretic hydroxycycloaliphatic acid process

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3065134A (en) * 1958-02-19 1962-11-20 Lab Jacques Logeais Soc D Expl Choleretic hydroxycycloaliphatic acid process

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