CH264602A - Process for the production of a new azo dye. - Google Patents

Description

  

  Process for the production of a new azo dye. Certain aminonaaphtholsulfonic acids have the ability to combine with 2 molecules of a diazo compound to form primary disazo dyes.

   In particular, some 1,8-aminonaphthol sulfonic acids, 2,3-aminonaphtholsulfonic acids and 2,5-aminonaphthol-7-sulfonic acid are suitable for this purpose, while 2,8-aminonaphthol-6-sulfonic acid ((hemic acid), 2,8- It is known that aminonaphthol-3,6-disulfonic acid (2 R-acid) and 1,5-aminonaphthol-7-sulfonic acid (M-acid) do not form any primary disazo dyes.

   It is indeed mentioned in French patent specification No. 843115 (page 3, lines 20 to 29) and in German patent specification No. 534891 (page 1, lines 24 to 51) that monoazo dyes, which are produced by combining di- azotized 3-chloro-4-aminobenzene-l-sulfonic acid with, gamma acid or

   of diazotized 2-amino-5-nit.robenzene-1-sulfonic acid with phenylgaminic acid in an acidic medium, should be further coupled with diazo compounds. However, due to the experimental verification, this patent information must be described as inapplicable.

   This finding is also in agreement with the numerous data in the literature, in which it is pointed out that the three aminonaphtholsulfonic acids in question can only be coupled once, i.e. either only acidic or only alkaline (cf. Fierz-David, Künsthühe organic dyes [1926], page 105; F.

   Mayer, Chemistry of Organic Dyes, Volume I, Page 38; Ullmann, Enzyklopädie der tech nischen Chemie, 2nd edition, Volume II, page 28, German patent specification No. 126802, page <B> 1). </B>



  The surprising finding has now been made that the azo dyes obtainable from the three named aminonaphtholsulfonic acids by acid coupling and which cannot be applied in the form of their N-acyl derivatives can easily be coupled with a second mole of a diazo compound.

   This completely new knowledge makes it possible to use the aminonaphtholsulfonic acids previously known as exceptional cases to produce new and valuable primary disazo or polyazo dyes of various shades, which is a significant enrichment of the technology.



  According to the invention, azo dyes of the general formula are used
EMI0001.0073
    where R is the remainder of an azo component, X is hydrogen or 80 "H, one Y is hydrogen and the other is L 'N <R, where acyl R' is hydrogen, alkyl, cycloalkyl, aralkyl, aryl or acy 1,

   in the 7-position and in coupling-capable positions of R, if any, are combined with Diazoverbin.dun- gen and the coupling products are treated with saponifying agents if necessary
EMI0002.0002
   in NIIR over. The starting dyes suitable for the new process can, for.

   B. by acidic coupling of any diazo compound with one of the above general formula underlying amino onaphtholsulfonic acid and. subsequent treatment with acylating agents are shown,

   like this in Switzerland. Patent No. 262278 is described. Acyl is the acid residue of any organic acid such as e.g.

   B. formic acid, carbamic acid, ethyl carbonic acid, acetic acid, chloroacetic acid, butyric acid, stearic acid, benzoic acid, nitrobenzae acids, anisic acids, cinnamic acid, naphthoic acids, alkyl and acylsulfonic acids, also the acid residue of polybasic hems, such as. B.

    To understand carbonic acid, oxalic acid, succinic acid, cyanoic acid, phthalic acid, etc.



  The starting dyes can by customary methods, mainly in the presence of acid-binding agents, such as. B. sodium acetate, sodium bicarbonate, potassium carbonate, sodium hydroxide solution, calcium hydroxide, ammonia, or suitable tertiary organic bases such as pyridine, can be coupled with any diazo or tetrazo compounds.

    For the saponification of the acylamino group, a treatment with saponifying agents such as soda, ammonia, arythydrate, sodium hydroxide solution, acetic acid or mineral acids can then be carried out at normal or elevated temperature. The new dyes, if they contain complex-forming groups, can be treated with metal donating agents in bulk or on the fiber.



  Depending on the nature of the diazo compounds used and the radical R, the new dyes are suitable for dyeing animal, vegetable or synthetic fibers or leather and are characterized partly by excellent lightfastness and partly by good washing, perspiration and resistance Milled authenticity.



  The present patent relates to a process for the production of a new azo-carbide and is characterized in that diazotized 1-naphthylamine is mixed with the acetylaminoazo-dye, which is obtained by acid coupling of diazotized 2-amino-5-nitrobenzene-1-sulfonic acid with, 2,

  8-aminonaphthol-6-sulfonic acid and subsequent acetylation are obtained, combined and the resulting coupling product. treated with saponifying agents to saponify the acetylamino group.



  In the following example, parts mean parts by weight.



  <I> Example: </I> 51 parts of the acetylaminoazo dye, which is obtained by combining diazotized 2-amine @ 5-nitrobenzene-1-su @ lfonic acid with 2,8-aminonaphthol-6-sulfonic acid in acidic medium and the following - Acetylation according to Switzerland. Patent No. 262278 obtained are in 500 parts of water with the addition of 4 parts of caustic soda and 20 parts of cale. Soda dissolved at room temperature.

   The ice-cold solution of the diazo compound of 14.3 parts of 1-naphthylamine is added to this clearly alkaline solution at 0 to 100 with thorough stirring. The coupling takes place immediately and is complete a short time after the addition of the diazo compound. The disazo dye deposited in brown-violet crystals is filtered, washed mvG dilute brine and dried in vacuo.



       The dyestuff thus obtained is reduced by means of tin chloride and hydrochloric acid as cleavage products 1-naphthylamine, 1,4-dianinobenzene-2-sulfonic acid and a very oxidizable triaminonaphthol-silicic acid,

      the solution of which, poured on filter paper in the air, immediately turns deep blue and otherwise behaves very similarly to the known 1.2.7-tria.mino-8-naphthol-3,6-disulfonic acid and therefore probably the constitution
EMI0002.0137
  
EMI0002.0138
  
    should own <SEP>.

           The new dye therefore differs sharply from the monoazo compounds obtainable by acidic or alkaline coupling of diazo compounds with 2,8-aminonaphthol-6-sulfonic acid, the reduction of which, in addition to the diazo components, results in much less oxidizable diaminonaphtholsulfonic acid, which on filter paper only turns brown-red .

   The new dye should therefore have the following constitution:
EMI0003.0010
    Repeated recrystallization from water gives it salt-free; after drying in air up to weight constancy it contains 5 mol of crystal water.



  The analysis gives "N" S = Na, for C_AH, HO1. 51T0:
EMI0003.0018
  
    Ber. <SEP> S <SEP> 8.05 <SEP> CH @ C0 <SEP> 5.40
<tb> Gef. <SEP> S <SEP> 8.08 <SEP> CH; CO <SEP> 5.35 The new disazo dye dyes wool from acid baths in alkaline, brown-violet shades of good lightfastness and excellent sweat and washfastness .



  For the saponification of the acetylamino group, the dye is heated to 80 to 90 for a short time in about 1% sodium hydroxide solution. It is then neutralized and the deposited dye is filtered and dried.



  The primary disazo dye thus obtained of the presumed constitution
EMI0003.0028
    is a dark powder that dyes wool from an acid bath in alkaline deep brown shades of good light fastness and excellent white and wash fastness.

 

Claims (1)

PATENT CLAIM: Process for the production of a new azo dyestuff, characterized in that dianotated 1-naphthylamine is used with the acetylaminoazo dyestuff, which is obtained by acid coupling of dianotated 2-amino-5-nitrobenzene-1-sulfonic acid with 2,8-aminona , ph-thol-6-sulfonic acid and subsequent acetylation is obtained, combined and the coupling product obtained is treated with saponifying agents for the purpose of saponifying the ethylamino group. The new dye, a dark powder, colors. Wool made from: acid bath in deep brown, light, white, wash and alkali-like tones.