Title of Invention	A PROCESS FOR THE PRODUCTION OF TRIAZO DYES
Abstract	ABSTRACT 666/MAS/97 "A process for the production of triazo dyes" This invention relates to a process for the production of triazo dyes. Ortho aminophenol of formula II is diazotized and coupled with meta-dihydroxy benzene or metal aminophenol. The mono azo compound obtained which is coupled with a diazonium salt of formula V to get the trisazo compound.

Full Text

The present invention relates to a process for production of trisazo dyes of the general formula I where R1 is hydrogen, C1-C4-alkyl, halogen, nitro, hydroxysulfonyl, sulfamoyl, mono- or di-C1~C4-alkylsulfamoyl, C1-C4-alkylsulfonyl or C1-C4-alkoxysulfonyl, R2 is hydrogen, halogen, nitro or hydroxysulfonyl, at least one of R1 and R2 being nitro, R3 and R4 are each independently of the other hydroxyl or amino, R5 is hydrogen, C1-C^alkyl, hydroxysulfonyl, sulfamoyl, mono- or di-C1-C^-alkylsulfamoyl, C1-C4-alkylsulfonyl, C1-C4-alkoxysulfonyl or carboxyl, R6 is hydrogen or C1-C4-alkyl, R7 is hydrogen, C1-C4-alkyl, hydroxysulfonyl, sulfa.ir.oyl, mono- or di-C1-C4-alkylsulfamoyl, C1-C4-alkylsulfonyl, C1-C4-alkoxysulfonyl, S02N{CH2COOH)2 or carboxyl, R8 is hydrogen, C1-C4-alkyl, hydroxyl, C1-C4-alkoxy, halogen or nitro, with the proviso that at least one of R5 and R7 is COOH or S03H and when R5 or R7 is S03H the other is COOH, or R3 and/or R4 are each amino or R1 is hydrogen or RG is alkyl, in free form or as transition metal complexes, and to their use for dyeing leather, textile fibers and paper. Acid trisazo dyes which produce brown hues are well known and are used for example for dyeing leather, textiles and paper (see for example DE-A-22 38 159, US-2 259 734 and WO 81/03179). The dyes were used either in free form or in the form of metal complexes, especially as copper complexes. 3owever, the known dyes leave something to be desired as regards their lightfastness, washfastness and perspiration fastness and their dyeing behavior, for example as regards the degree of Liquor exhaustion. [t is an object of the present invention to provide novel trisazo Jyes which are superior to the known dyes as regards Lightfastness, washfastness and perspiration fastness and/or Syeing behavior. ■to have found-that this object is achieved by the trisazo dyes of :he general formula I mentioned at the beginning. Suitable R1, R5, R6, R7 and R8 include for example the Ci-C4-alkyl radicals methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl and tert-butyl. Methyl is preferred. Suitable Rl, R5 and R7 include for example mono- or ii-Ci-Ca-alkylsulfamoyl radicals, Ci-C4-alkylsulfonyl radicals and :i-C4-alkoxysulfonyl radicals with the alkyl radicals mentioned. Suitable R8 includes for example Ci-C4-alkoxy radicals with the ilkyl groups mentioned. suitable R1, R2 and R8 include the halogens fluorine, chlorine, iromine and iodine, preferably chlorine and bromine. 'referred R1 and R2 are hydrogen, hydroxysulfonyl and nitro, in particular hydrogen and nitro, at least one of the radicals R1 or l2, preferably both, being nitro. R1 and R2 are each preferably lisposed meta to the diazo group. I3 and R4 are preferably identical. The diazo groups coupled to :he same phenyl ring are both preferably disposed ortho to them, resulting in a 1,2,4,5-substituted phenyl ring. Preferred R5 is COOH, SO3H, methyl and hydrogen, of which carboxyl is particularly preferred. Preferred R6 is hydrogen and methyl. Hydrogen is the preferred R6 in combination with COOB, SO3H or hydrogen as R5. R6 is preferably nethyl when R5 is methyl too. Preferred R7 is SO3B and COOH. Particularly preferred dyes are those in which either R5 or R7 is carboxyl. Preferred R8 is hydrogen, methyl and hydroxyl. Che trisazo dyes of the present invention can be used in the free Eorm or in the form of their metal salts. Suitable transition metals for complexing with the trisa2o dyes ire in particular the elements of subgroups 6, 7 and 8 of the periodic table and also copper, especially chromium, iron, ;obalt, nickel and copper, and iron complexes are particularly preferred. Particular preference is given to the iron complexes of the Eollowing trisazo dyes, which are obtained by reacting one mol equivalent of dye with 0.5 to 2 mol equivalents of iron salt: Preference is given to iron complexes of the dyes Ia-d with a 1:1 stoichiometry and to the iron complexes of the dyes la and b with a 2:1 stoichiometry of the starting materials (iron salt/dye). Suitable iron salts are water-soluble iron(II) salts such as iron(II) chloride, iron(II) sulfate, iron(II) carbonate and iron(II) acetate and preferably iron(lll) salts such as iron(III) sulfate, iron(IH) chlorate, iron(III) nitrate and especially iron(III) chloride. The dyes of the formula I can be prepared in a conventional manner, for example by diazotizing an aminophenol of the general formula II where R3 and R4 are each as defined above. The resulting monoazo compound IV where R5, R6, R7 and RB are each as defined above, to obtain the dyes of the general formula I. The aminoazo compounds V are obtained for example by reacting the diazonium salt of an amine VI and subsequent hydrolysis of the resulting monoazo compound to the aminoazc ** " The order of the coupling reactions can also be changed. The optionally subsequent metallization of the trisazo dye is effected by known methods. The dyes of the present invention are notable for high lightfastness, good washfastness and perspiration fastness properties, especially with respect to discolorations of cotton fabrics, and good dyeing properties, for example good liquor exhaustion, in the case of leather dyeings. The dyes are particularly suitable for dyeing leather, textile fibers and paper. Any kind of leather can be dyed, such as grain and sueds leather, chrome leather, retanned leather or velour leather from goat, sheep, cow and pig. Of the textile fibers, cotton, wool and pofyamide fibers are particularly suitable. Accordingly, the present invention provides a process for production of trisazo dyes of the general formula I where R1 is hydrogen, C]-C4-alkyl, halogen, nitro, hydroxysulfonyl, sultamoyl, mono-or di-C,-C4-allcylsuIfamoyl, Ci-C4-alkylsulfonyl or CrC4-alkoxysulfonyl, R2 is hydrogen, halogen, nitro or hydroxysulfonyl, at least one of R and R2 being nitro, R3 and R4 are each independently of the other hydroxyl or amino, R5 is hydrogen, C1-C14alkyl, hydroxysulfonyl, sulfamoyl, mono-or di-C1-C4-alkylsulfamoyl, C1-C4-alkylsulfonyl, C1-C4- alkoxysulfonyi or carboxyl, R is hydrogen or C|-C4-alkyl, R is hydrogen, hydroxysulfonyl, sulfamoyl, mono-or di-Ci-C4- alkyl sulfamoyl, Ci-C4-alkylsulfonyl, Ci-C4-alkoxysulfonyl, SOzN(CH2COOH)2 or carboxyl, R is hydrogen, hydroxy, CrC4-alkoxy, halogen or nitro, comprising the following steps, a. diazotizing an ortho-aminophenol of the general formula II, Examples Example 1 Preparation of the trisazo dye a) 25 g (0.182 mol) of sodium formaldehyde bisulfite were dissolved in 6 ml of water at 50°C. 14.3 g (0.104 mol) of anthranilic acid were added to the solution. The mixture was stirred at 95°C for 4 hours. 17.3 g (0.1 mol) of sulfanilic acid first diazotized in a conventional manner were then added at 25°C while the pH was held at 6.0 with sodium bicarbonate. The mixture was subsequently stirred at 0 - 5°C for 3 hours. 25 ml of 501 strength by weight sodium hydroxide were then added, and the mixture was heated at 90 °C for 4 hours. After cooling to 20°C, the pH was adjusted to 4.0 with hydrochloric acid, the suspension was subsequently stirred for 2 hours, and the product was filtered off with suction. b) 22.1 g (0.1 mol) of sodium picramate were diazotized in a conventional manner and coupled with 10.4 g (0.095 mol) of resorcinol at pH 9.0. The diazonium salt of 32.1 g (0.1 mol) of the product of a) was added to the suspension at pH 8-9. s After the coupling had ended, the pH was adjusted to 6.0 with dilute hydrochloric acid. 16.1 g (0.1 mol) of anhydrous iron(III) chloride were then added at 60°C, and the mixture was stirred at pH 4.0 for 1 hour. The precipitated trisazo dye was filtered off with suction and dried at 60°C, giving 136g of an NaCl- comprising solid. Iron complexes of the dyes listed in the following table taking x mol equivalent of iron and y mol equivalents of dye as the starting point were prepared in a similar manner: x:y i WE CLAIM: 1. A process for production of trisazo dyes of the general formula I where R1 is hydrogen, Q-C4-alkyl, halogen, nitro, hydroxysulfonyl, sultamoyl, raono-or di-C1-C4-alkylsulfamoyl, C]-C4-alkylsulfonyl or C|-C4-alkoxysulfonyl, R2 is hydrogen, halogen, nitro or hydroxysulfonyl, at least one of R1 and R2 being nitro, R3 and R4 are each independently of the other hydroxyl or amino, R3 is hydrogen, C1-C4-alkyl, hydroxysulfonyl, sulfamoyl, mono-or di-C1 -C4-alkylsulfamoyl, C1 -C4-alkylsulfonyl, C 10 -C4- alkoxysulfonyl or carboxyl, R is hydrogen or C]-C4-alkyl, R7 is hydrogen, hydroxysulfonyl, sulfamoyl, mono-or di-C1-C4- alkylsulfamoyl, C1-C4-alkylsulfonyI, C1-C4-alkoxysulfonyl, S02N(CH2COOH)2 or carboxyl, R8 is hydrogen, hydroxy, d-C4-alkoxy, halogen or nitro, comprising the following steps, a. diazotizing an ortho-aminophenol of the general formula II, d. coupling the diazonium salt of V with the monoazo compound IV to get the resulting trisazo dye of the general formula I 2. The process as claimed in claim 1, wherein the amino component of the gereral formula V is prepared by a process comprising the following steps e. diazotizing an amine of the general formula VI f. coupling the diazonium salt of VI with a compound VII to get the resulting amino component of the general formula V. 3. The process as claimed in claim 1, wherein in the compounds of general formulae I and II, R1 is nitro and R2 is nitro or hydrogen. 4. The process as claimed in claim 1, wherein in the compounds of general formulae I, V and VII, R5 is COOH, S03H, methyl or hydrogen. 5. The process as claimed in claim 1, wherein in the compounds of the general formulae I, V and VII, R6 is hydrogen or methyl. 6. The process as claimed in claim 1, wherein in the compounds of the general formulae I, V and VI, R7 is S03H or COOH. 7. The process as claimed in claim 1, wherein in the compounds of the general formulae I, V and VII, R6 or R7 is COOH. 8. The process as claimed in claim 1, wherein in the compounds of the general formulae I, V and VI, R8 is hydrogen or hydroxyl. 9. The process as claimed in claim 1, comprising the metallization of the triazo dye with copper, chromium, iron, cobalt or nickel. 10. .The process as claimed in claim 1 comprising the metallization of the triazo dye with iron. 11. The method for dyeing leather, textile fibers or paper, comprising applying thereto a triazo dye of claim 1. 12. A process for production of triazo dyes substantially as herein described and exemplified.

Documents:

666-mas-1997 abstract duplicate.pdf

666-mas-1997 abstract.pdf

666-mas-1997 claims duplicate.pdf

666-mas-1997 claims.pdf

666-mas-1997 correspondence others.pdf

666-mas-1997 correspondence po.pdf

666-mas-1997 description (complete) duplicate.pdf

666-mas-1997 description (complete).pdf

666-mas-1997 form-2.pdf

666-mas-1997 form-26.pdf

666-mas-1997 form-4.pdf

666-mas-1997 form-6.pdf

666-mas-1997 others.pdf

666-mas-1997 petition.pdf