Patent GB-850828-A (GB)
Title: New vinyl compounds and their manufacture
IPC: C07C49/203
Filed: 1957-10-28
Abstract: Polymers are prepared by treating with free-radical forming catalysts, vinyl compounds of the general formula <FORM:0850828/IV(a)/1> wherein X1, represents an acyl, carbalkoxy, car, baryloxy or nitrile group, X2 represents an acylcarbalkoxy or carbaryloxy, group, or X1 and X2 together represent a group which, together with their shared carbon atom, form a cyclohexane -1:3-dione, barbituric or pyrazol-5-one ring, and R1, R2, and R3 each represent hydrogen or an aliphatic, cycloaliphatic or aromatic radical or R1 has the aforesaid meaning and R2 and R3 together form a 6-membered cycloaliphatic ring.  Specified monomers are vinyl isopropenyl diethyl malonate, vinyl isobutenyl diethyl malonate, divinyl diethyl malonate, vinyl cyclohexenyl diethyl malonate, vinyl isobutenyl ethyl cyano acetate and 1-phenyl-3-methyl-4-vinyl -4-isopropenylpyrazol- 5-one-The preparation of the monomers is described and starting materials are specified yielding other monomers of the class defined.ALSO:The invention comprises vinyl compounds of the general formula: <FORM:0850828/IV(b)/1> wherein X1 represents an acyl, carbalkoxy, carbaryloxy or nitrile group, X2 represents an acyl, carbalkoxy or carbaryloxy group or X1 and X2 together represent a group which, together with their shared carbon atom, form a cyclohexane-1:3-dione, barbituric or pyrazol-5-one ring, and R1, R2 and R3 each represent hydrogen or an aliphatic, cyclo aliphatic or aromatic radical or R1 has the aforesaid meaning and R2 and R3 together form a 6-membered cyclo aliphatic ring, and their manufacture by reacting acetylene with a compound of the general formula: <FORM:0850828/IV(b)/2> the Rs and Xs being as above defined, at a temperature of 120 DEG -300 DEG C. in the presence of a compound of a metal from Group IIb.  The preferred starting materials are those in which X1 and X2 are carbalkoxy groups in which the alkyl radical contain 1-5 carbon atoms or in which X1 is a - CN group and X2 a carbalkoxy group containing a C1-5 alkyl group. The catalysts are preferably organic acid salts of the metals. Inert solvents such as hydrocarbons and ethers may be present. The acetylene is suitably used at pressures of 5-50 atmospheres but may be diluted with inert gases and then be used at 300 or more atmospheres.  Reaction may be effected in a closed vessel or by passing the reagents in vaporous form over the catalyst.  The vinyl products may be polymerised.  In Examples: (1) isopropylidene malonic acid diethyl ester is converted into vinyl isopropenyl diethyl malonate; (2) isobutylidene malonic acid diethyl ester into vinyl isobutenyl malonic acid diethyl ester; (3) ethylidene diethyl malonate into divinyl diethyl malonate; (4) cyclohexylidene diethyl malonate into vinyl cyclohexenyl diethyl malonate; (5) isobutylidene cyano acetic acid ethyl ester into vinyl isobutenyl ethyl cyano acetate; and (6) 1-phenyl-3-methyl-4-isopropylidene-pyrazolone-5 into 1-phenyl-3-methyl-4-isopropenyl-4-vinyl-pyrazolone-5-using zinc stearate, cadmium naphthenate, zinc naphthenate or mercuric acetate as catalyst.  Other starting materials mentioned are 5-iso, propylidene barbituric acid, isopentylideneacetyl acetone, 2-(phenyl ethylidene)-cyclohexanedione-1:3 and alkyl and aryl esters of ethylidene malonic acid, cyclohexylidene malonic acid, isobutylidene cyanacetic acid and isopropylidene aceto acetic acid.  Zinc acetate, zinc butyrate, and calcium naphthenate are other specified catalysts. The starting materials are prepared by condensing aliphatic, cycloaliphatic or araliphatic aldehydes or ketones having at least 2 carbon atoms and bearing at least one H-atom on the carbon adjacent the carbonyl group, with the active methylene groups of beta-diketones suitable functional derivatives of beta-keto acids and beta-dicarboxylic acids such as their alkyl and aryl esters and nitriles.