Patent GB-805664-A (GB)
Title: Cyclobutane derivatives
IPC: C08F22/04
Filed: 1955-12-07
Abstract: Methylenecyclobutanes having in 3-position a <FORM:0805664/IV (a)/1> CONHR, or aryl group (where R is a monovalent hydrocarbon radical having no ethylenic or acetylenic unsaturation) or having the 3- and 4 - position carbon atoms linked by a -CO-O-CO- or a <FORM:0805664/IV (a)/2> group, are polymerized alone or copolymerized with polymerizable ethylenically unsaturated compounds such as olefines (e.g. ethylene, propylene, butylene, and butadiene), vinyl and vinylidene halide (e.g. vinyl fluoride and vinylidene chloride), vinyl esters (e.g. vinyl acetate, benzoate, or laurate), vinyl ketones (e.g. methyl vinyl ketone and methyl isopropenyl ketone), acrylic and methacrylic acids and their esters, nitrile, and anhydrides (e.g. ethyl acrylate, methyl methacrylate, acrylonitrile), ethylene dicarboxylic acids, e.g. maleic and fumaric acids, and their esters, nitriles, and anhydrides, tetrafluoroethylene, trifluoroethylene, chlorotrifluoroethylene, and styrene.  The products having two carboxy or carbalkoxy groups are used to modify hydroxyl-containing polymers such as polyvinyl alcohol.  In examples, 3 - methylenecyclobutanecarbonitrile is copolymerized with styrene or maleic anhydride in benzene in presence of benzoyl peroxide. Specification 652,566 is referred to.ALSO:The invention comprises methylenecyclobutanes having in 3-position COOH,-COOR, <FORM:0805664/IV (b)/1> group (R being a monovalent hydrocarbon radical having no ethylenic or acetylenic unsaturation) or wherein the 3- and 4-position carbon atoms are linked by a -CO-O-CO-or a <FORM:0805664/IV (b)/2> group, and in particular methylenecyclobutanes of the formula <FORM:0805664/IV (b)/3> wherein X, Y and Z may each be COOH, <FORM:0805664/IV (b)/4> Y and Z may also be H or alkyl, Y may also be cycloalkyl, and X and Z may be joined to form the structure <FORM:0805664/IV (b)/5> A is H or the group R. The invention also comprises a method of producing the above by heating to 150-250 DEG  C. a mixture of an allene having at least one of the terminal carbon atoms of the allene group >C=C=C< unsubstituted, and a substituted ethylene having attached to a doubly bonded carbon atom of the ethylene linkage COOH, COOR, COR, CN, CONH2, CONHR, or aryl or having both ethylenic carbons joined by -O-CO-O- or <FORM:0805664/IV (b)/6> if desired, in presence of a polymerization inhibitor such as hydroquinone, phenthiazine, copper resinate, naphthylamines, and b -naphthol.  In examples: (1) allene is reacted with (a) acrylonitrile to give 3-methylenecyclobutane carbonitrile, (b) methacrylonitrile, to give 1-methyl-3-methylenecyclobutene carbonitrile, (c) a -ethylacrylonitrile to give 1-ethyl-3-methylenecyclobutane carbonitrile, (d) maleic dinitrile, to give 3-methylenecyclobutane-1,2-dicarbonitrile, (e) methyl methacrylate to give methyl 1-methyl-3-methylenecyclobutanecarboxylate, (f) methyl acrylate to give methyl 3-methylenecyclobutanecarboxylate, (g) diethyl fumarate to give diethyl 3-methylenecyclobutane-1,2-dicarboxylate, (h) diethyl itaconate, to give 1-carbethoxy-1-carbethoxymethyl-3-methylenecyclobutane, (i) 1,1-diphenylethylene, to give 1-methylene-3,3-diphenylcyclobutane, (j) styrene, to give 1-methylene-3-phenylcyclobutane, (k) maleic anhydride, to give 3-methylenecyclobutane - 1,2 - dicarboxylic anhydride, (l) indene, to give 1 (or 2)-methylene-1,2,2a,7a-7H-cyclobut[a]indene, of the formula <FORM:0805664/IV (b)/7> Also in examples: (2) 1,1-dimethylallene (i.e. 3-methylbutadiene-1,2 is reacted with acrylonitrile to give 3-methylene-2,2-dimethylcyclobutane carbonitrile and also 3-isopropylidene-cyclobutane - 1 - carbonitrile.  Alternative reactants are listed and other products specified are 3 - methylenecyclobutane carboxylic acid, 1 - methyl - 3 - methylenecyclobutane carboxamide or N-phenylcarboxamide, 1-acetyl-3-methylenecyclobutane, 1,2 - dicarboxy - 1 - carboxymethyl - 3 - methylene cyclobutane.  Specification 652,566, [Group IV (a)], is referred to.