PL162424B1 - Method for preparation of reactive azo monochlortriazine yellow - Google Patents

Abstract

1. Method of obtaining reactive azo monochlorotriazine yellow of general formula 1, where R means a hydrogen atom or methyl or sulfone group, R1 means a hydrogen, chlorine atom, or methyl or methoxy group, X means one of substituents - CH=CH2, -CH2CH2OSO3H, - CH2CH2OPO3H2, -CH2CH2Cl, -CH2CHCl2, -CH=CHCl, -NHCH2CH2Cl or -NHCH2CH2OSO3H, B means the remainder of general formula 2, where Z means a hydrogen atom or cyanogen or aminocarbonyl group, and R2 means a hydrogen atom or alkyl group containing 1-5 carbon atoms, if need be, substituted with a chlorine atom or hydroxyl, carboxyl or methoxy or ethoxycarbonyl, sulfone, amine or alkyl or dialkylamine group, or B means the remainder of general formula 3, where Y means a methyl or carboxyl group, and Ar means a phenyl or naphthyl remainder containing, apart from other substituents, at least one sulfone group by means of primary condensation of cyanuric chloride with diaminophenylene or toluenesulfonate or diaminophenylenodisulphuric acid, diazotisation of the obtained compound of general formula 4, where R bears the aforementioned meanings, and coupling of the obtained diazotised compound with a coupling component of general formula HB, where B bears the aforementioned meaning, and secondary condensation of produced dichlorotriazine colour with primary amine of general formula 6, where symbols bear the aforementioned meaning characterised in that cyanuric chloride is condensed with diaminophenylene or toluenesulfonate or diaminophenylenodisulphuric acid in the molar ratio of 1:1, the obtained compound of formula 4 is subject to diazotisation in the environment after condensation reaction and, to the mixture after diazotisation reaction, a coupling component in the acid form of paste or powder is introduced.<IMAGE>

Description

The subject of the invention is a method for the preparation of reactive azo yellows of moncoHorotrcaysl pyrazolone or 6-hydrocaypyridos-2 with a general formula of 1, in which R is a hydrogen atom or a methyl or sulfone group, R 2 is a hydrogen atom, chlorine or an mt 2 group: y1 or methoxy, i is one of -CH5CH4,

-CH ₂ CH ₂ 0PC ₃ H ₂ , -CH ₂ CH ₂ C1, -CH ₂ 'CHC1 ₂ , -CH = CHC1, -NHCH ₂ CH ₂ C1 or -NHCH ₂ CH ₂ 0S0 ₃ H, B is a residue of general R 2 and 2, in which 2 is a nitrogen atom or a cyano or annocarbonyl group, and R 2 is a hydrogen atom or an alkane group containing 1-5 carbon atoms, optionally substituted with a chlorine atom or a group hydroxyl, carboxyl, mtol ^^^ - or ethokaycarbonyl, sulfonic, amino or alkyl or dialkyl Sf or B means a residue of general formula 3, where Y is a methyl or carboxyl group, and Ar is a lenyl or saltyl residue containing among others substituents of at least one sulfo group. Compounds with the general formula 1, in which the symbols have the above meanings, are known compounds that are used as dyes, which are chemically bound in the dyeing and printing of cellulose or protein or polyamide fibers.

Known methods of obtaining the reactive dyes in question are described, for example, in the Polish patent description No. 113 110 and in the German patent description No. 2 927 718 or in European patent specifications No. 71 985, 72 557, 172 283 and 182 366. These methods are based on the diazotization of 1-acetyl-3- or -4-aminoph or -disuHnnic acid, the coupling of the obtained di3Zosloo compound with the plazolos-5 or 6-hydroxyplridin-2 derivative, used in the form of alkaline aqueous solutions, hydroUsing the acetylGamino group of the coupling product in acidic environment and successively condensation of the obtained ammonium dye with cyanuric chloride and the secondary condense of the produced dllhlorntraayo dye with an amine containing an aliaayic reactive system with aryl via a sulfone group.

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Other synthesis variants consist in the primary condensation of cyanuric chloride with diaminophenylene sulfinic acid or diaminophenyleneUuenesulfonic acid or diaminophenylene disulfinic acid, diazotization of the obtained dichloro-mayn, ^^^^ ego compound, coupling of the obtained diazonium compound and the secondary Erazolyroron derivative with the secondary 5-hydroxy-derivative component. a condensed dichlorotrythane dye for an amine containing an aliaatic reactive system. Odrnana wymmenionego the above method is the primary marianns C and cyanuric chloride or acid diaminoflnylθnosulfnfowym diamlnotoluerfosulfefowym or acid dlanleofenyllnodlsulfonowym, secondary kondennsaci the resulting compound with an arylamine dichlorotriazyoowegf cllCatyczny system comprising reactive, diazooJcelu o.yrιootzfelgo zwiiązku mofnfhlofooriazynowego and coupling the resulting diazonoowego nucleus with a derivative of 5-pyrazolone or 6-hydroxypyridone-2, used in the form of alkaline aqueous solutions. Another variation of the method consists in the primary condensation of cyanuric chloride with an arylamine containing an aliphatic reactive system, secondary condensation of the obtained dichlo-trlazephic compound with diamiephenyl sulfinic acid or diaminorfluenesulone or with diaminolenylene di-sulfonate or with a diaminolenylenedihydrochlorinated derivative or diaminolenylenedihydrochlorinated compound, 2, used in the form of alkaline aqueous solutions.

The dyes are bleached by exudate or, after adding fillers, stabilizing and / or dispersing and anti-dusting agents, they are dried in a spray dryer.

Known methods of obtaining the dyes moonfClophotelayenic derivatives of pyrazolone-5 or E-hydroxypyridone-S are, however, difficult due to the willo-effect nature of the synthesis process, the concentration of the dye produced in the reaction mass is relatively low and the purpose of isolating the dye by drying the reaction mass in a spray dryer is economic problematic. In addition, moonfClorotriazine dyes are often contaminated with by-products that repeat in the conjugation process, making isolation of the dye by salting out and filtering a necessity.

In the case of azo dyes, moonfClofoterayene derivatives of pyrazolone-5 or E-hydroxypyridone-S, complete dissolution of the above ^^ and ^ m ^ and ^^ passive components in an alkaline environment before the coupling process was considered a necessary condition for the proper course of the coupling process . Therefore, in the coupling methods known hitherto, the alkaline solutions of the inactive components were always prepared separately, and the acidic diazonium compounds were gradually introduced into the alkaline solutions of the inactive components.

It has surprisingly been found that the coupling reaction of a diazo-coupling of the general formula 4 or 5, in which the symbols have the above meanings, with pyrazolone-5 derivatives or with 6-hydroxypyridone-2 derivatives can be carried out in the presence of hydrotropes and optional surfactants, using the following defined methods. passive components in their acidic forms added to the diazonium compounds in the form of pastes or powders, after thorough mixing in an acidic environment and increasing the pH of the reaction mixture above 4.

The process of the invention produces reactive azo yellows of the general formula I, in which the symbols have the above meanings, by primary condensation of cyanuric chloride with diammophenylene or rolesulfoic acid or diaminofmylenedisUonic acid in a 1: 1 molar ratio for the diazotization of the resulting compound of general formula 4, in which R is as defined above and the coupling of the obtained diazonium compound with the inert HB, in which B is as defined above, and the secondary condensation of the produced dichlorotriazene dye with the atylamiene of general formula 6, in which the symbols have the above-mentioned meanings.

In this way, after the diazotization reaction, the passive component is introduced in the acid form of a paste or powder, and a hydrotropic agent, such as mofca, thiourea, caprolacMi, etc., and optionally a surfactant, such as e.g. , sodium salt of dibutylnaf ^^ ηοεα ^ nnowega, known as Nekal 3X, sodium salt of condensed in-induced aromatic sulfonic acids, known as Dyspergator NNO, polycondensation products of ethylene oxide,

162 424 known as Polikoli, condensation products of ethylene oxide with phenol derivatives, known as RokatenoH or condensation products of ethylene oxide with oleic alcohol derivatives, known as Rokandi, are mixtures of these agents and after thorough mixing in an acid medium, the pH of the reaction mixture is above 4 until the coupling reaction is completed by the gradual introduction of a solution of hydroxide or carbonate, or preferably sodium bicarbonate, or sodium or potassium salts of ethyl alcohol or polyphostoric acid, and condensation of the resulting diacetric acid dye, after optional separation from the reaction mass, with an arylamine with a total value of 6, which symbols have the above-mentioned meanings.

The process according to the invention produces reactive azo yellows of the general formula I, in which the symbols have the above meanings, also by primary condensation of cyanuric chloride with dlcmlmophenylene- or -toleslsulpholic acid or diaminophenylesodisulphoic acid in a 1: 1 molar ratio of the secondary conduit of the general formula formed by the compound 4, in which R is as defined above, with an arylamine of the general formula 6, in a molar ratio of 1: 1, in which the symbols have the above-mentioned meanings or by the primary route of cyanuric chloride and arylamine of the general formula 6, in which the symbols have the above the meanings given, the secondary condensation of the resulting dichlorotriazinic compound with diaramophenylene or -lolsosulfonic acid or diamlnophenylenediulphonic acid in a molar ratio of 1: 1 diaalvum of the compound obtained by one of the above methods of the compound mooslClorotrhase with the general formula 5, in which the symbols are a diazoselic compound with a passive component of the general formula HB, in which B is as defined above.

In this way, after the diazotization reaction, the passive component is introduced in the acid form of a paste or powder and a hydrotropic agent, such as Mlznsk ₁ thiourea, caprolactam etc. i iw ^ i ^ Si ^ £ ^ 1s: Łi the above-mentioned surfactant is a mixture of these of agents and, after thorough maturing in an acidic environment, it increases the pH of the reaction mixture above 4 until the coupling reaction is completed by the gradual introduction of a hydroxide solution or in 1, 2, 2, 3, 4, 3, sodium, sodium, or sodium salts or potassium orthophosphate or semi-soluble acid.

Moonlhlolotslazine dyes are separated by shaving sodium or potassium chlorides, deflicking the precipitate, atablilowαsle, after possible addition of fillers and anti-dusts, and dried. However, it has been found that it is more advantageous to isolate the product by drying the moosyllotyllazine dye in a spray dryer after the reaction mass. Drying of the post-reaction mass in su ^^^ rn :! The spraying can be carried out after adding an anti-aging, stabilizing, especially anti-dusting agent to this mass.

Some stabilizing agents can be used, for example: a mixture of mono-and disodium orthophosphate or disodium monosodium orthophosphate, sodium hexamaphosphate, known as polyphos or urine (.

The dispersing bacon can be used, for example, disodium salt of dlsaphthalnometasodlsulphonic acid, known as Nf / O dispersant, a by-product of cellulose production by the sulphite method, in which the salts are soda soda ash, known as lignin sulphonate.

I can also use agents based on mineral or organic oils, e.g. a mixture of spindle oil with a greasy emulsifier, known as Olan G. It is advantageous to use a dispersant or an anti-dusting agent, for example SBO, along with a dusting agent.

When stabilizing and dispersing agents have been used in primary or secondary condensation or coupling processes, they need not be added prior to the spray drying process.

The condensation of cyanuric chloride with αlαm.nofem / leno- or -toUesπosullsoic acids or with arylamines or with arylamines is carried out in a known manner, using the starting compounds in a different ratio in an acetone-aqueous medium or preferably in an aqueous medium .

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Oako diaminophenylene or -toluenesulfonic acids or diamlnophenylanedisulfonic acids are used, for example, 1,4-dlamlnoienylβnon-2-sulfonic acids, 1,4-diaminolenylan-2. S-disumonic,

1,4-d iamino phenylen-2 ^ -disumone, 1,3-d lamino phenylene-4-nriic, 1,3-dia-iooieoyleoo-4,6-disumino, 1 ^ -diamine N-Methylbenzene-S-sulfonic acid, 1, N-methylbenzene-S-sulfonic acid, 1,5-diaminn-6-methylbenzene-S-sulfonic acid, or 1,3-diamino-6-matylbeosane-4-sulfonic acid.

□ aco arylamines, containing an aliphatic reactive system bound to aryl via the -SOg- group, used for primary or secondary coronary! the following are used: 1-ammobenzene-S-sulfate losulfon, 1-aminobenzane-2- or 4-β-sulfate tylsulfone, 1-aminobenzene-S-vinylsullon, 1-aminobenzene-2- or -4-vinylsullon, la-ioobenzene -m-tonsy-3 - ^ - sulphate butylsullon, l-aminobenzonon4-mθUonky-3-wlioto ^ uUlnn, l-amlnobunzuno-4-mutyln-3-β-ethylsulphate, l-amlnobunzuno-4-meuγoton - ullnyt. l-amlnobunzθnon2-mθUyto-4- β-sulfur chanoethylosHon, l-aminobθnzθπnn22meUyton4-wlnylo3ulloo, l-aminobunzθno-2-mθUoksyt4-β-sulfur-chanostylsullon, l-aπnobunosullo-l-aπnobunosullon Methyl-4- β-tetranoethylsulfone, l-amino-2-mθtok8yt5-ιnθUyto-4-vinylsullnn, l-aminobenzene ^ -chlorine-3-wloylnsumon, 1.- ^ minobene ^ and ^ r ^ oo - ^ - β -chlnroethylsullon, l-amioobenzθnon3- β, -dichlornethylsulfoo, l-aminnbunzenon-3-β -chloroin IosuIIoo, l-amlnnbenzθnon4-mθUyto-3- β, β -dichytolmethylsulfone, l-4 β-aminobunzenchloro-l-4 β-aminobunzenchlorine ^ -chloro ^ - β-chloro-chloroγlosullnn, l-aminobenzene ^ - β -f osf OΓanne tylnsullno, 1-araionbunzuoo-3- β-chloroethylamidosullon, l-aminobuozeno-4- β-chlorornethylamidoθullnn, l-aminobenzene-4- β-sulfate ^^^ midosul.lon.

When the condensation reaction is carried out in an aqueous medium in the presence of surfactants, it is not necessary to use additional amounts of the aqueous agent in the coupling process in the coupling process.

□ As passive components defined by the general formula HB, in which B has the above meanings, for example, the following are used: 1-ethine-33-caramyl-4-methyl-6-hydroxypyridine-2,1-methyl-3-carbamyl-4-methyl-6 -hydroxypyridone -2,1-ethyl-3-cyano-4-methyl-6-hydroxyplridone-2,1-ethyl-4-methyl-S-hydroxypyridone-2, 1- / β -hydiOl ^^^ eet ^ 11 ^ - ^ S- ^ t ^^^ ηα ^ -π ^ tyl-e-hydroxypyridone-2, 1- (β-hydroxyethyl) -3-carb-yl-4-methyl-6-hydroxypyridone-2, 1- (y3-methoxyethyl) -3-cyano- or -3-carbamyl ^ -methyl-6-hydroxypyridone-2, 1- (y5-utnxyβtyl) -3-quarbammton4-m-uyto-6-hydroxyplridone-2,1-caboxy-euyl-3- cyJaoo- or N -carbamyl-N-methyl-N-hydroxy-pyridone-2,1-cyclic-3-carbonyl-2-methyl-6-hydroxy-pyridone-2,1-isoppyl-3-carbamyl-methyl -o-hydroxypyridone-2, 1- (N -carboxypyridone) -3-cyano- or -3-carbammyo-methyl-S-hydroxypyridone-2, 1- (β-milkyneUyl) -3-cyano- or -3- carbam ^ -4- ^ -yl-6-hydroxypyridone-2, 1- (N, N-diethylaminoethyl-Z-S-kabbamyl-4-methyl-^ -hydroxypyridone-2, 1- (beta -chloroethyl) -3- cyano- or ^^ θ ^^ υΙο ^ -πο tylo ^ -hydroxypyridone ^, Χ / β-suIIoutyl / ^ - ^ 3-cy aano- or -3-carbamyl ^ -methyl-6-hydroxypyridone-2, 2, 6-dihydroxy-3-cyano- or -3-carbam'oyl-ms-tylpyridine, 2,6-dihydrocay-4-methylpyridine, 1- (4 * -sulfolenyl) 33-trbokayplrazin-5, 1- / 4 '-sullnleoyln / -3 - ethylpyrazolone-S, 1- / 2' chloro-4'-sullolen-butyl opyr ^ c ^ sol ^ on-b, 1- / 2 ', 5' -dichlorn-4 ' -suif oUenylo / 33-mu tyloρiraznlnn-5,

1- / 2'-chlorc-S '-sulfophenyls ^ ZS-methylpyrazolone-S, 1- / 2'-r-1nro-5'-sumpyl / 3-larbokayplraznlnn-5, 2- / 4', 8 &quot; Dssumoloyl / 33-methylpyrazole-5 and 2- / 4 ', 8 ' -disulfoaphthyl) -3-prroxyplrazole-S.

As a result of the uposnbe-conjugation process according to the invention, the omnoronotriazine dyes are obtained in high yield and with a high degree of purity. The flax method makes it possible, compared to the known methods, to obtain mononnr-oΓotolayon dyes while limiting the amount of apparatuses used in known methods, and thanks to the elimination of the dissolution process of the passive component, this method reduces labor and shortens the dye production cycle. The coupling reaction in the method according to the invention takes place with the participation of diazonium cathions, and its result is determined by the appropriate selection of components. During the trials and tests, it turned out that the conjugation process of the active and passive components with the addition of hydrophilic agents, which is a new combination of the used substrates and possibly surfactants, does not require pre-treatment at low pH and the presence of acid products mixed reagents.

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The actual coupling process begins as the pH value increases, and the hydrotropic agents used increase the solubility of the ingredients and the resistance of the reactive system to hydrolysis. The coupling reaction starts in the low pH range, where the hydrolysis of the active chlorine atom in s-traazine is less than 3: 3, and the decomposition of the diazonium compound is practically imperceptible, resulting in high purity and high chemical yield of the dye. The use of hydrotropic agents and surfactants in the method according to the invention improves the rheological properties of the reaction mass in the coupling process, which allows to increase the concentration of the reagents used, thanks to which an increased equipment efficiency and a significant acceleration of the coupling reaction are obtained, and the dye production process can be carried out in a non-corrosive manner. . The poor resistance of the active ingredient, under the conditions used, to hydrolysis and decomposition of the diazonium group, as well as the increased rate of the coupling reaction allow the process to be carried out at temperatures higher than those used so far, which makes the coupling reaction heat more efficient to accelerate the course of the process.

The produced dyes, thanks to having two reactive systems in the molecule, are distinguished by a high degree of bonding to the fiber.

The invention is illustrated by the following Examples in which parts and percentages are parts and percentages by weight and degrees of temperatures are in degrees Celsius.

Example I. For a suspension of 9.25 parts of cyanuric chloride in 100 parts of water,

100 parts of ice and 0.1 part Nekalu BX rapidly added 13.4 parts of 1,3-diaminof confused 5-disuHnoowego dissolved in 200 parts of water and 4 parts of sodium woddrorlen ^{k. SIU} mixture was stirred for ¹ ~ ² hours at ^{O-50 A} C keep the ^pH environment of about 5. After piecwszorzędoweJ KMT ^^ maajj. 15 parts of 30% hydrochloric acid are added to the reaction mixture and then diazotized, 3.5 parts of sodium nitrite dissolved in 15 parts of water are introduced. About the produced Zlazonrow compound, 3 parts of sea water, 2 parts of NNO Dispersant are added and then 10 parts of 1-ethyr-33caBraamyl-4-netyl-6-hydroxypyridol-2 are added in the form of 40% pellet. It is mixed thoroughly in an acidic environment, and then the pH is raised to 7-7.5 by adding sodium carbonate solution. After the end of coupling to the obtained dye solution, dlchloΓolrlazloowegr is added to 14.5 parts of dichloroethyro33-n-mlnofrlylsulron hydrochloride dissolved in 100 parts of v / v, the whole is heated to 35-40 ° and the sodium hydroxide solution is added dropwise to the reaction mixture, keeping the pH of the reaction medium within the limits 6.5-8. After the completion of the secondary condensation and vinylation process, the mixture is neutralized with monohydrate phosphate to a pH of 7-7.2, the dye is removed with sodium chloride, filtered and dried. The produced mornoClorotriazine dye dyes polyamide fibers, lamellar and cellurozoor, yellow with a green shade. Wyalwoβnla are characterized by high luminosity and very good lightfastness L factors mol <re.

Example II. The procedure described in Example 1 is followed, replacing 1-ethyl-3-carbamyl-4-methyl-β-hydroxypyridone with an equivalent amount of 1- (2 ', 5' uhlon-i'-sulfophenyl) -3-methylpyrazolone- 5. A moonr-chlorotinazine dye is obtained, which is suitable for printing and dyeing articles of the kind to be yellow with a shade less green than the shade of the dye obtained by the method described in Example 1.

Further examples of the preparation of dyes by the method according to the invention are given in Table 1. The synthesis of dyes consists in the condensation of cyanuric chloride with the dLamna given in column 2, diazotization of the obtained moonrkrndrlacJl products, coupling of the obtained Zilzrlloo compounds in the presence of a hydrotropic agent and possibly a surface active component with the passive component given in column 3 , dodαo / anyn to the diazollooego of acid L kondensaccji prepared dye dichloro ir iazy of cwwego with the amine in column 4, wherein at (ji ^ f ^ dkLi use ^{a d} dru ^ y ^ of this krndensaα ^J l ι ^. ι? and derivative ³ , / 5 - ^d lc ¹ lrrortylos ^^ ^- nu A free reaction is carried out simultaneously with the condensation process.

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Table 1

Example □ lamina Passive component Amine 1 2 3 4 III 1,3-diaminophenylene-4,6-disulfonic acid 1- (5-hydroxyethyl) -3-carbamido-4-methylUo-6-hydroxypyr- don-2 β-halogen-3-aminolenyl sulfone IV jl-halogen Uo-3-amino-4-meeylphenylsul- l he V 1- (4'-sullolenyl) -3-carboxypyrazoUon-5 VI 1,3-Diaminolenylene-4'-deionic acid 1- / 4'-sullolenyl / -3-carboxypyrazo- Uon-5 ^b enzeno -Amino-3- 5 -siarczanoetylosulfon VII 1,3-diaminolene-4-suUoic acid VIII U-aminot) enzene-4- β-sulfate ethylsulfone IX U-amln-btnzθno-4-olny- Uosulfone V 1,4-diaminolenylene-2-sulfonic acid XI 1-ethylo-3-carbamido-4-methylUo-6-hydroxypyrydon-2 - XII U-amin-btnztno-4-mθty ^U o- ³ -β -c ^hU oroet ^y losul lon XIII 1,4-diaminolenyUene-2,5-disionic acid 1-Aminobenzno-4-mstoxyn-β-sulfate uosulfone

Example XIV. A solution of 26.8 parts of 1,3-phenylenediamine-4,6-disulfonic acid dissolved in 300 parts of water and 8 parts of sodium hydroxide is added to a suspension of 18.4 parts of cyanuric chloride in 300 parts of water at 2-5 °. Condensation is carried out at 0-1.0 ° C ^while maintaining the pH in the range ^5-6 by gradually introducing sodium carbonate solution into the reaction mass. After completion of the primary kondenssaji to the reaction mixture are added 28 parts of l-aminobenzenn --- / 3-sulfatoethylsulfone and heated ^{to a temperature} eratury ^{shaft 2} 0- ^- 0 ^for maintaining the ^{pH of the} mixture in the range of 5-6 ^by molten d ° d ^and Wani solution of sodium carbonate. Kondennsaci secondary process is monitored by chromatoggaflcznę and after noting its completion, and neutralization of the reaction mass is added 6.9 parts of sodium nitrite, and then, after cooling - rapid 110 parts of 10% hydrochloric Vasu ^{k. p} Reces diazotization of ^p rowadzi ^SIU at ⁰ -5 ° C. For formation ^{of the} n ^eg of the bond ^{at the} diazonium salt is added 10 parts of thiourea, 1.5 parts of wetting agents SBO and 18 - parts of 1,4-dimethyl-3-aabaamylo-6hhydroksypirydonu-2 in the form of a dry powder, and after thorough mixing in an acidic medium raises the pH of the reaction mechanine to 7-7.2 by adding disodium phosphate. The MnocClooctnasin dye is isolated by drying the reaction mass in a spray dryer. A light golden powder that dyes cellulose and polyamide fibers and the skin a greenish-yellow is obtained. The dye is characterized by a high degree of fiber bonding and a high degree of exhaustion from the dyeing bath.

Example XV. The method described in Example 14 is followed, replacing the thiourea with an equilibrium amount of mooznik or caprolactam. A dye is obtained which is identical to the dye smoked by the method described in Example 14.

Example XVI. To 9, - parts of cyanuric chloride in 100 parts of water, 100 parts of ice and 0.1 parts of Moisturizer S80, a solution of 14 parts of i.-aminophenzene-A- ^β- ethyl sulfate in ²⁰⁰ parts of water is added. ^K Jnr ^^ ^^ n cJ runs ^{it SIU} at? ¹ ° ^{0 o t} o maintain ^{the pH of} the reaction mass in ^g ranicac ^{H 4} - ^{5 p} slaughter stage (adding 20% sodium carbonate solution, or by slowly introducing dry sodium bicarbonate. After confirming completion of the primary condensate reaction, a solution of 10, - parts of sodium 1, - phenylenemnnnn4-sulfonic acid sodium salt in 100 parts of water is added to the reaction mass and the mixture is heated at 20-25 ° for --4 hours, until the secondary condensate is complete. . the mixture is then cooled with ice to a temperature of 5 ^{s 10%} solution of sodium neutralized to ^{pH 7,} 2 ~ ^{7 5} (added ^{- "rts 5} parts of sodium nitrite and 13.0 parts of concentrated hydrochloric acid. the process is carried out in diamwama tempe ^d ^^ sculpted ¹⁵ °. ° formed on CONCERNING ^ u ^{n d} iazon owrgo ^{d j} young es ^{IE 7} parts ureas ^k a and 8.8 parts le 6hhydroksypirydonu methyl-2-paste form, are mixed thoroughly in an acidic medium, and then it raises the pH of the reaction mass to 6-7 by adding ca. sodium carbonate. After the coupling process is completed, the monnnClonotylasein dye formed is salted out with sodium chloride, the precipitate formed is filtered off and dried in a vacuum dryer. The result is a dye with very good solubility in the reels, which dyes the cellulose fiber in a slightly alkaline environment yellow.

Example XVII. Oo 1,2 parts of sodium 1 - f eπylenodlamlnon4,6-disuHonowego at 4O ⁰ part ^rts ciac ^{h y} ochłodrnne water ^and the temperature 0 ° ottoło young ^j e ^{d 0,} d ² parts ^rts Nekalu and 18 BX ^ parts of ^Cyanuric Flork. CELO ^SC vesa ^SIU at ^0-5 ° for 2 hours, while maintaining the pH value of about 5 by gradual addition of sodium carbonate. After completion of the primary kondennaaci the reaction mixture is added 18 parts of 4 l ^{of -an} nbrπzenon.Ίnylosul one and ^{f -} czędci dispersant NNO, heated to a temperature of ^-5 ° C and -40 kondennsaci secondary process at a pH of 6-7, obtained by gradual addition of a solution of sodium hydropneumonia. The prepared product by mooooClonotolazynowy ^to Dani ^an ice cooled ^{SIU d} of trnperatua ^{y 0} - ¹⁰ °, ^d e ^j young man ^{rts -0 -0%} hydrochloric acid ^and di ^ kissing by entering 7 parts of sodium nitrite in portions -0 water. After completion of the diazotization process, 5 parts of monocock, 16.8 parts of carbamyl-4-methyl-6-hydroxy-plido-2 as a paste are added, thoroughly mixed and the sodium carbonate solution is introduced until the pH is 7-7.5. The porous mooonClonotnlazine dye is released into sodium chloride, the precipitate formed is filtered off and dried. The obtained dye dyes the target fiber reactive yellow.

Further examples of the preparation of dyes by the process of the invention are given in Table 2.

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The dye synthesis consists in the primary condensation of cyanuric chloride with the diamine given in column 2, then - on the secondary condensation of the produced dichlorotnasino compound with the amine given in the column 3 or on the primary condensation of the cyanurate chloride with the amine given in the column 3 of the secondary of dichlorotriazin with the diamine given in column 2, the diazotization of the resulting monochlorotΓCayyo compounds and the coupling of the obtained diazonium compounds in the presence of a hydrotropic agent and optionally a surfactant with the inactive component given in column 4. The obtained colored fibers, containing two reactive systems, dye cellulose and polyamide fibers, we and wool to yellow.

Table 2

Example Olanina Amine Passive component 1 2 3 4 XVIII 1,3-for-inophetyylene-A-sultonic acid 1-anlnrbsyzeno-4- ^ 5 siαrczayretylrsulfone 1- (4 ' -sulfony enyl) < 4 &gt; arboxypyrαzolry-5 XIX l-anlnrbsnzenor3 - $ phosphate ethylsulfone XX l-aminobenzene-S- β-chloroethylsulfone XXI 1,4-diaminophenylene 4 -suloic acid ; xiii 1-aminobsyzsno-4- (S-sulfanethylsulfone) 1- (2 ', 5'-dichloro-4-sulfophenyl) -3-methylpyrazolone-5 Xxiii 2- / 4 ', 8'-dieulfonaphthyl / -3-methylpyrazo- lon-5 XXII 1-etyl-3-aarbanyl- -4-methyl-6-hydroxypyridm-2 XXI 1,4-dlamlyofsnylene 4-sulfonic acid l-amlnobsnzsno-3- / 3 ~ -sulfateethylsul- phonamide N-ethyl-1-carbamyl-4-methyl-6h-hydroxypyridone-2 XXVI 1- ^ diaminofenyleno _4-l 6-dtsulrnrowy χχνι 1-aminotanzene - ^β- sulfate ethylsulfone

162 424

continued array

1 2 3 4 Xxviii ~ ^{1/5-H YD} roksy-3-carbamoyl-4-methyl-6-hydroxypyrid-2 XXIX 1,4-dimethyl-3-cyano-6-hydroxypyr- don-2 XXX 1,4-dimethyl-3-carbaryl-6-hydroxypyr- don-2 XXXI l-amino-4-methylbanzene-. /S-dichJ.oro- ethylsulfone

162 424

ΗΖΟτί

CH _S Yr ^of hoanao 1 Ar u z ór 2 AZÓrS £ £ tN-C ^ r ^N FLj) - -NN-C N and χγν ^X N = C 50.H 'and

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kuor 6

Publishing Department of the UP RP. Circulation of 90 copies

Price: PLN 10,000

Claims (3)

Patent claims 1. The method of obtaining reactive motothlototriazine azo yellows, the general formula I, in which R represents a hydrogen atom or a methyl or sulfone group, R 2 represents a hydrogen atom, a chlorine atom or a methyl or methoxy group, X represents one of the substituents -CH = CH ₂ , -CH ₂ CH ₂ 0S0 ₃ H, -CH ₂ CH ₂ 0P0 ₃ H ₂ , -CH ₂ CH ₂ C1, -CH ₂ CHC1 ₂ , -CH = CHC1, -NHCH ₂ CH ₂ C1 or -NHCH ₂ CH ₂ OSO ₃ H, B represents a residue of the general formula where Z is a hydrogen atom or a cyano or aminocarbonyl group, and R2 is a hydrogen atom or an alkyl group having 1-5 carbon atoms, optionally substituted with a chlorine atom or a hydroxyl, carboxyl, methoxy or ethoxycarbonyl group, sulfonic, amino or alkyl- or dialkylamino or 8 is a residue of the general formula III, in which Y is a methyl or carboxyl group, and Ar is a phenyl or naphthyl residue containing at least one sulfonate group along with other substituents, via the primary conductivity of cyanuric chloride with with diam.nophenylene or -toleotosulfotic acid or diamino-pheoylene sulphonic acid, diazotization of the obtained compound of general formula 4, in which R is as defined above, and coupling the obtained diazono compound with a passive component of general formula HB, in which B has the above-mentioned meanings and secondary the condensation of the resulting dichlorotriazole dye with the primary a single amine of the general formula 6, in which the symbols have the meanings as defined above, characterized in that the cyanuric chloride is condensed with dlamlotfeoylen- or -tolueneonosulfonic acid or diamlnofloylenodlβulfooov. ^, White in a molar ratio of 1: 1, is diazotized resulting compound of formula 4 in the environment after the reaction ktπdeπoscJi and to the mixture after the diazotization reaction introduces inert ingredient in the acid form of paste or powder and the center of hydrotrope such as mozr ^ ók and lwenoualnil surfactant and then, after thorough mixing in an acidic environment, it increases the pH of the mixture above 4 until the coupling reaction is completed, the resulting dye-dizhtro-tarzonooy condensate, after optionally removing it from the reaction mass, with a primary amine of general formula 6 and releasing the finished dye in a known manner by spray drying or after adding fillers, stabilizing and / or dispersing and anti-dusting agents, using a spray-drying agent such as 2-ethexy J-Sufo-succinate, Sodium salt of dibutylfealoosultotowlgt acid, sodium salt of condensed multi-core aromatic acid / acid pollen products sacZl of ethylene oxide, condensation products of ethylene oxide with phenol derivatives or condensation products of ethylene oxide with olefin alcohol derivatives or m.esraoinc of these flavors. 2. Specification of the basic compounds of the first year of formula 1, in which R is a hydrogen atom or a methyl or sulfone group, Rj is a hydrogen atom, chlorine atom, or a methyl group or a nttoxide group. X is one of the radicals -CH = CH2 "-CH 2 CH ₂ 0S0 ₃ H,? CH ₂ CH ₂ OPO ₃ H ₂ -SHoCK O1, -CHoCHC1 _2, -CH = CHC1, or -NHCHoCH ₂ OSO ₃ H, 3 is a residue of the general Y (or 2), where 2 is a hydrogen atom or a cyano or aminocarbonyl group, and R2 is a hydrogen atom or an alkyl group containing 1-5 carbon atoms, optionally substituted with a chlorine atom, or a hydroxyl, carboxyl group, methoxy- or ethokycka-btnyl, sulfonate, amine or alkyl- or dialkylounnoic (or 3 is a residue of the general formula III, where Y is a methyl or carboxyl group, and Ar is a phenyl or naphthyl residue, containing at least the least one sulphone group, by August ^{^} ^ wyrorr ędtweu kondensseci ^ cyanogen chloride with an acid or dlamlnoflπyllno- -toZeotyzulfotowyl or dlamioofloclentdlsultntowym, druotrrędtweu kondeπosazi formed compound of formula 4, wherein R is as defined above, with plBΓVJyrorzędooą amine of general formula 6, in which the symbols have the meanings given above or by the primary / primary condensation of cyanuric chloride with a primary amine of general 6, secondary condensation of the obtained dichlorothiazinic compound with diaminophenylene or -to-luenesulfonic acid or dlamlnophenylpodsulfonic acid, diazotization of the monosulfonic compound of the general formula 5, obtained by one of the above-mentioned methods, in which the symbols of the obtained compound have the meaning and the meaning given in the formula 5 a reactive component of the general rn and rH of HB, in which B is as defined above, characterized in that cyanuric chloride is subjected to a 1: 1 molar ratio of primary condensation with dlaminofesylesn- or toluenesulfinic acid or diamlsolesylesodi8ulfsnooye, and then subjected to the compound formed by Formula 4 is subjected to a 1: 1 molar ratio of secondary condensation with a primary amine of 6 to 6, or cyanuric chloride is subjected to a 1: 1 molar ratio of primary co-condensation with a secondary amine of 6 to 6, and then subjected to the resulting compound molar ratio of 1: 1 molar secondary condensation with acid diaminoph eny leno- or -tl ^ ι ^^ nosulfnlM ^ i ^ e or diamlnllesylenldsulnoic, and then the compound of formula 5 obtained by one of the methods defined above is diazotized, the mixture is introduced into the mixture after the diazotization reaction in acid paste or powder form and a hydrotropic agent , such as nk, thiourea, caprolacam and possibly a surfactant, and after thorough mixing in an acidic medium, it raises the pH of the mixture above 4 until the coupling reaction is complete, and the finished dye is ironed in a known manner by salting out or after adding the agents of wyppema spreading, stabilizing and / or dispersing and anti-dusting spray dries, where the surfactant is an agent such as 2-ethylhekayl sulfuric acid, sodium salt of dibutyl sulfuric acid, sodium salt of condensed olelecenic acid products, aromatic polydisulfonic acid products condensation of ethylene oxide with phenol derivatives or k-products ondθnsaaJl ethylene oxide with oleic alcohol derivatives or mixtures of these agents.