DE948278C - Process for the production of water-soluble leuco-sulfuric acid ester salts from barley dyes of the anthraquinone series that are difficult to esterify - Google Patents

Description

Process for the preparation of water-soluble leuco-sulfuric acid ester salts Made from vat dyes of the anthraquinone series that are difficult to esterify. Addition to the patent 857 996 The subject of patent 857 996 is a process for the production of water-soluble Leucosulfuric acid ester salts from vat dyes of the anthraquinone series that are difficult to esterify, according to which those vat dyes in the presence of finely divided copper or copper alloys, such as B. brass, with chlorosulfonic acid or an equivalent mixture of sulfur trioxide and hydrogen chloride reacted in a mixture of α-picoline and diethylcyclohexylamine be., where. the proportion of diethylcyclohexylamine is 10 to 60%.

The subject of additional patent 9i8 041 is a process in which an Instead of copper or copper alloys, the metals of the iron group, d. H. group VIII, period 3, of the periodic system individually, in a mixture or in combination with copper or copper alloys are used. Elsewhere is a procedure has been proposed in which to Place of Diethylcyclohexylamine the three isomeric .Diethyl- (monomethylcyclohexyl) -amines individually, be used in mixture or combination with diethylcyclohexylamine.

It has now been found that vat dyes which are difficult to esterify are used of the anthraquinone series in water-soluble leuco-sulfuric acid ester salts can, if you put those vat dyes in the presence of finely divided copper or Copper alloys and / or in the presence of at least one finely divided metal the iron group, d. H. . of Group VIII, Period 3, of the. Periodic Table with Chlorosulfonic acid or an equivalent mixture of sulfur trioxide and hydrogen chloride in a mixture of 2-methyl-5-ethyl-pyridine and diethyl-cyclohexylamine and or at least one diethyl (monomethylcyclohexyl )amine converts, the proportion of Diethylcyclohexylamine and / or diethyl- (monomethyl = cyclohexyl) -amine ia up to 6o% amounts to.

2-Methyl-5-ethyl-pyridine is understood to mean both the pure base and the 2-methyl-5-ethyl-pyridine, which is commercially available as a technical, anhydrous product. The present proceedings; - distinguishes itself from the processes protected by: the patents 857 996 and give öq.i its greater economic efficiency, since 2-1VIethyl-5-ethyl-pyridine is light and also at a lower purchase price than a-picoline (2-methyl-pyridine ) is available.

The proportion of diethylcyclohexylamine in the broom mixture is preferred and / or diethyl (monomethylcyclolhexyl) amine limited to 15 to 3: 5%. To obtain an optimal yield of leuco-sulfuric acid ester salt will depend on the one used Vat dye also includes the proportion of diethylcyclohexylamine within this mixing ratio and / or diethyl (monomethylcyclohexyl) amine the special behavior of the vat dye adjust.

The same explanations apply to the new method according to the invention, as in main patent 857 9i) 6 for the definition of vat dyes that are difficult to esterify: toffe of the anthraquinone series. This also applies to those used for esterification required substances, such as chlorosulfonic acid or an equivalent mixture of Sulfur trioxide and hydrogen chloride and diethylcyclohexylamine, as well as for the executions concerning the broom mixture in a suitable ratio, and for the working method for Implementation of the method according to the invention. Furthermore, the same explanations apply for the use of copper and copper alloys and those explanations which in the additional patent gii 8 o, 4i for the use of metals of the iron group were given, including the particular embodiment in which simultaneously a metal of the iron group and copper or copper alloys are used will.

The process is illustrated by the following examples. The specified Parts mean parts by weight. Example i In 16o parts of technical grade 2-methyl-5-ethylpyridine from the boiling point of 176 to 178 °, 20 parts are obtained in succession with cooling and stirring Chlorosulfonic acid, 25 parts of iron powder and 56 parts of diethylcyclohexylamine entered. After adding io parts of i, 5-Dibenzoylam.inoanthraquinone for 5 to 6 Heated to 67 to 6g ° with stirring for hours.

The reaction mixture can be worked up in the following way: The same is in a solution of 35.5 parts of calcined sodium carbonate in 6o Parts of water entered and the broom mixture under reduced pressure at 50 ° Distilled off bath temperature. The aqueous solution is decanted from the precipitated oil, the 01 dissolved in -ioo parts of alcohol and treated with 2o parts of 3 (o% sodium hydroxide solution and 2.5o parts of water for 30 minutes. 40 ° stirred. From the iron residue filtered off and concentrated under reduced pressure at a bath temperature of 5o ° Solution can be the leuco-sulfuric acid star salt of i, 5-dibenzoylaminoanthraquinone by looking; be obtained with sodium chloride in a yield of more than 20%.

Will. in the above example the amount of 2-methyl-5-äthylpyri: dins of; 16o parts increased to 224 parts and, for the rest. proceed in the same way, one obtains the leuco-sulfuric acid ester salt of i, 5-dibenzoylaminoanthraquinone also in good yield. Example 2 In 160 parts of 2-methyl-5-ethylpyridine are cooled and stirring 20 parts of chlorosulfonic acid, 10 parts of copper powder and 56 parts of diethylcyclohexylamine registered. After adding io parts of i, 5-dibenzoylaminoanthraquinone, during Heated to 55 to 58 ° with stirring for 5 to 6 hours. Otherwise, as in the example i proceed.

The yield of leuco sulfuric acid ester salt is over 0/0.

Instead of copper powder, brass powder can also be used with the same success be used. $ eisp iel 3 In 16o parts of 2hMethyl-5-äthylpyri.din are under Cool; and stirring 20 parts of chlorosulphonic acid, 10 parts of iron powder, 10 parts of copper powder and 56% diethylcyclohexylamine: entered. After adding io parts of i, 5-dibenzoyl-ami @ noanthraquinone will during. Heated to 55 to 58 ° for 5 to 6 hours.

After working up, as indicated in Example i, the leuco-sulfuric acid ester salt is obtained of the i, 4-dibenzoylaminoanthraquinone in a yield of over go%.

Example, 4 If you work in exactly the same way as in example i, but instead of 56 parts of diethyl- i cyclohexylamine, 62 parts of diethyl- (2-methyl-cyclohexyl ) -amine used, the leuco-sulfuric acid ester salt of i, 5-dibenzoylaminoanthraquinone is used obtained in good yield.

Diethyl- (2-methylcyclohexyl) -amine can be used with the same success also diethyl (3-methylcyclohexyl) amine, diethyl (4-methylcyclohexyl) amine or a mixture of the three homologues as well as a mixture of one or more of the three homologues with diethylcyclohexylamine can be used ..

EXAMPLE 2o parts of chlorosulfonic acid and 56 parts of diethylcyclohexylamine are introduced into 130 parts of 2-methyl-5-ethylpyridine with stirring and cooling. 10 parts of i, 5-dibenzoylaminoanthraquinone and 50 parts of a 40% proprietary 2-methyl-5-ethylpyridine paste from "Raney Nickel" are then added. (This paste is prepared by treating the aluminum-nickel alloy with aqueous sodium hydroxide solution, washing it with water and alcohol and displacing the adhering liquid with 2-methyl-5-ethyl-pyridine.) The mixture is heated with stirring for z to 3 hours to 50 to 55 °.

After further work-up according to Example i, the leuco-sulfuric acid ester salt is obtained des i, 5-dibenzoylaminoanthraquinone in a yield of: 6o%.

EXAMPLE 6 20 parts of chlorosulfonic acid, 25 parts of iron powder and 56 parts of diethylcyclohexylamine are added to 38 parts of 2-methyl-5-ethylpyridine, with cooling and stirring. After adding 10 parts of i, 4-dibenzoylaminoanthraquinone, the mixture is heated to 67 to 69 'for 4 hours while stirring. The rest of the procedure is as in example i.

The yield of leukosulfuric acid ester salt of the 1,4-dibenzoylaminoanthraquinone is 870/0. Example? In 160 parts of 2-methyl-5-ethylpyridine are added with cooling and stirring Entered 2o parts of chlorosulfonic acid and 25 parts of powdered cobalt. One stirs during 20 minutes at 10 to 15 ° there are 56 parts diethylcyclohexylamine and 10 parts i, 4-Dibenzoylaminoanthraquinone is added and the mixture is heated with stirring for 5 to 6 hours to 67 to 69 °.

The rest of the procedure is as in example i. The yield of leuco sulfuric acid ester salt of the 1,4-dibenzoylaminoanthraquinone is 52%. Example 8 In 16o parts of 2-methyl-5-ethylpyridine are with cooling and stirring 2o parts of chlorosulfonic acid, 25 parts of iron powder and 56 parts of diethylcyclohexyl.amine entered, after addition of i & parts of carbazolated Di- (5'-benzoylaminoi'-anthraquinoyl) -2, 8-diaminochrysen is for 8 hours heated to 65 to 69 ° with stirring.

The reaction mixture is calcined in a solution of 35.5 parts Sodium carbonate added in 600 parts of water and the breast mixture under reduced Pressure distilled off at 5o ° wheel temperature. The aqueous solution is from the precipitated The oil is decanted off, the oil is dissolved in 100 parts of alcohol and treated with 2o parts of 3oo / oiger Sodium hydroxide solution and 250 parts of water heated to 50 to 55 ° for 30 minutes.

From the iron residues filtered off and under reduced Pressure-concentrated solution can pass the leuco-sulfuric acid ester salt of the dye through Salting out with sodium chloride can be obtained in a yield of over 90%. example 9 In 24o parts of 2-methyl-5-ethylpyridine are with cooling and. Stir 3o parts Chlorosulfonic acid, 25 parts of iron powder and 84 parts of diethylcyclohexylamine entered. After adding 10 parts of the anthrimide from i, 3-dichloro-2-methylanthraquinone and i, 4-monobenzoyl-diaminoanthraquinone is stirred for 8 to 9 hours heated to 67 to 69 °.

Further work-up as in Example 8 gives the leuco-sulfuric acid ester salt of the dye in a yield of 6o%.

Claims (2)

PATENT CLAIMS: i. Process for the production of 'water-soluble Leuco-sulfuric acid ester salts from vat dyes of the anthraquinone series that are difficult to esterify according to patent 857 996 and the additional patent 918 041, characterized in that one those vat dyes in the presence of finely divided copper or copper alloys and / or in the presence of at least one finely divided metal from the iron group, d. H. of group VIII, period 3 of the periodic system, with chlorosulfonic acid or an equivalent mixture of Sch @ wefeltrioxyd and hydrogen chloride in one Mixture of 2-methyl-5-äthylpyrndin and diethylcyclohexylamine and / or at least a diethyl (monomethylcyclohexyl) amine, the proportion of diethylcyclohexylamine and / or diethyl- (monomethylcyclohexyl) -a @ min io to 6o%. 2. Procedure according to claim i, characterized in that the proportion of diethylcyclohexylami, n and / or diethyl (monomethylcyclohexyl) amine is 15 to 35%.