Patent GB-853479-A (GB)
Title: Photographic processes and azo dye developers for use therein
IPC: C07C215/82
Filed: 1957-01-25
Abstract: Compounds of formula:  <FORM:0853479/IV(b)/1> where R1 is an alkylene group, preferably of not more than 5 carbon atoms and especially ethylene, Z1 is alkyl, preferably lower alkyl, or halogen e.g. chlorine, m is 0, 1 or 2 and Y is a 2, 3-, 2, 5-or 3, 4- dihydroxyphenyl group which may contain alkyl or halogen groups which may be diacylated, the acyl groups being derived from aliphatic monocarboxylic acids, are prepared for use as intermediates in the production of textile and photographic dyes see Groups IV(c) and XX. The compounds and their preparation are described in Group IV(b) Specification 853,482.  The products may be obtained as their salts e.g. hydrobromides.  Specifications 804,971, 804,972 and 853,478 also are referred to.ALSO:The invention comprises dyes of formulae: I [M-N = N-]p Q II[M-N = N-Q1-N = N-]p Q2 <FORM:0853479/IV (c)/1> where M is Y-R1-Ar-(Z1)m or Y-Ar-(Z2)m, R1 is an alkylene group, Ar is an aryl radical, Z1 is alkyl or halogen, Z2 is alkoxy, alkyl or halogen, m is 0, 1 or 2, p is 1 or 2, Y is a 2, 3-, 2, 5- or 3, 4-dihydroxy-phenyl group which may be substituted by alkyl or halogen groups, Q, Q1 and Q2 are coupling component residues, R2 is H or alkyl, n is 0 or 1-5 and X is a benzene nucleus containing hydroxyl and/or amino groups in the #s or p positions with respect to each other and may contain other groups which do not destroy the silver halide developing ability of X.  They are made by diazotising appropriate amines corresponding to the M residues and coupling with the required Q component or by reacting compounds of formula M-N = N-Q-N(H)R2 with a functional derivative of an acid of formula X-(CH2)n COOH. Preferably R1 is CH2CH2, Z1 is a lower alkyl group, Z2 is a lower alkyl or alkoxy group or a halogen atom and R2 is a lower alkyl group.  Components indicated for Q, Q1 and Q2 are phenols, naphthols, anthrols, anilines, naphthylamines, pyrroles, pyrazolones and compounds containing aliphatic or alicyclic methylene groups activated by aldehyde, ester, keto or nitrile groups or compounds containing these groups in conjunction with an amide group. Indicated groups which may be present as substituents in the coupling components are alkyl, sulpho, alkoxy, aryl, aryloxy, amino, keto, alkylamino, arylamino, hydroxyl, cyano, alkylamido, arylamido, carbalkoxy, carboxamido and sulphamido.  Illustrative of specified coupling components are 4-benzyl -1- naphthol, aniline, p-cresol, 1-phenyl -3- acetamido -5- pyrazolone, 4- amino -1- naphthol, 4- sulpho -1- naphthol, 1-hydroxyanthracene, diketo-hydrindene, malononitrile, acetoacetanilide, 1- hydroxy -2-naphthanilide, 4- acetamido -a - naphthylamine, 2- cyanoacetylcoumarone, 1, 5- naphthalene diamine and 4- methoxy -a - naphthylamine.  Preferably the amine from which M is derived is paminophenethylhydroquinone examples of other compounds specified being 4- aminonaphthylethyl-, 2-(p-aminophenethyl) -4- chloro-, 2-(31- methyl -41- aminophenethyl)-, paminophenyl- and 4- amino -3- methylphenyl -1-hydroquinones. The preparation of these intermediates is described in the Group IV(b) Abridgment of Specification 853,482. The M components are used as their acyl, preferably di-acetoxy, derivatives, the free dihydroxy groups being obtained by hydrolysis after dye formation. Diazo components for dyes of formula II are obtained by coupling the above protected hydroquinones with the required Q1 component representative being the O, O1-diacetoxy derivatives of 2, 5- dimethoxy -4- [p-(21, 51- dihydroxyphenethyl)- and -(21, 51- dihydroxyphenyl)-phenylazo]- anilines and 4-[p-(21, 51- dihydroxyphenethyl)- phenylazo] -1- naphthylamine the former two compounds being preferred. Coupling is preferably effected at pH's of less than about 9. With compounds such as 1, 6- dihydroxynaphthalene and 1, 5- diaminonaphthalene two mols of diazo component may be coupled per mol of coupling component.  Preferred dyes of superior colour properties, and which are not pH sensitive, are obtained where coupling is effected in the #s-position to a hydroxyl group of a phenolic, especially naphtholic, coupler and the diazo component contains R1.  Indicated functional derivatives of acids of formula X(CH2)nCOOH are lactones and acid chlorides, e.g. homogentine acid lactone and gentine acid chloride. Preferably hydroxy and/or amino groups in residue X are protected before reaction with the required amine.  Protection may be effected by acylation or reaction with an alkyl chloroformate.  As well as being used as dye developers in photographic compositions (see Group XX) the dyes may be used to dye polyamides such as nylon.  Examples are provided of the preparation of the dyes and their use in photographic compositions and processes. Specifications 804,971, 804,972 and 853,478 also are referred to.