DE590581C - Process for the preparation of 4-aminodiphenylamine derivatives - Google Patents

Description

GERMAN EMPIRE

ISSUED ON
JANUARY 6, 1934

REICH PATENT OFFICE

PATENT LETTERING

M 590581 CLASS 12 q GROUP

I. G. Farbenindustrie Akt.-Ges. in Frankfurt a. M. *) Process for the preparation of 4-ammodiphenylamine derivatives

Patented in the German Empire on March 10, 1932

It has been found that uniform 4-aminodiphenylamine derivatives which in 3-Siellung by, an alkoxy or alkyl group are substituted, if you are in the 3-position with the groups mentioned substituted diphenylamines, which are not substituted in the 4-position, with a suitable diazonium compound couples and the resulting azo dye by reducing acting agent splits up in a manner known per se.

It is quite surprising that the presence of the above groups in 3-position the azo group completely unified-Hch. conducted after the 4 position.

The alkoxy and alkyl groups mentioned differ from one another in their selective effect in the coupling, so that in the presence of z. B. alkoxy in 3-position with simultaneous occupation of the 3'-StCUItIEg by alkyl a single coupling obtained in the o-position to the alkoxy group.

example 1

A prepared of 35 parts of sulfanilic acid, 300 parts of water, 7 parts of 960 / cent sulfuric acid and 14 parts of sodium nitrite suspension of the diazo compound is added at 10 to 15 ⁰ to a solution of 41 parts of 3-methoxy diphenylamine in 500 parts of xylene and 40 parts of pyridine. The two layers are emulsified for 8 hours by stirring well, the dye forming in the form of small red needles. When the coupling is complete, it is made alkaline with soda and the xylene is blown off with steam. The resulting solution of the dye sulfanilic acid χ 3-methoxydiphenylamine is mixed with 75 parts of 31.20 per cent sodium hydroxide solution, brought to the boil, then slowly 75 parts of zinc dust are introduced and the mixture is boiled until the dyestuff has broken down The 4-amino-3-methoxydiphenylamine initially separates out in the form of an oil and solidifies when it cools, with the boiling solution discolored. It is filtered off with suction and recrystallized from ligroin, whereby it is obtained in the form of almost colorless needles. It is identical with the 4-amino-3-methoxydiphenylamine described in patent specification 512722.

Example 2

The, as usual, from'5 4 parts of sulfanilic acid, 300 parts of water, 1.8 parts of 960 per cent sulfur

*) The patent seeker indicated the following as the inventors:

Dr. Arthur Zitscher and Dr. Wilhelm Seidenfaden in Offenbach a. M.

Feic acid and 22 parts of sodium nitrite, dissolved in 60 parts of water, the diazo compound produced is separated off by suction filtration, washed with 50 parts of 250% sodium chloride solution, stirred with 250 parts of alcohol and cooled to -J-- 10 °. In the thus obtained ■ suspension of the diazo compound of sulfanilic io / ₀ hydrochloric acid to wear 47.6 parts of finely powdered 3-methoxy-3'-chlorodiphenylamine and 7 parts of 32, a mixture is stirred 2 hours at 15 ⁰ and 6 hours at room temperature, whereby the azo dye is formed. The dye, which has been separated off in the usual way and washed neutral, is dissolved at the boil in 22 parts of 31.20% sodium hydroxide solution and 250 parts of water, and a hot sodium trisulfide solution prepared from 6 parts of sulfur, 35 parts of crystallized sodium sulphide and 32 parts by volume of 2N sodium hydroxide solution is added Maintained at the boil for 7 hours, during which time it is cleaved into sulfanilic acid and 4-amino-3-methoxy-3'-chlorodiphenylamine. Recrystallized from benzene, the base is obtained in the form of slightly colored needles with a melting point of 79 to 80 °; the acetyl product has a F. 136 to 137 ⁰ .

Example 3

37 parts of 3-methyldiphenylamine (Annalen der Chemie Volume 355 [1907], page 325) are added at -f io ° to a suspension of the diazo compound of sulfanilic acid in alcohol prepared according to Example 2, and 10 parts of 32.10% hydrochloric acid are added and stir until the azo dye formation is complete. The dye thus obtained was dissolved at 40 to 45 ⁰ to 60 parts 31,20 / cent sodium hydroxide solution and 300 parts of water, can then at this temperature a solution of 45 parts of sodium hydrosulfite in 150 parts of water enter and increases the temperature within ¹ J ₂ hours to 90 to 95 ⁰ , the 4-amino-3-methyldiphenylamine separating out as a viscous oil that solidifies in the cold, with discoloration of the dye solution. Recrystallization from a benzene-ligroin mixture gives the amine in the form of small, almost colorless columns. It's identical to that. 4-amino-3-methyidiphenylamine described in patent 512722.

Other 4-aminodiphenylamine derivatives of this type can also be obtained in an analogous manner be e.g. B.

4-Amino-3-ethoxydiphenylamine

4-amino-3-n-propyloxydiphenylamine

4-amino-3-n-butyloxydiphenylamine

4-Amino-3, 6-dimethoxydiphenylamine .... '. 4-Amino-3-methoxy-5-methyldiphenylamine _L.

4-amino-3-methoxy-6-methyldiphenylamine. . 4-amino-3-methoxy-3'-methyldiphenylamine.

4-amino-3-methoxy-2'-methyldiphenylamine.

4-Amino-3-methoxy-2'-chlorodiphenylamiii. . .

g ₀ 4 - amino: - 3 _: - methoxy - 2 ', 5' - dimethyldiphenylamine

4-Amino-3-methOxy-2'-methyl-5'-cblordiphenyl

arnin
⁵ x> 4-amino-3-m! Ethoxy-2 ', 5'-dichlorodiphenylamine

4-amino-3,6-dimethyldiphenylamine.

g '4-Amino-3-methyl-3'-chlorodiphenylamine .... (leaflets made of ligroin - F. y / to 78 ⁰

uncorrected)
(Leaflets, from benzene ~ j-ligroin - F. 52 to 53 ⁰ uncorrupted.)

(Needles from benzene - {- ligroin - F. 87 bis 88 ° uncorrected)

(Small needles made of benzene -} - Ligroin. - F. 117 up to 118 ° uncorrect.)

(Needles made of benzene 4- ligroin - F. 64 to 65 ⁰ uncorr.)

(Needles made of ligroin - F. 80 to 81 ° uncorrect.) (Needles made of methanol - F. 52 to 53 ⁰ uncorrect. - F. of the acetyl compound 166 to 167 ⁰ uncorrect.)

(Rhombs from ligroin tetrachloride -f- ¹⁰ ^ fabric - F. uncorr 60 to 61 ° -. F, the acetyl 144-145 ⁰ uncorr.)

(Needles made of benzene -j- ligroin - F. 84 to 85 ⁰ uncorr.)

(Nädelclien from ligroin - F. 89 or 90 ⁰ uncorr - uncorr F. of the acetyl compound 129 to 13o ° C.).

(Needles made of ligroin - F. 102 to 103 ⁰ uncorr.)

(Papers from benzene-f- ligroin - F. 116 up to 117 ° uncorrected)

(Needles made of benzene - {- ligroin - F. 86 to 87 ⁰ uncorrect.)

(Almost colorless viscous oil - bp _t 188 ° - F. of the acetyl compound 144 to 145 ⁰ uncorr.)

Claims (1)

Claim: Process for the preparation of 4-aminodiphenylamine derivatives, since * · * ¹¹ that such diphenylamine derivatives, which are occupied in the 3 * position by an alkoxy or alkyl group and are not substituted in the 4-position, are coupled with suitable diazonium compounds and the - azo dye formed in this way splits in a manner known per se.