CH661519A5 - MONOAZO CONNECTIONS. - Google Patents

Description

40 The invention relates to new compounds, their mixtures with one another and processes for their preparation.

The new compounds according to the invention correspond to formula I.

//

\ /. —N

\ / \. = • r

/

nhcor.

45

(Holy)

02n-

50

II \

no,

• -n = n - •

w /

(I),

wherein Rb R2 and R3 have the meaning given under formula I in claim 1, couples and the coupling product of formula II

cn

/

nhcor,

no "

o2n-

//

/

\

\ / • 3 •

\

-n = n

\ / • -n

/ \

Shark

/

nhcor.

(II),

with a metal cyanide in polar organic solvents or in water-containing polar organic solvents.

in which mean:

55 Rj is a branched C3 to C7 alkyl radical and

R2 and R3 independently of one another are a C to C4 alkyl radical.

Ri in the meaning of a branched C3 to C7 alkyl radical is, for example, an iso-propyl, iso-butyl, tert-io-butyl, 2-methyl-propyl, 2-methyl-hexyl, 3-methyl -hexyl-, 2,2-dimethyl-pentyl- and 1-ethyl-pentyl radical. In the preferred compounds Rj is a branched C3 or C4-alkyl radical, in particular the iso-propyl, 2-methyl-propyl and tert. Butyl residue.

65 R2 and R3 in the meaning of a Q- ^ V alkyl radical represent unbranched and branched alkyl radicals; it is, for example, the methyl, ethyl, n- and iso-propyl, and n- and tert-butyl radical. In preferred connections

gen R2 and R3 represent the same alkyl radical; in particular, it is a C3 and C4 alkyl radical.

Compounds whose number of alkyl carbon atoms of Rh R2 and R3 together are at least 7 and at most 12 are also preferred.

The invention further relates to mixtures of compounds which contain at least two compounds of the formula I which differ from one another in at least one of the substituents R], R2 and R3. The individual components are present in equal proportions in the preferred mixtures.

A particularly interesting mixture of two contains compounds of the formulas

/ ° 2

0 / * v / "\ / Wn)

° 2N-. ,_H - "

\ - / \ / \

I 661519

mei I, for example, such that a diazo component of the formula IV

NO,

\

cn

/

NHCORj and

C3H7 (n)

NO

/ 2nd

// \

// w / wn)

° 2N-, / -N = N - / \

\ 7 \ _ / \

\

cn

/

c4H9 (n)

NHCOR

and an interesting mixture of 3 contains e.g. the connections of the formulas

NO,

/

• // \

// \ / 0, N- »« -N = N - • »-N

2 \ / \ / \

C3H7 (n)

• = • C3H? (N)

cn

NO,

/

NHCOR and o2n-

// \ // \ / • -N = N -o »-N

C4Hg (n)

\ /

\ / \

• = • C4H9 (n>

CN

NO,

/

NHCOR and

// w

// \ /

C3H? (N)

0 N- «» -N = N - • «-N

2 \ / \ / \

C4H9 (n)

/

// w

02H- ^ "NH2

(IV),

\

Shark in which shark represents a halogen atom, diazotized and on a coupling component of the formula III

// \ / • -N

20 \ / \

(HI),

/

NHCOR,

R,

25th

wherein Rb R2 and R3 have the meaning given under formula I, couples and the coupling product of formula II

30th

NO,

// \

// \ /

(II),

0, N ~ «» -N = N - • * -N

2 \ / \ / \

\ / Shark NHCOR,

with a metal cyanide in polar, optionally water

40 containing organic solvents. Shark preferably means bromine.

With regard to the mixtures according to the invention, these can also be prepared in various ways, e.g. such that:

45

a) at least two compounds of the formula I are mixed with one another, or b) at least two compounds of the formula I are fused together, or so c) a diazo component of the formula IV

NO

/ 2nd

«77 1

55 0 N- «.-NH

2 \\ / 2

(IV),

\

Shark

60 wherein shark represents a halogen atom, diazotized and on a mixture of coupling components of formula III

CN

NHCOR,

where in the 2 and 3-mixture R] is identical and has the meaning given under formula I.

The compounds according to the invention and their mixtures can be prepared in a wide variety of ways; so you get the connections of the forums

// \ r

. .-N

65 \ / \

• = • r,

/

nhcor,

(HI),

661 519

4th

which differ in at least one of the substituents Rh R2 and R3 and in which Rb R2 and R3 have the meaning given under formula I, couples and the mixture of the coupling product is reacted with a metal cyanide in polar, optionally water-containing organic solvents.

If the process variant a) is used, the preparation of the mixture according to the invention consists in

that the individual compounds of the formula I are mixed dry or wet with one another at room temperature. It is advantageous to add dispersing agents, especially anionic or nonionic in nature and water, to this mixture and to grind this mixture with the aid of grinding aids (e.g. glass balls) to form a ready-to-use dispersion.

Anionic dispersants that are suitable for this are, for example, condensation products of naphthalenesulfonic acids and formaldehyde, in particular dinaphthylmethane disulfonates or modified ligninsulfonates.

Examples of known and particularly suitable nonionic dispersants are adducts of about 3 to 40 moles of ethylene oxide with alkylphenols, fatty alcohols or fatty amines.

If variant b) is used to prepare the mixture according to the invention, the compounds are melted together to form a homogeneous melt, then left to cool and optionally ground with anionic or nonionic dispersant and water in the presence of grinding aids; This variant also gives a ready-to-use dispersion.

Finally, in process variant c), the starting products of the formulas III and IV are known and can be prepared by known methods. For example, the coupling components of formula III are obtained in such a way that e.g. the corresponding acylamidoanilines of the formula V • - •

// w

—NH

\ / 2 V)

/

NHCORj with alkyl halides of the formula

R2-Hal or R3-Hal or alkyl sulfates of the formula

R2-0-S030H or R3-0-S0 3H

in the presence of acid acceptors, e.g. Alkali carbonates, especially sodium carbonate.

The coupling reaction of the coupling components of the formula III (individually or in a mixture) with the diazo component of the formula IV takes place in a known manner, the coupling products of the formula II or their mixture being obtained. This coupling product or the mixture can be isolated. The halogen atom in the diazo component is then replaced by the cyano group; this is done by reacting compound II or its mixture with metal cyanides. This reaction, which is preferably carried out with copper cyanide, is preferably carried out in a polar, optionally water-containing solvent, such as dimethyl sulfoxide, dimethyl

formamide, N-methylpyrrolidone or pyridine-water mixtures at a temperature of about 40 to 150 ° C, preferably 80 to 130 ° C.

5 Another way of producing the coupling components of the formula III is that one

Compound of formula VII R,

io II \ / 2

• «-N

\ / \ (VII),

• = • R_

/

nhcochj

15

to a compound of formula VI

r.

20 // \ / 2

• »-n

\ / \ (VI)

/ = • R3 nh,

25th

hydrolyzed and then with carboxylic acid halides of the formula

30 Hal-CO-R!

implements.

The new compounds of the formula I and their mixtures are used as dyes for dyeing and printing substrates, in particular textile materials, which can be dyed with disperse dyes. Before they are used, these compounds are advantageous and, if this has not already been done during production, are converted into dye preparations. For this purpose, they can be comminuted, 40 so that their particle size is on average between 0.01 and 10 | xm. The comminution can take place in the presence of dispersants. For example, the dried dye mixture is ground with a dispersant or kneaded in paste form with a dispersant and dried here in vacuo or by atomization. After the addition of water, the preparations thus obtained can be dyed, padded or printed in a long liquor (liquor ratio greater than 1: 5) or a short liquor (liquor ratio 1: 1 to 1: 5).

so The new compounds are excellently absorbed from aqueous suspension or dispersion onto moldings made from fully synthetic or semi-synthetic high-molecular substances in a blue shade. They are particularly suitable for dyeing, padding or printing fibers, threads 55 or nonwovens, woven or knitted fabrics made from linear, aromatic polyesters and from cellulose 2 '/ 2 acetate and cellulose triacetate. They can also be used to dye and print synthetic polyamides, polyolefins, acrylonitrile polymerization products and polyvinyl compounds. Particularly valuable colors are obtained on linear, aromatic polyesters. These are generally polycondensation products from terephthalic acid and glycols, especially ethylene glycol, or polycondensation products from terephthalic acid and 1,4-bis (hydroxymethyl) hexahydro-65 benzene.

The polyester fibers are dyed by processes known per se in the presence of carriers at temperatures between about 80 and 125 ° C. or in the absence of carriers

519

under pressure at about 100 to 140 ° C after pulling out. Furthermore, these fibers can be padded or printed with the aqueous dispersions of the compounds and the impregnation obtained can be fixed at about 140 ° to 230 ° C, e.g. with the help of water vapor, contact heat or hot air. Cellulose-2> / 2-acetate is preferably dyed between about 65 to 85 ° C and cellulose triacetate at temperatures up to 115 ° C.

Usually the usual dispersants already mentioned are added, which are preferably anionic or nonionic and can also be used in a mixture with one another.

The usual thickening agents will be used for padding and printing, e.g. modified or unmodified natural products, for example alginates, British gum, gum arabic, crystal gum, locust bean gum, tragacanth, carboxymethyl cellulose, hydroxyethyl cellulose, starch or synthetic products, for example polyacrylamides or polyvinyl alcohols.

The dyeings obtained have good coloristic properties; Particularly noteworthy is their ability to mix with any, especially yellow dyes and no "catalyc fading" applied to textile material, to show good pH resistance especially in the exhaust process and their very good and level build-up.

The following examples illustrate the invention. Temperatures are given in degrees Celsius; Unless otherwise stated, parts mean parts by weight.

example 1

10.5 parts (0.036 mol) - 3-dibutylamino-isobutyryl-ani-lid, prepared by hydrolysis of 3-dibutylaminoacetanide-lid with alcoholic aqueous hydrochloric acid and reaction of the 3-dibutylaminoaniline obtained with isobutyryl chloride or from isobutyrylaminoaniline by reaction with excess, are dissolved in 300 parts of 50% aqueous acetic acid, and a diazonium salt solution is added dropwise within 1/2 hour at 0-5 °, which solution is obtained by introducing 9.43 parts (0.036 mol) of 2,4-dinitro-6-bromine. aniline in 38 parts IN nitrosylsulfuric acid at about 20 ° and subsequent stirring for 2 hours at this temperature. The unusual compound of the formula o2n- *

/ NOz

'V

/

\ r

-N

N -

VnT

tìfico

/ \

nficocjl

, CH3

, CiiH9 (n) C ^ H9 (n)

ch3

The dyes of the formulas are obtained in an analogous manner:

/ N02

S \ «H Y 02N - () - N - N - \ / \

cn ch3

• CjHjCn) 'CjH7 (n>

db)

10 Melting point 204 to 260

Melting point of the bromine precursor 145 to 150

-NÛ2

15 BC

OzN - * ^ V-N "N

\ ✓

cn

\ / \

/ '=' ^ nhcochî ~ ych

CHi

Ci, H9 (n)

(lc)

Melting point 185 to 190 (sintering at 176 j melting point of the bromine precursor 156 to 160 (sintering at 1443);

25th

/ o 2nd

0 ^ -o- »- - -r> - <

• C2H *

CN

30th

35

/ I nhcoc ^

, CH3 ch3

'c2h5

(ld)

Melting point 185 to 192

Melting point of the bromine precursor 150 to 156:

/ NO 2

02N- ^ / * - N - N -S

C2Hs cn

40

frfic «

CzHs

; coch (ch2) 3ch3 ch2ch3

le)

Melting point 173 to 174 (sintering at 170) melting point of the bromine precursor 69 to 82;

o2n-

is filtered off, washed with water and dried. 18.1 parts (89.3% of theory) of dark blue powder with a melting point of 153 to 155 ° (sintering at 149 °) are obtained.

16.9 parts (0.03 mol) of it are dissolved in 63 parts of pyridine, mixed with 2.85 parts of copper-I-cyanide and 36 parts of water and stirred for 6.5 hours at 60-70 °, suction filtered at 50c , with 50 ° warm pyridine-water mixture, then washed with water and dried. The dye of the formula is obtained

50

\ / "\

/ NO 2 n

'CN

frflCOC ^ i

> "<

.CHj CH3 CH3

.c2h5

CzIIs

(10

Melting point 118 to 128 (sintering at 98) 55 melting point of the bromine precursor 141 to 148 (sintering at 130);

02N-

\ / * "\

/ NOz

K -N

60 OjN-

\ /

/ N02 ^ N

N -

y "V

y \

W

/ \

'cn brficl

COC ^

, ch3

, C 1.119 (11) C ^ H9 (n)

V

/ "<

■ C 3 H 7 (n)

'CN

there)

y c ^ 3

NHCOCHî - / CH CH3

CjH7 (n)

(lg)

'CH j as a green-brown powder with a melting point of 190 to 199 (sintering at 186). Yield 10.0 parts (65.4% of theory).

Melting point 214 to 260 Melting point of the bromine precursor 135 to 180

661 519

Example 2

5 parts of the dye (la) are mixed with 10 parts of a low-salt dispersant (dinaphthylmethanesulfonic acid type) and ground in 85 parts of water using 300 parts of glass balls of 0.5 mm in diameter in a micro-sol mill. The dispersion obtained can be used for dyeing polyester materials.

In the same way, dispersions of the dyes (1b), (1c) and (Id) or mixtures thereof, e.g. equal parts of the dyes (la) and (id), are produced and used.

Example 4

A dye mixture containing the dyes of the formulas (la), (lb) and o2n-

\

10th

/ 02 \

/

-N = N -

CN

frflCi cocjt

> -N, CH3

, C3H7 (n) • C „H9 (n)

(lb)

chi

Example 3

The dye mixture containing the dyes of the formulas (la) and (lb) in a ratio of about 50:50 wt .-% is obtained by equimolar amounts of the two coupling components of the formulas

, C3H? (N)

v_y \

and

/; NHCOqi

.CHj'CHi

C3H7 (n)

, / cocf '

, C ,, H9 (n) sCi | H9 (n)

'CH3

with a diazotized diazo component of the formula

/ NO z

N02 ~ y) - NH2

V

couples and converts the mixture obtained with CuCN to the corresponding mixture of the cyan derivatives. Diazotization, coupling and exchange of the bromine atom for cyano takes place under the conditions given in Example 1.

15 is obtained by coupling the isobutyrylaminoanilides obtained by mixed alkylation with equimolar amounts of n-propyl and n-butyl bromide with diazotized dinitrobromoaniline and converting the resulting mixture into a mixture with the corresponding cyano compounds. The 20 individual steps are carried out under the conditions given in Example 1.

Example 5

4,000 parts of polyester fabric (diols) are in 100,000 25 parts of a dye bath adjusted to pH 4, the 192 parts of a dispersion according to Example 2 (corresponding to 9.6 parts of dye and 50 parts of a wetting agent (eg fatty acid methyl tauride) and a dispersant (for example based on dinaphthyl methanesulfonate) contains, dyed for one hour at 130 ° C. This gives a strong blue color with very good light fastness.

Example 6

If dyeings are carried out according to Example 5, but with 5 the difference that the dyeings are buffered at pH 5, 6, 7 and 8, only a slight change in shade is found at pH 6.

C.

Claims (8)

661519 / 1 / "\ / A \ / 2 ° 2N, - «N \ =. • = • r, \ CN / nhcor. / 2 // \ \ / \ Shark is where shark represents a halogen atom, diazotized and on a mixture of coupling components of the formula III // \ / 20 * * ~ N \ / \ • = • r / nhcor, (HI), o2n- < • -nh- (IV), 25th which differ from one another in at least one of the substituents Rb R2 and R3 and in which Rh R2 and R3 have the meaning given under formula I in claim 1, and the mixture of the coupling product with a metal cyanide in polar organic solvents or in polar water-containing organic solvents implements. 2. Compounds according to claim 1, characterized in that Ri is a branched C3 or C4 alkyl radical. 2nd PATENT CLAIMS 1. Compounds of Formula I NO, 3. Compounds according to claim 1, characterized in that R2 and R3 independently of one another represent a C3 and C4 alkyl radical. 4. Compounds according to claim 1, characterized in that the number of alkyl carbon atoms of Rb R2 and R3 is at least 7 and at most 12. 5. Mixture of at least two compounds of the formula I according to claim 1, which differ from one another in at least one of the substituents Rb R2 and R3. 6. A process for the preparation of compounds of the formula I according to claim 1, characterized in that a diazo component of the formula IV no, 7. A process for the preparation of mixtures of compounds of formula 1 according to claim 5, characterized in that a diazo component of formula IV noCI). // \ 0, n— 10 2 \ / -nh, (IV), in which mean: R] is a branched C3 to C7 alkyl radical, and R2 and R3 independently of one another are a Q to C4 alkyl radical. 8. A process for the preparation of mixtures of compounds of the formula I according to claim 5, characterized in that at least two compounds of the formula I are mixed or melted together. Shark in which shark represents a halogen atom, diazotized and on a coupling component of the formula III