BE629707A - - Google Patents

Description

       

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 EMI1.1
 



  New vat dyes, their production method and their use.
 EMI1.2
 



  The pre-invention relates to novel pr6aioux working dyes, which carry two or more anthraquinone residues or an aystem which is caused by 4, of pr6t'ono. however at least 5 oastablo condenade nuclei, at least one arylainino group, whose atom atom must not

 <Desc / Clms Page number 2>

 
 EMI2.1
 Not represent a h6tdro-4to0 of a bdt6rooyolic ring, pure or mostly a croup * aryl-.tIt- and in addition at least by substituting 1i6 diroctoment 1 an aromatic ring of 6tdlnol external @ by ozoople to aroupo ary1Amino 44jh sealiona6, this substituent making the product soluble in water ot ";; 'ant itself constituted by a sullonic group
 EMI2.2
 or carboxylic.
 EMI2.3
 



  The definition .colorant. de ouvo * includes oolorrusts which iont trtorm68 by reduction in wlouco- 44rf, Y4 or cellar * # which. ae better affinity for the @ natural cellulose fibers * or rddndr60 'than the unreduced form and which can reconstitute the initial nystboo chroatophore by oxidation.

   Cocme vat dyes # on #entionno especially or from adria CU1thra.qu1non1 1ue reinforcing, for example two 9,10-d1010thraa4nique nuclei. non aodififa, or anthraduinoaoa which carry carbo- o7cljquo nuclei. and / or h6tfroayaliçuoa groffis by eondencatlon au which are formed of several uni68 tcthr <tquiooaiqua <which can be linked directly or by the interoidlaire of a bridge, as well as vat dyes of the croup of the per- r.yl1D.tltrbor. ydl1lj., D4pblbDot6trQoarboX7di1.1- des, good * - on aapbtoquiaoaor or tc41o! dos vat dyes.

   in addition to the predoit6a arylaaino groups and the solubilizing * .ubat1tUQA 'dyes, the dyes conforming to the 1A-.,. eAt1on can still be added the usual * substituents.

 <Desc / Clms Page number 3>

 
 EMI3.1
 taken in a working dye, for example with 4'hAloBno atoms, alkoxy groups or aoylumino groups.
 EMI3.2
 The coloring agents of
 EMI3.3
 tank which carry a carboxy- or sultopb4nyl-NR- oa aullonaphthyl-N1-lid dirootomont a carbon atom of an aromatic oyol of the moldculo of the dye.

   These dyes can ddr1 ?, eg exomple, dos compoude ci-aprbes dibon8cnthrono, inodibouzanthrorào, anthnthront, dibeaap3n- rbnoquinono, pyromthronu, flavcinthrone, indanthronot ao6- dianthrono, N, N'-nquinylyr1ldthyra, N, N'-dquin- 1ldthyra, 1 ', Z' - (1) -nnpttaoridono, t, 1'-diaathcirol.dooarbaaolo, tri- et t6trcnthr1midoobnzolo, 2 ', 2 "-di.ph6nylaathraqui noae-1,2 (N) -3,7 (N) -dithiasolo and aoylaminoanthraquinoneo, which is obtained by condensation of 2 moles of uno o- <Miin- anthraquinouel by exotiplo of 1-amino = thraquinont, 1-amir, o-4- or -3-benzoylM) iuo <tntbraquinonw or of inodi-bonsanthrono avoo a bonzbno-diourbozyohloruro or with a tri- or t4trGhaloadnopyrimiùine or uno di- or trioblootr16- sine * In addition to the anthraquinoniquon dyes herein, mentioned as high amounts of doa vat colorrite 10di;

  oIdel indigo or thioindigo and the substitutes or dyes of or dyes from the series of 14 acids perylnotótrGQarboxyli1U08, npht1notdtr.oarboay11qu .. or pyrbacquinone.
 EMI3.4
 



  As a substitute? lady dye solubilizer

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 EMI4.1
 water, we signal * the aulfonic group and the oarboxylic group as well as the 0-enter groups, for example nin6rru, also the sulfato group and also the thiosulfate groups.



  Of course, the vat dyes formulated with the invention can additionally carry the usual eubatitutuita for tolu dyes, for example halocbue atoms, alkyl or alkoxy groups, as well as reagent aubatituanta, for example. sulphate or thiosulphate group, halogbno atomos soindablen rG.to8 tfpoxy, pyrimidine or triazino nuclei with phonos, anilido or morcapto groups, dthylno-1mlne croupos, oto ...



  The ooniormoe vat dyes are obtained by the introduction of a solubilizing group in vat oolorants containing an arylamine group, or by the introduction of an arylanino fiToupo and <Jrentue 11 adorning at the same time a roups solubilizer, in the vat dye or in their intermediate matibros, which do not
 EMI4.2
 form by this introduction in dyes of open or
 EMI4.3
 can be transformed immediately on a dye * again in a known manner.



  The introduction of an arylamine group is obtained,
 EMI4.4
 for example, by dye reaction of a flower carrying a
 EMI4.5
 substituting doh4naoablo, for example a haloghno atom a -hou or -OU group, on phdnylaminez or naphthyl-cmines and, in case the starting oolorant does not contain

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 EMI5.1
 waaore a solubilizing group, by reaction with antln .-. ultoniu'8, naphthylamine-sulfoniquoal phdny11nocarboxylic or naphthylaminooarboxylic aoidoa.

   We can perform
 EMI5.2
 kill this reaction if dissolving agents are present or
 EMI5.3
 of dilution inortes ot b hot, preferably 4 tomp6ra- tur4 greater than 4 t00e, for example between 115 and 1800.
 EMI5.4
 We can introduce the groups solubilizing the
 EMI5.5
 produced in diroctent water, for example by sulfonation of tank colourant containing an arylamine group by means of ol4um or sulfuric acid coneontr6 cold or hot.



  We can 6Calenoat carry out this introduction by eot <5rifying
 EMI5.6
 the hydroxy group of vat dyes containing grouped back arylamino ot hydroxy groups by means of sulfa agonta
 EMI5.7
 Orguniquoe acylationtation or upstreams which contain in addition to Ilomplaceciont serving 4 aoylation, still a solubilizing croup linked to an aromatic rent.



  Conne organic acylation agorits of the above genus we mount especially the sulfobonsotques haloQ6nuros
 EMI5.8
 and composed of the typo
 EMI5.9
 

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 EMI6.1
 
 EMI6.2
 where X indicates an 8ultoArYlnQino aroupe and 1 a sulto aroupe. arylamino or an atom of chlorine.
 EMI6.3
 As an offset tank ooloranta containing
 EMI6.4
 arylonino ot hydroxy groups, it should be mentioned
 EMI6.5
 especially hydroxyalhylamides of carboxylic acids of
 EMI6.6
 Ouvo dye wearing don aryloaino groups and before
 EMI6.7
 all the sulfuric acids in the vat dye.



  The vat dyes in accordance with the invention can
 EMI6.8
 vent ÓUBleLlcnt to be obtained by aoylation of dye of work or intorcaddiairea containing den groups = Inoabnon and ae transforming by acylation of these grouped & MinOaànO & on dyes of cuvo, by means of agonte d '& 4ylation, which carry an arylooloo jroupo and / or a related aolubiliaenta group or an aromatic annuity, if the starting material does not already contain such aolubiliaenta groups.



  Like vat ocloranta or axitibroe 1ntuFIDJdliro. aoylables ot bearing (law grupos aminogbU * 4 On MàM tempts that an arylamiuo group, that we can use oomes antioroa de
 EMI6.9
 starting in the prooddd of the invention, we mention oeux
 EMI6.10
 which have a 9,10-dixoanthro4Qlul nucleus with only

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 EMI7.1
 three oonon8dti nuclei together and also coe = ino = thraquinonose which contain carbonoyolic or heterocyclic arottenic nuclei by condensation or which are formed by several units (5 anthraquinoniquos.

   Examples of co-genus are mentioned above all 2-aminoanthraquinonon and above all the 1-aminvoathraquiaoave containing a group -NU2 eoaoaltyl6 or free pr6ldrenoe, as well as position 4, 5, 6, 7 or 8 an arylaraino group, for example anilido, ohloranilino, o-, m- or p-methylanilido, 2-nQphtylino or 1-napbtylamino, of a group which may include 6Tontuollom.nt do @ gt * upos making the product soluble in water.

   We still have, for example # k oo subject the products 8uivuntl '1-aminc-4- (41-mdthyl- or 4'¯ohloroph (5nylaraino) -anthraqulnon, 1-amino-5- (4'-mdthyl- or 3' -ohlorophdnylamino) -anthraquinonot 1 | 4-dlaoino-2t3-di- (phdnylamino) -antbraquinona, 1 amino-4-phdnylaminoanthraquinon or 2-amtuo-6-phenylaminoanthraquinonel 1-amtnoS.ph6nylamino -iathino-phdnylamino, 6-amino-phdnylaminoanthraquinonou onino-8-phdnylaiainoanthroquinono, 1-amine-7-phdnyl & minoanthrnquinonoy 1-evmino-4- or -5- (a- or 3-nnphtylamino) -aathxeduinono, 1 - &) niao-4- or -5- (8'- ohloroaaphi, yl- (1 ') - amiao) -daihraquiaoao, 1,' 3-diamiao ..... phdnylnmiaoaathrncuinoao, 1 4-dia4lao-5-ph6s, ylruninoctnthrnquiaono,

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 EMI8.1
 1, '- 41Bmino-4,8-d1pbdDyl1noanthrqu1non.,

   as well as corresponding derivatives carrying in the moiety ph <5nyl- or naphthylarnino don cut carboxy and / or sulloniquang for example the acids 1-am1no-4-, -5- or -8-phdnylamino-anthraquinonic-3'- or -4t -aul! ouiquea, as well as the acids 1-amino-4-9 -5- or -8-phenylamincanthraquinona-21-carboxyli- (read fi As acylating agents can be used in the
 EMI8.2
 proceed from the invontion those which carry a substituted substituent
 EMI8.3
 bilinant linked to an aromatic route. Do @ acylating agents carrying such substituents aontp for example, those which include a sulfatop but do prdleronco a carbory group or especially a svlfoniquo croup. We can also use you as acylation upstreams not containing 801uùi118ta Rumps. especially when the aoyler ddpert dye contains a solubilizing rump linked to a flavoring rent.

   As examples of useful deacylating agents, we mention the baloadnuren or enlaydrieee of sulfonic acids and especially of carboxylic acids., For example the haloadnurea 48aoiao8 aliphatiquon ot do prdt6ronoo polyba- niquos, by oxofilplo those of oxalic acid. , acid sulfobonxofqaef of acian sulfoacidtiquo aid 8uoolniquo, clutriquo acid, phthalic acid, acid 100-ot tór6phthaliquo, azobenchne acid.

   dioarboxyliquo, Azodiph6ldlnArbXYlic acid,

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 EMI9.1
 pdrylenet6traoarboxydianilidodicarboxylic acid, anthanthrono-dioarboxyliquo acid, furss.sno- and thlophene-dicarboxylic acid ot especially halog6auren law of
 EMI9.2
 barbituric acid and oyanuric acid or condensate products, the use of which may result in
 EMI9.3
 directly to the prdoloux products conforming to the 1nQntion, which comprise two roatea arylaminoun4hxaquiconiquon $ among the aoylation agents cited in dornior place, one montionno partloulibromontt the chloride of the acid oyao6lw riquo ot las product of monoooadoneweion thereof, ohloruro of oyat¯urylo ot these produces analogues of monocondenantion with alcohols, phenolas, moroaptann dosages, ammonia and arrsinoa,

   in particular don sulto-aryleminois having or not the onr4otbe of a dye, thus
 EMI9.4
 than the following
 EMI9.5
 2,4,6-triehloropyriraidino, 2,4,6-tribrocopyrictidine, 2,4,3,6-ttraohloropyTiaidin, 2 # 4-diçhloro-6-mdthylpyrimidinot 2,4-iichloro-5-nitropyrimidino, 2,4-diohloro -3-nitro-6-adthylpyrimidine, Z, 4,6-triotsloro5-nitropyriaidiao, 2, 6-dlcbloropyrinildino-4-oarboxyohlorur,
 EMI9.6
 2, 6-diohloropyriraidino-3-oulfoohloride, ¯
 EMI9.7
 Z, 4-diohloropyrimidino-3-aulonic acid,

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 EMI10.1
 2 - () '- or 41-carboxyphdnylamino) -4t6-dichloropyrimidinot 2- (3'.

   or .'- cnrboxyph6nylnmino) -4 ", 6-triohloropyr1midine or '108 oompon6a having the formulas
 EMI10.2
 
 EMI10.3
 One can also carry out the acylation by means of
 EMI10.4
 the above acyltion agents containing a dichloro-ring
 EMI10.5
 triaziniquo, we first react the ohloruro of
 EMI10.6
 oyanurylo on a derivative of phenylaminoanthraquinone oontonant an aminogimmo groupable in a 1l1 molar ratio then the dichlorotriaainiquo compensation product obtained is then reacted on an identical or difidraquinone aminoanthraquinone, until all the halogen atoms are complete. less partially by stable ro.eto8.



  The reaction according to the invention donating the aforementioned diacylation agents on arylaainoanthraqulnonos containing dos ilroupos aninoaèno3 pout be carried out with the care of an organic solvent inorto, for example nitrobonabne, ohlorobona- no or c-dichlorobinzbno 4 to7p6raturo 41'To. In many cases, we can Óa!: \ 1Qa1t'nt. carry out the concoction on an aqueous medium, advantageously one pr4monco aQonte binding the acids # by oxonpio of sodium acetate, sodium hydroxide

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 sodium or sodium carbonate. In this case, the starting matilores are chosen so as to obtain products which bear at least one substituent which dissolves the product in
 EMI11.1
 water, which has an aromatic nucleus, of exterior pr4t6rnQ 'in particular a croup, aullonic or oarboxylic.

   When using starting materials which are free from sultunic or carboxylic groups, the resulting vat dyes should be subjected after ilocylation to the usual sulfonation to introduce one or more -803U groups. According to one of the variants of the process, one can use at the start ooloranta do vat bearing an oxylemino ot rent containing at least soft anthraquinoniquon residues or an openable system formed of at least 4 cores condensed together, then one introduced into the dyes of tank of this gonro at least one solubilizing substituent linked to a residue
 EMI11.2
 aronatiquop for example by sulfonation. Cotte sulfonation are very easy for the aforementioned arylamino components.



   Another variant of the method of the invention
 EMI11.3
 oonsiate b from vat dye which contain a substituent, for example an atomo of halogano exchangeable for an arylaminop group this is dah4naoanting this substituent, by oxqmple by condonnationi with don phtfnylaalnoe or naphthyl = inoup the products obtained can undergo aulfo additional nation.

   From the monoilnthràquino- niquen balogén4à, one particularly from the cc, -ohloro-

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 EMI12.1
 anthraquinone, one obtains by condensation with don diphinyl- minent by exemplo art, c la. o-, m- or p-phdaylbned1ud.ne,
 EMI12.2
 
 EMI12.3
 6galomoat of the vat dyes according to the invention, which
 EMI12.4
 
 EMI12.5
 contain anthraquinoniquos nuclei and arylanino groups. In addition, leu work dyes can be prepared;

   according to the invention we make rdaair don dye * appropriate vat, which brings to the monk a free minogenous group, on doa Qrylbloa6nuroo ot by introducing a group
 EMI12.6
 solubilizer, when the oolorant thus prepared does not
 EMI12.7
 not a tol groupo solubilizing lid b an aromatic annuity * We can finally prepare the vat dyes conferring to the invention by making reddish% bear dye appropride, 6ventuollomont oxomptu do Arylamino groups and carrying a faoilomont soindablo substituent, for example
 EMI12.8
 in a restaurant of triazino or do pyriaidino, on acids
 EMI12.9
 aminoeulfonic or = incoorboxyliquaup of pretrenoe aroua. ticks, until replacement of the labile substituent.



  The dyestuffs do Ouvo çonformen to the invention, which comprise an oarbazoliquo or oxdiamuliquop nucleus can also be obtained by traaotormation in oorbauoles, according to known methods, for example by transforming sulfoarylaminoantlirimidee into dao orlfoarylaminoanthrimido-carbazolon by means of of concentrated sulfuric acid, or by introducing by dehydratstioa, by

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 EMI13.1
 exemplo au moyon d'doido aulfuriquo concentra or dfoidumo 10 co4to oxdiatoliquo in don rylDinod1enthraqu1nono- oarboxyhydraaldoa, dyontuollemont aroa .ultonGt1oG aooeemi-
 EMI13.2
 aunt.
 EMI13.3
 a dçalomont dçalomont dos dye of bear containing aroupo.

   pure sulfoarylamino cyclination of o-carbQXY- & rylamiDo.ultoGryl1nothrBq1nQne8 or sulfo-arylamizo-1-arylamino-anthraqulnono-'11-carboxylic acids to form aoridonoa, or by treatment with aloalia- subotances of 1-ounino- 2-bromo-aulfoarylaaino- anthraduinonos or 2-amiao-1-ohloroaultoaeylapiaoa.atb.ra- quinoa .., for example at 16o..19p 'in the back solv = te orani-
 EMI13.4
 that @ $ using alkaline metal oarbonatoo to
 EMI13.5
 form the a indantlironon oorr'spondto8.



  Leu dye of the new conformge b6 the invention eonviccoeat tt the dye don matibron los more diverse, such as dea matibros fibrounon eyntlr6tiquoe or natural @ oommo loa 6thora ot oatora oollulooiquoa, leu polyester fibers ("Tdrylene" or "Dacron"), Ion polyamide fibers ("Nylon" oto ..), polyacrylonitrile fibroe ("OrlQn), polyurethane fibers 8, as well as wool and '44 solo and especially in dyeing and 4 printing of matibr4a tsx :

  3- natural cellulose or rjadndr4o @ * Ion 19 nroo6d6 c direct dyeing or rfpulstmant and above all according to the known printing and tould4ao proo4ù4. 1lgr4 their

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 EMI14.1
 solubility * in water, leu dye of oitvo in accordance with the invention comprising at least 4 cores oondeneée together or in soft monk unitdw anthraquinoniquoi give on back fibers pure collulonicluot Io prooddd tointurs in the tank, that is to say 4 by the application in prJdenoe of an alcoholic substance and of an alcohol x6 of the rotation, of the intensity and of the im- proccions which are distinguished by a boane trbe aolidity to the lumibro and a remarkable resistance to the ottoutu6 treatments in the presence of water and anabolic also by a good unison and a good slicing.

   Comparatiroment to oompoada exempta do grotipos sulfoniquoa having an anilido non 8ubatitu <î route (the * coloring comfortion 4 the inflation is distinguished by the fact that they turn from the dyes
 EMI14.2
 which exhibits a surprising resistance to the action of chlorine.
 EMI14.3
 ton tointuros and 1mproDa1oni obtained in this way will rdaiatont 4aaloont to dry cleaning and b6 migration.

   The tinted tinsue can therefore be coated with synthetic resin, for example Co polyrinyl chloride, without the dye migrating into the coating, which is particularly important for the manufacture of artificial leather. according to the invention are easily openable, which does not translate into due applications
 EMI14.4
 economical * and simple.
 EMI14.5
 Lea composed in accordance with the invention @ who carry

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 EMI15.1
 a substituent capable of reacting on the. fiber, can be fixed * in a soft manner on wool and cellulose, while the 8016 or lower weight #ulfoarylaminoanthraquinonet gives great dyes and iapreawiona, especially on wool, silk and suporpolyamidoa.
 EMI15.2
 



  Compared to conventional vat dyes,
 EMI15.3
 those which are in accordance with the invention have the advantage of offering a level mellower and a good trailing in the dye on the apparatus, they do not give a detoxified tint due to a removal of the r5oxycd dye, dull in case.
 EMI15.4
 foaming ot, when dyeing goods
 EMI15.5
 say wrapping, for example, of crossed coils or of knitting on uno euvo a aspo, the Zigaont4tioa which the dyeing of conventional openings require is not necessary for the dye of the invention in vutro, one can use them either. proodds do foulordago rapid silly form of solution and it is not necessary to transform them into fine dispersions for the vonto nor we do pltes epdcialoz # a * which suppresses the iaoonv6nienta quo cola entails (inatality of ptitoa,

   pou8i roe ot nSooaait6 of one or more sanipulations to obtain finely slide show powders).



  Pc more, they are generally very easily cuvablos, support already there. towp 6 eradicated ordinary and obviously by means of mild reduotaura agents. she presents a trbi

 <Desc / Clms Page number 16>

 good solubility in the tank ot give especially on regenerated cellulose viguourouse and very even * tointures, which have the same shade as the corresponding tointuroa on cotton $
In the non-limitative oxomploa below, the parts and for-oont are rounded off, unless otherwise stated, by weight and the temperatures are indicated in degrees oenti- grades * Between the parts on weight ot the parts on volume, there is the same ratio as ontro lo gram and cube oentimbtre.



     EXAMPLE 1
10 portions of the dry dye having the formula are gradually introduced
 EMI16.1
 obtained by condensing 62.6 parts of 1-amino-5-anilidonnthraquinone with 18.5 parts of cyanuryl ohloride in nitrobonzbne and the presence of pyridine at room temperature in 75 parts by volume of 15% oleum of SO3, As soon as a must be taken into

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 EMI17.1
 11 * 4u $ on rorao lo rn6lango in a 400 partion of gimodef on 4dpart lo produced by descent, it is washed with a moluttoix diluted with ohloruro do eodiura until 4 noutrtàlitd and we obohe you.

   The dye ainai uluenu oorroopond tt lu fur ..
 EMI17.2
 mule
 EMI17.3
 
 EMI17.4
 and he dyes the cotton we vat in purple shades 4Olid44, 1 one utility, \ instead of 62.6 part of tO # ino-3-anHldo-ttnthraquinono, the quality indicated in column II of the tnùloau below and Ion DÓr1Túe authrnquinoniquos indicated in column I, we obtain dye analozues aproa a 3ulfonctioa 4imilairo.

   The shades that give these coloring are ind1qu68o in the
 EMI17.5
 column III.

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 EMI18.1
 
<tb> I <SEP> II <SEP> III
<tb>
 
 EMI18.2
 1-ltJIIino-Mi U, lo..an thrQq uinono 62,6 blou 1-ainu-6-antlidu-nntlrayuiaono 6; 1,6 violet t-tnnino-6-anUido-nthTaquinon z violet Z-omino-5-anilicto -anthraQuinono 62.6 violut ..aaoina-6-.ailido-anthraquipone 62.6 violet 1-onina-5-ip-ufttylan, iliAo) -nnthraclui- 65 # 6 violet nono blet% 1-oniino-5 - (o -chloronHidoJ-Mithrftuinona 69.6 violet 1-am1no-4- (1-ncvbtyliDo) -anthr4qulnon. 72.6 blue 1-amina - (2-norhtyloacino) -aathreiduinono 72.6 blue 1 aaino-9- (2- naphthylafflino) ¯ixnthraquinono 72.6 violet EXAMPLE 2 40 parts of the dye of formula are dissolved
 EMI18.3
 (prepared according to Exomplo 1;

   therefore 2000 partiten volume of water and we r & alo the pH to 10.9 by means of 50 parts in

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 volume of normal sodium hydroxide solution @ The mixture is stirred, weighing 6 hours at 70-75, then the sodium hydroxide is added to excess. By salting, the non-reactive and soluble dye can be qualitatively cut in water, which corresponds to the formula
 EMI19.1
 He dyed the cotton according to the procedure indicated in back shades of violet of an exoollonto fastness to the light and to the treatments carried out in the presence of water.

   Under the same conditions, the dyes mentioned in the above table are also hydrolyzed to obtain corresponding vat dyes, which are not soluble.



     EXAMPLE 3
3 parts of the cororant mentioned in paragraph 1, Example 1 are stirred with 2 parts of aniline in 100 parts by volume of o-dichlorobensene, then the mixture is heated by refluxing 20 villages, 0.1 part of the mixture is present. pyridine.



  Allowed to cool, the product is separated by filtration,

 <Desc / Clms Page number 20>

 Wash it first with methanol, then with water and vacuum it $ bobo.



   10 parts of the dye thus prepared are introduced, using ordinary tompdraturo, into 80 parts by volume
 EMI20.1
 dioldum containing 1 'of free SO. Db8 uno prayed nontra lied. this colublo in water, we drink the mdlaztai on ice and we separate the product by filtration, we dissolve
 EMI20.2
 the residue in a dilute sodium hydroxide solution ot precipitated by salting the dye having the formula
 EMI20.3
 
 EMI20.4
 He dyed lo ooton back nunnooa purple *.



  EX11'LL 4 62.6 parts of 1-amino-4-anilido anthraquinono are heated, 700 part in volume of nitrobod8bno 800 in 1 part of pyridine and 22.6 parts of 2,4-diobloro-b. .phda, l-1,3,3-triaeiao spawning 3 hours at

 <Desc / Clms Page number 21>

 160 all shaking and finally another quarter of an hour
 EMI21.1
 more until reflux. After cooling # on .6pGro lo blou dye having the formula
 EMI21.2
 
 EMI21.3
 it is washed thoroughly with a <5tbanol and evacuated under vacuum 70 '.



   10 parts of the dye thus prepared are introduced,
 EMI21.4
 with stirring and b6 ordinary tonpdrature, in 75 parts by volume oleum containing free 131 41803. As soon as a setting is soluble in a dilute solution of sodium hydroxide, the mixture is sprayed with 400 sheets of ice and the dye is separated by filtration, the precipitate is then washed and dissolved in a dilute solution of. hydroxide
 EMI21.5
 sodium can be obtained pure galago lo dye which has become soluble in water. Co-dye toint cotton, settling the process * indicated in example 20, we nuanc @ s
 EMI21.6
 blue of a solidity romorquablo.



  If we use $ instead of phdnyldiohlorotriasiao, 24.2 parts of 2,4-dichloro-6-phdnylmino-193 # 5-

 <Desc / Clms Page number 22>

 triasino and if the dye obtained having the formula
 EMI22.1
 at the same sulphonation, a blue dye soluble in water is also obtained, which dyes the cotton in blue shades * EXAMPLE
Stirred for 3 hours and 150,313 homeland * of 1-amino-3-anilido-anthraquinone in 2000 parts .. by volume of trichlorobansbaopon precence of 5 parts by volume of thicnyl ohloride.

   of 2 parts by volume of pyridine and 102 parts of iaophthalic dichloride. After cooled * knot @ the product is separated by filtration, it is lifted thoroughly with methanol ot the @ echo we ride k 70,
10 parts of the dried dye are introduced into 50 parts by volume of acleum at 15% free SO 3, at room temperature. As soon as a neutralized setting is soluble in water, the mixture is poured onto 300 parts of ice.



  The precipitate is separated, resuspended in an excbe of dilute sodium hydroxide solution, added

 <Desc / Clms Page number 23>

 
 EMI23.1
 ohloruro de aodiun and we iaolo the dye by filtration.



  Lo ooloremt ainai pjrtfpar. 4 answers \ the formula
 EMI23.2
 
 EMI23.3
 and dyed the cotton, according to the method given in Example 20, violet shades of excellent light fastness were given to the pre-watered heat-treated treatments.



  If we use instead of 102 parts of isophthalic dichloride, the quantities iadiqu6oa in column II of the table dao various 41obloruroi dioarboxyliquoa of column 1 and neither we proceed onauito to the aulfonation by stirring of one of the oldumq we obtain dea coloranta similai.
 EMI23.4
 roa.

 <Desc / Clms Page number 24>

 
 EMI24.1
 



  II Carboxylic chloride Parts 0 0 C1-CC-C1 63.5 CI-C-CU -Cil -C-CI 7795 0 CI-C-C33-C-C1 7595 90 "TOT1 0 L ... r Ilo f1 -C -Cl 01-C - / \ - /) - C-01 140 0 0 il rv I C1-C-8 - C-Ci 156 01-CA-0- / ¯ \ -C-CX 148

 <Desc / Clms Page number 25>

 
 EMI25.1
 I II Carboxylic chloride parts ClC- -Clt. - -C-C1 147 0 0 Ol-CQ-ffl1-QC-Cl 148 CO-C1 Co-ci 0-11.11-6 153 0 0 Cl-C- () -, -NN --- c: -C1 229 0 NN 0 Il n Il Il Cl-COC '0 / CO-0-01 217 cl-C- -c-ci 138 C1-C- -C-C1 146 -C-Ci 170 .iaù3' "Cl-C- .Y.Cl i s4

 <Desc / Clms Page number 26>

 
 EMI26.1
 Instead of 1-amino-3-anilido-anthraquinone we can also use the derivative ion & nthraquinone contionade in column 1 of table fi (swearing at the example
 EMI26.2
 1.



  The acid chloride can be prepared beforehand
 EMI26.3
 in lo w8mo réolpient r6ctionnol, eloot-4-say to use it
 EMI26.4
 without the yeolor, the procedure is as indicated in Example 6.
 EMI26.5
 EX3 - :; iPLC 6 8.4 parts of ieophthalic acid are stirred and 8
 EMI26.6
 parts by volume of ohloruro do thionylo laying a half.
 EMI26.7
 houre at 1200 in 150 partio on volume of dry nitrobenzene # one preconco of 0.3 partio of pyridine. The solution is cooled to 80, 31.4 parts of 1-amino-4 are added. phdnylaminoanthraquinone ot the m61Ana8 is stirred for a further 3 hours at 1506. After cooling the product is isolated by filtration, washed with mdthanol and dried at 709.
 EMI26.8
 



  10 parts of the dye thus prepared are introduced
 EMI26.9
 at ordinary temperature in 70 parts by volume of oldun containing 15 free de3o3. After 2 hours, the mixture is poured over 400 parts of Ice cream, the stiffness is separated and
 EMI26.10
 lo washes to neutrality with a dilute solution of
 EMI26.11
 sodium ohloruro, then a le abchu. The water-soluble violet dye thus obtained meets the formula

 <Desc / Clms Page number 27>

 
 EMI27.1
 and he dyes the cotton, according to the curing-dyeing process, in shades of purple and solid.



   EXAMPLE 7
12.6 parts of the dicondensation product of perylene-3,4,9.10-tetracarboxylic acid and 1-aminobenzene-3-carboxylic acid are finally sprayed, the product is suspended in 130 parts of nitrobonsene. soc and 12 partioa of thionylo chloride and 0.5 part of pyridine are added, the mixture is then heated, stirring well for 2 hours at 95 - 100 then another 1 hour at 130 - 135 and finally onooro a domi-boure at 170 - 175.

   The excess thionyl chloride is removed by distillation. 16 parts of 1-amino-4-anilido-anthraquinono are then added to the reaction mixture, the condensation is carried out for 3 hours at 4 120-125, then for 3 hours at 140-145 and finally for another 1 hour at

 <Desc / Clms Page number 28>

 
 EMI28.1
 1700.

   After cooling down to ordinary air conditioning, we filter out the product, wash it with atrobeaubnop then with metlutaol and we empty it @bobo at 90
24 part of the condensation product is introduced
 EMI28.2
 thus prepared in 400 parts of o16um 2% 803, 0.01 h 4 - 8d, then the whole is stirred for a collision, the reverse side is left on the wall of the ice cream is isolated by filtration the free acid of the dye and washed. oelui-oi with water.
 EMI28.3
 The oaeor6 product is resuspended and the pU is rogulated to 8.0 by the addition of sodium hydroxide solution. The first dye is usually left empty.
A pulverulent dye of violet color is thus obtained, which gives a clear solution to water and
 EMI28.4
 dyed the cotton and the skin r6gdndrdo> melon the prooddé indicated,

   we dee nuance ViOlOttOS having do barter good voli. said'. to the treatments carried out in prdeonce of water ot a good slicing trbe. Co dye answers 5 the formula
 EMI28.5
 

 <Desc / Clms Page number 29>

 
 EMI29.1
 If Or utility, instead of the 16 parts of 1-omtao.



  4-anilido-.sathraquinone, 16 part @ of 1¯aaino-9¯anilldo anthraquinone we obtain a dye which dyes the ooton in a shade of burgundy.



     EXAMPLE 8
 EMI29.2
 One agitates by laying a dO! D1-hoU1o and a 1304 43 small 4'ldi 2 "-thiophbnod1orboliquo with 190 parts per volume of thionylo chloride in 2000 parts per volume of trichlorobonzbnop in the presence of 95 part of pyridine.



  The thionyl chloride is removed by distillation on exoaa and the acid chloride solution is added by. ti08 of 1-eraino-tanilido-aathraquinoao, then the mllango is stirred for 1 1/2 hours 1600. We then introduce 63 parts of 1-anino- * 4-'adthoxyanthroquinone and we stir * the whole for 2 hours 1 / 2 to 16t) e, After the oh'oid1..4nDln., The dark red oolorant is isolated by filtration # it is lare with a louse of trichlorobonzbnop then thoroughly avoo of aithmol and it is tied in a wrinkle at 70 '.



   10 parts of the dried dye are introduced into 60 parts by volume of oldum containing 15% free SOO. From
 EMI29.3
 that a prie * neutralia6o is soluble in water, on the back it is lying on the ice. it is precipitated and resuspended in a dilute solution of sodium hydroxide.
 EMI29.4
 sodiun. The dye having the formula

 <Desc / Clms Page number 30>

 
 EMI30.1
 This dye toint the cotton in shades of blue @.
 EMI30.2
 



  MCE LPLE 9 26.8 parts of t-omino-3'-nitreMtthr <tquinou in 250 parts by volume of tl'1ohlol'ob8Ds'ne and 0 # 5 part of pyridine are stirred at 130 for 2 hours with 23, 1 parts - 4-anilidobonsoyl chloride. After cooling @
 EMI30.3
 petroleum ethor is added and the precipitate is separated. In this way 1nitso-5 (p'aailido-bonsoylamiao) anthraquinone is obtained which is usually reduced to a minimum, the amine then binding ocylated with the aid of isophthalic dichloride. to obtain the golden yellow dye below;
 EMI30.4
 

 <Desc / Clms Page number 31>

 10 parts of the dry dye thus obtained are introduced at 3-10 and with good stirring in 60 parts by volume of oleum containing 2% free SO 3.

   As soon as a neutralized setting is found to be soluble in water, the mixture is poured onto 400 portions of ice, the dye is separated by filtration and the precipitate is resuspended in a dilute solution of sodium hydroxide taken in excess, By salting, we can isolate the water-soluble dye, which corresponds to the formula
 EMI31.1
 It dyes cotton on jounes shades with good solidities.

 <Desc / Clms Page number 32>

 
EXAMPLE 10 5 parts of the dye of formula
 EMI32.1
 
 EMI32.2
 (obtained by acylation of 1-asafno-3- (phydroxyaailido) anthraquinone by means of oyhthalic dichloride in aitrebonzbne)

   at ordinary temperature in 35 parts by volume of oldum b. 13% of SC) free. After about a half hour, a required neutralism has soluble in water. The sulfuric solution is poured over 400 parts of galace.
 EMI32.3
 the precipitate is separated by filtration and washed until neutral with a dilute solution of sodium chloride, The dye obtained corresponds to the formula

 <Desc / Clms Page number 33>

 
 EMI33.1
 
 EMI33.2
 and he dyes the cotton on purple nuonoos.
 EMI33.3
 EXAMPLE 11
 EMI33.4
 Was stirred at half an hour and at 1200 an extension of 10.1 parts of anthraquinone-2-carboxylic acid, 3.2 parts by volume of thio10 chloride, 175 parts by volume of dry nitrobenabne, in the presence of 0, 2 part in
 EMI33.5
 volume of pyridine.

   To this solution of acid chloride,
 EMI33.6
 12.6 parts of 1-aiaino-4-anilido-anthraquinone are added to 90 and the suspension is continued for 3 hours at 140-145. After cooling, the product is isolated by filtration, the filter gutO4 is melted with zothanol and the product is stripped empty.



  3 parts of the dye thus prepared are introduced, at room temperature, into 35 parts by volume of oldua at 14 4'SO) free. As soon as a neutralized catch is soluble in water, one verso lo melanac on alaze,

 <Desc / Clms Page number 34>

 
 EMI34.1
 the product is seized by filtration and the mixture washed in dilute sodium hydroxide toluion until the lava water is noutroa. This dye meets the formula
 EMI34.2
 and he dyes the cotton in purple shades *
If we use, instead of 10.1 parts of aid
 EMI34.3
 anthraquiaona-2-aarboxylic, 11.3 parts of '-Amine-onthraquinono-2-ocirboxylic acid, a dye which is more bluish * is obtained.

   Instead of 1-oaino-4-anilidoanthraquiaon one could also use the anthraquinone derivative mentioned in the table appended to Example 1.



  1 ::. '<1: .11..1: 12 One uses, 1 the place of 10.1 parts of cmthraquinou-2-carboxylic acid (example 11), 11.2'i parts of acid 1, 9-iso <tbiaaolonturaquinono-2-oarboxyli (], ue. The dyes obtained dye the cotton in slightly darker shades.

 <Desc / Clms Page number 35>

 



     EXAMPLE 13
At the place of 10.1 parts of aoido anthraquinono- 2-oarboxyliquo (example 11), we witilice 10.5 parts of
 EMI35.1
 pyra olanthrono-2-oarboxyliquo. The dye obtained has a property similar to that of diorite in oxomple 12.
EXAMPLE 14 37.6 parts of 1-araino-4- are suspended
 EMI35.2
 amilido-anthraquinonc-2-carboxychloride finomont pulvdried in 300 partios one volume of o-dichlorobonzbno. The mixture is stirred and a solution of 2.5 parts of hydrazine hydrate in 200 parts is added to ordinary tompdraturo.
 EMI35.3
 tioa of binary sodium hydroxide solution, then the mixture is continued to stir until the reaction is complete.



  Water vapor is distilled off dichlorobonzbno, the hydrazide obtained is separated off and washed until neutral with water, then lo oboho.
 EMI35.4
 



  10 parts of the dry hydrazido are dissolved, while stirring at room temperature, in 75 parts by volume of 23 free SO 2 olum, then briefly heated to 60. After cooling, loosely mixed over ice and filtered off the blue precipitate formed, then washed thoroughly with a dilute solution of sodium chloride.

   The dye obtained corresponds to the formula

 <Desc / Clms Page number 36>

 
 EMI36.1
 
 EMI36.2
 and he tints the cotton on blue shades
 EMI36.3
 Fo '{1: JU> LE t 10 parts of 4-anilido-anthraquinone 2, 1 (N) -bonaaoridono, prepared from 4-oblorGnthra- q.uinonō2,1- (N) ¯bonzaoridono are introduced and aniline or 1 from 4-amino-anthraqulnono-2,1 (N) -benzaorldone and oblorobonseneu in 70 parts by volume of ol6um a 3, by stirring the mixture well. Dba that a noutr11a 'take, have voluble in
 EMI36.4
 water, we treat the product as usual.

   The dye obtained toint the cotton has blue shades
 EMI36.5
 If we noumot to the aullonatioa the 4- (u-naphijrlamino). anthraquinono-2, t (N) -bonzaoridone h la plaoo do la 4¯anilidō antbxaqulnone-2, 1 (N) -bonzucridono, we obtain a dye of
 EMI36.6
 water-soluble vat, which covers the cotton in nuances
 EMI36.7
 16gbromont plus vardfitrr; 4

 <Desc / Clms Page number 37>

 
 EMI37.1
 ) n.:I1L,l :: 16 We choked on rfJUIIJC ot or l1ul tn '10 part @ of 4ibrollloA- \ thn.nth.-ono (Colon.- Imtox .V4 5V.3OO) during OJ bouroo in 230 part% we volume of anillao we presence of
 EMI37.2
 1 part of copper powder ot do 4.5 parts of copper acetate
 EMI37.3
 copper. After rotating, the mixture is poured over with dilute hydrochloric acid, then the precipitate is filtered off and washed with water until completely free.



  5 parts of the sobed dye were stirred in a mixture of 35 parts per volume of free oleum in 15 parts of the sobed dye, until a neutral set was tolerated in water. The oittonu dye answers 4 the formula
 EMI37.4
 
 EMI37.5
 ot he dyes the cotton on back shades purple @.



  EXK.U1.E: 4 155-1600 49.3 parts of Q14 chloride were stirred for 3 hours. Use formula

 <Desc / Clms Page number 38>

 
 EMI38.1
 
 EMI38.2
 Prepared from sodium 1-amino-anthraquinono-6-ultonate and an equivalent amount of tdr6phthali- quo dichloride in N-metbylpyrrolidone, in the presence of 3104 part of i-anino-5-aailido-anthraquinon in 500 parts by volume of arobonzbne ooof to which we added * 1 part of pyridino, then heat lo mdlnn0o finalooont for a quarter of an hour at reflux.

   Aprbo rofroidieuemgntp we can
 EMI38.3
 isolate the dye having the formula
 EMI38.4
 
 EMI38.5
 He dyes cotton in dea mono oc Y101ett ...

 <Desc / Clms Page number 39>

 
 EMI39.1
 EXAMPLE 18
 EMI39.2
 Shaking with a doml-boure and a 12 '- Ijot 1T, 2 parts of w, 3-.tbiophùnvdioarboliguo acid and 26 parts of thionylo obloruro in 700 parts by volume of tiriohlorobeaabne, to which was added 0.5. part of pyridine Aprba cooling to 90% p 72 part is introduced; of 1-amino-5- (31-carboxyanilido) -anthraquinorit and onhigh
 EMI39.3
 
 EMI39.4
 Enooro 3 hours on the 6th at 145-15u * After cooled..month, the dye is filtered off, washed with a louse of triohlorobonabne and evoo metha.avl.

   The oolublo violet dye in water obtained in this way corresponds to the formula
 EMI39.5
 
 EMI39.6
 and he dyes the cotton in shades of violottea having good quality *
 EMI39.7
 soliditdo.
 EMI39.8
 



  Instead of 1-afflino-5- (3'-oarboxyanilido) - anthraquinone, the derivatives 1.6, 1.7 and 1.8 can be used, obtaining the same result. Lo derivative 1.4 analocuo provides

 <Desc / Clms Page number 40>

 a blue colored vat dye which is soluble in water.



   The arboxy group of any aailido can also be found in the para position, in which case dyes having similar properties are obtained.



   The thiophenedicarboxylic acid can be replaced by a dicarboxylic acid or by any dichlorotriasin derivative.



   EXAMPLE 19
10 parts of "Vort Calodon RC" (Color Index N 69855 with ordinary tompdraturo) are introduced into 75 parts by volume of oleum at 15% free SO3. As soon as a neutralized setting is soluble in water, one Torso Mixing on ice, the product was isolated and the residue washed until neutral with dilute sodium chloride solution, then the dye was dried.
 EMI40.1
 

 <Desc / Clms Page number 41>

 and dyed the cotton we cure in Torte shades.



   EXAMPLE 20
Stirred with heating under reflux for 3 hours
 EMI41.1
 a mixture of 45 parts of 1-ohloro-3-bonzoylaalnoanthra quinone, 22.3-parts of m-nitranilino, 16p5 parts of ocrbonato do potassium, 195 part of copper aodtate and 0.6 part of ouivro in 150 t1o on volume of nitro-bonsbne. After cooling the odlango, the product is filtered off, washed thoroughly with methanol and boiled in hydrochloric acid.
 EMI41.2
 diluted.

   We wash the product until aoutrolit6 and we @bobo empty us 4 80,
30 parts of the component thus obtained are stirred in the presence of 60 parts of sodium sulfide for
 EMI41.3
 one hour on the baia-raario in 600 part by volume of alcohol @ We drive off 2/3 of the alcohol ot we twist the solution in 2 liters of water. The precipitate is separated by
 EMI41.4
 filtration, washed a. DoutrAllt4 and it is 4bobbed.



  20 parts of the compound thus obtained, 26.8 per. tics of 1-ohloro-5-bonzoylaminoanthraquinono, 11 parts of potuenium carbonate # 0.7 part of copper acetate are heated by refluxing for 3 hours in 200 parts bones by volume of nitrobonabno. After cooling down, the dye which corresponds to the formula is separated by filtration

 <Desc / Clms Page number 42>

 
 EMI42.1
 it is washed, it melts with methanol and it is dried,
10 parts of this dye were stirred at room temperature at 75 parts per volume of 15% free 303 oleum until a neutralized set was water soluble.

   We vorso lo mix on do la. ice cream and the product is processed as usual. The dye obtained dyes the cotton in bordeaux shades.



  Roofing process;
0.15 part of the dye prepared in Example 1 is introduced into 50 parts of water, then the solution is re-dissolved in a heated solution of 460 of 2 parts by volume of sodium hydroxide solution. to 36 Bé contain 1.2 parts of hydroeulfite in 350 parts * of water.

   10 parts of cotton are dyed in the bath thus mounted for 45 minutes, 12 parts of sodium chloride are added and the tompéroiature dyeing gradually up to

 <Desc / Clms Page number 43>

 
80. After the tointuro, the ooton is rinsed in cold running water until complete oxidation, it is acidified and it is soaped in broth. This gives a bright purple shade with excellent fastness *


    

Claims (1)

EMI44.1 Revendioationa. A-A process for obtaining vat dye, which carries at least one arylamino group ot at least one substituent solubilizing the product in water ot directly linked to an aromatic nucleus, preferably external, is EMI44.2 in particular a sulphonic or carboxylic group, proceeds characterized by the fact that one introduces to the monk a solubilizing group in a dye of tank containing at least EMI44.3 an arylamino group, or that at least one arylamino group is introduced into vat dyes or their intormddiairoa products, thus transforming this introduction into vat dyes, where one chooses the starting materials so that at least one of these materials carries a solubilizing group that is transformed, in the event that your intermediate materials are initially used, these dornibres in dea ooloranta do vat; this procedure can we also present EMI44.4 the particularit6o ouivantent te- on acyl of aroinoanthraquinono s, carrying an aoinogenic croup aoylablo ot an aryl route linked by means of a nitrogen atom ot possibly carrying 5 substitutes, on the aminoabne group acylablo prGoit6 by introducing in the dark or before or after a solubili substituent; nt the product in water, which is linked to an aromatic rent j 2 - the acylation is carried out so as to obtain <Desc / Clms Page number 45> EMI45.1 produced soluble in water, which bringing to the monk two EMI45.2 anthraquinone residues, 3 * - we treat arylaminoanthraquinononscontaining in the monk two anthraquinone rents or a curable system constituted by at least 4 ooadon nuclei on. char, by doa sultonating agents in order to introduce at least one oxilonic group 40. we acylate doa 1 -aaiino-4-, -5-0 -6-, -7- or -8- arylaminolU1thrQ.t1uinunes on the free aminogenic group, we introduce in mdae time before or after a lultont- group EMI45.3 what EMI45.4 50- agents are used as acylating oompoads h <Jt4rooyoli <iuos at least dibaloadude carrying 2 to 3 atoms of aucto in the h6trocyolic nucleus. 69- oor is used. acount of acylation of halo 4- aures of polybaniqueng organic acids in particular dioarboxydiohloruroa rolll4tillu'8 '7. as aoylation agents are used di-triohloro-1, 3,3-triaziaoa or tri- or tdtrochloropyrimi. dinos and we exchange dyontuellemont in the products obtained EMI45.5 doo atoms of chlorine labilos still pre-assembled by reaction EMI45.6 on back aainoa, back aoiea in08ultunique. or acids inoQArboliquo81 84- on cchanso in vat dyes, oomportaat aTantaseuaeoont at least 4 cores condensed together or at <Desc / Clms Page number 46> EMI46.1 minus 2 routoa anthr (ttlutnoni (luen ot a 4ahanQ9 * - ble substituent against an arylaraino group, for example a halocene atom this substituent for example by oondtnsation sno don acidon phdaylaminocultoniquec or n4phtylAmiDo8ultonlquo8 'on 90- haloGein reacted on 90- waidoa dioninobonxbno-sulfoaiqaet to obtain ddiv'8 diontliraquinonyliquosj 10 - according to a variant of prood4, we proobdo L the oarbaxoliuation of eullonrylnmiaonathrimidee to obtain closed Dultonrylainoantlllimidocarbnol'8 according to the known ourd6 aluminum concoction or chloride proodol'8 or we introduce into AryluaiDod1aDihraqu! - nonocarboxyhydraztdo3 by ocianion plump, by oxoaplo aa by means of aoido oulfuriquo concontr4 or 0'oldum, a nucleus dtoxdiAaol coci dvontuoHo [u \. 'ot avqc aulfonation oonoomi- tanto) 11. we oye11.0 o-oarboxyaryluainoaulfoaryl- aainoantlixaquinonoa or utilfoarylamino-1-aryl- a starch: ainocnthraquinono-2-carboxyliquo to obtain batch acridonte or we treat l-aisino-2-brooio-o ltobrulDno-1-aryl- a starch .U: 11DO -'- chloro-sultorJlinoC \ .nthrnqulnono .. by oxomple b 160 - 1904 donated organic solvents by alkaline carbonato3 do m5tnux to form the indsnthroaoe correapondantos) 120- we make a coloring donation of cura comprising <Desc / Clms Page number 47> advantageously at least 4 cores condensed together or at EMI47.1 monk 2 thrnquinon1quoe routes and at least one group = iaoabao free on dos aoideo halog <5nophdnyl- or baloud. nODaphthyluttoniquos or the corresponding carboxylic acids; D - A titro of new industrial products EMI47.2 colourant predpnrda colon lo process vfad under A and more part1oulibrrnont dou ooloranta do Ouve carrying a rosi @ of aromatic hydrocarbon containing possibly EMI47.3 subatituents ot lid via a nitrogen atom ot at least one substituent solubilizing the product in water, which have liu dirootomont to an aromatic nucleus of external preference, especially dyes of the abovementioned type, which contain at least soft roetea anthraquino- niquos or a cuvablo system with at least 4 condensed nuclei EMI47.4 onnetilble as well as an arylanino group, of which the asote atom is not lfaa the h6tdroabno atone of an hdtrocyclic nucleus, the above dyes can be further prJlontQr los lartioularitda 8uiva.ntOOI 13 - they are cunetitude by dos arylaminoanthraquinoncs, which carry a sulfonic or carboxylic group or both 4 at the same time in an anthraquinoniquo ring ot better still in an arylamino group, 14 - they are formed by 4, 5 6, 7 or 8- EMI47.5 arylaminoanthraquinonce comprising the monk's croup -S03i3 <Desc / Clms Page number 48> EMI48.1 and 2 anthraquinoniquos ttatea, lido together by means of a -llll-K-Nli- bridge, X denoting the residue of an organic polybaaiquo 15 acid - they are constituted by acylaminoanthraquinones, containing as acyl residue an annuity of triasin or non-halogenated pyrimidine; EMI48.2 16 - they are represented by acylamiaoantbrs- quinones containing an annuity linked on both sides by the intermediary of a -HH- uno arylAminoanthraqu1oooo bridge, this remainder being that of an organic polybaeic acid and especially of an acid aromatic dicarboxylic 17 * - they are formed by arylamino- derivatives EMI48.3 e.athraquiaoniluoa ot have sweet different anthxaquinoniquoa nuclei, of which at least one port a rump 8ultoa.rylamlno, ' C - A process of painting and printing of toxtilos aolluloaiquoa materials by means of the dyes referred to under EMI48.4 D, more particularly a method of tointuro consisting of using at any stage of the process a reductive agent or an alkaline substance; D - Materials or articles dyed or printed according to the procedure referred to under C.