DE748918C - Process for the production of nitrogen-containing naphthalene derivatives - Google Patents

Description

Process for the preparation of nitrogen-containing naphthalene derivatives It has been found that valuable nitrogen-containing naphthalene derivatives can be prepared if multiply halogenated naphthalenes which have at least two halogen atoms and at least one of them in the-position are reacted with compounds which contain at least one hydrogen atom bonded to nitrogen as well as linkable groups. -The dem- process as starting materials, containing at least two halogen atoms, naphthalenes can still further, for example by alkoxy groups, eg. B. methoxy groups, may be substituted. There come z. B. a, 6-dibromo, a, 6-dichloro and i, 6-dibromo-am, ethoxynaphthalene into consideration.

For the implementation with these halogenated naphthalenes, the various cyclic compounds that contain at least one nitrogen-bonded Hydrogen atom and linkable groups "contained in the molecule, are used, where optionally 2 or more per mole of a polyhalogenated naphthalene Moles "of the same or different such compounds simultaneously or in succession can take effect.

Suitable compounds are in particular those amines which are ring-shaped contain attached carbonyl groups. Such amines can be anthraquinone derivatives be, or they can belong to more highly condensed ring systems. Such connections are z. B. Anthraquinones, i - Aminoanthraquinone and the i-Aminoarylaminoanthraquinones, also Aminoacylaminoanthraquinones, wherein the acyl radical z. B. the remainder of an aliphatic, aromatic or heterocyclic acid, such as. B. carboxylic acid, such as i - Amino - .4 - benzoylaminoanthraquinone, i - Amino - 5 - benzoylaminoanthraquinone, i Amino-5-benzoylamino-8-methoxyanthraquinone, i-amino-.5, 8 = dibenzoylaminoanthraquinone, i-atninoanthraquinonoylaminoanthraquinone, further z. B. Aminopyranthrones and Aminodibenzanthrones, further those aminoanthraquinone derivatives whose i- and 9-positions are members of a "heterocyclic Ringes are, like amino - i, 9 - anthrapyrimidines, Amino-i, 9-antlirapyridone, Amino-i, 9-isothiazolanthrone and Amino - 1, 9 - pyrazolantlirone, finally too those aminoanthraquinone derivatives in which two are in o-position to one another Carbon atoms are members of a heterocyclic ring system, as z. B. is the case with .den Amino-i, 2-anthraquinone acridones. All of these connections may still contain substituents.

The implementation of the Halogennaphthaliiie with the amines, which at least Containing a reactive hydrogen atom is advantageous by heating of the components in solvents or diluents, such as amyl alcohol, nitrobenzene or naphthalene; and expediently in the presence of catalysts such as copper or @Copper compounds, as well as acid binding agents carried out. It can finally all halogen atoms present in the same reaction stage or in several stages are used one after the other for the implementation.

The naphthalene derivatives obtainable by the present process can be used as body colors for a wide variety of purposes. they are in addition, the majority of them are valuable intermediates for the manufacture of vat dyes, while some of them already represent vat dyes. It is known to have such condensations to be carried out with a-halogenated naphthalenes at high temperatures. With the lesser one The reactivity of the P-halogenated naphthalene was the success of the implementation not foreseen.

Example i 14.3 parts of 2,6-dibromonaphthalene, 2.4.5 parts of i-aminoanthraquinone. 15 parts of dehydrated sodium acetate, 15 parts of anhydrous sodium carbonate and 1.3 parts of copper chloride are distributed in 50 parts of dry nitrobenzene and the mixture is stirred at a temperature of from igo to 20o ° for 2.4 hours. The reaction mixture is filtered hot. the residue is washed out with nitrobenzene as well as benzene and alcohol and, for cleaning, partially with dilute hydrochloric acid, then boiled with alcohol. A violet-black, crystalline powder is obtained in good yield, the conc. Sulfuric acid turns olive green. has a melting point of 370 to 3S0 '=' and is not v küpt.

The 2,6-dibromonaphthalene used in this example was like prepared as follows: 70 parts of 2-amino-6-bromonaphthalene, .verden in the usual way dianotized with 23 parts of sodium nitrite and the diazo solution with copper bromide Heated to 5o °. The 2,6-dibroninaphthalene separates out with foaming. This is filtered. washed out and unicrystallized from chloroform or glacial acetic acid, colorless crystals with a melting point of 158 ° are obtained.

Example e .f, 3 parts of 2,6-dibromonaplithalin, 10, 5 parts of i-amino-5-benzoylaminoanthraquinone. 4 .; Parts calc. Soda,: f.5 parts of dehydrated sodium acetate and 0.4 parts of copper clilorfir are distributed in 90 parts of dry nitrobenzene and kept at a temperature of 190 to 200 ° for 16 hours. 1) The reaction mixture is filtered hot, the residue is washed with nitrobenzene, benzene and alcohol and boiled with dilute hydrochloric acid for purification. -A brown one is obtained in good yield. crystalline powder, which is in conc. Sulfuric acid dissolves with a grass green color and has a melting point above 35o °. From your nitrogen content of 6.78 0/0 (Bei. 6, g3 0, l0) it can be concluded that a di- (5'-1-) enzovlaminoi'-anthraquinonyl) -2, 6-diaininotiaphtlialin is present. .

The 2,6-dibromonaphthalene used in this example was like is prepared as follows: 63.2 parts of 2,6-naphthalenediamine are combined with 56 parts of sodium nitrite in usually tetrazotized and the tetrazo solution rides copper bromine to 70 '= heated. The 2,6-dibroinnaphthalene separates out with foaming. This is filtered off, washed out and crystallized from glacial acetic acid. whereupon colorless crystals of melting point 158 ° can be obtained.

Example 3 15 parts of anhydrous sodium bicarbonate and 15 parts of dehydrated sodium acetate are kept at the boil in 50 ° parts of nitrobenzene until 50 parts of nitrobenzene have distilled off. After cooling to 200 °, 14.3 parts of 2,6-di) roiniiaphtlialin are used. 35, a parts of aniino-.l-ben7ovlaminoantlirachinon and 1.3 parts of Ktipferchloriir added. and the reaction mixture is stirred at 195 ° to 205 ° for hours. It is then filtered, washed with nitrobenzene and with benzene and alcohol and the product obtained is boiled for further purification with dilute hydrochloric acid, filtered off, washed and dried. -You get a brownish black, crystalline powder in good yield, the conc. Sulfuric acid turns olive green, melts over 350 " and does not vat. On the basis of the analysis, the di- (d .'-benzoylamino-i'-antlirachinonyl) -2,6-diaminonaphthalene is present. Example 4 2.5 parts 2; 6- Dibromonaphthalene, 5.4 parts of amino-5-acetylaminoanthraquinone, 2.3 parts of dehydrated nitrium acetate and 0.2 parts of copper chloride are distributed in 72 parts of dry nitrobenzene and heated to the boil with stirring The residue is washed with nitrobenzene, benzene and alcohol, boiled with dilute acid, filtered, washed and dried, giving a brown-black powder in good yield which dissolves in concentrated sulfuric acid with an olive-brown color, does not melt at 46o ° and does not vat.

In the same way, 2, 6-dibromonaphthalene and 2 are obtained from 1 mole Mol i-Amino-5- (o'-chloro) -benzoylaminoanthraquinone is a brown-black powder that does not yet melt at 46o ° and does not condense. 2,6-Dibromonaphthalene is also obtained from 1 mole and 2 moles of i-amino-5- (m -chlor) -benzoylaminoanthraquinone a brown-black powder, that is in conc. Sulfuric acid with brown olive green color: dissolves and does not vat.

The reaction product of i Mal 2,6-dibromonaphthalene and 2lVlol i-amino-5- (p = clilor) -benzoylaminöanthrach.inon is a brown-black powder, which is in conc. Sulfuric acid dissolves olive green, does not yet melt at 46o ° and does not vat.

In the same way, from 1 mole of 2,6-dibromonaphthalene and 2 moles of i amino-5- (P -methoxy) -benzoylaminoanthraquinone, a brown-black powder is obtained, which is in conc. Fused acid with an olive-green color dissolves, does not yet melt at 46 ° and does not cure. 'Example s i4,3. Parts 2, 6-dibromonaphthalene, 35.2 parts of 4-aminoanthraquinone-2, i- (hT) -benzolacridon, 1 5 parts of anhydrous' -, \ Tatriumcarbonat, 15 parts of dehydrated sodium acetate and 1.5 parts of cuprous chloride are used in parts of dry 45o - Nitrobenzene distributed and stirred for 24 hours at the zoo up to 2o6 °. -After the reaction is complete -is filtered hot, washed with nitrobenzene, benzene and alcohol., Boiled with dilute acid, filtered, washed and dried .: The in. The dye obtained in good yield is a greenish-black powder which dissolves brownish-red in sulfuric acid, does not yet melt at 460 ° and dyes cotton from a burgundy vat in green tones.

Example 1 "6 .--. Z, 86 parts 2, 6-dibromonaphthali.n, 7.1 parts S-aminoanthraquinone-2, i- (N) -benzolacridone, -3 parts of anhydrous sodium carbonate, 3 parts of dehydrated Sodium acetate and 0.26 parts of copper chloride are dissolved in 90 parts of dry nitrobenzene distributed and stirred for 24 hours at 195 to 2oo °. When the reaction is complete, filtered hot, washed with nitrobenzene, benzene and alcohol, with dilute hydrochloric acid boiled, filtered, washed and dried. The one obtained in good yield Dye is a blue-black powder that is in conc. Sulfuric acid with red Color dissolves, does not yet melt at 46o ° and cotton from red-violet vat in blue-violet, real tones.

- Example ? 5.7 = parts of 2, 6-dibromonaphthalene, 3.7 parts of amino-4-anilinanthraquinone, 6 parts of anhydrous sodium carbonate, 6 parts of dehydrated sodium acetate and 0.52 parts of copper chloride are distributed in igo parts of dry nitrobenzene and for 24 hours stirred at i95 to 200 °. After the reaction has ended, the product obtained is worked up in the manner described above. It is a black-blue, crystalline powder which melts at 38o to 39o ° with decomposition, does not evaporate and dissolves in concentrated sulfuric acid with a blue color.

On the basis of the analysis, the di- (4'-anilino-i'-anthraquinoyl) -2, 6-diaminonaphthalene.

By appropriate implementation of 1 mole of 2, 6-dibromonaphthalene and 2 12o1 i = amino-.t - methoxyanthraquinone -. you get a black-blue powder, which does not yet melt at 46o °, with a green color in conc. Sulfuric acid dissolves and not condensed.

EXAMPLE S 14.3 parts of 2,6-dibromonaphthalene are reacted with 5 parts of aminodibenzanthrone in the presence of 1.3 parts of copper chloride, 15 parts of anhydrous sodium carbonate and i 5 parts of dehydrated sodium acetate in 480 parts of boiling, dry nitrobenzene. The ProcluÜt worked up in the usual way is a black powder that does not yet melt at "46 °, dissolves in concentrated sulfuric acid finitely yellow-green color and dyes cotton from a blue vat in gray-green tones. -Example 9 5.72- parts: 2 , 6-Dibroninaphthlialin, _i2, 10 parts of 4-amino-N-xethyl: -i, 9-anthrapyridine, 6 parts of anhydrous 1 'atrium carbonate, 6 parts of dehydrated sodium acetate and 0.52 parts of copper chloride are for 24 hours with i Two parts of dry nitrobenzene are heated to about 200 °, then filtered while hot and the residue is purified as usual. A blue-black, crystalline powder is obtained which dissolves in concentrated sulfuric acid with a violet color, does not yet melt at 46 ° and does not evaporate.

In a corresponding manner, 2,6-dibromonaphthalene is obtained from 1 mole and 2 moles of 5 aminoisothiazolantlirone a black-violet crystal powder that is about 39o ° melts, in conc. Sulfuric acid with a yellow-green color dissolves and does not vat.

With 4-aminopyrazolantlirone, a brown powder is obtained, which at 46o ° does not yet melt, in conc. Sulfuric acid dissolves brown and does not vat. . Example io 2.86 parts 2, 6-dibroinnaplithalin, 5.4.3 "file 5-ainino-i, 9-antlirapyrimidiit, 3 parts of dehydrated sodium acetate, 3 parts of anhydrous sodium carbonate and o.26 Parts of copper chloride are dried in 90 parts with stirring for 24 hours Nitrobenzene heated to the boil. It is then filtered hot and the residue as usual cleaned. A black-blue, crystalline powder is obtained in good yield, which dissolves yellow-green in (conc. sulfuric acid, does not yet melt at 46o ° and Cotton from yellow-brown vat dyes blue.

Example ii 14.3 parts of 2,6-dibroinnapltthalene, 35.4 parts of aminoanthanthrone. 15 parts of anhydrous sodium carbonate, 1 5 parts of dehydrated sodium acetate and 1.3 parts of copper chloride are dissolved in 480 parts of iron-clad nitrobenzene with stirring during 2-. Heated to 20o to 205 ° for hours. It is then filtered hot and the residue cleaned as usual. A dark blue powder which in conc. Sulfuric acid with a brownish green color dissolves, does not yet melt at 460 ° and dyes cotton from a violet vat in brown-violet tones.

Example i-5.8 parts of 2,6-dibromonaphthalene, 7 parts of amino-5-benzoylaminoanthraehinone, 3 parts of anhydrous sodium carbonate, 3 parts of dehydrated sodium acetate and 0.25 parts of copper chloride are distributed in 1.5 parts of dry nitrobenzene and for 16 hours heated to 155 to 16o ° with stirring. It is then filtered hot. A dark powder separates from the filtrate when it cools down, completely only after the addition of alcohol. Sulfur satee green dissolves and does not condense. Product requires -Man this body to your usual way with a second mole of i-amino-5-benzoylaininoanthrachinon doing, one obtains the 0 oak product as in Example 2. Example 13 i of r moles of Example 12, paragraph, is provided can be reacted in the usual way with 1 mole of i-amino-4-benzoylaminoanthraquinone. 'You get a brown-black, crystalline powder that: I in conc. Sulfuric acid with a green color dissolves, melts above 300 ° and does not vat.

A similar product is obtained when 1 mole of 2,6-dibromonaphthalene simultaneously with i mole r amino-5-benzoylaminoanthraquinone and i-amino-4-benzoylaminoanthraquinone is implemented.

If one replaces in the example r2, paragraph i. the i-amino-5-benzoylaminoanthrachiiron by r-amino-4-henzoylaminoanthraquinone. this is how a black-brown powder is obtained, (It dissolves in conc. sulfuric acid with a green color and does not encapsulate it. Sits this condensation product with i mole of amirio-5-benzoy-laininoanthracliinon in the usual way, you get the same product as in paragraph i of the Example 13.

Example r4 38 parts of the reaction product from 1 mol of 2,6-dibromonapltthalene and i mole of i amino-5-benzoylaminoanthraquinone, obtained according to Example 12, paragraph r, i9 parts -. -Amino - r, 9 - anthrapyrimidine, 20 parts of anhydrous sodium carbonate, 2o parts of dehydrated sodium acetate and 2 parts of copper chloride are in 65o parts Distributed dry nitrobenzene and heated with stirring for 24 hours at Zoo to 2o6 °. Now it is filtered hot. When the filtrate cools, a dark brown color separates out Powder that is in conc. Sulfuric acid with brown color dissolves and is difficult condensed.

Example 15 2.86 parts of 2,6-dihromnaphthalene, 3.4 parts of 5-aminoanthraquinone-2, i (i "1) -benzolaeridone, 2 parts anhydrous sodium carbonate, 2 parts dehydrated 1 Sodium acetate and 0.2 parts of copper chloride are dissolved in 90 parts of dry nitrobenzene distributed and heated with stirring to 15o 'for 24 hours, then to r7o ° for 5 hours. It is then filtered hot. This separates from the filtrate after cooling Reaction product from. It is filtered, washed with nitrobenzene, benzene and alcohol and after drying it receives a blue-black powder, which is in conc. sulfuric acid dissolves with red-brown color,