Patent GB-880989-A (GB)
Title: Preparation of tetracyanoethylene and chlorotricyanoethylene and derivatives thereof
Filed: 1959-09-07
Abstract: Tetracyanoethylene and/or chlorotricyanoethylene are prepared by reacting a dichlorodicyanoethylene with a metal cyanide such as an alkali metal cyanide or a double metal cyanide in which one of the metals is an alkali metal and the other is a heavy metal. The above reaction may be modified for the preparation of certain tricyanovinyl derivatives (some of which are stated to be dyestuffs) by adding to the reaction mixture a compound or compounds capable of reacting with the tetracyanoethylene or chlorotricyanoethylene as soon as formation takes place.  Such compounds are (1) primary aromatic amines having neither hydrogen nor halogen bonded to the 2- and 6-ring carbon atoms and having hydrogen bonded to the 4-ring carbon atom, these yield 4-tricyanovinyl derivatives; (2) secondary and tertiary aromatic amines in which hydrogen is bonded to the 4-ring carbon, these yield 4-tricyanovinyl derivatives; (3) heterocyclic amines in which the ring is resonance stabilized, contains at least one carbon bonded to hydrogen and has only two bonds of the nitrogen attached to the ring, these yield a -tricyanovinyl derivatives or, less preferentially, b -tricyanovinyl derivatives; (4) primary and secondary aliphatic and cycloaliphatic amines and aralkylamines, these yield N-tricyanovinyl derivatives; (5) primary aromatic amines in which at least one of the 2- or 6-ring carbon atoms is attached to hydrogen or halogen, these yield N-tricyanovinyl derivatives; (6) primary aromatic amines having no hydrogen attached to the 2-, 4- and 6-ring carbon atoms, these yield N-tricyanovinyl derivatives; (7) secondary aromatic amines having no hydrogen attached to the 4-ring carbon atom, these yield N-tricyanovinyl derivatives; (8) heterocyclic secondary amines in which the ring is resonance stabilized, contains no ring carbon atoms attached to hydrogen and has only two bonds of the nitrogen attached to the ring, these yield N-tricyanovinyl derivatives; (9) phenols containing at least one hydrogen bonded to a ring carbon other than meta to the hydroxyl group, these yield para-tricyanovinyl derivatives; (10) azomethines of the type R-CH=X, where R is hydrogen, alkyl, cycloalkyl, aralkyl, aryl or dialkylamino and X is hydroxy, alkoxy, aralkoxy, aryl, amino, ureido, thioureido or guanidino, these yield derivatives in which the tricyanovinyl group replaces the hydrogen atom shown in the formula of the starting material; (11) Azomethines of the type <FORM:0880989/IV (b)/1> wherein n and m are zero or one, R1 and R3 are hydrogen or hydrocarbyl radicals, R2 is hydrogen, alkyl, cycloalkyl, aralkyl, aryl or a heterocyclic radical having an aromatic character (e.g. thienyl, pyrryl, endolyl, furyl, oxazolyl, pyridyl and quinolyl), R4 is a 1,4-arylene or a heterocyclic radical having an aromatic character, R5 is 2,5-furylene or 2,5-pyrrlene, R6 is vinylene and R7 is aryl, hydroxy, alkoxy, carbamyl, thiocarbamyl, amidino or a heterocyclic radical having an aromatic character, these yield derivatives in which the tricyanovinyl group replaces the hydrogen atoms shown attached to R4 and R5, respectively; (12) 1-acyl-2-aryl-hydrazines in which the aryl radical has a hydrogen atom in the 4-ring position, these yield derivatives in which the tricyanovinyl group replaces the hydrogen atom in the said 4-position; (13) Vinyl amines such as Fischer's base (2-methylene-1,3,3-trimethylindoline), these yield derivatives in which the tricyanovinyl group replaces a hydrogen atom on a vinyl carbon atom not attached to a nitrogen atom; and (14) aminoarylolefins such as 1,1-bis(para-dimethylaminophenyl)-ethylene, these yield derivatives in which the tricyanovinyl group replaces a hydrogen atom or one of the carbon atoms of the ethylene group.  The tetracyanoethylene product may be isolated by conversion to the corresponding 1,1,2,2-tetracyanoethanesulphonic acid or salt thereof by reaction with an aqueous sulphite or bisulphite solution.  The tetracyanoethylene may be regenerated by oxidation of the sulphonic acid with an oxidant of a strength sufficient to oxidise sulphite to sulphate.  The tetracyanoethylene also yields coloured p  complexes with benzene, xylene, anisole and anthracene.  The latter complex deposits crystals of the Diels-Alder adduct of tetracyanoethylene and anthracene on standing.  Reference has been directed by the Comptroller to Specifications 755,702, 757,773 and 767,423.ALSO:Tetracyanoethylene and/or chlorotricyanoethylene are prepared by reacting a dichlorodicyanoethylene with a metal cyanide such as an alkali metal cyanide or a double metal cyanide in which one of the metals is an alkali metal and the other is a heavy metal. The above reaction may be modified for the preparation of certain tricyanovinyl derivatives (some of which are stated to be dyestuffs) by adding to the reaction mixture a compound or compounds capable of reacting with the tetracyanoethylene or chlorotricyanoethylene as soon as formation takes place.  Such compounds are (1) primary aromatic amines having neither hydrogen nor halogen bonded to the 2- and 6-ring carbon atoms and having hydrogen bonded to the 4-ring carbon atom, these yield 4-tricyanovinyl derivatives; (2) secondary and tertiary aromatic amines in which hydrogen is bonded to the 4-ring carbon, these yield 4-tricyanovinyl derivatives; (3) heterocyclic amines in which the ring is resonance stabilised, contains at least one carbon bonded to hydrogen and has only two bonds of the nitrogen attached to the ring, these yield a -tricyanovinyl derivatives or, less preferentially, b -tricyanovinyl derivatives; (4) primary and secondary aliphatic and cycloaliphatic amines and aralkylamines, these yield N-tricyanovinyl derivatives; (5) primary aromatic amines in which at least one of the 2- or 6-ring carbon atoms is attached to hydrogen or halogen, these yield N-tricyanovinyl derivatives; (6) primary aromatic amines having no hydrogen attached to the 2-, 4- and 6-ring carbon atoms, these yield N-tricyanovinyl derivatives; (7) secondary aromatic amines having having no hydrogen attached to the 4-ring carbon atom, these yield N-tricyanovinyl derivatives; (8) heterocyclic secondary amines in which the ring is resonance stabilized, contains no ring carbon atoms attached to hydrogen and has only two bonds of the nitrogen attached to the ring, these yield N-tricyanovinyl derivatives; (9) phenols containing at least one hydrogen bonded to a ring carbon other than meta to the hydroxyl group, these yield para-tricyanovinyl derivatives; (10) azomethines of the type R-CH=X, where R is hydrogen, alkyl, cycloalkyl, aralkyl, aryl or dialkylamino and X is hydroxy, alkoxy, aralkoxy, aryl, amino, ureido, thioureido or guanidino, these yield derivatives in which the tricyanovinyl group replaces the hydrogen atom shown in the formula of the starting material; (11) Azamethines of the type <FORM:0880989/IV (c)/1> and <FORM:0880989/IV (c)/2> wherein n and m are zero or one, R1 and R3 are hydrogen or hydrocarbyl radicals, R2 is hydrogen, alkyl, cycloalkyl, aralkyl, aryl or a heterocyclic radical having an aromatic character (e.g. thienyl, pyrryl, endolyl, furyl, oxazolyl, pyridyl and quinolyl), R4 is a 1,4-arylene or a heterocyclic radical having an aromatic character, R5 is 2,5-furylene or 2,5-pyrrylene, R6 is vinylene and R7 is aryl, hydroxy, alkoxy, carbamyl, thiocarbamyl, amidino or a heterocyclic radical having an aromatic character, these yield derivatives in which the tricyanovinyl group replaces the hydrogen atoms shown attached to R4 and R5 respectively; (12) 1-acyl-2-arylhydrazines in which the aryl radical has a hydrogen atom in the 4-ring position, these yield derivatives in which the tricyanovinyl group replaces the hydrogen atom in the said 4-position; (13) Vinyl amines such as Fischer's base (2-methylene-1,3,3-trimethylindoline), these yield derivatives in which the tricyanovinyl group replaces a hydrogen atom on a vinyl carbon atom not attached to a nitrogen atom; and (14) aminoaryl olefins such as 1,1-bis (para-dimethylaminophenyl)-ethylene, these yield derivatives in which the tricyanovinyl group replaces a hydrogen atom on one of the carbon atoms of the ethylene group. The tetracyanoethylene product may be isolated by conversion to the corresponding 1,1,2,2-tetracyanoethanesulphonic acid or salt thereof by reaction with an aqueous sulphite or bisulphite solution.  The tetracyanoethylene may be regenerated by oxidation of the sulphonic acid with an oxidant of a strength sufficient to oxidise sulphite to sulphate.  The tetracyanoethylene also yields coloured complexes with benzene, xylene, anisole and anthracene. The latter complex deposits crystals of the Diels-Alder adduct of tetracyanoethylene and anthracene on standing.  Reference has been directed by the Comptroller to Specifications 755,702, 757,773 and 767,423.