Patent GB-1000527-A (GB)
Title: Phthalocyanine fibre reactive dyes and the preparation thereof
IPC: C09B62/036
Filed: 1963-10-25
Abstract: The invention comprises dyes having the general formula <FORM:1000527/C4-C5/1> in which Me is copper, cobalt or nickel, Pc is the phthalocyanine nucleus, R and R1 are hydrogen, C1-C4 alkyl groups, 2-hydroxyethyl, 2-cyanoethyl, benzyl, phenyl, sulphophenyl, carboxyphenyl, or cyclohexyl or -3-N,N-dimethyl-, aminopropyl, or R and R1 together are <FORM:1000527/C4-C5/2> R11 is hydrogen, a C1-C4 alkyl group, 2-hydroxyethyl or 2-cyanoethyl, a is 0-2, b is 1-3, c is 1-3, a + b + c is 3-4, A is a C2 or C3 alkylene radical or a sulphonated, alkylated or halogenated arylene group, B is 2,3 - dichloro-quinoxaline, 2-chloro-quinoxaline, 3-chloro-quinoxaline or 1,4-dichloro-phthalazine group, M (the salt of the sulphonate) is sodium, potassium, ammonium or hydrogen.  The above dyes are made by a 2-stage process in which firstly a metal phthalocyanine polysulphonyl chloride is condensed with a base selected from, ammonia, alkyl monoamines, dialkylmonoamine arylmonoamines, sulphoanilines, carboxyanilines or N-monoalkylanilines, and a diamine R11NH-A-NHR11 in which A and R11 are as above.  A molar excess of the amine and the diamine are used, the reaction conditions being 5-60 DEG  C. in aqueous media at pH 7.5-9. The compound obtained has the formula <FORM:1000527/C4-C5/3> This compound is then condensed at 15-40 DEG  C. in aqueous media at pH 6-8 with 1-2 moles of 2,3 - dichloro - 6 - quinoxalinecarbonyl chloride, or 2 - chloro - 6 - quinonalinecarbonyl chloride, or 3 - chloro - 6 - quinoxalinecarbonyl chloride or 1,4 - dichloro - 6 - phthalazinecarbonyl chloride, which may be added as a powder or in a solution of an organic solvent.  The dyestuff is obtained by salting out.  The diamines used in the first condensation may be obtained by hydrolysis of acetylated amines following the condensation process.  Many examples of amine bases and diamines used in the first condensation process are given.ALSO:1,4-dichloro-6-pathalazinecarbonyl chloride is prepared by reacting trimellitic anhydride with hydrazine hydrate in glacial acetic acid to give 1,4 - dihydroxy - 6 - pethalazine carboxylic acid which is then reacted with phosphorus pentachloride and oxychloride to yield the desired product.  2-chloro-, 3-chloro-, and 2,3-dichloro-6-quinoxaline carboxyl chlorides are prepared from the corresponding hydroxy carboxylic acid by reaction with phosgene in the presence of p-xylene and dimethyl formamide.ALSO:Cellulosic materials are dyed by conventional methods using novel dyes of formula <FORM:1000527/D1-D2/1> in which Me is copper, nickel or cobalt, Pc is the phthaloxyanine nucleus, R is hydrogen, C1-C4 alkyl, 2-hydroxyethyl, 2-cyanoethyl, benzyl, phenyl, sulfophenyl, carboxyphenyl, cyclohexyl, or 3-N, N-dimethylaminopropyl, R1 is the same as R or R and R1 together are -(CH2CH2)2O, R11 is hydrogen, C1-C4 alkyl, 2-hydroxyethyl or 2 cyanoethyl, a is 0-2, b is 1-3, c is 1-3, a + b + c = 3-4, A is a C2-C3 alkylene radical or a sulfonated, alkylated or halogenated arylene group, B is a 2, 3-dichloroquinoxaline or 2-chloroquinone-aline, or 3-chloroquinoxaline or 1, 4, -dichloro-phthalazine group and M (the salt of the sulfonate) is sodium, potassium, ammonium or hydrogen.