Patent GB-784843-A (GB)
Title: New basic phthalocyanine dyestuffs and a process for their production
IPC: C09B47/12
Filed: 1954-12-21
Abstract: The invention comprises basic phthalocyanine dyestuffs having one to four radicals of formula: <FORM:0784843/IV (b)/1> attached to a phthalocyanine radical, wherein R1 is an hydrogen atom or an alkyl radical, R2 is an acyclic bivalent radical which may contain a further <FORM:0784843/IV (b)/2> group and R3 and R4 are aliphatic radicals or together with the adjacent nitrogen atom form a heterocyclic ring.  The dyestuffs may be prepared by reacting a phthalocyanine dyestuff which contains one to four replaceable halogen atoms (a) with a tertiary amine of formula: <FORM:0784843/IV (b)/3> wherein R1 to R4 have the aforementioned meanings, or (b) with an aliphatic primary or secondary amine containing at least one halogen atom and reacting the halogen compound thus prepared with a secondary amine.  Method (b) may give dyestuffs wherein R1 is an <FORM:0784843/IV (b)/4> group.  Dyestuffs containing carboxylic acid halide, sulphonic acid halide or halogenoalkyl groups may be used as starting materials.  Specified tertiary amines for use in method (a) are 1-amino-2-dimethylamino-ethane, 1-amino-3 - dimethylaminopropane, 1 - diethylamino-3-amino-n-pentane and the amide of methyl-aminoacetic acid and 1-diethylamino-4-amino-n-pentane. Specified halogen-containing amines for use in method (b) are b -chloro-ethylamine, b  : g  - dibromopropylamine, 1 - amino - 4 - chlorobutane and b  : b 1 - dichlorodiethylamine. Specified secondary amines for use in method (b) are dimethyl-, diethyl- and diethanolamines, piperidine, pyrrolidine and pyrroline.  Instead of using phthalocyanine dyestuffs, intermediates containing a replaceable halogen atom, which upon completion of the above reactions are converted into phthalocyanine dyestuffs, may be used. The reaction medium may be an excess of the base employed in the reaction, an inert organic solvent such as benzene or acetone, or water.  Acid-binding agents such as an excess of the base, an alkali metal carbonate, sodium hydroxide or sodium bicarbonate may be present.  Reaction temperatures between 0-100 DEG  C. are specified. The dyestuffs may be used to dye plastics, varnishes, cotton, cellulose materials, wool, polyamides or polyacrylonitrile.  In examples: (1) copper or nickel phthalocyanine is treated with a mixture of chlorosulphonic acid and thionyl chloride to give the corresponding -(3)-di- or tri-sulphochloride which is reacted with 1 - amino - 2 - dimethylamino - ethane, or 1-amino - 3 - dimethylamino - propane, or 1-diethylamino - 4 - amino - n - pentane or the amide of methylaminoacetic acid and 1-diethyl-amino - 4 - amino - n - pentane; (2) copper phthalocyanine-4 : 41-disulphonic acid is treated with a mixture of chlorosulphonic acid and thionyl chloride and the resultant sulphochloride reacted with 1-amino-3-dimethylaminopropane or 1-amino-2-dimethylamino-ethane; (3) as in (2) using 3 : 31-diaza - copper phthalocyanine-4 : 41-disulphonic acid and 1-diethylamino-4-amino-n-pentane; (4) as in (2) using 4 : 41 - diphenyl - copper phthalocyanine-411 : 4111-disulphonic acid and 1-amino-3-dimethylamino-propane; (5) as in (2) using 4 : 41 : 411 : 4111 - tetraphenyl - copper phthalocyanine and 1 - diethylamino - 4 - amino - n-pentane; (6) as in (2) using cobalt phthalocyanine - 4 : 41 : 411 : 4111 - tetrasulphonic acid and 1-amino-3-dimethylamino-propane or 1-diethylamino-4-amino-n-pentane; (7) a copper phthalocyanine containing three or four chloromethyl groups is reacted with 1-diethylamino-4-amino-n-pentane; (8) as in (2) using a copper phthalocyanine obtained from diphenylsuphone-3 : 4-dicarboxylic acid-31-sulphonic acid and 1-amino-2-dimethylamino-ethane; (9) as in (2) using 4 : 41 : 411 : 4111 : 5 : 51 511 : 5111-octaphenyl copper phthalocyanine and 1-amino-2-diethylamino-ethane; (10) copper phthalocyanine - (3) - di - and - tri - sulphochloride is reacted with b -chloroethylamine and the resultant sulphonamide reacted further with dimethylamine or diethylamine or diethanolamine or 1-amino-3-dimethylaminopropane; (11) as in (10) but using 2 : 3-dibromopropylamine and dimethylamine; (12) as in (10) using 4 : 41 : 411 : 4111-copper phthalocyanine - tetra - (p - phenyl - sulphochloride) or -sulphochloride, b -chloroethylamine and dimethylamine.