CA1070693A - Water-soluble benzoxanthene and benzothioxanthene compounds, process for preparing them and their use as dyestuffs - Google Patents

Abstract

Abstract of the disclosure:
New benzoxanthene- and benzothioxanthene-dicarboxylic acid imide compounds containing in the aliphatic or aromatic imide radical one or two water-soluble groups but no sulfo group in the benzene nuclei of the xanthene skeleton, had been found which are suitable as dyestuffs for dyeing or printing natural or synthetic polyamide and have very good dyeing and fastness properties, especially a good fastness to alkali and a good dyeing behavior to texturized polyamide fibres contain-ing differently drawn fibre moieties which were dyed in even shades.

Description

107~693 Prom German O~enlegungsschri~t No. 2 017 764 water-soluble benzo-xanthene and benzothioxanthene dyestuffs of the general ~ormula (I) i` I 1 i ~O
R' . _ are known, in which X is an oxygen atom or a sulfur atom, Y is an oxygen atom or a , N-R-group, wherein R is hydrogen or an optionall~ substituted alkyl, cycloalkyl or aryl radical, a heterocyclic radical, a hydroxy or amino group, and R'l and R'2 represent h~drogen atoms, halogen atoms, alkyl or alkoxy groups and n stands for an integer of 1 to 3. The compounds of this formula ~I) are prepared by sul~onating in known manner compounds of the general formula (II) O

~ 1 ~ (Il) . R'2 ~herein R'l, R'2, X and Y have the above meanings.
The Of~enlegungsschrift does not contain any data about the position of the sulfo group in the benzoxanthene-/benzothioxanthe~e body since in the . ~ ,. ....:~.

.

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. . . - . , ~ 1070693 course of sulfonation m~xtures of isomers are apparently~ formed; in this pro-cess sulfonation takes place exclusively in the aromatic rings, preferably on the benzoxanthene or benzothioxanthene dyestuff nucleus. Accordingly, no compounds are described which carry a sulfonic acid group in the side chain , N-R-group in final position. For in this known process, fuming sulfuric acid is preferably used to effect the sulfonation of the nucleus; with the rather low temperature of 70 - 100C a mixture of mono- and disulfonated pro-ducts ~Example 1) is formed, at higher temperatures of 125 - 130C, however, a product is obtained the nuclei of which are sulfonated twice (Example 2).
German Offenlegungsschrift No. 2 150 879 als~ d~scribes the use of such ; nucleus-sulfonated dyestuffs of the formula ~I) for the dyeing and printing of fibr0 materials of natural and synthetic polyamides and polyurethanes.
Moreover, it describes dyestuffs carrying in the aliphatic side chain a sul-fonic acid group via the imide, N-R; but they additionally contain at least . i , .
;~ a further sulfonic acid group in the benzoxanthene or benzothioxanthene ring ~ skeleton.
These dyestuffs sulfonated in the benzoxanthene and benzothioxanthene nuclei provide very brilliant dyeings, but with regard to some properties they do not entirely comply with the requirements for dyestuff in our day. Espe-cially the sensitivity towards alkalis of the dyeings prepared with these dye-~ stuffs is cr~ticized. Furthermore, they do not provide even dyeings on materi-als of texturized polyamide fibres showing different drawing.
~, Now, better novel water-soluble compounds have been found which do not contain sulfo groups in the benzoxanthene and -thioxanthene skeleton and ~" correspond in the form of the free acid to the general formula (1)

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~070693 R ~ D)n . X ~1) Especially the alkali metal and alkaline earth metal salts thereof as well as ammonium salts are preferred. As alkali salts there may be men-tioned the sodium and potassium salts.
In the general formula (1) X is oxygen or sulfur, Rl, R2, R3 and R4 are identical or different and each of them is hydrogen, halogen, espe-cially chlorine or bromine, hydroxy, nitro, alkyl having 1 to 4 carbon atoms, preferably the methyl or ethyl group, or alkoxy having 1 to 4 carbon atoms, preferably the methoxy or ethoxy group, B is an alkylene radical having 1 to 6 carbon atoms, such as -CH2-, -CH2-CH2- or -CH2-CH2-1CH-CH2-, a cycloaliphatic ~ group, as for example a cyclohex~lene radical, or CH3 r a radical of the formula -NH-, -NH-S02-, -NH ~ , -NH ~ -O-CH2-, -0-CH2-CH2 or a three-valent nitrogen atom a benzene or naphthalene or a benzyl radical, the aromatic nuclei of which may be substituted by alkyl and or alkoxy radi-cals each having 1 to 4 carbon atoms and or chlorine and may contain alkylene ` radicals having 1 to 4 carbon atoms, to which the radical W is bound, D is a benzene radical, naphthalene, carboxylic acid ester, carboxylic acid amide or ac~l radical of a lower aliphatic carboxylic acid, of the benzoic acid or 2Q naphthoic acid or an aliphatic or aromatic sulfonic acid amide radical, pre$erafily~ a phenylsulfonic acid amide or p-toluene-sulfonic acid amide - ' .
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. 070693 radical, a sulfamoyl or carbamoyl radical or a radical of the ormula -O-CO-R, -NH-CO-R, -N(alkyl)-CO-R, -NH-S02-R, -N(alkyl)-S02-R, -S02-NH-R, -CO-MH-R or -CO-N(alky~l)-R, -S02N~alkyl)-R, wherein R is a straight-chain or branched alkyl radical having 1 to 6 carbon atoms or the phenyl radical, which may be substituted by chlorine, methyl, ethyl, methoxy and/or ethoxy groups (the various alkyls mentioned above stand ~or alkyl or alkylene radicals having 1 to 4 carbon atoms, preferably 1 to 2 carbon atoms, such as for methyl or ethyl or methylene or ethylene), W is a sulfo, sulfato, thiosulfato, phosphato, phosphonic acid or phosphonic acid semi-ester group ~-PO(OR5)(0H) or its alkali salt), wherein R5 is an alkyl radical having 1 to 5 carbon atoms or a benzyl radical bound to B and/or D
or 2, n is O or 1.
The novel compounds of the formula ~1) may be prepared in different ways, for example a) by reacting, in one reaction step, the dicarboxylic acid or the anhydride thereof of the general formula ~2) or ~3) ., Rl ~ COOH RR3 0 ~COOH
' ~ X J~ ~X ~
R2 R4 R2 ~R4 . (2) (3) .~ith an amine o~ the general ~ormula ~4) ,~
. -- 4 --,.'~, ~

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, H2N ~ B ~D) ~ ~W)m wherein Rl, R2, R3, R4, B, D, W, m and n have the above meanings, to form the imide, or b) b~ introducing the water-solubilizing group W into suitable imide derivatives of the above-mentioned benzoxanthene or benzothioxanthene-dicarb-ox~lic acids of the formula (2) which contain in the imide radical the above-mentioned radical B or D or B-D~
Yariants o~t~e method b) are, for example the following ones:
1. Reaction of the hydroxy compound of the formula ~5) Rl ~ N ~ B-(D)n ~ m 1~ R ~ X

:' 2 4 wherein Rl, R2, R3, R4, B, D, X, m and n have the above meaning, but with the proviso that the hydroxy group is not directly bound to an aromatic radical, ~ith a corresponding esterifying agent, the group W thus introduced being one .of the above-mentioned ester radicals, except the thiosulfate radical;
2. lntroduction of the water-solubilizing group W which is already contained in bound form in a molecule portion of the radical B or D or B-D, ~, for example b~ reaction of compounds of the formula ~6) ., .
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- lQ7~693 ~3 Rl ~ N - E - Z
~ ~ O (6) wherein Rl, R2, R3, R4 and X have the above meanings, E is a molecule portion of the radical B or D or B-D with a terminal -CH2-group and Z is a hydroxy or amino group, with a corresponding compound of the formula (7) completing the radical of the formula members B, D or B-D, . A G ~ )m ~7) : wherein A is the radical of the formula Cl-S02- or Cl-CO, G is the remaining : completing part of the radical B, D or B-D, as for example the radical R
defined in formula (1), or by reaction of compounds of the formula (8) R 1 ~N - E - Z

1() 2 ~J~o (W)!n ~8) ~th-~a c~rre~pondin~ compound of the formula (9) completing the rest of the ~ormula memBers B, D or B-D

A - G ~ (~)m (9) ' _ 6 --.
:.............. "' ' ~
.

~erein Rl, R2, R3, R4, E, Z, A, G and ~ have the above meanings, ml is the integer 1 or 2 and m2 stands for zéro or 1 and the sum (ml ~ m2) is 1 or 2.
The above-mentioned reaction of condensation of compounds of the formula (2) or ~3) with compounds of the formula (4) is preferably carried out in a solvent at temperatures between 50 and 200& , at best at a tempera-ture bet~een 80 and 150C, and if desired under pressure as well as at a pH
value of 4 to 10, preferably of 6 to 9. As solvents there are used dimethyl-formamide, alkylglycols, for example ethyleneglycol-monomethyl or -monoethyl ethers, lower alkanols, for example methanol, ethanol or butanol, or mixtures of these solvents, mixtures of these solvents with water, preferably only ~ater.
Among the processes introducing ~Rt~r~salubilizinggroups into a ~enzoxanthene or benzothoxan~hene-imide derivative in analogy to the above-mentioned process b) the following special variants of the process may be pointed out:
b.-l) Conversion of a compound of the formula (10) R3 o Rl ~ { B ~ ~D2n ~ ~J Clo) - R2 ~4 . ~herein Rl, R2, R3, R4, B, D and n have the meaning indicated for the formula Cl), into a compound of the formula (1), wherein W stands for the sulfate 2Q group and m = 1, by reaction with sulfuric acid, preferably concentrated sul-~uric acid, at temperatures of from 0 to 40C, preferably at room temperature C15 - 25C).

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lQ70693 ; In this esterification care has to be taken that there is especially no local overheating to avoid sulfonation in the benzothioxanthene or benzo-xanthene nuclei.
.-2) Conversion of a compound of the formula (10) into the phosphato compound thereof with concentrated phosphoric acid or polyphosphoric acid at temperatures between 80 and 200C, preferably between lOO and 150C.
Among the compounds prepared in paragraph b,-l) and b.-2) of the formula ~1) those are preferred in which n is zero and B is an alkrlene ; radical having 1 to 6 carbon atoms, especially a radical of the formula -CH2 or CH2-CH2- or an aromatic radical, especially the benzene radical (phenylene) which may be substituted by alkylene radicals, as for example the radical of the formulae -CH2 ~ CH - or - ~ - CH2-b.-3) The conversion of compounds of the formula ~ll) Rl ~ N (CH2)q OH
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into compounds of the formula ~12~

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1070~93 Rl ~ N - (CH2)q-0- Al- Ar -S03H

X ~ ~ (12) in hhich X, Rl, R2, R3 and R4 have the above meanings, q stands for an integer af:l.to 6, Al for a sulfonyl or carbonyl group and Ar is an aromatic radical, ~or example a phen~lene or naphthylene radical, by means of aryldisulfo-monochlorides or -sulfochlorides of arylcarboxylic acids, for example the benzoic acid-3-sulfochloride, in pyridine.
In this reaction the sulfochlorides used of the aromatic carboxylic acids react via a complex compound of the pyridine as carboxylic acid chlor-rides.
lQ b.-4)Conversion of compounds of the formula ~13) : R4 Rl ~ N - ~CH2) -NH-R5 ~ ~ ~ O (13) ~: R2 R3 into compounds of the formula (14) .
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': ' ' ' ' ': ~' ' ~ ' , : ' " '. ' ': ' 1~70~i93 ' Rl 3 ~ N - (CH2) -N -S02-Ar-S03H
R5 ~14) . R2 R4 . in which X, Rl, R2, R3, R4, Ar and q have the above meanings and R5 is hydrogen or an alkyl group having 1 to 4 carbon atoms, preferably the methyl or ethyl group, by reaction with aryldisulfomonochlorides, in which process the formation of amide is carried out in known manner in an organic solvent andtor water in the presence of an acid-binding agent.
b.-5) Conversion of compounds of the formula (15) ; R

R1 ~N - (CH2)q~ COC1 1~) ~ ~15) into compounds of the formula (16) .'. O
R1 ~<~1N - (CH2) -CO-IN-R-SO3H

.. R2 R4 "..~

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, ~ ' , ~070693 wherein Rl, R2, R3, R4, X, q and R5 have the above meanings and R is an al-kylene radical having 1 to 6 carbon atoms, preferably the methylene radical or the ethylene radical, or the radical of the formula CH2~

by reaction in known manner, with an amine of the formula R5 - NH - R - S03H, wherein R5 and R have the meanings mentioned, in water and/or in an organic solvent in the presence of an acid-binding agent.
To isolate the compounds obtained according to the different vari-ants of the process described above the reaction mixture, if necessary (cf.
process b.-l and b.-2), is stirred with ice water in usual manner, and the pH is adjusted to 5 - 7 with sodium carbonate solution; the novel compound is subsequently salted out with sodium or potassium chloride, suction-filtered and dried.
The dicarboxylic acids used as starting compounds and the anh~drides thereof of the general formulae (2) and (3) as well as the imides thereof of the general formulae (10), (11) and (13) and the carboxylic acids required for preparing the acid chlorides (15) may be obtained for example according to the process described in German Patent Specification no. 1 297 259 and in German .~ 2Q Auslegeschriften Nos. 1 569 761 and 1 770 818. -The novel compounds of the formula ~1) have proved excellentl~ suit-able as brilliant dyestuffs for dyeing and printing natural and synthetic ~ fibre material containing carbonamide groups, as for example wool, silk, syn-- thetic polyamide fibres or polyurethane fibres. They yield on these materials intense reddish to greenish yellow very brilliant dyeings, which partly have an intense green fluorescence and show a fastness to light and to wetting .
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which is unusually high ~or this class o~ dyestu~s. Their dyeings and prints are generally distinguished by a very good fastness to light in a dry and wet state, by good to very fastness to washing, also in the presence of perborates or peroxides as well as other bleaching agents, such as hypochlorite, as well as ~y a good acidic and alkaline fastness to perspiration, cross-dyeing, pot-ting, fulling, water, sea water, alkalis, acid and rubbing. These novel dye-stuffs also have a good absorption capacity with the fibres mentioned above, a good color build-up and accordingly, a high tinctorial strength. The dye-ings obtained with these dyestuffs are furthermore characterized by a very good evenness; they provide even dyeings on texturized polyamide material.
It may also be pointed out that the novel dyestuffs have a very good solubility in water, even in cold water, that they cause no or only an insignificant blocking when dyeing in dyestuff mixtures, that they show a good resisting property in the dyeing of mixed fabrics, especially at the higher temperatures of about 100 to 230C necessary for example for the thermofixation process, and that their aqueous dyestuff solutions, padding -I liquors and printing pastes have a good viscosity property and a small sensi-tivity towards electrolytes.
~1 The dyestuffs are above all superior to the dyestuffs of next com-!.1 2Q parable structure from German Offenlegungsschriften Nos. 2 017 764 and 2 150 879 in respect of various tinctorial properties and fastnesses to use and to processing, for example absorption capacity, color intensity, the even ~ dyeing of texturized polyamide containing differently drawn fibre moieties, ;~ fastness to alkalis and fastness to alkaline perspiration. On the fibre ma-terial mentioned, some of these dyestuffs also provide in mixture with suit-able blue dyestuffs very brilliant green shades having a very good fastness to - light and to wetting.
An~ther advantage o~ the novel compounds is their technically easy ` - 12 _ . - ~
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- ~ 1070693 preparation. Starting from the benzoxanthene or benzothioxanthene-dicarboxylic acids prefera61y used, or the anh~drides thereof having the general formula C2) or (3) the compounds of the invention are obtained by reaction with the amine of the general formula ~4) in only one reaction step; the novel compounds are generally obtained with a very good yield and a very pure form. Moreover, this reaction may be carried out in water.
Among the novel compounds those are particularly interesting in ~hich the individual radicals of the formulae having the general formula ~1) have the following meanings: Rl or R2 or R3 is a meth~l or methoxy group, the other two, each are hydrogen atoms, and R4 is hydrogen, or Rl, R2, R3 and R4 are hydrogen each, X is oxygen or sulfur, the entire radical of the formula ~ B - (D)n ] forms an alkylene radical having 1 to 6 carbon atoms, prefer-aBly two carbon atoms, or a radical of the formula ~ alkylene-, - NH ~ , - NH ~ , .

- alkylene ~ , - alkylene alkylene-, - alkylene - 0 - C0 - ~ W
; or ~alky~lene - C0 - N - alkylene-alkyl w~erein alkylene is an alkylene radical having 1 to 6 carbon atoms and alkyl is an alkyl radical having 1 to 4 carbon atoms, preferably the methyl or ethyl radical, W stands for the sulfonic acid group, for the sulfato, phosphato or thiosul~ato group, and m is 1 or 2.

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'' ~070693 A particularly~ ad~antageous and pre~erred variant thereo~ are the compounds of the formula (1), wherein Rl, R2, R3, R4 and X and W have the above meaning just mentioned, n is zero, m is 1 and B has the meaning men-tioned for the formula ~1), but is especially a phenylene or naphthylene group ~ith one or t~o terminal alkylene radicals having 1, 2 or 3 carbon atoms, preferably the radical of the formula " ~ or ~ c~2- ~

especially preferred for B is an alkylene group having 1 to 6 carbon atoms, ; having preferably 1, 2 or 3 carbon atoms.
' 10 ~specially excellent representatives of this class of compounds, N~ich may be favorably synthesized are compounds corresponding to the general formula C17~
~,~
.- O

. ~ N - B - W

~ ~ o ~ (17) t .~
~herein B stands for a radical of the formula ~ -CH2 - CH2 -, -CH2 - CH2 CH2 ~ 2 ;: and W ls the thiosulfato or phosphato group, especially the sulfo or sulfato gr~up .
The ~oll~ing Examples illustrate the in~ention, Parts and percent-ages are By~ ~eight unless stated other~ise.

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EXAMPLE 1:
.
30.4 ~arts o~ benzothioxanthene-3,4-dicarboxylic acid anhydride were suspended in 330 parts o~ dimethylformamide and refluxed for 8 hours together with a solution of 14.5 parts of 2^amino~ethane-sulfonic acid and 7.8 parts of potassium carbonate in 180 parts of water. A~ter cooling to room temperature 200 parts of a 15% potassium chloride solution were added until the imide com-pound had completely precipitated. After some time the whole was suction-filtered, washed wi~h a 10% potassium chloride solution and dried at 100C.
A~out 47 parts of benzothioxanthene-3,4-dicarboxylic acid-N-~-sulfethyl imide o$ the formula :' O

,. ~ N-CH2-CH2-S3H
~ ~S~ ~ ' were obtained in the form of the potassium salt. This novel compound dissolves in water with a yellow color and provides according to usual dyeing processes on wool and polyamide brilliant golden yellow dyeings having a good fastness to light and to wetting.
EXAMPLE 2:
32 Parts of 10-methoxybenzoxanthene-3,4-dicarboxylic acid anhydride ~^ere introduced into a solution of 13.1 parts of 2-amino-ethane-sulfonic acid and 5.3 parts of sodium carbonate in 500 parts of water and heated, while stirring, in the pressure autoclave for 6 hours at 140C. After cooling the i~i~de compound obtained was completely precipitated with 40 parts of sodium chloride, suction-filtered and washed with a 10% sodium chloride solution.

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~ After drying 43 parts of a compound were obtained which had in form of the : free acid the following formula:

H3C0 ~ ~ 2-CH2-SO3H

~or an easier use as dyestuff the compound was ground. It dis-! solves in water with a yellow color and a green fluorescence and is excellent-ly suitable for dyeing and printing natural and synthetic polyamides, whereby very ~rilliant greenish yellow shades were and are obtained.
EXAMPLE 3:
15 Parts of 9-methyl-benzoxanthene-3,4-dicarboxylic acid anhydride ~ere suspended in 180 parts of monoethylglycol and heated for 6 hours to 140C
in a stirring autoclave together with a solution of 7.5 parts of 2-amino-ethane-sulfonic acid and 5.2 parts of sodium bicarbonate in 90 parts of water.
After cooling the imide compound thus prepared was salted out with a saturated sodium chlsride solution, suction-filtered, washed and dried. About 21 parts of a compound wereobtained which corresponds in form of the free acid to the general formula , O

,~ /` ~O
'' /~~

.. , ~.
~ ~` - 16 ---` 1070693 It provides on wool and synthetic polyamide dyed according to pro-cesses usual ln technique, very brilliant greenish yellow dyeings having a very good fastness to use.

In analogous way as described in Example 2, 32 parts of 6-methoxy-benzoxanthene-3,4-dicar60xylic acid anhydride were reacted with 13.7 parts of 2-amino-ethane-sulfonic acid. After salting out and washing with a 10% sodium chloride solution, about 43 parts of a compound were obtained which had in ~crm of the free acid the ~ollowing formula - , .

~ 2 2 3 :-10 ~0~'~

~ OCH3 : .
~ ith this compound dyeings of a brilliant rellow color were and are obtained on synthetic polyamide fibre materials according to usual dyeing pro-cesses.
EXAMPLE 5:
29 Parts of benzoxanthene-3l4-dicarboxylic acid anhydride were : suspended in 450 parts of monoethylglycol and stirred with a solution of 19 parts of 2-aminoethyl-thio-sulfuric acid and 13.5 parts of sodium bicarbonate in 160 parts of water for 7 hours at 95C. Then the whole was cooled to 50C, and 550 parts of a 15% sodium chloride solution were added. The imide pre-cipitated was suction-filtered, washed with a 5% sodium chloride solution, dried at 100C and ground. About 48 parts of a compound were obtained which correspond~ in the form of the free acid to the formula ~. - 17 -: ~

:

.

, ' ' ~ , , ~` N-CH2-CH2~S~sO3H
,~bo : o It provides on wool and polyamide brilliant greenish ~ellow dyelngs having a good fastness to use.

17.3 Parts of 2-aminoethanol-sulfuric acid ester were dissolved ~ith 23 parts of sodium bicarbonate in 180 paTts of water, then 250 parts of dimethylformamide were added and 32 parts of 10-methoxybenzoxanthene-3,4-dicarboxylic acid anhydride were introduced. The suspension was stirred for 8 hours at 95C and at a pH value of 7 to 7.5. When the reaction was finished, 10 the imide obtained was precipitated with 200 parts of a 15% sodium chloride solution, suction-filtered, washed with a 10% sodium chloride solution, dried at 80C and ground. About 43 parts of a compound were obtained which has in form o~ the free acid the formula : O

~ N-CH2-CH2-O~O3H
H3Co ~

., , ~t shows an orange yellow color. It provides on wool and polyamide ~i~bres greenish yellow very bTilliant dyeings and prints, having a good fast-' ~ .
. ,.

- ' , : ~70693 ness to use according to dyeing and printing processes usual in technique.
EXAMPLE 7:
8.5 Parts of 10-methoxybenzoxanthene-3,4-dicarboxylic acid-N-~-hydroxy-ethyl imide were introduced into 90 parts of polyphosphoric acid and slowly heated to 140C while stirring. StirTing was continued for 8 hours at this temperature. Then the reaction mixture was poured into ice and the phos-phato compound obtained was salted out with potassium chloride and suction-filtered. The moist filter cake was stiTred in water and neutralized with potassium carbonate. After clarifying filtration of the solution and spray-drying, about 9.2 parts of the compoùnd o~ the formula :
O
H3C(1 ~ I CH2-CH2-OPO~OH)2 ' ~ere obtained as potassium salt. It provides on synthetic polyamide a very Brilliant greenish yellow dyeing having a very good fastness to use.

14.5 Parts of phen~lhydrazine-2,5-disulfonic acid were dissolved with 2.8 parts of sodium acetate and 9 parts of sodium carbonate in 40 parts o~ ~ater. Then 200 parts of monoethyl glycol were added and 16 parts of 10-methoxybenzoxanthene-3,4-dicarboxylic acid anhydride were introduced; the suspens~on ~as heated ~or 12 hours at 140C in a stirring autoclave. After co~ling the reaction mixture was diluted with 1000 parts of water and filtered ~ ~ . ~ - 19 -k ~, ~, .
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hot ~ith addition o~ kieselguhr. The hydrazide compound obtalned was pre-cipitated ~rom the filtrate by sodium and potassium chloride, wash0d with saturated sodium chloride solution and dried at 100C. About 27 parts of the compound of the formula H3CO N-NH ~

~ere obtained as potassium and sodium salt. According to technically usual dyeing and printing processes it provides a brilliant yellow color on syn-thetic polyamide fibres.
EXAMPLE 9:
The reaction of 16 parts of 10-methoxy~benzoxanthene-3,4-dicarboxylic acid anhydride ~ith 20 parts of the sodium salt of the 4-aminobenzyl-sulfonic acid according to the conditions mentioned in Example 8 provided about 25 parts o~ the compound of the formula O
H3CO ~ N ~ ~3 CH2-503H

. o~

as potassium or sodium salt. rt y~ields on synthetic polyamide ~ibre materials ver~ brilliant yello~ dyeings having a very good ~astness to light.

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1~70693 .. . .
EXAMPLE 10:

Into a mixture of 5 parts of the hydroxy compound of the formula O

~ N CH2_cH2_oH

and 50 parts of pyridine, 7 parts of benzoic acid-3-sulfochloride wereintro-duced while stirring at 20 - 30C during 30 minutes. Stirring was continued ~or one hour at 30 - 40C and for 2 hours at 40 - 50C, whereby a complete dissolution took place. At 40C 50 parts of water were added dropwise and stirring was continued for one hour at 60 - 70C. To precipitate the compound formed, 200 parts of a saturated sodium chloride solution were added at 25C;
lQ the precipitated product was suction-filtered, washed with saturated sodium chloride solution and dried at 60C in vacuo. 10.4 Parts of a compound were obtained which had in the form of the free acid the following formula:
O

-CH2-CH2--C ~ S03H

D

r T~is dyestu~f provides on synthetic polyamide fibre material a ,,:
brilliant greenish yello~ dyeing.

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~070693 EXAMPLE 11:
To a mixture of 5 parts of the acid chloride of the formula O

COC I

prepared from the corresponding carboxylic acid ~ith thionyl chloride, and150 parts of acetone, a solution of 4.5 parts of N-methyltaurine as sodium salt in 50 parts of water was added dropwise while stirring, at 5 - 10C
within one hour. Then stirring was continued for 3 hours at 10 - 20C and for 5 hours at 20 - 30C, the pH value being maintained at 6 - 7. After the reaction 100 parts each of a saturated sodium chloride solution and potassium chloride solution were added. The precipitate was suction-filtered. The moist filter cake was washed with a saturated sodium chloride solution and then stirred in 400 parts of water. After clarifring ~iltration o~ the solu-tion and spray-drying 3.4 parts of the compound of the formula O

~ ~ ~\rl N-CH2-CO- ~N-CH2-CH2-S03H
H3C ~ ~ ~ " ~ CH3 .' ~
', ~ere o~tained as ~otassium/sodium salt. This d~estuff provides on synthetic polyamide fibre material a brilliant greenish yellow color.
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Claims (17)

THE EMBODIMENTS OF THE INYENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILE OE IS CLAIMED ARE DEFINED AS FOLLOWS:

1. A water-soluble compound which in the form of the free acid corresponds to the general formula (1) ( 1 ) wherein X is oxygen or sulfur, Rl, R2, R3 and R4 are identical or different and each of them ls hydrogen, halogen, hydroxy, nitro, alkyl having 1 to 4 carbon atoms or alkoxy having 1 to 4 carbon atoms, B is an alkylene radical having 1 to 6 carbon atoms, a cyclohexylene radical or a radical of the formula -NH-, -NH-SO2-, , , -O-CH2-, -O-CH2-CH2-or a three-valent nitrogen atom or a benzene or naphthalene or a benzyl radical, the aromatic nuclei of which may be substituted by alkyl and/or alkoxy radicals each having 1 to 4 carbon atoms and/or chlorine and may contain alkylene radical having 1 to 4 carbon atoms, to which the radical W is bound, D is a benzene radical, naphthalene, carboxylic acid ester, carboxylic acid amide or acyl radical of a lower aliphatic carboxylic acid, of the benzoic acid or the naphthoic acid or an aliphatic or aromatic sulfonic acid amide radical, W is a sulfo, sulfato, thiosulfato, phosphato, phosphonic acid or phosphonic acid semiester group -PO(OR5)(OH), wherein R5 is an alkyl radical having 1 to 5 carbon atoms or a benzyl radical bound to B and/or D, m is 1 or 2 and n is zero or 1.

2. Process for preparing the compounds of the formula (1) claimed and defined in claim 1, which comprises a) reacting, to form the imide in one reaction step, the dicarboxylic acid or the anhydride thereof of the general formula (2) or (3) (2) (3) with an amine of the general formula (4) (4) wherein X, R1, R2, R3, R4, B, D, W, m and n have the meanings of claim 1, or b) introducing the water solubilizing group W into suitable imide derivatives of the above-mentioned benzoxanthene or benzothioxanthene-dicarboxylic acids of the formula (2) containing in the imide radical the above-mentioned radical B
or D or B-D.

3. A compound as claimed in claim 1, wherein D is a phenylsulfonic acid amide or p-toluene-sulfonic acid amide radical, a sulfamoyl or carbamoyl radical or a radical of the formula -O-CO-R, -NH-CO-R, -N(alkyl)-CO-R, -NH-SO2-R, -N(alkyl)-SO2-R, -SO2-NH-R, -CO-NH-R, -CO-N(alkyl)-R, or -SO2-N(alkyl)-R
wherein R is a straight-chain or branched alkyl radical having 1 to 6 carbon atoms or the phenyl radical, which may be substituted by chlorine, methyl, ethyl, methoxy and/or ethoxy groups.

4. A compound as claimed in claim 1, wherein one of the radicals R1, R2 or R3 is methyl or methoxy and the two others represent each hydrogen, or R1, R2 and R3 each represent hydrogen, R4 is hydrogen, the formula radical -[B-(D)n]
stands for an alkylene radical having 1 to 6 carbon atoms of the formula ,, ,, ,, or , wherein alkylene is an alkylene radical having 1 to 6 carbon atoms and alkyl is an alkyl radical having 1 to 4 carbon atoms, W stands for the sulfonic acid group, the sulfato, phosphato or thiosulfato radical, X is oxygen or sulfur and m is the number 1 or 2.

5. A compound as claimed in claim 4, wherein the formula radical -[B-(D)n] is the ethylene radical.

6. A compound as claimed in claim 4, wherein the formula radical -[B-(D)n] is the ethylene radical, W is the sulfo, sulfato, thiosulfato, phosphato or sulfobenzoyloxy group and m is 1.

7. A compound as claimed in claim 4, wherein the formula radical [B-(D)n] is the group -NH, or the benzene nucleus.

8. A compound as claimed in claim 4, wherein R1, R2, R3, R4, X and W have the meanings given in claim 4, the formula radical -[B-(D)n] is a radical of the formula or or stands for an alkylene group having 1, 2 or 3 carbon atoms and m stands for 1.

9. A compound as claimed in claim 1 of the formula wherein p stands for an integer of 1 to 6 and W stands for the sulfo, sulfato, thiosulfato, phosphato or phosphonic acid group or the phosphonic acid semiester group of the formula -PO-(OR5)OH, wherein R5 is an alkyl radical having 1 to 5 carbon atoms.

10. A compound as claimed in claim 1 of the formula wherein B stands for a radical of the formula -CH2-CH2-, -CH2-CH2-CH2- or and W is the thiosulfato, phosphato, sulfo or sulfato group.

11. The compound according to claim 1 of the formula

12. A compound as claimed in claim 1, 3 or 4, in the form of an alkali metal salt, alkaline earth metal salt or ammonium salt.

13. A compound as claimed in claim 1, 3 or 4, in the form of a sodium or potassium salt.

14. A dyeing or printing process wherein a compound as claimed in claim 1 or a compound prepared according to claim 2 is used.

15. A process as claimed in claim 14 wherein nitrogen-containing fibrous material is dyed.

16. Leather of fibrous materials of wool, silk, polyamides or poly-urethanes and natural or synthetic polyamides containing blended fabrics which have been dyed or printed with a dyestuff as claimed in claim 1.

17. Fibre material of polyamide dyed or printed with a compound defined in claim 1 or prepared according to claim 2.