DE122606C - - Google Patents

Description

IMPERIAL

PATENT OFFICE.

- JVl 122606 CLASS 22 * ?.

oxydiphenylamine.

[In patent specification 12256g, the illustration is of rhodan derivatives of Dinitrooxydiphenylamine described, which according to the general formula

NO

CN

are composed, in which X is the remainder of the o- or p-amidophenol respectively. the carboxylic and sulfonic acids of the latter.

Furthermore, in the patent specification 122605 des has further shown that these derivatives are mixed with sulfur and sulfur-alkali Provide dyes which dye unheated cotton in greenish gray-black tones, which are transformed into vivid blue tones by alkaline oxidizing agents can.

It has now been shown that derivatives of the dinitrooxydiphenylamines which contain sulfhydryl (SH) instead of the rhodan residue or a xanthogenic acid residue are converted in the sulfur-alkaline-sulfur melt into dyes which are extraordinarily similar to the corresponding dyes obtained from the rhodan derivatives mentioned. Since the mentioned rhodium derivatives, xanthogen derivatives and thiophenols all form the group

C ₆ H ₂ - (NOJ ₂ XS-

included together (see the following Formulas)

, -5 - CiV

NO ₀

-S-CS-

NO ₂

Ä-SH O ₂ N-KJ

OC ₂ H ₅ ,

O ₂ NK

so this group is believed to be responsible for the resemblance of the three compounds produced when the three compounds are heated Dyes be decisive.

In the representation of this sulfhydryl respectively. Xanthogen derivatives of dinitrooxydiphenylamines one expediently starts from the Dinitrochloroxydiphenylaminen, which one goes through Exposure to equimolecular amounts of o- or p-amidophenol and dinitro-m-dichloro

benzene, and which are composed according to the following formula:

NO.,

NO,

i-Cl

where X denotes the p- or o-amidophenol radical. · ...... '.

If one runs on these products, expediently in alcoholic solution or If a suspension, an alcoholic solution of potassium sulfhydrate or a solution of xanthogenic acid salts act, then the second chlorine atom is replaced by the -SW group or the -S- CS-OC ₂ H- ^ group, and so the above mentioned, previously unknown Thiophenolbezw. Xanthogenic acid derivatives obtained.

The thiophenols can also be represented in such a way that those in the patent 122569 described Dinitrorhodanoxydiphenylamine in alcoholic solution with Treated potassium sulf hydrate, the rhodan residue being replaced by the thiophenol residue.

As already mentioned, all of these products, when fused with sulfur and Alkaline sulfur dyes, which are described in the patent 122605 extraordinarily are similar. Like these, they dye cotton in deep greenish black tones, which when treated with alkaline ones Oxidizing agents or vivid indigo blue when steaming in the presence of oxygen Skip tones that have the most excellent fastness properties.

Insofar as it is the preparation of these dyes from the sulfhydryl compound discussed above acts, their representation and fusion with sulfur alkali can be made into one single operation combine in such a way that the dinitrochloroxydiphenylamines mentioned used for dye melting.

The procedure is illustrated by the following examples:

Example 1.

Preparation of m-dinitrochlor-p'-oxydiphenylamine from 1 mol. Symmetrical dinitro-m-dichlorobenzene and ι Mol. p-Amidophenol.

100 parts dinitro-m-dichlorobenzene, 45 parts p-Amidophenol base and 75 parts of crystallized sodium acetate are dissolved in 500 parts of alcohol Heated for 4 hours to 40 to 50 ° and finally 2 hours to 55 to 60 °.

After cooling, the reaction product deposited in red crystals is filtered off, with water to remove common salt etc. w. washed, pressed and dried.

A very similar procedure is followed using o-amidophenol in place of the p-amidophenol.

The ρ-amidophenol product is insoluble in water and crystallizes from alcohol, in which it is sparingly soluble, in short red prisms of m.p. 228 °.

The DinitiOchlor-o-oxydiphenylamine obtained by means of a molecule of o-amidophenol differs differs from the corresponding paraoxy derivative previously described by its lighter weight Solubility in alcohol and by its melting point, which is 195 °.

Example 2.

Effect of potassium sulfhydrate on m-dinitrochlor-p'-oxydiphenylamine.

ι 5 5 parts dinitrochlor-p'-oxydiphenylamine, obtained according to Example i, become more alcoholic with 500 parts of spirit and 400 parts 9 proc. Potassium sulfhydrate solution stirred. The mixture warms up weakly and changes color dark. It is now boiled for about half an hour until the sandy crystalline powder of the starting material is obtained has turned into shimmering crystals. After cooling, it is sucked off and with a little alcohol and then washed with water, pressed and so on.

The reaction can be temperature already at low Tempe, 50 ^0, carried out for example; in this case, however, a longer reaction time is required.

The thiophenol derivative thus obtained is insoluble in benzene and water, sparingly soluble in hot alcohol, more easily in hot acetone and hot glacial acetic acid. From the solutions it crystallizes in yellow-red flat needles or flakes which evaporate at 307 ^0th

A similar procedure is followed when using m-dinitrochlor-o'-oxydiphenylamine. The product thus obtained forms a yellow-red crystal powder, which at 302 ° fizzled out.

. Example 3.

Effect of potassium sulfhydrate on m-dinitrorhodane-p'-oxydiphenylamine.

33.2 parts of the dinitrorhodanep'-oxydiphenylamine obtained by the process of patent specification 122569 are heated to the boil with 300 parts of alcohol, and 80 parts of alcoholic potassium sulfhydrate solution (9 per cent.) Are added, with complete dissolution at first. After a short time, crystals begin to separate. Boil for about '/ ₄ hour to complete the reaction, läfst cool, filtered off and washed with alcohol and water. The product is identical to that shown in Example 2.

Potassium sulfhydrate acts in the same way on m-dinitrorhodane-o'-oxydiphenylamine. a.

Instead of potassium sulfhydrate, sodium or sodium can of course also be used in all cases Calcium sulfhydrate can be used.

Example 4.

Action of xanthate on m-dinitrochlor-p'-oxydiphenylamine.
155 parts of m-dinitrochloro-p'-oxydiphenylamine and 80 parts of potassium xanthate are stirred with 600 parts of alcohol and boiled for about an hour. After cooling, it is suctioned off, the reaction product is washed with water to remove the potassium chloride, pressed, etc.

The product is insoluble in water and ligroin, slightly soluble in alcohol, ether, benzene, readily soluble in acetone and glacial acetic acid heifsem, krystallisirend therefrom in fine needles which sinter at 11 ° and 5 melts at 125 to 130 ^0th

The action of Xanthogena takes place in the same way: on m-Dimtrochloro'-oxydiphenylamine. The product thus obtained is a yellow powder which sinters at 125 ⁰ and is melted at 155 to I6O °.

Example 5.

Fusion of the reaction product from potassium sulfhydrate and m-dinitrochloro-p'-oxydiphenylamine respectively the latter with sulfur and sulfur

alkali.

75 parts crystallized sulphurous sodium, 24 parts powdered sulfur, and 40 parts Water are heated in an iron kettle equipped with a stirrer and an oil bath solved. After cooling to approx. 40 °, 30 parts of the are gradually added with stirring registered according to Example 2 or 3 thiophenol obtained, the temperature around approx. 30

The mixture is then heated with stirring

gradually to 160 to 180 °, until the reaction mass is completely dry and easy to powder.

You proceed in exactly the same way using the product represented by means of o-amidophenol, or in the case of direct use of m-Dinitrochloroxydiphenylamine.

Example 6.

Fusion of the product of the action of xanthogenic potassium on m-dinitrochlor-p'-oxydiphenylamine with sulfur and alkali sulfur.

75 parts crystallized sulphurous sodium, 24 parts powdered sulfur, and 40 parts Water are heated in an iron kettle equipped with a stirrer and an oil bath solved. 'After cooling down to approx. 40 ° with stirring gradually 30 parts of the xanthogenic acid derivative obtained according to Example 4 entered, the temperature increasing by approx. 30 °. One then heats under Stir gradually to 160 to 180 ° until the Reaction mass is completely dry and can easily be powdered.

The procedure is exactly the same using the o-amidophenol represented xanthogenic acid derivative.

Claims (1)

Patent claim: Modification in the method of representation protected by patent 122605 Substantive dyes, consisting in the fact that instead of the rhodan derivatives of the main. Patent here the corresponding thiophenol or xanthogenic acid derivatives of the m-Dinitrooxydiphenylamine or subjects the m-Dinitrochloroxydiphenylamine itself to the sulfur-alkali metal melt.