Patent GB-713865-A (GB)
Title: Improvements in the production of dyestuffs of the phthalocyanine series
IPC: C09B47/08
Filed: 1951-11-30
Abstract: Dyestuffs of the phthalocyanine series are obtained by reacting at elevated temperatures salts of phthalocyanines containing mercapto groups with salts of halogencarboxylic or organic halogensulphonic acids or their functional derivatives or by reacting at elevated temperatures halogenphthalocyanines, particularly halogenmethyl phthalocyanines, with organic mercapto compounds containing carboxylic or sulphonic acid groups or their salts or functional derivatives, and if desired converting the resulting products by known methods into their ternary sulphonium salts.  Suitable phthalocyanines containing mercapto groups include di-, tri-, or tetra-mercapto-copper phthalocyanine, mono-, di- or tri-mercapto-cobalt- or iron-phthalocyanine, di-, tri-, tetra-, or penta-(mercaptomethyl)-copper phthalocyanine mono-, di-, or tri-(mercaptomethyl)-cobalt- or nickel-phthalocyanine or the metal free di- or tri-(mercaptomethyl)-phthalocyanines.  Specified halogencarboxylic and halogen sulphuric acid are chloracetic acid, monoacetic acid, alpha or betachloropropionic acid, alpha- or gamma bromobutyric acid omega chlorvaleric acid, chlor-ethane sulphonic acids chlorbenzoic acids or chlorbenzene sulphonic acids, or the amides, esters or nitriles corresponding to the said acids, e.g. chloracetic acid methyl or ethyl ester, chloracetamide, chloracetonitrile or omega-chlorvaleronitrile. These carboxylic or sulphonic acids may contain in addition to the halogens, any other non-reactive substituents e.g. hydroxy or nitro groups.  Suitable compounds of this type are 4-chlor-5-nitrobenzene sulphonic acid, 5-chlor-2-nitrobenzoic acid, 2-nitro-5-chlorbenzene-sulphonic acid, chlorolactic acid, or alpha-halogen-gamma-hydroxybutyric acids or their internal esters such as alpha-chlor-or-brom -gamma-butyrolactone.  Specified halogenated phthalocyanines are tetra bromo copper or tetrabromo cobalt phthalocyanine, chloromethylated or bromomethylated phthalocyanines such as mono-, di-, tri-, terra- or penta-chloro or mono-methylphthalocyanines of copper, cobalt, iron, nickel, aluminium, and other metals or the corresponding halogenated metal-free phthalocyanines.  Specified mercapto-carboxylic and mercapto sulphonic acids are thioglycollic, thiolactic, beta-mercapto propionic, alpha- or gamma-mercaptobutyric, alpha-mercapto-isobutyric or isovaleric, thiosalicyclic, 3- or 4-mercaptobenzoic, 2-mercaptotoluic, 6-mercapto-oxylic, 2- or 8- mercaptonaphthalene carboxylic 4-mercaptophthalic, alpha-mercaptophenyl acetic, and thiophenol-, thiocresol and thio-naphthol sulphonic acids, and their esters, amides or nitriles, e.g. thioglycollic acid methyl or ethyl ester, thiosalicyclic acid methyl or phenyl ester, thioglycollic acid amide, or the thiolactones derived from mercapto-carboxylic acid such as gamma-thiobutyrolactone, gamma- or delta-thiovalerolactone.  These compounds may contain besides the mercapto group still further non-reactive substituents e.g. non-diazotisable amino groups as in the case of cystein or methylaminothiophenol sulphonic acids, or halogens, as in the case of 5- or 4-bromo-3-mercaptobenzoic acid. The mercapto compounds are preferably used in the form of their salts e.g. their alkali metal salts.  If thiolactones are used they must be converted into the alkali metal salts of the corresponding mercapto acids. Water, alcohols, glycols, glycol semi-ethers, dioxane, or mixtures thereof may be employed as solvents or diluents.  The reaction temperature is generally from 30 to 200 DEG C and preferably 70-110 DEG C, and the reaction is preferably effected in the absence of oxidizing agents e.g. in the presence of nitrogen.  The dyestuffs obtained are phthalocyanine or phthalocyaninemethylene thiocarboxylic or thiosulphcyanine or phthalocyaninemethylene thiosulphonic acids which are soluble in water in the form of their alkali, ammonium, or amine salts.  When functional derivatives of the halogen carboxylic or halogen sulphonic acids are used water-insoluble dyestuffs are usually obtained which can be converted to a water soluble form by alkaline saponification or by conversion into their ternary sulphonium salts by treatment with alkylating agents such as sulphuric or sulphonic acid esters.  The dyestuffs when water-soluble are often suitable for printing textiles and the water-insoluble dyestuffs can in many cases be used as vat dyestuffs.  The free carboxylic or sulphonic acids can often be converted into pigment dyestuffs with heavy metal salts or basic dyestuffs.  Examples are given for the production of dyes from the following reactants: (1) the sodium salts of a mixture of metal-free di-and tri-(mercaptomethyl)-phtholocyanine and sodium dichlorate; (2) an alkaline solution of the sodium salt of di-(mercaptomethyl)-cobalt-phthalocyanine (obtained by heating di-(chlormethyl)-cobalt-phthalocyanine with thiourea and a little water, leading nitrogen over the reaction mixture, and adding an aqueous solution of sodium hydroxide) and chloracetic acid; a similar result is obtained from the corresponding iron phthalocyanine; (3) chloracetic acid and an alkaline solution of the sodium salts of a mixture of di- and tri-mercapto-copper-phthalocyanine obtained by heating a mixture of a copper phthalocyanine polysulphide (formed by reduction of a mixture of copper phthalocyanine di- and trisulphochlorides with iron and hydrochloric acid) with caustic soda solution and an aqueous solution of sodium sulphide; (4) chloracetic acid methyl ester and the mixture obtained by adding caustic soda solution to the addition product of tetra-(chlormethyl)-copper-phthalocyanine and thiourea in the presence of water, leading in nitrogen, heating, and then adding hydrochloric acid and ethyl alcohol; the dyestuff is rendered water-soluble by heating with diethyl sulphate; (5) 3-nitro-4-chlorobenzene-1-sulphonic acid and an alkali solution of di-(mercaptomethyl)-cobalt-phthalocyanine; (6) omega-chlorvaleronitrile and the product obtained by heating the addition product of trichlor-copper phthalocyanine and thiourea with aqueous sodium hydoxide solution while leading nitrogen through the mixture; the dyestuff product is made water-soluble by heating with diethyl sulphate; (7) potassium 5-chlor-2-nitrobenzoate and the potassium salt of dimercapto-copper-phthalocyanine; (8) alpha-bromobutyrolactone and a solution of the sodium salt of di-(mercaptomethyl) -cobalt phthalocyanine obtained by adding a solution of sodium hydroxide to di-(chlormethyl)-cobalt-phthalocyanine which has been converted to the corresponding thiourea derivative by heating with concentrated aqueous thiourea solution, and heating in an atmosphere of nitrogen; the corresponding iron or copper phthalocyanines may also be used; (9) di-(chlormethyl)-cobalt phthalocyanine and the disodium salt of thioglycollic acid; (10) thioglycollic acid (dissolved in an alcoholic solution of osdium ethylate) and a mixture of metal free di- and tri-chlormethyl)-phthalocyanine; (11) tetrabromo copper phthalocyanine and the disodium salt of gamma-mercaptobutyric acid; (12) tera-(chlormethyl)-copper-phthalocyanine and gamma-thiobutyrolactone, the latter being first introduced into a solution of sodium hydroxide in methanol under an atmosphere of nitrogen; (13) tri-(chlormethyl)-copper phthalocyanine and thioglycollic acid methyl ester, the dyestuff obtained being rendered water-soluble by heating with dimethyl sulphate; thioglycollic acid amide may be used instead of thioglycollic acid methyl ester; (14) a mixture of di- and tri-(chlormethyl)-cobalt phthalocyanine and the dipotassium salt of 2-amino-methoxy-thiophenol sulphonic acid mixture obtained by sulphonation of 2-amino-5-methoxy-benzthiazole with oleum followed by heating with a solution of potassium hydroxide in ethyl alcohol; (15) the dipotassium salt of thiosalicylic acid and di-(chlormethyl)-cobalt phthalocyanine; the corresponding iron phthalocyanine may also be used; (16) tri-(chlormethyl)-copper phthalocyanine and the disodium salt of thioglycollic acid, the product may be heated with diethyl sulphate; corresponding barium salt may also be used; (17) tetra-(mercaptomethyl)-copper phthalocyanine (dissolved in caustic soda solution) and the ester of chloracetic acid and gamma-ethyl hexanol; (18) di-(chlormethyl)-cobalt phthalocyanine and gamma-thiobutyrolactone the latter being first dissolved in a solution of sodium hydroxide in ethanol while leading nitrogen through the solution.