PL162423B1 - Method for preparation of reactive azo yellow - Google Patents

Abstract

Method of obtaining reactive azo yellow of general formula 1, where R means a hydrogen atom or methyl or sulfone group, and B means the remainder of general formula 2, where X means a hydrogen atom or cyanogen or aminocarbonyl group, and R1 means a hydrogen atom or alkyl group containing 1-5 carbon atoms, if need be, substituted with a chlorine, bromine atom or hydroxide, methoxylene, ethoxylene, carboxylene, methoxy - or ethoxycarbonyl, sulfone, amine or alkylamine 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, if need be, apart from other substituents, at least one sulfone group, by means of condensation of cyanuric chloride with diaminophenylene or toluenesulfonate or diaminophenylenodisulphuric acid, diazotisation of obtained compound of general formula 4, where R bears the aforementioned meanings, and coupling the obtained diazotized compound with a coupling component of general formula HB, where B bears the aforementioned meanings 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 post-condensation environment and the coupling compound in an acid form of paste or powder and hydrotropic agent, such as urea, caprolactam and, if need be, surface-active agent such as 2-ethylhexyl sulfosuccinate, sodium dibutyl naphthalene sulfonate acid are introduced to the mixture after diazotisation.<IMAGE>

Description

The subject of the invention is a process for the preparation of reactive yellows of azo derivatives of pyrazolone or 6-hydroxypyridilSl-2 of the general formula 1, in which R represents a hydrogen atom or a methyl or sulfonic group, and B 1 is a residue of the general formula 2, in which X represents a hydrogen atom or a group cyano or aminocarbonyl, and R5 is hydrogen or an alkyl group containing 1-5 carbon atoms, optionally substituted with chlorine, bromine or hydroxyl, ethoxy, ethoxy, carboxyl, methoxy or ethoxycarbonyl, sulfone, amino or alkyl, and αSπ or 8 is a residue of the general formula 3, in which Y is a methyl or carboxyl group and Ar is a phenyl or naphthyl residue optionally containing at least one sulfo group in addition to other substituents.

Compounds of general formula I, in which the symbols have the above meanings, are known compounds which are used as dyes for dyeing and printing cellulose fibers yellow or as intermediates in processes for the production of mole-chlorotrlazinyl dyes.

Known methods for the preparation of coated reactive dyes are described, for example, in Polish Patent Nos. 56 BlO, 101 487, 105 186, 108 257, 111 141, 111 285, 112 794,

122823 and in the European Patent Specification No. 198 796, as well as in K. Vnkatarian's Mololography The Chemmstry of Synthetic Oyee ”Yolume VI, pp. 213-228, New York edition 1972.

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The methods consist in the diazotization of 1-scstyl-mino-3- or -4-amyl-phenylene monol or disulfonic acid, coupling the resulting diazonium compound with a pyrazolone-5 or 6-hydroxypyridone-2 derivative used in an alkaline aqueous solution, hydroUsing the acetarvalent group of the coupling product 1 the condition of the obtained aml ^ az ^ e dye from chlorine cyanide, followed by separation of the dichlootrizinous dye, stabilization and drying

In the case of using the described dichlorotrizine dyes of formula I as intermediate products in the production of monzlClorotri6zine dyes, they are often used without being distilled from the mixture after the condensation reaction of the adnoisovβgl dye with cyanuric chloride.

Other synthesis variants consist in the simple-order condensation of cyanuric chloride with diimisophenylsulfonic acid or dlaminolamΐΐηοβυΐίnoic acid, or with diaminophenylenediaulloic acid, in order to combine the obtained compound of dichlorothiβznovithin with the 5-dihydrochloride derivative with the 5-derivative compound. The obtained chlorotrienne dye is stabilized and dried or separated by desiccation, filtration of the precipitate, and then stabilized and dried, or the produced dichlorotrieynne dye is used as a transition product to the secondary condenium.

The known methods of obtaining dyes for chlorotazinium derivatives of pyrazolone or 6-hydroxypyridose-2 are, however, difficult due to the superficial coating 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 the spray dryer is economic reasons problematic. In addition, tricnne dichlon dyes are often contaminated with by-products from the coupling process, whereby isolation of the dye by drying and filtration becomes a necessity.

In the production of azo dyes of the chlorotlazine derivatives of plrazolium or 6-hydroxypyridose-2, the complete dissolution of the above ^ ^ and ^ and ^ and ^ higher passive components in the alkaline environment before the coupling process was considered to be a necessary condition for the proper course of the coupling process. Therefore, the alkaline solutions of the passives were always prepared separately before the coupling process.

It has surprisingly been found that the coupling reaction of the compound diazoniowsgc linkage of general 4, in which R is as defined above, with pirαcolon-5 derivatives or

6-Hydroxypydone-2 can be carried out in the presence of hydrotropes and, optionally, surfactants, by using the above-mentioned passives in their acid forms, added to the suspensions of diazinizing compounds in the form of pastes or powders, after thorough washing in an acidic environment and suspending the pH above 4.

The process according to the invention produces reactive azo yellows of the general formula I, in which the symbols have the above meanings, by the condensation of cyanine chloride with di-αminophylnyliso- or -toUenlouulfonic acid or diaminophezylenedisullonooyl, dosing the resulting compound of the general formula 4, in which R is as given above the meaning and coupling of the obtained compound with the reactive component of the general formula HB, in which B is as defined above.

In this way, cyanuric chloride is condensed with diαminofθnylanl- or -toluernsuHn ^ Nym acid or diaminophenylenediline in a molar ratio lii, the obtained compound of formula 4 is diazotized in the medium after the condensation reaction and a passive component in the acid form of paste or powder is introduced into the mixture after the diazotization reaction. hydrotroploy,

Such as, for example, urea, caprolactam, etc., and, if appropriate, a surfactant, such as, for example, 2-ethylhexyl sulfoburezrinin, known under the name ZOCL SBO, sodium salt of dibutylcnaftalphaleno8ullonoago, known as Nakal BX, sodium salt of condensed polynuclear aromatic sulfuric acids, known as under the name O ^ ^s (^ ^ai ^! ^^ ^t o ^r NNO, polycondensation products of ethylene oxide, known as Polikol, condensation products of ethylene oxide with phenol derivatives, known as Rokaaenols or condensation products of ethylene oxide

162 423 with oleic alcohol derivatives, known as Rokanoli, is a mixture of these agents, and after thorough mixing in an acidic medium, it raises the pH of the reaction mixture above 4 to complete the coupling reaction, by gradually introducing a solution of hydroxide or carbonate or preferably sodium bicarbonate

After the coupling reaction is completed, the dichlorotrizine dye is isolated by salting out with sodium or potassium chloride and filtering the precipitate of the dye off. It has been found, however, that it is more advantageous to isolate the product by drying the reaction mass after the coupling reaction, especially in a spray dryer. Drying the reaction mass in a spray dryer can be carried out after adding the agent to this mass, they will be fluffing, stabilizing and / or dispersing agents, wetting and anti-dusting agents. The following can be used as stabilizing agents: a mixture of mono- and disodium or monopotassium and disodium orthophosphosphate orthophosphates, sodium hydroxide known as Polyphos or urea. Osko dispersants can be used e.g. the sulphitating method, containing the sodium salts of lignosionic acids, known as ligπinβulronlenes. As anti-dusting agents, for example, agents based on mineral or aluminum oils can be used, e.g. a mixture of spindle oil with a non-ionic emulsifier, known under the name Olanu G.

The condensation of cyanuric chloride with diaminophenylene or -toUuθnosulfonic acid is carried out in a known manner using the starting compounds in an equimolar ratio in an acryohydrate environment or in an aqueous medium in the presence of surfactants. 1,4-diaminophenylene-2-8ulronic, 1,4-diaminophenylene-5-dlsulronic, 1,4-diaminophenylene-2,6-forulronic, 1,3-dlaminophanylene-4-sulfooic _t 1,3-damminoloylen-4.6 -disulne, 1,4-dlamino-2-methylbαozeno-5-sulfonic, 1,5-diamino-6-methylrbeπzθno-3-8ulfrnroy or 1,3-diamlno-6-methylbenzene-4-sulrone.

If the condensation reaction is carried out in an aqueous medium in the presence of surfactants, it is not necessary to use an additional amount of an auxiliary agent in the coupling process in the coupling process according to the invention.

□ as passive components defined by the general formula HB, in which B has the above meanings, for example, the following are used: 1 * · -tyro-3-kthaamyl-4-miltylO "6-hydroxypyridone-2,1-methyl--carbβyl-4-millilO “6-hydroxy-yplridone-2, l-ethyl-tactin-4ααθtyro66-hydroc8yplridone-2, 2,6-dihydroxy-cyano- or -S-carbemyl ^ -methylpyridine, l-βtyr-44ma) _β tyro66-hydrocβyplridone -2,2,6-dihydroxy-4-methylpyridine, 1- / (3-hydroxy-yl) -3-cyano- or -3-kαrbamyCo-4-methyllr-hydroxypyridone-2, 1- (β-methoxypropopyCo) - 3-cyjαoo- or -3-karbemylo ^{mstylo-4-hydroxy-6-p} and ^ryd on-2, 1 / t -ethoxy ^yl / -3-cyano-performance βΓ ^^ ^^ ^b ^ Ιο- ββΐγ ^^ - η ^^ ^^ Ιίβγρχ η- ^2, l-karbokeymetylo ^ -cyJano- or karbatrloo4 -3-methyl-5-hydrokβypitydon-2, l-cyklohokaylo ^ -cyjano- or -3-katbαmylo-4-mθtylr -6-Hydroxyplridone-2,1-zzopropyl-cyano- or 3-carbamyl-4-methyl-6-hydroxypitidone-2, 1- / <-kαtbok3ypPpl0yCo / -3-jyjαoo- or -3-carbeaylo-4-Qθtylo -6-hydroxypyrdrn-2, 1- (f -aminooyl) ^ -cyano- or -3-kαrbamyCo-4-mβlyl-6-hydroxypyridone-2, 1- / β -N, N-dimβyloθłγlo / -3-cyjaoo- or -3-carbmyl-4-methylthr-6-hydrrkθypyridone-2, 1- / (¾ -chloro- or -brmortyl / -3-cyaoo- or -3- ^{karbemylo-4-methyl-6-y} hydroksypir don-2, ¹ - / 0 -sulfoetylo / -3ccJeno- l.ub - ³ -kar ^b aaylo-4-methyl-6-rr hy ^d r ^k L ^{YP YD} on- 2, l- / 4 * -8ulrlfnnyro / -3-carrokβyρirairlro-5, 1- / 4'-βulfolenyl / 3-matclopyrβiolon-5, 1- / 2 *, 5 * dljhlrΓoleoylo / -3-mβtclrpitazolro-5, l - (2'-chloro-4 * -sulfophenyl) -3-methyl- or -3-carbocaine azolone, 1- (2 * -methclr-5 * -sulfophenyl) -3-mβtyl- or -3-carbokeyplresolone- 5 and 2- / 4 *, B * -diauHonephthylZ-S-methyl- or -3-carbokayplrazolone-5.

As a result of the coupling process according to the invention, the above-mentioned dichlorotinum dyes are obtained with high efficiency and with a high degree of purity. This method makes it possible, in comparison with known procedures, to carry out the operation of obtaining dichlorothiazide dyes in one apparatus, thanks to which the process of dissolving the passive component is eliminated, resulting in a reduction in labor. Coupling reaction

162 423 in the process according to the invention takes place with the participation of diazonium cations, and its result is determined by the appropriate selection of components. During trials and tests, it turned out that the coupling process after the binding of the active and passive components, which is a new combination of the used substrates with the addition of hydrotropes and possibly surfactants, does not require pre-treatment at low pH and the presence of addition products of known reagents. The actual coupling process starts with increasing the pH value, and the hydrotropic agents used increase the pH value. the solubility of the ingredients and the resistance of the reactive system to hydrolysis. The coupling reaction begins in the low pH range, where the hydrolysis of the active chlorine in s-tnasin is non-invasive, and the degradation of the diazonium compound is practically imperceptible, which results in high purity and high chemical yield of the dye. The use of hydrotropic agents in the process according to the invention, preferably urea and surfactants, improves the theological properties of the reaction in the coupling process, which allows to increase the concentration of the reagents used, due to the time it is possible to increase the efficiency of the equipment and to significantly accelerate the coupling reaction. The high resistance of the active ingredient to hydrolysis and decomposition as well as the increased rate of the coupling reaction allow the process to be carried out at higher temperatures than previously used, which makes it possible to use the heat of the coupling reaction without the need for cooling, e.g. without adding ice. According to the invention, the process of producing dichlorotrlayin dyes can be carried out without waste.

Wynnlazek illustrates the following examples where parts and percentages mean? parts and percentages by weight and degrees of teeparature are given in degrees Celsius.

Example 1. A slurry of 20 parts of cyanuric chloride in 50 parts of water, 150 parts of ice, and 0.1 parts of SBO humidifier, a weakly alkaline solution of 21 parts of sodium acid and, 3-dieminofnylθno-4-uulphyonic acid in 200 parts of water, at 5-6 ° teiperture to complete the condoRna process. Here, 100 parts of ice and 12 parts of 30% sodium hydroxide solution are added until the pH is 7-7.5 and 7 parts of sodium nitrite are added. Then the reaction easy to quickly introduced into 30 parts of 30% hydrochloric waeu ^k. The reaction ^di azowania t ^{o p} rowadzi in teipθratuzze 0- ⁶ °. ^p zamilczeniu diazotization of the suspension is added 10 parts eooznika 1 part Oyspargatora NNO 1 32.3 parts of 1- / 2 * 5 * 4 * -dichlżzo--sulfofθnylo / 3-imβtylopir8Zolonu-5 as a 70% paste 1 in the accurate Sodium carbonate is added until the pH is 7-7.2. Coupling is carried out in teipθratuzza 15-20 °. After the coupling reaction is completed, 3 parts of disodium phosphate, 1 part of monosodium phosphate are added to the post-reaction solution,

0.3 parts of water in water and 1 part of Olanu SA and spray dried in a dryer. 95.2 parts of dichlorotriayine dye are obtained, which dyes cellulose fibers yellow with a complex shade.

Example II. The procedure described in Example 1 is followed, where in the conjugation process, 8 parts of caprolactant urea 1 Oyspargator NNO are added, and after coupling - the acid phosphate 1 is added to 4 parts of polyphosphate. 92 parts of the dichloro-zizzy dye, identical in terms of the chemical structure, of the dyes of the zirconium dye in Example 1, with a slightly higher concentration, are rubbed.

Example III. Dissolve 13.4 parts of i, 3-iinine-diethyl-4,6-dSuilfooowago in 200 parts of water and 4 parts of sodium hydroxide. The otzzyeαyy solution is added rapidly to the hinge 9.25 parts of cyanuric chloride in 150 parts of water, 100 parts of ice, 0.1 parts of Nekal ΘΧ and our whole for 1-2 hours in teiparetuzza 0-5 °, maintaining the pH of the environment around 5 After completion of the primary condensation, 12.5 parts of 30% hydrochloric acid and 25 parts by volume of 2N sodium nitrite solution are added to the prepared easy. After the diazotization is complete, 3 parts of the compound are added to the post-reaction easy and 10 parts of 98% l-ethro-3-azrαaiyiż-4-ethyl-6-hydrocaypi ^ dmu ^ in the form of a dry powder are introduced and the coupling reaction takes place intensively in an acidic environment » Then the reaction mixture leads to the hardening of war6

162,423 to pH 6.8-7 by gradually adding 10% sodium carbonate solution and adding 2 parts of anhydrous dieodium phosphate, 4 parts of anhydrous monopotassium phosphate and 0.5 parts of Olan G and spray drying. Dichlorotriazine dye is obtained, dyeing cellulose fibers yellow with a green shade of high brightness. Dyes are distinguished by outstanding lightfastness and washing fastness.

Example IV. For a suspension of 9.25 parts of cyanuric chloride in 30 parts of acetone,

100 parts of water and 100 parts of ice are added to a solution of 13.4 parts of 1,3-phenylndiamine-4,6-d18 phenylene acid in 200 parts of water; with a temperature of 0-5 and pH 4-5. The mixture is stirred for 2 hours at 0-5 °. After the completion of the condensation, 15 parts by volume of 30% hydrochloric acid are added to the reaction mixture and the mixture is diazotized, introducing 12.5 parts by volume of a 4 N sodium nitrite solution. 5 parts of urea, 0.05 parts of SBO moisturizer, 0.05 parts of Rokanol K-20 are added to the obtained suspension of the diazonium compound. After thorough mixing, 9.7 parts of 1 / (> -hydrocytyl / -3-cyano-4) are added in portions. -iethyl-6H-hydroxyplridone-2 in the form of 40% pellet. The reaction mixture is then adjusted to a pH of 6-6.5 with sodium bicarbonate. The dye produced is released with sodium chloride and filtered off. The resulting paste of a dichloromethane dye is obtained. is used for secondary condensation with moddratlrαml or mixed thoroughly with 2 parts anhydrous disodooegl phosphate and 4 parts anhydrous meget phosphate and dried under vacuum.

The dye produced dyes polyamide and wool fibers yellow with a green shade, but much redder than the shade of the dye obtained by the method described in Example 3.

EXAMPLE 5 With sodium carbonate, a solution of 26.8 parts of 1,4-phenyldiamlnO12,5-di-ullyneglacid is added to an aqueous suspension of 18.5 parts of cyanuric chloride,

0.1 part of SBO hydrogenator and stirred at 0-5 ° C, gradually add just enough dilute sodium hydroxide solution to make the solution slightly acidic. After the condensation is complete, the reaction mass is acidified with 30 parts of 30% strength hydrochloric acid and diazotized with 25 parts of 1 vial a 4N aqueous sodium nitrite solution. Then 10 parts of urea and 32.3 parts of l-2 ', 5'-dichlorifanyl / 3-y-tzl-5-praoolnl-4'-sulfnic acid are added in the form of a 40% paste to the prepared diazonium compound. The whole is homogenized exactly and the t2dodium phosphate is introduced in portions until the pH is 6.5-7.2. After completion of the coupling added 2 parts olate G and spray-dried at suszarni- tamparat ^office e ^pneumatic part inlet 15 O 1 ⁸ O ° and the outlet / 0-80 °. ^ y ^ kissing with ^about LT ni.e ^{pzl y} n ^y soszek, stable to the storage, coloring cellulosic fibers on a pure red shade yellows.

Further examples of the synthesis of dichlorotrizzyl dyes are given in the table, the method of condensation of cyanuric chloride with the acids for yiyofayzlθnl8ullnlowyyi given in column 2, of the obtained condensation products and coupling of the obtained di-αzlniosol compounds with pyrazolone-5 or 6-pyrazolone derivatives in the third-cell-2-cell dyes , wool and polyamide fibers yellow.

{Example 2 diαyinofanzXβno- acid 1 1 Pyrazolone-b derivatives { Hue and sul ^ new 1 1 | or 6-hzdrlkθypyridonu-2 i coloring 1 ! 2 1 1 __________ 3 _____________________ __ 4 AND VI [1,3-di0minofayzlano- 1 1 1- (4'-sulfofernlo) -3-ka rbokey—} pyrazolone- and green and -4-sullnπowz 1 1 VII * 1,4-diayinophanylano- 1 1 - - - 1 inert ! 2-aullonooy 1 1 1 1 VIII 1 1 1 1 1 1 1 l- _/ ^ <^ * aUJllofy1y ^ o _i -33matzlo- J plrazolone-5! reddish IX 1 - 1 1 1 1 1 1 vol 1 2- / 4 '^' - disulfonaphthyl / -3- mm th ^ pyrazolone j red X and 1,3-diayiyofanylayo- 1 1 | 1- (2'-chloro-4'-8ulfofanzlo) green 1—— '4,6-diθullyoowz 1 1 -. 4. -3-oatyl.opiazllon-5 [ . - - ..... u.

c. d. we% t * y

162 423

C-d.

- _r. 2 and ----- ~ ---------- 5 ---------- ! 4 XI 1,3-dianinophenyl- • l-raetyl-3-cyno-4-methyl · 1 - [green 4,6-dieulfonic acid • -6 "hydroxyplridone-2 • 1 XII 1 1 1 1 and 1-methyl-3-kebbamyl-4-me | tylo-6-hydrokeypyridone-2 1 1 1 XIII 1 Ł 1,4-diaminophenyl- • 1 - / (S-hydroxyethyl / - ! inert 1 1 1 1 1 -2,5-disulfonic J -3-cyano-4-methyl-6-hydro 1 J xypyridone ^ AND 1 AND 1 1 XIV 1 1 1 1,3-diemino-6-methyl- J 1-ethyl 33-cyano-4-methyl- J green 1 1 benzene-4-eum it you and -6-hγdrnkecPi · Γydnn-2 1 1 | XV 1 1 1 1 in e « } l-e t yno44-! netyl-6-hydrn * keypi.rydon-2 vol I _ _ 1 1 1 vol XVI 1 1 1, 3-die <ninophenylene- and 1-carbokeymethyl-S-ker- | 1 1 1 1 1 1 -4,6-desulfonyl | bβmyCo-4-fnβtylo-6-hydrnkec and pyridone-2 1 1 . 1 1 1 1 1 1

formula 1 ch ₅ hcDnK ^{0 n} ~ \ r,?

pattern2 pattern-rj

162 423

Publishing Department of the UP RP. Circulation of 90 copies

Price: PLN 10,000

Claims (1)

Patent claim A method of obtaining reactive azo yellows of the general formula I, in which R is a hydrogen atom or a methyl or sulphonic group, and B is a residue of the general formula II, in which X is a hydrogen atom or a cyano or aminocarbonyl group, and R5 is a hydrogen atom or an alkyl group having 1-5 carbon atoms, optionally substituted with chlorine, bromine, or hydroxyl, methoxy, ethoxy, carboxyl, Mthxy- or ethoxycarbonyl, sulfone, amino or alkylaamine, or B is a residue of general formula 3, in which Y is a methyl group or carboxylic acid, and Ar is a phenyl or naphthyl residue optionally having at least one sulfonic group next to other substituents, by condensation of cyanuric chloride with diaminophenylene or -toluene sulfonic acid or dianisofesylnodilane, diazotization of the resulting compound of formula IV, wherein R is the meaning given above and the coupling of the obtained diazonium compound after the passive component for the formula HB, in which B is as defined above, characterized in that cyanuric chloride is condensed with diarninophenyl or toleenesulfonic acid or diemiso-anylenedisulfonic acid in a molar ratio of 1: 1, and the resulting compound of formula 4 is condensed in the reaction medium after the reaction Condemnation 1 introduces into the mixture after the diazotization reaction the passive component in acid form of a paste or powder, and a hydrotropic agent such as urea, caprolactan and optionally a surfactant such as Z-ethylhexyl sulfosuccinate, sodium dibutylnaphthalβn sulfonic acid, sodium salt of condensed olives, polycondensation products of ethylene oxide, condensation products of ethylene oxide with phenol derivatives or condensation products of ethylene oxide with derivatives of lleSn alcohol, or a mixture of these agents, and after thorough mixing in an acidic environment, increases the pH of the reaction mixture above 4 until the coupling reaction is completed, then the color develops in a known manner by salting or, after adding filler, stabilizing and / or dispersing, wetting and anti-dusting agent or agents, and dried in a spray dryer.