DE844777C - Process for the production of Kuepen dyes - Google Patents

Description

Process for the preparation of vat dyes It has been found that valuable vat dyes can be prepared by using compounds of the general formula where R1 is a non-connectable radical consisting of at least four fused rings and R2 and R3 denote radicals which can be bonded, treated with carbazolating agents.

The compounds of the formula given which are used as starting materials in the present process can be obtained, for example, by reacting 3 ', 6'-dihalophthaloyl compounds of the corresponding polynuclear radicals with connectable amines. Some of the phthaloyl compounds mentioned are known and some are new. If they are not known, they can be prepared by methods known per se, in particular by reacting 3, 6-dihalophthalic acids or their anhydrides with polynuclear hydrocarbons, e.g. B. fluoranthene, pyrenoline, and in particular pyrene and their substitution products are obtained (see. The German patents 590579, 624918 and 733756). Suitable radicals R1 of the formula given above are, for example, those which are essentially aromatic in nature and are derived in particular from an angularly fused four-ring compound which, in addition to six-membered carbon, contain at most one five-membered carbon ring and are free from methylene groups.

To implement such 3 ', 6'-Dihalophthaloylverbindungen can a wide variety of connectable amines can be used. First and foremost, be here Aminoanthraquinones called, in which the amino group used for the reaction is expedient occupies an a-position. These aminoanthraquinones can otherwise be free of substituents be or contain substituents that are usually found in vat dyes, z. B. halogen atoms, alkoxy groups, acylamino, especially benzoylamino groups and amino groups in which at least one hydrogen atom is replaced by an aliphatic or aromatic radical, e.g. B. in turn an anthraquinone residue is replaced. as Examples can be i-aminoanthraquinone, i-amino-4-, -5- or -8-benzoylaminoanthraquinone, Aminoanthraquinone acridones and anthrimides, especially dianthrimides with a free amino group, e.g. B. 4-Amino-i, i'-dianthrimide may be mentioned.

The implementation of the 3 ', 6'-dihalophthaloyl compounds mentioned with the mentioned amines can be connected in a known manner, for. B. by heating in high-boiling solvents such as nitrobenzene or naphthalene, expediently under Addition of acid-binding and possibly catalytically active agents (copper or Copper connections). The starting materials obtained in this way can in some cases with advantage with substituting, preferably with halogenating Agents are treated, e.g. B. with sulfuryl chloride in the presence of a halogen carrier like iodine.

The compounds used as starting materials for the present process the formula mentioned above can, if desired, in other ways, for example by reacting aminophthaloyl compounds with halogen substitution products connectable compounds are obtained.

According to the present process, these starting materials are now carbazolating Means treated. Among the latter, aluminum chloride is particularly important technically to mention. The carbazolation reaction can be carried out in a suitable diluent, if desired containing aluminum chloride melt or with an aluminum chloride addition compound be made. As such, the mixtures of aluminum chloride with sodium chloride can be used Mixtures of aluminum chloride with tertiary bases, especially pyridine and pyridine homolo = gene, aluminum chloride sulfur dioxide addition compounds and similar carbazolating Funds are used. Depending on the choice of diluent and raw material it may be useful to carry out the carbazolation at relatively low temperatures, z. 13. below 100 °, or at an elevated temperature, e.g. B. between ioo and 12o °, and even higher temperature, e.g. B. 14o ° and above to perform.

In many cases it is beneficial to use in the carbazolation reaction resulting hydrogen-rich compounds of a deliydration or w. Oxidation reaction to submit, e.g. B. by allowing nitrites, hypochlorites, chromates to act and älinliclien oxidizing agents, inshesondcre in acidic, z. B. sulfuric acid, Solution.

The products obtained by the present process are Kizpen dyes and are likely to conform to the general formula where R1 is a non-connectable radical having at least four fused rings, and R2 and R3 denote radicals which can be hooked. Here, Ri can in particular stand for a fluoranthene or preferably a pyrene radical and optionally also carry substituents, while R. B. Antliracliinon- or Diantlirimidreste can be.

The present 1, # iil> en dyes can in the usual way for Dyeing and printing a wide variety of fibers, especially those containing cellulose Fibers such as cotton, linen, rayon and rayon made from regenerated cellulose, be used. They can also serve as pigment dyes and are suitable also for the conversion into leuco ester salts, which in turn are based on those for this class of dyes known methods of dyeing or printing can be used.

The present `` 'ci-faliren allows i.a. making more valuable olive to gray dyes. These include in particular those that can be dyed in a strongly alkaline bath at a high dyeing temperature.

It has already been proposed that compounds which are isomeric with the starting substances used in the present process should be treated with carbazolating agents, see French patent 725 350. The products obtained according to the present process differ in part in terms of their color shade , partly through better authenticity properties and applicability. The following examples explain the present invention without, however, restricting it in any way. The parts mean parts by weight and the percentages mean percentages by weight.

Example i 60 parts of aluminum chloride are introduced into 130 parts of dry pyridine and 10 parts of pyridine are allowed to distill off. At a temperature of 121 to 23 °, 6 parts of the condensation product of 3 ', 6'-dichloro-3, 4-phthlialoyl tyren and i-Aniittoatitliracliitioti of the formula added and stirred at this temperature for 1 hour; the carbazolation is then ended. The melt is poured into water, made alkaline with sodium hydroxide solution, crushed with sodium hydrosulfite and a small amount of impurities is filtered off. After blowing out with air, filtering off, washing out and drying, the dye is a dark powder that dissolves in concentrated sulfuric acid with a reddish-brown color and dyes cotton from a red-brown vat in blackish, real brown tones. If, after blowing out and filtering off, the dye is post-oxidized in a sulfuric acid solution with dichromate at an elevated temperature, somewhat greener nuances are obtained.

Dyes that color in very similar shades are obtained if the carbazolation is carried out at a temperature of 140 °, or if one only 30 parts of aluminum chloride and about 70 parts of pyridine were used.

The starting product used in this example can be prepared as follows: 24 parts of 3 ', 6'-dichloro-3, 4-phthaloylpyrene (made from 1'yren and 3, 6-dichlorophthalic anhydride according to German patent specification 589 145 and subsequent elimination of water with phosphorus pentoxide in trichlorobenzene, orange needles, mp 336 to 338 ° '), 28.8 parts of α-aminoanthracliition, 13.3 parts of anhydrous sodium carbonate and 1.2 parts of copper acetate are boiled in 480 parts of dry nitrobenzene for 8 hours with stirring held. The precipitated condensation product is filtered off with suction in the cold with nitrobenzene, then washed out with alcohol and boiled with dilute hydrochloric acid. A crystalline, violet powder with a melting point of 390 to 393 ° is obtained, soluble in concentrated sulfuric acid with an olive-green color.

In an analogous manner from 24 parts of 3 ', 6'-dichloro-3, 4-phthaloylpyrene and 33.3 parts of a technical mixture of i-amino-6 and 7-chloroanthraquinone produced reaction product results after the carbazolation described in the first paragraph a dye that dyes cotton in yellowish brown tones. Examples that in example i (penultimate paragraph) described condensation product of 3 ', 6'-dichloro-3, 4-phthaloylpyrene and i-aminoanthraquinone are separated with sulfuryl chloride chlorinated with the addition of iodine and according to the example i, i. Paragraph, procedure described fused with aluminum chloride and pyridine. The dye forms a black Powder that dissolves in concentrated sulfuric acid with a brownish-purple color and Dyes cotton from a reddish brown vat in brown tones.

If the condensation product of 3 ', 6'-dichloro-3, 4-phthaloylpyrene and i-aminoanthraquinone is brominated in chlorosulfonic acid and subsequently, as in Example i, i. Paragraph, described, carbazolated, a similar dye is obtained as in i. Paragraph of this example. Example 3 54 parts of aluminum chloride and 11.2 parts of sodium chloride are melted at i2oa and 2.0 parts of the condensation product of 3 ', 6'-dichloro-14-phthaloylpyrene and i-aminoanthraquinone (cf. formula, example i) are entered. After stirring for 2 hours at 130 to 135 °, the mixture is poured into water and ice, suction filtered, made into a paste, acidified with 10% sulfuric acid and post-oxidized with 0.6 parts of sodium nitrite. After filtering off, washing out and drying, the dye forms a dark powder "which dissolves in concentrated sulfuric acid with a yellow-olive color and dyes cotton in blackish olive tones.

EXAMPLE 4 19 parts of aluminum chloride are added to 38 parts of nitrobenzene, and 2 parts of the condensation product of 1 mole of 3 ', 6'-dichloro-3, 4-phthaloylpyrene and 2 moles of i-amino-4-1> enzoylaminoanthraquinone are then added. While stirring, the temperature is increased in 1 / x hour to go ° and kept at this temperature for 1 hour. After discharging into water, the nitrobenzene is removed with steam. The dye is filtered off. washed out and re-oxidized with sodium nitrite for further cleaning in a sulfuric acid solution. It forms a black powder that dissolves in concentrated sulfuric acid with a dirty green color and turns cotton from a reddish-brown vat a blackish brown.

A similar product, which was a little blacker in color, was arrived at if, instead of nitrobenzene-aluminum chloride, the known melt of aluminum chloride, Table salt and sulfur dioxide is used.

The condensation product of 1 mole of 3 ', 6'-dichloro-3, 4-phthaloylpyrene and 2 moles of i-amino-5-benzoylaminoanthraquinone results in the carbazolation with the aluminum chloride-nitrobenzene mixture mentioned in the first paragraph at 75 to 8o ° or with the im 2. Paragraph mentioned mixture in brown tones coloring dyes. Example s 1.5 parts of the condensation product of 1 mole of 3 ', 6' - dichloro - 3n 4 - phthaloylpyrene and 2 moles of 4-amino-i, i'-dianthrimide of the formula are entered at 100 ° in a melt of 2o parts of aluminum chloride and 5o parts of dry pyridine. The temperature is now increased to 140 ° to 142 ° in a quarter of an hour while some of the pyridine is distilled off at the same time, and the mixture is stirred at this temperature for a further half of an hour. The melt is then discharged into water, made alkaline with sodium hydroxide solution and vat with hydrosulfite. After a little residue has been filtered off, the dye is blown out with air, suction filtered, washed out and dried. It is a dark powder that dissolves in concentrated sulfuric acid with a dark brown color and dyes cotton from a reddish-brown vat in black-olive, very real shades.

Similar dyes are obtained if the reaction time increases i is extended to 2 hours or if the mixture is stirred at 128 to 132 ° for 2 hours.

The starting product used in this example is obtained as follows: 6 parts of 3 ', 6'-dichloro-3, 4-phthaloylpyrene (see Example 1), 13.4 parts of 4-amino-i, i'-dianthrimide, 3, 3 parts of soda and 0.3 part of copper acetate are kept at the boil with 156 parts of nitrobenzene for 8 hours. After cooling, the quantitative condensation product which has precipitated out can be filtered off, washed out and boiled with dilute hydrochloric acid. It forms a black, crystalline powder that dissolves in concentrated sulfuric acid with a green to olive green color. Example 6 If the condensation product obtained in the last paragraph of Example 5 is subsequently chlorinated with sulfuryl chloride with the addition of iodine at 6o to 70 °, and then, as in Example 5, 1 or 24 paragraph, is given with aluminum chloride and pyridine 14o ° fused, a black powder is obtained which dissolves in concentrated sulfuric acid with a black-brown color and dyes cotton from a brown vat in olive-gray, very real shades. Post-oxidation with sodium nitrite in a sulfuric acid solution makes the color a little more red-sticky.

A very similar dye is obtained if you add 5 parts of the post-chlorinated condensation product with 25 parts of aluminum chloride and 55 parts Pyridine treated as indicated at 14o to 142 °.

Through stronger chlorination at a higher temperature of the condensation product (of the last paragraph of Example 5) there are about 2 atoms of chlorine in the molecule a. By fusing with aluminum chloride and pyridine as described in the example 5, 1st and 2nd paragraph, you get a dye that is in concentrated sulfuric acid with brown color loosens and cotton from brown vat in strong, very real ones black olive tones.

Example ? 30 parts of aluminum chloride and 3.6 parts of table salt are used intimately mixed and fused at 14o °. Now at 140 to t45 ° 1.5 parts of the condensation product of 3 ', 6' - dichloro-3, 4-phthaloylpyrene and 5-amino-i, i'-dianthrimide entered and stirred for 2 hours at 165 to 168 °. After pouring into ice and water, it is acidified with dilute sulfuric acid and post-oxidized with 0.9 parts of sodium dichromate at ordinary temperature. Man receives a brown-black powder that dissolves in concentrated sulfuric acid with dirty purple Dye dissolves and dyes cotton from a reddish brown vat in yellowish brown tones.

The condensation product used in the first paragraph of this example can be made from 1 mole of 3 ', 6'-dichloro - 3, 4 - phthaloylpyrene and 2 moles of 5 - aminoi, i'-dianthrimide prepared in the usual way with the addition of copper salts in boiling nitrobenzene will.

EXAMPLE 8 12 parts of the compound normally obtained from 1 MOI of 3 ', 6'-dichloro-3, 4-p'hthaloylpyrene and 2 mol of 4-aminoanthraquinone-2, i- (N) -1', 2 '- (N) -benzacridone obtained condensation product of the formula are introduced at 100 ° into a melt of 20 parts of aluminum chloride and 300 parts of dry pyridine and the temperature is increased to 14o to 142 ° while distilling off pyridine. After stirring for 3 g / 4 hours at this temperature, the mixture is poured into water, made alkaline, vat and some undissolved material is filtered off. By blowing out with air, the dye is obtained as an olive-black powder, which dissolves in concentrated sulfuric acid with a brown-black color and dyes cotton from a black-brown vat in pure olive-green, very real shades.

Example 9 20 parts of aluminum chloride and 50 parts of dry pyridine are heated to boiling and 10 parts of pyridine are allowed to distill off. At a temperature of 121 to 123 ° 2 parts of the condensation product of the probable formula entered and stirred at this temperature for 2 hours. It is then poured into water, made alkaline with sodium hydroxide solution and vat with sodium hydrosulfite, something insoluble is filtered off and the dye is blown out with air. It forms a dark powder that dissolves in concentrated sulfuric acid with a black-olive color and dyes cotton from a red-brown vat in olive tones.

The condensation product used in the first paragraph is made by heating of 1 mole of 3 ', 6'-dichloromonophthaloylpyrenoline (available from British patent 476 988 by fusing pyrenoline with 3, 6 - dichlorophthalic anhydride with aluminum chloride @ common salt at 150 °) and 2 mol of i-aminoanthraquinone in nitrobenzene with the addition of copper salts.

Example io 1.5 parts of the from 1 mol of 3 ', 6'-dichloromonophthaloylpyrenoline (See British patent specification 476,988) and 2 moles of 4-amino-i, i'-dianthrimide condensation product obtainable by heating in nitrobenzene with the addition of copper acetate are at 100 ° in a melt of 20 parts aluminum chloride and 50 parts dry Pyridine entered and the temperature increased to 14o to 142 °, with a small amount of pyridine distilling off. Then 2 hours at i4o to i42 ° stirred and the reaction mass discharged into water, with phenolphthalein alkaline sodium hydroxide solution and vat with sodium hydrosulfite. After filtering off little insolubles the dye is blown out with air, filtered off, washed out and dried. It forms a dark powder that dissolves in concentrated sulfuric acid with brown Color dissolves and cotton from a brown vat in strong, greenish olive tones colors.

Example ii 2 parts of the condensation product of 1 mole of dichlorophthaloyl fluoranthene and 2 moles of α-aminoanthraquinone of the probable formula below are entered at 125 to 135 'in a melt of 10 parts of aluminum chloride and 30 parts of pyridine. The temperature is now increased to 150 to 16 °!, With part of the pyridine distilling off. After two hours of stirring at 150 to 160 °, the reaction has ended. The melt is stirred into 1,000 parts of 50% sodium hydroxide solution, vat and small amounts of insolubles are filtered off. The dye, which is completely precipitated by the introduction of air, is filtered off with suction, washed and dried. It is a dark powder that dyes cotton from an olive vat in real, olive-brown tones.

The starting product used in this example can be prepared as follows: 4.01 parts of 3 ', 6'-dichlorophthaloylfluoranthene (available from German Patent 624 9r8), 4.46 parts of α-aminoanthraquinone, 3 parts of sodium acetate and 0.3 part of copper chloride are heated to boiling for 15 hours with stirring in 85 parts of dry nitrobenzene. The reaction product that has precipitated is suctioned off while warm, washed with nitrobenzene and alcohol and boiled with dilute hydrochloric acid and alcohol. When dried it is a black powder that dissolves in sulfuric acid with a green color and melts at 45o ° with decomposition.

Example 1: 2 2 parts of the condensation product from i moles of 3 ', 6' - Dichlorophthaloylfluoranthene and 2 moles of 4-amino-i, i'-dianthrimide are after in example i i, paragraph i, process described with 10 parts of aluminum chloride and 30 parts of pyridine fused. The dye thus obtained turns dark colored powder, the cotton from the olive vat in blackish-brown, real Tones colors.

The starting product used in this example is a black one Powder that dissolves in sulfuric acid with a gray-green color and below 450 'does not melts. It can be prepared according to the procedure given in example i i, paragraph 3 will. Example 13 An intimate mixture of 25 parts of aluminum chloride and 4 parts Sodium chloride is liquefied by introducing sulfur dioxide. In the resulting 2 parts of the condensation product from 1 mol of 3 ', 6'-dichlorophthaloylfluoranthene are now carried in the melt and 2 moles of i-amino-5-benzoylaminoanthraquinone. After stirring for one hour each The reaction has ended at 40 ° to 45 ° and 85 ° to 90 °. One carries the conversion mixture on ice, 2o parts of concentrated hydrochloric acid are added, heated to the boil and sucks off the precipitated dye. It is washed acid-free and then distributed in 2oo parts of 50% sulfuric acid. It is now cooled to 0 to 5 °, gives 0.6 parts of sodium nitrite are added and the suspension is stirred for several hours at 0 to 5 °. The dye obtained in this way is filtered off with suction, washed and pasted with water. He dyes cotton from an olive vat in blackish brown tones.

The starting product used in this example is a black one Powder that dissolves in concentrated sulfuric acid with a gray color and at 43o ° melts with decomposition. It can be according to that described in example i i, paragraph 3 Procedure can be obtained.

Example 14 2 parts of the starting product used in Example 13 are at 5o to 55 ° in the mixture of 5 parts of aluminum chloride and 5o parts entered dry nitrobenzene. After five hours of stirring at 5o to 55 ° carries if the reaction mixture is poured into ice water, 3o parts of concentrated hydrochloric acid are added added and the nitrobenzene is distilled off with steam. The failed dye is filtered off, washed and pasted with water. He dyes cotton from olive Vat in brown tones.

Claims (4)

PATENT CLAIMS: i. Process for the preparation of vat dyes, characterized in that compounds of the general formula in which R, a group consisting of at least four fused rings, which cannot be linked and R2 and R3 denote residues which can be linked, A treated with carbazolating agents. 2. The method according to claim i, characterized in that the remnants that can be vetted R, and R3 are anthraquinone residues. 3. The method according to claims i and 2, characterized characterized in that R, an angularly fused four-ring aromatic radical, which in addition to carbon six-membered rings contains at most one carbon five-membered ring and is free of methylene groups, .represents. 4. The method according to claims i and 2, characterized in that R 1 represents a pyrene radical.