DE205036C - - Google Patents

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- M 205036 CLASS 12 #. GROUP

Patented in the German Empire on August 14, 1907.

It is well known that benzoyl-o-benzoic acid and certain derivatives of the same go away when treated vigorously with concentrated sulfuric acid in anthraquinone or its derivatives. For example, according to the procedure patent specification 148110, class 12 q m-amino or m-oxybenzoyl-o-benzoic acid or their halogen derivatives when heated to high temperatures with concentrated sulfuric acid Monoamino- or monooxyanthraquinones and halogen derivatives obtained the same. It is also an aminooxynaphtoylbenzoic acid by heating by itself or with a high-boiling solvent in a Aminooxynaphtacenchinon have been converted (see. Patent 183629, cl. 12 q).

It has now been shown that the derivatives of diaminobenzoylbenzoic acid of the constitution

CO

CO ₂ H

NH ₉

NH ₀

in which both amino groups are meta to the carbonyl group, one Conversion to the corresponding anthraquinone derivatives are capable and that they do so with surprising ease and extraordinary goes smoothly. Suitable for this condensation are those by substitution in the benzoyl or in the phthalic acid residue or derivatives of this acid derived from both benzene nuclei, provided an ortho position to the carbonyl is unoccupied.

The condensation takes place, for example, as soon as the diaminobenzoylbenzoic acid derivatives mentioned are heated on their own or in inert liquids, such as water, salt solutions, alcohol or nitrobenzene; further it can be achieved by treatment with acidic agents such as with dilute mineral acids or acid salts, particularly light and smooth but with organic acids.

For the preparation of the diaminobenzoylbenzoic acid derivatives mentioned Serving di- and polynitrobenzoylbenzoic acids can be obtained by treating the corresponding substituted o-Benzoylbenzoic acids in sulfuric acid solution with nitric sulfuric acid and possible Represent purification of the products obtained. The reduction of these nitro compounds too the aminobenzoylbenzoic acids can in the usual manner, for. B. with iron and acetic acid take place in aqueous or aqueous-alcoholic solution.

The diaminoanthraquinone derivatives obtainable by the present process are said to be Starting materials for the representation of dyes are used.

Example 1.

ι · 3 · χ-T ri am inom ethyl anthraquinone. a) 125 parts of p-toluic-o-benzoic acid
CO

55

60

COOH

CH *

are dissolved in 300 parts of monohydrate and at 0 to 5 ⁰ initially 270 parts of 4%

Nitrating acid, then 230 parts of oleum of 70 percent 5 O _{3 allowed} to flow in slowly. The reaction mixture is stirred for a further 40 hours at ordinary temperature, then poured onto ice, the acid which has separated out is filtered off and washed. The crude acid can be purified by converting it into the poorly soluble sodium salt. Crystallized from glacial acetic acid, the acid has a melting point of 217 to 218.5 °; it is not very soluble in water, easily soluble in hot organic agents and crystallizes out on cooling; with excess sodium hydroxide solution it gives a dark brown solution with decomposition.

For the representation of the triamino-p-toluyl-abovezoic acid can the trinitro - ρ - toluyl - ο-benzoic acid in the usual way with iron and acetic acid can be reduced. Those from the lye by precisely neutralizing with Triaminotoluyl-o-benzoic acid isolated from mineral acid decomposes at high temperature Transition to the anthraquinone derivative; in It is not very soluble in the cold with organic substances.

b) 120 parts of triamino-p-toluyl-o-benzoic acid are dissolved in dilute ammonia with slight warming, the filtered solution is gradually poured into 500 parts of boiling glacial acetic acid, the ι · 3-x-triamino-2-methylanthraquinone separates quantitatively in the form of yellow-red needles. 'The product is pure immediately; the melting point is above 300 °; it dissolves in more concentrated Sulfuric acid almost colorless; this solution is heated with the addition of boric acid reddish; occurs when the sulfuric acid solution is mixed with formaldehyde in the cold a deep, pure blue color. In low-boiling organic agents, the compound is difficult, in high-boiling, z. B. nitrobenzene, more soluble in the heat.

Triamino-p-toluyl-topzoic acid can also be used Immediately heat with glacial acetic acid, whereby the triaminomethylanthraquinone is heated to the boiling point of the Glacial acetic acid separates into crystals.

Furthermore, the conversion into the triaminomethylanthraquinone can be brought about by Heating the acid alone to higher temperatures, e.g. above 300 °, or through boiling the triamino-p-toluylo-benzoic acid for several hours with water or the solutions of sodium acetate, common salt, copper sulfate or other salts, or by brief heating with nitrobenzene and other inert liquids. Furthermore, instead of the Glacial acetic acids, such as dilute acetic acid or dilute mineral acids, are used will. The condensation takes place with such ease that already in the course the reduction partially results in the formation of the anthraquinone derivative; this can be off the iron sludge in a suitable manner, e.g. B. obtained by dissolving with nitrobenzene will.

Example 2.

Representation of the 1 ■ 3-diamino-2-methylanthraquinone.

250 parts of p-tolyl-o-benzoic acid are dissolved in 1500 parts of monohydrate and gradually added to 315 parts 4oprozentige nitrating acid at a temperature not exceeding -5 ^0. The temperature is then kept at 0 ° for about 50 to 55 hours and then the reaction mixture is poured onto ice, filtered off with suction and washed.

The nitro product obtained is reduced with iron and acetic acid and can from the Reduction liquor can be obtained by acidification. A significant part of the educated Diamirfo-p-toluyl-o-benzoic acid condenses already in the reducing liquid to the anthraquinone. This can come from the iron mud z. B. can be obtained by undressing with alcohol.

In order to convert the crude diamine acid separated from the reducing liquor into the anthraquinone derivative, it is dissolved in glacial acetic acid and heated to the boil for ^{1 to 1} _{2 hours.} The crude 1 · 3-diamino-2-methylanthraquinone separated by pouring into water can be purified by digestion with dilute alkali or ammonia and subsequent crystallization from glacial acetic acid. It is then obtained in the form of yellow-red, fine needles with a melting point of 273 to 276 °; its solution in concentrated sulfuric acid is pale yellow and turns deep blue when a little formaldehyde is added.

Example 3.
ι · 3 - diamino-2-methoxyanthraquinone.

a) 260 parts of p-anisoylbenzoic acid
CO

COOH

(cf. Ber. 19 [1886], p. 2103) at 0 to 15 ° in a mixture of 2000 parts of monohydrate and 1200 parts of sulfuric acid gradually entered; then at ο to 5 ° 315 parts of 4% nitrating acid are added added dropwise. After stirring for 6 to 8 hours at the same temperature, the Solution slowly in ice water. The dinitro acid precipitated in this way can pass through Converting into the sodium salt and salting out the same are purified. The several times off

Acid recrystallized acid does not melt very sharply at 205 to 215 °.

For the reduction, a hot solution of 55 parts of the purified dinitro acid in 750 parts of dilute alcohol with stirring in one with 400 parts of water, 100 parts Iron and 100 parts of acetic acid charged kettle at 80 "gradually added. After After heating for about 2 hours, the alcohol is evaporated off, 50 parts of soda are added to the residue and the mixture is filtered. From the received Solution filtered and completely neutralized with dilute sulfuric acid. The so in granular form precipitated diamino - ρ - anisoyl - ο - benzoic acid mostly brownish in color and melts at 215 °, with the elimination of water in the ι · 3-diamino-2-methoxyanthraquinone passes over; it dissolves easily in alkalis and diluted Mineral acids, fairly light in hot water and hot alcohols, heavier in benzene, toluene, or xylene.

b) The ι · 3-diamino-2-methoxyanthraquinone is obtained by heating 10 parts of diamino acid with 100 parts of glacial acetic acid ^{for 1 ^ hour and precipitating with water.} It forms red-yellow needles with a melting point of 225 to 230 °. With sulfuric acid, it gives a yellow solution which turns wine-red when heated with boric acid. In the cold, the sulfuric acid solution with a little formaldehyde gives a blue-black liquid which, when a little ice is added, first turns dirty-red, then red-violet. The 1 · 3-diamino-2-methoxyanthraquinone is somewhat soluble in hot water, easily soluble in hot glacial acetic acid and other organic agents and crystallizes out when these solutions cool.

Claims (1)

Patent claim: Process for the preparation of derivatives of ι 3-diaminoanthraquinone, consisting therein that one derives by substitution in the benzoyl or in the phthalic acid radical or in both benzene nuclei Derivatives of diaminobenzoyl-o-benzoic acid, in which the two amino groups in the same nucleus, namely in "the meta positions to the carbonyl group, for alone or in the presence of indifferent liquids or with acidic liquids Means heated.