DE2460491A1 - PROCESS FOR THE MANUFACTURING OF XANTHENE DYES - Google Patents

Description

HOECHST AKTIENGESELLSCHAFT. ■.

File number: HOE 74 / F 386

Date: December 18, 1974 Dr.ST/St

Process for the production of xanthene dyes.

The present invention relates to an improved process for the preparation of xanthene dyes.

From the German patents 848 231 and 895 O4l is a Process for the production of xanthene dyes is known consists in that the inner salt of a 9- (2'-SuIfophenyl) ■ xanthen-9-ol compound or its in the sulfophenyl radical still further Substituent-containing derivatives in the 3j6-position Have exchangeable atoms or groups, with primary or secondary amines and the resulting dyes, if appropriate sulfonated. In this way, acidic wool dyes with good fastness properties are obtained.

Particularly good dyes are obtained by this process,
if you start from the inner salts of the 316-dihalo-9- (2'-sulfophenyl) -xanthene-9-ols, the reaction being carried out in such a way that the xanthene compound with a strong
excess amount of the amine using the same
Amine or another polar compound as a solvent. The hydrohalic acid released in this reaction is bound as a salt by the excess amine. This salt, the excess free amine and any additional solvent used are washed out with aqueous acid after the reaction has ended. From the after

609 8 27/0786

Filtering off the dye remaining waste water can do that Amine .so \ iie, if necessary, only partially recover the solvent are separated, which brings with it a considerable loss of material and a high level of wastewater pollution.

The reaction can also be carried out in this way by the known processes be that the xanthenol compound with a vastly excess amount of primary or secondary amino groups carrying aromatic or aliphatic sulfonic acids or carboxylic acids or their Na salts using polar Reacts solvents. The hydrogen halide released during this reaction acid forms the free sulfonic or carboxylic acids from any sodium salts used. Included it is found that these free acids, in contrast to the salts, have a very greatly reduced reactivity. For this Reason, when using the free acids as well as the salts, high molar excesses have to be used. Nevertheless it is often not possible to achieve a complete exchange of both halogen atoms.

The proportions of the simply converted xanthydrol compound remaining in the product lead, however, due to their low color strength, their strongly deviating shade, their very low brilliance, their very low lightfastness and their different dyeing behavior to an impairment of the dye quality.

Another disadvantage is that the melt-off components used in large excess are either in the product or remain in the wastewater, both of which are undesirable because either the coloring behavior (color strength, drawing characteristics, Structure) is worsened or the wastewater pollution is greatly increased and in any case with a considerable loss of material goes hand in hand.

609827/07 86

It has now been found that one can overcome these disadvantages in production of xanthene dyes of the general formula (I)

(D

< ^S0 3 ^H) m

(in which R ^ and R are the same or different and each means an optionally substituted aliphatic or optionally substituted araliphatic or cycloaliphatic radical or R ^ can also mean a hydrogen atom or a carbocyclic aromatic or heterocyclic radical or R ₁ and R together with the N- Atom form a heterocyclic radical, optionally containing further heteratoms, the benzene nucleus A may optionally also contain substituents and m denotes the number 1, 2, 3 >> or zero),

by reaction of the inner salts of 3 »6-dihalo-9- (2'-sulfophenyl) -xanthene-9-ols of the general formula (II)

(II)

(in which X stands for a halogen atom, preferably a chlorine atom, and A has the above meaning),

with primary or secondary amines of the formula (III)

R.

HN

(III)

609827/0786

(with R. and R of the above meaning)

in a polar solvent and optionally subsequent Sulphonation can be avoided by implementing the Xanthenol of the formula (II) with the amine of the formula (III) in a stoichiometric amount and in the presence of an inorganic one acid-binding agent and / or an acid-binding tertiary aliphatic N-containing heterocyclic, preferably aromatic Connection.

⁺ 'Amine or one

Substituents in the benzene nucleus A are, for example, halogen atoms, such as chlorine and bromine atoms, alkyl groups of 1 to 5 carbon atoms, Alkoxy groups of 1 to 5 carbon atoms, aryl radicals, such as the optionally phenyl radicals still containing substituents, hydroxyl, carboxylic acid, carbalkoxy groups with 2 to 6 carbon atoms, carbonamide, Sulphonic acid, sulphonamide, ß-hydroxy-ethylsulfonyl and Mentioning ß-sulfato-ethylsulfonyl groups. If the core carries A at the same time hydroxyl and carboxy groups, this compound can of the formula (I) or (II) are also present as metal complex compounds.

The inventive method is carried out so that one 1 mole of the xanthenol compound with 2 to about 2.2 moles of the amine in a polar solvent free of acidic groups at elevated temperatures Temperature converts and the hydrogen halide released during the reaction by adding the hydrohalic acid binds at least an equivalent amount of the acid-binding agent.

As primary or secondary aliphatic, araliphatic, cycloaliphatic, aromatic or heterocyclic amines of the formula (III) come into consideration, for example:

Mono- or dialkylamines with 1 to 6 carbon atoms in the alkyl radical, such as methyl, ethyl, propyl, butyl, isopropyl or pentylamine, Dimethyl, diethyl, dipropyl or dibutylamine, optionally with substituents in the alkyl radical, such as hydroxy, cyano, lower. Alkoxy,

609827/07 8 6

2A60-491

lower carbalkoxy- _t sulfonic acid or carboxylic acid groups; cycloaliphatic amines such as cyclopentaylamine and cyclohexyl amine; araliphatic amines, such as phenethylamine, benzylamine and benzylethylamine; aromatic amines such as aniline or N- (alkyl 1-4) anilines and their in the alkyl radical or benzene through halogen atoms such as chlorine or bromine atoms, lower alkyl groups such as methyl, ethyl or propyl groups, lower alkoxy groups such as methoxy -, Xthoxy or propoxy groups, lower carbalkoxy, sulfonamide, hydroxy, sulfonic acid, carboxylic acid, ß-hydroxyethylsulfonyl, ß-sulfatoethylsulfonyl or nitro groups substituted derivatives; Naphthylamines, aminoanthraquinones; 5- or 6-membered heterocyclic amines, such as aminothiazoles, aminopyrazoles, aminotriazoles, aminopyridines and their benzo derivatives, morpholine, piperidine and piperazine.

If the amines contain sulfonic acid groups, one uses they are expediently in the form of their salts, for example as the sodium or potassium salt. If the free sulfonic or carboxylic acid is used, an appropriate amount of the acid-binding agent is also added, which is suitable for converting the acids into the corresponding To transfer salts.

Both water and organic compounds are used as solvents, such as B. methanol, ethanol, propanol, butanol, glycol, glycerine, Diglycol, polyglycols, alkyl glycols, phenyl glycol, alkyl polyglycols, benzyl alcohol, propylene glycols, acetonitrile, Dimethylformamide, N-methylpyrrolidone-2, dimethylacetamide, Dimethyl sulfoxide or mixtures of these solvents are suitable. The amount of solvent used depends according to the viscosity of the reaction mass. It is expedient to use the solvent in an amount that is just sufficient to keep the reaction mass, present as a homogeneous solution or fine suspension, easily stirrable.

Acid-binding inorganic agents are, for example, oxides, hydroxides, carbonates, acetates, borates or phosphates of alkali or alkaline earth metals, such as calcium or magnesium oxide, Sodium, potassium, calcium or magnesium hydroxide,

6 0 9 8 2 7/0786 " ⁶ "

2 4 6 H '9 1

Sodium or potassium carbonate, sodium bicarbonate, sodium acetate, Borax or Dx or trisodium phosphate are suitable, furthermore aluminum oxide or hydroxide.

Of the organic compounds, tertiary aliphatic amines include, for example, triethylamine, tripropylamine, tributylamine, Dxcyclohexyläthylamin or Triethanolamin, as N-containing heterocyclic Compounds such as pyridine or quinoline into consideration. The acid-binding agent is used in a stoichiometric amount or in a slight excess, that is to say per mole of xanthenol compound 2 moles of acid binding agent are required. If primary or secondary amines which contain free sulfonic acid groups are used in the reaction, at least 4 moles of acid binding agent required if the amines have a Contain sulfonic acid group.

The reaction temperature, like the reaction time, depends on the reactivity of the amine used and can vary between move about 20 C and about 18o C. If the required If the reaction temperature is above the boiling point of the solvent used, it is also possible to work under increased pressure.

The following procedure, which is the least, is particularly advantageous Wastewater pollution brings with it: When using a just sufficient amount of glycol as Solvents and magnesium oxide as an acid-binding agent result in most cases in a heterogeneous, easily stirrable form Reaction mass in which the xanthenol compound reacted on both sides is almost completely insoluble, while the possibly Xanthenol compounds still present in small quantities on one side and various ones that were brought in with the starting materials Impurities are very soluble. After the reaction has ended, the dye is filtered off with suction and washed with freed a little water from the glycol and the magnesium chloride formed. The glycol mother liquor and the wash water are combined and by clarifying filtration from that at the union itself

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ORIGINAL INSPECTED

forming small precipitate freed. The remaining glycol-water mixture can be used instead of fresh glycol for the next reaction batch, with the water is distilled off again before or during the reaction. In this way, only the desired, xanthene dye reacted on both sides and one small amount of solid sewage residue in appearance. Wastewater pollution from inorganic or organic compounds completely omitted.

The reaction mass can also be worked up by stirring it into water and the precipitated product directly sucked off, or that one from the aqueous dye solution when using the dye is salted out by water as the reaction medium and then filtered off with suction and dried.

The dyes obtainable according to the invention have a high Purity, which leads to an increased brilliance of the colorations produced with it. In the dyes can optionally further sulfo groups are introduced by post-sulfonation, whereby a better water solubility is achieved.

The dyes and their sulfonation products dye wool and silk as well as synthetic fibers that carry basic groups, such as For example polyamide, modified polyester and polyacrylonitrile or regenerated protein fibers in bright red to blue shades. The colorations are remarkable Authenticity properties. Particular mention should be made of the light, alkali, carbonization and deca fastness. The dyes can be applied according to the known dyeing process and have an excellent leveling ability.

In the following examples, which serve to illustrate the invention, parts mean parts by weight; the data in % stand for percent by weight. The parts by weight relate to parts by volume as the grams to cubic centimeters.

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example 1

40.5 parts of the inner salt of Z , G-dichloro-9-phenyl-xanthydrol-2'-sulfonic acid are placed in 120 parts of ethylene glycol. 36 parts of metanilic acid and 7 parts of magnesium oxide are added and the reaction mixture is heated to 140 ° C., whereupon red and violet color changes rapidly. The mixture is stirred for two hours at 140 ° C., then 1 part of magnesium oxide is added; then the mixture is stirred for a further two hours. The clear melt obtained is poured into 500 parts of a cold saturated saline solution with stirring, the precipitated dye is filtered off with suction, washed with saline solution and dried at 60.degree. There are 100 parts of a saline dye of the formula

NaO S

obtained, which is very soluble in water and wool from a boiling aqueous dyebath with formic acid or sulfuric acid / sodium sulfate was adjusted to a pH of approx. 3-4, dyes in a very brilliant, strong violet shade. His Dyeings have excellent fastness properties. Of these, especially the light fastness, the decade fastness, the To emphasize the carbonization fastness and the alkali fastness.

In a corresponding manner, this dye can also be used for silk, synthetic polyamide fibers, regenerated protein fibers and basic modified polyacrylonitrile fibers are dyed, which also results in strong dyeings with good fastness properties receives.

Examples 2-31

Further dyes listed in Table 1 below can be prepared using the procedure described in Example 1

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of the above formula (I) produce when one of equivalent amounts of the corresponding starting compounds of the formulas (II) and (III) and the equivalent amount of magnesium oxide goes out.

Table 1 example

Shade on wool

-

SO

dito

bluish purple

red-violet

CH,

SO _x Na 5

dito

red-violet

SO _x Na CH
3

dito

violet

H - / Λ- SO _x Well ditto

OCH,

bluish purple

SO _{x well}

dito

bluish purple

H CH ^ O. dito

SQ, well

violet

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- ίο -

ίο -

Example R, -

Dye on wool

SO

SO _x Na 3 bluish red

10

HO

ditto reddish blue

12th

13th

OH

H -NH

SO _x Na 3 ditto reddish blue

ditto reddish purple

c - <\ /} - ^so x ^N a ditto red-purple

5 ν V

16

Gl ditto red-violet

SO _x Na 3

SO _x Na 3 same as red-violet

17th

/ VSO _x Na (

SO

bluish purple

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Example R _x

Shade on wool

18th

NaO ₂ S

violet

SO _{x well}

SO _{x well}
3

ditto bluish red

20th

COONa

SO, well
3

violet

21

COONa

COONa

bl on

22nd

// - ^S0 3 ^Well

SO ₅ Well

SO _x = - ^ 3

OCH-red-violet

CH _x

-CH-CH ₀ -SO _x Na 2 5

SO

flnoresz. yellowish red

, -CH ₀ -CH ₀ -SO _x Na ditto 2 2 fluoresc. bluish red

CH.

dito

OCH,

SO _x Na 3 red-violet

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example

Shade on wool

26th

CH

SO ₂ ITa SO.

red-violet

H -CH ₂ -CH ₂ -COONa ditto fluoresc. bluish red

28

-CH ₀ -CH ₀ -SO _x Na ditto d d. ο fluoresc. bluish red

29

CH ₂ -CH ₂ -SO ₅ Na ditto fluoresc. bluish red

30th

CH-

SO _x Na 3

SO

violet

H -CH,

COONa SO

V 3 fluoresc. blue-H -I pungent red

SO _x Na 3

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Example 32

121.5 parts of the inner seize of 3, S-dichloro-ii-phenyl-xanthydrol-2'-sulfonic acid, 750 parts of water, 24 parts of magnesium oxide and 122 parts of 3-amino-4-methoxy-benzenesulfonic acid are stirred in an autoclave heated to 140 ° C. within 1 hour, a pressure of 4-5 atmospheres being established. After a further stirring time
After 5 hours, the mixture is cooled to 60.degree. 150 parts of sodium chloride are added. After cooling to room temperature with stirring, the crystalline precipitate is filtered off with suction and dried at 60.degree. 250 parts of a pure dye are obtained
formula

OCH ₃

NaO ₃ S

S0 "Well

which is very, well soluble in water and wool from a boiling point
dyes aqueous dyebath with a pH of 3-4 in a very strong, bluish shade of violet.

Example 33

Is used in Example 32 instead of 3-amino-4-methoxy-benzenesulfonic acid an equivalent amount of the 3-amino-4-methyl-benzenesulfonic acid and works in the manner indicated in Example 32, the corresponding methyl-substituted ones are likewise obtained in good yield Dye that dyes wool in a brilliant red-violet shade.

Example la - 33a

Leave the dyes prepared according to Examples 1-33
can be produced in the same way in high yield and in good purity if, for example, acid-binding agents are used

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- 14 -

Calcium hydroxide, Aluminiviahydrox.vi, sodium acetate, sodium phosphate or pyridine in equivalent menga grazed.

Example 34

a.) 40.5 parts of the inner salt of 3,6-dichloro-9-phenylxanthydrol-2 * -sulfonic acid are stirred in 250 parts of ethylene glycol for a short time. After adding 26 parts of 3-chloroaniline the reaction mixture is heated to 145-15O ° C. within one hour. It will be at this temperature for an hour stirred; then 4 parts of magnesium oxide are added in small portions over the course of one hour; it becomes a Stirred for a further hour and cooled to 100.degree. The educated, well filtering, fine precipitate is sucked off, washed with 200 parts of water and dried at 80.degree. 57 parts of a finely powdered formic acid in 85% strength are obtained dye powder soluble with violet color. The dye owns the formula

Cl

Cl

b.) After a sulfonation by means of sulfuric acid according to a method customary in the art, for example according to the procedure described in the above-mentioned German patents, and after conversion into its sodium salt a dye which is readily soluble in water is obtained, which combines wool, silk and basic modified synthetic fibers from one aqueous dyebath with a pH between 3 and 5 in a brilliant violet shade with good fastness properties colors.

G.) The mother liquor obtained under a.) And the wash water are united and formed by an optionally

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- 15 -

BATH ORIGINAL

minor rainfall cleared. This filtrate can be used for a new approach to the dye production described under a.) instead of fresh ethylene glycol can be used again, but this is now in this reaction mixture contained water distilled off before or during the reaction.

Examples 35-90

Further dyes listed in Table 2 below can be prepared using the procedure described in Example 34 of the above formula (I), if one of equivalent amounts of the corresponding starting compounds of Formulas (II) and (III) and the equivalent amount of magnesium oxide. The compounds produced in this way can optionally are then sulfonated.

Table 2 example

Yield shade to full

bluish tint Red

99 %

violet

37 38

39

dito

dito

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96

98 %

98 %

bluish red

bluish red

Red

. - 16 • ORIGINAL BATHROOM

Example R

yield

Full shade

40 H.

CH-

%

bluish red

41 H.

CH

ditto % red

42 H.

ditto% blue

43 H.

dito

OCH, %

reddish purple

44

H - ^ Λ-Cl ditto % violet

45 H.

dito

NH,

reddish blue

46 H.

dito

NH,

%

bluish red

dito %

fluoresc.

48

98

bluish red

49 H - ^ j) ditto

ΌΗ %

bluish purple

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Example R "

Yield shade on wool

50 CH-

80 % red-violet

CH-

ditto 97 % purple

52

53

H - / V CH-, ditto

54- H

55 H.

dito.

dito

ditto 99% purple

90 % red-violet

90 % bluish red

95 % bluusticMg violet

56

Cl

57 H.

CH-

dito

y- CH-, ditto 9? % purple

99 % purple

58

NO.

dito

97% red

59 H </> - ^Ν = ^Ν Λ /> ditto

99 % reddish blue

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Example R Yield shade on wool

60 H.

\ N // ^0CK 5 OCH.,

% ' purple

61 H.

w /, - OCH, ditto % bluish purple

62 H.

63 H.

Cl

CH.

Cl ditto 96 %

bluish red

ditto 96 %

bluish red

64 H.

Cl

OCH, ditto 98 % red-violet

65 H.

Cl ditto 97 %

bluish red

66 H.

Cl ditto 92 % red-violet

67 H.

68 H.

ditto 90 % purple

ditto 94 % red

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Example R "

Yield shade on wool

69 H.

98 % bluish red

70 H -Λ N-SO ₂ MH ₂ ditto 97 % red-violet

71 -CH ₂ CH ₂ CN -I Λ ditto 95 % bluish red

72 H.

OH

ditto 96% purple

73 H.

OH ditto 93 % bluish purple

74 -COCH-

ditto 92% photo violet

75 H -4 Λ-COEH ₂ same as 97 % reddish blue

76 H.

^ -HH-COQH, ditto 97% blue

77

ditto 98 % purple

:,) _o ditto 98 % red-violet

OCH

79 H - /> S0 ₂ CH ₂ CH ₂ 0H ditto 95% violet

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example

Yield shade to full

80

OCH.

%

bluish purple

ditto 96 % purple

82

83 -CH,

ditto 96%

bluish red

ditto 97% red-violet

ditto 93

red-violet

86

88

CH,

V ^S0 3 98

SO.

OCH

SO.

CH. violet

% red-violet

% purple

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example

R, yield shade on wool

Cl CH.

97 % purple

90

^CH

Cl 97% red-violet

- 22 -

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Example 91

40.5 parts of the inner salt of 3,6-dichloro-9-phenyl-xanthydrol-2'-sulfonic acid are stirred in 200 parts of ethylene glycol or 250 parts of Ethylenglykolmon oät hy lather for a short time. After adding 19 parts of aniline, the reaction mixture is heated to 135-140 ° C. over the course of one hour, with stirring for one hour this temperature is maintained and 4 parts of magnesium oxide are then added in portions over the course of one hour. Afterward the mixture is heated to 145-15O ° C. and stirred for one hour at this temperature. After cooling to 80 ° C, 500 parts by volume Water added. After stirring for 30 minutes, the mixture is filtered off with suction, the crystalline product is washed with water and dried at 60.degree. There are 49 parts of a dye of the formula

obtained in the form of a fine powder, which is for example in glacial acetic acid or in dimethylformamide with a bright purple color solves.

Examples 35a-91a

The dyes obtained according to Examples 35-91 can be prepared equally well if magnesium oxide is used instead equivalent amounts of sodium acetate, sodium carbonate, sodium bicarbonate or calcium oxide are used as the acid-binding agent.

Examples 92-116

Further dyes listed in Table 3 below can be prepared using the procedure described in Example 91

- 23 -

6 0 9 8 2 7 / j 7 8 6

" ²³ " ■ 2460 /; 91

of the above-mentioned formula (I) if one of equivalent amounts of the corresponding starting compounds of the formulas (II) and (III) and the equivalent amount of magnesium oxide goes out.

Tabel example

Yield hue

on wool

92

CH

94 %

blue-violet

-C I

Xg ^ ^

dito

OCH-

98 % purple

94-

-C- N

Il Il

N CH

dito

96 % red

95

Cl

CH-N

CH = N

dito

99 % red

96

dito

92% red

98

CH,

CH.

ditto 99 % red-violet

dito

99 % cloudy

violet

99

CH

3 Tl

NH _V C = O

dito

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91 % blue tinged purple

- 24 ~

example

Yield hue

on wool

100 CH.

98 % purple

101 H.

N.

dito

NH ^ Cl

95 % purple

102

^ NH-NH

H -C I ditto ^ CH-C = O

93 % blue

103 H N

NH

dito

104 H.

^ NH

dito

90 % bluish

Red

91 % purple

105

H -C \ ditto

^ NH-C = NH

85 % red-violet

106

^Η Λ /> ^C ^ _H 1 J · ^dit °

98 % blue

10? H -C.

NH

ditto 92% purple

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Example R

Yield hue

on wool

108 H.

CH-

SO

95 % purple

109 CH-

ditto 97 % red-violet

.110 H

SO

% purple

111 H.

.CH, ι S0, ^w
- CHV 3 (S ^ f 3 ₉₈ o _{/ o}

fluoresc.

bluish tint

Red

112 -CH

-CH? ditto 97 % ditto

. H

-CH ₂ CH ₂ OH ditto 95 % ditto

114 -CH ₂ CH ₂ OH -CH ₂ CH ₂ OH ditto 95 % ditto

115 H.

ditto 96% ditto

116 H.

ditto 97 % ditto

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Example 117

40.5 parts of the inner salt of 3, e-dichloro-g-phenyl-xanthydrol-2'-sulfonic acid are mixed with 33 parts of p-phenylenediamine in 200 parts of propylene glycol- (1,2) with stirring at room temperature; violet color appears immediately. The reaction mixture is heated to 100 ° C. and stirred for three hours at this temperature, the reaction mixture turning a deep blue. After cooling to 80 ° C., 300 parts of water are added with stirring, and after some time the precipitated product is filtered off with suction, washed with water and dried. A yield of 98 % of theory is obtained. a dye of the formula

which is for example in glacial acetic acid or dimethylformamide with intense blue color dissolves.

Example 118

40.5 parts of the inner salt of 3,6-Diehlor-9-phenyl ~ xanthydrol-2 · Sulfonic acid are dissolved in 180 parts of water and after addition heated to boiling of 22 parts of m-phenylenediamine and 4 parts of magnesium oxide. There is a rapid reaction with a blue color. After a reaction time of six hours below the boiling point, the reaction mixture is cooled to room temperature and the fancy dye to which the formula

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- 27

24GCH91

comes, suctioned off, washed with water and dried. Yield: 85% of theory Th.

It dissolves in ethanol with a reddish blue color.

Example 119

a.) 43.5 parts of the inner salt of 3,6-dichloro-9-phenylxanthydrol-4'-methoxy-2'-sulfonic acid are stirred well in 200 parts of water and after adding 4 parts of magnesium oxide heated to 95 C. In the course of two hours 28 parts of p-phenetidine were added dropwise. The mixture is then heated to a gentle reflux and for eight hours at this Stirred temperature. The resulting violet dye (63 parts) precipitates in crystalline form and becomes after cooling the reaction mixture is filtered off with suction to room temperature, washed with water and dried. He owns the formula

OC ₂ H ₅

b.) By sulfonation with sulfuric acid in accordance with the methods customary in the art and common processes and subsequent conversion of the acidic dye thus produced into its sodium salt a dye which is readily soluble in water is obtained, v / elcher wool at a pH of 3-5 in a brilliant violet hue dyes with excellent fastness properties.

c.) The synthesis of the dye prepared under the above paragraph a.) can also be carried out at higher temperatures, e.g. at 130 C, be carried out using an autoclave, with one in a shorter reaction time in equally good yield and Purity receives the dye mentioned.

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Example 120

40.5 parts of the inner salt of 3, e-dichloro-Q-phenyl-xanthydrol-2'-sulfonic acid are together with 47 parts of 4-amino-diphenylsulfone, 4 parts of magnesium oxide and 200 parts of glycerine heated to 150-16O ° C and stirred for four hours at this Temperature held. The reaction mixture is then cooled to 95 ° C. and 200 parts of water are added. The failing one violet dye is filtered off, washed with water and dried. He owns the formula

Yield: 90 % of theory

Example 121

48.5 parts of the inner salt of 3, 6-5-dichloro-9-phenyl-xanthydrol-2 ·, 4-disulfonic acid are suspended in 250 parts of ethylene glycol and, after addition of 6 parts of magnesium oxide and 22 parts of o-toluidine, to 14O- Heated to 145 ° C. After a reaction time of 4 hours at this temperature and after cooling to 90 ° C., the reaction mixture is poured into 500 parts of water, then diluted sulfuric acid is added to a pH of 2 and the mixture is stirred for some time. The precipitated dye is filtered off with suction, washed neutral with water and dried at 60.degree. The in a yield of 95 % of theory resulting red-violet dye has the formula

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Example 122

a.) 40.5 parts of the inner salt of 3, e-dichloro-9-phenylxanthydrol-2'-sulfonic acid are in 250 parts of diglycol along with 8.5 parts of anhydrous sodium acetate and 25 parts 2,5-dimethylaniline heated to 145-150 ° C with thorough stirring; the reaction mixture is stirred for four hours at this temperature, then, after cooling to 90 ° C., up Poured 250 parts of water and stirred for 30 minutes. The dyestuff which precipitates out is filtered off with suction, washed with water and dried at 80.degree. The in a yield of 96% of theory The fine-grained dye obtained dissolves easily in 85% formic acid with a red-violet color. He has the following Formula:

-CHr

CH

b.) Instead of sodium acetate, acid-binding agents can be used also calcium hydroxide, magnesium oxide, calcium oxide or pyridine are used in the reaction described under a.). The dye indicated there is obtained in equally good quality Yield and purity.

c.) The dye produced under a.) is sulfonated by a sulfonation process customary in the art; he dyes wool at a pH of 3-5 from a boiling aqueous dyebath in a brilliant red-violet shade of high color strength and excellent fastness properties.

Example 123

40.5 parts of the inner salt of 3, e-dichloro-g-phenyl-xanthydrol-2'-sulfonic acid are stirred in 200 parts of water and after the addition of 18 parts of morpholine and 4 parts of magnesium oxide

- 30 -

609827/0786

95-100 C heated. After a reaction time of six hours At this temperature, the resulting red solution is evaporated to dryness on a rotary evaporator or in a spray dryer isolated. A dye of the formula is obtained in good yield

that dyes wool in brilliant red tones,

Example 124

If you proceed as described in Example 123, instead of morpholine 14 parts of l-cyano-2-amino-ethane as reactive Amine, a red dye of the formula is obtained in good yields

NC-CII ₂ -CH ₂ -NH

that dyes wool in brilliant red tones.

- 31 -

609827/0786

Claims (7)

Patent claims: 1. Process for the preparation of xanthene dyes of the general Formula (I). (D _{(in which R 1} and R ″ are identical or different and each denotes an optionally substituted aliphatic or optionally substituted araliphatic or cycloaliphatic radical, or IL can also denote a hydrogen atom or a carbocyclic aromatic or heterocyclic radical, or R 1 and R ″ together with the N -Atom form a heterocyclic radical, optionally containing further heteratoms, the benzene nucleus A may also contain substituents and m is the number 1, 2, 3, 4 or zero), by reaction of the inner salts of 3,6-dihalo-9- (2 '- sulfophenyl) -xanthene-9-ols of the general formula (II) (ID (in which X stands for a halogen atom, preferably a chlorine atom, and A has the above meaning), - 32 - 609827/0786 - 32 with primary or secondary amines of the formula (III) (with R ₁ and R _{2 of} the above meaning) in a polar solvent free of acid groups and, if necessary, subsequent sulfonation, characterized in that the reaction of the xanthenol of the formula (II) with the amine of the formula (III) in a stoichiometric amount and in the presence of an inorganic acid-binding agent and / or an acid-binding agent tertiary aliphatic amine or an N-containing heterocyclic, preferably aromatic, Verb in dun g ν orη immt. 2. The method according to claim 1, characterized in that one primary or secondary aliphatic, araliphatic, cycloaliphatic, aromatic or heterocyclic amines are used. 3. The method according to claim 1, characterized in that one Primary or secondary aliphatic, araliphatic, cycloaliphatic, aromatic or heterocyclic amines are used in the form of their salts with inorganic or organic bases. 4. The method according to claim 1 to 3, characterized in that the acid-binding agents are oxides, hydroxides, carbonates, . Acetates, borates or phosphates of alkali or alkaline earth metals or aluminum is used. 5. The method according to claim 1 to 3, characterized in that organic bases are used as acid-binding agents. 6 «« The dyes produced according to claim 1. - 33 - 609827/07 86 7. Use of the dyes prepared according to claim 1 for dyeing wool, silk and synthetic fibers containing basic groups. 609827/0786