DE79082C - Process for the preparation of polyazo dyes from dioxydiphenylmethane - Google Patents

Description

IMPERIAL

PATENT OFFICE.

In the molecule of the dioxydiphenylmethane can not only, as indicated in patent no will intervene, an azo group, but the compounds of the type identified in Patent No. 74629 are capable of each other still to combine with a second molecule of a diazo compound, so that if on ι mol. of the methane derivative mentioned, 2 mol. of the same or different diazo compounds come into play, two azo groups enter the molecule of the body mentioned.

One uses as diazo compounds the intermediate products that are formed by Accumulation of 1 mol. Tetrazodiphenyl or tetrazoditolyl or tetrazodiphenol ether and ι mol. A sulfonic acid of an aromatic amine, such as. B. sulfanilic acid or naphthionic acid, this creates dyes that contain the azo group four times. The two molecules the intermediate products can either be the same or different, and it can also be one of these by a simple diazo body such as diazobenzene chloride, diazobenzenesulfonic acid or diazonaphthalene sulfonic acid, in the latter case one to azo dyes which contain the azo group three times. All of the combinations mentioned still have the property dyeing unheated cotton in an alkaline bath.

The dye that z. B. is obtained from ι mol. Dioxydiphenylmethane, 1 mol. Des Intermediate products "tetrazodiphenyl sulfanilic acid" and 1 mole of the intermediate product »Tetrazodiphenyl-naphthionic acid is likely to have the following constitutional formula:

CH ₀

The constitution of the product of action of diazonaphthalene chloride on benzidinedisazo- , H ₄ -N = NC ₁₀ H _{6 -SO 3} Na, \ NH ₂

Dioxydiphenylmethane naphthoic acid is represented by the following scheme:

SO ₃ Na

CH

■ N

-.NC ₁₀ H ₇ .

I. Dye from ι Mol. Dioxydiphenylmethane and 2 Mol. Intermediate »Tetrazodiphenyl -

Sulfanilic acid ".

18.4 kg of benzidine are converted into the tetrazo compound in the usual way with the aid of 60 kg of hydrochloric acid of 2 1 ^{0 B. and 13.8 kg of sodium nitrite.} The same is then allowed to flow into a solution of 19.5 kg of sulfanilic acid soda and 40 kg of acetic acid soda with thorough stirring. The intermediate product obtained after two to three hours of exposure is introduced into a solution of ι o kg of dioxydiphenylmethane, 3.5 kg of caustic soda and 50 kg of carbonate of soda in 500 l of water. After standing for a short time, the mixture is boiled and the dye obtained is salted out. When dried, it is a red-brown powder that is easily soluble in hot water, and it dyes unheated cotton and yellow in an alkaline bath.

The solution of the dye in concentrated sulfuric acid is red-violet.

II. Dye from diazobenzene chloride and

Benzidine-disazo-dioxydiphenylmethane - sulfanil-

acid.

The intermediate product shown according to Example I. is carried in a solution of 20 kg Dioxydiphenylmethane, 7 kg of caustic soda and 40 kg of carbonate of soda in 500 Γ Water a. After standing for a short time, add another 40 kg of carbonate of soda and one solution of diazobenzene chloride prepared from 9.3 kg of aniline, 30 kg of hydrochloric acid and 6.9 kg of nitrite added. After several hours of exposure at normal temperature is heated to 60 to 70 ° C. and filtered off to complete the reaction. The dye is very sparingly soluble in hot water and is best used as a paste. It dyes unheated cotton yellow in an alkaline bath. The ones with this dye The colorations obtained stand out from those of the Congo yellow by their solidity against acids and especially against alkalis.

The solution of the dye in concentrated sulfuric acid is brown.

III. Diazobenzenesulfonic acid and dye

Benzidine-disazo-dioxydiphenylmethane - sulfanil-

acid.

To represent this dye, the 9.3 kg of aniline in the above example are replaced by 19.5 kg of sulphanilic sodium bicarbonate. The dye obtained is very light in hot water soluble and can only be precipitated from a neutral solution with a lot of table salt. Dried notes it is a dark brown powder, the unheated cotton in an alkaline bath, am best with the addition of table salt, turns yellow-brown.

The solution of the dye in concentrated sulfuric acid is brown.

IV. Dye from 1 mol. Dioxydiphenylmethane and 2 mol. Intermediate product "Tetrazodiphenyl-naphthoic acid" (Patent No. 39096).

The 19.5 kg of sulphanilic acid are replaced in Example I. Soda through 24.5 kg of naphthoic acid soda.

The dried dye is dark brown, shiny bronze in hot water easily soluble powder; he dyes unheated cotton in an alkaline bath ponceauroth.

The solution of the dye in concentrated sulfuric acid is blue.

V. Dye from 1 mol. Dioxydiphenylmethane and 2 mol. Intermediate product "Tetrazoditolyl-Naphthionic acid" (Patent No. 39096).

In Example I, the 18.4 kg of benzidine are replaced by 21.3 kg of tolidine and the 19.5 kg of sulfanilic acid Soda through 24.5 kg of naphthoic acid soda.

The dried dye forms a brown, bronze-shimmering color that is light in hot water soluble powder; he dyes unheated cotton yellow-red in an alkaline bath.

The solution of the dye in concentrated sulfuric acid is blue.

VI. Dye from 1 mol. Dioxydiphenylmethane, ι mol. Tetrazodiphenyl-sulfanilic acid and ι Mol. Tetrazodiphenyl - naphthionic acid (Patent No. 39096).

The benzidinedisazo-dioxydiphenylmethane-sulfanilic acid obtained according to Example II 40 kg of carbonate of soda are added; the intermediate product is then added to this mixture Tetrazodiphenyl naphthoic acid, obtained from 18.4 kg benzidine, 60 kg hydrochloric acid, 13.8 kg of nitrite, 24.5 kg of naphthoic acid soda and 40 kg of acetic acid soda. The reaction mass is boiled after standing for a while and the dye formed is salted out. He puts a dried dark brown, in hot Water is a readily soluble powder and dyes unheated cotton in an alkaline bath yellow-red.

The solution of the dye in concentrated sulfuric acid is gray-violet.

VII. Dye from 1 mol. Dioxydiphenylmethane, ι mol. Tetrazoditolyl - naphthoic acid (patent No. 39096) and 1 mole of tetrazodiphenol-methyl-

ether naphthoic acid.

Tolidine-disazo-dioxydiphenylmethane-naphthoic acid is first prepared dar; this compound is obtained by the method given in Example I. from 21.2 kg of tolidine, 60 kg

Claims (4)

Hydrochloric acid of 21 ⁰ B., 13.8 kg of sodium nitrite, 24.5 kg of soda naphtionsaurem 40kg acetate of soda, 20 kg Dioxydiphenylmethan, 7 kg caustic soda and 40 kg of sodium carbonate. To the obtained Reactionsproduct is added after standing for a further 40 kg of carbonic acid soda, and then the intermediate Product Tetrazodiphenol-methyl ether-Naphfionsä'ure obtained from 24.4 kg dianisidine, 60 kg of hydrochloric acid 21 ⁰ B., 13.8 kg of sodium nitrite, 24 , 5 kg of naphthoic acid soda and 40 kg acetic acid soda. After a short time the mixture is boiled and the dye obtained is salted out, which when dried is a dark brown powder and dyes unheated cotton in an alkaline bath with a burgundy red color. The solution of the dye in concentrated sulfuric acid is blue. VIII. Dye from diazonaphthalene chloride and tolidine-disazo-dioxydiphenylmethane - naphtion- acid. 40 kg of carbonate of soda and then a solution of diazonaphthalene chloride prepared from 14.3 kg of a-naphthylamine, 30 kg of hydrochloric acid and 6.9 kg of nitrite are added to the compound tolidinedisazo - dioxydiphenylmethane-naphthoic acid obtained according to Example VII. After several hours of exposure at normal temperature, the reaction is completed by heating to 60 to γο ° and the dye formed is salted out. When dried, it forms a dark brown powder which is easily soluble in hot water and dyes unheated cotton yellow-red in an alkaline bath. The solution of the dye in concentrated sulfuric acid is blue. IX. Α-Diazonaphthalene sulfonic acid dye
and tolidine-disazo-dioxydiphenylmethane Naphthoic acid. In Example VIII, the 14.3 kg of a- naphthylamine is replaced by 24.5 kg of naphthoic acid sodium. The dye is a dark brown powder that is easily soluble in hot water and dyes unheated cotton yellow-red in an alkaline bath. The solution of the dye in concentrated sulfuric acid is blue. · Pat ε nt claims ρ ruche: ι. Process for the preparation of polyazo dyes by the action of 1 mol. Dioxydiphenylmethane to 2 moles of diazo compounds, at least one of which is the intermediate from 1 mole of tetrazodiphenyl, Tetrazoditolyl or tetrazodiphenol ether and ι mol. A sulfonic acid of an aromatic Represents amine. 2. Representation of yellow to red nouns cotton dyes according to the process of patent claim 1. by combining ι mol. Dioxydiphenylmethane with 2 mol. Of the intermediate product from ι mol. Tetrazodiphenyl and 1 mol. Sulphanilic acid, or 1 mol. Tetrazodiphenyl and ι mol. Naphtionic acid (Patent No. 39096), or ι mol. Tetrazoditolyl. and 1 mole of naphthoic acid (Patent No. 39096). 3. Representation of yellow-red and burgundy nouns cotton dyes according to the method of patent claim 1. by combining 1 mol. Dioxydiphenylmethane with ι mol. Of the intermediate 'productes from 1 mol. Tetrazodiphenyl and ι mol. Sulphanilic acid and 1 mol. Of the intermediate from ι Mol. Tetrazodiphenyl and ι Mol. Naphtionic acid (Patent No. 39096), or 1 mole of the intermediate product from 1 mole of tetrazoditolyl and 1 mole of naphthoic acid (Patent No. 39096) and 1 mole of the intermediate from 1 mole of tetrazodiphenol methyl ether and 1 mole. naphthoic acid. 4. Representation of yellow and yellow-red nouns cotton dyes according to the The method of patent claim 1 by combining 1 mole of dioxydiphenylmethane with: a). 1 mol. Of the intermediate product from 1 mol. Tetrazodiphenyl and 1 mol. Sulfanilic acid and 1 mole of diazobenzene chloride or diazobenzenesulfonic acid; b) ι Mol. Productes of the intermediate from ι Mol. Tetrazoditolyl and 1 mol. Naphtionsäure (patent no. 39096) and ι Mol. Diazonaphtalinchlorid or a- Diazonaphtalinsulfosäure.