Patent GB-812957-A (GB)
Title: Monoazo-dyestuffs of the naphthylamine series and process for their manufacture
IPC: C09B62/00
Filed: 1955-07-29
Abstract: The invention comprises dyestuffs of formula R-N = N-R1-X where R is a naphthylamine sulphone or sulphonamide residue bound to the azo link in a position vicinal to the amino group, R1 is the residue of a diazo-component of the benzene series and X is a substituted amino group having a labile substituent, the residue -R1-X containing a sulphonic acid group.  Labile substituents are stated to be exchangeable substituents which easily split off in alkaline media with the taking up of the electron pair of the bond, e.g. a sulphuric or sulphonic acid ester group or a halogen atom.  Preferred are dyestuffs where R is a 2-naphthylamine monosulphonamide residue bound to the azo link in the 1 position and X is an acylated amino group, the acyl residue of which has an aliphatically bound halogen atom and especially dyestuff of formula <FORM:0812957/IV (c)/1> where Q is a sulphonamide group and A an NH2 group or a residue bound to the triazine ring through an O, S or advantageously an N bridge and which contains a SO3H group when R1 does not.  The dyestuffs may be made by coupling a naphthylamine sulphone or sulphonamide in an acid medium with a diazo compound of an amine of formula H2N-R1-X, especially of formula <FORM:0812957/IV (c)/2> where Y is a sulphonic acid group and A is NH2 or a residue of an alkyl-, dialkyl-, aralkyl-, cycloalkyl-, alkaryl- or arylamine bound to the nucleus through the N atom. Coupling components specified are 1-naphthylamine-4- and -5 - sulphonic acid N - methyl - anilide and -5-sulphonic acid methylamide, 2-naphthylamine-6-methyl-, -ethyl-, -p-tolyl- and -phenyl-sulphones, 2 - naphthylamine - 5-, -6-, -7- and -8 - sulphonamides, -3,6- and -5,7 - disulphonamides, 2 - amino - 8 - naphthol - 3,6 - disulphonamide, 2 - amino - 3- and -5-naphthol - 7 - sulphonamides, 2 - methyl-, -b -oxyethyl- and -phenyl - amino- and -amino - 8 - naphthol - 6 - sulphonamides, 2 - amino - 8 - naphthol - 6 - sulphonic acid methyl, ethyl, b -oxyethyl, b -oxypropyl, 31-methoxypropyl, cyclohexyl, phenyl, dimethyl, diethyl, N-methylphenyl, N-ethylphenyl and N-methyl-N-b -oxyethyl amides and the corresponding methyl, chloromethyl and phenyl sulphones. Advantageously the labile substituent is in an acyl residue, e.g. the b -, preferably a -, position of an aliphatic acyl residue or in a heterocyclic compound.  Specified compounds from which the amines H2N-R1-X are derived are b -chloropropionyl, sulphochloracetyl, chloracetyl, chlorethane sulphonyl, chlormethane sulphonyl, ethanesulphonyloxyacetyl and benzene- and p-toluenesulphonyloxyacetyl chlorides, 2,4,6-trichlor-1,3,5-triazine and compounds of formula <FORM:0812957/IV (c)/3> where A is an NH2 group or a residue advantageously containing 12 C atoms at most which is bound directly or through an O, S or N bridge to the triazine nucleus.  Indicated compounds containing at most 12 C atoms and which on reaction with cyanuric halides yield compounds of the above formula are ammonia, aliphatic and aromatic hydroxy-compounds, mercaptans, amines, amides, aminoalcohols, aminoacids and urethanes.  Indicated as diazo components are the condensation products of 1 mol. of 2,4-dichloro-quinazoline with 1 mol. of 2,5-diaminobenzene-1-sulphonic acid, of 1 mol. of 2,4-dichloro-pyrimidine or chloracetyl or chlorpropionyl chloride with 1 mol. of 2,4- or 2,5 - diamino - benzene - 1 - sulphonic acid of 1 mol. of 2,4- or 2,5-diaminobenzene-1-sulphonic acids with 1 mol. of the condensation products of 1 mol. of cyanurine chloride with 1 mol. of methyl, esteryl or butyl alcohol, phenol, o-, m- or p-cresol, 4-sec.-butyl- and -tert.-amylphenol, dialkyl-phenols, p-chlorphenol, thiophenol, ammonia, methyl-, dimethyl-, ethyl-, diethyl-, isopropyl-, butyl-, hexyl-, phenyl-, tolyl-, 4-chlorophenyl-, N-methyl-phenyl- and -cyclohexyl-amines, ethanol-amines, b -oxypropylamine, acetamide, butyramide, urea, thiourea, p-toluenesulphonamide, glycocoll, methyl and ethyl esters of aminocarbonic acid, aminoacetic acid ethyl ester and aminoacetamide, or of 1 mol. of the following diamines: 1,3- or 1,4-diaminobenzene, 4,41-diamino- and 4,41-dimethyl - 3,31 - diamino - diphenylmethane, 4,41-diaminodiphenyl, 4,41- or 2,41 - diamino-or 4,41 - dichloro - 2,21 - diamino - diphenyl ether, 4,41- or 2,21-diamino-diphenyl sulphide, 4,41- or 3,31 - diaminodiphenyl sulphone, 2,5-diaminobenzene-1-methyl or -ethyl sulphone, 2,5 - diamino - 41 - methyl - 1,11 - diphenyl sulphone, 2,5 - diamino - 1,11 - diphenyl sulphone, 2,5 - diaminobenzene - 1 - sulphonamide, -sulphonic acid methyl ethyl-, phenyl-, p-tolyl-, dimethyl-, diethyl-, cyclohexyl- or N-methyl- or -ethyl-anilides with 1 mol. of the condensation product of 1 mol. of cyanuric chloride with 1 mol. of 1- or 2-naphthylamine-4- or -6-sulphonic acid or aniline-3- or -4-sulphonic acid.  The dyestuffs may also be made by condensing, advantageously in the presence of an acid-binding agent in an organic medium or at a lower temperature in an aqueous medium, 1 mol. proportion of a compound of formula R-N = N-R1-Z where R and R1 are as above and Z is an amino group containing at least one reactive H atom with 1 mol. proportion of a reactive halogen-compound which contains, in addition to the halogen atom an exchangeable substituent and, if the initial dyestuff has no sulphonic acid group, a sulphonic acid group.  The starting dyestuffs in the latter modification may be made by coupling one of the above-mentioned coupling components in an acid medium with a diazo-compound which contains an additional substituent convertible to an amino group and effecting such a conversion after the coupling. Diazo components mentioned for this modification are 3- and 4-nitroanilines, 4-nitro-41-amino-diphenyl and monoacyl derivatives of the diamines indicated above and their mono-acyl derivatives.  The dyestuffs dye materials made from leather, silk, wool, superpoly-amides and -urethanes from a weakly alkaline to a weakly acid bath.  Examples and tables are provided illustrating the preparation of the dyestuffs from certain of the above-indicated reactants and their use in dyeing wool and superpolyamides in red shades, coupling components used additional to those already specified are 2-amino-8-naphthol-6-sulphonic acid -21-methyl-, and -ethyl-, -21,51- and -21,61-dimethyl- and -21 - chloro - 61 - methyl - phenylamides, -N -b  - oxyethylanilide, -methylfuryl- and -butylamides and 2-naphthylamine-6-sulphonic acid -N-methyl anilide and additional values for A are propyl-, dodecyl- and 31,41-dichlorophenyl-amino, methyl and phenyl.