Patent GB-985982-A (GB)
Title: Improvements in or relating to water-soluble disazo dyestuffs bearing one or two heterocyclic reactive groups
Inventor: UEHLINGER HANSPETER
IPC: C09B62/012
Filed: 1961-03-03
Abstract: The invention comprises disazo dyes of formula <FORM:0985982/C4-C5/1> and their chromium and cobalt complexes, where R1 is a benzene, diphenyl or naphthalene residue, R2 is a benzene or naphthalene residue, coupled twice, in each case in ortho position to a hydroxy or amino group, which latter may be monosubstituted, X is a metallizable substituent, one y is H or a group comprising a triazine or pyrimidine nucleus containing at least one radicle of formula <FORM:0985982/C4-C5/2> where Hal is Cl or B2, and the other y is a group comprising a triazine or pyrimidine nucleus containing at least one radicle of formula <FORM:0985982/C4-C5/3> where Hal is Cl or Br, and where R1 and R2 and the nucleus A together contain the number of solubilizing groups required for water solubility of the dye and further substituents if desired.  The dyes, and their chromium and cobalt complexes, may be made by coupling in either order, 1 mol. of an appropriate diazo compound corresponding to R1, and 1 mol. of an appropriate benzenic diazo compound corresponding to A, with 1 mol. of a coupling component corresponding to R2, to form a disazo dye which must contain in at least one of the radicles of the diazo component at least one reactive triazine or pyrimidyl group introduced before, during or after the coupling and bearing at least one <FORM:0985982/C4-C5/4> radicle, plus at least the required number of water-solubilizing groups, and which may be treated with a metallizing agent during, or after, its formation.  In a modification of the above process 1 mol. of a diazo compound of an amine of formula y1-R1-NH2 where y1 is H, OH or SH, a substituent convertible into an amino group, which may be monosubstituted, or a reactive triazinyl or pyrimidyl group combined directly or through -O-, -S-, -NH- or -N- (possibly substituted alkyl)- and which contains at least one <FORM:0985982/C4-C5/5> radicle may be coupled with 1 mol. of a compound of formula <FORM:0985982/C4-C5/6> or a chromium or cobalt complex thereof, where y2 has any of the values of y, except that both of them cannot be H and the dye thus obtained is treated when y1 and/or y2 are OH or SH or a substituent which may be converted into an amino group, which may be monosubstituted, if necessary after conversion of the substituent, or substituents, with an amino group, with an appropriate reactive triazinyl or pyrimidyl compound and, if desired, metallizing the disazo dye during or after its formation. Also, 1 mol. of a diazo compound of an amine of formula <FORM:0985982/C4-C5/7> may be coupled with 1 mol. of a compound of formula y1-R1-N=N-R2-H with subsequent procedure as above.  1,2-metal complexes are obtained.  Indicated substituents are sulpho, alkylsulphonylamino, which may be substituted on the N atom, e.g. diethylamide, 3 - hydroxypropylamide, 3 - methoxybutylamide, 2-methyl-, methoxy- or chloro-phenylamide, N-methyl-N-phenylamide, benzylamide or cyclohexylamide, halogen, alkyl, alkoxy, nitro or acrylamino groups.  Indicated compounds which contain at least two radicles of formula <FORM:0985982/C4-C5/8> include triazines, e.g. tetrameric chloro- or bromo-cyano (see Specification 943,264), cyanuric chloride, primary condensation products of a compound of formula <FORM:0985982/C4-C5/9> where Hal is Cl or Br and 2 is the radicle of a primary or secondary aliphatic, alicyclic, aromatic or heterocyclic amine, preferably aniline and its alkyl, sulpho and carboxy derivatives, of a low molecular mono- or dialkylamine or ammonia, 2,4,6-tri-chloro- and -bromo-pyrimidines and their derivatives containing in the 5 position, e.g. a methyl, carboxylic acid amide, sulphonamide, which may be substituted on the N atom, carboethoxy, benzoyl, alkyl, chlorovinyl, carboxymethyl or a bromomethyl group, 2,4,5,6-tetrachloropyrimidine, 2,6 - dibromopyrimidine - 4 - carboxylic acid ethyl ester, 2,5,6-trichloto-4-methylpyrimidine, 2,6 - dichloro - 4 - trichloromethylpyrimidine and a radicle containing a methylene group between two pyrimidine nuclei.  The dyes and their metal complexes colour wool, silk, leather, synthetic polyamide fibres and fibres of natural or regenerated cellulose in brown shades. Dyeings may be after-chromed on the fibre.  Numerous examples are provided of the preparation of the dyes and their complexes and the use of the latter in printing cotton and viscose, specified reactants being selected from those indicated above, the values for R2 being derived from compounds which include 1,3-dihydroxybenzene, 1,3-dihydroxy- and -diamino-4-chloro- and -methyl-benzenes, 1-amino-3-phenol, 2-amino- and phenylamino-5-naphthol-7-sulphonic acids and 1-amino-8-naphthol-3,6-disulphonic acid.  Reference has been directed by the Comptroller to Specifications 797,946, 904,581, 904,582, 913,767, 916,094, 922,526, 954,427 and 958,026.ALSO:Heterocyclic diazo dyes of formula <FORM:0985982/D1-D2/1> and their chromium and cobalt complexes, where R1 is a benzene, diphenyl or naphthalene residue, R2 is a benzene or napthalene residue, coupled twice, in each case in ortho position to a hydroxy or amino group, which latter may be monosubstituted, X is a metallizable substituent, one y is H or a group comprising a triazine or pyrimidine nucleus containing at least one <FORM:0985982/D1-D2/2> Hal radicle, where Hal is Cl or Br, and the other y is a group comprising a triazine or pyrimidine nucleus containing at least one <FORM:0985982/D1-D2/3> Hal radicle, where Hal is Cl or Br, and where R1 and R2 and nucleus A together contain the number of solubilizing groups required for water-solubility of the dye, and further substituents if desired, are used in printing compositions for wool, silk, leather, synthetic polyamide fibres and fibres of natural and regenerated cellulose. Brown shades are obtained.  The metalfree dyes may be chromed on the fibre.  In examples, which illustrate the printing of cotton and viscose, the parts contain conventional ingredients such as urea, sodium alginate, sodium 1-nitro-benzene-3-sulphonate and sodium carbonate and the dyes are 1, 2-metal complexes.  The preparation of the dyes and reactants used are in Division C4.  Reference has been directed by the Comptroller to Specifications 797,946, 904,581, 904,582, 913,767, 916,094, 922,526, 954,427 and 958,926.