DE1276257B - Substituted dihydroxyphenylamino-anthraquinones which are poorly soluble in water and process for their preparation - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY GERMAN 4S07VW PATENT OFFICE Int. Cl .:

C09b

EDITORIAL

German class: 22 fa - 3/02

Number: 1276257

File number: P 12 76 257.1-43 (G 38274)

Filing date: July 23, 1963

Opening day: August 29, 1968

It has been found that new, valuable, substituted dihydroxyphenylamino-anthraquinones which are sparingly soluble in water can be obtained of formula I receives

Y ₁ O OH

in which one of Yi and Ya is the hydroxyl group and the other is the nitro group, Z is oxygen or sulfur, Ri and R2 are independently hydrogen or a low molecular weight alkyl group, in particular the methyl or ethyl group, R is hydrogen, a low molecular weight alkyl group or halogen, preferably chlorine or Bromine, and η is a positive integer of at most 4, if one is a dihydroxy-dinitro-anthraquinone of the formula II,

Y ₁ O OH

Substituted substances that are sparingly soluble in water
Dihydroxy-phenylamino-anthraquinones and
Process for their manufacture

Applicant:

J. R. Geigy A. G., Basel (Switzerland)

Representative:

Dr. F. Zumstein, Dr. E. Assmann

and Dr. R. Koenigsberger, patent attorneys,

8000 Munich 2, Bräuhausstr. 4th

Named as inventor:

Dr. Hans Peter Kölliker, Münchenstein;

Dr. Alfred Staub, Binningen;

Dr. Peter Hindennann, Bottmingen (Switzerland)

Claimed priority:

Switzerland of July 24, 1962 (8908)

NO,

in which Yi and Y2 have the meaning given under formula I. have, with an amine of the formula III

(III)

in which Z, R, Ri, R2 and η have the meaning given under Formula.I, reacts and optionally after-halogenating the dye obtained.

R in the meaning of a low molecular weight alkyl group is preferably the methyl group, but can also be an ethyl group; R means halogen, so it is z. B. to chlorine or bromine.

Dyes of the formula I in which «1 or 2 and Z denotes oxygen are preferred because of their easy accessibility.
Dihydroxy-dinitro-anthraquinones of the formula II which can be used as starting materials according to the invention can belong to the 1,5-dihydroxy-anthraquinone series (anthrarufin) or the 1,8-dihydroxy-anthraquinone series (chrysazine); mixtures of these isomers can often advantageously also be used in the process according to the invention.

As inventively reacted amines of the formula III come z. B. in question: 3-amino-diphenyl ether or -thioether, 4-amino-diphenylether or thioether, 3-amino-2'-methyl or ^ '- ethyl diphenyl ether or thioether, 3-amino-3'-methyl or -3'-ethyl-diphenyl ether or thioether, 3-amino-4'-methyl- or -4'-ethyl diphenyl ether or thioether, 4-amino-2'-methyl or - ^ '- ethyl diphenyl ether or thioether, 4-amino-3'-methyl or -S'-ethyl-diphenyl ether or thioether, 4-amino-4'-methyl- or -4'-ethyl-diphenyl ether or thioether, 3-amino-2'-chloro- or -2'-bromo-diphenyl ether or -thioether, 3-amino-3'-chloro- or -3-bromo-diphenylether or -thioether, 3-amino-4'-chloro- or -4'-bromo-diphenyl ether or thioether, 4-amino-2'-chloro or -2'-bromo-diphenyl ether or thioether, 4-amino-3'-chloro- or -3'-bromo-diphenyl ether or

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thioether, 4-ammo-4'-chloro- or -4'-bromo-diphenyl ether or -tfcioether, 3-amino-3 ', 5'-dimethyl diphenyl ether or thioether, 4-amino-3', 5 ' -dimethyldiphenyl ether or thioether, + -amino-S'-chloro-4'-methyl-diphenyl-diphenyl ether or thioether, 4-amino-3-chloro-4'-methyl-diphenyl ether or -thioether, 4-amino-3,5 dimethyl diphenyl ether or thioether, 4-amino-3,5 ₅ 4'-trimethyl diphenyl ether or thioether, 3-amino-2,4-dimethyl diphenyl ether or thioether, 4-amino-2,3,5 , 6-tetramethyl-diphenyl ether or thioether, 4-amino-3,5-diethyl-diphenyl ether or thioether or 4-amino-3-methyl-5-ethyl-diphenyl ether or thioether.

The amino-diphenyl oxygen ethers are because of their greater stability under the reaction conditions preferred to the corresponding thioethers.

These amines are obtained, for example, by condensation of a p-nitro-halogenobenzene, which is still may contain low molecular weight alkyl groups, with an alkali salt of an optionally alkyl- and / or halogen-substituted hydroxybenzene or mercaptobenzene to the corresponding nitro-diphenylether or -thiuäther and subsequent reduction the nitro group to the amino group or by condensation of an m-bromoaniline with one of the above-mentioned hydroxy- or mercaptobenzolates in the presence of copper.

The reaction of the reactants to the compounds of formula I with advantage but organic in a fraction boiling at 120 to 200 ⁰ C, inert solvent such as butanol, Glykclmonoäthyläther, dimethylformamide is carried out with an excess of amine in the melt at 100 to 200 ⁰ C, or preferably an optionally substituted hydrocarbon such as chlorobenzene, dichlorobenzene and, in particular, nitrobenzene.

If the new dihydroxyphenylamino-anthraquinones are to be post-halogenated, happens expediently with elemental chlorine or bromine or with sulfuryl chloride in one against halogen inert solvents such as nitrobenzene or chloroform, or in sulfuric acid.

The dihydroxyphenylamino-anthraquinones which can be prepared according to the invention of the formula I usually crystallize out of the reaction mixture. she are made by filtration, diluting the mixture with water or a low molecular weight alcohol or by removing the organic solvent by distillation or steam distillation obtained and can be purified by recrystallization.

In the pure state, the new dyes of the formula I represent bronzing, crystalline, deep-colored compounds They dissolve in hot organic solvents with a pure blue color. According to the invention Preparable dyes of the formula I are suitable for dyeing hydrophobic synthetic Fiber material from aqueous dispersion, e.g. B. for dyeing cellulose di- or triacetate, in particular but for coloring polymeric esters of aromatic polycarboxylic acids with polyvalent ones Alcohols, for example from polyethylene glycol terephthalate fibers.

The dyeing of fibers of polymeric esters of aromatic polycarboxylic acids with polyhydric alcohols, with the aqueous dispersions erfmdungsgemäß producible dyes is preferably carried out at temperatures of from about 100 ^c C under pressure. Very good dyeings are also obtained if these fibers impregnated with concentrated aqueous dispersions of the invention producible dyes, dries the squeezed fabric and then fixed, the color at temperatures of 180 to 250 ⁰ C. However, the dyeing can also be carried out at the boiling point of the dyebath in the presence of dye carriers, such as phenylphenol or polychlorobenzene compounds. The drawability of the dyes can often be further improved by mixing two or more anthraquinone dyes which can be prepared according to the invention. The blue dyeings produced on the fibers mentioned with dyes which can be prepared according to the invention have a considerably improved sublimation and lightfastness compared to dyeings with known dyes of a similar constitution and are very good wetfast.

In comparison with the one from the German explanatory document 1 042 160, Example 9, known dye mixture, which by reacting 1,5-dioxy-4,8-dinitro- and 1,8-dioxy-4,5-dinitro-anthraquinone is obtained with p-anisidine, this has the invention by reacting l, 5-dioxy-4,8-dinitroanthraquinone and!, S-dihydroxy ^ S-dinitro-anthraquinone dye mixture prepared with 4-amino-4'-methyl-diphenyl ether has the technical advantage, To give terephthalic acid polyethylene glycol ester dyeings of better fastness to sublimation.

Unless expressly stated otherwise, the parts given in the examples are parts by weight. The temperatures are given in degrees Celsius. Parts by weight relate to parts by volume same ratio as grams to cubic centimeters.

example 1

33 parts of l, 5-dihydroxy-4,8-dinitro-anthraquinone and 46.25 parts of 4-amino-diphenyl ether are in 500 parts of 2-ethoxyethanol heated to 120 ° to 125 ° for 5 hours, the solution gradually becoming colors deep dark blue. The resulting dye of the formula

OH

HO O NH

precipitates in fine violet-blue crystals on cooling the solution; it is filtered off and dries. After recrystallization from 2-ethoxyethanol, the product melts at 239 to 240 °; it solves in concentrated sulfuric acid when heated with yellow-green, in pyridine or in a xylene mixture with blue color.

The finely divided dye dyes polyester fibers in an aqueous dispersion in very real, clear, blue Shades.

If, instead of the 46.25 parts of 4-aminodiphenyl ether, the same number of parts of 3-aminodiphenyl ether is used and heated to the specified temperature for 18 hours, a somewhat reddish tint is obtained blue dye with similarly good fastness properties.

In the above example, instead of 33 parts!, S-dihydroxy- ^ S-dinitro-anthraquinone is used 33 parts of 1,8-dihydroxy-4,5-dinitro-anthraquinone and instead of 46.25 parts of 4-amino-diphenyl ether 50.25 parts of 3-aniino-diphenyl sulfide and otherwise proceed As indicated in the example, a very similar, slightly greenish bluish dye is obtained of the same excellent fastness properties.

2 parts of the finely ground dye obtained in accordance with paragraph 1 are dissolved in 4000 parts of water dispersed. To this fine distribution, 12 parts of the sodium salt o-phenyl-phenol and 12 parts of diammonium phosphate and dyes 100 parts of a terephthalic acid polyglyco ester fabric for 1.5 hours at 95 to 98 °. The staining is rinsed and with dilute sodium hydroxide solution and a dispersant, e.g. B, the condensation product of naphthalenesulfonic acid and formaldehyde, washed thoroughly. It is light, wet and sublimation-fast blue coloring.

B e i s ρ i e 1 2

33 parts of 1,8-dihydroxy-4,5-dinitro-anthraquinone are successively added to 400 parts of distilled nitrobenzene at room temperature and entered 40.7 parts of 3-amino-diphenyl ether. The mix will heated to 180 ° to 185 ° over the course of 30 minutes with thorough stirring and a stream of nitrogen at the same time passed over the surface of the solution. At this temperature the solution changes color over the course of 3 hours deep blue. The solution is cooled to 50 ° and treated with 3000 parts of methanol. Included the pigment of the constitution separates

HO O OH

O ₂ NO NH

Solution precipitates the condensation product of the formula O ₂ NO OH

after removal of the solvent by distillation with steam. It is filtered off, dried and recrystallized from pyridine. Very fine, blue crystals with a melting point of 209 to 210 ° are obtained in this way. In concentrated sulfuric acid it dissolves with dark green, in pyridine and in a technical xylene mixture with blue color.
The dye colors polyester material in fine grain; divided aqueous dispersion in greenish blue, very good wet, sublimation and lightfast colors.

One uses 1,5-dihydroxy-4,8-dinitro-antbrachinone instead of the 33 parts as many parts 1,8-dihydroxy-4,5-dinitro-anthraquinone are obtained.

a very similar, still somewhat greenish blue dye of the same excellent Fastnesses.

Example 4

A mixture of 16.5 parts of 1,5-dihydroxy-4,8-dinitro-anthraehinone and 16.5 parts of 1,8-dihydroxy-4,5-dinitro-anthraquinone is used together with 50.8 parts of 4 - amino - 4 '- methyl - diphenyl ether in 350 parts of nitrobenzene are heated to 180 ° to 185 °. To The resulting mixture of dyes is IV2 hours of the formulas

O ₂ NO OH

40

45

almost quantitatively as a very fine dark powder. This is filtered off and recrystallized from 2-ethoxyethanol. Violet crystals are obtained which melt at 206 ° to 207 ° and are concentrated Dissolve sulfuric acid with a brownish yellow color, in pyridine and a xylene mixture with a blue color.

The dye dyes fabrics made of polyester fibers in an aqueous dispersion in clear blue, excellent light, wet and sublimation-fast colors.

A very similar, somewhat greener-tinged dye is obtained by using 40.7 parts 4-Amino-diphenyl ether instead of the same number of parts 3-Amino-diphenyl ether.

Example 3

O ₂ NO

CH,

60

To a suspension of 33 parts of 1,5-dihydroxy-4,8-dinitro-anthraquinone in 350 parts of nitrobenzene were 50.25 parts of 4-amino-diphenylthioether given, and the mixture is heated to 180 to 185 ° until there is no starting material can prove more. From the deep blue formed by stirring the deep blue solution into 800 parts ice-cold methanol precipitated. The precipitate is filtered off by washing with hot methanol freed from adhering nitrobenzene and then dried.

The dye dissolves in concentrated sulfuric acid with greenish yellow, in pyridine and a Xylene mixture with blue color. The dye dyes polyester fibers in a fine aqueous dispersion in deep blue Shades of excellent fastness properties.

A much greener dye is obtained using 54.83 parts of 4-amino-4'-methyl-diphenylthioether instead of the 50.8 parts

4-Amino-4'-methyl-diphenyl ether, a slightly reddish one Dye by replacing 50.8 parts of 4-amino-4'-methyl-dip'henyl ether with 47.18 parts 3-amino-diphenyl ether.

2 parts of the finely ground dye mixture obtained in accordance with paragraph 1 are in 4000 parts Water, which is 2 parts of a condensation product of naphthalenesulfonic acids and formaldehyde contains, distributed. The pH of the dyebath is adjusted to 6.5 using acetic acid. One goes with now 100 parts of terephthalic acid polyglycol ester fabric

Y ₁ O OH

40 °, heated in the autoclave to 120 ° within 15 minutes and held at this temperature for% hours. The dye is rinsed with water and then soaped. You get a clear blue Coloring that is extremely fast to light, wet and sublimation.

The following table gives the color shades of dyeings on textile material made of polyethylene glycol terephthalate which are obtained with other dyes analogous to those described in Examples 1 to 7 Operation can be produced.

Y ₂ O NH-A

= A

No. 'Y. . Y ₂ • OH -NH- CH ₃ -NH-A • CH ₃ hue -NH- <p O · 1 NO ₂ OH OH C ₂ H ₅ > - o - q> blue 2 OH NO ₂ -NH- > -o- CH ₃ blue 3 NO ₂ - OH -NH- > blue 4th NO ₂ NO ₂ > —O— < Reddish blue -NH- CH ₃ <p Q 5 NO ₂ NO ₂ -NH- I.
CH ₃ > - ο - < I.
CH ₃ blue 6th OH > —S— < I.
CH ₃ blue -NH- CH ₃ 7th OH > —Ο— < I.
CH ₃ Reddish blue

continuation

10

No.

Y ₁

NH-A

hue

NO ₂

OH

NO ₂ I.
OH/

OH

NO ₂

NO ₂
NO ₂

OH
NO ₂

OH

ι NO,

OH

NO ₂

OH

NO ₂

OH 1

NO ₂ /

NO ₂

OH

-NH

-NH -NH

-NH -NH

OH

OH

NO ₂ OH

NO ₂

-NH -NH

-NH -NH

-NH

CH ₃

OH

NO ₂

OH

-NH

_NH

-NH

C ₂ H

₂ H ₅

■ ο

C ₂ H ₅

Cl

CH ₃

C ₂ H ₅

CH ₃

Cl

CH ₃

CH ₃

C ₂ H ₅

C ₂ H ₅

CH ₃

Cl

CH,

CH,

blue

Blue blue

Blue blue

Blue blue

Blue blue

blue

Reddish blue

blue

blue

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11

continuation

12th

No.

Y ₁ Y ₂ OH NO ₂ OH NO ₂ ' OH NO ₂ NO ₂ OH OH NO ₂ NO ₂ OH OH NO ₂ NO ₂ OH NO ₂ OH OH NO ₂ NO ₂ OH
ft

- NH-A

hue

26th

28 29.

31:

-NH

Br
CH ₃

-NH

CH ₃

CH ₃

NH- <> S-

CH ₃ NH- <VO

-NH

Cl
CH ₃

CH ₃

-NH

Br

CH ₃

-NH

NH

-NH

-NH

-NH

CH ₃

CH ₃

C ₂ H ₅

Cl

C ₂ H ₅
CH ₃

blue

blue

Reddish blue

blue

blue

blue

I.
CH ₃

blue

Reddish blue

blue

blue

blue

continuation

No. Yi Y ₂ - NH - <( - NH-A CH ₃ hue 32 NO ₂ OH blue

Example 5

33 parts!, S-dihydroxy- ^ S-dinitro-anthraquinone are mixed with 53.25 parts of 4-amino-3,5-dimethyl-diphenyl ether. This mixture is within 10 minutes in 350 parts of 180 ° hot nitrobenzene entered in small amounts. Afterward the solution is stirred well under nitrogen for 20 hours at this temperature on the descending condenser. It turns an intense blue. By distilling off most of the solvent in the Vacuum and trituration of the distillation residue with methanol,

O ₂ NO OH

Cooling crystallizes the product of the formula
O ₂ NO OH

45

the condensation product of the constitution is obtained as a fine dark blue-violet powder. By multiple recrystallization from 2-ethoxyethanol is obtained map the dye in pure form as purple crystals with a melting point of 251 to 252 °. He loosens in concentrated sulfuric acid with blue, in pyridine and in a technical xylene mixture with reddish blue Colour. In an aqueous dispersion, the dye dyes polyester fibers in intense reddish-tinged blue shades of excellent light, sublimation and water fastnesses.

Very similar shades of the same excellent fastness properties are obtained through use of 56.75 parts of 4-amino-3,5,4'-trimethyldiphenyl ether, 60.25 parts of 4-amino-2,3,5,6-tetramethyl diphenyl ether, 57.25 parts of 4-amino-3,5-dimethyl-diphenylthioether, 53.25 parts of 3-amino-2,4-dimethyl-diphenyl ether or 58.25 parts of 4-amino-3,5-diethyl diphenyl ether instead of the 53.25 parts of 4-amino-3,5-dimethyl-diphenyl ether. If you replace on the other hand in all these cases the 33 parts of 1,5-dihydroxy ^ e-dinitro-anthraquinone by as many parts!, S-dihydroxy ^ S-dinitro-anthraquinone, so obtained there are somewhat less reddish blue shades with the same good fastness properties.

60 Example 6

66 parts of LS-dihydroxy ^ S-dinitro-anthraquinone and 96.5 parts of 4-amino-4'-chloro-diphenyl ether are in 400 parts of nitrobenzene for 1 hour under one weak nitrogen stream heated to 185 to 190 °, with about 5 parts of water on the descending condenser distill off and a blue solution is formed. At the

the end. A further amount of the product mentioned can be isolated from the mother liquor by concentration will. Its melting point after recrystallization from nitrobenzene is 265 to 267 °.

It is a bronzing crystal powder and dissolves in pyridine or in xylene with blue, in more concentrated Sulfuric acid with green color.

The dye dyes textile material made of polyethylene glycol terephthalate from fine aqueous distribution and with the addition of o-phenyl-phenol and a fatty alcohol polyethylene condensation product in reddish blue, excellent sublimation-fast colors of good lightfastness.

In the above example, the 96.5 parts of 4-amino-4'-chloro-diphenyl ether are replaced by the same amount of 4-amino-2'-chloro-diphenyl ether or by 117 parts of 4-amino-3 ^/ methyl-4'-chlorine -diphenyl ether replaced, dyes with very similar properties are obtained. Example?

46.8 parts of the dye of the formula prepared according to Example 1

O ₂ NO OH

HO O NH

are dissolved hot in 200 parts of dry nitrobenzene. It is allowed to cool to 20 to 25 ° and added dropwise then a solution of 16 parts of bromine in 40 parts of dry nitrobenzene is added over the course of one hour. The mixture is stirred for a further 15 hours at 20 to 25 °, the monobrominated in the diphenyl ether group Dye gradually precipitates. Precipitation is completed by diluting the mixture with methanol. The new dye dyes polyester fibers from an aqueous dispersion in slightly reddish shades of blue than the unbrominated dye, and the coloring is excellent in sublimation fastness.

A dye monohalogenated in the diphenyl ether group with very similar properties is obtained if, from the condensation product of!, S-dihydroxy ^ S-dinitro-anthraquinone with 4-Amino-3'-methyl-diphenyl ether goes out and this condensation product is post-brominated or in

post-chlorinated in an analogous manner by introducing chlorine into the nitrobenzene solution.

Claims (6)

Patent claims: 1. Anthraquinone dyes of the formula
Y ₁ O OH IO in which one of Yi and Yo is the hydroxyl group and the other is the nitro group, Z is oxygen or sulfur, Ri and R _{2 are} independently hydrogen or a low molecular weight alkyl group, R is hydrogen, a low molecular weight alkyl group or halogen and η is a positive integer of at most 4 . 2. Process for the preparation of substituted dihydroxyphenylamino-a'nthraquinones which are sparingly soluble in water, characterized in that there is a dihydroxy-dinitro-anthraquinone of the formula Y ₁ O OH 35 Y ₂ O NO ₂ in which one of Yi and Y> denotes the hydroxyl group and the other denotes the nitro group, with an amine of the formula in which Z is oxygen or sulfur, Ri and R2 are independently hydrogen or a low molecular weight alkyl group, R is hydrogen, a low molecular weight alkyl group or halogen and η is a positive integer of at most 4, to an anthraquinone dye of the formula Yj O OH in which Yi, Y2, Z, R, Ri, R2 and η have the meanings given above, are reacted and the dye obtained is optionally post-halogenated. 3. The method according to claim 1, characterized by the use of a mixture of 1,5 - dihydroxy - 4,8 - dinitro - anthraquinone and 1,8-dihydroxy-4,5-dinitro-anthraquinone. 4. The method according to claim 1 and 2, characterized by the use of an amine of the formula given in which η is 1 or 2. 5. The method according to claim 1 to 3, characterized by the use of an amine given formula, in which Z is oxygen. 6. The method according to claim 1 to 4, characterized in that one is a dihydroxy-dinitroanthraquinone of the formula given with an amine of the formula given in an inert high-boiling organic solvent at 120 up to 200 C. H ₇ N '' Considered publications:
German Auslegeschrift No. 1 042 160;
published documents of the Belgian patent No. 612 278. When the application was announced, a coloring table provided with explanations was displayed. 809 598/509 8.68 © Biindesdruckerei Berlin