Patent GB-1043025-A (GB)
Title: Cyanamido compounds and their preparation
IPC: C07D307/22
Filed: 1965-03-30
Abstract: Compounds containing cyanamido groups are prepared by reacting organic compounds containing at least one carbon-hydrogen bond and free from carbon-carbon unsaturation with cyanogen azide at 25-150 DEG C.  Cyanogen azide is explosive and should be prepared and reacted in a liquid medium, e.g. in situ in aliphatic compound or in a solvent such as acetonitrile, propionitrile, ethyl acetate, amyl acetate, dimethyl formamide, isooctane, tetrachlorethane, carbon tetrachloride, methylene chloride and dibromoethane. Specified organic compounds are cyclopropane, cycloheptane, cyclohexane, cyclooctane, decahydronaphthalene, nitrocyclohexane, chlorocyclohexane, cyclohexane carboxylic acid, cyclohexane carbonitrile, bicyclo [2.2.1]heptane, methane, propane, isooctane, dodecane, nonadecane, octadecane, 2,2,4-trimethylpentane, 1-nitrooctane, 2-chloropropane, t.-butyl chloride, ethyl acetate, octyl acetate, 1,4-dicyanobutane, sebacic acid, butyramide, dioxane, tetrahydrofuran, diethyl ether, ethylene glycol dimethyl ether and methyl ethyl ketone.  The preparation of cyanogen azide from sodium azide and cyanogen chloride in acetonitrile is described and in examples cyanogen azide is reacted with (2) 2,3-dimethylbutane, (3) n-hexane, (4) 2,2-dimethylbutane, (5) methylcyclohexane, (6) cyclopentane, (7) cyclooctane, (8) methylcyclopentane, (9) 1,1-dimethylcyclohexane, mixtures of cyclohexane with (10) cycloheptane, (11) 2,2,3,3-tetramethylbutane, (12) bicyclo[2.2.1]heptane and (13) bicyclo[2.2.2]octane, (22) cyclohexane and (23) adamantine. Cyclohexylcyanamide prepared by (22) is hydrolysed to cyclohexylurea by aqueous sulphuric acid, and 1-cyanamidoadamantine prepared by (23) is hydrolysed to 1-aminoadamantine by refluxing with sodium hydroxide in diethylene glycol.ALSO:Organic polymers containing at least one C-H bond and free from C to C unsaturation are reacted with cyanogen azide at 25 DEG  to 150 DEG  C.  Specified polymers are polyvinyl acetate, polyethylene, polypropylene, polyisobutylene, polystyrene, polymethyl vinyl ketone, polymethyl methacrylate, polymethyl acrylate, polyacrylonitrile, polyvinyl fluoride, polyvinylidene chloride, vinylidene fluoride/hexafluoropropylene copolymer, polyoxymethylenes, copolymers of formaldehyde with ethylene, propylene, ethylene oxide and trifluoroacetaldehyde, hydrogenated natural rubber, polypivalolactone and polymerized lactic and glycolic acids. Cyanogen azide is explosive and should be handled and the reaction effected in liquid media, e.g. acetonitrile, propionitrile, ethyl acetate, amyl acetate, dimethyl formamide, isooctane, tetrachlorethane, methylene chloride and dibromo-ethane.  In examples, (1) polyvinyl fluoride, (14) polyethylene film, (15) polypropylene film, (16) non-woven polypropylene fabric, (17) polyvinyl fluoride film, (18) woven polypivalolactone fabric, (19) polypivalolactone powder, (20) an alkyl capped formaldehyde polymer, and (21) a vinylidene fluoride/hexafluoropropylene copolymer are treated with cyanogen azide in media comprising acetonitrile, ethyl acetate and/or methylene chloride.  The products have improved dyeability.ALSO:The dye affinity of organic polymers containing at least one C-H bond and free from C-C unsaturation is increased by reacting the polymers with cyanogen azide at 25 to 150 DEG C. Cyanogen azide is explosive and should be prepared and reacted in a liquid medium, e.g. aliphatic hydrocarbons or halogenated hydrocarbons, esters, amides or nitriles.  Specified polymers are polyvinyl esters and ketones, polyolefins, polystyrene, polyacrylic and polymethacrylic esters, polyacrylonitrile, vinyl and vinylidene halide polymers, polyoxymethylenes, copolymers of formaldehyde with ethylene, propylene, ethylene oxide and trifluoroacetaldehyde, hydrogenated natural rubber, polypivalolactone and polymerized lactic and glycollic acids.  In examples (14) polyethylene film, (16) non-woven polypropylene fabric and (18) fabrics woven from polypivalolactone fibres are treated with solutions of cyanogen azide and subsequently dyed.