Patent GB-846601-A (GB)
Title: Vinyl hydantoins
Inventor: JONES WILLIAM OWEN
IPC: C07D233/80
Filed: 1958-01-13
Abstract: The invention comprises polymers and copolymers of vinylhydantoins of formula:  <FORM:0846601/IV(a)/1> where R1 is alkyl and R2 is alkyl, carboalkoxyalkyl, aryl, aralkyl, cycloalkyl, cycloalkyl-alkyl, aralkenyl or heterocyclic, or R1 and R2 together form a polymethylene or alkyl-substituted polymethylene ring; R3 is vinyl, alkyl or aryl; and R4 is vinyl, acyl or hydrogen, at least one of R3 and R4 being vinyl.  (For preparation see Group IV(b)).  The copolymers may be formed by the copolymerisation of two or more vinylhydantoins or by copolymerising at least one vinylhydantoin with at least one compound containing at least one ethylenic linkage.  Bulk, solution, suspension or emulsion polymerisation may be used. Water or an inert organic liquid, e.g. benzine may be present. Temperature up to about 100 DEG C. are preferred and one or more catalysts, especially free radical catalysts such as berzoyl peroxide, hydrogen peroxide, azobisiso-butyronitrile, and di-t-butyl-peroxide, are preferably used.  Examples describe the preparation of polymers of: 3-vinyl-5,5-dimethyl-; 3-vinyl-5-ethyl-5-methyl-; 3-vinyl-5-methyl-5-isobutyl-; 3-vinyl-5-phenyl-5-undecyl-; 1,3-divinyl-5-methyl-5-thiemyl-; 3-vinyl-5,5-cyclohexylspiro-; 3-vinyl-5,5-cyclopentylspiro-; 1,3-divinyl-5-methyl-5-phenyl-5-phenyl-; 3-vinyl-5-methyl-5-carbethoxymethyl-and 3-vinyl-5-methyl-5-styryl-hydantoin; of the copolymers of 3-vinyl-5,5-dimethyl-hydantoin with vinyl acetate, acrylonitrile, vinyltoluene and styrene; and of a terpolymer of 3-vinyl-5,5-cyclohexylspirohydantoin, 3-vinyl-5,5-dimethylhydantoin and 3-vinyl-5-ethyl-5-methylhydantoin.ALSO:The invention comprises vinylhydantoins of formula :-<FORM:0846601/IV(b)/1> where R1 is alkyl and R2 is alkyl, carbo-alkoxyalkyl, aryl, aralkyl, cycloalkyl, cycloalkylalkyl, aralkenyl, or heterocyclic ; or R1 and R2 together form a polymethylene or alkyl-substituted polymethylene ring ; R3 is vinyl, alkyl or aryl ; and R4 is vinyl, acyl or hydrogen, at least one of R3 and R4 being vinyl.  They are prepared by reacting the corresponding hydantoin in which the vinyl group or groups are replaced by hydrogen, in solution or suspension in an inert liquid with acetylene at a pressure within the range 1-30 atm. and at a temperature within the range 140-250 DEG C. in the presence of a vinylation catalyst.  Specified p  inert liquids are hydrocarbons and halogenated hydrocarbons ; specified catalysts are cadmium and zinc oxides and their salts with weak acids.  A polymerisation inhibitor may be present. Anhydrous conditions are preferred.  When starting with a hydantoin in which both the 1- and 3- positions are vacant, a mixture of 3-monovinyl and 1, 3-divinyl derivatives normally results, but by controlling the quantity of acetylene at least a 90% proportion by weight of the monovinyl compound may be obtained or alternatively by continued vinylation it is possible to obtain predominantly divinyl derivative.  The products may be polymerised (see Group IV(a)).  The vinylhydantoins may be hydrogenated to the corresponding ethyl compounds.  Starting materials prepared in exapmles by the reaction of a cyanide and ammonium carbonate with the appropriate ketone are :-(17) 5-undecyl-5phenylhydantoin from laurophenone ; (27) 5,5-(2-methylcyclohexyl)-spirohydantoin from methylcyclohexanone; (35) 5-methyl-5-carbethoxymethylhydantoin from acetoacetic ester and (36) 5-methyl-5-hexahydrobenzylhydantoin from cyclohexylacetone : also prepared are (28) 3-ethyl-5,5-dimethylhydantoin by reacting ethyl bromide with the potassium derivative of 5,5-dimethylhydantoin and 1-acetyl-5,5-dimethylhydantoin by the action of acetic anhydride on 5,5-dimethyl hydantoin.