DE2447024A1 - NEW WATER-SOLUBLE BENZOXANTHENE AND BENZOTHIOXANTHENE COMPOUNDS, METHODS FOR THEIR PRODUCTION AND THEIR USE AS COLORS - Google Patents

Description

New water-soluble benzoxanthene and benzothioxanthene compounds, Process for their preparation and their use as dyes

German Offenlegungsschrift 2,017,764 discloses water-soluble ones Benzoxanthene and benzothioxanthene dyes of the general formula (I)

(D

^(S0 3 ^H) n

known, in which X is an oxygen or sulfur atom, Y is an oxygen atom or a ^ N-R group, in which R is hydrogen or an optionally substituted alkyl, cycloalkyl or aryl radical, a heterocyclic radical, a hydroxyl or Represents amino group, and R * and R 'hydrogen atoms, halogen atoms, Mean alkyl or alkoxy groups and η for a number of 1 to 3 stands. The compounds of this formula (I) are prepared by adding compounds of the general formula (II)

009315/1111

with R-, Ro, X and Y above meanings known per se Sulfated way.

In this publication, no information is given about the position of the sulfo group in the benzoxanthene / benzothioxanthene body, since isomer mixtures are evidently formed in the sulfation; In this process, the sulphonation takes place exclusively in the aromatic rings, preferably on the benzoxanthene or benzothioxanthene dye core. Accordingly, no compounds are described which are in the side chain as a ^ N-R group terminally carry a sulfonic acid residue. The well-known at this one Nuclear sulphonation process carried out is preferred with fuming Sulfuric acid carried out; at the rather low temperature of 70 - 100 ° C creates a mixture of mono- and disulphurised product (Example 1), at higher temperatures of 125 - 130 C, however, is a doubly nucleus sulfated product (Example 2) was formed.

Furthermore, in the German Offenlegungsschrift 2 150 87 9 Use of such nucleus sulfated dyes of the formula (T) for dyeing and printing fiber materials made from natural and synthetic polyamides and polyurethanes. In addition, dyes are known from there that are in the aliphatic Side chain carry a sulfonic acid group via the imide residue ^ N-R; however, they also contain at least one other Sulphonic acid group in the benzoxanthenes or benzothioxanthene ring structure.

δ 0 9 8 1 5/1 Π 1 - 3-

These sulfated in the benzoxanthene and benzothioxanthene nuclei Although dyes produce very brilliant colors, they are satisfactory some properties do not fully meet the demands made on dyes today. In particular, the alkali sensitivity of the dyeings produced with them criticized “Dyeing alongside they materials made of textured polyamide fibers, which differences in stretching do not show evenly.

With the present invention, there have now been better, new, water-soluble ones Compounds found that contain no sulfo groups in the benzoxanthene and -thio = xanthene skeleton and which are in the form of free acid of the general formula (1)

B- (D)

ία

(1)

correspond, in particular their alkali and alkaline earth and ammonium salts. Sodium and sodium salts are preferred as alkali salts Potassium salts too.

In the general formula (1):
X is an oxygen or sulfur atom,

R ₂ , Rg and R ₄ are identical or different and each is a hydrogen atom, a halogen atom, in particular a chlorine atom, the bromine atom, the hydroxy, the nitro, an alkyl group of 1 to 4 carbon atoms, preferably the methyl or Ethyl group, or an alkoxy group of 1 to 4 carbon atoms, preferably the methoxy or ethoxy group,

B is a divalent or trivalent bridge member, for example an alkylene radical of 1 to 6 carbon atoms, such as -CH ₀ -, -CH ₀ -CH ₀ - or

-CH ₂ -, -

603815/1111

^ "TT" "

¹ CH ₀ -CH ₀ -CH-CH ₀ -. or a cycloaliphatic group, such as.

du Δ \ £ d "

CH ₃
a cyclohexyl radical, or a radical of the formula

-NH-, -NH-SO ₀ -, -NH-f

, -0-CII ₂ -, -0-CH ₂ -CH ₂ -

or a trivalent nitrogen atom or a mononuclear or binuclear aromatic, alkyl, aromatic or heterocyclic Group, such as, for example, a benzene or naphthalene nucleus or a benzyl radical, whose aromatic nuclei are replaced by alkyl or alkoxy radicals can be substituted by 1 to 4 carbon atoms or chlorine and / or alkyleni'este can contain 1 to 4 carbon atoms which the remainder W can be bound,

D is a bivalent or trivalent benzene radical or naphthalene radical or a carboxylic ester, carboxamide or acyl radical aromatic or aliphatic carboxylic acid, for example formic acid, acetic acid, valeric acid or benzoic acid or Naphthoic acid, or an aliphatic or aromatic sulfonic acid amide residue, preferably of the benzene series, e.g. phenylsulfonic acid or p-toluenesulfonic acid, or a sulfonamido or carbonylamido radical, but especially a radical of the formula

-0-CO-R, -NH-CO-R, -N (AlkyI) -CO-R, -NH-SO ₂ -R, -N (AlkyI) -SO ₂ -R, -SOo ₁ -NH-R , -CO-NH-R or -CO-N (AlkyI) -R, ^ SO ₂ N (alkyl) -R,

in which R is a branched or straight-chain alkyl radical of 1 to 6, preferably 2 to 4 carbon atoms, or the Is phenyl radical, which is replaced by chlorine, methyl, ethyl, methoxy and / or ethoxy groups can be substituted (alkyl stands for an alkyl radical of 1 to 4 carbon atoms, preferably for the methyl or ethyl group), or an alkylenephenyl radical, for example the formula

609815/1111

W is a water-solubilizing residue bonded to B or D. can be, for example, a sulfonic acid residue, the sulfato group

(-OSOoH), Thiosulfate- (-SSO ₀ H), Phosphate »- (-OPOoH ₀ ), Phosphonic« j ο Δ

acid (-PO (OH) ₀ ) or phosphonic acid group (-PO (OR-) (OH)), in which R _{K is} a lower alkyl or benzyl radical,

m is 1 or 2,
η is 0 or 1.

The new compounds of the formula (1) can be used in " Manner - to make in different ways, for example by

a.) the dicarboxylic acid or its anhydride of the general formula (2) or (3)

^R 3.

with an amine of the general formula (4)

(D)

(W)

Bl

(4)

in which R ₁ , Kg »R ₃ » R ₄₁ B, D, W, m and η have the abovementioned meanings, reacts with formation of iinide in one reaction stage, or

b.) into suitable imide derivatives of the above-mentioned benzoxaathene or benzothiarcanthendicarboxylic acids of the formula (2), which are im

609 815/1111

Imide radical the abovementioned radical B or D or B-D or a Contain precursor thereof which introduces the water-soluble group V /.

Process variants according to the invention of procedure b.) Are: 1.) Implementation of the hydroxyl compound of the formula (5)

(OH) _m (5)

wherein R ", R ₀ , R

-, xv _o , x ^, R., B, D, X, m and η have the above meaning

JL & t O * x

have, but with the proviso that the hydroxy group does not is bound directly to an aromatic nucleus, with a corresponding Veresterutigsmittel, the so introduced group W one of the above-mentioned ester residues, with the exception of the thiosulfate residue, represents;

2.) Introduction of the water-solubilizing group W, which is already in a part of the molecule of the radical B or D or B-D is contained bonded, for example by reaction of compounds or formula (6)

N-E-Z

(6)

15/1111

where R ",

..., R ₀ , Ro »R / i ^u * id X have the meanings given above,

X & o 4

Molecular part of the radical B or D or B-D with. one final

standing -CH ₂ group and Z is the hydroxy or amino group, with a corresponding, the remainder of the formula members B, D or BD supplementing compounds of the formula (7)

rW)

(7)

where A is the radical of the formula Cl-SO ₂ - or Cl-CO-, G is the remaining supplementary part of the radical B, D or BD, such as, for example, the radical R defined in formula (I),

or by reacting compounds of the formula (8)

(8th)

with a corresponding compound of the formula (9) supplementing the remainder of the formula members B, D or B-D

A-G- (W)

IDc

(9)

in which R ^, R ₂ , R ^, R., E, Z, A, G and W have the abovementioned meanings, m. denotes the number 1 or 2 and m "denotes zero or 1, the sum (m ^ + m ₂ ) = m with the above

609815/1111

244702A

Meaning is.

The above-mentioned condensation reaction of compounds of formula (2) or (3) with compounds of formula (4) is preferred in a solvent at temperatures between 50 and 200 ° C., most advantageously between 80 and 150 ° C., and optionally under pressure and at a pH of 4 to 10, preferably 6 to 9, carried out. The solvents used are preferably Dimethylformamide, alkyl glycols, such as, for example, ethylene glycol mono = methyl or monoethyl ether, lower alkanols such as methanol, Ethanol or butanol, or mixtures of these solvents, mixtures of these solvents with water, but advantageously only water.

From the method of introducing the water-solubilizing agent Groups in a benzoxanthene or benzothioxanthene derivative analogous to the above-mentioned process b.) Are the following special ones Process variants highlighted:

b.-l). conversion of a compound of formula (10)

with R-, Ro »Ro, R ₄ , B, D and η of the meanings given for formula (1), into a compound of the formula (1) in which W stands for the sulfato group (-OSO ₃ H) and ra = 1 is, by reaction with sulfuric acid, preferably concentrated sulfuric acid, at temperatures from 0 to 40 ° C., preferably at room temperature (15 to 25 ° C.).

In this esterification reaction, care must be taken that, in particular locally, no overheating occurs to sulfonation

609815/1111

to be avoided in the benzothxoxanthene or benzoxanthene nuclei.

b.-2). Conversion of a compound of the formula (10) into its phosphato compound by means of concentrated phosphoric acid or

Polyphosphoric acid at temperatures between 80 and 200 ° C., preferably between 100 and 150 C.

Of those under paragraph b.-l). and b, -2). Compounds of the formula (1) prepared are preferred in which n = 0 and B is an alkylene radical of 1 to 6 carbon atoms, in particular a radical of the formula -CH ₂ - or -CH ₂ -CH ₂ -, or an aromatic radical , in particular the berisol radical, which can be substituted by alkylene radicals, such as, for example, the radical of the formula

is.

b.-3). The conversion of compounds of formula (11)

in compounds of formula (12)

- (CH ₂ ) _q -O- A ₁ - Ar - SO ₃ H

(12)

809815/1111

- OK -

in which X, R-, R ₂ , R ₃ and R. have the abovementioned meanings, q is a number from 1 to 6, A- is a sulfonyl or carbonyl group and Ar is an aromatic radical, for example a phenylene - Or naphthylene radical, with aryl disulfo-monochlorides or sulfochlorides of aryl carboxylic acids, such as, for example, of benzoic acid-3-sulfochloride, in pyridine.

The sulfochlorides used react in this reaction the aromatic carboxylic acids via a complex compound des Pyridines as carboxylic acid chlorides.

b.-4). Conversion of compounds of the formula (13)

N - (CH ₂ ) _q -NH ~ R ₅
0

(13)

in compounds of formula (14)

N - (CH ₂ ) _q -N -SO ₂ -Ar-SO ₃ H

(14)

in which X, R-, R ₂ . R ₃ > ^ 4 »Ar and q have the abovementioned meanings and R _{5 stands} for hydrogen or an alkyl group of 1 to 4 carbon atoms, preferably the methyl or ethyl group, by reaction with aryl disulfo-monochlorides, where

609815/1111

24A7024

Amide formation in an organic solvent and / or water in The presence of an acid-binding agent is carried out in a manner known per se.

b.-5). Conversion of compounds of the formula (15)

N - (CH ₂ ) _q - COCl

(15)

in compound of the formula (16)

- (CH ₀ ) -CO-NR-SOoH

in which R-, R ₂ , R ", R ₄ , X, q and R _{5 have} the abovementioned meanings and R is an alkylene radical of 1 to 6 carbon atoms, preferably the methylene radical or the ethylene radical, or the radical of the formula

means, by, reaction with an amine of the formula

R ₅ -NH-R-SO3H,

609 815/1111

in which Rg and R have the meanings just mentioned, in Water and / or in an organic solvent in the presence of an acid-binding agent in a manner known per se.

To isolate the various process variants described above Compounds obtained, the reaction mixture, if necessary (see method b.-l. and b.-2), in Usually stirred with ice water and adjusted to a pH of 5-7 with soda solution; the new connection is then made with Salt out sodium or potassium chloride, vacuum and dry.

The dicarboxylic acids used as starting compounds and their anhydrides of the general formulas (2) and (3) and their imides of the general formulas (10), (11) and (13) and the for the preparation of the acid chlorides (15) required carboxylic acids can, for example, according to the in DT-PS 1,297,259 and in German Auslegeschriften 1,569,761 and 1,770,818 can be obtained.

The new compounds of formula (1) have proven to be excellent Way as brilliant dyes for dyeing and printing natural and synthetic carbonamide groups Fiber material, such as, for example, wool, silk, synthetic polyamide fibers or urethane fibers, proved to be suitable. You surrender on these materials strongly reddish to greenish yellow, very brilliant colorations, some of which are intensely green fluoresce and for the dye class unusually high light and wetness. Their dyeings and prints are generally characterized by very good lightfastness in the dry and in the wet state, due to good to very good fastness properties to laundry, even in the presence of perborates or peroxides as well other bleaching agents, such as hypochlorite, as well as good acid and alkaline perspiration fastness, over-dyeing, potting, fulling, Water, sea water, alkali, acid and rubbing fastness. These new dyes also have good drawability

8 0 9 8 15/1111 -13-

2447Q24

to the above fibers, a good color structure and accordingly high color strength. The dyeings obtained with them are furthermore distinguished by very good levelness; text-virtual Polyamide material stains them evenly.

In particular, they are structurally closest comparable dyes from DT-OS 2 017 764 and 2 150 879 in various dyeing properties and usage and manufacturing _{authenticity 9,} for example drawability, color strength,

Marking behavior, alkali fastness, alkaline perspiration fastness, substantially superior. On the fiber materials mentioned, some of these dyes also deliver in mixtures with suitable ones Blue dyes, highly brilliant green tones with very good light and wet fastness properties.

Another advantage of the new connections is their technically simple production. The benzoxanthene or benzothioxanthene dicarboxylic acids preferably used as starting compounds or their anhydrides of the general formula (2) or (3) give with the amine of the general formula (4) in only one Reaction stage the compounds according to the invention, which are generally obtained in very high yield and in very pure form. In addition, this reaction can be carried out in water.

Of the new compounds, those in which the individual Formula residues of the general formula 1 ^ have the following meanings:

Η- or R ₂ or R "is a methyl or methoxy group, in the other case a hydrogen atom, and R ₄ is hydrogen, or R ^, R ₃ , R" and R ₄ are each a hydrogen atom,

X is an oxygen or sulfur atom, the formula radical - £ b - (D) ~ l together form an alkylene radical from 1 to θ carbon atoms, preferably from two carbon atoms, or one

SO 9 S1S / 1 1 1 1

- 14 -

Remainder of the formula

- NH - SO _r

-Aikylen

- Aikylen - O - CO

Aikylen,

-NH J

-Aikylen

or

-Alkyleu - CO - N

Alkyl

Aikylen -,

Aikylen- _t

where alkylene is an alkylene radical of 1 to 6 carbon atoms and alkyl an alkyl radical of 1 to 4 carbon atoms, preferably methyl or Ethyl radical, means

W stands for the sulfonic acid group, for the sulfato, phosphato or thiosulfate residue, and

m is 1 or 2.

Of these, particularly advantageous and preferred embodiments of the invention are those compounds of the formula (1) for which R-, R ₂ , R ₃ , R _A and X and W have the meanings just mentioned, η is zero, m = 1 and B is the meaning given for formula (1), but in particular the meaning of a phenylene group or naphthylene group with one or two terminal alkylene radicals of 1, 2 or 3 carbon atoms, preferably the radical of the formula

or

has, especially

CH ₂ -

however, preferred and advantageous the meaning of an alkylene group from 1 to 6 carbon atoms, preferably from 1, 2 or 3 carbon atoms.

809815/1 1 1 1

- 15 -

Particularly excellent representatives that can be synthesized cheaply
this class of compounds according to the invention are compounds which correspond to the general formula (17)

(17)

correspond, in which B stands for a radical of the formula

-CH ₂ -CH ₂ -, -CH ₂ -CH ₂ -CH ₂ - or

V CH - / 2

and W is the thiosulfato or phosphato group, in particular
but is the sulfo group or sulfato group.

The following examples serve to illustrate the invention. The parts given there are parts by weight.

609815/1 1 1 1

2U7024

example 1

30.4 parts of benzothioxanthene-S ^ -dicarboxylic anhydride are in 330 parts of dimethylformamide and suspended together with a solution of 14.5 parts of 2-aminoethanesulfonic acid and 7.8 parts Potassium carbonate in 180 parts of water heated under reflux for 8 hours. After cooling to room temperature will be complete Precipitation of the imide compound obtained was added to 200 parts of a 15% strength potassium chloride solution. After a while you suck off washed with a 10% strength potassium chloride solution and dried at 100 ° C., about 47 parts of benzothioxanthene-S ^ -dicarboxylic acid-N-ß-sulfethylimide are obtained the formula

^ N-CH ₂ -CH ₂ -SO ₃ H

in the form of the potassium salt. This new compound dissolves in water with a yellow color and results from conventional dyeing processes brilliant, golden yellow dyeings on wool and polyamide with good light and wet fastness properties.

Example 2

32 parts of 10-methoxybenzoxanthene-3,4-dicarboxylic acid anhydride are used registered in a solution of 13.7 parts of 2-Aminoäthansulfonsäure and 5.3 parts of sodium carbonate in 500 parts of water and im Pressure autoclave heated for 6 hours at 140 ° C. with stirring. After cooling, the imide compound obtained is 40 parts Sodium chloride completely precipitated, filtered off with suction and washed with a 10% sodium chloride solution. Receives after drying about 43 parts of a compound which, in the form of the free acid, has the following formula:

0 9 8 15/1111 -17-

N-CH ₂ -CH ₂ -SO ₃ H

It is ground to make it easier to use as a dye. she dissolves in water with yellow color and green fluorescence and is ideal for dyeing and printing natural and synthetic polyamides, with high-brilliance and greenish tones yellow shades can be achieved.

Example 3

15 parts Si-methyl-S ^ benzoxanthene -dicarbonsaureanhydrid are suspended in 180 parts Monoäthylglykol and heated together with a solution of 7.5 parts of 2-Aminoäthansulfonsäure and 5.2 parts of sodium bicarbonate in 90 parts of water, 6 hours in a stirred autoclave at 140 ⁰ C . After cooling, the iniide compound produced in this way is salted out with a saturated sodium chloride solution, filtered off with suction, washed and dried. About 21 parts of a compound are obtained which, in the form of the free acid, have the general formula

N-CH ₂ -CH ₂ -SO ₃ H

owns. She delivers on wool and synthetic polyamide, according to in the technique customary colored, very brilliant, greenish tint yellow colorations with good fastness properties.

6098 15/1111 "" ¹⁸

Example 4

In a manner analogous to that described in Example 2, 32 parts of 6-methoxy-benzoxanthene-3,4-dicarboxylic acid anhydride with 13.7 parts are grounded 2-Amiuoäthansulfonsäure implemented. After salting out and washing With a 10% saline solution, about 43 parts of a compound are obtained which, in the form of the free acid, has the following formula:

N-CH ₀ -CH ₀ -SOoH

dl £ l O

With this compound, colorings on synthetic polyamide fiber materials of brilliant color are obtained by customary dyeing processes Yellow.

Example 5

29 parts of benzoxanthene-S ^ -dicarboxylic anhydride are used in 450 Parts suspended morioethylglycol and treated with a solution of 19 Parts of 2-aminoethylthiosulfuric acid and 13.5 parts of sodium bicarbonate Stirred in 160 parts of water at 95 ° C. for 7 hours. It is then cooled to 50 ° C .; 550 parts of a 15% sodium chloride solution are admitted. The precipitated Tmid is filtered off with suction, washed with a 5% sodium chloride solution and dried at 100.degree and ground. About 48 parts of a compound are obtained which, in the acidic form, have the formula

-CH ₂ -CH ₂ -S-SO ₃ H

- 10

SOS 8 IS / 1 1 1 1

owns. On wool and polyamide, it delivers brilliant, green tones yellow colorations with good fastness properties.

Example 6

17.3 parts of 2-aminoethano-sulfuric acid ester are mixed with 23 parts Sodium bicarbonate dissolved in 180 parts of water, then 250 parts of dimethylformamide and 32 parts of 10-methoxybenzoxanthene-3,4-dicarboxylic anhydride are added registered. The suspension is stirred for 8 hours at 95 ° C. and a pH of 7 to 7.5. To When the reaction has ended, the imide obtained is precipitated with 200 parts of a 15% strength sodium chloride solution, filtered off with suction, with a Washed 10% sodium chloride solution, dried at 80 C and ground. About 43 parts of a compound are obtained, which in acidic form the formula

-CH, .- CIU-OSO-H

and has an orange-yellow color. It supplies wool and polyamide fibers using dyeing processes that are customary in the art greenish yellow, very brilliant dyeings and prints with good fastness properties.

Example 7

8.5 parts of 10-methoxybenzoxanthene-S ^ -dicarboxylic acid-N-ß-hydroxyethylimide are registered in 90 parts of polyphosphoric acid and slowly heated to 140 ° C. with stirring. At this temperature will Stirred for 8 hours. The reaction mixture is then poured onto ice and the phosphate compound obtained is salted out with potassium chloride and sucked off. The moist filter cake is in water

609815/1 1 1 1

- 2o -

2U7Q24

stirred and neutralized with potassium carbonate. After the solution has been filtered clear and spray-dried, about 9.2 parts of the compound of the formula are obtained

^H 3 ^C0

as the potassium salt. On synthetic polyamide, it provides a highly brilliant, greenish yellow color with very good fastness properties.

Example 8

14.5 parts of phenylhydrazine-2,5-disulfonic acid are mixed with 2.8 parts of sodium acetate and 9 parts of sodium carbonate in 40 parts of water solved. Then 200 parts of monoethylglycol are added and 16 parts of 10-methoxybenzoxanthene-S ^ -dicarboxylic anhydride are added; the suspension is heated in a stirred autoclave at 140 ° C. for 12 hours. After cooling, the reaction mixture is mixed with 1000 parts of water diluted and filtered hot with the addition of kieselguhr. The hydrazide compound obtained is removed from the filtrate by .Sodium and potassium chloride precipitated, washed with saturated sodium chloride solution and dried at 100.degree. You get about 27 parts the compound of the formula

HO ₃ S

~ 21 -

609815/1 111

2U7Q24

as potassium-Z-sodium salt. It delivers according to what is customary in technology Dyeing and printing process on synthetic polyamide fibers a brilliant yellow.

Example 9

The reaction of 16 parts of 10-methoxybenzoxanthene-3,4-dicarboxylic anhydride with 20 parts of the sodium salt of 4-aminobenzylsulfonic acid according to the conditions mentioned in Example 8
provides about 25 parts of the compound of formula

H ₃ CO

CH ₂ -SO ₃ H

as potassium or sodium salt. With it, highly brilliant, yellow colorations with very bright colors are created on synthetic polyamide fiber material
good lightfastness.

Example 10

In a mixture of 5 parts of the hydroxy compound of the formula

H ₃ CO

N - CH ₂ -CH ₂ -OH 0

and 50 parts of pyridine are added with stirring at 20 to 30 ° C. for 30 minutes, 7 parts of benzoic acid-3-sulfochloride. Afterward is 1 hour at 30 to 40 ° C and 2 hours at 40 to 50 ° C

609315/1 11

~ 22 -

stirred, complete solution occurs. Then 50 parts of water are added dropwise at 40.degree. C. and at 60 to 70.degree. C. for a further 1 hour stirred. To precipitate the compound formed, 200 parts of a saturated sodium chloride solution are added at 25 ° C .; the deposited product is filtered off with suction, washed with saturated sodium chloride solution and dried at 60 ° C. in vacuo. 10.4 parts of a compound are obtained which, in the form of the free acid, has the following formula:

H ₃ CO

SO ₃ H

This dye delivers on synthetic polyamide fiber material a brilliant, greenish yellow color.

Example 11

To a mixture of 5 parts of the acid chloride of the formula

prepared from the corresponding carboxylic acid with thionyl chloride and 150 parts of acetone is added dropwise with stirring at 5 to 10 ° C within 1 hour. A solution of 4.5 parts of N-methyltaurine as the sodium salt in 50 parts of water. Then 3 h at 10 to 20 ° C and 5 hrs is. Then stirred at 20 to 30 ⁰ C, the pH is maintained at 6 to 7. After the reaction, 100 parts each of a saturated sodium chloride and potassium chloride solution are added to »

- 23

6 Q 9 8 1 5/1 1 1 1

given. The precipitate is sucked off. The moist filter cake is washed with a saturated sodium chloride solution and then stirred in 400 parts of water. After clarifying the Dissolution and spray drying give 3.4 parts of the compound of the formula

N-CH ₂ -CO-N-CH ₂ -CH ₂ -SO ₃ H

as potassium / sodium salt. On synthetic polyamide fiber material a brilliant, greenish yellow is obtained with this dye.

- 24 -

60981 5/1111

Claims (3)

Patent claims: 1. Water-soluble compounds in the form of the free acid of the general formula (1) B- (D) _n (W) _1n (D correspond, in which mean:
X eiu oxygen or sulfur atom, R-, R ", Ro and R ₄ are identical or different and each is a hydrogen atom, a halogen atom, the hydroxy, nitro, an alkyl group of 1 to 4 carbon atoms or an alkoxy group of 1 to 4 carbon atoms, B is a bivalent or trivalent bridge member, D is a bivalent or trivalent benzene radical or naphthalene radical or a carboxylic acid ester, carboxamide or acyl radical of an aromatic or aliphatic carboxylic acid or an aliphatic or aromatic sulfonic acid amide or a sulfonamido or carbonylamido radical, W is a water-solubilizing residue that can be bonded to B or D,
m is 1 or 2 and η is O or 1. 2. Process for the preparation of the compounds of the formula (1) mentioned and defined in claim 1, characterized in that that he a.) the dicarboxylic acid or its anhydride of the general formula (2) or (3) 609815/1111 - 25 - 2U7024 COOH COOH with an amine of the general formula (4) H ₂ N B (D) (4) wherein X, R ₁ , R ₂ >Ro> R4 »B, D, W, m and η have the meanings given in claim, is reacted with imide formation in a reaction stage, or b.) into suitable imide derivatives of the above-mentioned benzoxanthene or benzothioxanthendicarboxylic acids of the formula (2) which, in the imide radical, have the abovementioned radical B or D or B-D or a Contain precursor thereof, the water-solubilizing group W introduces. . 3. Use of those mentioned and defined in claim 1 or the compounds of formula (1) prepared according to claim 2 as dyes, 09 8 1.5 / 1 1 1 1