Patent GB-840170-A (GB)
Title: Vinyloxyalkylamidonitriles and preparation thereof
IPC: C08F16/28
Filed: 1956-11-21
Abstract: Polymers and copolymers useful in adhesives, coatings and textile finishes, are made from compounds of the formula CH2=CH-O-Z-N(CO-R)-A-CN where A is methylene, ethylene, isopropylene, cyclohexylidene or -CR1R2-, where R1 is C1-C8 alkyl and R2 is H, methyl or ethyl; R is H, C1-C18 alkyl, C6-C10 aryl (including halo-aryl), C1-C4 alkoxy, benzyloxy, or alkoxyalkyl of 1-4 carbon atoms in each part; and Z is C2-C6 alkylene; when R is H the acylated N atom must be flanked by two -CH2- groups in Z and A respectively. The compounds can be polymerized in bulk with boron fluoride etherate.  Copolymers can be made by bulk, solution, aqueous emulsion or suspension procedures, preferably using freeradical catalysts such as azo-isobutyronitrile or dimethyl azo-isobutyrate.  The other component of the copolymer can be an acrylic ester (methyl, ethyl, butyl, 2-ethylhexyl, 3:5:5-trimethylhexyl, dodecyl, ethoxyethyl, butoxyethyl, phenoxyethyl, cyclohexyl or benzyl), an acrylamide, acrylonitrile, a methacrylic ester (methyl, ethyl, propyl, butyl, hexyl, octyl, dodecyl, cetyl, ethoxyethyl, butoxyethyl, cyclohexyl or benzyl), methacrylonitrile, dimethylaminoethyl vinyl ether, styrene or vinyl-pyridine.  Examples are given of the preparation of the following copolymers in bulk using azoisobutyronitrile: (1) N-(b -vinyloxyethyl)-formamido-acetonitrile and methyl methacrylate, which can be cast to a film from ethoxyethyl acetate; (2) a -[N-(b -vinyloxyethyl)-acetamido]-propionitrile and ethyl acrylate; (3) b -[N-(b -vinyloxyethyl) - ethoxycarbonylamino] - propionitrile and acrylonitrile, which can be extruded to fibres and films from dimethylformamide; and p  (4) a  - [N - (b  - vinyloxyethyl) - acetamido]-isovaleronitrile, methyl methacrylate and styrene.ALSO:The invention comprises compounds of the formula CH2=CH.O.Z.N(CO.R).A.CN where A is methylene, ethylene, isopropylene, cyclohexylidene or -CR1R2- where R1 is C1-C8 alkyl and R2 is H, methyl or ethyl; R is H, C1-C18 alkyl, C6-C10 aryl, C1-C4 alkoxy, benzyloxy, or alkoxyalkyl of 1-4 carbon atoms in each part; and Z is C2-C6 alkylene; when R is H the acylated N atom must be flanked by two -CH2- groups in Z and A respectively.  The compounds are made from the amino-nitriles CH2=CH.O.Z.NH.A.CN by reaction with (a) an acyl halide in the presence of a tertiary amine, (b) an alkyl or benzyl chloroformate in the presence of an aqueous inorganic base or a tertiary amine, or (c) an alkyl formate or methoxyacetate in an anhydrous solvent.  Examples are given of the use of amino-nitriles in which A is methylene, ethylene, ethylidene, isopropylidene, isobutylidene and cyclohexylidene, and Z is ethylene, propylene, trimethylene, isobutylene and hexamethylene.  Acylating agents used are methyl formate, acetyl chloride, propionyl chloride, palmitoyl chloride, benzoyl chloride, methyl methoxyacetate and ethyl chloroformate. Further starting materials are mentioned in which A is also propylidene, butylidene, pentylidene, hexylidene, octylidene, nonylidene, diethylmethylene, methyl-isopropyl-methylene, ethylpropyl - methylene, methyl - butyl - methylene and methyl-hexyl-methylene, R is also propyl, butyl, undecyl, tridecyl, heptadecyl, tolyl, 2 : 4-dimethylphenyl, naphthyl, p-chlorophenyl, ethoxymethyl, butoxymethyl, ethoxyethyl and butoxypropyl, and Z is also tetramethylene and trimethyl-trimethylene.  It is stated that when R is phenyl or naphthyl it can be substituted by alkyl, chlorine or bromine, The products react with alcohols to give acetals and with dicyandiamides to produce the acylguanamines of Specification 840,169.  The nitrile group can be reduced to amino, and the catalytic hydrogenation of the vinyl group is mentioned in one case. Amino-nitriles of the formula CH2=CH O.Z.NH.A.CN are prepared by reacting aminoethers CH2=CH.O.Z.NH2 with acrylonitrile, methacrylonitrile, crotononitrile or with a cyanhydrin HO.CR1R2.CN which may be formed in situ from HCN and the appropriate aldehyde or ketone.  Examples are given of the reaction between glycollonitrile, lactonitrile, isobutyraldehyde cyanhydrin, acetone cyanhydrin, cyclohexanone cyanhydrin, methacrylonitrile, crotonitrile and acrylonitrile on the one hand and b -aminoethyl, b -amino-isobutyl, g -aminopropyl and 6-aminohexyl vinyl ethers on the other.  Additional groups are mentioned for A and Z as above.ALSO:Compounds of the formula CH2=CH,O,Z,N (CO,R),A,CN are used as lubricating and softening agents for textiles, expecially cotton and rayon, e.g. in dressings and sizes.  In the formula A is methylene, ethylene, isopropylene, cyclohexylidene or -CR1R2-, where R1 is C1-C8 alkyl and R2 is H, methyl or ethyl; R is H, C1-C18 alkyl, C6-C10 aryl, C1-C4 alkoxy, benzyloxy, or alkoxyalkyl of 1-4 carbon atoms in each part; and Z is C2-C6 alkylene; when R is H the acylated N atom must be flanked by two -CH2- groups in Z and A respectively.  Suitable compounds are mentioned.ALSO:Compounds of the formula <FORM:0840170/III/1> are used as lubricating and softening agents for leather, e.g. in shoe polishes.  In the formula A is methylene, ethylene, isopropylene, cyclohyxylidene or -CR1R2-, where R1 is C1-C8 alkyl and R2 is H, methyl or ethyl; R is H, C1-C18 alkyl, C6-C10 aryl, C1-C4 alkoxy, benzyloxy, or alkoxyalkyl of 1-4 carbon atoms in each part; and Z is C2-C6 alkylene; when R is H the acylated N atom must be flanked by two -CH2- groups in Z and A respectively. Suitable compounds are mentioned, e.g. N - (b  - vinyloxyethyl) - N - (b -cyanoethyl)-palmitamide.ALSO:Fungicidal and insecticidal compositions comprise as active ingredient a compound of the formula CH2 = CH.O.Z.N(CO.R).A.CN where A is methylene, ethylene, isopropylene, cyclohexylidene or -CR1R2-, where R1 is C1-C8 alkyl and R2 is H, methyl or ethyl; R is H, C1-C18 alkyl, C6-C10 aryl, C1-C4 alkoxy, benzyloxy, or alkoxyalkyl of 1-4 carbon atoms in each part; and Z is C2-C6 alkylene; when R is H the acylated N atom must be flanked by two -CH2- groups in Z and A respectively.  As an example N-(b -vinyl-oxyethyl) - formamido - acetonitrile can be used in a spray solvent such as naphtha or a methylated naphthalene.  Other compounds are mentioned.