DE1961786A1 - Azo dyes - Google Patents

Description

Azo dyes

Priority: 9 ", 12th 1968 - Great Britain

The invention relates also to new azo dyes and in particular to new azo dyes that can be used to dye textile materials, paints, printing inks, rubber, natural, artificial and synthetic polymeric materials and fiber-forming materials are suitable »

According to the invention, there are new water-insoluble azo dyes suggested that free from sulfonic acid and carboxylic acid groups " and are free of cationic groups and the formula:

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(D

- 2nd

have, in which Z stands for a hydrogen atom or an alkyl, aralkyl, cycloalkyl, aryl or heterocyclic radical which can be substituted, T for a hydrogen atom, a group -GN, -CONR ¹ R ² , -COR ¹ or -OH or an alkyl, aralkyl, cycloalkyl, aryl or heterocyclic radical, which can be substituted, and I represents a hydrogen atom, a group -CH, -COOR ¹ , -CONR ¹ R ² or -COR or represents a Alkyl, aralkyl, cycloalkyl, aryl or heterocyclic3 radical, which can be substituted, ^ and D stands for an optionally substituted divalent aryl radical which contains at least two aryl nuclei, the azn groups being bonded to different aryl nuclei »

The azo dyes according to the invention can be used in a number tautomeric forms exist. For the sake of convenience, the dyes have only been given in one of these tautous forms, but it should be noted that this description applies to dyes in any of the possible tautomeric Forms

and R each independently represents a hydrogen atom or an alkyl, aralkyl, cycloalkyl, aryl or heterocyclic radical which may be substituted can stand, or together with the nitrogen atom to which they are attached, the radical of a 5- or 6-membered group form heterocyclic ring compound.

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a -

Throughout the specification , the terms "lower alkyl" and "lower ^{alkoxy 1} * refer to alkyl and alkoxy radicals containing 1-4 carbon atoms.

The optionally substituted alkyl radicals represented by Z, T "! _T « jj2 _f al, ^ d η ² are preferably optionally substituted lower alkyl radicals. Ale spe-

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Specific examples of such radicals should be mentioned: methyl, ethyl, n-propyl, -n-butyl, hydroxy-lower alkyl, such as ß-hydroxyethyl, lower alkoxy-lower alkyl, such as ß- (methoxy- or ethoxy) ethyl, cyanomethyl, carbampylmethyl, carbethoxy- ■ methyl and acetylmethyl. The methyl radical is particularly preferred, except in the case of Z where methyl and ethyl are preferred will.

As examples of aralkyl radicals, which are represented by Z, T ¹ , T ² , R ¹ and R ² , the following should be mentioned: benzyl and β-phenylethyl. As an example of cycloalkyl radicals represented by Z, T ¹ , T ² , R ¹ and R ² , there should be mentioned cyclohexyl. The optionally substituted aryl radicals represented by Z, T ¹ , T ² , R ¹ and R ² are preferably optionally substituted phenyl radicals. Specific examples of such radicals are: phenyl, tolyl, chlorophenyl, methoxyphenyl and ethoxyphenyl. The optionally substituted heterocyclic radicals represented by Z, T ¹ , T, R and R ² are preferably substituted 5- and 6-membered heterocyclic rings. Al · specific examples of such radicals should be mentioned: 2-pyridyl, 2-thiazolyl, 1-piperidinyl and 1-morpholnyl.

As examples of 5- and 6-membered "nitrogen-containing Ige heterocyclic rings, the union of R and R with the Nitrogen atoms should be mentioned: piperidine, morpholine, piperazine and pyrrolidine.

2 It is preferred that T be cyano and that Z be

Hydrogen atom or a lower alkyl (especially methyl or ethyl), phenyl or substituted phenyl group.

The divalent aryl radical represented by D may be a naphthylene radical containing two or more condensed aro-

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has matic rings »which may have substituents, such as chlorine, bromine, lower alkyl» such as methyl, lower alkoxy, such as methoxy, cyano, nitro or acetylamino. The divalent aryl radical represented by D can also be a divalent radical by adding two arylene radicals, such as phenylene or naphthylene, through a direct bond, through a saturated hydrocarbon group such as -CHo-, through an unsaturated hydrocarbon group such as -CHaCH-, or through a bridging atom or a bridging group containing a heteroatom, such as -0 -, - CO ₂ SO ₂ -, -S-, -KH-, -OCH ₂ -CH ₂ O-, -CONH- or -NH-CO-NH-, are connected to each other.

As examples of cationic groups that are not present in the new dyes, the following should be mentioned: quaternary Ammonium, cyclanmonium, hydrazinium, sulfonium and iaothiouronium groups.

According to the invention, a process for the preparation of the new azo dyes is also proposed, which is carried out by _{tetrazotizing a diamine of the formula NH 2} -D-NH ₂ and coupling the resulting tetrazo compound with a coupling component which is carried out in one of the possible tautomeric forms the formula

¹ «2

HO

1 2

can be represented in which D, T, T and Z have the meanings given above.

The tetrazotization and the coupling can in this process run in the normal way * however you will

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preferably carried out in an aqueous medium at a pH in the range 4-10

The coupling components of the formula (2) can in turn be obtained by a number of processes, as described for example in "Heterocyclic Compounds - Pyridines and its derivatives - Part 3", which is published by Klingsberg and published by Interscience Publishers in Was published in 1962. Typical processes are, for example: (1) condensation of compounds of the formula T ¹ COCH ₂ COO-alkyl and T ² CH ₂ C00-alkyl in the presence of an excess amine of the formula Z-MH ₂ ; (2) cyclization of one Oil, ß-

disubstituted glutaconamide of the formula

j2 \

Alkyl-OOC.CHpC * C CONHZ, which itself by condensation

of compounds of the formulas T ¹ COCHgCOO-alkyl and T ² CH ₂ CONHZ in the presence of a basic catalyst

can; or (3) cyclization of a &, e-disubstituted gluta-

conamids of the formula: 7, which itself

ZNHCOCH, = C.COO-alkyl

can be obtained by condensation of compounds of the formula T COCH ₂ COHNZ and T ² CH ₂ COO-alkyl. ·

Specific examples of coupling components of the formula (2) are: 2,6-dihydroxypyridine, 2,6-dihydroxy-3-cyano-4-methylpyridine, 1- (methyl- or ethyl) -3-cyano-4-methyl-6- hydroxypyrid-2-one, 1- (ß-hydroxyethyl- or Ti ^ Hethoxypropyl) -3-cyano-4- (methyl-, phenyl- or ethyl-) - 6-hydroxypyrid-2-one _f 1- (phenyl-, p-Tolyl- or p-anisyl) -3-cyano-4- (methyl- or phenyl) -6-hydroiypyrid-2-one, 1-phenyl-3- (carbonamido- or carboethoxy) -4- (methyl- or Phenyl) -6-hydroxypyrid-2-one, 2 _t 6-dihydroxy-3- (carbonamide-, carboethoxy-, carbodiäthylamido) -4 * -methylpyridine, 2,6-dihydroxy-3- (carbonamido or

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carboethoxy) pyridine, 2,6-dihydroxy-3-carbonane) ± do-4-phenylpyridtn, 2 _f 6-dihydroxy-3-cyano-4-carbonamidopyridine, 2,6-dibydroxy-3 ^ yano-4 ~ (N- phenyl-carbonamido) pyrldine, ethyl-2, ö-dihjrdroxy-J-cyanopyrid-a-ylacetate, 2,6-dihydroxy-3-cyanopyrid-4-ylacetate, 2,6-dihydroxy-3,4-di (carbonamide) -pyridine, 2 _t 6-DihydiOxy -; ^ - carbonamido-4-cyanopyridine _f 2,6-Dlhydroxy-4-ethyl-pyridine, 2,6-dihydroxyieonicotlnaaid, 2,6-dihydroxy-ieonicotinic acid diethylamide, 2,6- Dihydroxy-4-cyano-pyridine, 2 _t 6-dihydroxy-4-phenylpyridine, 2 _f 6-dihydroxy-4- (p-hydroxyphenyl) pyridine _f 2,6-dihydroxy-4- (p-ethoxyphenyl pyridine, 2,4, 6-trihydrorypyridine and 2,6-dihydroxy-3-cyano-4-ethoxycarbonylethylpyridine.

Specific examples of diamines where the two amino groups are bound to -different aryl nuclei and the Verdes can at erfindxzngegea & fien Tenrendet method are: 3.3 ^<- * DiehlorobenBidin, ToI id in, dianisidine, 4 _f 4'-diaminodiphenyl sulfone, 1, 5-Diaminoanthrmchinon, 2,6-Diaainonaphthalin, 1,4-Diaainoanthrachinon, 4.4 ^f -Diaainodiphenyläther, 4,4'-Diaoinodiphenylharnstoff, 4,4 '~ Diasdnobeneophenon, 4,4'-Diaoinobensanilid, 2,5,2' , 5'-Tetrachlorobenzidin, Bensidineulfon, 4,4'-Dia »inoBtilben and 4,4 ¹ -diaminodiphenylaBin.

The erfindungsgea & Ben waeeerunlCelichen azo dyes are excellent for dyeing τοη synthetic textile materials, especially cellulose acetate and τοη Zellulosetriacetattextilaaterialien, Polysaidtextilasterislien as sB PolyhexaaetnylenadipoBiidtextiliBaterialien _v and preferably aromatic Polyestertextilaaterialien such * o. Polyethylene terephthalate textiles. These textile materials can be in the form of twisted threads, yarns or woven or knitted textile materials.

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■ γ

These textile materials are appropriately dyed by immersing the textile material in a dyebath which is an aqueous dispersion of one or more of the azo dyes and preferably contains a non-ionic, ionic and / or anionic surface-active agent, followed by the dyebath Heated to a suitable temperature for a period of time. In the case of secondary cellulose acetate textile materials, it is preferred to carry out ^{the dyeing process at a temperature between 60 and 85 ° C.} Ia the case of ZEI lulosetriacetat- or Polyaaidtextilaaterialien it is preferred to "carry out the dyeing process at 95-10O ⁰ C. In the case of aromatic polyester textile materials, the dyeing process can be carried out either at a temperature between 90 and 100 ^° C. (preferably in the presence of a carrier such as diphenyl or ortho-hydroxydiphenyl) or at a temperature above 100 ^° C. (preferably at a temperature between 120 ° C. and 150 ⁰ C) are carried out under superatmospheric pressure. Alternatively, the aqueous dispersion of the azo dye can be applied to the textile material by a padding or printing process and subsequent heating or steaming of the textile material. In such a process, preference is given to a binding agent such as EB Gum tragacanth. Gum arabic or battery alginate to be incorporated into the aqueous dispersion of the monoazo dyes mentioned.

At the end of the dyeing process, it is preferred to use the dyed To rinse textile material in water or to soap briefly before the dyed textile material is finally dried »Im In the case of aromatic polyester textile materials, it is also preferred to treat the dyed textile material in an alkaline to treat aqueous solution of sodium hydrosulfite before the Soap treatment is carried out to remove loosely bound dye from the surface of the fabric.

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-JBT-

The azo dyes have an excellent affinity and excellent structural properties in synthetic textile + «Rials and especially in the case of aromatic polyester textile materials, so that deep color tones can be obtained. the The resulting colorations, whose hue goes from yellow to blue, have excellent fastness to light, to wet treatments and especially to dry heat treatments »such as occurred for example during flattening.

The azo dyes according to the invention can optionally be used dyes are applied openly to synthetic textile materials together with other dispersion, as for example in British patents 806271, 835819, 840903, 847175, 852493, 859899, 865328, 872204, 894012, 908656, 909843, 910306, 913856, 919424, 944513, 944722, 953887, 959816, 960235 and 961412.

The new azo dyes according to the invention can be used either individually or in mixtures in the form of clay, dry powders as all pigments for coloring paints, with they produce bright yellow to blue shades with good fastness to light, heat and solvents, if they are incorporated into alkyd or other color media. Alternatively, the azo dyes can be used as pigments for coloring Clay artificial polymeric materials can be used, such as "clay polyvinyl chloride, polyethylene, polystyrene and cellulose acetate"

By grinding the azo dyes with water and with a dispersing agent such as disodium djLnaphthylmethanedi-ß-sulfonate, can the new inventions dyes according to the invention in the form of Pigment pastes can be obtained that are suitable for manufacture

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τοπ emulsion paints, for coloring wallpaper, for printing Clay textiles, for dyeing paper and paper laminates, for mixing in color carriers or lithographic varnish or for use in bulk pigmentation of fiber-forming materials such as viscose. In these applications, they are known for their luminosity and for their authenticity remarkable to light and solvents.

The azo dyes according to the invention can also in situ Textile materials are made. For example, you can impregnate the textile materials with an alkaline solution of the coupling component and then with a solution or a suspension of the tetrazotized diamine (or a stable salt thereof such as the zinc chloride complex) to form the insoluble dye on the fiber. Optionally, the tetrazonium salt can be converted into a stable derivative such as bis (diazoamino) compound and converted into Mixture with the coupling component are applied to textile materials, the insoluble dye then is developed on the fiber, e.g. through an acidic aftertreatment or through neutral steaming.

The invention is illustrated in more detail by the following examples in which the parts are expressed by weight.

Example 1-

5 t 1 parts are au in one mixture x 60 parts water and 10 parts of a 1-one are stirred in hydrochloric acid and at a temperature below 5 ⁰ C by adding 2 hone a slipway aqueous Natriumnitntlösung tetrazotized · skilled a 30 minute 3 '3'-DiChIOrObOnSIdIn permanent Stirring, the tetrazo solution is filtered off and over a period of 15 minutes to a stirred ice-cold solution of 6 parts of 2,6-dihydroxy

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3-cyano-4-methylpyridine in 100 parts of water and 20 parts 10N aqueous sodium hydroxide solution was added. The mixture is stirred for a further 15 minutes, and the precipitated disazo dye is isolated by filtration, washed with water and dried «

When he used as a pigment for coloring τοη paints then the dye gives a strong bluish-red color tune.

example 2

Instead of the 6 parts of 2,6-dihydroxy-3-cyano-4-methylpyridine from Example 1, 10.2 parts of 1- (2,4-iylyl) -3-cyano-4-methyl-6-hydroxypyrid-2-one are used used. The disazo dye obtained

results in a red shade in paints «

Example 3

Instead of the 6 parts of 2,6-dihydroxy-3-cyano-4-methylpyridine of Example 1 are 9.1 parts of i-phenyl-O-cyano-A-methyl-6-hydroxypyrid-2-one used. Bs becomes a red disazo dye obtain.

example A.

Instead of the 6 parts 2,6-Dihydrory-3-cyano-4-Bethylpyridin of Example 1 are 12.9 parts of 1- (2,5-diethoxy-4-chlorophenyl) -3-cyano-4- »ethyl-6-hydroxypyrid-2-one used. A red disazo dye is obtained.

Examples 5-51

The procedure of Example 1 is repeated, using the diamines and coupling components indicated in the following can be used. Disazo dyes with the specified color shades are obtained. These dyes can by normal

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Measure to be incorporated into paints, where they give strong hues.

An aqueous dispersion of these dyes, which can be used for dyeing, is obtained by grinding the dye in water in the presence of a dispersant, such as sodium dinaphthylmethane-2 _f 2 ¹ -disulfonate, using a ball mill. These dispersions are used in the usual way for high-temperature natural dyeing of polyester textile materials, in particular in the presence of a carrier.

Aqueous dispersions which are produced by grinding these dyes in water in the presence of a dispersant, such as BB Natriumdinaphthylmethan-2 _r 2 'di8ulfonat In a KtagelaiUhle, are suitable for use in emulsion "paints, in dyeing tone wallpaper, when" coloring τοη Paper and paper laminates, when printing τοη textiles, when incorporated into color media or lithographic varnishes or for use in mass pigmentation, such as, for example, in mass fragmentation τοη viscose.

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O (D OO

example Tetrazo component Coupling component scarlet fever It _μ VJI 3> 3 * -dlahlorobenzidine 2 1 6 ~ dihydroxypyrldine orange 6th » 1-Ethyl-3 ~ oyano ~ 4-methyl ~ 6 ~ hydroxypyrid-2-one acharlach 7th •1 1 -ethyl ^ -cyano - ^ - phenyl-ö- hydroxypyrid-2-one ti 8th η 1-phenyl-S-carbamoyl ^ - iaethyl-6-kydroacypyrid-2-one M. 9 η 3-cyano-4-carbainoyl-2,6- dihydroxypyridine 10 η 3-cyano-4-N, N-diethylcarb- Il amoyl-2,6-dihydroxypyridine 11th Il 3-oyano-4- (piperidin-1'-yl- carbamoyl) -2,6-dihydroxy η pyridine 12th H 3-cyano-4- (morpholin-1 * -yl- Il carbamoyl) -2,6-dihydroxy- pyridine η 13th η 3-cyano-4-ethoxycarbolnyl- reddish methyl-2, 6-dihydroxypyridine yellow 14th η 3? 4-dicarbomoyl-2,6-dihy- droiypyridine H 15th η 4-methyl-2, 6-dihydroxy pyridine 16 η 2 _f 6-üihydroxyieonicotin- amide

example Tetraaco component - Clutch component hue Red 17th 3,3'-dichlorobenzidine 2,6-Dihydroxyieonicotinic acid
diethylamide reddish
yellow Red 18th N 4-phenyl-2,6-dihydroxypyrid in yellow blue red 19th ti 2,4,6-trihydroiypyridine soharlach Red 20th 4 ', 4' -diaminodiphenyl ether 2,6-dihydroxypyridine yellow Il 21 4 f 4'-diaminodiphenyl methane It η chestnuts 22nd 4 '»4'-diaminodiphenyl ether 3-cyano-4-methyl-2 _f 6-dihydroxy-
pyridine η Brown 23 4 »4 '-diominodiphenyl methane H It blue 24 4,4'-diaminobenzophenone Il chestnuts
Brown 25th 4 * 4 * -diaminodiphenyl-sulfone It Red 26th 4,4'-r ^ iaminodiphenylamine H chestnuts
Brown 27 414 '-diaminod iphenylhamst of f M. yellow 28 4 4'-D4 _fl miT) ol> Apo? Pr) 1T1 <? M. H 29 ι ■ fr * ™ * Tf ΙΑΪΤΙαΙΤιΟΛΛΌΛ fffl ^ l ι Ü ITl η * 30th 1,5-diaminoanthraquinone N 31 4,4 · -ßiasiinoetilbene H 32 Tolidine Il 33 Dianisidine 3-Cjano-4-methyl-2, 6-dihydroxy-
pyridine 34 4 _y 4 * -diaminodiphenyl ether hydroxypyrid-2-one 35 4 »4'-diaminodiphenyl methane η

■ (O example Tetrasocoagponents M. It IuppiungwtoBponente N hue I. CD 00
K) 36 4 ₍ 4 * -diaminodiphenyl-eulfone 1αthyl-3-cyano-4-aβtbyl-6-hydroxy- η σ> η 4 ·, 4 '-diaminodiphenylaethane pyrid-2-one Red GO ^ 37 4,4 * -dimainodiphenylam η l- (T-methoxypropyl) -5-oyano-4- bluish
Red OO CJ 38 4 ₁ 4 -DJ nmAnnAi ph * rtyl-hftrn- N ■ ethyl-6-hydroxypyrid-2-one Red 0 » • toff η 1- (Y-4! Etbx> xypyropyl) -3-O3raao-4- 39 4,4'-diaminodiphenylethane ■ ethyl-6-hydroxypyrid-2-one yellow N 40 4 '14 * -diÄjninodiphenylur- 1-ethyl-3-cyano-4-phenyl-6-hydroxy- • toff BtOff pyrid-2-one bluish- 1-Phβnyl-3-cy »no-4- ■ βthyl-e- Red 41 hydroxypyrid-2-one Red 1- (p-.folyl) -3-oyano-4- «thyl-6- 42 1- (p-anisyl) -3-cyano ~ 4 ~ methyl-6- N hydroxypyrid-2-one 43 1-phenyl-3 "-carbamoyl-4- * iDethyl-6- N 44 5-carbemoyl-4-methyl-2,6-dihydroxy H pyridine 45 3-ethoxycarbonyl-4-ethyl-2,6- η 46 dihydroxypyridine N 3-0yano-4-carbai> oyl-2,6-dihydroxy-
pyridine ^v 47 I * "flieiiyl ^M * 7 ^^ sycucio — 4 * ^>> Betnyl ^{a |>} o * ^K. η hydroxypyrid-2-one 48 yellow . 49 η

example Tetra component Coupling component hue 50
51 4 ' ₁ 4'-diaminodiphenyl methane
H 1 - (2, S- ^ imethoxy ^ -chlorophenyl) -
3-O3rano-4-n »thyl-6-hydroaqypyrid-
2-on
3,4-dicyano-2,6-dihydroxypyrldine yellow
H

Claims (1)

-Mr-Air ' P r. tentana claims (. 1) Water-soluble Azofarbstof f β, dio aregruppen free of sulfonic acid and J & rbonsä ^ and are free of cationischen Qruppen and di * formula HO (I) have, where Z stands for a hydrogen atom or an alkyl » Aralkyl, cycloalkyl * aryl or heterocyclic radical stands, which can be substituted, T stands for a hydrogen 12 1 atöm, a group -CH, -COHR B, -COR or -OH or an alkyl, aralkyl, cycloalkyl, aryl or heterocyclic radical, which can be substituted, and T represents a hydrogen atom a group -CX, -COOR ¹ , -COHR ¹ R ² or -COR ¹ or represents an alkyl, aralkyl, cycloalkyl, aryl or heterocyclic radical which can be substituted, and D stands for an optionally substituted divalent aryl radical which has at least two Contains aryl nuclei, the aso groups being bound to different aryl nuclei. 2. Azo dyes according to Claim 1, characterized in that T ^{1 stands} for a methyl group. 3 » azo dyes according to one of claims 1 or 2, characterized in that T ^{2 stands} for a cyano group. ^F 1 2 R and each R 'stoffaton in water or a alkyl "independently aralkyl, Cyoloalkyl-, aryl or heterocyclieohee radical welohes may be substituted, or etehen teMolnesa the nitrogen atom are bonded to the Si · old, form the radical of a 5- or 6-membered heterocyclic ring union, 009829/1381 OR5GINAL INSPECTED 4. Azo dyes according to any one of claims «1 to 3» thereby characterized in that Z is a methyl or Ethyl group. 5 "Azo dyes according to one of claims 1 hie 3" characterized in that Z stands for a hydrogen atom ο 6 ο azo dyes according to one of claims 1 to 3 »thereby characterized in that Z stands for an optionally substituted phenyl group. 7. Azo dyes according to one of claims 1 to 6, characterized in that D contains two arylene radicals »which are linked to one another by a direct bond are. 8. azo dyes according to any one of claims 1 to 6, characterized characterized in that D contains two arylene radicals which are linked to one another by a saturated hydrocarbon group. 9. Azo dyes according to one of Claims 1 to 6, characterized characterized in that D contains two arylene radicals, which are replaced by an unsaturated hydrocarbon * -. group are connected to each other. 10. Azo dyes according to any one of claims 1 to 6, characterized characterized in that D contains two arylene radicals formed by one atom or one containing a heteroatom Group are connected to each other. 009829/1381 12. Process for the preparation of the azo dyes according to Claim 1, characterized in that a diamine of the formula HHg-D-NHg is tetrazotized and the resulting tetrazo- Connection with a coupling component of the formula Ό _T 2 1 9 " couples, in which D, T ¹ , T * and Z have the meanings given above. 13. Use of the azo dyes according to claim 1 in the form of a aqueous dispersion for dyeing τοη synthetic textile materials. 14. Use according to claim 13 »characterized in that the dispersion is heated ^{to a temperature of at least 60 ° C.} 15 · Use according to claim 13 »characterized by the fact that the aqueous dispersion is applied to the textile material is applied by padding or printing, and the textile material is heated or steamed. 16. Use according to one of claims 13 or 14, characterized characterized in that the azo dye is produced in situ. 009829/1381