CH643581A5 - CHROME COMPLEX DYES. - Google Patents

Description

The present invention relates to new chromium complex dyes of the formula

-R,

-R

Me

©

(I)

converted into the 50 1: 1 chromium complex by reaction with a chromium-releasing agent and then converted to the 1: 2 Cr complex with the non-metallized dye of the formula (III) or (II).

The 1: 1 Cr complex of the formula (II) is preferably prepared by attaching the dye of the formula (III) to the same. 55 The monoazo dyes of the formula (II) can be prepared in a known manner by coupling diazotized 2-amino-1-hydroxy-4-sulfo-6-nitro- or 6-chlorobenzene onto a pyrazolone of the formula (IV)

60

h <A>

(IY)

I.

R-t

65

are obtained, those of the formula (III) by coupling a diazotized aminophenol of the formula (V)

643 581

(?)

HO

-V.

(YI)

E

wherein R, R3, R2 and Ri have the meaning given.

Suitable pyrazolones of the formulas (IV) and (VI) are, for. B. 3-methyl-pyrazolone-5,3-ethyl-pyrazolone-5,3-butyl-pyrazolone-5, 3-phenyl-pyrazolone-5, pyrazolone-5-carboxylic acid-3, pyrazolone-5-carbonamide-3, Pyrazolone-5-carboxylic acid ethyl ester-3,3-cyanopyrazolone-5, l-phenyl-3-methyl-5-pyrazolone, l- (2'-, 3'- or 4'-chlorophenyl) -3-methyl-5 -pyrazolone, l- (2 ', 5'- or 3' -4'-dichlorophenyl) -3-methyl-5-pyrazolone, l- (2'-, 5'-dibromophenyl) -3-methyl -5-pyrazolone, l- (2 \ 4 ', 6'-trichlorophenyl) -3-methyl-5-pyra-zolon, l (4'-bromophenyl) -3-methyl-5-pyrazoion, l- (2' -Chlor-6 -'- methyl-phenyl) -3-methyl-5-pyrazolone, l- (4'-methyl-phenyl) -3-methyl-5-pyrazolone, l- (2'-ethylphenyl) -3- methyl-5-pyrazolone, l- (4'-methoxyphenyl) -3-methyl-5-pyrazolone, l- (2'-, 3'- or 4'-nitrophenyl) -3-methyl-5-pyrazolone, l- Phenyl-3-aminocarbonyl-5-pyrazolone, l-phenyl-3-cyano-5-pyrazolone, l-phenyl-3-carboxy-5-pyrazolone, l, 3-diphenyl-5-pyrazolone, l-phenyl- 3-methoxycarbonyl-5-pyrazolone, 1- (3'-sulfodimethylamide phenyl) -3-methyl-5-pyrazolone.

Examples of suitable diazo components of the formula (V) are:

2-amino-l-hydroxy-benzene, 4- or 5-chloro-2-amino-hydroxy-benzene, 4- or 5-nitro-2-amino-hydroxy-benzene, 4- or 5-methyl-2 -amino-hydroxy-benzene, 4-methoxy-2-amino-hydroxy-benzene, 4,6-dichloro-2-amino-hydroxy-benzene, 4,6-dinitro-2-amino-hydroxy-benzene, 4-chlorine -5-nitro-2-amino-hydroxy-benzene, 6-chloro-4-nitro-2-amino-hydroxy-benzene, 4-chloro-6-nitro-2-amino-hydroxy-benzene, 6-nitro -4-methyl-2-amino-hydroxy-benzene, 2-amino-l-hydroxy-benzene-4- or 5-methylsulfone, 2-amino-1-hydroxy-benzene-4- or 5-phenyl sulfone, 2-amino-l-hydroxy-benzene-4- or 5-sulfonamide, 2-amino-l-hydroxy-benzene-4- or 5-sulfomethylamide, 2-amino-l-hydroxy-benzene-4 - or 5-sulfodimethylamide, 2-amino-l-hydroxy-benzene-4- or 5-sulfanilide.

The dyes of the formula (II) or (III) are generally converted into the 1: 1 chromium complex by customary methods known per se, e.g. by reacting the metal-free dye in an acidic medium with a set of trivalent chromium, such as chromium formate, chromium sulfate or chromium fluoride, at the boiling point or, if appropriate, at temperatures exceeding 100 ° C. Trivalent chromium can also be produced in the reaction mixture from chromium-VI compounds if a reducing agent is added at the same time, such as, for. B. glucose. The metallization can also be carried out in the presence of organic solvents. It is preferred to work in organic solvents such as alcohols or ketones and preferably with the exclusion of water.

The reaction of the 1: 1 chromium complex of the dye of the formula (II) or (III) with the metal-free dye of the formula (III) or (II) is conveniently carried out in an alkaline to weakly acidic medium in an open or closed vessel in the usual or elevated temperature, e.g. B. at temperatures between 50 ° C and 120 ° C.

You can in organic solvents, e.g. B. alcohols or ketones work or in aqueous solution, with additions of solvents such as e.g. of alcohols or dimethylformamide can possibly promote the implementation. It is generally advisable to react with equivalent amounts of the chromium-containing 1: 1 complex and the metal-free dye 5 with one another, the molecular ratio between metal-free dye and 1: 1 complex advantageously being at least 0.85: 1 and at most 1: 0.85 amounts to; an excess of metal-containing dye generally has a less disadvantageous effect than that of metal-free dye. In general, the closer this ratio is to 1: 1, the more advantageous the result.

Instead of uniform dyes of the formula (II) or (III), mixtures of corresponding dyes can also be used. In this way you often get interesting nuances. 15 The new, chromium-containing mixed complexes obtainable by the above processes are advantageously isolated in the form of their salts, in particular alkali metal salts, especially sodium salts, or also ammonium salts or salts of organic amines with a positively charged nitrogen atom and are suitable for dyeing and printing a wide variety of substances , but especially for dyeing nitrogenous materials, such as silk, leather and especially wool, as well as for synthetic fibers made of polyamides or polyurethanes. They are especially for dyeing from weakly alkaline, neutral or weakly acidic, e.g. B. Acetic acid 25 bath suitable. The dyeings obtained in this way are uniform and have good fastness to light, washing, decaturing and carbonization.

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

30th

40

example 1

0.1 mol of 1: 1-Cr complex dye, prepared by coupling diazotized 6-nitro-2-aminophenol-4-sulfonic acid to 1-phenyl-3-methyl-5-pyrazolone and then chromating with 0.1 Mol of monoazo dye, prepared by coupling diazotized 5-nitro-2-aminophenol to 3-methyl-5-pyrazo-ion, stirred in 1.21 water. The suspension obtained is heated to 90-95 ° C. and adjusted to pH 8.5-8.5 by dilute sodium hydroxide solution. The mixture is stirred until the starting dyes are no longer detectable, then 260 g of sodium chloride are added, the pH is adjusted to 5 with a little acetic acid and the precipitated chromic complex dye is suctioned off at 65.degree. After drying, a dark brown powder is obtained, which dissolves in water with a red color and dyes wool and polyamide from a weakly acid bath in red tones with good lightfastness and good wet fastness properties.

55

60

65

o2u - (/ = H-a |.

CHs

H

643 581

4th

Example 2

0.1 mol of 1: 1 Cr complex dye, prepared by diazotizing 6-nitro-2-aminophenol-4-sulfonic acid, coupling to 3-methyl-5-pyrazolone and chromating, together with 0.1 mol of dye prepared by diazotizing 5-nitro-2-ami- 5 nophenol and coupling to 3-methyl-5-pyrazolone, in 1 liter.

The water is stirred, heated to 80-85 ° C and adjusted to pH 9 with dilute sodium hydroxide solution. The mixture is stirred at this pH until the starting components are no longer detectable, 200 g of potassium chloride are added, the pH is adjusted to 6.5 6.5 with dilute acetic acid and the mixture is filtered off with suction at 50 ° C. When dried, the dye is a dark brown powder that dissolves in water and colors wool and polyamide from a weakly acid bath in clear red tones. In the acidic form, the dye corresponds to the formula

15

Analogously, when using the properties listed in the table with similar properties, wool and polyamide are dyed in orange monoazo dyes I and II chromium-mixed-compléx dyes to bluish red tones.

Example No.

Azo dye I

Izo dye II

3rd

OH

CV

OH

Wrong

HO ^ U ^

H

4 '

OH

./CE,.

V HoV

HO3S.

OH

X / N = îk / CBs o2AX HO-V1

• H

5

OH

xJHOV

OH

o2r ^

H

6

OH '

yj HO-V

■ H0 ^ Ò)

Cl

OH

^ CHg

• o2ir ^^ HO- ^ ir11 H

5

643 581

643 581 6

Ex. Mr.

Azo fax I

Azo fax II

14

OH

■ HOJ rjj

OH

. y ^ = ^ Y ~ Y0Bs

Pef ^ HCXNr *

4rxr "H

15

HoJ Q.

OH

6 '-

SOgNHCHg H

16

! OH

HoJ | ^ j

OH

1 S - N-. (^ SBt

O

' H

so- * ™ * •

2 ^ CHg

17th

OH

° 2li H, / CHg rT Ii

• HO - ^ - S ^

HoJ

OH

HUO2Ecr ^ isr csg H

18th

OH

OnK 'J> ^ JI = K ^ / GHg <■ HO ^ fP ^

H ° 3 Ô

•OH

'^> V / IT = ljfv. ■ / CHg ito2sr ^^ HO ^ B ^ / \ H

CHg GHg

19th

OH

Ou W; X JT = Hv, / CE,

X ^ HCrM

HO »S f ^ Ti kjj

OH • '

JNv ^ = HN—

ÖT-JM-

S% .0% '. ■ H

20th

OH

02I ^ = ij / C%

. IO3H ^

OH

IN. K.-OB,

çr * XJ>

S02H5-Ç ^.

7

643 581

643 581

E.g. Mr. |

28

Azo dye I

Azo dye II

COOH

U.N.

Lu Ti

CLir ^^

1

Example No.j azo dye I

Azo dye II

! OH

35 | U HO V

j so3H h

!

OH

Ogir ^ / 'HO ^ F ^

jv'Cl

JST ■

36

OH

cUyr ^ ^ CHs knH

,

OH

Jy-x- *. ./CEg o2F ^ J • HO-V

H

•

"-

38

. H . ... ... ...... r

OH! . • OH -cvl ^ ïf = ïk / CHg i ./C%

. yj HQA-K ^ • • 1 HO ^ IP

SO, H. ^ F)! free E

1

39

OH! OH ClsJs ^ = Sv / CHg j .CHg

Hju> I oiAJ.

■ Ò: j '■ 1 / ""

i

40

41

OH j

Cll.M ^ OBg ï

y = X ^!

ÖOgH

° H "

Jv ^ = 1S rCBs yj Jü>

SOgNK, H

OH

|

k> |

i

OH

—JfGäs

Hg N02 H0 ^ 3! P ^

H

42

OH i

[OH

Vr ^ Yf 0B ° i.fVH = YP

HO ^ Sï ^ î HCf N

L3h -Q j k <j | E

. i

643 581 10

Ex. Mr.

Azo dye I

Azo dye II

43

OH

S03h rTl

1 ■ U

OH

f-CB3

HOgS ^ - ^ HO- ^ ir / \ s CBg CBg

1 '

! OH. j -CL- / GH,

44 | y ^ ■

'j SOgH

!

1

OH

JYN = 1S-— •

HÜ ^ T1 "'

so2 'H i 2. NHCHg

45

; oh

! Gl> CE,

j.

SOgH Js'

OH

Jv "s TCB3

CO /

S02CBg H

46

OH

^ CBg

SC ^ H f ^ ll KU

OH

9 "Af"

. SO2HH h

■■■■ ô.

47

OH

■ to '

SOgH | ^ | j oh

Mon? *

CHg H

48

OH

Cl> v / F = Ik / -CBg ity Ji ■ jr HO ^ NT

S Og H

OH

■:

11 E

49

OH

CLX / IJ = ÎK -j / CBg •

HO ^ IT ^

kn ^

OH

CS ^ = IV ^ CH3

HO ^ ÎT ^ Cl H ". ■

11

643 581

Example no

Azo dye II

• TT = T <k ^ f! TT-

jy

F = l ^ / CB *

.O

SOgH

H

■ CHg

53

Cl ^

54

= IK - COOH

SOgH

55

56

CONHj

OH

O-IT

• W = T ^

hX1 ^

H

643 581

M

Claims (8)

643 581 2nd PATENT CLAIMS 1. Chromium complex dyes of the formula SOsH Me io (I) 15 20th wherein R and Ri represents a hydrogen atom or an optionally substituted alkyl group or an aryl group, with the proviso that at least one of the radicals Rj or R represents hydrogen or optionally substituted alkyl; Z is a chlorine atom or the nitro group, R2 and R3 represent an optionally substituted alkyl group, an aryl, carboxylic acid, carbonamide or cyano group; the radicals Xj, X2, X3 are hydrogen, halogen, nitro, optionally substituted alkyl, optionally substituted alkoxy, aryl sulfone, alkyl sulfone, optionally substituted sulfonamide Me + is a cation. 2. Dye according to claim 1, wherein one R or Rx = H, the other R or Rj = phenyl optionally substituted by halogen or Cl-C4-alkyl. 3. A dye according to claim 1, wherein Z = N02. 4. A dye according to claim 1, wherein X2 = N02 or optionally substituted sulfonamide. 5. A dye according to claim 1, wherein Xi = NO2 X3 = Cl or CH3 X2 = H 6. Dyes according to claim 1, wherein R2 and R3 = CH3 or CONH2. 7. Dyes according to claim 1, wherein R = H and Rx = phenyl, optionally substituted by halogen or C 1 -C 4 -alkyl. 25th wherein R and Ri represents a hydrogen atom or an optionally substituted alkyl group or an aryl group, with the proviso that at least one of the radicals Ri or R represents hydrogen or optionally substituted alkyl; Zist is a chlorine atom or the nitro group, R2 and R3 represent an optionally substituted alkyl group, aryl, carboxylic acid, carboxylic acid ester, carbonamide or cyano group; the radicals Xl5 X2, X3 are hydrogen, halogen, nitro, optionally substituted alkyl, optionally substituted alkoxy, arylsulfone, alkylsulfone, optionally substituted sulfonamide; Me + is a cation. The aryl radicals can optionally contain further substituents. Preferred alkyl groups are those with 1-12 C atoms, in particular those with 1-4 C atoms, which may optionally be further substituted, such as. B. by cyano, halogen in particular chlorine, phenyl, hydroxy, Ci -C4 alkoxy. Preferred aryl radicals are in particular optionally substituted phenyl radicals with substituents such as halogen, in particular Cl and BR, NO2, Cx-C4-alkyl, Q-C4-alkoxy, cyano. The sulfonamide groups and carbonamide groups can be mono- or disubstituted by optionally substituted alkyl, in particular Q-C4-alkyl or optionally substituted phenyl, the substituents mentioned above being suitable. Preferred carboxylic ester groups are C 1 -C 4 -alkyl carbonate groups. The new chromium complex dyes can be prepared by dyeing the formula in a manner known per se 30th 35 (II) 40 or . . QH XjvJv / iT = îï 45 Xj R (III)