CA1064916A - Process for the preparation of xanthene dyestuffs - Google Patents
Process for the preparation of xanthene dyestuffsInfo
- Publication number
- CA1064916A CA1064916A CA242,170A CA242170A CA1064916A CA 1064916 A CA1064916 A CA 1064916A CA 242170 A CA242170 A CA 242170A CA 1064916 A CA1064916 A CA 1064916A
- Authority
- CA
- Canada
- Prior art keywords
- carbon atoms
- acid
- hydroxy
- alkoxy
- radical
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B11/00—Diaryl- or thriarylmethane dyes
- C09B11/04—Diaryl- or thriarylmethane dyes derived from triarylmethanes, i.e. central C-atom is substituted by amino, cyano, alkyl
- C09B11/10—Amino derivatives of triarylmethanes
- C09B11/24—Phthaleins containing amino groups ; Phthalanes; Fluoranes; Phthalides; Rhodamine dyes; Phthaleins having heterocyclic aryl rings; Lactone or lactame forms of triarylmethane dyes
Abstract
Abstract of the disclosure:
A process for the preparation of xanthene dyestuffs of the general formula , (in which R1 and R2 are identical or different, each re-presenting an optionally substituted aliphatic or op-tionally substituted araliphatic or cycloaliphatic radical, or R1 represents also a hydrogen atom or a carbocyclic aromatic or heterocyclic radical, or R1 and R2 together with the N-atom form a heterocyclic radical optionally containing further hetero-atoms, the benzene nucleus A may optionally contain substituents, and m stands for the integer 1,2, 3, 4 or zero) had been found wherein the inner salt of a 3,6-dihalogeno-9-(2'-sulfophenyl)-xanthene-9-ol of the formula (in which X stands for a halogen atom and A has the above-mentioned meaning) is reacted with a primary or secondary amine of the formula , (in which R1 and R2 have the meanings specified as above) in a polar solvent which is free from acid groups;
to obtain the sulfo compounds, the product is subsequently sulfonated. The improvement in this process is to carry out the reaction of the xanthenol with the amine in stoichio-metrical amounts and in the presence of an inorganic acid-binding agent and/or an acid-binding tertiary aliphatic or cycloaliphatic amine, of pyridine or of a pyridine deri-vative. The novel process has the advantage of yielding dyestuffs of high quality with a strong color intensity and brilliancy, a high fastness to light and a uniform dyeing behaviour. Furthermore, the dyestuffs are obtained in very good yields avoiding the high charge of the waste water of present processes of the dyestuff itself or its starting components used in excess.
A process for the preparation of xanthene dyestuffs of the general formula , (in which R1 and R2 are identical or different, each re-presenting an optionally substituted aliphatic or op-tionally substituted araliphatic or cycloaliphatic radical, or R1 represents also a hydrogen atom or a carbocyclic aromatic or heterocyclic radical, or R1 and R2 together with the N-atom form a heterocyclic radical optionally containing further hetero-atoms, the benzene nucleus A may optionally contain substituents, and m stands for the integer 1,2, 3, 4 or zero) had been found wherein the inner salt of a 3,6-dihalogeno-9-(2'-sulfophenyl)-xanthene-9-ol of the formula (in which X stands for a halogen atom and A has the above-mentioned meaning) is reacted with a primary or secondary amine of the formula , (in which R1 and R2 have the meanings specified as above) in a polar solvent which is free from acid groups;
to obtain the sulfo compounds, the product is subsequently sulfonated. The improvement in this process is to carry out the reaction of the xanthenol with the amine in stoichio-metrical amounts and in the presence of an inorganic acid-binding agent and/or an acid-binding tertiary aliphatic or cycloaliphatic amine, of pyridine or of a pyridine deri-vative. The novel process has the advantage of yielding dyestuffs of high quality with a strong color intensity and brilliancy, a high fastness to light and a uniform dyeing behaviour. Furthermore, the dyestuffs are obtained in very good yields avoiding the high charge of the waste water of present processes of the dyestuff itself or its starting components used in excess.
Description
~6~6 The present invention relates to an improved process for the preparation o~ xan-thene dyestuf~s.
In German Patent Speci~ications Nos. 848 231 and 895 041, a process for the preparation of xanthe~e dyestuffs has been described, according to which the inner salt of a 9-(2'-sulfo-phenyl)-xanthene-9 ol compound and/or the derivatiYes thereof containing ~urther substituents in -the sulfophenyl radical and having exchangeable atoms or groups in the 3,6-positions9 a~e reacted with primary or secondary amlnes, and the dyestu~fs obtained are optionally sulfonated. According to this method, acid wool dyestu~fs having good fastness properties are ob-tained.
Particularly good dyestuffs are obta.ined according to this process, if the inner salts of -the ~76~dihalogen~-~2'-sulfo-~
phenyl)-xanthene~9 ols are used aæ starting products, th~
rcaction being carried out in such a way that the xanth~nol cornpo~d is reacted with a stron~ly excess amount o~ the amine, while using the same amine or ano-ther polar compound as solvent.
The hydro-hali.de set ~ree in the course of this reaction is bound by the excess amine as salt. This salt, the excess free amine as well as the solvent which has optionally been used, are washed out with an aqueous acid after the reaction has b~en completed. However, the amine and, optionally, the ~olvent can only partl~llly be soparated .~rom the waste water which rernains a~ter the d~estuf~ has been fil-tered o~f, which leads to a considerable loss o~ material as well as to a high c~lar~e o~ ~he w~ste wa-t~r.
According to the kno~ processes, it is also possible to 29 carry out the reaction in such a way that the xanthenol . ~ 2 - ~
~ 86 compound is reacted with a strongly excess amount of aromatic or aliphatic sulfonic acids and/or carboxylic acids which carry primary or secondary amino groups, or with the sodium salts thereof in polar. solvents. The hydro-halide set free in the cou~s~ of th-s rQ~ct~ f^rms ~nm, the snd~-1m ~lt-c on-t~on~llv used the free sul~onic -and/or carboxylic acids. It becomes evident by this process that these ~ree acids, in contra-distinction to the salts, have a reactivity that has been very strongly reduced. For this reason it is necessary to use high molar excess a~ounts of amine when the free acids as well as the salts are used. In spite of this fact it is often not possible to obtain a complete exchange of the two halogen atoms.
However; the proportions of the xanthydrol compound, which only exchanged one halogen atom and remciins in the reaction product, result in a deterioration of the dyestuff qu~lity~
owing to their low color intensity, their strongly deviating shades, their extremely low brilliancy, their very poor fast-ness to light, and their different dyeing behavior.
Besides, the drawback that the components used in a high excess amount remain either in the product or in the waste water is undesirable in either case, since the dyeing behavior (tinctorial strength, af~inity to the fiber~ build--up) is deteriorated, or the charge o~ the waste water is stron~ly increased, which is in any case accompanied by a considerable loss of material~
I-~ ha~ llOW been ~ou~d that these dra~backs in the pre-parat.ion of xanthene dyestu~fs of the ~reneral formula (I) ~649~6 I/N ~ ~ N~
L ~ 3 ---t------- (503H)m (in which Rl and R2 are identical or different aliphatic, araliphatic or cyclo-aliphatic radicals, each being optionally substituted by halogen, hydroxy, alkoxy, amino, cyano, carboxylic acid and/or sulfonic acid, or Rl represents also a hydrogen atom or a carbocyclic aromatic or heterocyclic radical, or Rl and R2 together with the N~atom form a heterocyclic radical optionally contain-ing further hetero atoms, the benzene nucleus A may optionally contain substi-tuents, and m stands for the integer 1, 2, 3, 4 or zero), which comprises react-ing the inner salts of 3,6-dihalogeno-9-t2'-sulfophenyl)-xanthene-9-ols of the general formula (II) ( ) ~ (II) ~1 (in which X stands for a halogen atom, preferably a chlorine atom~ and A has the above-mentloned meaning~ with primary or secondary amines of the formula tIII~
~Rl HN~ (III) (in which Rl and R2 have the meanings specified as above) .~
in a polar solvent, and optionall~ sulfonating the product sub-sequentl~, can be avoided if the reaction of the xanthenol o~
the formula (II) with the amine of the formula (III) is ef fected in a stoichiometrical amount and in the presence o~ an in~ liC ~cid~ ig h~ a'~û~ Gl a~ acld-bi~d~g tart & - y aliphatic amine or a N-containing heterocyclic, pre.~erably aromatic, compound.
As subs~i-tuents in the benzene nucleus A there are to be ~entioned, ~or example, halogen atoms, such as chlorirle and brom~ne atoms, alkyl groups having from 1 to 5 carbon atoms~
alkoxy groups ha~ing ~rom 1 to 5 carbon atoms, aryl radicals, such as the phenyl radical optionally containing substit~lents, hydroxy, carboxylic acid or carbalkoxy groups having from 2 to 6 carbon atoms, carbonamide, sulfonic acid, sulfonamide, B-hydroxy-ethylsulfonyl and ~-sulfa~o-ethylsulfonyl groups.
If the nucleus A carries hydroxy and carboxy ~roups at the same time, this compound of the ~ormula (I) and/or (II) may also be presen-t as a complex metal compound.
The process of the invention is carried out in such a way that 1 mole o~ the xanthenol compound is reacted w.ith 2 to about 2.2 moles o~ the amine in a polar solvent ~ree ~rom acid groups, at an elevated temperature, and ~he hydrohalic acid ~e~ ~ree in the course oP the reaction is bound by adding a~ amount ~.~ the acid-binding a~ent which is at least equi-valent to the amount o~ ~he hgdrohalic acid.
As prl~ar~ or secondary aliphatic, arali.phatic, cyclo~
aliphatic, aroma-tic or heterocyclic amines o~ the ~ormula (XII), ~here may be mentioned, ~or example:
29 Mono- or dialkylamines ha~ing ~rom 1 to 6 carbon atoms in H~E 74/~` ~8 69L9.'lG
each alkyl radical, such as methyl-, ethyl-9 propyl-, butyl-, isopropyl-, or pentylamine, dimethyl-, diethyl-, dipropyl-, or dibutylamine, optionally with substituents in the alkyl radical, such as hydroxy or cyano groups, lower alkoxy, lower c~balko.~3, sul40r.~c ao-~- or o~boY31ic ~oi A gr~Upc; cyo1O-aliphatic amines, such as, for example, cyclopentylamine and cyclohexylamine, araliphatic amines 9 such as phenethylamine 9 benzylamine and benzylethylamine; aromatic amines, such as, ~or example, aniline or N-(alkyl 1-4)-anilines and the deri-vatives thereof which are substituted in the alkyl radical by halogen, such as chlorine, lower alkoxy groups~ lower carb-alkoxy, hydroxy or cyano groups J and/or in the benzene nucleus by halogen atoms, such as chlorine or bromine atoms, lower alk~l groups, such as methyl, ethyl or propyl groups9 lower alkoxy groups, such as methoxy9 ethoxy or propoxy groups, lower carbalkoxy, sulfonamide or hydroxy groups, sulfonic acid or carboxylic acid groups, B-hydroxyethylsul~onyl, ~-sul~ato-ethylsulfonyl, or nitro groups; naphthylamines~ amino-anthra-quinones; 5- or 6-membered heterocycllc amines9 such as amino~
thiazoles, aminopyrazoles, aminotriazole~, aminopyridine~ a~d the benzoderivatives thereo~9 morpholine, piperidine and piperazine.
If the amines contain ~ulfonic acid groups, they are suitably used in the form of their salts, for example as sodium or potassium salt. If the ~ree sulfonic acid or carb-oxylic acid ls used, a corre~ponding amount of the acid-binding agent is additionally added~ which is capable o~ con-verting the acids in-to the corresponding salts.
29 As solvents, there may be used water, as ~ell as orga~ic _E _ 4/F 386 .
compounds, such as ~or example, methanol 9 ethanol, propanol, butanol 9 glycol, glycerin, diglycol, polyglycols, alkylgylcols~
phenylglycol, alk~lpolyglycols, benzylalcohol, propylene~glycols~
acetonitrile, dimethylformamide, N-methylpyrrolidone-2, di-meth,Tlacetamide; dimethv1Sul~oxide or mixtures of these solvents. The amount of the solvent used depends on the vis-cosity of the reaction mass. The solvent is suitably used i~
an amount which is just sufficient to keep the reaction mass, which is present as a homogeneous solution or fine suspension9 in a condition so as to be stirred easily.
As acid-binding inorganic agents there are suitable, for example5 ox.idesJhydroxides~ carbonates, hydrogenocarbonates, acetates~ borates or phospha-tes of alkali metals or alkaline earth metal.s or of ammonia, such as calcium or magnesium oxide, sodium, potassium, calcium or magne~ium hydro~ide, sodi.um or potassium carbonate, sodium bicarbonate 9 sodium acetate, borax or di or trisodium phosphate, moreover, aluminum oxide or -hydroxide.
Of the organic compounds~ there may be mentioned as tert.iary aliphatic amines, ~or example, triethylamine, tripropylamine, tributylamine, dicyclohex~let~ylamine or triethanolamine, and as N-containing heterocyclic compounds, ~or example, pyridinè
or ~uinolin~. IThe acid-bind-ing agen-t is u5~d in a stoichio-metrical amount or in a slight excess amount, i.e. per mole o~
xan~henol compound 2 moles o~ acid-binding agent are required.
I~ in the reactlon primary or secondary amines are used which contain free sul~onic acid groups, at least 4 moles of acid--~ binding agent are required as ~ar as the amines contain ¢ne 29 ~ulfonic acid group.
HOE ?4!F 386 1~i493L6 The reaction temperature, as well as the reaction time, depends on the re~ctivi~y of the amine used and may be in the range of from about 20C to about 180C. If the reaction te~perature required is above the boiling point of the solvent used, tne reac-tion may also be carried out under increaseu pressure.
The following method of operation is particularly ad-~antageous which involves but a slight charge of the waste water:
I~ an ~mount o~ glycol which is just suf~icient as solvent, and magnesium oxide as acid-binding agent are used, a hetero-geneous reaction mass which can well be stirred is obtained in most cases, in which mass the xanthenol compound after it has been bilaterally reacted is almost completely insoluble, whereas the xan-theno-l compound which has been unila-terally reacted and may still be present in a small amount, as well as various impurities which have been introduced together with the starting materialst are very well soluble. After the reaction has b~en cornpleted, the dyestuff is suction-filtere~
and is freed ~rom glycol and from the magnesium chloride forrned b~ washing with a little water. The glycol mother li-~uor and the wash water are combined and are .~reed :~rom th~
small amo~t o~ precipltate forrned a~ter their combina-tion J
by way of a clari~ying ~iltration. The remaining glycol-water ~5 mixture may be used for the next reaction mixture instead of fresh glycol, the wat~r being eliminated by distillation be~ore or during the react.ion. B~ way o~ this method, only the desired xanthene dyes-tuf~ which has been bilaterally 2g reacted9-as well as a small amount of a solid clari.~ying resi.due are obtained as the products of the total reaction mixture.
There is no charge of the waste water by inorganic or organic compounds.
The working-up o~ the reaction mass may also be effected in such a way that the mass is introduced into water by stir-ring and the precipitated product is directly suction-filtered9 or that~ with the use of water as reaction medium, the dyestuf~
is salted out from the aqueous dyestuff solution and is sub-sequently suction-filtered and dried, or that the entire reaction mixture is evaporated to dryness, or the dyestuf~ is isolated by spray-drying.
The dyestuffs obtaînable according to the invention have a high degree of purity which leads to an increased brilliancy o.~ the dyeings prepared with them. By way o~ a subsequent sulfonation, ~urther sul.~o groups may optionally be introduced into the dyestu~fs, which results in a better water-solubility.
The dyestu~.~s as well as their sul~onation products dye wool and silk as well as synthetic ~ibers carrying basic groups, such as, .for example, polyamide ! modified polyes~er and poly-acrylonitrile fibers or regenerated protein fibers in bright red to blue color shadesc ~he dyeings are distinguished by remarkable ~astness prop0rties, o~ whlch there are to be meIItioned~ in particul~r, the f~stness to ligh~ ~o alkalis, to carboniæing and to decating. The dyestuf~s can be applied aocording to the known dyeing processes and show an excellent levelling capac.ity, 0~ the dye~tu~fs which can be prepared according to the invention, there are to be mentioned particularly those in 29 which in the general ~ormula I R1 and R~ are identical or _ g _ 3~6 different and each represents an aliphatic, araliphatic or cycloaliphatic radical optionally substituted, ~or example, by halogen atoms, such as chlorine or bromine atoms, hydroxy or alkoxy groups, in particular those having from 1 to 4 carbon atoms9 amino, cyano, carboxylic acid- and/or SUil~ ac-iu groups, the radical being for example an alkyl radical having from 1 to 8 carbon atoms or a phenylalkyl radical optionally being substituted in the benzene nucleus and carrying from 1 to 4 carbon atoms in the alkyl portion, or a cyclohexyl or cyclop~ntyl radical, or R1 may also represent a hydrogen atom or a carbocyclic aromatic radical, such as a phenyl or naphthyl radical, or a heterocyclic radical, each may be substituted for example by halogen atoms, such as chlorine or bromine atoms, alkyl groups, especially those having from 1 to 4 carbon atoms, alkoxy group~, especially those with 1 to 4 carbon a~oms, hydroxy, amino, alkylamino groups, parti.cularly those having ~rorn 1 to 4 carbon atorns, dialkylamino groups, especially with alkyl radicals ha~ing each 1 to 4 carbon a-toms, nitrile, carb-oxylic acid, carbo~ylic acid ester groups, such as carboxylic ~n acid phenyl and carboxylic acid alkyl ester groups havin~ ~rom
In German Patent Speci~ications Nos. 848 231 and 895 041, a process for the preparation of xanthe~e dyestuffs has been described, according to which the inner salt of a 9-(2'-sulfo-phenyl)-xanthene-9 ol compound and/or the derivatiYes thereof containing ~urther substituents in -the sulfophenyl radical and having exchangeable atoms or groups in the 3,6-positions9 a~e reacted with primary or secondary amlnes, and the dyestu~fs obtained are optionally sulfonated. According to this method, acid wool dyestu~fs having good fastness properties are ob-tained.
Particularly good dyestuffs are obta.ined according to this process, if the inner salts of -the ~76~dihalogen~-~2'-sulfo-~
phenyl)-xanthene~9 ols are used aæ starting products, th~
rcaction being carried out in such a way that the xanth~nol cornpo~d is reacted with a stron~ly excess amount o~ the amine, while using the same amine or ano-ther polar compound as solvent.
The hydro-hali.de set ~ree in the course of this reaction is bound by the excess amine as salt. This salt, the excess free amine as well as the solvent which has optionally been used, are washed out with an aqueous acid after the reaction has b~en completed. However, the amine and, optionally, the ~olvent can only partl~llly be soparated .~rom the waste water which rernains a~ter the d~estuf~ has been fil-tered o~f, which leads to a considerable loss o~ material as well as to a high c~lar~e o~ ~he w~ste wa-t~r.
According to the kno~ processes, it is also possible to 29 carry out the reaction in such a way that the xanthenol . ~ 2 - ~
~ 86 compound is reacted with a strongly excess amount of aromatic or aliphatic sulfonic acids and/or carboxylic acids which carry primary or secondary amino groups, or with the sodium salts thereof in polar. solvents. The hydro-halide set free in the cou~s~ of th-s rQ~ct~ f^rms ~nm, the snd~-1m ~lt-c on-t~on~llv used the free sul~onic -and/or carboxylic acids. It becomes evident by this process that these ~ree acids, in contra-distinction to the salts, have a reactivity that has been very strongly reduced. For this reason it is necessary to use high molar excess a~ounts of amine when the free acids as well as the salts are used. In spite of this fact it is often not possible to obtain a complete exchange of the two halogen atoms.
However; the proportions of the xanthydrol compound, which only exchanged one halogen atom and remciins in the reaction product, result in a deterioration of the dyestuff qu~lity~
owing to their low color intensity, their strongly deviating shades, their extremely low brilliancy, their very poor fast-ness to light, and their different dyeing behavior.
Besides, the drawback that the components used in a high excess amount remain either in the product or in the waste water is undesirable in either case, since the dyeing behavior (tinctorial strength, af~inity to the fiber~ build--up) is deteriorated, or the charge o~ the waste water is stron~ly increased, which is in any case accompanied by a considerable loss of material~
I-~ ha~ llOW been ~ou~d that these dra~backs in the pre-parat.ion of xanthene dyestu~fs of the ~reneral formula (I) ~649~6 I/N ~ ~ N~
L ~ 3 ---t------- (503H)m (in which Rl and R2 are identical or different aliphatic, araliphatic or cyclo-aliphatic radicals, each being optionally substituted by halogen, hydroxy, alkoxy, amino, cyano, carboxylic acid and/or sulfonic acid, or Rl represents also a hydrogen atom or a carbocyclic aromatic or heterocyclic radical, or Rl and R2 together with the N~atom form a heterocyclic radical optionally contain-ing further hetero atoms, the benzene nucleus A may optionally contain substi-tuents, and m stands for the integer 1, 2, 3, 4 or zero), which comprises react-ing the inner salts of 3,6-dihalogeno-9-t2'-sulfophenyl)-xanthene-9-ols of the general formula (II) ( ) ~ (II) ~1 (in which X stands for a halogen atom, preferably a chlorine atom~ and A has the above-mentloned meaning~ with primary or secondary amines of the formula tIII~
~Rl HN~ (III) (in which Rl and R2 have the meanings specified as above) .~
in a polar solvent, and optionall~ sulfonating the product sub-sequentl~, can be avoided if the reaction of the xanthenol o~
the formula (II) with the amine of the formula (III) is ef fected in a stoichiometrical amount and in the presence o~ an in~ liC ~cid~ ig h~ a'~û~ Gl a~ acld-bi~d~g tart & - y aliphatic amine or a N-containing heterocyclic, pre.~erably aromatic, compound.
As subs~i-tuents in the benzene nucleus A there are to be ~entioned, ~or example, halogen atoms, such as chlorirle and brom~ne atoms, alkyl groups having from 1 to 5 carbon atoms~
alkoxy groups ha~ing ~rom 1 to 5 carbon atoms, aryl radicals, such as the phenyl radical optionally containing substit~lents, hydroxy, carboxylic acid or carbalkoxy groups having from 2 to 6 carbon atoms, carbonamide, sulfonic acid, sulfonamide, B-hydroxy-ethylsulfonyl and ~-sulfa~o-ethylsulfonyl groups.
If the nucleus A carries hydroxy and carboxy ~roups at the same time, this compound of the ~ormula (I) and/or (II) may also be presen-t as a complex metal compound.
The process of the invention is carried out in such a way that 1 mole o~ the xanthenol compound is reacted w.ith 2 to about 2.2 moles o~ the amine in a polar solvent ~ree ~rom acid groups, at an elevated temperature, and ~he hydrohalic acid ~e~ ~ree in the course oP the reaction is bound by adding a~ amount ~.~ the acid-binding a~ent which is at least equi-valent to the amount o~ ~he hgdrohalic acid.
As prl~ar~ or secondary aliphatic, arali.phatic, cyclo~
aliphatic, aroma-tic or heterocyclic amines o~ the ~ormula (XII), ~here may be mentioned, ~or example:
29 Mono- or dialkylamines ha~ing ~rom 1 to 6 carbon atoms in H~E 74/~` ~8 69L9.'lG
each alkyl radical, such as methyl-, ethyl-9 propyl-, butyl-, isopropyl-, or pentylamine, dimethyl-, diethyl-, dipropyl-, or dibutylamine, optionally with substituents in the alkyl radical, such as hydroxy or cyano groups, lower alkoxy, lower c~balko.~3, sul40r.~c ao-~- or o~boY31ic ~oi A gr~Upc; cyo1O-aliphatic amines, such as, for example, cyclopentylamine and cyclohexylamine, araliphatic amines 9 such as phenethylamine 9 benzylamine and benzylethylamine; aromatic amines, such as, ~or example, aniline or N-(alkyl 1-4)-anilines and the deri-vatives thereof which are substituted in the alkyl radical by halogen, such as chlorine, lower alkoxy groups~ lower carb-alkoxy, hydroxy or cyano groups J and/or in the benzene nucleus by halogen atoms, such as chlorine or bromine atoms, lower alk~l groups, such as methyl, ethyl or propyl groups9 lower alkoxy groups, such as methoxy9 ethoxy or propoxy groups, lower carbalkoxy, sulfonamide or hydroxy groups, sulfonic acid or carboxylic acid groups, B-hydroxyethylsul~onyl, ~-sul~ato-ethylsulfonyl, or nitro groups; naphthylamines~ amino-anthra-quinones; 5- or 6-membered heterocycllc amines9 such as amino~
thiazoles, aminopyrazoles, aminotriazole~, aminopyridine~ a~d the benzoderivatives thereo~9 morpholine, piperidine and piperazine.
If the amines contain ~ulfonic acid groups, they are suitably used in the form of their salts, for example as sodium or potassium salt. If the ~ree sulfonic acid or carb-oxylic acid ls used, a corre~ponding amount of the acid-binding agent is additionally added~ which is capable o~ con-verting the acids in-to the corresponding salts.
29 As solvents, there may be used water, as ~ell as orga~ic _E _ 4/F 386 .
compounds, such as ~or example, methanol 9 ethanol, propanol, butanol 9 glycol, glycerin, diglycol, polyglycols, alkylgylcols~
phenylglycol, alk~lpolyglycols, benzylalcohol, propylene~glycols~
acetonitrile, dimethylformamide, N-methylpyrrolidone-2, di-meth,Tlacetamide; dimethv1Sul~oxide or mixtures of these solvents. The amount of the solvent used depends on the vis-cosity of the reaction mass. The solvent is suitably used i~
an amount which is just sufficient to keep the reaction mass, which is present as a homogeneous solution or fine suspension9 in a condition so as to be stirred easily.
As acid-binding inorganic agents there are suitable, for example5 ox.idesJhydroxides~ carbonates, hydrogenocarbonates, acetates~ borates or phospha-tes of alkali metals or alkaline earth metal.s or of ammonia, such as calcium or magnesium oxide, sodium, potassium, calcium or magne~ium hydro~ide, sodi.um or potassium carbonate, sodium bicarbonate 9 sodium acetate, borax or di or trisodium phosphate, moreover, aluminum oxide or -hydroxide.
Of the organic compounds~ there may be mentioned as tert.iary aliphatic amines, ~or example, triethylamine, tripropylamine, tributylamine, dicyclohex~let~ylamine or triethanolamine, and as N-containing heterocyclic compounds, ~or example, pyridinè
or ~uinolin~. IThe acid-bind-ing agen-t is u5~d in a stoichio-metrical amount or in a slight excess amount, i.e. per mole o~
xan~henol compound 2 moles o~ acid-binding agent are required.
I~ in the reactlon primary or secondary amines are used which contain free sul~onic acid groups, at least 4 moles of acid--~ binding agent are required as ~ar as the amines contain ¢ne 29 ~ulfonic acid group.
HOE ?4!F 386 1~i493L6 The reaction temperature, as well as the reaction time, depends on the re~ctivi~y of the amine used and may be in the range of from about 20C to about 180C. If the reaction te~perature required is above the boiling point of the solvent used, tne reac-tion may also be carried out under increaseu pressure.
The following method of operation is particularly ad-~antageous which involves but a slight charge of the waste water:
I~ an ~mount o~ glycol which is just suf~icient as solvent, and magnesium oxide as acid-binding agent are used, a hetero-geneous reaction mass which can well be stirred is obtained in most cases, in which mass the xanthenol compound after it has been bilaterally reacted is almost completely insoluble, whereas the xan-theno-l compound which has been unila-terally reacted and may still be present in a small amount, as well as various impurities which have been introduced together with the starting materialst are very well soluble. After the reaction has b~en cornpleted, the dyestuff is suction-filtere~
and is freed ~rom glycol and from the magnesium chloride forrned b~ washing with a little water. The glycol mother li-~uor and the wash water are combined and are .~reed :~rom th~
small amo~t o~ precipltate forrned a~ter their combina-tion J
by way of a clari~ying ~iltration. The remaining glycol-water ~5 mixture may be used for the next reaction mixture instead of fresh glycol, the wat~r being eliminated by distillation be~ore or during the react.ion. B~ way o~ this method, only the desired xanthene dyes-tuf~ which has been bilaterally 2g reacted9-as well as a small amount of a solid clari.~ying resi.due are obtained as the products of the total reaction mixture.
There is no charge of the waste water by inorganic or organic compounds.
The working-up o~ the reaction mass may also be effected in such a way that the mass is introduced into water by stir-ring and the precipitated product is directly suction-filtered9 or that~ with the use of water as reaction medium, the dyestuf~
is salted out from the aqueous dyestuff solution and is sub-sequently suction-filtered and dried, or that the entire reaction mixture is evaporated to dryness, or the dyestuf~ is isolated by spray-drying.
The dyestuffs obtaînable according to the invention have a high degree of purity which leads to an increased brilliancy o.~ the dyeings prepared with them. By way o~ a subsequent sulfonation, ~urther sul.~o groups may optionally be introduced into the dyestu~fs, which results in a better water-solubility.
The dyestu~.~s as well as their sul~onation products dye wool and silk as well as synthetic ~ibers carrying basic groups, such as, .for example, polyamide ! modified polyes~er and poly-acrylonitrile fibers or regenerated protein fibers in bright red to blue color shadesc ~he dyeings are distinguished by remarkable ~astness prop0rties, o~ whlch there are to be meIItioned~ in particul~r, the f~stness to ligh~ ~o alkalis, to carboniæing and to decating. The dyestuf~s can be applied aocording to the known dyeing processes and show an excellent levelling capac.ity, 0~ the dye~tu~fs which can be prepared according to the invention, there are to be mentioned particularly those in 29 which in the general ~ormula I R1 and R~ are identical or _ g _ 3~6 different and each represents an aliphatic, araliphatic or cycloaliphatic radical optionally substituted, ~or example, by halogen atoms, such as chlorine or bromine atoms, hydroxy or alkoxy groups, in particular those having from 1 to 4 carbon atoms9 amino, cyano, carboxylic acid- and/or SUil~ ac-iu groups, the radical being for example an alkyl radical having from 1 to 8 carbon atoms or a phenylalkyl radical optionally being substituted in the benzene nucleus and carrying from 1 to 4 carbon atoms in the alkyl portion, or a cyclohexyl or cyclop~ntyl radical, or R1 may also represent a hydrogen atom or a carbocyclic aromatic radical, such as a phenyl or naphthyl radical, or a heterocyclic radical, each may be substituted for example by halogen atoms, such as chlorine or bromine atoms, alkyl groups, especially those having from 1 to 4 carbon atoms, alkoxy group~, especially those with 1 to 4 carbon a~oms, hydroxy, amino, alkylamino groups, parti.cularly those having ~rorn 1 to 4 carbon atorns, dialkylamino groups, especially with alkyl radicals ha~ing each 1 to 4 carbon a-toms, nitrile, carb-oxylic acid, carbo~ylic acid ester groups, such as carboxylic ~n acid phenyl and carboxylic acid alkyl ester groups havin~ ~rom
2 to 6 carbon atoms, carboxylic acid amide, sul~onic acid, sul~onic acid amide~ trifluoromethyl, alkylsul~onyl groups, ~specially those with 1 to 4 carbon atoms, ~-hydroxyethyl-sul~onyl, ~-sul~ato-ethylsul~onyl groups, arylazo groups9 such as phenylazo groups, arylamino ~
groups, such as phenylamino groups, aryloxy, such as phenoxy groups, arylsul~onyl, such as phenylsul~onyl groups, or nitro groups, or R1 and R2 toge-ther with the ~-atom form a hetero-2~ cyclic radical which optionally contains further hetero-atoms, ~ ~6 such as N- or 0-atoms~ the benzene n~cleus A optionally contains as substituents halogen atoms such as chlorine or bromine atoms, alkyl groups~especially those with 1 to 4 carbon atoms, alkoxy groups~particularly those having from 1 to 4 carbon atoms, aryl sucn as pnenyl groups, or SUDStilUled phenyl, hydroxy9 carboxylic acid~ carboxylic acid ester groups such as carboxylic acid phenyl and carboxylic acid alkyl ester groups having ~rom 2 to 6 carbon atoms, carboxylic acid amide, sulfonic acid, sulfonic acid amide, B-hydroxyethylsulfonyl or ~ sulfatoethylsulfonyl groups, and m stands for the integer 1 2, 3, 4, or zero.
The process o~ the in~ention is particularly preferred for those dyestu~fs of the f~rmula I, while usin~ compounds o~ the ~ormulae II and IXI, in which R1 represents a hydrogen atom or an alkyl radical o~ ~om 1 to 6 carbon atoms which may be substituted by 1 or 2, pre-ferably on~ substituent selected ~rom the group consisting f halogen5 such as chlorine and bromine, hydroxy, cyano, alkoxy having from 1 to 4 carbon atoms, carbalkoxy with 2 to 5 ca~bon atoms, sulfo and carboxy, R2 stands for an alkyl radical having ~rom 1 to 6 carbon atoms, which may be subs-tituted by 1 or 2 9 pre~erabl~ one substituent selected ~rom the group consisting o~ phe~yl~ sul~ophenyl, hydro~y, cyano, al~oxy group having ~rom 1 to 4 carbon atoms, carbalkoxy group having ~rom 2 to 5 carbon atoms, sul~o and carboxy group~ or represents a cyclo-hexyl or cyclopent~l or the phenyl radical which ma~ be sub-stituted by 1, 2 or 3, pre~erably 1 or 2, substituents selec-ted from the group consis-ting o~ halogen, such as chlorine or 29 bromlne, alkyl having from 1 to 4 carbon atoms, alkoxy with - ~6 ~6~6 1 to 4 carbon a~oms, car~a~koxy with 2 to 5 carbon atorns, sulfonamide, N-(lower alkyl)-sul~onamide, N,N-di-(lower alkyi)-sulfonamide, sul~o, carboxy, hydroxy, B-hydroxyethylsulfonyl, B-sul~atoethylsul~onyl, nitro, amino, dimethyl~mino, diethylamino, phenylamino, phenylazo and acetylamino7 or stands for the naph-thyl radical which may contain 1,2 or 3 substituents selected ~rom the group consisting of-sulfo9 carboxy, carbonamide, sulfon amide, chlorine and alkyl with from 1 to 4 carbon atoms)or re-presents the thiazole, pyrazole 9 triazole, pyridine 9 ben~thia-zole~ benzpyrazole, or benztriazole radical, or R1 and R2 to-~
gether with the N-atom represent the morpholine, piperidine or piperazine ring, the benzene nucleus A may contain 1 or 2 ~ub-stituents selected from the group consisting o~ halogen, alkyl having ~rom 1 to 5 carbon atoms, alkoxy with 1 to 5 carbon atolns, phenyl, hydroxy, carboxylic acid, carbalkoY.y wi-th 2 to 6 carbon atoms, carbonamide, sulfonic acid, sul~onamide9 ~-hydroxy-ethylsul~onyl and B-sulfato-ethylsulfonyl, and Jn s-tands ~or the inte~er zero, 1,2,3 or 4~
moreover~ for those dyestuffs and starting compo~mds in which R1 represen-ts a hydrogen atom, an alipha-tic radical optionally substi-tuted by substituents, especially 1 or 2, pre~erably 1 substituent selected from the group consisting o:~ halogcn a ~ s, such a~ chlorine or bromine ~tom9, pre.~erably chlorine atoms~
hydroxy, alkoxy groups, especially those having ~rom 1 to 4 carbo~ atoms, amino, cyano, carboxylic acid or sulfonic acid groups, sai~ aliphatic radical being ~or example, an alkyl radical having ~rom 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms 9 R2 represen-ts a phenyl or naphthyl radical 29 optionally substituted by substituents, especially 1 to 3, _ 12 --HOE ~ /F 386 1~4~6 preferabl~ 1 or 2 substituents selected from the group con -sisting o~ halogen atoms, such as chlorine or bromine atoms, preferably chlorine atoms, alkyl groups, especially those having from 1 to 4 carbon atoms, alkoxy groups, particularly those with i to 4 carbon atoms, ~ydroxy, amino, alkylamino groups, especially those with 1 to 4 carbon atoms, dialkyl-amino groups, especially those with 1 to 4 carbon atoms in each alkyl radical9 nitrile, carboxylic acid amide, trifluoro-methyl, alkylsulfonyl groups9 particularly those having from 1 to 4 carbon atoms, B-hydroxyethylsulfonyl, ~-sulfatoethyl~
sul~onyl and nitro groups, and A has the meaning specified as above.
The ~ollowing Examples serve to illustrate the invention;
the parts are parts by weight, the percentages stand for per cent by weight. The parts by weight are to the parts by volume as is the gram to the cubic centime-ter.
40~5 Parts of the inner salt of the 3,6-dichloro-9-phenyl-xanth~drol-2'-sulfonic acid were introduced into 120 parts of ethylene glycol. 36 Parts of metanilic acid and 7 parts o~
magnesium oxide were added, and the reaction rnixture was heated up to 140C, in which process a red and violet dyeing was obtained ~ast. The reactio~ mixture was co~t~nued to be stirred for 2 hours at 140C, subsequently 1 part of magnesiu~
oxide was added; then the mixture was again stirred for another 2 hours~ The clear- melt ob-tained was in~loducefl5 while stirring, into 500 parts of a cold-saturated sodium chloride solution, the precipita~ed dyestuf~ was suction-filtered, was 29 washed with sodium chloride solution and dried at 60C.
.
.
100 Parts of a dyestuf~ containing sodium chloride were ob-tained which had the formula Nl~ ~O~NJI~¢~
groups, such as phenylamino groups, aryloxy, such as phenoxy groups, arylsul~onyl, such as phenylsul~onyl groups, or nitro groups, or R1 and R2 toge-ther with the ~-atom form a hetero-2~ cyclic radical which optionally contains further hetero-atoms, ~ ~6 such as N- or 0-atoms~ the benzene n~cleus A optionally contains as substituents halogen atoms such as chlorine or bromine atoms, alkyl groups~especially those with 1 to 4 carbon atoms, alkoxy groups~particularly those having from 1 to 4 carbon atoms, aryl sucn as pnenyl groups, or SUDStilUled phenyl, hydroxy9 carboxylic acid~ carboxylic acid ester groups such as carboxylic acid phenyl and carboxylic acid alkyl ester groups having ~rom 2 to 6 carbon atoms, carboxylic acid amide, sulfonic acid, sulfonic acid amide, B-hydroxyethylsulfonyl or ~ sulfatoethylsulfonyl groups, and m stands for the integer 1 2, 3, 4, or zero.
The process o~ the in~ention is particularly preferred for those dyestu~fs of the f~rmula I, while usin~ compounds o~ the ~ormulae II and IXI, in which R1 represents a hydrogen atom or an alkyl radical o~ ~om 1 to 6 carbon atoms which may be substituted by 1 or 2, pre-ferably on~ substituent selected ~rom the group consisting f halogen5 such as chlorine and bromine, hydroxy, cyano, alkoxy having from 1 to 4 carbon atoms, carbalkoxy with 2 to 5 ca~bon atoms, sulfo and carboxy, R2 stands for an alkyl radical having ~rom 1 to 6 carbon atoms, which may be subs-tituted by 1 or 2 9 pre~erabl~ one substituent selected ~rom the group consisting o~ phe~yl~ sul~ophenyl, hydro~y, cyano, al~oxy group having ~rom 1 to 4 carbon atoms, carbalkoxy group having ~rom 2 to 5 carbon atoms, sul~o and carboxy group~ or represents a cyclo-hexyl or cyclopent~l or the phenyl radical which ma~ be sub-stituted by 1, 2 or 3, pre~erably 1 or 2, substituents selec-ted from the group consis-ting o~ halogen, such as chlorine or 29 bromlne, alkyl having from 1 to 4 carbon atoms, alkoxy with - ~6 ~6~6 1 to 4 carbon a~oms, car~a~koxy with 2 to 5 carbon atorns, sulfonamide, N-(lower alkyl)-sul~onamide, N,N-di-(lower alkyi)-sulfonamide, sul~o, carboxy, hydroxy, B-hydroxyethylsulfonyl, B-sul~atoethylsul~onyl, nitro, amino, dimethyl~mino, diethylamino, phenylamino, phenylazo and acetylamino7 or stands for the naph-thyl radical which may contain 1,2 or 3 substituents selected ~rom the group consisting of-sulfo9 carboxy, carbonamide, sulfon amide, chlorine and alkyl with from 1 to 4 carbon atoms)or re-presents the thiazole, pyrazole 9 triazole, pyridine 9 ben~thia-zole~ benzpyrazole, or benztriazole radical, or R1 and R2 to-~
gether with the N-atom represent the morpholine, piperidine or piperazine ring, the benzene nucleus A may contain 1 or 2 ~ub-stituents selected from the group consisting o~ halogen, alkyl having ~rom 1 to 5 carbon atoms, alkoxy with 1 to 5 carbon atolns, phenyl, hydroxy, carboxylic acid, carbalkoY.y wi-th 2 to 6 carbon atoms, carbonamide, sulfonic acid, sul~onamide9 ~-hydroxy-ethylsul~onyl and B-sulfato-ethylsulfonyl, and Jn s-tands ~or the inte~er zero, 1,2,3 or 4~
moreover~ for those dyestuffs and starting compo~mds in which R1 represen-ts a hydrogen atom, an alipha-tic radical optionally substi-tuted by substituents, especially 1 or 2, pre~erably 1 substituent selected from the group consisting o:~ halogcn a ~ s, such a~ chlorine or bromine ~tom9, pre.~erably chlorine atoms~
hydroxy, alkoxy groups, especially those having ~rom 1 to 4 carbo~ atoms, amino, cyano, carboxylic acid or sulfonic acid groups, sai~ aliphatic radical being ~or example, an alkyl radical having ~rom 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms 9 R2 represen-ts a phenyl or naphthyl radical 29 optionally substituted by substituents, especially 1 to 3, _ 12 --HOE ~ /F 386 1~4~6 preferabl~ 1 or 2 substituents selected from the group con -sisting o~ halogen atoms, such as chlorine or bromine atoms, preferably chlorine atoms, alkyl groups, especially those having from 1 to 4 carbon atoms, alkoxy groups, particularly those with i to 4 carbon atoms, ~ydroxy, amino, alkylamino groups, especially those with 1 to 4 carbon atoms, dialkyl-amino groups, especially those with 1 to 4 carbon atoms in each alkyl radical9 nitrile, carboxylic acid amide, trifluoro-methyl, alkylsulfonyl groups9 particularly those having from 1 to 4 carbon atoms, B-hydroxyethylsulfonyl, ~-sulfatoethyl~
sul~onyl and nitro groups, and A has the meaning specified as above.
The ~ollowing Examples serve to illustrate the invention;
the parts are parts by weight, the percentages stand for per cent by weight. The parts by weight are to the parts by volume as is the gram to the cubic centime-ter.
40~5 Parts of the inner salt of the 3,6-dichloro-9-phenyl-xanth~drol-2'-sulfonic acid were introduced into 120 parts of ethylene glycol. 36 Parts of metanilic acid and 7 parts o~
magnesium oxide were added, and the reaction rnixture was heated up to 140C, in which process a red and violet dyeing was obtained ~ast. The reactio~ mixture was co~t~nued to be stirred for 2 hours at 140C, subsequently 1 part of magnesiu~
oxide was added; then the mixture was again stirred for another 2 hours~ The clear- melt ob-tained was in~loducefl5 while stirring, into 500 parts of a cold-saturated sodium chloride solution, the precipita~ed dyestuf~ was suction-filtered, was 29 washed with sodium chloride solution and dried at 60C.
.
.
100 Parts of a dyestuf~ containing sodium chloride were ob-tained which had the formula Nl~ ~O~NJI~¢~
3 ~ S 03 ~ - J :~;U3-N a and which was very well soluble in water and dyed wool in a very brilliant violet shade of a strong color intensity from a boiling aqueous dye bath~ the pH ~alue of which had been adjusted by means of formic acid or sul~uric acid/sodium sulfate to abou-t 3 to 4. The dyeings showed excellent ~astness proper-ties 9 to mention i~ particular the fastness to light, to decatizing, to carbonizing and to alkali.
In an analogous manner this dyestu~f could al~o dye silk synthetic polyamide ~ibers 9 regenerated protein fibers, as well as basically modi~ied polyacrylonitrile ~ibers, in which process dyeings having also a strong color intensit~ as well as good ~astness properties were obtained.
E X A M P L E S 2 ~o 31 __ In a manner analogous to -the process described in Example 1 ~ur-ther dyestu~s corresponding to the ~ormula (I) mentioned abo~e could be pre~pared if equivalent amoun-ts o~ the corre-spond~n~ ~tarting compounds o~ ^the ~ormulae (I.~) and (XII) ancl the equivalent amo-~t o~ magnesium oxide were used; these dyestu~s are specif~ed in the following Table 1.
~ ~9 T A B_L E _1 Example R1 R2 A Color shade on wool 2 H ~ SO3Na , ~ SO3 bluish violet 3 H ~ ditto red-violet S03Na
In an analogous manner this dyestu~f could al~o dye silk synthetic polyamide ~ibers 9 regenerated protein fibers, as well as basically modi~ied polyacrylonitrile ~ibers, in which process dyeings having also a strong color intensit~ as well as good ~astness properties were obtained.
E X A M P L E S 2 ~o 31 __ In a manner analogous to -the process described in Example 1 ~ur-ther dyestu~s corresponding to the ~ormula (I) mentioned abo~e could be pre~pared if equivalent amoun-ts o~ the corre-spond~n~ ~tarting compounds o~ ^the ~ormulae (I.~) and (XII) ancl the equivalent amo-~t o~ magnesium oxide were used; these dyestu~s are specif~ed in the following Table 1.
~ ~9 T A B_L E _1 Example R1 R2 A Color shade on wool 2 H ~ SO3Na , ~ SO3 bluish violet 3 H ~ ditto red-violet S03Na
4 CH3 - ~ ditto red-violet . H ~ dit-to violet SO3Na CH3 6 H ~ SO3Na ditto blu:ish ~iolet 7 Il ~ OCH3 ditto bluish violet - S03Na a H CH3 ~ ^ ditto ~iolet S03Na . . 15 --:~06~L6 Example ~1 ;R2 A Color shade on wool 9 H C ~ ~ bluish red S03~a H HO ditto reddish blue - ~03Na C~
11 X ~ ditto violet _~ S03Na 0~
12 H ~ S03N~ ditto reddish blue OH
13 H -~I ~ ditto reddish violet S03Na 14 C2H5 ~ ~ S03Na di-tto red-violet 15H ~ -- Cl ditto red~iolet S03N~
16H ~ CI~3 ditto red-v~olet 17 ~ . ~ 3 ~ bluish violet C~I3 Cl _ 16 -.
Example R1 R2 A Color shade on wool 18 H ~ ~ so3~ violet NaO3S
19 ~ SO3Na di~tO bluish red H ~ ~ viole~
COONa ~ $O3N~
21 ~ COONa ~ so30 blue COONa 22 H ~ ~~SO3Na ~ SO30 red~iolet 3 :
; CH3 l SO ~ ~luorescent 23 H I . fi ~1 3yellowish red -CH-CH2-S03Na '~ ~
2~ CH -C~ C~ SO Na ditto ~luore,scent ~ ~ 2 3 bluish red C~I di.~to red-violet ~3 ~03Na - - ~7 -.
H ~ ~
1064~6 Exarnple R1 R2 A Color shade on wool 2~ H ~ ~ 3 red~violet S03Na 27 ~ -CH2-CX2-COONa ditto fluorescent bluish red 28 H -CH2-C~2-S03Na dit~o ~luorescent - 29 C2H5 -CH2-CH2-$0 Na ditto fluorescent ~ bluish red -~0 CH ~ SO~ viole-t COONa 31 H -CH2 S03~ fluOresoent ~ ~ bluish red S03Na .
E X A M P 1. E 3~:
121.5 Parts o~ the inner salt o~ the 3~6-dichloro~9-phe~yl-xanth~drol-7~-sul~onic acid, 750 parts o~ water, 24 parts of magnesium oxide and 122 parts of 3-arnino-4-methoxy-benzene-~ul~onic acid were h~ated. in an au~oclave ~Ip to 140Ct while s-tirring ~or 1 hour, in whiGh process a pressure o~ 4 to 5 atmospheres was estabJ.ished. After having been stirred ~or 29 another 5 hours9 the reaction mixture was cooled to 60~.
. - 18 -, H ~
~6~L6 150 Parts o~ ~,odium ohloride were added. A~ter the mixture had been cooled to room temperature, while stirring, the crystalline precipitate was suction-~iltered and ~as dried at 60C.
250 Parts of a pure dyestuff were obtained which had the formula c OCH3 OC~
~ ~ ~ o ~ Nl ~ -Na~ S ~ So ~~) So N
and which was very well water-soluble and dyed wool from a boiling aqueous dye bath having a pH value o~ 3 to 4 in a bluish violet shade of a very s-trong color intensity.
E ~ A M P L ~ 3~:
.____ If in Example 3Z an equivalent amoun-t o~ 3-amino-4-rnethyl-~
~5 benzene-sulfoni.c acid was used instead of th~ 3-amino-4-metho benzene-æul~onic ac;id and the reaction was carried out ac cording to the method indicated in E~ample 32, the correspond.ing methyl-substituted dyestuf~ was obtained also in a good yield, which dyed wool in a brilliant red-violet color shade~
E X A M P L E S 1a to 33a:
The dyestuf~s prepared accordin~ to Exampl~ 1 to ~3 could be prepared in the ~am~ manner and wit~ a high ylelcl as well as a good purity, i~ as acid-binding agent there was used, ~or example, calcium hydroxide, aluminum hydroxide9 sodium aceta-te7 ~5 trisodium-phosphate, or pyridine in an equival~nt amount.
E _ A M P L F ~
a) 40 5 Parts of the inner salt of 3~6-dichloro~9-phenyl-- xanthydrol-2'-sul~onic acid were stirred for a short time 29 in 250 parts of ethylene-glycol. A~ter 26 parts o~ 3-chloro - 19 -.
~ 1~649~
aniline had been added, the reaction mixture was heated within one hour up to 145 to 150Co At this temperature the mixture was continued to be stirred for another hour;
subsequently 4 parts o~ magnesium oxide were added in ~mal l por*ion~ wi-~hin one hsur. then the mixture was stir-red ~or another hour and was cooled to 100C. The ~ine precipitate formed which could well be filtered was sucti.on-~iltered, was washed with ~00 parts of water and dried at 80C. 57 Parts of a pulverulent dyestu~f powder were ob-tained which was soluble in 85 % formic acid with a violet color shade. The dyestuff had the ~ormula ~(C)~
CL ~ S3( ) C1 b) A~ter a sul~onation by way o~ sul~uric acid in accordance with a technically common process, ~or example according to the process described in the above-mentiQned German Patent Speci~ications, and af-ter the conversion into it.s sodium sal-t, a dye~tuff was obtained which was well water-~olublo and whioh dy~d wool? ~ilk and ba~sical.~y modified synthetic fibers ~rom an aqueous dye bath having a pH value o~ between 3 and 5, in a brilliant violet color shade having good ~astness properties.
c) The mother liquor obtained under a) and the wash wa-ter were combined and were clarified ~rom a sl1ght precipitate wh.ich had been ~ormed~ This filtrate could be used again for a 29 new reac-tion mi~ture :~or a dyes-tuff preparation as des--- ~0 --9~6 cribed under a), instead o~ fresh ethylene-glycol. In this second process, however9 -the water which was now contained in the reaction mlxture was eliminated by distillation before or during the react.ion.
T' ~ ,~, M p T E ~ ~ to an.
-In a manner analogous to the pro~ess de~ribed in Example ~4, further dyestuf~s corresponding to the above-mentioned formula (I) could be prepared, i~ equivalent amounts of the corresponding starting compounds of the formulae ~II) and (III) and the equivalent amount of magnesium oxide were used.
These dyestuffs are specified in the following Table 2.
The compounds thus prepared could optionally be sulfonated a~terwards.
____ __ Example R1R2 A Yi~ld Color shade on wool ~35 H ~ ~ 3 98 % bluish red Cl 36 H ~ 5 , 99 % violet aH
37 H ~ 3 ditto 96 % blul~h red C~3 38 H ~ C~I3 dit~o ~8 % bluish red 39 H ~ No2 ditto 98 ~o red ~L~3.
9~6 Example R1R2 A ~eld Color shade on wool ~ ~ ~ S~30 97 % bluish red 41 H ~ ditt 9O % red 3 ~ -42 H - ~ NH ~ ditt 95 % blue , 43 H ~ d.itto 99 % redd1sh viole~
OC~I3 44 H ~ C1 di~to 96 % violet H ~ d.itto 93 % reddish blue : N~l2 ~ ~ *6 ~ H ~ ditto 98 % bluish red ~? . .
47 H -aH2 ~ dit~o 95 % red ~luoro~cen-t 48 H ~ N~ 3 ditto 98 % bluish r~d : 49 H ~ ditto 9O ~Q bluish Vl' olet OH
;
. - 22 -: :, ~L~64~L6 Example R1 R2 . A Yield Color shade on wool CH3, . -~ ~S03a 80 % red-violet 51 H ~CE3 dit~o 97 % vi ~let 52 H ~ CH3 ~ ditto 99 % viole-t ~ . .
53 H ~ dit~o 9 ~ red~riolet . ~ .
54 H 0~0 ditto 9 % blllish l~ed ~ d-it,t 95 % l~lui~h ~riole-t I~3 56 H ~ OC~I~; di tlto 97 ~ violet Cl 57 ~ C ~. C.H~; di.tto 99 % viole t a~3 58 H ~?N0 di tto 97 % red 59 H -~N-N ~) ditto 99 % reddish blue lOG4916 Example ~1R2 A Yield Color shade on wool H~ OCH3 ~ S03 97 ~6 violet 61 H~ OCH3 ditto 98 % bluish violet 62 X ~ Cl di-tto 96 % bluish red CX3~
63 H ~ CH3 . ditto 96 % bluish red al 64 H ~j Cl ditto 9~ % red ~iolet OCH~5 H ~ Cl ditto g7 % bluish red ~6 H ~ ditto 92 % red-~iolet Cl 67 ~ 2 di t; to 9o % violet 68 H ~ ditto 91~ ~h red N (C2H5) `:
H~6_ ~06~9'1~ .
Example R1 ~2 A Yield Color shade on 69 H CN3 CH3 ~ 9B k bluish red 7 H ~ , red-~iolet 71 -CH2CH2CN ~ ditto 95 yO bluish red 7~ H ~ dit~ 96 % viole t OX
73 H~9- O~ dit to C~3 % blui~h violet 7~t -COCH~$ ~ dittO 92 % red~violet .
H~ C0~2 dit;to 97 % reddish blue r--~
76 H <__~NH-COC~I3 dit~o 97 Y blu~
77 EI -~-Q-~ c;it~o 98 Yo violet 78 H ~SQ2N(C~T3)2 ditto 98 % red-viole-t ,= ~ .
79 H ~SO2CH2CE120H ditto 95 % violet ~ 25 , ., ,~, ....
HOE 74lF 386 1~ 6~6 Example R1 R2 A Yield Color shade on wool SO CH CH OH SO ~ 94 %
H ~ 2 2 2 ~ 3 bluish violet OCH
81 H ~ di~o 96 % violet C~
82 H ~ ~ di~o 98 % violet 83 -CH3 ~ c~r3 di~o. 96 % bluish red ~ C2H5 ~ di~o 97 h red viole-t , -C4H9 . ~ di~o 93 ~ red-violet 86 H ~ C2H5 ~ so3 98 % violet OC2~I5 87 ~I C~I3 ~ ~ ~ 96 % red-violet 88 H - ~ ~ 3 95 % violet C~I3 , .
~OE 7 ~
Example R1 R2 A Yield Color shade on wool .. .... , , _ 89 H ~ ~ 97 % ~iolet Cl C~3 ~;0 '~
9o CH3 ~ C2H5 ~ red-violet ~i E X ~ M P L E 91:
40.5 Par-ts of -the inner salt o~ 3,6-dichloro-9-phen~l-xanthydrol-2'~sulfonic acid were stirred in 200 parts o~ ethyl-ene-glycol or 250 parts o~ e.~hylene-glycol monoethyle-ther for a short time. A~ter 19 parts of aniline had been added, the reacti.on mixture was heated wi-thin one hour up to 135 to 14~~p was maintained at this temperature ~or one hour, while being stirred, and was then mixed portionwise within one hour with 4 parts of magnesiv~ oxide. Subsequently the mixture was heated up to 145 -to 150C and was stirred for one hour at this temperature A~ter the mix-ture had been cooled to 80C, 500 parts by volume o~ water were added. A.~ter ~he reaction mix-ture had b~en stirred ~or 30 minutes~ it was suction ~ilt~red, the cr~stalline product wa.s washed with water and was dried at 60C. 49 Parts of a d~estuff were obtained in the form of a ~ine powder, which had the formula ~7H~ O ~,NI~
29 ' ~S03(-'~
~L~ 3~6 1~6~16 and which was soluble ~or example in glacial acetic acid or in dime~hylformamide wi.th a bright violet color shade.
E X A M P L E S 35 a to 91 a.
The dyestuf~s obtained according to Examples 35 to 91 could also be prepared easiiy9 iI i~ ead 01 magllesi~m o~ide a~ acid-binding agent, there were used equivalent amounts o~ sodium acetate, sodium carbonate, sodium bicarbonate 7 or calcium oxideO
E X A M P L E S 92 to 116: .
~ . -Acc,ording to the process described in Example 91, further dyestu~fs corresponding to the above-mentioned formula (I) could be prepared, i~ equivalent amount~ o~ the corresponding starting compounds of the formulae (II) and (III) and the equivalent amount o~ magnesium oxide were used, said dyestu~
having been specified in the following Table 3.
, HOE ~386 1~6~6 ' Example R1 R2 A Yield Color shade on wool 92 ~ SO3~ 94 % l~lu~ o' ~t 93 H C---N~3 3 9~ % violet 94 H -C - N d~to 96 % red - N CII
H 3 / ~ red CH O N
96 H "N~ di~to 92 % red 97 CH3 ~ d.itt;o 99 % reà~viole t 98 3 ~ di:ll;o 99 % dull violet ~`NI~ 91 y" blu sh ~ ,. .~ . .
H_E~ LF 386 Example R1 R2 A Yield Color shade on wool 100 3 ~N l~J ~ 3 98 % violet 101 r~ Cl ~iolet NH-N~I
102 HC I dit:to 93 % blue ~ CH-C=0 10~ ~ N~ di i~o 90 % bluish red ~ .
104 HN~CH di~;o 91 % viole t N~
105 ~N-N-[3 dl~o 85 ~red v.iole~
~ NX- C
106 H -~ a~ ~3 ditto 9~ %blue 107 H C~N~3 dib;o 9~ %violet F',OE 741 1~6~
Example R1 R2 A Yield Color shade on wool 108 H ~ ~ S03~ 95 % violet OC2ns 109 3 ~ di~o 97 % red-violet 110 H ~ ~ S0 ~ violet . Cl 111 H -CH 3 ~ 3 98 % ~luorescent ~-CH3 ~ bluish red 11 ~CH' 3 C~I- CH3 di~o 97 % di~o CH~ 3 113 H -CH2C~I20H di~o 95 % dl~o-114-CH2c~I2H -C~I2CH~OH di~o 95 % d.t.~o 115 H -C~2- ~ di.~;o 96 % di~to 116 ~ -C~I2--C~2 ~ dl~to 97 % di~o .
HOE_ 74/F_386 ~6919~6 E X A M P L E 117:
__.__ _ ~ 3 Parts o.~ p-phenylene-diamine were added to 40.5 parts of the inner salt of ~,6-dichloro-9-phenyl-xanthydrol-2~-sulfonic acid in 200 parts of propylene-glycol~(1,2), while stirring at roor,. te.. ~Lature; the reac~ion ~iY~ture bac~m.e ~olet ~mmedi~P1y It was then heated to 100C and stirred at this temperature ~or 3 hours, in the course of which it got a deep blue shade.
After the mixture had been cooled to 80C 9 300 parts of water were added, while stirring7 the precipitated product was suction-~iltered after some time, was washed with water and dried. A dyestuff of the formula l N ~ ~ (~) ~ ~
was obtained in a yield o~ 98 % o~ the theory, which could be dissolved, for example, in glacial acetic acid or dimethyl-formamide with an in-tensely bl.ue color ~hade.
~ 40.5 Parts of the inner salt o~ 3,6-dichlorow9-phenyl-xanthydrol-2~ sul~onic ac.id were dissolved in 180 parts o~
wa~er, 22 part~ o.~ m-phenyle~1e~diamine and L~ Parts o~ magnesium oxide were added, and the whole was brought to the boil.
In the course of this reac~ion, a blue dyeing was obtained fas-t.
~fter a reac-tion time o~ 6 hours at boiling temperature, the reaction mi.xture was cooled to room temperature, and the pre-ci.pitated dyestu~f having the formula Hol~ 7 ~1364~
N~ ~ O ~ N1 . NH2 ~ so3 NH~
was suction-filtered, washed with water and dried. The yield obtained was 85 % of the theory.
The product could be dissolved in ethanol with a reddish blue color shade, E X A M P L E 119:
a) 43.5 Parts of the inner salt o~ 3,6--dichloro-9~phenyl-xanthydrol-4'-methoxy-2'-sulfonic acid were well stirred with 200 parts of water and were heated to 95C, after 4 parts o.~ magnesium oxide had been added. In the course o~ 2 hours, 2.8 parts o~ p~phenetidine were added dropwi.se.
Subsequently the mix-ture wa~ heated -to slight re~lux and was continued to be stirred at this temperature for 8 hours.
The violet dyestuf.~ formed precipitated in a crystalline form and was suction-filtered after the reaction mixture had been cooled to room temperature. The dyestu.~f was washed wlth wat~r and dr~ed~ It had the ~ormula 115C~ ~ ~ C ~ ~ OC?ll5 ~S03 ~ Yield: 63 Par-ts, . OC113 b) B~ a sul.fonat.ion with sulPuric acid according to processes 29 which are cor~mon L~ technology9 and by way of a subseq-lent ,~ - 33 ~
- ~6 1~6~9~;
conversion of the acid dyestu~f thus pre~ared into the sodium ~alt thereof, a dyestuff was obtained which was well soluble in water and which dyed wool at a pH value of ~rom 3 to 5 in a brilliant violet color shade with excel-lent fastness propertiesa c) The synthesis of the dyestuff prepared according to the above-given paragraph a) could also be carried ou-t at higher temperatures9 for example at 130C~ while using an autocla~e~ by which process the above-mentioned dyestu~f was obtained a~ter a shorter reaction ~ime, however, in the sa~e good yield and purity~
40,$ Par-ts of the inner sal-t o~ 3,6-dichloro-9-phenyl xanthydrol-2~ sulfonic acid were heated up to 150 to 16QC
.15 together with ~7 parts of 4-amino-diphenyl-sulfone, 4 parts o~
ma~nesium oxide and 200 parts o~ glycerin, and the reaction mixture was maintained at this tempera-ture for 4 hours, while stirring. Subsequently the reaction mixture was cooled to : gsc and was mixed with 200 parts of water. The precipitating violet dyestuf~ was suction-fil-tered, was washed with wa-t~r and dried. It h~d the ~ormula ~ ~ ~'~ )X~
~ S~
The y.ield was 90 % o~ the theory.
.. _ 29 48.5 Parts o~ the inner salt of ~,6-dichloro-9--phenyl _ ~L~ _ .
.,.~.~ ,.
1~ 6~6 xanthydrol~2'~4'-disulfonic acid were suspended in 250 parts of ethylene-glycol and were heated up to 140 to 145Cg a~ter 6 parts of magnesium oxide and 22 parts of o-toluidine had been added. After a reaction time o~ 4 hours at this tempera-ture and after cooling to YU~~, the reaction mixture was in-troduced into 500 parts of ~ater, and diluted sulfuric acid was added until a pH value o~ 2 was reached, thereafter stir-red for some t.ime. The precipitated dyestuff was suction-filtered, was washed with water until neutral and was dried at 60C. The red violet dyestuff obtained in a yield of 95 ~
of the theory had the formula CH3 CI~3 ~N~L~ O ~¢~N}I~¢
~ C~3 ( E X A M P L E 122-_ a) A mix~ure of 40 . 5 parts of the inner salt of 3,6~dichloro-9-phenyl xanthydrol-2'-sulfonic acid, 250 parts of di-glycol, 8.5 parts o~ anhydrous sodium ace~ate and 25 parts of 2,5-dimethgla~ was heated up to 145 to 150C whlle s-tirring well; s~irrlng was continued for 4 hours at ~his temperaturc. After having been cooled to 90C~ the reaction 25 ~ mixture was poured onto 250 parts of water, and the whole wa~ stirred for 30 minutes. The precipitated dyestuf~ ~Yas suc-tion-fil-tered, washed with water and driecl a-t 80C~
The pulverlllent dyestuff obtained in R yield of 96 ~ of the 29 theory could easily be dissol~ed in 85 ~ formic acid and H0~ 7 ~ 38~
~LQ6~
showed a red-violet oolor shade. It had the following ~ormula:
H3C C~13 r ¢~
C~3 ~;~v3 ~~^3 b) Instead of sodium acetate, there could also be used calcium hydroxide~ magnesium oxide, calcium oxide, or pyridine as acid-bindi~g agents in the reaotio~ described under a) above. The dyestuff mentioned in saicl para~raph was ob-tained in the samè good yield and purity.
c) The dyestu~f prepared u~der a) above was sulfonated ac-cordin~ to a technically conunon ~ulfonation process; it dyed wool at a pH value Or rrom 3 to 5 from a boiling aqueous dye bat~ in a brilliant recl-violet color shade of a high color irlt0nsity and with excell~nt rastness proper~
ties~
E X A M P L E~
40.5 Parts o~ the inner salt of 3/6 dichloro-9-phenyl-xanthydrol-2'-sulfonic acid were stirrecl in 200 parts of water ~or so111e time and wore hoated up to 95 to 100C, a~-tor 18 parts Or morpholir1e ancl1~ parts o~ magnesium oxi.de had been aclded~
~t~r a roaation time Or 6 hour~ at th:Ls teolperature, tho red solutlon obtained wa9 evaporated to dryness at the rotary evaporator or was isolated in the spray-drier. A dyestuff having the rormula 2g ~ ~ S03(-) . ~
. ' _ 36_ a~
~6 was obtained in a good yield, which dyestu~f dyed wool in brilliant red shades.
E X A M P L E 121i:
If the reaction was carried out according to the method described in Exa~ple 123! while usin~, however, 14 parts of 1-cyano-2-amino-ethane as reactive amine instead of mol~Pholine~
a red dyestuf~ of the formula Nc-clI2-cIl2-NII ~ ~ I~-C1~2 C~I2CN
" ¢~
.
was obtained in a good yi.eld, which dyed wool in bri.lliant red ~hades~
1~ The ~ollowing Table contains further clyestuffs whi.ch could be obtainad according to the in~ention process and which have bee.n prepared according to one of the above-specified methods, as well as the color shades on wool which were obtaiIled with said d~estuf~s:
- HOE_ ~4/F ~
9~
R1 R2 A y ield Golor shade on wool . .
-CH2-C~E~-Cl -c~I2-cH2-cl ~sO (~) bluish red - H ' CH2-CH2-0cH3 dittQ 98 % ditto -H 2 2 ~CH3 oittO
--H -cH2-cH2--cN ditto 95 ~0 ditto _~ ~3 ditto 92 % ditto .
-H ~CN ditto 94 % violet -H _~--COOCH3 ditto 92 Z ditto -H --~02C~I3 ditto 90 % ditto -H ~o2~ ditto 86 % ditto C~12 ~H2 ~ S03N~
- H ~ ditto ~36 % violot -H ~ ¢~ 91 % ditto (-) ' ' ' S03 90 ~0 d:Ltto OH
' HOE 74/1~ 386 ~6~9~6 R R2 A YieldC'olor shade on wool , _ . . ~
SO ( ) reddi sh -}I$~ ~/ 3 ~9 % violet f~3.~,U~,H3 -H ~ / 87 % ditto H5 COONH~
-H ~ 96 % violet ~H3 -SO2N ( C~13 ) 2 ¢~,S03-) viol~?t C~13 S02~ 2-C1120~1 ~OC1~3 ~ 3 82 % vio~0t S02-CTI2-C~12-oS03H
~ 3~ ~
11 X ~ ditto violet _~ S03Na 0~
12 H ~ S03N~ ditto reddish blue OH
13 H -~I ~ ditto reddish violet S03Na 14 C2H5 ~ ~ S03Na di-tto red-violet 15H ~ -- Cl ditto red~iolet S03N~
16H ~ CI~3 ditto red-v~olet 17 ~ . ~ 3 ~ bluish violet C~I3 Cl _ 16 -.
Example R1 R2 A Color shade on wool 18 H ~ ~ so3~ violet NaO3S
19 ~ SO3Na di~tO bluish red H ~ ~ viole~
COONa ~ $O3N~
21 ~ COONa ~ so30 blue COONa 22 H ~ ~~SO3Na ~ SO30 red~iolet 3 :
; CH3 l SO ~ ~luorescent 23 H I . fi ~1 3yellowish red -CH-CH2-S03Na '~ ~
2~ CH -C~ C~ SO Na ditto ~luore,scent ~ ~ 2 3 bluish red C~I di.~to red-violet ~3 ~03Na - - ~7 -.
H ~ ~
1064~6 Exarnple R1 R2 A Color shade on wool 2~ H ~ ~ 3 red~violet S03Na 27 ~ -CH2-CX2-COONa ditto fluorescent bluish red 28 H -CH2-C~2-S03Na dit~o ~luorescent - 29 C2H5 -CH2-CH2-$0 Na ditto fluorescent ~ bluish red -~0 CH ~ SO~ viole-t COONa 31 H -CH2 S03~ fluOresoent ~ ~ bluish red S03Na .
E X A M P 1. E 3~:
121.5 Parts o~ the inner salt o~ the 3~6-dichloro~9-phe~yl-xanth~drol-7~-sul~onic acid, 750 parts o~ water, 24 parts of magnesium oxide and 122 parts of 3-arnino-4-methoxy-benzene-~ul~onic acid were h~ated. in an au~oclave ~Ip to 140Ct while s-tirring ~or 1 hour, in whiGh process a pressure o~ 4 to 5 atmospheres was estabJ.ished. After having been stirred ~or 29 another 5 hours9 the reaction mixture was cooled to 60~.
. - 18 -, H ~
~6~L6 150 Parts o~ ~,odium ohloride were added. A~ter the mixture had been cooled to room temperature, while stirring, the crystalline precipitate was suction-~iltered and ~as dried at 60C.
250 Parts of a pure dyestuff were obtained which had the formula c OCH3 OC~
~ ~ ~ o ~ Nl ~ -Na~ S ~ So ~~) So N
and which was very well water-soluble and dyed wool from a boiling aqueous dye bath having a pH value o~ 3 to 4 in a bluish violet shade of a very s-trong color intensity.
E ~ A M P L ~ 3~:
.____ If in Example 3Z an equivalent amoun-t o~ 3-amino-4-rnethyl-~
~5 benzene-sulfoni.c acid was used instead of th~ 3-amino-4-metho benzene-æul~onic ac;id and the reaction was carried out ac cording to the method indicated in E~ample 32, the correspond.ing methyl-substituted dyestuf~ was obtained also in a good yield, which dyed wool in a brilliant red-violet color shade~
E X A M P L E S 1a to 33a:
The dyestuf~s prepared accordin~ to Exampl~ 1 to ~3 could be prepared in the ~am~ manner and wit~ a high ylelcl as well as a good purity, i~ as acid-binding agent there was used, ~or example, calcium hydroxide, aluminum hydroxide9 sodium aceta-te7 ~5 trisodium-phosphate, or pyridine in an equival~nt amount.
E _ A M P L F ~
a) 40 5 Parts of the inner salt of 3~6-dichloro~9-phenyl-- xanthydrol-2'-sul~onic acid were stirred for a short time 29 in 250 parts of ethylene-glycol. A~ter 26 parts o~ 3-chloro - 19 -.
~ 1~649~
aniline had been added, the reaction mixture was heated within one hour up to 145 to 150Co At this temperature the mixture was continued to be stirred for another hour;
subsequently 4 parts o~ magnesium oxide were added in ~mal l por*ion~ wi-~hin one hsur. then the mixture was stir-red ~or another hour and was cooled to 100C. The ~ine precipitate formed which could well be filtered was sucti.on-~iltered, was washed with ~00 parts of water and dried at 80C. 57 Parts of a pulverulent dyestu~f powder were ob-tained which was soluble in 85 % formic acid with a violet color shade. The dyestuff had the ~ormula ~(C)~
CL ~ S3( ) C1 b) A~ter a sul~onation by way o~ sul~uric acid in accordance with a technically common process, ~or example according to the process described in the above-mentiQned German Patent Speci~ications, and af-ter the conversion into it.s sodium sal-t, a dye~tuff was obtained which was well water-~olublo and whioh dy~d wool? ~ilk and ba~sical.~y modified synthetic fibers ~rom an aqueous dye bath having a pH value o~ between 3 and 5, in a brilliant violet color shade having good ~astness properties.
c) The mother liquor obtained under a) and the wash wa-ter were combined and were clarified ~rom a sl1ght precipitate wh.ich had been ~ormed~ This filtrate could be used again for a 29 new reac-tion mi~ture :~or a dyes-tuff preparation as des--- ~0 --9~6 cribed under a), instead o~ fresh ethylene-glycol. In this second process, however9 -the water which was now contained in the reaction mlxture was eliminated by distillation before or during the react.ion.
T' ~ ,~, M p T E ~ ~ to an.
-In a manner analogous to the pro~ess de~ribed in Example ~4, further dyestuf~s corresponding to the above-mentioned formula (I) could be prepared, i~ equivalent amounts of the corresponding starting compounds of the formulae ~II) and (III) and the equivalent amount of magnesium oxide were used.
These dyestuffs are specified in the following Table 2.
The compounds thus prepared could optionally be sulfonated a~terwards.
____ __ Example R1R2 A Yi~ld Color shade on wool ~35 H ~ ~ 3 98 % bluish red Cl 36 H ~ 5 , 99 % violet aH
37 H ~ 3 ditto 96 % blul~h red C~3 38 H ~ C~I3 dit~o ~8 % bluish red 39 H ~ No2 ditto 98 ~o red ~L~3.
9~6 Example R1R2 A ~eld Color shade on wool ~ ~ ~ S~30 97 % bluish red 41 H ~ ditt 9O % red 3 ~ -42 H - ~ NH ~ ditt 95 % blue , 43 H ~ d.itto 99 % redd1sh viole~
OC~I3 44 H ~ C1 di~to 96 % violet H ~ d.itto 93 % reddish blue : N~l2 ~ ~ *6 ~ H ~ ditto 98 % bluish red ~? . .
47 H -aH2 ~ dit~o 95 % red ~luoro~cen-t 48 H ~ N~ 3 ditto 98 % bluish r~d : 49 H ~ ditto 9O ~Q bluish Vl' olet OH
;
. - 22 -: :, ~L~64~L6 Example R1 R2 . A Yield Color shade on wool CH3, . -~ ~S03a 80 % red-violet 51 H ~CE3 dit~o 97 % vi ~let 52 H ~ CH3 ~ ditto 99 % viole-t ~ . .
53 H ~ dit~o 9 ~ red~riolet . ~ .
54 H 0~0 ditto 9 % blllish l~ed ~ d-it,t 95 % l~lui~h ~riole-t I~3 56 H ~ OC~I~; di tlto 97 ~ violet Cl 57 ~ C ~. C.H~; di.tto 99 % viole t a~3 58 H ~?N0 di tto 97 % red 59 H -~N-N ~) ditto 99 % reddish blue lOG4916 Example ~1R2 A Yield Color shade on wool H~ OCH3 ~ S03 97 ~6 violet 61 H~ OCH3 ditto 98 % bluish violet 62 X ~ Cl di-tto 96 % bluish red CX3~
63 H ~ CH3 . ditto 96 % bluish red al 64 H ~j Cl ditto 9~ % red ~iolet OCH~5 H ~ Cl ditto g7 % bluish red ~6 H ~ ditto 92 % red-~iolet Cl 67 ~ 2 di t; to 9o % violet 68 H ~ ditto 91~ ~h red N (C2H5) `:
H~6_ ~06~9'1~ .
Example R1 ~2 A Yield Color shade on 69 H CN3 CH3 ~ 9B k bluish red 7 H ~ , red-~iolet 71 -CH2CH2CN ~ ditto 95 yO bluish red 7~ H ~ dit~ 96 % viole t OX
73 H~9- O~ dit to C~3 % blui~h violet 7~t -COCH~$ ~ dittO 92 % red~violet .
H~ C0~2 dit;to 97 % reddish blue r--~
76 H <__~NH-COC~I3 dit~o 97 Y blu~
77 EI -~-Q-~ c;it~o 98 Yo violet 78 H ~SQ2N(C~T3)2 ditto 98 % red-viole-t ,= ~ .
79 H ~SO2CH2CE120H ditto 95 % violet ~ 25 , ., ,~, ....
HOE 74lF 386 1~ 6~6 Example R1 R2 A Yield Color shade on wool SO CH CH OH SO ~ 94 %
H ~ 2 2 2 ~ 3 bluish violet OCH
81 H ~ di~o 96 % violet C~
82 H ~ ~ di~o 98 % violet 83 -CH3 ~ c~r3 di~o. 96 % bluish red ~ C2H5 ~ di~o 97 h red viole-t , -C4H9 . ~ di~o 93 ~ red-violet 86 H ~ C2H5 ~ so3 98 % violet OC2~I5 87 ~I C~I3 ~ ~ ~ 96 % red-violet 88 H - ~ ~ 3 95 % violet C~I3 , .
~OE 7 ~
Example R1 R2 A Yield Color shade on wool .. .... , , _ 89 H ~ ~ 97 % ~iolet Cl C~3 ~;0 '~
9o CH3 ~ C2H5 ~ red-violet ~i E X ~ M P L E 91:
40.5 Par-ts of -the inner salt o~ 3,6-dichloro-9-phen~l-xanthydrol-2'~sulfonic acid were stirred in 200 parts o~ ethyl-ene-glycol or 250 parts o~ e.~hylene-glycol monoethyle-ther for a short time. A~ter 19 parts of aniline had been added, the reacti.on mixture was heated wi-thin one hour up to 135 to 14~~p was maintained at this temperature ~or one hour, while being stirred, and was then mixed portionwise within one hour with 4 parts of magnesiv~ oxide. Subsequently the mixture was heated up to 145 -to 150C and was stirred for one hour at this temperature A~ter the mix-ture had been cooled to 80C, 500 parts by volume o~ water were added. A.~ter ~he reaction mix-ture had b~en stirred ~or 30 minutes~ it was suction ~ilt~red, the cr~stalline product wa.s washed with water and was dried at 60C. 49 Parts of a d~estuff were obtained in the form of a ~ine powder, which had the formula ~7H~ O ~,NI~
29 ' ~S03(-'~
~L~ 3~6 1~6~16 and which was soluble ~or example in glacial acetic acid or in dime~hylformamide wi.th a bright violet color shade.
E X A M P L E S 35 a to 91 a.
The dyestuf~s obtained according to Examples 35 to 91 could also be prepared easiiy9 iI i~ ead 01 magllesi~m o~ide a~ acid-binding agent, there were used equivalent amounts o~ sodium acetate, sodium carbonate, sodium bicarbonate 7 or calcium oxideO
E X A M P L E S 92 to 116: .
~ . -Acc,ording to the process described in Example 91, further dyestu~fs corresponding to the above-mentioned formula (I) could be prepared, i~ equivalent amount~ o~ the corresponding starting compounds of the formulae (II) and (III) and the equivalent amount o~ magnesium oxide were used, said dyestu~
having been specified in the following Table 3.
, HOE ~386 1~6~6 ' Example R1 R2 A Yield Color shade on wool 92 ~ SO3~ 94 % l~lu~ o' ~t 93 H C---N~3 3 9~ % violet 94 H -C - N d~to 96 % red - N CII
H 3 / ~ red CH O N
96 H "N~ di~to 92 % red 97 CH3 ~ d.itt;o 99 % reà~viole t 98 3 ~ di:ll;o 99 % dull violet ~`NI~ 91 y" blu sh ~ ,. .~ . .
H_E~ LF 386 Example R1 R2 A Yield Color shade on wool 100 3 ~N l~J ~ 3 98 % violet 101 r~ Cl ~iolet NH-N~I
102 HC I dit:to 93 % blue ~ CH-C=0 10~ ~ N~ di i~o 90 % bluish red ~ .
104 HN~CH di~;o 91 % viole t N~
105 ~N-N-[3 dl~o 85 ~red v.iole~
~ NX- C
106 H -~ a~ ~3 ditto 9~ %blue 107 H C~N~3 dib;o 9~ %violet F',OE 741 1~6~
Example R1 R2 A Yield Color shade on wool 108 H ~ ~ S03~ 95 % violet OC2ns 109 3 ~ di~o 97 % red-violet 110 H ~ ~ S0 ~ violet . Cl 111 H -CH 3 ~ 3 98 % ~luorescent ~-CH3 ~ bluish red 11 ~CH' 3 C~I- CH3 di~o 97 % di~o CH~ 3 113 H -CH2C~I20H di~o 95 % dl~o-114-CH2c~I2H -C~I2CH~OH di~o 95 % d.t.~o 115 H -C~2- ~ di.~;o 96 % di~to 116 ~ -C~I2--C~2 ~ dl~to 97 % di~o .
HOE_ 74/F_386 ~6919~6 E X A M P L E 117:
__.__ _ ~ 3 Parts o.~ p-phenylene-diamine were added to 40.5 parts of the inner salt of ~,6-dichloro-9-phenyl-xanthydrol-2~-sulfonic acid in 200 parts of propylene-glycol~(1,2), while stirring at roor,. te.. ~Lature; the reac~ion ~iY~ture bac~m.e ~olet ~mmedi~P1y It was then heated to 100C and stirred at this temperature ~or 3 hours, in the course of which it got a deep blue shade.
After the mixture had been cooled to 80C 9 300 parts of water were added, while stirring7 the precipitated product was suction-~iltered after some time, was washed with water and dried. A dyestuff of the formula l N ~ ~ (~) ~ ~
was obtained in a yield o~ 98 % o~ the theory, which could be dissolved, for example, in glacial acetic acid or dimethyl-formamide with an in-tensely bl.ue color ~hade.
~ 40.5 Parts of the inner salt o~ 3,6-dichlorow9-phenyl-xanthydrol-2~ sul~onic ac.id were dissolved in 180 parts o~
wa~er, 22 part~ o.~ m-phenyle~1e~diamine and L~ Parts o~ magnesium oxide were added, and the whole was brought to the boil.
In the course of this reac~ion, a blue dyeing was obtained fas-t.
~fter a reac-tion time o~ 6 hours at boiling temperature, the reaction mi.xture was cooled to room temperature, and the pre-ci.pitated dyestu~f having the formula Hol~ 7 ~1364~
N~ ~ O ~ N1 . NH2 ~ so3 NH~
was suction-filtered, washed with water and dried. The yield obtained was 85 % of the theory.
The product could be dissolved in ethanol with a reddish blue color shade, E X A M P L E 119:
a) 43.5 Parts of the inner salt o~ 3,6--dichloro-9~phenyl-xanthydrol-4'-methoxy-2'-sulfonic acid were well stirred with 200 parts of water and were heated to 95C, after 4 parts o.~ magnesium oxide had been added. In the course o~ 2 hours, 2.8 parts o~ p~phenetidine were added dropwi.se.
Subsequently the mix-ture wa~ heated -to slight re~lux and was continued to be stirred at this temperature for 8 hours.
The violet dyestuf.~ formed precipitated in a crystalline form and was suction-filtered after the reaction mixture had been cooled to room temperature. The dyestu.~f was washed wlth wat~r and dr~ed~ It had the ~ormula 115C~ ~ ~ C ~ ~ OC?ll5 ~S03 ~ Yield: 63 Par-ts, . OC113 b) B~ a sul.fonat.ion with sulPuric acid according to processes 29 which are cor~mon L~ technology9 and by way of a subseq-lent ,~ - 33 ~
- ~6 1~6~9~;
conversion of the acid dyestu~f thus pre~ared into the sodium ~alt thereof, a dyestuff was obtained which was well soluble in water and which dyed wool at a pH value of ~rom 3 to 5 in a brilliant violet color shade with excel-lent fastness propertiesa c) The synthesis of the dyestuff prepared according to the above-given paragraph a) could also be carried ou-t at higher temperatures9 for example at 130C~ while using an autocla~e~ by which process the above-mentioned dyestu~f was obtained a~ter a shorter reaction ~ime, however, in the sa~e good yield and purity~
40,$ Par-ts of the inner sal-t o~ 3,6-dichloro-9-phenyl xanthydrol-2~ sulfonic acid were heated up to 150 to 16QC
.15 together with ~7 parts of 4-amino-diphenyl-sulfone, 4 parts o~
ma~nesium oxide and 200 parts o~ glycerin, and the reaction mixture was maintained at this tempera-ture for 4 hours, while stirring. Subsequently the reaction mixture was cooled to : gsc and was mixed with 200 parts of water. The precipitating violet dyestuf~ was suction-fil-tered, was washed with wa-t~r and dried. It h~d the ~ormula ~ ~ ~'~ )X~
~ S~
The y.ield was 90 % o~ the theory.
.. _ 29 48.5 Parts o~ the inner salt of ~,6-dichloro-9--phenyl _ ~L~ _ .
.,.~.~ ,.
1~ 6~6 xanthydrol~2'~4'-disulfonic acid were suspended in 250 parts of ethylene-glycol and were heated up to 140 to 145Cg a~ter 6 parts of magnesium oxide and 22 parts of o-toluidine had been added. After a reaction time o~ 4 hours at this tempera-ture and after cooling to YU~~, the reaction mixture was in-troduced into 500 parts of ~ater, and diluted sulfuric acid was added until a pH value o~ 2 was reached, thereafter stir-red for some t.ime. The precipitated dyestuff was suction-filtered, was washed with water until neutral and was dried at 60C. The red violet dyestuff obtained in a yield of 95 ~
of the theory had the formula CH3 CI~3 ~N~L~ O ~¢~N}I~¢
~ C~3 ( E X A M P L E 122-_ a) A mix~ure of 40 . 5 parts of the inner salt of 3,6~dichloro-9-phenyl xanthydrol-2'-sulfonic acid, 250 parts of di-glycol, 8.5 parts o~ anhydrous sodium ace~ate and 25 parts of 2,5-dimethgla~ was heated up to 145 to 150C whlle s-tirring well; s~irrlng was continued for 4 hours at ~his temperaturc. After having been cooled to 90C~ the reaction 25 ~ mixture was poured onto 250 parts of water, and the whole wa~ stirred for 30 minutes. The precipitated dyestuf~ ~Yas suc-tion-fil-tered, washed with water and driecl a-t 80C~
The pulverlllent dyestuff obtained in R yield of 96 ~ of the 29 theory could easily be dissol~ed in 85 ~ formic acid and H0~ 7 ~ 38~
~LQ6~
showed a red-violet oolor shade. It had the following ~ormula:
H3C C~13 r ¢~
C~3 ~;~v3 ~~^3 b) Instead of sodium acetate, there could also be used calcium hydroxide~ magnesium oxide, calcium oxide, or pyridine as acid-bindi~g agents in the reaotio~ described under a) above. The dyestuff mentioned in saicl para~raph was ob-tained in the samè good yield and purity.
c) The dyestu~f prepared u~der a) above was sulfonated ac-cordin~ to a technically conunon ~ulfonation process; it dyed wool at a pH value Or rrom 3 to 5 from a boiling aqueous dye bat~ in a brilliant recl-violet color shade of a high color irlt0nsity and with excell~nt rastness proper~
ties~
E X A M P L E~
40.5 Parts o~ the inner salt of 3/6 dichloro-9-phenyl-xanthydrol-2'-sulfonic acid were stirrecl in 200 parts of water ~or so111e time and wore hoated up to 95 to 100C, a~-tor 18 parts Or morpholir1e ancl1~ parts o~ magnesium oxi.de had been aclded~
~t~r a roaation time Or 6 hour~ at th:Ls teolperature, tho red solutlon obtained wa9 evaporated to dryness at the rotary evaporator or was isolated in the spray-drier. A dyestuff having the rormula 2g ~ ~ S03(-) . ~
. ' _ 36_ a~
~6 was obtained in a good yield, which dyestu~f dyed wool in brilliant red shades.
E X A M P L E 121i:
If the reaction was carried out according to the method described in Exa~ple 123! while usin~, however, 14 parts of 1-cyano-2-amino-ethane as reactive amine instead of mol~Pholine~
a red dyestuf~ of the formula Nc-clI2-cIl2-NII ~ ~ I~-C1~2 C~I2CN
" ¢~
.
was obtained in a good yi.eld, which dyed wool in bri.lliant red ~hades~
1~ The ~ollowing Table contains further clyestuffs whi.ch could be obtainad according to the in~ention process and which have bee.n prepared according to one of the above-specified methods, as well as the color shades on wool which were obtaiIled with said d~estuf~s:
- HOE_ ~4/F ~
9~
R1 R2 A y ield Golor shade on wool . .
-CH2-C~E~-Cl -c~I2-cH2-cl ~sO (~) bluish red - H ' CH2-CH2-0cH3 dittQ 98 % ditto -H 2 2 ~CH3 oittO
--H -cH2-cH2--cN ditto 95 ~0 ditto _~ ~3 ditto 92 % ditto .
-H ~CN ditto 94 % violet -H _~--COOCH3 ditto 92 Z ditto -H --~02C~I3 ditto 90 % ditto -H ~o2~ ditto 86 % ditto C~12 ~H2 ~ S03N~
- H ~ ditto ~36 % violot -H ~ ¢~ 91 % ditto (-) ' ' ' S03 90 ~0 d:Ltto OH
' HOE 74/1~ 386 ~6~9~6 R R2 A YieldC'olor shade on wool , _ . . ~
SO ( ) reddi sh -}I$~ ~/ 3 ~9 % violet f~3.~,U~,H3 -H ~ / 87 % ditto H5 COONH~
-H ~ 96 % violet ~H3 -SO2N ( C~13 ) 2 ¢~,S03-) viol~?t C~13 S02~ 2-C1120~1 ~OC1~3 ~ 3 82 % vio~0t S02-CTI2-C~12-oS03H
~ 3~ ~
Claims (8)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. Process for the preparation of xanthene dyestuffs of the general formula (I) (in which R1 and R2 are identical or different, each representing an aliphatic, araliphatic or cycloaliphatic radical, each being optionally substituted by halogen, hydroxy, alkoxy, amino, cyano, carboxylic acid and/or sulfonic acid, or R1 represents also a hydrogen atom or a carbocyclic aromatic or heterocyclic radical, or R1 and R2 together with the N-atom form a heterocyclic radical optionally containing further hetero-atoms, the benzene nucleus A may optional-ly contain substituents, and m stands for the integer 1, 2, 3, 4 or zero), by reacting the inner salts of 3,6-dihalogeno-9-(2'-sulfophenyl)-xanthene-9-ols of the general formula (II) (II) , (in which X stands for a halogen atom and A has the above-mentioned meaning), with primary or secondary amines of the formula (III) (III) (in which R1 and R2 have the meanings specified as above) in a polar solvent which is free from acid groups, and optionally sulfonating the product sub-sequently, which comprises carrying out the reaction of the xanthenol of the formula (II) with the amine of the formula (III) in a stoichiometrical amount and in the presence of an inorganic acid-binding agent and/or an acid-binding tertiary aliphatic or cycloaliphatic amine, of pyridine or a pyridine deriva-tive.
2. A process according to claim 1 wherein an amine of formula (III) is used which is free from sulfonic acid or carboxylic acid groups.
3. A process according to claim 1 wherein an amine of formula (III) con-taining a sulfonic acid and/or carboxylic acid group is used in the form of its salt with an inorganic or organic base.
4. Process as claimed in claim 1, wherein in the formulae I, II and III
R1 and R2 are identical or different and each represents an aliphatic, arali-phatic or cycloaliphatic radical each optionally substituted by halogen atoms, hydroxy, alkoxy, amino, cyano, carboxylic acid- and/or sulfonic acid groups, or R1 may also represent a hydrogen atom or a carbocyclic aromatic or heterocyclic radical substituted by halogen atoms, alkyl, alkoxy, hydroxy, amino, alkylamino, dialkylamino, nitrile, carboxylic acid, carboxylic acid ester, carboxylic acid amine, sulfonic acid, sulfonic acid amide, trifluoromethyl, alkylsulfonyl, .beta.-hydroxyethylsulfonyl, .beta.-sulfatoethylsulfonyl, arylazo, arylamino, aryloxy, arylsulfonyl, or nitro groups, or R1 and R2 together with the N-atom form a heterocyclic radical optionally containing further hetero-atoms, the benzene nucleus A may contain as substituents halogen atoms, alkyl, alkoxy, aryl, hydroxy, carboxylic acid, carboxylic acid ester, carboxylic acid amide, sulfonic acid, sulfonic acid amide, .beta.-hydroxyethylsulfonyl or .beta.-sulfatoethylsulfonyl groups, and m stands for the in-teger 1, 2, 3, 4, or zero.
R1 and R2 are identical or different and each represents an aliphatic, arali-phatic or cycloaliphatic radical each optionally substituted by halogen atoms, hydroxy, alkoxy, amino, cyano, carboxylic acid- and/or sulfonic acid groups, or R1 may also represent a hydrogen atom or a carbocyclic aromatic or heterocyclic radical substituted by halogen atoms, alkyl, alkoxy, hydroxy, amino, alkylamino, dialkylamino, nitrile, carboxylic acid, carboxylic acid ester, carboxylic acid amine, sulfonic acid, sulfonic acid amide, trifluoromethyl, alkylsulfonyl, .beta.-hydroxyethylsulfonyl, .beta.-sulfatoethylsulfonyl, arylazo, arylamino, aryloxy, arylsulfonyl, or nitro groups, or R1 and R2 together with the N-atom form a heterocyclic radical optionally containing further hetero-atoms, the benzene nucleus A may contain as substituents halogen atoms, alkyl, alkoxy, aryl, hydroxy, carboxylic acid, carboxylic acid ester, carboxylic acid amide, sulfonic acid, sulfonic acid amide, .beta.-hydroxyethylsulfonyl or .beta.-sulfatoethylsulfonyl groups, and m stands for the in-teger 1, 2, 3, 4, or zero.
5. Process as claimed in claim 1, wherein in the formulae I, II and III R1 represents a hydrogen atom, an aliphatic radical optionally substituted by halogen atoms, hydroxy, alkoxy, amino, cyano, carboxylic acid or sulfonic acid groups, and R2 represents a phenyl or naphthyl radical optionally substituted by halogen atoms, alkyl, alkoxy, hydroxy, amino, alkylamino, di-alkylamino, cyano,carb-oxylic acid amide, trifluoromethyl, alkylsulfonyl, .beta.-hydroxyethylsulfonyl, .beta.-sulfatoethylsulfonyl or nitro groups.
6. Process as claimed in claim 1, wherein in the formulae I, II and III R1 represents a hydrogen atom or an alkyl radical of from 1 to 6 carbon atoms, which may be sub-stituted by halogen, hydroxy, cyano, alkoxy having from 1 to 4 carbon atoms, carbalkoxy with 2 to 5 carbon atoms, sulfo and/or carboxy, R2 stands for an alkyl radical having from 1 to 6 carbon atoms, which may be substituted by phenyl, sulfophenyl, hydroxy, cyano, alkoxy group having from 1 to 4 carbon atoms, carbalkoxy group having from 2 to 5 carbon atoms, sulfo and/or carboxy groups,or re-presents a cyclohexyl or cyclopentyl or the phenyl radical which may be substituted by halogen, alkyl having from 1 to 4 carbon atoms, alkoxy with 1 to 4 carbon atoms, carb-alkoxy with 2 to 5 carbon atoms, sulfonamide, N-(lower alkyl)-sulfonamide, N,N-di-(lower alkyl)-sulfonamide, sulfo, carboxy, hydroxy, .beta.-hydroxyethylsulfonyl, .beta.-sulfato-ethylsulfonyl, nitro, amino, dimethylamino, diethylamino, phenylamino, phenylazo and/or acetylamino, or stands for the naphthyl radical which may contain sulfo, carboxy, carbonamide, sulfonamide, chlorine and/or alkyl with from 1 to 4 carbon atoms, or represents the thiazole, pyrazole, triazole pyridine, benzthiazole, benzpyrazole or benz-triazole radical, or R1 and R2 together with the N-atom represent the morpholine, piperidine or piperazine ring, the benzene nucleus A may contain halogen, alkyl having from 1 to 5 carbon atoms, alkoxy with 1 to 5 carbon atoms, phenyl, hydroxy, carboxylic acid, carbalkoxy with 2 to 6 carbon atoms, carbonamide, sulfonic acid, sulfonamide, .beta.-hydroxy-ethylsulfonyl and/or .beta.-sulfato-ethylsulfonyl, and m stands for the integer zero, 1, 2, 3 or 4.
7. Process as claimed in claim 1 which comprises using as acid-binding agents oxides, hydroxides, carbonates, hydrogenocarbonates, acetates, borates or phosphates of alkali metals or alkaline earth metals or of aluminum or ammonia.
8. Process as claimed in claim 1, which comprises using organic bases as acid-binding agents.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19742460491 DE2460491A1 (en) | 1974-12-20 | 1974-12-20 | PROCESS FOR THE MANUFACTURING OF XANTHENE DYES |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1064916A true CA1064916A (en) | 1979-10-23 |
Family
ID=5934067
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA242,170A Expired CA1064916A (en) | 1974-12-20 | 1975-12-19 | Process for the preparation of xanthene dyestuffs |
Country Status (9)
| Country | Link |
|---|---|
| JP (1) | JPS5187534A (en) |
| BE (1) | BE836944A (en) |
| CA (1) | CA1064916A (en) |
| CH (1) | CH584736A5 (en) |
| DE (1) | DE2460491A1 (en) |
| FR (1) | FR2295083A1 (en) |
| GB (1) | GB1503380A (en) |
| IT (1) | IT1051449B (en) |
| NL (1) | NL7514581A (en) |
Families Citing this family (33)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2529903A1 (en) * | 1975-07-04 | 1977-01-27 | Bayer Ag | DYE LASER |
| DE2657218A1 (en) * | 1976-12-17 | 1978-06-22 | Hoechst Ag | UNSYMMETRIC XANTHENE DYES, METHOD OF MANUFACTURING AND USING them |
| DE2657217A1 (en) * | 1976-12-17 | 1978-06-22 | Hoechst Ag | PROCESS FOR PREPARING UNSYMMETRIC XANTHENIUM COMPOUNDS |
| US4264507A (en) * | 1979-04-24 | 1981-04-28 | Polaroid Corporation | Novel xanthene dye developers |
| US4598158A (en) * | 1981-12-18 | 1986-07-01 | Polaroid Corporation, Patent Dept. | Novel image dye-providing materials and photographic products and processes |
| US4386150A (en) | 1981-12-18 | 1983-05-31 | Polaroid Corporation | Novel image dye-providing materials and photographic products and processes |
| JPH0987534A (en) * | 1995-09-25 | 1997-03-31 | Konica Corp | Ink jet recording fluid |
| GB2311075A (en) * | 1997-04-26 | 1997-09-17 | Zeneca Ltd | Ester or amide containing xanthene dyes for use in ink jet or hot melt inks |
| ATE233795T1 (en) | 1999-04-23 | 2003-03-15 | Molecular Probes Inc | XANTHENE DYES AND THEIR APPLICATION AS LUMINESCENCE-CANCELING COMPOUNDS |
| US6323337B1 (en) | 2000-05-12 | 2001-11-27 | Molecular Probes, Inc. | Quenching oligonucleotides |
| US7176317B2 (en) * | 2003-06-26 | 2007-02-13 | Xerox Corporation | Colorant compounds |
| JP4621040B2 (en) * | 2004-02-27 | 2011-01-26 | キヤノン株式会社 | Dye body, aqueous dispersion, ink, ink tank, recording unit, recording apparatus and recording method using the same |
| BRPI0503921A (en) * | 2004-06-18 | 2006-07-18 | Oreal | cosmetic composition, processes for dyeing keratin fibers, process for lightening keratin fibers, multi-compartment device, use of hydroxyalkylated compound and use of a dye composition |
| US7326258B2 (en) | 2004-06-18 | 2008-02-05 | L'oreal S.A. | Compositions comprising hydroxyalkyl direct dyes, implementation processes and uses thereof |
| JP5451556B2 (en) | 2009-09-18 | 2014-03-26 | キヤノン株式会社 | Dye compound |
| JP5919830B2 (en) * | 2011-02-08 | 2016-05-18 | 住友化学株式会社 | Colored photosensitive resin composition |
| JP6047885B2 (en) * | 2011-03-08 | 2016-12-21 | 住友化学株式会社 | Colored photosensitive resin composition |
| KR102066650B1 (en) * | 2011-08-03 | 2020-01-16 | 스미또모 가가꾸 가부시키가이샤 | Compound and process for producing the same |
| JP6060478B2 (en) * | 2011-08-03 | 2017-01-18 | 住友化学株式会社 | Compound and production method thereof |
| CN104011142B (en) * | 2011-12-26 | 2016-11-16 | 富士胶片株式会社 | There is the compound of ton skeleton, coloured composition, ink for ink-jet recording and ink jet recording method |
| JP5836200B2 (en) | 2012-05-30 | 2015-12-24 | 富士フイルム株式会社 | Compound having xanthene skeleton, coloring composition, ink for ink jet recording, and ink jet recording method |
| EP2669338B1 (en) * | 2012-05-31 | 2017-04-05 | Fujifilm Corporation | Coloring composition, ink for inkjet recording and inkjet recording method |
| JP5978015B2 (en) * | 2012-06-07 | 2016-08-24 | 住友化学株式会社 | Method for producing compound |
| JP2014059538A (en) * | 2012-08-23 | 2014-04-03 | Nippon Kayaku Co Ltd | Colored resin composition |
| EP2781514B1 (en) * | 2013-03-21 | 2015-11-18 | Canon Kabushiki Kaisha | Compound, ink, ink cartridge and ink jet recording method |
| JP6167124B2 (en) * | 2014-03-27 | 2017-07-19 | 富士フイルム株式会社 | Compound, coloring composition, ink jet recording ink, ink jet recording method, ink jet printer cartridge, color filter, color toner, and transfer ink |
| EP2933296A1 (en) * | 2014-04-17 | 2015-10-21 | DyStar Colours Distribution GmbH | Fluorescent reactive dyes, process for the production thereof and their use |
| WO2017006940A1 (en) * | 2015-07-09 | 2017-01-12 | 富士フイルム株式会社 | Compound, coloring composition, ink for inkjet recording, inkjet recording method, inkjet printer cartridge, and inkjet recorded article |
| JP6937110B2 (en) * | 2016-11-07 | 2021-09-22 | 東友ファインケム株式会社Ｄｏｎｇｗｏｏ Ｆｉｎｅ−Ｃｈｅｍ Ｃｏ．， Ｌｔｄ． | Compound |
| JP6937109B2 (en) * | 2016-11-07 | 2021-09-22 | 東友ファインケム株式会社Ｄｏｎｇｗｏｏ Ｆｉｎｅ−Ｃｈｅｍ Ｃｏ．， Ｌｔｄ． | Colored resin composition |
| JP6911604B2 (en) * | 2017-07-20 | 2021-07-28 | 東洋インキＳｃホールディングス株式会社 | Colorants for color filters, coloring compositions for color filters, and color filters |
| JP2021095561A (en) * | 2019-12-17 | 2021-06-24 | 保土谷化学工業株式会社 | Xanthene dye, coloring composition including the same, color filter colorant, color filter and method for manufacturing xanthene dye |
| KR20240021930A (en) * | 2021-07-13 | 2024-02-19 | 다이요 홀딩스 가부시키가이샤 | Xanthene compounds and methods for producing them |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR1078437A (en) * | 1951-12-31 | 1954-11-18 | Hoechst Ag | Dyes of the triphenyl-methane series and their preparation process |
-
1974
- 1974-12-20 DE DE19742460491 patent/DE2460491A1/en not_active Withdrawn
-
1975
- 1975-12-13 IT IT3047775A patent/IT1051449B/en active
- 1975-12-15 NL NL7514581A patent/NL7514581A/en not_active Application Discontinuation
- 1975-12-17 CH CH1637375A patent/CH584736A5/xx not_active IP Right Cessation
- 1975-12-18 GB GB5184975A patent/GB1503380A/en not_active Expired
- 1975-12-19 CA CA242,170A patent/CA1064916A/en not_active Expired
- 1975-12-19 JP JP15067575A patent/JPS5187534A/en active Pending
- 1975-12-22 BE BE163007A patent/BE836944A/en unknown
- 1975-12-22 FR FR7539265A patent/FR2295083A1/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| FR2295083B1 (en) | 1979-06-22 |
| IT1051449B (en) | 1981-04-21 |
| NL7514581A (en) | 1976-06-22 |
| FR2295083A1 (en) | 1976-07-16 |
| CH584736A5 (en) | 1977-02-15 |
| BE836944A (en) | 1976-06-22 |
| GB1503380A (en) | 1978-03-08 |
| JPS5187534A (en) | 1976-07-31 |
| DE2460491A1 (en) | 1976-07-01 |
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