DE3544574A1 - Cationic pyrazole azo compounds - Google Patents

Abstract

Cationic pyrazole azo compounds of the formula <IMAGE> in which R1 denotes methyl, ethyl, hydroxyethyl or 2-hydroxypropyl, R2 denotes C3-C6-alkyl, R3 denotes C3-C6-alkyl, hydroxyethyl or 2-hydroxypropyl, R4 denotes hydrogen, methyl or methoxy, each R5, independently of the others, denotes hydrogen, chlorine, methyl or methoxy, n denotes 1, 2 or 3 and A<-> denotes an anion, where the molecule contains at most one of the hydroxyalkyl groups mentioned, are described. These compounds can be used as dyestuffs for dyeing or printing, e.g., polyacrylonitrile materials, red finish dyeings being obtained.

Description

Dr. F. Zumstein sehV-iJft £ .'Assmann ^ _. . j_ _.

Dipf.-lng. F- Klingseisen - Dr. F- Zumstein jun- ^ O 4 4 O / 4

PATENT LAWYERS

APPROVED REPRESENTATIVES AT THE EUROPEAN PATENT OFFICE
REPRESENTATIVE BEFORE THE EUROPEAN PATENT OFFICE

CIBA-GEIGY AG

Basel (Switzerland) 1-15202 / +

Cationic pyrazole azo compounds

CH.

»
4th

wherein

R ^ methyl, ethyl, hydroxyethyl or 2-hydroxypropyl,
R ₂ C ₃ -C ₆ -alkyl,

R ₃ C_-C ₆ -alkyl, hydrox7ethyl or 2-hydroxypropyl,
R is hydrogen, methyl or methoxy, each

R ^ independently of the other hydrogen, chlorine, methyl or
Methoxy, η 1, 2 or 3 and

The invention relates to new cationic pyrazole azo compounds, 1

Process for their production and their '.' 'Use as dyes r'

for dyeing or printing cationically dyeable materials, '■■

preferably made of polyacrylonitrile, acid modified polyamide or \

acid modified polyester. f-

Cationic pyrazole-azo compounds with optionally N-substituted j

ated anilines as coupling components are from a large number of J

known from publications. See, for example, US-A-3,435,022, F

GB-A-I, 404,097, GB-A-I, 438,386, FR-A-I, 392,581, FR-A-I, 392,645, |

SU-A-914,603 (CA. Vol. 97, 111285). I.

The new cationic pyrazole azo compounds according to the present f

Invention correspond to formula g

354457A

A ^ mean an anion,

wherein the molecule has at most one of the said hydroxyalkyl groups contains.

The alkyl radical R _£ or R ₃ can be straight-chain or branched. The isopropyl or n-propyl radical is preferred. The index η stands in particular for 1 or 2, preferably for 1.

The anion can be any inorganic or organic anion which only acts as a counterion for the positive charge on the pyrazole nitrogen. It can be compared to the one introduced during the Qaternization Anion can be identical, but it can also be introduced subsequently by exchanging a different anion. Examples of possible anions are: halide (e.g. chloride, bromide or iodide), boron tetrafluoride, rhodanide, sulfate, methyl sulfate, ethyl sulfate, aminosulfonate, Perchlorate, carbonate, bicarbonate, phosphate, phosphomolybdate, Phosphotungstate, phosphotungstamolybdate, benzenesulphonate, Naphthalene sulfonate, 4-chlorobenzenesulfonate, oxalate, Maleate, formate, acetate, propionate, lactate, succinate, Chloroacetate, tartrate, methanesulfonate or benzoate ions, or complex anions such as that of chlorozinc double salts.

Halide, sulfate, methyl sulfate, ethyl sulfate, phosphate, benzenesulfonate, 4-chlorobenzenesulfonate, oxalate, Formate, acetate and methanesulfonate ions as well as the complex anions mentioned.

It goes without saying that the invention also includes all possible tautomeric forms of the compounds of formula (1), e.g. the following:

at *

tr «· t

: ^Λ 3

-N = N-B

A ^ V

-3

R ₁ -N. > -N = NB

I I

etc.

In the above formulas, B means - <

In the context of the compounds of the formula (1), particular mention should be made of those in which R ₁ denotes hydrogen, and those in which R 1 denotes hydrogen.

Preferred compounds of the formula (1) are those in which R represents methyl or ethyl, in particular methyl.

Of particular practical interest are those pyrazole-azo compounds according to the invention in which R and R are independent of one another G-C -C alkyl, especially those in which R "and R are the same are and are preferably propyl.

The new cationic pyrazole-azo compounds are technically good accessible and can be prepared by processes known per se. For example, they can be obtained by one Amine of the formula

J ^ _

HI

(2)

diazotized, with an aniline of the formula

O)

couples and the azo compound obtained with a compound of formula

R ₁ -A

(4)

quaternized, where in the above formulas IL, R, R, R TL and η are defined as in formula (I) and A denotes a radical which can be converted into the anion A ^ during the quaternization.

The amines of the formula (2) (see e.g. the pressure mentioned on page 1 Fonts), the anilines of the formula (3) and the quaternizing agents of the formula (4) are known or can be used in a manner known per se to be easily made

The anines of the formula (2) are diazotized in a manner known per se, for example with sodium nitrite in acidic, e.g. B. hydrochloric acid, sulfuric acid or phosphoric acid, aqueous medium. The diazotization can, however, also with other diazotization agents, for example with

Nitrosylsulfuric acid can be carried out. An additional |

Acid be present in the reaction medium, e.g. phosphoric acid, J.

Sulfuric acid, acetic acid, hydrochloric acid or mixtures of these acids, §

e.g. mixtures of phosphoric acid and acetic acid. Appropriate is |

the diazotization at temperatures from -10 to 30 ⁰ C, for example from -10 ⁰ C |

to room temperature. _s

The coupling of the diazotized amine of the Ί? ΟΏηεΙ (2) on the coupling _t

I component of the formula (3) is also carried out in a known manner, with |

for example in acidic, aqueous or aqueous-organic medium, above I

partly at temperatures of -10 to 30 ⁰ C, in particular below 10 ⁰ C. As Ϊ

Acids are used e.g. hydrochloric acid, acetic acid, sulfuric acid or ^

Phosphoric acid. Diazotization and coupling can, for example, in the k

One-pot process, i.e. in the same reaction medium, carried out |

will. ι

The quaternization is expediently carried out in an indifferent ',

organic solvent, for example in a hydrocarbon - "?

substance, chlorinated hydrocarbon or nitro hydrocarbon, such as
Benzene, toluene, xylene, tetrachloroethane, chloroform, carbon tetrachloride, mono- or dichlorobenzene or nitrobenzene, all in one
Acid amide or acid anhydride, such as dimethylformamide, N-methylacetamide
or acetic anhydride, in dimethyl sulfoxide or in a ketone,
such as acetone or methyl ethyl ketone. Instead of an organic
Solvent can also be an excess of the alkylating agent
be used. But it can also work in an aqueous medium
«Earth, for example in an aqueous suspension or in glacial acetic acid. the
Quaternization is advantageous at elevated temperature, e.g.
30-200 ⁰ C, in particular 80-150 ⁰ C, optionally with the addition of
acid-binding agents, such as an inorganic base, e.g.
Magnesium oxide, magnesium carbonate, soda, calcium carbonate or
Sodium bicarbonate and optionally under pressure. the
the most favorable conditions in each case can be determined by a preliminary test %

easily determine. I.

Suitable quaternizing agents R ..- A are, for example, alkyl halides, such as Methyl or ethyl chloride. Methyl or ethyl bromide or methyl or Ethyl iodide, but above all alkyl sulfates such as dimethyl or diethyl sulfate, and alkyl esters of aromatic sulfonic acids such as methyl p-toluoisulfonate or methylbenzenesulfonate and ethylene oxide or propylene oxide. The radical A thus means, for example, halogen (in particular chlorine, bromine or iodine), CH SO, -, C H SO - or

"^ / · ~ ⁵⁰ 3 ~ ^(R 6 ^{= H} » Hai-ogen »methyl).

After the quaternization, the new cationic pyrazole azo compounds can be separated from the reaction medium and dried or used directly as a solution. If desired or necessary, it is possible to exchange the anion S ^ in the compounds of the formula (1) for another anion. For better isolation, the compounds of the formula (1) can be precipitated from the reaction medium, for example, by converting them into a salt that is sparingly soluble in it, that is to say exchanging the anion A accordingly. This can be done, for example, by adding a halide (conversion into a halide; AF ^ Hal) or, for example, ZnCl

Θ 2θ /

and NaCl (conversion into a zinc chloride double salt A-ZnCl, / T) take place ("salting out").

The new cationic pyrazole-azo compounds of the formula (1) are used as dyes for dyeing and, with the addition of binders and solvents, for printing materials which can be dyed with cationic dyes, in particular textile fiber materials; these materials consist, for example, of homopolymers or copolymers of acrylonitrile ( polyacrylonitrile) or synthetic polyamides or polyesters which are modified by acidic groups. In addition, the new cationic azo compounds are also used to dye wet tow (dyeing fibers in the gel state), plastic compounds, preferably made from the specified polymers, and tannin cellulose materials, leather and paper. The mentioned use of the azo according to the invention

Compounds, as well as a process for dyeing or printing the aforementioned materials, which consists in adding one or to apply several of the compounds of the formula (1) to said materials or to incorporate them into them are also objects of the present invention as well as the colored material obtained by this coloring process.

For dyeing with the cationic dyes of the general formula (1), flakes, fibers, threads, tapes, woven fabrics of any knitted fabric made of polyacrylonitrile or copolymers of acrylonitrile containing at least 85% acrylonitrile are particularly suitable with other vinyl compounds such as vinyl chloride, vinylidene chloride, Vinyl fluoride, vinyl acetate, vinyl pyridine, vinyl imidazole, vinyl alcohol, acrylic and methacrylic acid esters and amides, as. Dicyanethylene. Flocks, fibers, threads, tapes, woven or knitted fabrics made from acid-modified synthetic materials, in particular 312S sstie ** modified aromatic pole ^v sstsr? 2 sos? Is acid-modified polyamide fibers, can also be dyed. Acid modified aromatic polyesters are, for example, polycondensation products of sulfoterephthalic acid and ethylene glycol, ie polyethylene glycol terephthalates containing sulfonic acid groups.

Dyeing is preferably carried out from an aqueous neutral or acidic medium by the exhaust process, optionally under pressure or by the continuous process. One enters the dyebath with the material to be dyed, for example at about 40 to 60 ^° C., and then dyed at high temperature. It is also under pressure over 100 ⁰ C, color eg 110-130 ⁰ C, in a Druckfärbeapparat. If textile material is dyed, it can be in the most varied of forms, for example as fibers, threads, woven fabrics, knitted fabrics, piece goods or finished goods.

The erfindungsgeraässen pyrazole-azo compounds of the formula (1) lead, if they are applied to the above-mentioned materials, they result in red colorations or prints, which are characterized by very good properties, especially high pH stability, steam fastness, very good

- ο -

Characterized by drawability and high lightfastness. The dyeings obtained shows? Surprisingly no "first brake", i.e. no decrease in license fastness after a short exposure time, e.g. within of the first 30 hours, as can often be observed in dyes of a similar constitution.

The compounds of the formula (1) according to the invention can be used as dyes for the o \ -ü. purposes described as single compounds. at least 2 compounds of formula (1) may be used or in Mix _fa to contain.

The following examples illustrate ^r j.xe invention further; Unless otherwise stated, parts and percentages are based on weight. Melting points are uncorrected.

Example 1;

a) 43.2 parts of 1-phenyl-3-methyl-5-amino-pyrazole are dissolved in 203 parts of 68% sulfuric acid at 50-55 ⁰ C, cooled to -5 ° C to -10 ⁰ C and by dropwise addition of 79.4 parts of 40% nitrosylsulfuric acid riazotized for 30 minutes. After stirring for one hour at the same temperature, a solution of 44.2 parts of NN-dipropylaniline in 100 parts of glacial acetic acid and 50 parts of propionic acid is added dropwise to the diazo solution at -5 ⁰ C to -10 ^e C.

After two hours of stirring at the same temperature, the reaction mixture is at 0-5 ^c C a mixture of 750 parts of ice and water was added dropwise, ^ obei simultaneously by dropwise addition of 1164 parts of 15% sodium hydroxide solution, a constant pH of 2-2.5 is adhered to. The azo compound is extracted from the suspension obtained with 1300 parts of methylene chloride and the extract is dried over sodium sulfate. After the solvent has been distilled off, 84 parts of the azo compound of the formula are obtained

u * «- fy« w2

I Il

obtain. Melting point: 90-93 ° C.

b) 52 parts of the azo compound of the formula (L · -) 24.3 parts of magnesium oxide and 650 parts. Ethylene chloride are heated to 75-80 ° C. 72 parts of dimethyl sulfate are added dropwise in 60 minutes and the mixture is stirred for 3 hours at the temperature mentioned. The solvent is removed by distillation, dissolving the reaction product zurückgcllicbene in 1500 parts of water, heated to 70 ⁰ C and clarified by filtration. At room temperature, the solution is adjusted to pH 4 with 2N hydrochloric acid and the reaction product is salted out by adding 215 parts of sodium chloride and 14 parts of zinc chloride. The precipitated product is filtered off and dried. 53 parts of the quaternized azo compound of the formula are obtained in this way

I Il

S \

: .- n (c ₃ h ₇ ) ₂

-ZnCl ₄

Melting point: 162-172 ° C.

35U574

- 10 -

Example 2: The procedure according to the procedure given in Example 1, and sets as the diazo component l-phenyl-S-methyl-S-aminopyrazole, as a coupling component an appropriately substituted aniline and an appropriate, the radical R introductory quaternizing a _# is obtained in the following table indicated quaternized azo compounds of the formula

sy

Tabel:

link
No. ^R l ^R 2 R ₃ ^R 4 iznClJ ⁰ nuance
on
Poly
acrylic
nitrile 201 CH ₃ -C ₄ H ₉ -C ₄ H ₉ H fzuCl ^ ⁰ Red 202 CH.OH *) UC ₃ H ₇ UC ₃ H ₇ H | ^ZnC1 4 ^ö Red 203 CH ₃ UC ₃ H ₇ C ₂ H ₄ OH H i ^ZnC1 ? _n Red 204 CH ₃ UC ₃ H ₇ UC ₃ H ₇ OCH ₃ i ^ZnC1 4 ^ Red 205 CH ₃ UC ₃ H ₇ UC ₃ H ₇ CH ₃ | ^ZnC1 4 " Red 206 CH ₃ CH (OH) CH **) UC ₃ H ₇ UC ₃ H ₇ H I ^ZnC1 4 Red 207 CH ₃ -C ₄ H ₉ C ₂ H ₄ OH H —ZuCX,
2 * + -> «k Red 208 CH ₃ ⁿ " ^C 5 ^H ll C ₂ H ₄ OH H Ι ^Ζη01 4 ^Θ Red 209 CH ₃ CH (OH) CH ₂ -C ₄ H ₉ -C ₄ H ₉ H fznCl20 Red 210 CH ₃ HC ₅ H ₁₃ UC ₆ H ₁₃ H 2 4 Red 211 CH ₄ OH *) nC ₆ H ₁₃ HC ₆ H ₁₃ H —ZnCl f Red 212 C ₂ H ₄ OH *) HC ₆ H ₁₃ UC ₆ H ₁₃ CH ₃ Red 213 CH ₃ -C ₄ H ₉ -C ₄ H ₉ CH ₃ Red

• · « 4 tt

- 11 -

*) The quaternization is carried out with ethylene oxide.

**) The quaternization is carried out with polypropylene oxide * The compounds (101) and 201) - (213) can also be stripped with another anion, for example as chloride, iodide, bromide or acetate, if they are mixed with a corresponding salt, e.g. NaCl, KBr, KI, Na acetate, etc.) are salted out of the reaction solution. she

but can also be used directly, e.g. as methosulphates (A ^ = CH S0, ^ <> are isolated (compounds (201), (203) - (205), (207), (208), (210) and (213), which are quaternized with dimethyl sulfate).

Example 3: Polyacrylonitrile fiber fabric is introduced into an aqueous bath at 60 ^° C. in a liquor ratio of 1:80, which contains 0.125 g of glacial acetic acid, 0.375 g of sodium acetate and 0.075 g of the dye formula (LO1) (or the corresponding amount of a solid or liquid Preparation of this dye). The mixture is heated to the boil within 20 to 30 minutes and the bath is kept at this temperature for 90 minutes. After rinsing, a brilliant red colored fabric is obtained. The coloring shows very good calibration properties.

Example 4: Fabric made from acid-modified polyester fibers is introduced into an aqueous bath at 20 ° C. in a liquor ratio of 1:30, which contains 6 g of sodium sulfate, 2 g of ammonium sulfate and 0.15 g of the dye of the formula Q-Ol) or the corresponding Contains amount of a solid or liquid preparation of this dye. A pH of 5.5 is set with formic acid. One erwämt in a closed vessel within 45 minutes to 120 ⁰ C and maintains this temperature with shaking for 60 minutes at. After rinsing and drying, a brilliant red colored fabric is obtained. The dyeing has very good fastness properties.

If one sets in the examples. 3 and 4 in place of the compound of formula (LOl) one of the formula (2O3) - (213), we obtain "n for the used tissues also roue dyeings with similarly good specially chaften a.

Claims (1)

Patent claims: 1. Cationic pyrazole azo compounds of the formula ■ m Π Il, · - ». R _{1 is} methyl, ethyl, hydroxyethyl or 2-hydroxypropyl, R _{2 is} C ₃ -C ₆ -alkyl, R ₀ CC, -alkyl, hydroxyethyl or 2-hydroxypropyl, J JD R, hydrogen, methyl or methoxy, each R independently of the other hydrogen, chlorine, methyl or Methoxy, η 1, 2 or 3 and
A mean an anion wherein the molecule has at most one of the said hydroxyalkyl groups contains. 2. Cationic pyrazo! Azo compounds according to claim 1, wherein η stands for 1. 3. Cationic pyrazole azo compounds according to claim 1 or 2, wherein R, and R are hydrogen. 4. Cationic pyrazole-azo compounds according to one of the Anene claims 1 to 3, wherein R is methyl or ethyl, especially methyl. 5. Cationic pyrazole-azo compounds according to any one of claims 1-4, wherein R- and R independently of one another are C -C ^ -alkyl. JL 1 Jo - 13 - 6. Cationic pyrazo! Azo compounds according to claim 5, wherein R and R are the same and mean propyl. 7. A process for the preparation of cationic ones as defined in claim 1 Pyrazo1 — azo compounds, characterized in that one Amine of the formula diazotized, with an aniline of the formula couples and the azo compound obtained with a compound of the formula R-A quaternized, where in the above formulas R, R, R, RR _{un (} } _nw i _e are defined in claim 1 and A denotes a radical which can be converted into the anion A during the quaternization. the cationic pyrazole azo compounds defined in claim i as dyes for dyeing or printing cationically dyeable materials. 9. Use according to claim 8 for dyeing or printing Materials, preferably textile fiber materials, made of polyacrylonitrile, acid-modified polyamide or acid-modified polyester « • * aar « fm - 14 - 10. The material dyed or printed according to claim 8 or 9. 11. The textile material dyed or printed according to claim 9 Polyacrylonitrile. FO 7.1 RI / gb * / sl *