CH661739A5 - CATIONIC PYRAZOLE AZO COMPOUNDS. - Google Patents

Description

The invention relates to new cationic pyrazole azo compounds and a process for their preparation.

Cationic pyrazole azo compounds with optionally N-substituted anilines as the coupling component are known from a large number of publications.

'- / - • N ® / 2

"A <

I -fr-R-

V

Ì ©

.A.

, 0

-tt-R "

V

, 0

3rd

661 739

B means in the above formulas

/ 3rd

A 'thus preferably means halogen (in particular chlorine, bromine or iodine), alkyl-S04- or

\

Of particular note in the context of the compounds of formula (1) are those in which R4 is hydrogen and those in which Rs is hydrogen.

Preferred compounds of the formula (1) are those in which R 1 is methyl.

Of particular practical interest are those pyrazole azo compounds according to the invention in which Rs and R3 are the same and mean propyl.

The new cationic pyrazole azo compounds are technically easily accessible and can be prepared by processes known per se. They can be obtained, for example, by using an amine of the formula f3

"left

V-hh2

I.

'-t ~ Rs

V 5

diazotized with an aniline of the formula

(2)

<* -N

3rd

(3)

couples and the azo compound obtained with a compound of the formula

Ri-A '

(4)

quaternized, wherein in the above formulas Ri, R2, R3, R4 and Rs are as defined in formula 1 and A 'is a radical which can be converted into the anion A® during quaternization.

The amines of formula 2, the anilines of formula 3 and the quaternizing agents of formula 4 are known or can be easily prepared in a manner known per se.

To carry out the process, the amine of the formula 2 is diazotized in a customary manner and coupled to the aniline of the formula 3, advantageously at temperatures below 10 ° C., for example in glacial acetic acid.

Following the coupling reaction, the quaternization with the compound of formula 4 takes place in a known manner; this can e.g. in glacial acetic acid or in an inert solvent such as chlorobenzene, optionally in the presence of an inorganic base, or optionally in aqueous suspension, or else without solvent in an excess of the quaternizing agent at a temperature of, for example, 20 ° C. to 120 ° C.

Suitable quaternizing agents Ri-A 'are e.g. Alkyl halides such as methyl or ethyl chloride, methyl, ethyl or butyl bromide or methyl or ethyl iodide, but especially alkyl sulfates such as dimethyl, diethyl and dibutyl sulfate, and alkyl esters of aromatic sulfonic acids such as methyl p-toluenesulfonate, methylbenzenesulfonate and the n- and iso-propyl and n-, sec- and tert-butyl esters of benzene sulfonic acid, and ethylene oxide or propylene oxide. The rest

/%

* X> "S ° 3-V =.

(Ró = H, halogen, methyl).

m

After 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 A ° for another anion in the compounds of formula 1.

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: u materials which can be dyed with cationic dyes, in particular textile fiber materials; these materials are e.g. from homopolymers or copolymers of acrylonitrile (polyacrylonitrile) or synthetic polyamides or polyesters, which are modified by acidic groups. Furthermore, the new cationic azo compounds are also used for dyeing wet cables, plastic materials, preferably from the specified polymers, as well as leather and paper.

It is preferably dyed from an aqueous neutral or .sn acidic medium by the exhaust process, optionally under pressure or by the continuous process. If textile material is dyed, it can be in a wide variety of forms, for example as fiber, thread, fabric, knitted fabric, piece goods or finished goods. ^ The pyrazole azo compounds of the formula I according to the invention, when applied to the materials mentioned above, lead to red colorations or prints which are distinguished by very good properties, above all high pH stability, fastness to steaming, very good drawability and high ■ <"Characterize light fastness. The dyeings obtained surprisingly show no" first brake ", ie no decrease in light fastness after a short exposure time, for example within the first 30 hours, as is frequently observed with dyes of similar constitution.

The following examples further illustrate the invention; parts and percentages are by weight unless otherwise specified. Melting points are uncorrected.

example 1

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

After two hours of stirring at the same temperature f ", the reaction mixture obtained becomes one at 0-5 ° C

A mixture of 750 parts of ice and water was added dropwise, while a constant pH of 2-2.5 is maintained by the dropwise addition of 1164 parts of 15% sodium hydroxide solution. The azo compound is extracted from the suspension obtained with 1300 parts of n ~> 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

661 739

4th

(100)

-,

) - »(c3h;) 2

11 II /

V "" N- \

I «

^ \

I II

V "

receive. Melting point: 90-93 ° C.

b) 52 parts of the azo compound of the formula 100, 24.3 parts of magnesium oxide and 650 parts of 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 distilled off, the reaction product which remains is dissolved in 1500 parts of water, heated to 70 ° C. and filtered clear. 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. This gives 53 parts of the quaternized azo compound of the formula

Example 2

If one proceeds according to the process given in Example 1 and uses l-phenyl-3-methyl-5-aminopyrazole as the diazo component, an appropriately substituted aniline as the coupling component and a suitable quaternizing agent which introduces the rest of Ri, the result is that obtained in Quaternized azo compounds of the formula given in the table below

20th

© / "% /"% A

i0

i

/ \ \ •

R,

(101)

-,

Ar

CH. ,

II

"• -N = N- </ -N (C H,)

\ / *: •

3 7'2

©

1 2 © 2Z "C14

Melting point: 162-172 ° C.

5

table

661 739

Connection no.

201

202

203

204

205

206

207

208

209

210

211

212

213

■ R.

ch,

c.h.oh *) 2 4

ch "

ch,

CH,

CH3CH (OH) CHp ch.

ch.

ch3ch (oh) ch2

ch.

c.h.oh *) 2 4

C ^ OH *) ch "

r "

n_CAH9

n-C3H7 n-C3H7 n-C3H7

n "C3H7

n ~ C3H7

n "C4H9

n "C5Hll n" C4H9

n "C6H13

n-C6H13

n "C6H13 n_C4H9

r.

n ~ C4H9 n "C3H7 C2H4OH

n-C3H7 n-C3H7

n "C3H7

c h oh

1 4

c.h.oh

2 4

n ~ C4H9 n-C6H13

n "C6H13

n "C6H13 n-C4H9

R4

h h h high

CH3 h h

h h

h h

ch3 ch.

.0

l Jo

^ -ZnCl

4, o

■ KnCir

2 ©

jZnci lZnC14 "20

2ZnC14

jZnCl ^ O

G

-i-ZnCl.

G

yZnCl

IZnCl ^ ö

Nuance on

Poly

acrylic-

nitrile red red red red red red red red red red red red red

*) The quaternization is carried out with ethylene oxide.

**) The quaternization is carried out with propylene oxide.

Compounds 101 and 201 to 213 can also be isolated with another anion Ae, e.g. as chloride, iodide, bromide or acetate, if they are mixed with a corresponding salt, e.g. NaCl, KBr, KJ, Na acetate etc. are salted out of the reaction solution. You can also e.g. are isolated as methosulfates (Ae = CHbSO «! 0) (compounds 201, 203 to 205, 207, 208, 210 and 213, which are quaternized with dimethyl sulfate.

Example 3

Polyacrylonitrile fiber fabric is introduced at 60 ° C. in a liquor ratio of 1:80 into an aqueous bath which contains 0.125 g of glacial acetic acid, 0.375 g of sodium acetate and 0.075 g of the dye of the formula 101 (or the corresponding amount of a solid or liquid preparation of this dye) per liter. The mixture is heated to boiling within 20 to 30 minutes and the bath is kept at this temperature for 90 minutes. After rinsing, a fabric dyed in brilliant red is obtained. The coloring has very good tightness properties.

Example 4

Tissue made from acid-modified polyester fibers is placed at 20 ° C. in a liquor ratio of 1:30 in an aqueous bath which contains 6 g of sodium sulfate, 2 g of ammonium sulfate and 0.15 g of the dye of the formula 101 or the corresponding amount of a solid per liter or liquid preparation of this dye. A pH of 5.5 is set with formic acid. The mixture is heated in a closed 55 vessel to 120 ° C. within 45 minutes and this temperature is maintained with shaking for 60 minutes. After rinsing and drying, a fabric dyed in brilliant red is obtained. The dyeing has very good fastness properties.

60 If, in Examples 3 and 4, instead of the compound of the formula 101, one of the formula 201-213 is used, red dyeings with similarly good properties are likewise obtained on the fabrics used.

G

Claims (9)

661739 2nd PATENT CLAIMS 1. Cationic pyrazole azo compounds of the formula CH3 I J I! V, / 2 k © diazotized with an aniline of the formula "A R ^ ^ - »- N \ / V See, for example, US-A-3,435,022, GB-A-1,404,097, GB-A-1,438,386, FR-A-1,392,581, FR-A-1,392,645, SU-A-914,603 (C.A. Vol. 97,111285). The new cationic pyrazole azo compounds according to the present invention correspond to the formula X »-H-N-rW \ =. 1 R4 bliss Ri methyl, ethyl, hydroxyethyl or 2-hydroxypropyl, R2 C3-C6-alkyl, Rj C3-Ce-alkyl, hydroxyethyl or 2-hydroxypropyl, R4 is hydrogen, methyl or methoxy, Rs is hydrogen, chlorine, methyl or methoxy and A® is an anion, wherein the molecule contains at most one of the hydroxyalkyl groups mentioned. 2. Cationic pyrazole azo compounds according to claim 1, wherein R4 and Rs are hydrogen. 3. Cationic pyrazole azo compounds according to claim 1 or 2, wherein Ri is methyl. 4. Cationic pyrazole azo compounds according to any one of claims 1 to 3, wherein R2 and R3 are the same and are propyl. 5. A process for the preparation of cationic pyrazole azo compounds defined in claim 1, characterized in that an amine of the formula CH3 I J II II I. .A. CH. ß 1 .A. wherein Ri methyl, ethyl, hydroxyethyl or 2-hydroxypropyl, R2 C3-C6-alkyl, R3 C3-C6-alkyl, hydroxyethyl or 2-hydroxypropyl, 20 R4 hydrogen, methyl or methoxy, Rs is hydrogen, chlorine, methyl or methoxy and Ae is an anion, wherein the molecule contains at most one of the hydroxyalkyl groups mentioned. 25 The alkyl radical R2 or R3 can be straight-chain or branched. The isopropyl or n-propyl radical is preferred. The Anion A® can be any inorganic or organic anion that only acts as a counterion for the positive charge on the pyrazole nitrogen. It can be identical to the anion introduced during quaternization, but it can also be introduced afterwards by exchanging another anion. Examples of possible anions are: halide (e.g. chloride, bromide or iodide), boron tetrafluoride, rhodanide, sulphate, methyl sulphate, ethyl sul-j? fat, aminosulfonate, perchlorate, carbonate, bicarbonate, phosphate, phosphoromolybdate, phosphorus tungstate, phosphorus tungsten molybdate, benzenesulfonate, naphthalenesulfonate, 4-chlorobenzenesulfonate, oxalate, maleinate, formate -, propionate, lactate, succinate, chloroacetate, tartrate, 40 methanesulfonate or benzoate ions, or complex anions, such as that of double chlorine salts. Halide, sulfate, methyl sulfate, ethyl sulfate, phosphate, benzenesulfonate, 4-chlorobenzenesulfonate, oxalate, formate, acetate and methanesulfonate ions and the complex anions mentioned are preferred. It goes without saying that the invention also includes all possible tautomeric forms of the compounds of formula 1, e.g. the following: CH " CH. couples and the azo compound obtained with a compound of the formula Ri-A ' quaternized, wherein in the above formulas Ri, R2, R3, R4 and Rs are as defined in claim 1 and A 'is a radical which can be converted into the anion A® during quaternization. R -N • -N = N-B i © V, 0 ^ \ HER- b0 V fS Rj-N. N = N-B