DE745373C - Process for the preparation of water-soluble acylaminoazo dyes - Google Patents

Description

It has been found that new, valuable acylaminoazo dyes are obtained if one water-soluble aminoazo dyes that are not different from aminoaroylamino compounds derive as a middle or end component, are not aminooxy compounds and in which the voice of the primary amino groups and the azo groups have at least three is acylated in liquid tertiary bases.

These acylaminoazo dyes are different from those which are in many cases according to the procedures customary up to then, acylating in an aqueous medium in the presence acid-binding substances. This is likely due to that amino groups that are difficult to react, e.g. B-. due to an o-sulfonic acid group j easily acylated when the acylation is in pyridine or other suitable tertiary; -Ba.gen is carried out. It can also the case that primary amino groups are acylated in such a way that the two Hydrogen atoms are replaced by acyl radicals.

The acylating agents that can be used include: acetyl chloride, Acetic anhydride, benzoyl chloride, nitrobenzoyl chlorides, anisoyl chlorides, Naphthoyl chloride, 2, 3 - oxynaphthoic acid chloride, benzene or toluene sulfonic acid chlorides, Cinnamic acid chloride, aryloxyacetic acid halides, such as phenoxyacetic acid chloride, and acylating agents, which are derive from polybasic acids such as isocyanates, mustard oils, terephthalic acid dichloride or malonyl chloride.

The new dyes surpass those acylated in the usual way from the British Patent 341 898 known dyes in the light fastness.

The following examples provide information on the implementation of the new process and the properties of the acylaminoazo dyes obtained:
5

Example i

2i, i parts by weight of the monoazo dye, prepared from diazotized i-aminonaphthalene-4-sulfonic acid and i, 3-diaminobenzene-4-sulfonic acid, are finely divided in 200 parts by weight of pyridine. 35 parts by weight of benzoyl chloride are added to the suspension at 40 °. The reaction mixture is heated to 90 ^{3 for one} hour and the dibenzoyldiamino compound of the monoazo dye is deposited from the solvent. It is a red-yellow powder and dyes wool brown-yellow.

Replaces the i-aminonaphthalene-4-sulfonic acid by the appropriate amount of dehydrothiotoluidine monosulfonic acid and treat the monoazo dye as above with Benzoyl chloride, a benzoylated dye is obtained, the cotton yellow colors.

Similar dyes are formed when the benzoyl chloride is replaced by 3-nitrobenzoyl chloride, 4-chlorobenzoyl chloride or butyric acid chloride.
30th

Example 2

53.9 parts by weight of the disazo dye obtained by combining diazotized 2-aminonaphthalene-4, S-disulfonic acid with i-amino-3-methylbenzene, again Diazotizing and combining with a second mole of i-amino-3-methylbenzene are in Treated 1000 parts by weight of pyridine with 28 parts by weight of benzoyl chloride. The con- Densation compound is deposited as soon as free amino groups can no longer be detected. It is a red-brown powder that turns cotton yellow-brown.

If the benzoyl chloride is replaced by another acylating agent, e.g. B. by Dichlorobenzoyl chloride, 1 - naphthoyl chloride, phenoxyacetic acid chloride, acetic anhydride, Propionic anhydride or lauric acid chloride, one arrives at similar ones Dyes.

In the starting dye, the individual components can be replaced by their equivalents without the coloring properties of the final dyes significantly changed will.

So the initial component can be i-aminonaphthalene-3,6-disulfonic acid, i-aminonaphthalene-5-sulfonic acid or i-aminobenzene-3- or -4-sulfonic acid can be replaced.

The middle component can be aniline (expediently in the form of <w-methanesulfonic acid), also by i-amino-2-methoxy-5-methylbenzene, i-aminonaphthalene, i-amino-2-methoxy- or -2-ethoxynaphthalene, i-aminonaphthalene-6- or - "- sulfonic acid, I-amino-2-methoxy- or ^ -ethoxynaphthalene-o- or -7-sulfonic acid are replaced, the end component by the above middle components or by i, 3-diaminobenzene, i, 3-diamino-4-methylbenzene, 1,3-diaminobenzene-4- or -5-sulfonic acid or 1,3-diamino ~ 4-nitrobenzene.

Example 3

I mole of one of the trisazo dyes obtained by diazotizing the diazotizable starting dyes of the previous example and combining with 1,3-D1-aminobenzene-4-sulfonic acid, e.g. B. the dye from ι mol of diazotized 2-aminonaphthalene-4, 8-disulfonic acid and 1 mol of i-amino-3-methylbenzene, further diazotizing and combining with ι MoI i-amino-3-methylbenzene, further ^{diazotizing and \ T} ereinigen with 1 mol 1,3-diaminobenzene-4-sulfonic acid are dissolved in 8g of 10 to i5fachen amount of pyridine was added at 40 ⁰ with 5 moles of benzoyl chloride. The mixture is gradually heated to 90 ° and this temperature is maintained for 1 hour. After this time, the dibenzoyldiamino compound is deposited and dried. It dyes cotton lightfast and etchable orange-brown.

If the benzoylation is carried out in the presence of dimethylaminobenzene, so a dye with a somewhat brownish tinge is obtained. The condensation can also in the presence of tripropylamine, the benzoylation also with benzoic anhydride be performed.

Further brown dyes are also produced if one uses the dye in the previous paragraph replacing the benzoyl chloride with another acylating agent, e.g. B. by dichlorobenzoyl chloride, 4-nitro or 3-nitrobenzoyl chloride, naphthoic acid chloride, phenoxyacetic acid chloride, Phenylacetic acid chloride, acetic anhydride, propionic anhydride, butyric anhydride or lauric acid chloride. In the starting dye, the individual components can be replaced by their equivalents without these changes in the properties of the acylation resulting in significantly different end dyes. So z. B. the end component, the i, 3-diaminobenzene-4-sulfonic acid, through the following end components are replaced:

ι, 3-diaminobenzene-5-sulfonic acid, ι, 3-diaminobenzene-2-methyl-5-sulfonic acid,

i. 3-diaminobenzene-4-methyl-5-sulfonic acid, i, 3-diaminobenzene-4-phenoxy-4'-sulfonic acid, ι, 3-diaminobenzene-2-methoxy-5-sulfonic acid ι, J-Diaminobenzo ^ ethoxy ^ sulfonic acid,

ι, 3-diaminobenzene,

ι, 3-diamino-4-niethylhenzene, ■ · ■.

I, 3-diamino-4-nitrohenzoi, i, s-Diamino- ^ cWorbenzol.

When using a non-sulfonated end component, it will be advisable to use a To introduce sulfonic acid group more into the other part of the azo dye molecule, such Dyes can be used as middle components instead of the 2 molecules i-amino-3-methylbenzene contain the following components in whole or in part:

Aniline (useful in the form of co-methane

sulfonic acid),
i-Amino-2-methylbenzene (useful in

Form of co-methanesulfonic acid), i-Amino-2-methoxybenzene (useful in

Form of co-methanesulfonic acid), i, 3-Diammo-4-methylbenzene, i-amino-2-methoxy- or -2-ethoxy-

5-methylbenzene,
i-Amino-2,5-dimethoxy- or diethoxybenzene,

i-Amino-3-acetylaminobenzene, ι-Aminonäphthalin,
ι -amino-2-methoxynaphthalene, i-aminonaphthalene-6- or -7-sulfonic acid, ι -amino ^ -methoxynaphthalm-ö- or -7-sulfonic acid.

The initial component can finally be replaced by the following compounds:

2-aminonaphthalene-3, 6-disulfonic acid, 2-aminonaphthalene-6, 8-disulfonic acid, 2-aminonaphthalene-4, 7-disulfonic acid, 2-aminonaphthalene-3, 6, 8-trisulfonic acid, 2-aminonaphthalene-8-sulfonic acid, 2-aminonaphthalene-6- or -7-sulfonic acid, i-aminonaphthalene-4- or -s-sulfonic acid, i-aminonaphthalene-3,6-disulfonic acid, i-aminonaphthalene-3, 6, 8-trisulfonic acid,

i-aminonaphthalene-4, 7-disulfonic acid,
i-aminobenzene-4-sulfonic acid,
i-aminobenzoI-2, 4- or -2, 5-disulfonic acid, i-amino ^ -chlorobenzene-s-sulfonic acid,
ι-amino-4-nitrobenzene-2-sulfonic acid.

Monoazo dyes, such as 4-Amino-i, i'-azobenzene-4- or -3-sulfonic acid or 4-Amina-i, i'-azobenzene-3, 4'-disulfonic acid, be used.

Claims (1)

Claim: Process for the preparation of water-soluble acylaminoazo dyes !!, thereby characterized in that one has water-soluble aminoazo dyes that are not derive from aminoaroylamino compounds as middle or end components, are not aminooxy compounds and in which the sum of the primary amino groups and the azo groups is at least three, in liquid tertiary ones Bases acylated. To distinguish the subject of the application from the state of the art, the granting procedure the following publications have been considered: German patents No. 270 831, 437071, 261047, 479 9 ^ 6, 583070, 638830; French Patent No. 798 107; British patents - 342,807, 34-1898; U.S. Patent No. 1,845,426; AWerhalden, Handbook of biological working methods, Volume 1, 2, 1 (1927), p. 957; Houben, The Methods of Organic Chemistry, Volume III (1930), p. 942.