DE236375C - - Google Patents

Description

IMPERIAL

PATENT OFFICE.

. From the monoanthraquinonylurea
(A-NH-CO-NH ₂ )

Dianthraquinonyl or anthraquinonylarylureas derived by substitution in the NH ₂ group have not yet become known, neither those of the α nor the β series.

It has now been found that the ß-series

ίο or those of the ß, α series are essentially can be obtained in two ways:

i. The bodies of the type of dianthraquinonylureas A-NH-CO-NH-A, in which A denotes the same ß-anthraquinonyl radical, can be produced by heating the ß-anthraquinonyl urethanes or the corresponding ß-anthraquinonylurea chlorides with the relevant ß-aminoanthraquinone. So z. B. by heating the ß-anthraquinonyl urethane, which is mentioned in patent 167410, with ß-aminoanthraquinone a yellow, alkali-insoluble body, which is to be understood as ß, ß-dianthraquinonylurea. The same body is also formed when the urea chloride is heated. B. ' obtained when excess phosgene is introduced into a cold suspension of ß-aminoanthraquinone in nitrobenzene, with ß-aminoanthraquinone. Furthermore, the same body is formed, but with a poorer yield, when the ß-aminoanthraquinonylurea chloride is heated on its own in the presence of alkalis or water or when the impure hydrochloric acid is heated

Examples:

ß-Aminoanthraquinone-containing chloride, as you can by introducing the calculated amount of phosgene into a suspension of ß-aminoanthraquinone, z. B. in toluene is obtained.
2. The bodies of the type

A-NH-CO-NH-R,

wherein R is either an anthraquinonyl radical different from A, e.g. B. an a- or a ß-anthraquinonyl radical, or an unsubstituted or substituted aryl radical, such as phenyl, tolyl, xylyl, naphthyl, etc., is obtained by heating the ß-anthraquinonylurea chlorides or, albeit less smoothly, by heating the ß-anthraquinonyl urethane with an amine of the aromatic series, z. B. with α- and ß-aminoanthraquinone, aniline, toluidine, naphthylamines, etc.

These ß-anthraquinonylurea derivatives or aryl substitution products of the mono-ß-anthraquinonylureas should serve as starting materials for other valuable dyes ■ and are valuable vat dyes themselves. '·

i. 30 kg of ß-anthraquinonyl urethane will be mixed with 22.5 kg of ß-aminoanthraquinone and heated quickly and for a short time to about 250 °. The resulting yellow reaction product is purified with nitrobenzene. In Acids and alkalis is the so obtained

Body insoluble; With alkaline hydrosulphite ¹ solution it forms a red vat from which cotton and wool in particular are dyed in yellow tones.
When preparing larger quantities, it is expedient to proceed in such a way that a high-boiling solvent, such as, for example, naphthalene, is added for the purpose of better temperature equalization. If you go instead of

ίο ß-Anthraquinonyl urethane from the one mentioned above Product of the action of excess phosgene on ß-Aminoaiithraquinone in Nitrobenzene in the cold (ß-anthraquinonylurea chloride) and heats it up with ß-aminoanthraquinone, an analogous result is obtained. For the production of ß-anthraquinone urea chloride the procedure is such that in a suspension of 22.3 parts of ß-aminoanthraquinone in about 200 parts by weight Nitrobenzene introduces excess phosgene in the cold and stirs until the The orange-yellow color of the ß-aminoanthraquinone changed to a gray-white color and until the hydrochloric acid ß-aminoanthraquinone has gradually disappeared. The resulting Crystal pulp is filtered off with suction and washed with benzene; after the benzene has been eliminated the chloride obtained mixed with 23.3 parts of ß-aminoanthraquinone and with or without Addition of naphthalene or another solvent or with or without additives heated by an alkaline substance. The product has the same properties as before described.

The same result is obtained if one uses β-anthraquinonylurea chloride heated by itself with or without the addition of alkalis, but with the participation of water is necessary. For example, those mentioned above are obtained by heating Suspension of ß-anthraquinonylurea chloride in a technical, not further dried Nitrobenzene substantial amounts of ß, ß-dianthraquinonylurea; so when heated of 50 g of ß-anthraquinonylurea chloride in 1000 g of technical, perfectly clear, only not particularly dried nitrobenzene and suction of the product formed in the Heat 28.5 g, that is about 75 percent of theory, of ß, ß-dianthraquinonylurea. The same yield is obtained when the β-anthraquinonylurea chloride is heated with three times the amount of water to 100 ° and purification of the resulting product with nitrobenzene; so z. B. from 127 g of β-anthraquinonylurea chloride 79 g ß, ß-Dianthraquinonylurea (= about 77 percent of theory) obtained.

If the ß-aminoanthraquinone is replaced by a-aminoanthraquinone, ie if ß-anthrachyonylurea chloride is heated with a-aminoanthraquinone, a reaction product is obtained which has greenish, yellowish tones in the vat; The body is also obtained by heating the ß-anthraquinonyl urethane with ß-aminoanthraquinone, but it is much more impure and mixed with other bodies of unknown composition. If one replaces the a-aminoanthraquinone by a a, a-diaminoanthraquinone, heating them so ß-Anthrachinonylharnstoffchlorid (2 mol.) With α, α-diaminoanthraquinones, so obtained brown vat dyes.

2. The arylated mono-ß-anthraquinonylureas are most easily obtained from the corresponding aforementioned ß-anthraquinonyl urea chloride, which you, as indicated above is, for example, by the action of phosgene on ß-aminoanthraquinone in a cold suspension of nitrobenzene is obtained by reacting it with aromatic Amines, ζ. B. aniline, toluidines, naphthylamines, etc. You can also use them if not even in the pure state, due to rapid heating of the anthraquinonyl urethanes with high-boiling ones obtained aromatic amines, z. B. when using ß-anthraquinonyl urethane and p-toluidine clearly form two bodies.

The following procedure is used to produce these valuable ß-derivatives:

Molecular parts of fi-anthraquinonyl urethane and p-toluidine are heated rapidly so that the p-toluidine comes to the boil; one cools off and washes with alcohol. The dye is a yellowish powder that is in the essentially as a mixture of p-tolyl-ßanthraquinonylurea with ß, ß-dianthraquinonylurea and dyes cotton and wool in the vat in yellow tones.

In the pure state, the p-Tolylß-anthraquinonylurea is obtained, if you start from the aforementioned ß-anthraquinonylurea chloride instead of ß-anthraquinonyl urethane and this reacts with p-toluidine; one proceeds, for example, so that one 28 kg ß-anthraquinonylurea chloride with 21 kg p-toluidine, with or without the addition of about 50 kg of nitrobenzene, stirred and then heated on the water bath; one then dilutes with nitrobenzene, siphoned off, washed with ether and then with water. The received The product is a yellow powder, the wool and cotton in the vat are yellow Colors tones.

If the p-toluidine is replaced by the corresponding amount of aniline, ß-naphthylamine, etc., this gives the corresponding mixed ureas. The same are yellow powders and In the vat, wool and cotton dye yellow, the ß-naphthylamine in a little more orange-colored Töneli.

The following table gives an overview of the properties of a number of the new 55 Products:

5
Dye off body paint Solution in conc.
H.SO, colour
the vat coloring
in the vat
on wool
and cotton ß-anthraquinonyl urethane
¹⁰ or urea chloride
+ ß-aminoanthraquinone
(P, ß-dianthraquinonyl-
urea) yellow Orange red red-brown yellow ß-anthraquinonyl urine
¹ ^ substance chloride + a-amino
anthraquinone (ß, a-Dian-
thrachinonylurea) green yellow red-brown
Brown red-brown yellow 2 mol. Ss-anthraquinonyl-
urea chloride
²⁰ + ι mol ι 4-diamino-
anthraquinone Brown , red-brown red-brown red-brown 2 mol. Ss-anthraquinonyl-
urea chloride
+ ι Mol. ι · 5-diamino-
^a ** anthraquinone Brown red-brown red-brown Brown 2 mol. Ss-anthraquinonyl-
urea chloride
+ ι Mol. ι · 8-diamino-
anthraquinone Brown orange yellow red-brown yellow-brown ß-anthraquinonyl urine
material chloride + Armin
(Phenyl-ß-anthraquinone
nylon urea) yellow Orange red red-brown yellow ß-anthraquinonyl urine
substance chloride + p-toluidine
(p-tolyl-ß-anthraquinone
nylon urea) ■. ' yellow brownish red red-brown yellow ^ ₀ ß-anthraquinonyl urine
substance chloride + ß-naphthyl-
amine (ß-naphthyl-ß-anthra-
quinonyl urea) yellow Orange red red-brown yellow ß-anthraquinonyl urine
45 chloride + diphenyl
amine (diphenyl-ß-anthra-
quinonylurea) yellow red-brown yellow

Claims (1)

Patent claim:
Process for the production of ß, ß- or ß, ü-dianthraquinonylureas or of aryl-substituted products of the mono-ßanthraquinonylureas, consisting in that one ß-anthraquinonyl urethanes or ß-Anthraquinonylurea chlorides with aromatic Amines (aminoanthraquinones, arylamines, etc.) are converted, or that 105 ß-Änthraquinonylurea chlorides for themselves with or without the addition of alkalis Heated presence of water.