DE956261C - 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 from vat dyes of the anthraquinone series that are difficult to esterify In the Swiss Patent specification 229z 804 discloses a process for the preparation of water-soluble leuco-sulfuric 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 the proportion of diethylcyclohexylamine is from 22o to 6o%.

In a further development of this method is proposed in one case instead of copper or copper alloys the metals of the iron group, d. H. Group VIII, period 3, of the periodic table individually, in mixture or to be used in combination with copper or copper alloys while in another case, instead of diethylcyclohexylamine, the three isomeric diethyl (monomethylcyclohexyl) amines can be used individually, in a mixture or in combination with diethylcyclohexylamine should.

There has also been a process for the preparation of water-soluble leuco-sulfuric acid ester salts from difficultly esterifiable vat dyes of the anthraquinone series in the proposal, according to which those vat dyes in the presence of at least one finely divided metal, such as iron, cobalt, nickel, copper and copper-containing alloys, with chlorosulfonic acid or a equivalent mixture of sulfur dioxide and hydrogen chloride in a mixture of dialkylformamide (where alkyl is CH, or C2H.) and diethylcyclohexylamine and / or at least one diethyl (monomethylcyclohexyl) amine, the proportion of diethylcyclohexylamine and / or diethyl ( monomethylcyclohexyl) amine is 10 to 70%.

It has now been found that vat dyes which are difficult to esterify can be used of the anthraquinone series in water-soluble leuco-sulfuric acid ester salts can, if you those vat dyes in the presence of at least one finely divided Metal, such as B. iron, cobalt, zinc, copper and copper-containing alloys with Chlorosulfonic acid or an equivalent mixture of sulfur trioxide and hydrogen chloride in a mixture of at least one inert liquid diluent and diethylcyclohexylamine and / or at least one diethyl (monomethylcyclohexyl )amine converts, the Proportion of diethylcyclohexylamine and / or diethyl (monomethylcyclohexyl) amine 3o to 9o0 / 9.

Among vat dyes of the anthraquinone series that are difficult to esterify are understood to mean those which, according to the usual esterification processes, only produce low, d. H. The yields of leuco-sulfuric acid ester salts are inadequate or only minimal for the technology or those products result which are produced according to the usual application processes no longer or only partially converted back into the vat dye. One simple test method to determine whether a vat dye within the meaning of the invention is difficult to esterify, is in the Swiss patent 2,92 8o4. described. Such vat dyes of the anthraquinone series which are difficult to esterify can be found z. B. in the following classes: i. i-Aroylaminoanthraquinones, which in q.-, 5- or 8-position are substituted by an acylamino, alkoxy or halogen group, mainly but diaroylaminoanthraquinones and their derivatives substituted in the benzene nuclei, 2. anthraquinone carbazoles, 3. anthrimides, q .. anthraquinone acridones.

The chlorosulfonic acid can be used as such or partially or completely in the form of an equivalent mixture of sulfur trioxide and hydrogen chloride or in the form of an SO. addition product of the base used and a hydrochloride the base used are introduced into the reaction mixture.

Inert diluents include such liquid substances to understand that are in no way involved in the esterification process according to the invention chemically participate. Furthermore, they must have a solvent or a dispersibility for the addition product of chlorosulfonic acid to diethylcyclohexylamine or Have diethyl (monomethylcyclohexyl) amine. Such inert diluents can both pure and technical, d. H. up to 9.10 / a water-containing products be brought to use.

Particularly suitable inert diluents are, for example: Acetone, chloroform, i, .2-dichloroethane, tetrachloroethane, n-propyl chloride, n-propyl bromide, n-butyl chloride, sec-butyl chloride, tert-butyl chloride, sec-butyl bromide, tert-amyl chloride, Acetonitrile, gasoline (i29 to 16o °), benzene, monochlorobenzene, o-dichlorobenzene, nitrobenzene, Toluene, xylene or dioxane.

The amount of inert liquid diluent required for implementation can also be made from a mixture of any amounts of various inert liquids Thinners exist.

Diethylcyclohexylamine or diethyl (monomethylcyclohexyl) amines can be used both as a pure base or as a technical, i.e. H. to 0.1% water-containing Products are brought into use. Among diethyl (monomethylcyclohexyl) amines the three methyl homologues of diethylcyclohexylamine are to be understood; these are: Diethyl (2-methylcyclohexyl) amine, diethyl (3-methylcyclohexyl) amine and diethyl (q.-methylcyclohexyl) amine. It can also only one of the diethyl (monomethylcyclohexyl) amines mentioned or a mixture of two or three of the said diethyl- (monomethylcyclohexvl) -aniine or, if desired, a mixture of at least one diethyl (monomethylcyclohexyl) amine be used with diethylcyclohexylamine.

The use of a mixture of at least one inert diluent and diethylcyclohexylamine and / or at least one diethyl (monomethylcyclohexyl) amine in suitable proportions is of decisive importance for the new process, and indeed it has been found that the proportion of diethylcyclohexylamine and / or Diethyl (monomethylcyclohexyl) amine in a mixture to obtain technically usable results must be at least 3911 / o and not exceed 99%; preferably but the proportion of diethylcyclohexylamine and / or diethyl (monomethylcyclohexyl) amine in the mixture limited to d.o to 7011 / o. To achieve an optimal yield Depending on the vat dye used, one will also use the leuco-sulfuric acid ester salt within this mixing ratio the proportion of diethylcyclohexylamine and / or diethyl (monomethylcyclohexyl) amine the special behavior of the vat dye adjust.

If the diethylcyclohexylamine and / or the diethyl (monomethylcyclohexyl) amine are replaced z. B. by dimethyicyclohexylamine, cyclohexylamine or triethylamine, so obtained at most insignificant amounts of leuco-sulfuric acid ester salts in addition to unusable ones Products. Only the use of diethylcyclohexylamine or its methyl homologues in combination with at least one inert diluent such favorable result in terms of the yield of leucosulfuric acid ester salt.

In the process according to the invention, the metal used is finely divided iron, Cobalt, zinc, copper or a copper alloy is used. Under the term »fine distributed "is z. B. to understand the powder form used up to now.

According to a particular embodiment of the new method, it is possible, the implementation not only in the presence of one of the metals mentioned, but to be carried out in the simultaneous presence of several of the metals mentioned. Preferably but for practice the use of iron, due to its economic efficiency, preferred. The new process can optionally also be carried out with the exclusion of oxygen be performed; furthermore, the metal used can be used beforehand Esterification process and in the absence of the vat dye to be esterified Subject to activation process. will. . The new method according to the invention is characterized compared to the aforementioned process by its much greater economic efficiency because, on the one hand, the use of an expensive base mixture is not mandatory and, on the other hand, a wide range of inexpensive diluents for practical use are available and alternative options are always adapted to the market situation exist.

The procedure is illustrated by the following examples. The specified Parts mean parts by weight. Example i To a mixture of 80 parts of i, 2-dichloroethane and i2o parts of diethylcyclohexylamine are added 40 parts of chlorosulphonic acid with stirring and cooling added dropwise, 10 parts of brass powder and 10 parts of i, 5-dibenzoylaminoanthraquinone admitted. The mixture is heated to 58 to 60 ° for 5 hours while stirring.

For work-up, the reaction mixture is poured into 1,000 parts of an 80% sodium carbonate solution and the i, 2-dichloroethane and the diethylcyclohexylamine are removed by distillation in vacuo (bath temperature 50 °). The resulting precipitate is separated off by filtration and stirred with a solution of 100 parts of alcohol and 2o parts of a 3oo% sodium hydroxide solution in 250 parts of water for 30 minutes at 35 to 40 °. The leuco-sulfuric acid ester salt of i, 5-dibenzoylaminoanthraquinone is obtained by salting out with common salt in a yield of over 90% from the solution which has been filtered off from the metal residues and concentrated under reduced pressure at a bath temperature of 50 °.

With the same success, brass powder can be used in place of io parts 10 parts of copper powder are also used.

If instead of 80 parts of i, 2-dichloroethane, 80 parts of n-methyl chloride, 80 parts of sec-butyl chloride or 80 parts of tert-butyl chloride are used the leuco-sulfuric acid ester salt is also in good yield.

Instead of io parts of i, 5-dibenzoylaminoanthraquinone, under otherwise identical conditions, it is also possible to convert io parts of the anthrimide from i, 3-dichloro-2-methylanthraquinone and i, 4-monobenzoyldiaminoanthraquinone into the corresponding leuco-sulfuric acid ester salt. Example 2 - To a mixture of 12o parts of diethylcyclohexylamine and 80 parts of i, 2-dichloroethane are added, with stirring and cooling, 40 parts of chlorosulfonic acid, iö parts of i, 4-dibenzoylaminoanthraquinone and 10 parts of iron powder, the latter in the course of 30 minutes with stirring in a Mixture of, for example, 2o parts of a-picoline and 3o parts of a-picoline chlorohydrate. 2o ° has been activated, added. The mixture is heated to 55 ° to 60 ° for 5 hours with stirring and worked up according to Example i. The leucosulfuric acid ester salt of i, 4-dibenzoylaminoanthraquinone is obtained in a yield of 96%.

Instead of io parts iron powder, io Parts of a cobalt powder activated in the same way are used.

Instead of iao parts of diethylcyclohexylamine, 124 parts of diethyl-, 2-methylcyclohexyl) amine are used is used, the leucosulfuric acid ester salt is likewise obtained in one yield of over 9o 1 / o.

With the same success, instead of diethyl (2-methylcyclohexyl) -amine, also the diethyl- (3-methylcyclohexyl) -amine, the diethyl- (4-methylcyclohexyl) -amine or a mixture of two or three of these homologues as well as a mixture of one or more of these homologues with diethylcyclohexylamine can be used. Example 3 To a mixture of 80 parts of i, 2-dichloroethane and 12o parts of diethylcyclohexylamine 4o parts of chlorosulfonic acid, io parts of i -benzoylamino-4- (q .'-dimethylsulfamido) -benzoylaminoanthraquinone and 10 parts of zinc dust were added. The reaction mixture is stirred for 3 hours at 10 °. After the work-up according to example i, the leuco-sulfuric acid ester salt of i-benzoylamino-4- (4 @ -dimethy lsulfamido) -benzoylaminoanthraquinones in a yield of over 8o %.

Instead of 10 parts i-benzoylamino-4- (4'-dimethylsulfamido) -benzoylaminoanthraquinone 10 parts of i, 4-dibenzoylaminoanthraquinone or 10 parts of i-benzoylamino-4-methoxyanthraquinone can also be used Convert into the leuco-sulfuric acid ester salt with an equally good yield.

Furthermore, the io parts zinc dust with the same result also replace iron powder with 10 parts. Are instead of 8o Parts of i, 2-dichloroethane used 80 parts of chloroform, the leukosch- # vefelsäureesteralz is obtained also in a yield of over 80%.

With the same success the 80 parts of chloroform can be converted by 80 parts Acetone, 8o parts of dioxane or a mixture consisting of 2o parts of i, 2-dichloroethane, 20 parts of chloroform, 20 parts of acetone and 20 parts of dioxane are replaced. example 4 While stirring and cooling, diethylcyclohexylamine is added to a mixture of 10 parts and 80 parts of i, 2-dichloroethane successively 40 parts of chlorosulfonic acid, 10 parts Brass powder and 10 parts of the carbazolated di- (5'-benzoylamino-i'-anthraquinonyl) -2, 8-diaminochrysens entered and then 5o ° for 5 hours with stirring warmed up.

Working up is carried out according to Example i. The leuco sulfuric acid ester salt is obtained in a yield of over 80%.

Instead of 10 parts of carbazolated di- (5'-benzoylamino-i'-anthraquinonyl) -2, 8-diaminochrysen can do io parts of i-benzoylamino-5-chloroanthraquinone with the same success be converted into the leuco-sulfuric acid ester salt.

Replace the 10 parts brass powder with 10 parts according to the example 2 activated iron and / or cobalt powder, you get the same result.

If 80 parts of i, 2-dichloroethane are used instead of 80 parts, i-2,2 tetrachloroethane, 8o parts amyl chloride, 100 parts acetonitrile or io) parts o-Dichlorobenzene, good yields of leuco-sulfuric acid ester salt are also obtained obtain.

Instead of 80 parts of i, 2-dichloroethane, only 20 parts thereof is used, the leuco-sulfuric acid ester salt is obtained under otherwise identical conditions in a yield of only 40%. Example 5 To one made in the cold Mixture of 80 parts of acetone, 12 parts of diethylcyclohexylamine and 40 parts of chlorosulfonic acid 15 parts of copper powder and 10 parts of i, 4-dibenzoylaminoanthraquinone are added. To 2 hours of stirring at 50 ° is worked up according to Example i. The leuco sulfuric acid ester salt falls in a yield of 80 0%.

The 8o parts of acetone can be as successful as 8o parts Chloroform, 80 parts of trichloroethane, 80 parts of n-propyl bromide or 80 parts of sec-butyl bromide be replaced.

Example 6 To a solution of 12 parts of diethylcyclohexylamine in 80 parts of dioxane are stirred and cooled 40 parts of chlorosulfonic acid and io Parts of i, 5-dibenzoylaminoanthraquinone were added. After adding 15 parts of brass powder the mixture is heated to 55 ° to 60 ° for 5 hours while stirring, and work is carried out the reaction mixture according to Example i. The yield of leuco sulfuric acid ester salt is 92 0/0.

A similar result is obtained if instead of 15 parts Brass powder a mixture of 10 parts copper powder and 5 parts iron powder is used will.

If the 80 parts of dioxane are replaced by 100 parts of toluene, 100 parts of monochlorobenzene, 100 parts of o-dichlorobenzene, 100 parts of xylene or 100 parts of nitrobenzene, good yields of leucosulfuric acid ester salt are also obtained. Example 7 To a mixture of 80 parts of diethylyclohexylamine 28 parts of chlorosulfonic acid and 150 parts of i, 2-dichloroethane are added with stirring and cooling , then 10 parts of 2, 5, 6, 7, 8-pentachloro-3, 4-phthalyl-acridone and 4 parts of brass powder are added and heated under Stirring for 2 hours to 50 °. If the reaction mixture is worked up as in Example i, the leucosulfuric acid ester salt of 2, 5, 6, 7, 8-pentachloro-3,4-phthalyl-acridone is obtained in a yield of over 80% .

Instead of 4 parts brass powder, 4 Parts copper powder or 5 parts advantageously activated cobalt powder will.

Leave in place of 2, 5, 6, 7, 8-pentachlor-3, 4-phthalylacridone under otherwise identical conditions, also 10 parts 2, 5, 7-trichloro-3, 4-phthalylacridone or 10 parts of 2-p-chlorobenzoylamino-3, 4-phthalyl-acridone in the leuco-sulfuric acid ester salt convict.

Furthermore, instead of 80 parts can also be used with the same success Bring i, 2-dichloroethane 8o parts of dioxane to use.

Claims (2)

PATENT CLAIMS: i. Process for the preparation of water-soluble Leucosulfuric acid ester salts from vat dyes of the anthraquinone series that are difficult to esterify, characterized in that those vat dyes in the presence of at least a finely divided metal such as iron, cobalt, zinc, copper and copper-containing Alloys with chlorosulfonic acid or an equivalent mixture of sulfur trioxide and hydrogen chloride in a mixture of at least one inert liquid diluent and diethylcyclohexylamine and / or at least one diethyl (monomethylcyclohexyl) amine converts, the proportion of diethylcyclohexylamine and / or diethyl (monomethylcyclohexyl) amine 3o to 9o o / o. 2. The method according to claim i, characterized in that the proportion of diethylcyclohexylamine and / or diethyl (monomethylcyclohexyl) amine 4o to 75%.