Patent GB-827569-A (GB)
Title: Improvements in the production of tetrazaporphins containing methylene-aryl-sulphonic acid groups
IPC: C09B47/12
Filed: 1957-12-04
Abstract: Arylmethyltetrazaporphins whose aryl radicals contain sulphonic acid groups and unsubstituted or alkylated or acylated hydroxyl or sulphydryl groups are made by reacting at elevated temperature a halogenmethyltetrazaporphin with an hydroxy- or mercapto- and/or aminohydroxyaryl compound whose hydroxyl, sulphydryl and amino groups may be alkylated or acylated and whose aromatic rings may bear further substituents such as halogen atoms, carboxylic acid, carboxylic acid ester, formyl, alkyl, aryl and/or nitro groups, or its sulphonic acid in aqueous sulphuric acid whose specific gravity is greater than 1.6, or in anhydrous sulphuric acid and/or in chlorosulphonic acid.  When sulphonic acids are used they may be in the pure isolated form or in the form of the reaction mixture obtained by sulphonation of the corresponding aromatic compounds. The arylmethyltetrazaporphins obtained may be subsequently sulphonated, alkylated or acylated. Hydroxy-, mercapto- and aminohydroxy-aryl sulphonic acids specified include 1-hydroxy-benzene - 2 -, - 3 - or - 4 - sulphonic acid or - 2 : 4 - disulphonic acid, 1 - methylmercapto-benzene - 4 - sulphonic acid, 2 - hydroxy-naphthalene - 6 - sulphonic acid, 1 - hydroxy-3 - aminobenzene - 6 - sulphonic acid and 1-methoxy - or 1 - ethoxy - benzene - 6 - sulphonic acid.  Non-sulphonated hydroxy-, mercapto- and aminohydroxy-aryl compounds specified include 1-hydroxy-2-, -3- and -4-methylbenzene, 4 - hydroxydiphenyl, 1 : 4 - di-hydroxybenzene, hydroxychlor - and hydroxynitro - benzenes, 1 - hydroxybenzene - 2-carboxylic acid methyl or ethyl ester, thiophenol, 1 - methyl - 2 - amino - 4 - hydroxybenzene, 1 - hydroxy - 2 -, - 4 - or - 8 - amino-naphthalene, anisole, phenetole, phenyl acetate, alpha- or betanaphthylacetate, 1-hydroxy-3 - N : N - dimethylamino - or - 3 - N : N - di-ethylamino - benzene, 1 - ethoxy - 3 - N : N - di-ethylaminobenzene and 1 - hydroxy - 4 - acetyl-aminobenzene. Halogen-methyl tetrazaporphins specified include bis-, tris-, tetrakis-, pentakis-, hexakis-, heptakis-, and octakis-(chlormethyl) phthalocyanines of copper, nickel, cobalt, iron, molybdenum or aluminium or the corresponding metal-free compounds, bis-, tris-or tetrakis-(bromomethyl) copper phthalocyanine, chlormethylphthalocyanines containing phenyl or phenylsulphone groups such as tetrakis - (chlormethyl) - tetraphenyl copper phthalocyanine, chlormethyl-aza- and naphthophthalocyanines, tetrakis - (chlormethyl)-tetrachlor copper phthalocyanine, and chlormethyl derivatives of tetramethyl- or tetraphenyl - dibenzotetraza - porphins, octaphenyl-tetrazaporphins, or tetramethyl - tetraphenyl-tetrazaporphins.  In examples there are reacted (1) bis-(chlormethyl)- or -(brommethyl) copper phthalocyanine with phenol; (2) tetrakis-(chlormethyl) copper phthalocyanine with phenol, the product being alkylated with dimethyl sulphate; (3) tetrakis-(chlormethyl) copper or nickel phthalocyanine or tris-(chlormethyl) iron, aluminium or metal-free phthalocyanine with 2-hydroxynaphthalene sulphonic acid sodium salt; (5) a mixture of tris- and tetrakis-(chlormethyl) copper phthalocyanine or tetrakis-(chlormethyl)-tetraphenyl copper phthalocyanine with a reaction mixture from the sulphonation of phenol, anisole or 1-hydroxy-4-chlor-benzene; (7) tetrakis-(chlormethyl) copper or nickel phthalocyanine, tris-(chlormethyl) iron phthalocyanine or tetrakis-(chlormethyl)-tetraphenyl copper phthalocyanine with 1-hydroxy-2-aminobenzene-4-sulphonic acid; (8) a mixture of tris- and tetrakis-(chlormethyl) copper phthalocyanine or tris-(chlormethyl) cobalt phthalocyanine with 1- or 2-hydroxy-7-amino-naphthalene; (10) bis-(chlormethyl) copper phthalocyanine or its disulphonic acid or bis-(chlormethyl)-diaza copper phthalocyanine with 1 - hydroxy - 2, - 3 - or - 4 - aminobenzene, the product being sulphonated with oleum or by introducing sulphur trioxide or sulphuric acid containing sulphur trioxide into the reaction mixture; (11) a mixture of tris- and tetrakis-(chlormethyl) copper phthalocyanine with 1-amino - 2 - or - 4 - methoxybenzene, and tetrakis - (chlormethyl) - tetrachlor copper phthalocyanine with 1-amino-4-methoxybenzene; in further examples, tetrakis-(chlormethyl) copper phthalocyanine is reacted with (4) 1-hydroxybenzene-2-carboxylic acid or -2-aldehyde; (6) 1- or 2-hydroxynaphthalene or 1,3 - dihydroxybenzene; and (9) 1 - amino-4-ethoxybenzene or methyl phenyl thioether. Specifications 691,905, 713,865, 749,692 and 762,778 are referred to.