DE2055918A1 - Basic Chmo phthalone dyes free of sulfonic acid groups, their production and use » - Google Patents

Description

Dr. W. Schciik. Dipl.-Ing. P. Wirth

Dipi.-lr.y. G. L.V. in-nbsrg

Dr. V. Schrnied-Kowarzik

Dr. P. Weinhold, Dr. D. Gudel

6 Frankfurt / M., Gr. Eschenheimer Str. 39

SANDOZ AG. Basel, Switzerland

Case 150-3111

Basic quinophthalone dyes free from sulfonic acid groups, their preparation and use

(Additional registration for Oase 150-3110) P Zfό ~ T

The invention relates to those substituted in the 4-position ^ -Hydroxyquinophthalone dyes, which are excellent for dyeing, padding and printing textile material, which consists of acrylonitrile polymers or acrylonitrile copolymers or contains such.

The new basic quinophthalone dyes free of sulfonic acid groups correspond to the formula

X-Y-Z-K

(D,

R.
wherein X -S-, -SO ₂ -, -0- or -Λ-,

Y is an optionally substituted divalent 109822/2049

Hydrocarbon radical, which can be interrupted by heteroatoms,

the direct bond or an optionally substituted alkylene radical, an anion and
the group of the formula

R.

-N-

or

mean,

(II), (III).

(IV)

(V)

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wherein R represents a hydrogen atom or an optionally

substituted hydrocarbon radical, R _{1 is} an optionally substituted alkyl

or cycloalkyl radical or together with R "and the adjacent N atom for a heterocycle, R_ for an optionally substituted alkyl

or cycloalkyl radical or together with R, and the adjacent N atom for a heterocycle, R and R ₂ , each for a hydrogen atom or for

identical or different, optionally substituted alkyl or cycloalkyl radicals or for identical or different acyl radicals, R (- and Rg each for an optionally substituted hydrocarbon radical,
R "for an optionally substituted alkyl or cycloalkyl radical,

Rg for an optionally substituted hydrocarbon radical,

Rq for an optionally substituted amino group or for an optionally substituted hydrocarbon radical,

R._ for an optionally substituted hydrocarbon radical,

Z, for a carbon or nitrogen atom, R, together with R- and / or

R ₂ together with R ₂ , and the N atoms adjacent to these substituents

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and R-; or 5 ο

r- and R-; 5 ο

R ₁ - R / - and R "can form heterocycles together with the neighboring N atom,

the group of the formula (IV) -Z ^ -N> v de :: i radical of a multi-link

dry, saturated or partially saturated, optionally further substituted ring and the group of the formula (V) -Z _Jj & - the remainder of an unsaturated, optionally substituted one Mean ring and the aromatic rings B and / or D can be further substituted.

The dyes of ^the formula (i) can be obtained by using a compound of the formula

Shark

(VI),

HC

wherein Hai represents a halogen atom, with a compound the formula

HXYZK A ^Q (VII)

implements.

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Dyes of the formula

X-Y-Z-K,

(VIII)

wherein K, is a group of the formula (II) or (III), can be made using a compound of the formula

X-Y-Z-A

in which A is a radical that can be converted into an anion, with a compound of the formula

R.

N-N

R.

(X)

^{> R} 7

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(XI)

implements.

Dyes of the formula

X-Y-Z-K,

(XII),

wherein K _{p is} a group of the formula (III), (IV) or (V) can be obtained by using a compound of the formula

X-Y-Z-N

(XIII)

X-Y-Z-

(XIV)

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X-Y-Z-

(XV),

wherein the group ~ ^ _J ^ ~ ^R 8 is ^{the radical of a} saturated or partially saturated, optionally substituted ring and the group of the formula -zT ^ i is the radical of an unsaturated, optionally substituted ring, quaternized to a compound of the formula (XII). Good dyes conform to the formula

SYZK _Λ

(XVI)

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or the formula

S - alk - K

(XVII),

wherein alk denotes an optionally substituted, straight-chain or branched alkylene radical.

Dyes of the formula

SCL -Y-Z-

(XVIII)

can be obtained by oxidizing a compound of formula (XVI).

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The new dyes are also used for dyeing or printing synthetic polyamides or synthetic polyesters, which are modified by acidic groups. Such polyamides are known, for example, from Belgian patent specification 706.104. The corresponding polyesters are from the USA patents 3.OI8.272 or 5O79.723 known.

Dyeing is generally particularly advantageous in aqueous, neutral or acidic medium at temperatures of 60-100 ° C or at temperatures above 10O ⁰ C under pressure, this also be obtained without the use of retarders level dyeings.

Mixed fabrics, which contain a polyacrylonitrile fiber content, can be colored very well. Those dyes which have good solubility in organic solvents are also used for coloring natural plastic masses or dissolved or undissolved plastic or natural resin masses suitable. It has been shown that it is also advantageous to use mixtures of two or more of the new dyes or can use mixtures with other cationic dyes; ie. the dyes can be easily combined. she are also used to color plastic masses or leather or to color paper.

Levels are obtained in particular on acrylonitrile polymers or copolymers, but also on other substrates Dyeings with good lightfastness and good wetfastness.

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The new dyes can be converted into dye preparations. Processing e.g. in stable liquid or solid Coloring preparations can be made in a generally known manner, e.g. by grinding or granulating or then also dissolving in suitable Solvents, optionally with the addition of an auxiliary, e.g. a stabilizer.

Halogen is in any case to be understood as meaning bromine, fluorine or iodine, but preferably chlorine. Hydrocarbon radicals are, for example, optionally substituted Alkyl, such as cycloalkyl radicals or optionally substituted Aryl radicals, e.g. cyclohexyl, alkylcyclohexyl »or Phenyl residues.

Alkyl radicals, e.g. straight-chain or branched alkyl radicals mostly 1 to 12, or 1 to 6 and preferably 1, 2, 3 or 4 carbon atoms. If these radicals are substituted, included they in particular halogen atoms, hydroxyl or cyano groups or aryl radicals, such as, for example, phenyl radicals; Alkyl stands for such cases for an aralkyl radical, e.g. a benzyl radical. Alkoxy radicals contain, for example, 1 to 6 and preferably 1, 2 or 3 carbon atoms.

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Alkylene radicals can be straight-chain or branched and, for example be substituted by halogen atoms, hydroxyl or cyano groups j they can be 1 to 6 and preferably 1 to j Contain carbon atoms.

Divalent radicals can be, for example, optionally substituted hydrocarbon radicals, such as optionally substituted Alkylene or alkenylene radicals, phenylene or cyclohexylene radical, where in general the alkylene radicals are replaced by heteroatoms, such as oxygen, sulfur or nitrogen atoms can be interrupted. Divalent radicals can also be the -SOp-, -S-, -0- or -N- group. Rj. And Rp, together with the neighboring N atoms, can be heterocycles form, e.g., a pyrrolidine, piperidine, morpholine, aziridine or piperazine ring.

The radical R, together with R and / or the radical R ₂ together with R ₁ , and any N atoms adjacent to these substituents, can form a saturated or unsaturated, advantageously 5- or 6-membered heterocycle, for example a pyrazolidine, pyridazine or pyrazoline ring, for example trimethylene pyrazolidine or tetramethylene pyrazoline, etc. The radicals R ^ and Rg together with the adjacent 'N atom can form a heterocycle, for example a pyrrolidine, piperidine, morpholine, aziridine or piperazir ring.

The radicals R, -> Rg and R ₇ , together with the adjacent N atom, can form a heterocycle, for example a group of the formula

109822/2 049

- N - CH ₂ - CH ₂ - N

'CH ₂ - CH ₂ '

or represent a pyridinium ring.

_ © The groups of the formula - ^

or -ZL N stand

for example for the residues of saturated or partially saturated, or unsaturated, optionally substituted multi-membered rings, preferably 5- or 6-membered rings, which optionally contain further cycloaliphatic,

heterocyclic or aromatic rings can be fused. These groups can therefore e.g. for a pyridine, Quinoline, piperidine, pyrrolidine, morpholine, aziridine, piperazine, isoquinoline, tetrahydroquinoline, pyrazole, triazole, Pyridazine, imidazole, pyrimidine, thiazole, benzothiazole, Thiadiazole, indazole, imidazole, pyrrole, indole, oxazole, isoxazole or tetrazole ring, etc.,

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The radicals A are preferably those of the hydrogen halide acids; A preferably represents chlorine or Bromine. Further Saureres te A are, for example, those of Sulfuric acid, a sulfonic acid or hydrogen sulfide.

The anion A exchange with other anions, e.g. with the help of an ion exchanger or by reaction with salts or acids, if necessary in several stages, e.g. via the hydroxide or the bicarbonate.

θ
Anion A is understood to mean both organic and inorganic ions, such as halogen, such as chloride, bromide or iodide, sulfate, disulfate, methyl sulfate, aminosulfonate, perchlorate, carbonate, bicarbonate, phosphate , Phosphorus molybdate, phosphorus tungstate, phosphorus wolf rammolybdate, benzenesulphonate, naphthalene sulphonate, 4-chlorobenzenesulphonate, oxalate, maleate, acetate, propionate, lactate, succinate, chloroacetate, tartarate, methanesulfonate or benzoate or complex anions such as that of zinc chloride double salts.

The rings B and / or D can be further substituted, in particular by non-water-solubilizing substituents, for example by halogen atoms, alkyl, alkoxy, hydroxyl, cyano, amino, trifluoroalkyl, trichloroalkyl or urechane groups, etc.

The implementation of a compound of formula (VI) with a Compound of the formula (VII) can according to known

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Methods are carried out, e.g. in an inert solvent, optionally with the addition of an alkaline compound and, if necessary, at elevated temperatures, possibly under pressure.

The implementation -. ^:; Iner compound of formula (IX) with a compound of formula (X) or (XI) is preferably carried out in an organic solvent ™ and at temperatures from -50 ⁰ C to +250 C, preferably at -10 ⁰ C to +120 ⁰ C.

The quaternization can also be carried out by customary methods, for example in an inert solvent or optionally in aqueous suspension or without solvent in an excess of the quaternizing agent, if necessary at elevated temperature and in optionally buffered medium. Quaternizing agents are, for example, alkyl chloride, bromide-P or iodide, alkyl sulfates, such as dimethyl sulfate, benzyl chloride _{, e.g. CH 2} = CH - CO - NHp / HCl, alkyl chloroacetate, ß-chloropropionic acid amide, epoxides such as ethylene oxide, propylene oxide, epichlorohydrin, etc.

Quaternizing agents are e.g. R ₇ -A, R _Q -A or -R ₁₀ -A *

From the German Auslegeschrift 1 286 666 1; t including the dye the formula

109822/2049

CH OSO J-

known for coloring polyacrylonitrile. It is surprising that the compounds of the formula (I) are also based on polyacrylonitrile colored, have an improved permutite water resistance.

In the following examples, parts are parts by weight, percentages are percentages by weight; the temperatures are in degrees Celsius specified.

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'- 16 Example 1

21 parts of 4- (diethylaminoethyl) mercapto ^ -hydroxyquinophthalone are dissolved in 300 parts of Ch. '. orbenzene at room temperature " 6.8 parts of dimethyl sulfate are added dropwise to this solution at 20-25 °; a yellow precipitate forms. After the addition of the dimethyl sulfate, the Stir the yellow suspension for some time at 20-25 °, then separate the yellow precipitate and crystallize it out Dimethylformamide. A reddish-tinged yellow crystal powder with a melting point of 229-230 ° is obtained. With the received Dye can color polyacrylonitrile in real yellow tones.

Example 2

14.2 parts of 4- 2-hydroxyethyl mercapto- ~ j -3-hydroxyquinophthalone produced by reacting 4-bromo-3-hydroxyquinophthalone 2-mercaptoethanol in the presence of potassium carbonate and 2-ethoxy

ethanol, are dissolved in 28o parts of dry chlorobenzene at 80 °. In the absence of humidity, the the yellow-orange mixture was added dropwise 5 »2 parts of thionyl chloride within 2-3 hours. Then you hold the mixture Hours at 100-120 °, until a thin-layer chromatogram shows that only traces of starting material in addition to 4-r2-chloroethyl mercapto ^ J -3-hydroxychincphthalone are present. Now it is concentrated to dryness under vacuum, with 16.2 parts of an orange-yellow crystallized compounds occur.

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These orange-yellow crystals are heated in 80 parts of pyridine to 100-110 °; the mixture is 12 hours at this Temperature stirred. After cooling to 50-60 °, the mixture is added dropwise with 160 parts of chlorobenzene, filtered off the precipitate formed and washed with chlorobenzene until the Expiration is colorless. After drying, an orange-yellow powder is obtained which contains polyacrylonitrile fibers in pure yellow tones good lightfastness.

Example 5

16.2 parts ^ -jjS-ChlorMethylmercapto-J -3-hydroxychlnophthalone are for 24 hours with a solution of 2.64 parts Dimethylhydrazine stirred in 200 parts of water at 50-60 °, after which a large part of the orange-yellow powder used has gone into solution.

The undissolved residue is filtered off and salted from the The dye was released by the addition of common salt. To Filtration and drying give an orange-yellow powder.

Polyacrylonitrile fibers are thus included in pure yellow tones

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Dyeing instructions :

20 parts of the dye from Example 1 are mixed with 80 parts of dextrin mixed in a ball mill for 48 hours. 1 part of the so obtained The preparation is made into a paste with 1 part of 40 # acetic acid, 200 parts of demineralized water are poured over the porridge and briefly boiled. Dilute with 7000 parts of demineralized Water, adds 2 parts of glacial acetic acid and goes at 60 ° with 100 parts

' Put polyacrylonitrile fabric into the bathroom. The material can be pretreated beforehand for 10 to 15 minutes at 60 ° in a bath consisting of 8000 parts of water and 2 parts of glacial acetic acid.

The mixture is heated to 98-100 ° within 20 minutes and cooked for 1 1/2 hours long and rinse. A yellow dyeing with good lightfastness is obtained and good wet fastness properties.

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Claims (12)

Claims where X
Y κ® -S-, -SO ₂ -, -0- or -N-, an optionally substituted, divalent hydrocarbon radical which is replaced by heteroatoms can be interrupted, the direct bond or an optionally substituted alkylene radical,
an anion and
the group of the formula Θ
-N- 5 ^l 7 109822/2049 (II), (m) or mean, 10 Ci (IV) (V) where R R. R- for a hydrogen atom or an optionally substituted hydrocarbon radical, for an optionally substituted alkyl or cycloalkyl radical or together with R _p and the adjacent N atom for a heterocycle, for an optionally substituted alkyl or cycloalkyl radical or together with R, and the adjacent N- Atom for a heterocycle, and R ₂ , each for a hydrogen atom or for identical or different, optionally substituted alkyl or cycloalkyl radicals or fl ^: identical or different acyl radicals, 109822/2049 (M Rj-. and Rg each for a possibly substjfcuier- th hydrocarbon residue,
R ₁₇ for an optionally substituted alkyl or cycloalkyl radical, Ro for an optionally substituted hydrocarbon radical, Rq for an optionally substituted amino group or for an optionally substituted hydrocarbon fre s t, R ₁₀ for an optionally substituted hydrocarbon radical, Z, for a carbon or nitrogen atom, R, together with R, and / or Rp together with R ^ and the N atoms adjacent to these substituents,
R, - and R ^ or Rc Rg and R „together with the neighboring N atom Can form heterocycles, the group of the formula (IV) -Z ^ NC the remainder of a multi-member dry, saturated or partially saturated, optionally further substituted ring and the group of the formula (V) - The remainder of an unsaturated, optionally substituted one Mean ring and the aromatic rings B and / or D can be further substituted. 109822/2049 2. SuIfonsäuregruppeη free quinophthalone dyes according to claim -1 that of the formula XYZK ₁ (VIII). correspond, wherein K, denotes a group of the formula (II) or (III). 3. Quinophthalone dyes free of sulfonic acid groups according to claim 1 that of the formula X-Y-Z-K, (XII), correspond, wherein K _{2 is} a group of the formula (III), (IV) or (V). 4. Quinophthalone dyes free of sulfonic acid groups according to patent 109822/2049 claim 1 that of the formula S-Y-Z-K (XVI) correspond. 5, quinophthalone dyes free of sulfonic acid groups according to Claim 1 of the formula S - alk - K (XVII) correspond, wherein alk is an optionally substituted, straight-chain or branched alkylene radical. 6. Process for the preparation of free basic sulfonic acid groups 109822/2049 Quinophthalone dyes of the formula (I) according to claim 1, characterized in that a compound of the formula Shark (VI), wherein Hai represents a halogen atom, with a compound the formula H-X-Y-Z-K (VII) implements. 7. A process for the preparation of quinophthalone dyes of the formula (VIII) according to claim 2, characterized in that that you can get a compound of the formula X-Y-Z-A OH 109822/2049 in which A is a radical that can be converted into an anion, with a compound of the formula R. N-N: ¹ p (X) implements " Rr 6 ^R 7 (XI) 8. A process for the preparation of quinophthalone dyes of the formula (XII) according to claim 2, characterized in that that you can get a compound of the formula X-Y-Z-N (XIII). XYZ- Z ^ Ji -R 109822/2049 (XIV) X-Y-Z- in which the group ~ \ ~ ^ $ - ^r ö denotes ^the remainder of a saturated or partially saturated, optionally substituted ring and the group of the formula -% T ^ K denotes the remainder of an unsaturated, optionally substituted ring, to a compound of the formula (XII) quaternized. 9. Use of the dyes of the formula (I) according to claim 1 for dyeing, padding or printing fibers, threads or textiles made from them that are made from acrylonitrile polymers or copolymers exist or such contain. 10. Use of the dyes of the formula (I) according to claim 1 for dyeing, padding or printing synthetic polyamides or synthetic polyesters, which by acidic groups are modified. 109822 / 20A9 11. Use of the dyes of the formula (I) according to claim 1 for dyeing ocer printing on plastics, leather and paper. 12. The according to claims 9 and 10 colored, padded and printed textiles . The materials dyed and printed according to claim 11. The patent attorney (Dr. y / 'Schmied- ^ owarzik) 109822/2049