Patent GB-877361-A (GB)
Title: Production of alpha, beta-unsaturated carboxylic acids and their esters
Inventor: STILZ WALTER
IPC: C07C69/602
Filed: 1959-10-16
Abstract: a -b -unsaturated carboxylic acids and esters thereof such as Vitamin A acid, crocetin, bixin, isocrocetin and isonorbixin diethyl esters are prepared by reacting a compound of general formula, <FORM:0877361/IV (b)/1> in which R1, R2, R3, R4, R5, R6 represent a hydrogen atom or an alkyl, cycloalkyl, aralkyl, or aryl radical and n represents 0, 1, 2, 3, or 4, with a compound containing at least one carbonyl group in the presence of a proton acceptor and preferably in an inert liquid or solvent. Compounds containing carbonyl groups such as aldehydes and ketones are listed and proton acceptors are basic compounds such as alkali or alkaline earth metal hydroxides or alcoholates or amides, diethylamine or dibutylamine, and basic ionexchange resins, and the liquid media may be hydrocarbons, alcohols, glycols, ethers or polar organic solvents such as formamide, or water.  The temperature of reaction is between 0 and 100 DEG C. and the esters may be saponified for example, with aqueous alcoholic caustic potash.  Examples describe the preparation and purification of (1) norbixin diethyl ester from 2,6,11,15 - tetramethyl-hexadecaheptaene-(2,4,6,8,10,12,14) - dial - 1,16) and phosphonic acetic acid ester, (2) isocrocetin diethyl ester 1,14 - bis-carbethoxy-2,5,10,13-tetramethyltetra-decaheptaene - (1,3,5,7,9,11,13) from 2,7 - dimethyl - octatriene - (2,4,6) - dial - (1,8) and 1-carbethoxy-2-methyl-propene-(1)-diethyl - phosphonate-(3), (3) isonorbixin diethyl ester, (1,18-bis - carbethoxy-2,7,12,17-tetramethyl-octadecanonaene - (1,3,5,7,9,11,13,15,17) from 2,7 - dimethyl - octatriene - (2,4,6) - dial - (1,8) and 1-carbethoxy - 2 - methyl-pentadiene-(1,3)-diethyl phosphonate-(5), (4) homo-isopreno-vitamin A acid ethyl from b -ionylidene-acetaldehyde and 1-carbethoxy-2,6-dimethyl - heptatriene - (1,3,5)-diethyl phosphonate-(1), (5) sorbic acid or ethyl sorbate from crotonaldehyde and phosphonic acetic triethyl ester and carbethoxymethyl phosphonic acid dimethyl ester (6), (8), trans- and 2,6-dichloro-cinnamic acid from benzaldehyde and 2,6-dichlorobenzaldehyde and phosphonic acetic acid triethyl ester and carbethoxy-methylphosphonic acid dimethyl ester respectively, (9) 2-furyl-b -acrylic acid from furfural and phosphonic acetic acid triethyl ester, (10) p-nitrocinnamic acid ethyl ester from p-nitrobenzaldehyde and carbethoxymethyl-phosphonic acid diethyl ester, (11) vitamin A acid from b -ionylidene-acetaldehyde and 1 - carbethoxy - 2 - methylpropene - (1) - diethylphosphonate - (3), (12) crocetin-diethyl ester from 4,8 - dimethyldodecapentaene-(2,4,6,8,10)-dial-(1,12) and triethyl a -methylphosphoneacetate (13) cyclohexylidene acetic acid methyl ester from cyclohexanone and carbomethoxy methyl phosphonic acid butyl ester (14) cyclooctylidene-acetic acid ester from cyclooctanone and carbomethoxy - methyl - phosphonic acid triisopropyl ester (15) p-dimethylamino cinnamic acid from p-dimethylaminobenzaldehyde and carbomethoxymethyl-phosphonic acid diethyl ester (16) cinnamalacetic acid methyl ester from cinnamaldehyde and carbmethoxymethyl phosphonic acid methyl ester, (17) 1-carbethoxy-2-methyl-3,3-diethoxy-propene-(1) from methyl glyoxal diethyl acetal and carbethoxy-methyl-phosphonic acid diethyl ester and (18) methyl sorbate from crotonaldehyde and carbmethoxy-methyl-phosphonic acid diethyl ester and (19) piperonylacrylic acid methyl ester from piperonal and carbmethoxy-methyl-phosphonic acid diethyl ester.  The products are suitable as foodstuff and pigment dyes, pharmaceuticals, and stabilizers for plastics.  Phosphonic acid derivatives of general formula  <FORM:0877361/IV (b)/2> where R1-R6 are as in I and m is 1, 2, 3 or 4, are prepared by reacting a compound of formula <FORM:0877361/IV (b)/3> where Y is a halogen atom or a toluene-p-sulphonyl radical with a phosphorous acid ester of formula <FORM:0877361/IV (b)/4> in which R7, R8, R9 represent alkyl, cycloalkyl, aralkyl or aryl radicals, and examples are g -phosphonic-b -methyl crotonic, o -phosphonic-b - and g -methyl-sorbic, 7-phosphonic-2.6 and 1.5-dimethyl-heptatriene-(1,3,5)-carboxylic acid-(1), and their esters and examples are given of their preparation.