Patent GB-1008636-A (GB)
Title: Basic dyes containing hydrazinium groups
Inventor: ENTSCHEL ROLAND
IPC: C09B1/28
Filed: 1962-04-24
Abstract: The invention comprises basic dyes of formula <FORM:1008636/C4-C5/1> wherein A is the radical of a dye free from carboxylic and sulphonic acid groups, y is a substituted or unsubstituted methylene group or a divalent or trivalent group bound through the methylene group to the adjacent N atom, R1 is an alkyl, cycloalkyl or aralkyl radical which may be substituted or, together with R2 and the adjacent N, a heterocyclic ring system or, together with y and the adjacent N atom, a heterocyclic ring system or, together with y, A and the adjacent N, a heterocyclic ring system, R2 is an alkyl, cycloalkyl or aralkyl radical which may be substituted or, together with R1 and the adjacent N a heterocyclic ring system, R3 is hydrogen or an alkyl radical which may be substituted or a phenyl radical, R4 is hydrogen or an alkyl radical which may be substituted, n is 1 or 2, m is 1 or 2 when n is 1, or 2 when n is 2 and X is an anion equivalent to the dye cation and wherein R1 has a meaning different from methyl when R2 is methyl and R3 and R4 are hydrogen or methyl.  The dyes are prepared by (1) reacting 1 mol of a compound of formula <FORM:1008636/C4-C5/2> wherein E is the acid radical of an ester and B is A or the radical of a compound permitting by azo coupling or by condensation the formation of a dye A, with n mols of a compound of formula <FORM:1008636/C4-C5/3> and converting B into A when necessary; (2) reacting 1 mol of <FORM:1008636/C4-C5/4> with n mols of a compound of formula <FORM:1008636/C4-C5/5> quaternating the product and proceeding as in (1) if appropriate; (3) reacting 1 mol of a compound of formula <FORM:1008636/C4-C5/6> wherein the alkylene chain may be branched and contains 1-3 carbon atoms with n mols of a compound R2-NH-NH-R3 and converting B into A where appropriate (in a first stage of this reaction the hydrogen atom linked to the same nitrogen atom as R2 is condensed with one acid radical E and in a second stage the nitrogen atom is quaternated and linked to y and alkylene to form a ring) and (4) reacting 1 mol of an amine of formula <FORM:1008636/C4-C5/7> with n mols of bromamine or chloramine and converting B into A where appropriate. Process (4) may be modified by using starting materials wherein R2 is hydrogen and quaternating the reaction products.  The dyes are preferably used to dye polyacrylonitrile materials.  In examples the preparation of mono- and dis-azo, nitro, methine, styryl and anthraquinone dyes is described.ALSO:The preparation of hydrazine derivatives used as dyestuff intermediates is described.  In Examples: (4) <FORM:1008636/C2/1> wherein K is a group of formula <FORM:1008636/C2/2> is prepared by treating 1 mol. of bis-(N,N-diethyl-beta-aminoethyl)-aniline with 2 mols. of chloramine; (5) <FORM:1008636/C2/3> is prepared by reacting N-phenyl-N1-hydroxy-ethylpiperazine with chloramine; (6) <FORM:1008636/C2/4> is prepared by condensing N-b -chloroethyl-N-ethyl-metatoluidine with an excess of monoethylhydrazine; (7) <FORM:1008636/C2/5> is prepared by quaternating the compound described in (6) is treated with dimethyl sulphate; (9) <FORM:1008636/C2/6> is prepared by condensing N,N-di-beta-chloroethyl-aniline with monomethyl hydrazine.