DE565968C - Process for the preparation of halogenated pyridinoanthraquinones - Google Patents

Description

Process for the preparation of halogenated pyridinoanthraquinones It has been found that reactive organic compounds are obtained when one produces such pyridinoanthraquinones in which hydrogen at least partially is replaced by halogen. This can e.g. B. by treating pyridinoanthrachirions or their derivatives, such as nitro, sulf'D or. Pyridinoanthraquinones containing amino groups, with halogen or halogen-releasing agents, optionally in the presence of halogen carriers, take place. The halogen can also be introduced into pyridinoanthraquinones in the manner that aminopyridinoanthracliinones are diazotized and the diazo group is known per se Way exchanged for halogen. One can also proceed in such a way that one halogenated Aminoanthraquinones in which at least one o-position to an amino group is unoccupied is, with glycerine or the like. compounds capable of forming a pyridine ring, which contain a chain of at least three carbon atoms, e.g. chlorohydrins, in the presence of an oxidizing agent in acidic solution, expediently at temperatures between 100 and 170 degrees. This occurs as a result of the use of oxidizing agents no benzanthrone formation. These reactions can also be matched with the appropriate Representatives of the anthracene series or with the esters of the corresponding anthrahydroquinones be carried out, in which cases simultaneously or subsequently to the anthraquinone derivative must be oxidized. Likewise, instead of the aminoanthraquinones themselves, their N-substitution products or compounds which react like aminoanthraquinones or are able to pass into such during the reaction, or also such intermediates are applied, which according to known methods in aminoanthraquinones of the marked Art are transferable. Low halogen containing halopyridinoanthraquinones can halogenated even further by the action of halogen or halogen-releasing agents will.

The halogen substitution products of the various pyridinoanthraquinones and their derivatives are generally approximately colorless or pale yellow in color Bodies that are relatively easy to deal with in concentrated sulfuric acid mostly yellow to orange-red in color, while their vat solutions are mostly orange in color to are colored blue. The reaction products can, if necessary, simultaneously with the representation or then according to the usual methods, z. B. by crystallization or boiling with organic solvents or via their salts with strong acids, or by sublimation, Umküpen or treatment with Oxidizing agents are cleaned.

Containing chlorine, bromine, iodine or several of these halogens at the same time Pyridinoanthraquinone derivatives can be used as intermediates for the manufacture of Find dyes or other bodies use. Example i 50 parts of 2 (N) -i-pyridinoanthraquinone are in Soo parts of trichlorobenzene after adding 5 parts of iodine while passing in heated to boiling for several hours by chlorine gas. After cooling down, you vacuum it reaction product deposited in the form of yellow needles. According to the analysis lies a monochloro derivative; it dissolves orange in concentrated sulfuric acid, its vat solution is purple.

From 3-cyano-2 (N) -i-pyridinoanthraquinone (obtainable from 3-bromo-2 (N) -i-pyridinoanthraquinone by heating with copper cyanur in pyridine) one obtains in an analogous manner a violet-blue vat-producing, chlorine-containing reaction product; Likewise, 2 (N) -i-pyridinoanthraquinone-3-carboxylic acid (obtainable from the above cyan derivative by saponification) or 3-mercapto-2 (N) -i-pyridinoanthraquinone (obtainable from 3-bromo-2 (N) -ipyridinoanthraquinone by boiling with sodium sulphide) in the treatment described into a chlorine-containing reaction product. EXAMPLE e 30 parts of i-chloro-2-aminoanthraquinone are dissolved in 40o parts of sulfuric acid, whereupon 25 parts of sodium nitrobenzenesulfonate, 30 parts of 85% glycerol and 42 parts of water are added. The mixture is heated to between 1o5 and 1150 for about 1 to 2 hours and, when the reaction has ended, 3o parts of water are allowed to flow in. After cooling, the sulfate of the reaction product, which has separated out in crystalline form, is filtered off with suction and broken down in the usual way. The i-chloro-2 (N) -3-pyridinoanthraquinone thus obtained is a gray powder which can be obtained in crystalline form from high-boiling solvents. Example 3 100 parts of i (N) -2-pyridinoanthraquinone are distributed in 500 parts of nitrobenzene with stirring. After adding 0.5 parts of iodine and 150 parts of sulfuryl chloride, the mixture is warmed to 90 to 100 °, held for several hours, then allowed to cool and the separated chloro-i (N) -2-pyridinoanthraquinone is filtered off with suction. It is a yellow powder, dissolves in concentrated sulfuric acid with a yellow color and gives orange vats. Example 4 25 parts of 2-amino-3-bromoanthraquinone are dissolved in 300 parts of concentrated sulfuric acid, whereupon 17 parts of nitrobenzenesulfonic acid, 20 parts of 90% glycerol and 3o parts of water are added. The mixture is warmed to 10 to 1 50 for about 11/2 hours, after which zoo parts of water are stirred in. The sulfate of the reaction product, which separates out in crystalline form, is suction filtered and the 3-bromo-2 (N) -i-pyridinoanthraquinone is obtained as a yellow powder in the usual way. It can be recrystallized from organic solvents and then has a melting point of 23o °. The solution color in sulfuric acid is yellow, the vat is purple-tinged red.

Example s 50 parts 2 (N) -3-pyridinoanthraquinone (prepared from i-chloro-2 (N) -3-pyridinoanthraquinone of the example: 2 by dehalogenation) are under Stirring dissolved in fioo parts of chlorosulfonic acid. After adding 0.5 parts of iodine and 50 parts of bromine are slowly heated to 65 ° to 70 ° and held there until all the bromine has been consumed is, lets cool, diluted with a little sulfuric acid, poured into ice water, boiled briefly, sucks off the reaction product and dries. The bromo-2 (N) -3-pyridinoanthraquinone thus obtained is a straw-yellow powder, crystallizes in yellowish needles, dissolves green-yellow in concentrated sulfuric acid and yields yellow-green vats.

In an analogous manner, i-chloro-2 (N) -3-pyridinoanthraquinone is obtained by heating 12 parts in 100 parts of monohydrate and 2o parts of oleum with 5 parts of iodine to 14o to 15o0 Reaction product containing chlorine and iodine.

Example 6 50 parts of 8-chloro-i-aminoanthraquinone are dissolved in 70 ° parts of concentrated sulfuric acid, whereupon 35 parts of nitrobenzenesulfonic acid, 45 parts of 90% glycerol and 70 parts of water are added. The mixture is heated to between 10 and 120 for about 1 1/2 to 2 hours, poured into plenty of water, small amounts of impurities which have separated out are suctioned off and the liquid is made alkaline. A yellow-brown precipitate separates out, which is filtered off with suction, washed neutral and dried. The 8-chloro-i (N) -2-pyridinoanthraquinone obtained in this way can be purified further by recrystallization and then has a melting point of 197 '. It is also easily soluble in dilute acids; the solution color in sulfuric acid is yellow-red. In the same way, 5-chloro-i-aminoanthraquinone is obtained from 5-chloro (N) -2-pyridinoanthraquinone with a melting point of 257 to 258 ° and from 4-chloro-i-aminoanthraquinone from 4-chloro-i (N) - 2-pyridinoanthraquinone with a melting point toi °.

Example ? 10 parts of 3-oxy-2 (N) -i-pyridinoanthraquinone (obtainable from 3-oxy-2-aminoanthraquinone by condensation with glycerol in the presence of sulfuric acid) are dissolved in about zoo parts of 2% sodium hydroxide solution. 60 parts of bromine are then added and the mixture is heated to 95 to 100 ° for several hours, then allowed to cool and the reaction product obtained in excellent yield is filtered off with suction. It is a yellow powder that dissolves golden yellow in concentrated sulfuric acid and violet in sodium hydroxide solution, and with alkaline hydrosulfite gives a red-brown vat.

From 8-chloro-i (N) -2-pyridinoanthraquinone, heating with 3 parts of bromine without the use of a diluent, but in the presence of 0.05 parts of iodine, gives a brownish-red bromochlorine derivative, ~ o to 80 °, which by treatment with N atrium bisulphite solution turns into a sulphonic acid that pulls yellow-red on wool from an acidic bath. Example 8 14 parts of amino-2 (N) -i-pyridinoanthraquinone (obtained by nitration of 2 (2 \ T) -i-pyridinoanthraquinone in sulfuric acid solution and reduction of the resulting nitro derivative) are dissolved in 20 parts of sulfuric acid and at 10 to 2o ° the calculated amount of nitrosylsulfuric acid is added. After a short time, it is poured onto ice and the clear yellow-brown solution is stirred into an aqueous solution of potassium iodide. With vigorous foaming, a red-brown mass separates out, which, after briefly heating the reaction mixture, is filtered off with suction and dried. The resulting monoiodo-2 (N) -i-pyridinoanthraquinone can, for example, be recrystallized from trichlorobenzene and has a melting point of 2130. EXAMPLE 9 100 parts of i-chloro-2 (N) -3-pyridinoanthraquinone (shown according to Example 12) are in 100 parts Chlorosulfonic acid dissolved with stirring. After adding 10 parts of sulfur, 0.5 parts of mercury and 100 parts of bromine, the mixture is heated to 80 ° until all the bromine has been consumed. Then you let it cool down and work up in the usual way. The bromo-i-chloro-2 (N) -3-pyridinoanthraquinone obtained, a yellowish powder, crystallizes in pale yellow needles, dissolves in concentrated sulfuric acid with a yellow-green color and gives yellow-green vats.

On a similar journey one obtains from 3-bromo-2 (N) -i-pyridinoanthraquinone a tribromo-2 (N) -i-pyridinoanthraquinone. Example io io parts of dipyridinoanthraquinone, that one from 2,6-diaminoanthraquinone by treatment with glycerol and sulfuric acid obtained, are in r-oo parts oleum with 11.5% content of free S 0s after addition heated by 50 parts of bromine with stirring for several hours at 6o to 65 °. After this Cooling is worked up in the usual way. The bromodipyridinoantlirachinone obtained represents a yellow powder made from organic solvents or from sulfuric acid can be recrystallized; it dissolves in the latter with a golden yellow color; his The vat solution is purple.

From q.-methoxy- i (N) -2-pyridinoanthraquinone (obtainable from i-amino-q. = Methoxyanthraquinone by treating with glycerine and sulfuric acid) is concentrated by chlorination Sulfuric acid obtained an orange-colored chlorine derivative. Example ii Solve io Parts of 2-amino-3-bromoanthraquinori in zoo parts of concentrated sulfuric acid adds 3o parts of water and 2o parts of sodium nitrobenzenesulfonate are added and the mixture is stirred io Classify monoacetin. The mixture is then heated to from 110 to 115 ° for 1 to 2 hours pour the reaction mixture into water. The precipitate is filtered off with suction and dried. The reaction product is recrystallized from trichlorobenzene; it represents a yellow Crystal powder with a melting point of 23o ° and is identical to that according to the example available 2 (N) -i-pyridino-3-bromoanthraquinone.

Instead of monoacetine, other glycerine esters can also be used use, as well as epichlorohydrin.

Claims (1)

PATENT CLAIM: Process for the preparation of halogenated pyridinoanthraquinones, characterized in that pyridinoanthraquinones are donated with halogen or halogen Means, optionally in the presence of halogen carriers, treated, .Or Arriinopyrxdinoanthraquinones are diazotized and the diazo group is known per se Way replaced by halogen, or halogenated aminoanthraquinones with glycerol or similar compounds suitable for the formation of a pyridine ring, which form a chain of at least three carbon atoms in the presence of an oxidizing agent condensed in acidic solution, expediently at temperatures between zoo and 17o °.