DE139581C - - Google Patents

Description

IMPERIAL

PATENT OFFICE.

In the patent 136777 it has been shown that in anthraquinone derivatives which contain several negative substituents, only part of the substituents through the remainder a secondary base of the aliphatic series can be replaced and that the so formed, still containing negative substituents (such as, for example, halogens, nitro groups, hydroxyl groups) tertiary bases further condensed with another secondary amine of the aliphatic series can be.

These tertiary bases, which still contain negative substituents, can now also be found, as has been found was to condense with primary amines of the aromatic series, which is strong basic character of the starting materials could not be foreseen without further ado. It This creates color bodies, which in the form of their sulfonic acids wool in red, blue to color green tones, the nuance of the relative position of the substituents is dependent. If, for example, the substituents are in the 1-5 or 1 · 8-position, so if red to red-violet dyes are obtained, the substituents are in the p-position, see above pure blue to green dyes are obtained (see patent specification 127458).

The process generally consists in that the still containing negative substituents tertiary bases can be heated with the aromatic amine. The scientific study of the products thus obtained has show that when using dialkyl-substituted Bases in the course of the reaction, an alkyl group is split off by derivatives of the Monoalkylamidoanthraquinones are obtained.

The following examples serve to explain the procedure:

Example 1.

10 kg of ι · 5-nitrodimethylamidoanthraquinone are heated with 100 kg of p-toluidine for about 2 hours at 180 °. It is allowed to cool to about 80 ° and mixed with alcohol. On cooling, the 1 · 5-monomethylamido-p-toluidoanthraquinone formed separates out in crystallized form. If necessary, it is dissolved in concentrated hydrochloric acid, any insoluble by-products are filtered off from this solution, precipitated with water and recrystallized from pyridine and methyl alcohol. So long needles with a melting point of 19g ^{0 are obtained} .

The above 1x5-nitrodimethylamidoanthraquinone is prepared according to Example 4 of patent 136777. Its properties are completely analogous to those of the 1 × 8 derivative.

Example 2.

If in the previous example the ι · 5-nitrodimethylamidoanthraquinone is replaced by the ι · 5 -Bromodimethylamidoanthraquinone (obtainable according to the process of patent 136777 by condensation of 1 mole of dimethylaniline with ι Mol. ι · 5 -Dibromoanthraquinone), so arrives by exchanging the bromine atom for the arylido radical to the same product.

Example 3.

10 kg of 1 x 4-chlorodimethylamidoanthraquinone are heated with 100 kg of p-toluidine to 180 ° until the gradually turned green-blue Do not melt on further heating

Nuance change shows more. Then one lets cool to about 60 ° and mixed with about the same volume of methyl alcohol. After standing for 12 hours, the color body formed precipitated in crystallized form. However, as further investigation has shown, it is not uniform. It consists of by far the largest amount from 1 · 4-MeihyIamidop-toluidoanthraquinone together with small amounts of ι · 4-di-p-toluidoanthraquinone (quinizarin green). The two dyes can be obtained by treating with a mixture of alcohol and smoking Hydrochloric acid, in which quinizarin green is insoluble, while 1 x 4-methylamido-p-toluidoanthraquinone is soluble in it. The sulphonic acid of the latter dyes unheated wool an extraordinarily clear green-blue Nuances do not matter.

ao example 4.

5 kg of ι · 5-dinitro-4 · 8-tetramethyldiamidoanthraquinone (obtained from 1 · 5-dinitro-4 · 8-dichloroanthraquinone by replacing the chlorine atoms with the dimethylamine radical, see patent specification 136777) are mixed with 50 kg of p-toluidine heated to about 200 ^0. After only a few hours the exchange of the nitro groups for the toluidine residue is complete, which is evident from the transition from the initially red color of the solution to green. It is then poured into dilute hydrochloric acid, filtered, washed out and dried. The product thus obtained dissolves in aniline, pyridine, chloroform and glacial acetic acid with green, in concentrated hydrochloric acid with purple color.

Example 5.

10 kg · ι 4 - Oxydimethylamidoanthrachinon (. Cf. Patent 136 777) are mixed with 100 kg of p-Tolnidin and 5 g of boric acid so long heated to about 180 to 200 ⁰ until the melt has a green-blue color adopted. The product isolated in a known manner and shown in pure form is identical to the 1 ^ -methylamido-p-toluidoanthraquinone described in Example 3.

The properties of some of the products available in this way are summarized in the following table: . . ·.

Name and formula
the connection

solution

in
Chloroform solution

in
Glacial acetic acid

solution
in more concentrated
hydrochloric acid

Solution in a mixture of

same

Volume of alcohol and smoking

hydrochloric acid

Solution in concentrated sulfuric acid

ι · 5 - methylamidoanilidoanthraquinone

NHCH ₃ , CO,

lively
blue red

ι · 5 - methylamido - ρ - toluidoanthraquinone

JVHCH ₃

blue red

NHC ₁ H ₁

ι · 8 - methylamidoanilidoanthraquinone
NHC ₆ H, NHCH ₃ , CO,

violet

^N c <r

ι · 8 - methylamido - ρ - toluidoanthraquinone

NHC ₁ H ₁ NHCH ₃ , CO,

red-violet • 6

.5

CD

heavy
soluble,
violet

insoluble

easy
soluble,
violet

heavy
soluble,
violet

rather difficult to dissolve,

purple red

almost colorless,

will be at

Heat

with boric acid violet

almost insoluble

pale yellow, becomes with heating when heated

Boric acid purple

red-violet

almost colorless

violet

pale yellow

Name and formula
the connection

solution

in
Chloroform solution

in
Glacial acetic acid

solution
in more concentrated
hydrochloric acid

Solution in

a mixture of the same

Volume of alcohol and smoking

hydrochloric acid

Solution in concentrated sulfuric acid

ι · 4 - methylamido-p - toluidoanthraquinone

NHCH ₃

pure
green Blue

· 5 - Di - ρ - toluido - 4 · 8 - dimethylamidoanthraquinone

CH ₃ -HN

green

C ₁ H ₇ HN

NH-CH ₃

heavy

soluble,

purple red

easy

soluble,

blue red

greenish slate blue

violet

Claims (1)

Patent claim: Process for the representation of color bodies of the anthracene series, which at the same time contain aryl contain amido and alkylamido groups therein consisting that one tertiary amido anthra-yellow, when warming violet-blue violet. nonderivate, which apart from one or more tertiary aliphatic amido groups substituted one or more times by halogen atoms, nitro groups or hydroxyl groups are condensed with primary aromatic amines.