DE1070314B - Process for the production of vat dyes - Google Patents

Description

It is known Bz-1-benzanthronyl-l-aminoanthraquinone or to treat its derivatives with alkaline condensation agents (German patent specification 212 471). The one obtained by this process from Bz-1-benzanthronyl-1-amino-5-aminoanthraquinone available vat dye of the following constitution

Method of manufacture
of vat dyes

NH ₂

Applicant:

Farbwerke Hoechst Aktiengesellschaft

formerly Master Lucius & Brüning,

Frankfurt / M., Brüningstr. 45

Dr. Heinrich Greune f, Frankfurt / M.-Höchst,

Dr. Hans Schlichenmaier, Lindau (Lake Constance),

and Dr. Heinrich Pohlmann,

Frankfurt / M.-Unterliederbach,

have been named as inventors

dyes cotton from the vat in blue-gray tones.

Furthermore, from the German patent specifications 520 876,

522 970 and 844 781 it has become known that acylation of this dye with z. B. benzoyl chloride

where R is an alkyl or aryl group and R 'is an amino or acylamino group, with alkaline condensate

or benzoic anhydride, or by treatment with agents, fused and the vat thus obtained acylating agents that differ from nuclear halo dyes of the formula

derive genated aryl monocarboxylic acids, such as. B.

o- or p-chlorobenzoyl chloride, produce vat dyes can dye cotton or rayon in olive tones. But neither the acylated nor the not acylated dyes are sufficient, especially in their soda

kochechthcit, the requirements of dyeing practice. _λ NH

It has now been found that valuable new f ' "" ** -, -''\

Obtains vat dyes of very good fastness to soda, |

if you go through in the 2-position of the benzanthrone Alkyl or aryl radicals substituted Bz-1-halobenzanthrones with 1,5-diaminoanthraquinones or their monoacyl compounds converts the benzanthronylamino-anthraquinone compounds obtained from the following composition

optionally treated with acylating agents.

If one leads the merger of the benzanthronylamino-anthraquinone compounds, which contain an acylamino group in the 5-position, for example with alcoholic By using caustic potash in the usual way, the acylamino group is saponified and the free ones are obtained Amines. If you want to avoid saponification, you can treat as described in Example 8 or 9 make the French patent 697 231 in such a way that the compounds with alkaline Condensing agents that contain practically no hydroxyl groups, e.g. B. Aniline Sodium or Sodium Alcoholate, fuses in aniline at around 140 to 170 ° C.

909 687/341

3 4

The new vat dyes obtained, which are free by alkaline fusing of this anthrimide

Contain amino group or an acylamino group, according to the instructions in Example 1, one obtains

In addition to excellent lightfastness, they also have a vat dye that swells at 384 to 385 ° C

very good fastness to washing and soda cooking. They mean melts. Its solution paint in concentrated sulfur

therefore compared to the above-mentioned known coloring acid is green. Preserves on cotton or rayon

materials represent a significant technical advance. from a blue vat a gray of remarkably good quality

Fastness to chlorine and very good washing, soda cooking and

Example 1 light fastness.

14.2 parts by weight of Bz-I-bromo-Bz-2-äthylbenzanthron io "'

from mp 192 to 194'C, obtainable by bromicrene of 14 parts by weight of the Bz-2-ethylbenzanthrone obtainable according to Example 3 with bromine and sulfuryl chloride in gray vat dye are in 360 parts by weight of chloroform, with 14.4 parts by weight of l-amino-chlorobenzene with 14 parts by volume of m-chlorobenzoychloride 5-benzoylaminoanthraquinone with the addition of 0.5 Ge heated to boiling for 5 hours. It is allowed to cool and parts by weight of copper powder and 13.5 parts by weight are filtered off with suction from the crystalline dye thus obtained. The anhydrous sodium carbonate in 200 parts by weight melts at 375 to 376 ° C. Its solution color is heated to boiling in concentrated nitrobenzene for 10 hours. After the trated sulfuric acid is green. It dyes cotton when it cools, the crystalline Bz-2-ethyl-Bz-1-benzan-gray-blue vat is sucked off after hanging in a yellow-throated H-amino-5-benzoj'laminoanthraquinone pungent khakiton. The dyeings are very good and dry. It is in excellent yield 20 fastness properties, especially very good light and sclimilzt at 309 to 311 ⁰ C; its solution color in washing, soda boiling and chlorine fastness,
concentrated sulfuric acid is purple-tinged brown. Is as Acylierungskomponentc used in place of 45.0 parts by weight of the above anthrimide be in the m-chlorobenzoyl chloride, the o-methoxybenzoyl chloride, 110 to 120 ⁰ C in a melt of 56 parts by weight of one obtains a vat dye, the vegetable potassium hydroxide and 135 parts by weight of monoethanolamine single 25 fibers also worn in a khakiton of very good and kept for 1 hour at this temperature with fastness properties, in particular very good washing, stirring. Then you put the melt on ice, soda boiling, chlorine and light fastness, dyed. When oxidized, the leuco compound obtained by turning l-aminoanthraquinone ^ -carboxylic acid chloride air stream, sucks off and dries. The vat obtained as an acylation component gives a brown dye with the free amino group and provides a gray vat dye with similar good properties. Powder that melts at 365 ° C and dissolves in concentrated sulfuric acid with a green color. He colors Bcisr / 1 S
Cotton from the vat in gray tones of very good '^

Authenticity properties. 19.1 parts by weight of Bz-1-bromo-Bz-2-phenylbenzanthrone

B 'sm 1 2 ^{35 who <} ^ ^{en mr} * 17.1 parts by weight of l-amino-5-benzoylarrüno-

"anthraquinone in 120 parts by weight of naphthalene

15 parts by weight of the addition of 0.3 parts by weight of copper oxide and 8 parts by weight of dye described in Example 1 are heated in 375 parts by weight of chlorobenzene anhydrous sodium carbonate for 12 hours with 15 parts by weight of m-fluorobenzoyl chloride at 215 to 220 ° C. for 5 hours. At about 80 ° C, 120 boilers are heated to the boil. After cooling, the toluene in 40 parts by weight is added. The dyestuff obtained after cooling with an excellent yield is filtered off with suction and the precipitate is filtered off with suction and dried through and through. Its melting point is 385 ° C, naphthalene removed by steam distillation. The anthrimide obtained in its solution color in concentrated sulfuric acid melts green after recrystallization. On cotton, a blue vat is made from nitrobenzene at 327 to 329 ° C.
Khakiton with very good fastness properties, in particular 45 5 parts by weight of this anthrimide is worn at 90 ° C. particularly very good washing, soda boiling, chlorine and in a melt of 6.25 parts by weight caustic potash and light fastness. 7.5 parts by weight of ethanolamine and holds at this ρ _j .,. , ₃ temperature 2 strokes with stirring. Then you put the ^b P melt on ice, oxidize it with air and suck the

31.0 parts by weight of Βζ-Ι-ΒΐΌΐη-Βζ-2-isopropylbcnzan- 50 obtained vat dye. Its solution color in

Throne from 170 to 171 ° C, produced by brominating concentrated sulfuric acid, is green. On cotton

the condensation of anthrone with α-isopropyl gives a very gray color from the blue vat

acrolein in sulfuric acid in the presence of an oxidation- good fastness properties,

by means of available Bz-2-Isopropylbcnzanthrons from _.

F. 119 to 120 "C, with 29.1 parts by weight 55 Example 6

1-Amino-5-benzoylaniinoanthraquinone, 1.0 part by weight, 3.7 parts by weight of that obtainable according to Example 5

Natural copper C and 28.1 parts by weight of anhydrous dye are used in 150 parts by weight of chlorobenzene

Sodium carbonate in 400 parts by weight of nitrobenzene 6.8 parts by weight of benzoyl chloride for 5 hours to the boil

Heated to the boil for 10 hours. The heated in exquisite and worked up in the usual way. The received

Yield obtained anthrimide forms red-brown crystals, θο dye stains cotton from a navy blue vat

which melt at 335 ° C and are concentrated in hanging in olive tones. Own the colorations

Sulfuric acid, dissolve with a purple-tinged brown color. an excellent light, washing, soda boiling and chlorine

The same anthrimide is obtained when looking for authenticity.

Example 7 instead of Bz-1-bromo-B2-2-isopropylbenzanthrone

Bz-1-chloro-Bz-2-isopropyl benzanthrone from 180 to 65

181 ° C, obtainable by chlorination of Bz-2-isopropyl-8.08 parts by weight of Bz-1-bromo-Bz-2-methylbenzanthrone

benzanthrone with sulfuryl chloride in chlorobenzene at 60 from melting point 230 to 231 ⁰ C, obtainable by

up to 70 ° C, with l-amino-5-benzoylaminoanthraquinone bromination of Bz-2-methylbenzanthrone, with

.implemented. It is advisable to heat not 10, but 8.55 parts by weight of l-Ammo-5-benzoylaminoanthrachi-

20 hours. 70 non, 0.3 parts by weight of copper powder and 8 parts by weight

Claims (1)

5 6 divide anhydrous sodium carbonate in 120 weight - you get a gray-black powder share nitrobenzene heated to boiling for 10 hours. After dye, which is in concentrated sulfuric acid with When it cools, the resulting anthrimide is sucked off, the green color dissolves and the vegetable fiber from purple washed with a little chlorobenzene and colored the vat in real gray tones with water, dissolved out the excess sodium carbonate. The 5 5 parts by weight of the dye obtained are in Bz-2-methyl-Bz-1-benzanthronyl-1-amino-S-benzoyl-125 parts by weight of chlorobenzene with 5 parts by weight aminoanthraquinone is heated to the boil for 5 hours in excellent yield, hold, it melts at 352 ° C with foaming. Its left to cool and sucked off. The one in very good Solution color in concentrated sulfuric acid is purple. Yield obtained dye represents fine, olive-colored 10 parts by weight of the above compound are used in io needles which are in concentrated sulfuric acid Dissolve 110 to 120 "C in a melt of 12.5 parts by weight with green paint. It colors the vegetable fibers Caustic potash and 30 parts by weight of Äthanqlamin entered from a gray-blue vat in greenish olive tones of and stirred at 110 to 120 ° C for 1 hour. A sample shows good fastness properties. after blowing out with air under the microscope none The Bz-1-chloro-Bz-2-n-pentylbenzanthrone can be .Yellow crystals more, the melt is on ice 15 analogous to the information in Example 3 by chlorinating the given the leuco compound through a stream of air by condensation of anthrone with a-n-pentylacrolein oxidized, filtered off with suction, washed neutral and dried. available Bz-2-n-Pentylbenzanthrons from the melting The dye obtained with the free amino group is produced at 90 "C. a-n-pentylacrolein is according to the represents a gray-black powder. The product is described in German Patent 875,194 To get it completely pure, it becomes available in 20 times the amount 20 procedures. Boiling point at a pressure of concentrated sulfuric acid and the green colored 31 mm: 75 to 78 ° C. Solution by the addition of 50 ° / ₀ sulfuric acid at Instead of Bz-l-chloro-Bz-2-n-pentylbenzanthrons Let down 20 ° C to 75 ⁰ / o sulfuric acid. You can also use the corresponding bromine compound from Crystalline deposited dye is filtered off with suction and used with a melting point of 121 to 122 ° C.
Washed with water until neutral and dried. 35 7.95 parts by weight of the dyestuff purified in this way are used in Example 9
in 200 parts by weight of chlorobenzene with 8 parts by weight Benzoyl chloride heated to boiling for 5 hours. 50.6 parts by weight of that obtainable according to Example 3 are left cool down and work up in the usual way. The in gray vat dye will be in 1000 parts by volume excellent yield obtained dye dissolves in 30 chlorobenzene with 44 parts by weight of m-methylsulfonyl concentrated sulfuric acid with a green color. It stains benzoyl chloride slowly heated to boiling temperature. the from gray-blue cotton vat in green-tinged olive temperature is kept at 125 to 130 ° C for 10 hours, Tones which are characterized by excellent fastness properties, especially then, are allowed to cool and the resulting ones are vacuumed very good fastness to light, washing and chlorine, crystalline dye. The solution color in concentrated to draw. 35 trated sulfuric acid is green. The dye stains Example 8 Cotton from a blue vat in olive tones. The colorations have very good fastness properties, especially one o ^ parts by weight of Bz-l-chlorine-Bz ^ -n-pentylbcnzanthron, very good fastness to light, washing and soda cooking,
yellow crystals with a melting point of 103 to 109 ° C, 7.4 parts by weight of l-amino-5-benzoylarninoanthraquinone, 40 claim:
6.8 parts by weight of anhydrous sodium carbonate and 0.5 parts by weight of cupping powder are heated to boiling for 10 hours in 100 parts by weight for the production of vat dyes, share nitrobenzene. This is characterized in that the Bz-2-n-pentyl-Bz-l-benzane of the benzanthrone obtained in good yield in the 2-position is represented by alkyl or aryl radicals subthronyl-l-amino-5-benzoylaminoanthrachmone red- * 5 Substituted Bz-1-halobenzanthrones with 1,5-diaminobrown crystals with a melting point of 280 to 281 ° C and the vat thus obtained 9 parts by weight of the above anthrimide are at 50 dyes, optionally with acylating agents 110 to 120 ° C treated in a melt of 11.5 parts by weight.
Caustic potash registered in 27 parts by weight of ethanolamine "and stirred at this temperature for 1 hour. The melt Documents considered: is worked up according to the information in Example 7, and German Patent No. 520 876. A coloring table was displayed when the application was announced. ® 909 687/341 11:59