CH572082A5 - Sulphonic acid-free basic dyes - for dyeing and printing acrylonitrile or vinylidene cyanide polymer-contg textiles polyesters and polyamides - Google Patents

Abstract

Title dyes of formula:- F circled positive-/(CHR1)xO-Q/yA- (I) (where F + is a cationic gp. contg. dye residue, esp. an azo-, styryl, azomethine- or methine-dve residue; x is 1, or 3; y is 1,2,3 or 5; A- is an anion; Q is an opt. substd. biphenylyl, dibenzofuranyl, carbazolyl, dibenzothiophenyl, dibenzothiphenedioxydyl, dibenzothiophenemonoxydyl, fluorenyl or fluorenonyl gp. and R1 is H, Ph, cycloalkyl, 1-4C alkyl opt. substd. by halogen, 1-4C alkoxy or phenoxy) are used for dyeing or printing fibres, filaments or fabrics contg. acrylonitrile or vinylidene cyanide (co)polymers or acid gp. modified polyamides or polyesters, and for bulk-dyeing natural or synthetic resins.

Description

  

  
 



   The invention relates to a process for the preparation of basic azo compounds which are free from sulfonic acid groups and which contain one or more cationic groups and / or one or more substituents which enable the addition of a proton and one or more groups of the formula
EMI1.1
 contain, in which
R13 is hydrogen or an optionally substituted alkyl radical and
X is 1, 2 or 3 and the aromatic ring B can be further substituted and the azo dyes of the formula
EMI1.2
 correspond to where
D the remainder of a diazo component,
K is the remainder of a coupling component,
An anion and
Y '1, 2 or 3, characterized in that in a compound of the formula
EMI1.3
 wherein
D 'the remainder of a diazo component and
K 'mean the remainder of a coupling component,

   the ring B can be substituted and D 'and / or K' contains at least one quaternizable group, this group is quaternized. Basic triazolium azo dyes are advantageously prepared.



   The basic compounds can contain an ammonium, hydrazinium, cycloimmonium or etherified hydroxylammonium group as the cationic group; However, they can also contain a protonizable primary, secondary or tertiary amino group or one of the aforementioned cationic groups and a protonizable amino group.



  Basic azo dyes of the formula which contain no sulfonic acid groups
EMI1.4
 wherein
R the atoms or groups of atoms necessary to form an unsaturated, optionally substituted hetero ring containing at least five members and
Z denotes oxygen, sulfur or nitrogen and minnesrens a scauomscne uruppe Im Kest K unciiocier In the ring of the formula R Z or in a ring fused to this ring, one can obtain if an azo compound of the formula dyes of the formula
EMI1.5
  those in the coupling component K 'and / or in the group of the formula
EMI2.1
 or contains at least one quaternizable group in a ring fused to this group, quaternized.

  Basic azo dyes of the formula which contain no sulfonic acid groups
EMI2.2
 wherein the optionally substituted, optionally having a fused ring, hetero ring of the formula
EMI2.3
 contains at least one quaternized group can be obtained by using a compound of the formula
EMI2.4
 in the hetero ring R N or in a ring fused to this hetero ring, quaternized.



   The invention also includes the preparation of sulfonic acid group-free basic azo compounds of the formula
EMI2.5
 wherein
R, an optionally substituted alkyl or alkenyl radical and
R2 denotes an optionally substituted alkyl, aralkyl, alkenyl or aryl radical. These dyes can be obtained using an azo compound of the formula
EMI2.6
 wherein
R2 'denotes hydrogen or R2 denotes quaternized. The basic azo compounds free of sulfonic acid groups of the formula
EMI2.7
     wonn
R, an optionally substituted alkyl or alkenyl radical and
R3 denotes hydrogen or an optionally substituted hydrocarbon radical can be obtained by using a compound of the formula
EMI3.1
 quaternized.



   The coupling components can belong to the benzene, naphthalene or heterocyclic series or, if they contain a methylene group capable of coupling, to the aliphatic series. The invention particularly includes azo compounds of the formula
EMI3.2
 wherein the radicals R4 and R5 each denote hydrogen or an optionally substituted hydrocarbon radical, the aromatic ring D 'can be further substituted and the radicals R4 and Rs together with the N atom bonded to these radicals can form a saturated or partially saturated heterocycle;

   or azo compounds of the formula
EMI3.3
 wherein the radicals R6 and R, each hydrogen or an optionally substituted hydrocarbon radical, the aromatic rings Z1 and / or Z2 can be further substituted and the radicals R6 and R, together with the N atom bonded to these radicals, a saturated or partially saturated heterocycle can form; or azo compounds of the formula
EMI3.4
 or azo compounds of the formula
EMI4.1
 wherein
R8 and R9 are each hydrogen, an optionally substituted alkyl, aryl, alkoxy or aryloxy radical,
EMI4.2
 -SO2-NH-R10 or -CO-NH-RtO and R10 denote an optionally substituted hydrocarbon radical.



   Basic azo compounds free of sulfonic acid groups of the formula
EMI4.3
 where R "is hydrogen or an optionally substituted hydrocarbon radical, Rl is an optionally substituted alkyl or alkenyl radical,
R2 is an optionally substituted alkyl, aralkyl, alkenyl or aryl radical,
R12 is an optionally substituted hydrocarbon radical, R13 is in each case hydrogen or an optionally substituted alkyl radical and Ae is an anion.



  and the aromatic rings B and / or D 'can be further substituted, can be obtained by using an azo compound of the formula
EMI4.4
 quaternized.



   In the cationic compounds, the anion An can be exchanged for other anions, e.g. B. with the help of an ion exchanger or by reacting with salts or acids, optionally in several stages, e.g. B. via the hydroxide or the bicarbonate. The quaternization can optionally be carried out with a compound of the formula R, A (XXII), wherein
A denotes a radical which can be converted into an anion AO during the reaction.



   According to the inventive method, azo compounds of the formula
EMI5.1
 where R14 is an optionally substituted alkyl, aralkyl, aryl or cycloalkyl radical, R15 is hydrogen, an optionally substituted alkyl or alkoxy or halogen, R16 is an optionally substituted alkyl, aralkyl or aryloxyalkyl radical, Rlz and R18 are each hydrogen, an optionally substituted one Alkyl, alkoxy, aryl or aryloxy radical,
EMI5.2
   -5O2-NH-R19 or -CO-NH-R19 and R, g denote an optionally substituted hydrocarbon radical.



   The azo dyes belong, for example, to the mono- or polyazo series, where they are metal complex compounds, such as. B. 1: 1 or 1: 2 metal complex compounds.



   Anion An is understood to mean both organic and inorganic ions, such as, for. B. halogen, such as chloride, bromide or iodide, sulfate, disulfate, methyl sulfate, aminosulfonate, perchlorate, carbonate, bicarbonate, phosphate, phosphomolybdate, phosphotungstate, phosphotungframolybdate, benzenesulfonate, Naphthalene sulfonate, 4-chlorobenzenesulfonate, oxalate, maleate, acetate, propionate, lactate, succinate, chloroacetate, tartrate, malate, methanesulfonate or benzoate ions or complex anions, such as that of chlorozinc double salts.



   The compounds of the formula (IV) are free from water-solubilizing anionic groups, in particular from sulfonic acid groups.



   Halogen is to be understood in any case as bromine, fluorine or iodine, in particular chlorine.



   Hydrocarbon radicals are, in particular, optionally substituted alkyl, cycloalkyl, phenyl or naphthyl radicals.



   Alkyl or alkenyl radicals can be straight-chain or branched and can contain 1 to 18 or 1 to 12, preferably 1 to 6, carbon atoms; low molecular weight alkyl radicals usually contain 1 to 4 carbon atoms.



   If these radicals are substituted, they contain in particular a hydroxyl group, a halogen atom, the cyano or an aryl group. In such cases, alkyl can be substituted for an aralkyl, e.g. B. stand a benzyl radical. Cycloalkyl radicals contain, for example, 5 to 7 carbon atoms and are advantageously cyclohexyl radicals, which are usually by alkyl or
Alkoxy groups or halogen can be substituted.



   Aryl radicals mainly represent optionally substituted phenyl radicals; but they can also stand for naphthyl radicals.



   The radicals R4 and R5 or R5 and R7, together with the N atoms bonded to these radicals, can represent a 5- or 6-membered, saturated or partially saturated heterocycle, for example a pyrrolidine, piperidine,
Morpholine or piperazine ring.



   The coupling components belong, for example, to the aromatic series, e.g. B. the benzene or naphthalene series, which carry a coupling enabling substituent, z. B. amino- or hydroxybenzenes, amino- or hydroxynaphthalenes; but also coupling components of the heterocyclic series, such as the pyrazolone or amino-pyrazole series, the barbituric acid series or coupling components of the aliphatic series, e.g. B. the alkali, alkene or alkyne series with a couplable methylene group, z. B. Acylessigsäurearylamide, Acylessigsäurealkylamides, malonic acid or malononitrile derivatives, etc. The diazo components belong to the benzene or naphthalene series.



   All residues of an aromatic character, e.g. B. aromatic carbocyclic radicals, such as the rings B and / or D 'and / or D and / or Zl and / or Z2 or heterocyclic radicals, e.g. B.



  aromatic heterocyclic radicals can each carry substituents, especially non-water-solubilizing substituents, e.g. B. halogen atoms, nitro, amino, cyano, rhodium, hydroxy, alkyl, alkoxy, trifluoroalkyl, trichloroalkyl, phenyl, phenyloxy, alkylamino, dialkylamino, acyl, acyloxy, acylamino - such as B. urethane, alkylsulfonyl, arylsulfonyl, sulfonic acid amide, alkyl sulfonic acid amide, dialkyl sulfonic acid amide, aryl sulfonic acid amide group, arylazo, z. B.



  Phenylazo, diphenylazo, naphthylazo, etc.



   Protonizable groups are to be understood as meaning those nitrogen-containing radicals which can form salts in an acid medium, in particular a mineral acid medium, with the addition of a proton and thus make the dye water-soluble.



   Hetero rings that contain at least five members are e.g. B. thiazole, thiadiazole, triazole, imidazole, indazole, oxazole, pyridine, pyrimidine, pyridazine, pyrazine, benzthiazole, oxadiazole, quinoxaline, quinazoline, quinoline, phthalazine, pyrazole, indolenine, etc. and their derivatives.



   The quaternization can be carried out by conventional methods, e.g. in an inert solvent or, if appropriate, in aqueous suspension or without a solvent, in an excess of the quaternizing agent, if necessary, at elevated temperature and in an optionally buffered medium. Quaternizing agents are, for example, alkyl halides, e.g. B. methyl or ethyl chloride, bromide, or iodide, alkyl sulfates such as dimethyl sulfate, benzyl chloride, acrylic acid amides / hydrohalides, z. B. CH2 = CH-CO-NH, / HCI, chloroacetic acid amide, epoxides such as ethylene oxide, propylene oxide, epichlorohydrin, etc.

 

   Quaternizing agents are, for example, compounds of the formula R1-A, in which A is a radical which can be converted into an S anion.



   The new compounds can be converted into coloring preparations. The processing z. B. in stable, liquid or solid dye preparations can be done in a well-known manner, for. B. by grinding or granulating or then also by dissolving in suitable solvents, optionally with the addition of an auxiliary e.g. a stabilizer.



   Such preparations can be obtained, for example, according to the information in French patents 1,572,030 and 1,581,900.



   The new compounds are used for dyeing or printing fibers, threads or textiles made therefrom, which are made from homopolymers or copolymers of acrylonitrile or as.



  -Dicyanäthylens exist or contain such.



   You can also dye or print synthetic polyamides or synthetic polyesters which have been modified by acidic groups. Such polyamides are known, for example, from Belgian patent specification 706 104. Corresponding polyesters are known from U.S. Patent 3,379,723.



  The compounds are also used to color plastics, leather and paper. It is particularly advantageous to dye in an aqueous, neutral or acidic medium at temperatures from 60 ° C. to the boiling point or at temperatures 100 ° C. under pressure.



   Level dyeings with good lightfastness and good wetfastnesses are obtained, e.g. B. good fastness to washing, perspiration, sublimation, pleating, decatur, ironing, steam, water, seawater, dry cleaning, over-dyeing and solvents; They also have good salt compatibility and are readily soluble, especially in water. Furthermore, the dyes have good boiling fastness, good pH stability and reserve z. T. foreign fibers; They also have good cooking temperature stability and are quick-setting in combination with other coloring agents.



   Those compounds which have good solubility in organic solvents are also suitable for coloring natural plastic compositions or dissolved or undissolved plastic, synthetic resin or natural resin compositions.



  Some of the new compounds can be used, for example, to dye tannin cotton and regenerated cellulose.



   It has been shown that mixtures of two or more of the new compounds or mixtures with other cationic dyes can also advantageously be used.



   In the following examples, the parts are parts by weight, the percentages are percentages by weight and the temperatures are given in degrees Celsius.



   example 1
19 parts of 3-phenoxymethyl-5-amino-1, 2,4-triazole are dissolved in 150 parts of glacial acetic acid at 70 "and diluted with 10 parts of propionic acid and 18 parts of phosphoric acid. The mixture is cooled to 0" and 21 parts of 4N sodium nitrite solution are added dropwise to.



  The diazo solution is added dropwise within 30 minutes to a solution consisting of 15 parts of diethylaniline, 5 parts of aminosulfonic acid, 50 parts of glacial acetic acid and 25 parts of water.



  At the same time, 100 parts of ice are added to keep the temperature at 0-5. The dye solution is diluted with 160 parts of isopropanol and 100 parts of ice and the pH is adjusted to 5 by adding 110 parts of sodium acetate. The dye crystallizes out on further stirring. It is filtered off with suction, washed twice with 100 parts of water each time and dried in vacuo at 50 ".



   30.5 parts of the dried and finely ground dye are stirred in 300 parts of butanol, 3.5 parts of magnesium oxide and 25 parts of dimethyl sulfate are added and the suspension is heated to 45-50 for 3 hours. After cooling to room temperature, the dye solution is extracted twice with 150 parts of 26% brine each time and concentrated in vacuo at 50-60. The residue is dissolved in 300 parts of 800 water, mixed with 15 parts of Hyflo and 10 parts of Norit Supra and, after 15 minutes, filtered through a talc filter.



  It is rewashed with 750 parts of 50 "water and the dyestuff is salted out with 15 parts of zinc chloride and 55 parts of sodium chloride. The mixture is stirred overnight, the crystalline dyestuff is filtered off with suction and washed with a total of 100 parts of 5% sodium chloride solution. After drying at 40 "in a vacuum one obtains
EMI6.1
 the polyacrylonitrile and acid modified polyester fibers dyes in bluish-red shades.



   Example 2
8.4 parts of 3-amino-1,2,4-triazole are dissolved in 22 parts of 62% strength nitric acid and 18 parts of water. 20 parts of ice are added and 20.8 parts of 4N sodium nitrite solution are added dropwise over the course of 20 minutes. After 30 minutes, the excess nitrite is destroyed with 0.5 part of aminosulfonic acid and the diazo solution within 20 minutes to a solution consisting of 24.1 parts of N-ethyl-N-2'-phenoxy ethyl-aniline, 25 parts of glacial acetic acid and 10 Share ice, added dropwise.



  The pH is blunted to 3.5-4.0 by adding concentrated sodium hydroxide solution, the dyestuff suspension is stirred and the dyestuff which has precipitated out is filtered off. The dye, dried in vacuo, is finely suspended in 150 parts of benzene and 35 parts of cyclohexane, filtered and washed with 100 parts of cyclohexane.



   26.8 parts of the dried and finely ground dye are suspended in 80 parts of water, 3.5 parts of magnesium oxide and 18 parts of dimethyl sulfate and heated to 45-50 for 30 minutes. After cooling to room temperature, the solution is diluted with 800 parts of water, mixed with 2.5 parts of Norit Supra and filtered through a talc filter. The dye, which is salted out by the addition of 10.2 parts of zinc chloride and 80 parts of sodium chloride, is filtered, washed with 100 parts of a 10% aqueous sodium chloride solution and dried in vacuo at 50 ".
EMI6.2
  



  the polyacrylonitrile and acid modified polyester fibers dyes in red tones.



   Example3
Shade of staining
Polyacrylonitrile
The dyes listed below can be prepared by one of the processes described in Examples 1 and 2:
EMI7.1
 Example 4
EMI7.2
 Example 5
EMI7.3
 Example 6
EMI7.4
   Example 7
EMI8.1
 Example 8
EMI8.2
 bluish red Example 9
EMI8.3
 Example 10
EMI8.4

The following table lists the structure of other dyes which can be prepared by a process according to the invention. They correspond to the formula
EMI8.5
  wherein
R, Rt and R4 to R9 have the meanings given in the table.



   As anions As, those listed in the description come into question.
EMI9.1


<tb>



  E.g. <SEP> No. <SEP> R <SEP> R1 <SEP> R4 <SEP> R5 <SEP> R6 <SEP> R7 <SEP> R8 <SEP> Rg <SEP> Nuance <SEP> of the <SEP> Coloring <SEP> on <SEP> poly
<tb> <SEP> acrylonitrile
<tb> 11 <SEP> H <SEP> -CH3 <SEP> H <SEP> -CH3 <SEP> H <SEP> -CiH5 <SEP> H <SEP> Cl <SEP> red
<tb> 12 <SEP> H <SEP> do. <SEP> H <SEP> do. <SEP> H <SEP> do. <SEP> -Cl <SEP> Cl <SEP> red
<tb> 13 <SEP> H <SEP> do. <SEP> H <SEP> do. <SEP> H <SEP> do. <SEP> -CH3 <SEP> H <SEP> red
<tb> 14 <SEP> H <SEP> do. <SEP> H <SEP> do. <SEP> -CH <<SEP> do. <SEP> H <SEP> H <SEP> bluish <SEP> red
<tb> 15 <SEP> H <SEP> do. <SEP> H <SEP> do. <SEP> H <SEP> -C2H4-O O <SEP> H <SEP> H <SEP> red
<tb> 16 <SEP> H <SEP> -C2H5 <SEP> H <SEP> -C2H5 <SEP> H <SEP> -C2H5 <SEP> H <SEP> H <SEP> red
<tb> 17 <SEP> -CH3 <SEP> -CH3 <SEP> H <SEP> -CH3 <SEP> H <SEP> do. <SEP> H <SEP> H <SEP> red
<tb> 18 <SEP> O "CH2 <SEP> do. <SEP> H <SEP> do.

  <SEP> H <SEP> do. <SEP> H <SEP> H <SEP> bluish <SEP> red
<tb> 19 <SEP> 0 <SEP> do. <SEP> H <SEP> do. <SEP> H <SEP> do. <SEP> H <SEP> H <SEP> do.
<tb>



  20 <SEP> do. <SEP> -C2Hs <SEP> H <SEP> -C2Hs <SEP> H <SEP> do. <SEP> H <SEP> H <SEP> do.
<tb>



   In the following table II the structural composition of further dyes is given which can be prepared by a process according to the invention.
They correspond to the formula
EMI9.2
 wherein
R1, RR, R1o-Rl2 and X have the meanings given in the table.



   As the anion An those listed in the description come into question.



  Table II
EMI9.3


<tb> e.g. <SEP> No. <SEP> R1 <SEP> R5 <SEP> R6 <SEP> R11 <SEP> R12 <SEP> R7 <SEP> R10 <SEP> X <SEP> Nuance <SEP> der <SEP> coloring <SEP> on <SEP> polyacrylnitnl
<tb> 21 <SEP> -CH3 <SEP> -CH3 <SEP> H <SEP> Cl <SEP> H <SEP> -C2H5 <SEP> C2H5 <SEP> 1 <SEP> bluish <SEP> red
<tb> 22 <SEP> do. <SEP> do. <SEP> H <SEP> -CH3 <SEP> H <SEP> do. <SEP> do. <SEP> 1 <SEP> do.
<tb> 23 <SEP> do. <SEP> do. <SEP> H <SEP> Cl <SEP> Cl <SEP> do. <SEP> do. <SEP> 1 <SEP> do.
<tb> 24 <SEP> do. <SEP> do. <SEP> -CH3 <SEP> H <SEP> H <SEP> do. <SEP> do. <SEP> 1 <SEP> do.
<tb> 25 <SEP> do. <SEP> do. <SEP> -OCH3 <SEP> H <SEP> H <SEP> do. <SEP> do. <SEP> 1 <SEP> do.
<tb> 26 <SEP> do. <SEP> do. <SEP> -C1 <SEP> H <SEP> H <SEP> do. <SEP> do. <SEP> 1 <SEP> red
<tb> 27 <SEP> do. <SEP> do.

  <SEP> H <SEP> H <SEP> H <SEP> -CH3 <SEP> -CH <<SEP> 1 <SEP> bluish <SEP> red
<tb> 28 <SEP> do. <SEP> do. <SEP> H <SEP> H <SEP> H <SEP> -C2H5 <SEP> -CH2 {) <SEP> 1 <SEP> red
<tb> 29 <SEP> -C2Hs <SEP> -C2Hs <SEP> H <SEP> H <SEP> H <SEP> do. <SEP> -C2H5 <SEP> 1 <SEP> red
<tb> 30 <SEP> -CH3 <SEP> -CH3 <SEP> H <SEP> H <SEP> H <SEP> do. <SEP> do. <SEP> 2 <SEP> bluish <SEP> red
<tb> 31 <SEP> do. <SEP> do. <SEP> H <SEP> H <SEP> H <SEP> do. <SEP> -CH2 <SEP> O <SEP> 2 <SEP> red
<tb>



   In the following Table III the structural structure of further dyes is given which can be prepared by a process according to the invention. They correspond to the formula
EMI10.1
 wherein
R1, R5, R11-R14 and X have the meanings given in the table.



   As anions AO, those listed in the description are suitable.



  Table III Ex. No. R1 R5 R "R12 X R, 3 R14 shade of coloration on polyacrylonitrile 32 -CH3 -CH3 H H 1 -CH3 -CH3 violet 33 do. Do. H H 1 do. -C2H4COOC2H5 do.



  34 do. do. H H 1 do. -C2H4COOC4H9 do.



  35 do. do. H H 2 do. -CH3 reddish 36 do. do. H H 2 do. -C2H4COOC4H9 do.



   The following Table IV shows the structure of other dyes which can be prepared by a process according to the invention. They correspond to the formula
EMI10.2
 wherein
R, R1, R5 and X have the meanings given in the table.



   As the anion A #, those listed in the description are suitable.



  Table IV
EMI10.3


<tb> Example <SEP> No. <SEP> R1 <SEP> R5 <SEP> X <SEP> R <SEP> Nuance <SEP> of the <SEP> coloring <SEP> on <SEP> polyacrylic
<tb> <SEP> nitrile
<tb> <SEP> Al <SEP>, aJ
<tb> 37 <SEP> -CH3 <SEP> -CH3 <SEP> 1 <SEP> reddish <SEP> yellow
<tb> <SEP> V <SEP> tH3
<tb> <SEP> 3
<tb> 38 <SEP> do. <SEP> do. <SEP> 2 <SEP> do. <SEP> do.
<tb>

 

   <SEP> CH
<tb> 39 <SEP> do. <SEP> do. <SEP> 1 <SEP> (<SEP> CN <SEP> do.
<tb>



  40 <SEP> do. <SEP> do. <SEP> 2 <SEP> do. <SEP> do.
<tb>



  40 <SEP> do. <SEP> do. <SEP> 2 <SEP> do. <SEP> do.
<tb>



     Dyeing instructions for leather Spray dyeing of vegetable or combined tanned leather.



   The dry leathers are treated with a solution consisting of:
3 g / l of the dye from Example 1 with
3 g / l acetic acid 85% and
Add 30 g / l of cationic emulsifier to 1 liter with water and inject 1 to several times.



   The leathers, rinsed, dried and trimmed in the customary manner, have a bluish red, very level coloration.

 

Claims (1)

PATENT CLAIMS I. Process for the preparation of basic azo compounds free from sulfonic acid groups which contain one or more cationic groups and / or one or more substituents which enable the addition of a proton and one or more groups of the formula EMI11.1 contain, wherein R13 is hydrogen or an optionally substituted alkyl radical and X is 1, 2 or 3 and the aromatic ring B can be further substituted and the azo dyes of the formula EMI11.2 correspond to where D the remainder of a diazo component, K is the remainder of a coupling component, An anion and Y 'mean 1, 2 or 3, 663 characterized in that in a compound of the formula EMI11.3 wherein D 'the remainder of a diazo component and K 'mean the remainder of a coupling component, the ring B can be substituted and D 'and / or K' contains at least one quaternizable group, this group is quaternized. II. Use of the azo compounds prepared by the process according to patent claim I for dyeing leather.