CA1088051A - Chromium complex dyes, process for their manufacture and use thereof - Google Patents

Abstract

Abstract of the Disclosure Chromium complex dyed of the formula (1)

Description

$~1~8051 The present invention provides chromium co~plex dyes of the formula 02~

(1) '1 ~

L
N = N - Ar wherein Xl represents a hydrogen or halogen atom, a Cl-C5-alkyl group, a Cl-C2-alkoxy group, a nitro group, a C2-C3-alkanoylamino or C2-C3-alkoxycarbonylamino group, B M ~ represents a cation, and Ar represents the radical of an aromatic or hoto~ocycl;c diazo component which carries one to three SO3H and/or COOH groups, preferably one to three SO3H groups or one SO3H and one COOH group, and is optionally further substituted by halogen,.Cl-C5-alkyl, Cl-C2-alkoxy or nitro.

- -- , .: - . :

~o~sl Ar is primarily a naphthalene or benzene ring which carries 1 to 3, preferably 1 or 2, sulpho groups, and is optionally further substituted by chlorine, nitro, Cl_C5_alkyl or C~-Cz-alkoxy. The term l'halogen" denotes herein fluorine and chiefly chlorine and bromine.

The novel dyes are obtained by reacting one of the azo dyes of the formula OH HO

(2) 02N ~ N =N ~

or a disazo dye of the formula OH HO
N = N

N = N Ar with a chromium donor to give the 1:1 chromium comp~ and subse~
quently reacting this latter with the non-metallised dye of the formula (3) or (2) to give the 1:2 complex. Preferably the 1:1 chromium complex of the monoazo dye of the formula (2) is prepared and then reacted with the disazo dye of the formula (3).

.

~08B05~
, .
Instead of containing hydroxyl groups, the starting dyes of the formula (2) or (3) can also contain groups from which hydroxyl groups are formed during the chroming, for example low molecular acyloxy or al~oxy groups,in particular methoxy groups.

The monoazo dyes can be prepared in conventional manner by coupling a l-hydroxy- or l-alkoxy_2_aminonitrobenzene to ~-naphthol. In preferred monoazo ccmpounds of the formul~ (2), Xl represents a hydrogen or chlorine atom, a nitro or methyl group.

The disazo dyes of the formula (3) are obtained by coupling for example the diazonium ccmpound of an amine Ar_NH2 with a l_hydroxy-2_aminobenzene the amino group of which is protec_ ted by acylation. The azo dye obtained is then diazotised after liberation of the amino group by saponification and coupled to 3_naphthol. Suitable arylamines of the formula Ar_NH2 are for example: 2_, 3_ or 4_sulphoaniline, aniline-2,4_disulphonic acid, anthranilsulphonic acid, 4_methyl-2_ or -3-sulphoaniline, 4_chloro-3-sulphoaniline, 4_nitro-2-sulphoaniline, 4_methoxy_3-sulphoaniline, 2_naphthylamine_ 6,8-disulphonic acid, l_naphthylamine_4_, -6- or -7-sulphonic acid, l-naphthylamine-4,8-disulphonic acid, l-naphthylamine-

3,6,8-trisulphonic acid etc.

, . .
, . : . : :. .:
., 3L08~3051 The conversion of the azo dye of the formula (2) or (3) into the 1:1 chromium complex is carried out by conventional methods which are known per se, for example by reacting it in an acid mediu~ with a salt of trivalent chromium, for example chromium formiate, chromium sulphate, chromium chloride hexahydrate or chromium fluoride, at boiling tempe-rature or, if appropriate, at temperatures exceeding 100C.
Trivalent chromium can also be obtained in the reaction mixture from chromium (VI) compounds, for example chromate, by simultaneously adding a reducing agent. The metallising can be carried out in an aqueous, aqueous-organic or organic medium.

The reaction of the 1:1 chromium complex of the dye of formula (2) or (3) with a dye of the formula (3) or (2) is advantageously carried out in a neutral to weakly alkaline medium, in an open or closed apparatus~at elevated tempera-ture, for example at temperatures between 50 and 120C.

The process can be carried out in organic solvents, for example alcohols or ketones or in an aqueous solution, in which case, if appropriate, the addition of solvents, for example of alcohols, formamide etc , can promote the reaction.
It is usually advisable to react as far as possible equiva-lent amounts of the chromium-containing 1:1 complex and of the metal-free dye, the molecular ratio between metal-free dye and 1:1 complex advantageously being at least 0.85:1 and - 5 ~

.

' at most 1:0.85.

The chromium-containing mixed complexes of the present invention which are obtained by the above process are iso-lated with advantage in the form of their salts, in particu-lar their alkali, for example lithium, salts, above all, sodium salts, or also ammonium salts. They are suitable for dyeing and printing nitrogen-containing material such as wool, silk, synthetic polyamide material and, in particular, for dyeing leather. The dyes containing 1 to 2 sulpho groups are suitable above all for dyeing wool, silk and synthetic polyamide; and the leather dyes can contain 1 to 3 sulpho groups. Black or brownish-black shades of good covering power are obtained in all cases. The dyes give level dyeings with good fastness to light, washing, water, perspiration, alkali, acid, dry cleaning, diffusion and rubbing. The novel dyes are also suitable for use in mixtures.

The following Examples illustrate the invention, the parts and percentages being by weight unless otherwise indicated.

~: :

. ~ ,,, . ~ .

. , , i-~, , , .. ~ .
: .:., ;:. ~ :
. ...

~;

3QSl `- Example 1 ~2 ~ N = N - ~ l Cr 2 Na ~3 / \

~ S03 30.9 Parts of the monoazo dye obtained from diazotised 5_nitro-2-amino_l_hydroxybenzene and 2_hydroxynaphthalene are stirred with 26.65 parts of chromium chloride hexahydrate in 500 parts by volume oE ethylene glycol at 120 to 125C
until such time as the starting compound has disappeared To the solution of the 1:1 chromium complex dye are then added 49 8 parts of the disazo dye obtained from diazotised 3_amino-4-hydroxyazobenzene_(l')-naphthalene_6'_sulphonic acid and 2_hydroxynaphthalene and 80 parts by volume of 20%

sodium carbonate solution and the mixture is stirred for a further 1 to 2 hours at 80 to 85C to effect addition l~hen the reaction is complete, the asymmetric chromium_containing dye is precipitated by a saturated solution of sodium chloride, filtered off and dried. The product is a black .

. .
.. ..
- - - ~

10~05~

solution and colours wool or polyamide material as well as leather in fast black shades from a weakly acid bath.

Example 2 02~

Cr 2 Na ~9 o/l \o N - N

l ~ 3 30.9 Parts of the monoazo dye obtained from diazotised 5_nitro_2 amino_l_hydroxybenzene and 2-hydroxynaphthalene are suspended in 300 parts by volume of n-butanol. After addition of 26.65 parts of chromium chloride hexahydrate, the mixture is stirred at 110 to 116C while the water which forms is separated as an azeotrope. The chroming is complete after approx. 3 to 4 hours. To the dye solution are then added 44.8 parts of the disazo dye obtained from diazo-tised 3-amino-4-hydroxyazobenzene~ sulphonic acid and 2_hydroxynaphthalene and 20 parts of calcined sodium . , - -: - ,:
: - - ;, -; - ~
.
. ,. . , . : . --. -.
. : - ~ - :

carbonate. The batch is then stirred at 110~ to 117C until the addition reaction is complete. The reaction mixture is subsequently filtered until clear and evaporated to dryness to yield a black powder which dissolves in water to and dyes wool or polyamide material from a neutral to weakly acid bath in black shades of good fastness properties.

Example 3 i \ I 1 ~

N

N ~ S03 44.8 Parts o~ the disazo dye obtained from diazotised 3-amino-4_hydroxyazobenzene-3'-sulphonic acid and 2-hydroxynaphthalene are suspended in 400 parts by volume of n-butanol. After addition of 26.65 parts of chromium chloride hexahydrate, the mixture is stirred while the water which forms is separated as an azeotrope. The chroming is complete after approx. 3 to

4 hours. To the dye solution are then added 30.9 parts of the :
. ~,, ;, . , - .
.. - : . : -: . , ! .

monoazo dye obtained from diazotised 4-nitro-2-amino-1-hydroxybenzene and 2-hydroxy-naphthalene and 20 parts of calcined sodium carbonate. The reaction mixture is then stirred until the addition reaction is complete, subsequently filtered until clear if necessary, and evaporated to dryness to yield a black powder which dissolves in water and colours leather, wool and polyamide material from a weakly acid bath in fast brownish-black shades of good fastness properties.

Black and brownish-black dyes with similar properties are obtained by reacting the mono- and disazo dyes as described in Examples 1 to 3 to give asymmetrical 1:2 chromium complexes.

- 10 _ .
~ ~: ', - . : .
. .

~o~ 5~

No. Monoazo dye Disa~o dye . .. . _._ . .
~ ~ o~

_ so3~
. .
. OH HO
2. OH 1~ 50~ H

. _ _ _ OH HO

3 . ~( ~N =N~ N--N ~) ,~ ~ ~
- . . .- . . . .
- . : : ...................... ,: :; : : - . ~ .
,- ,. ~ . .. .

l~B051 . _ No. Monoazo dye Disazo dye _ .
OH HO

4. ~2 ~

_ . OH HO
OH HO ~N=N~
S. 2 ~CI~3 N~s3}(U

Oll HO
01 HO ¦ (~--N=N~
6. ~N=N~) N

1 L~

.. ..

.... ..... ~ . ~.. . ;
,. ... .. .. . .
., .. , ... .. .... . ~ . ..
. ., ;
.. ... ,. .,. ~. ..

~38Q51 , No. Monoazo dye Disazo dye _ __ 7. ~( ~N=N~ ~ ~N--N~

. N C~ 503H

_ .
8. 2~ N=Na~ U

. , , . 0}~ ~O
,~ '"~

.

_ 13 -- . : - ,. .. . : . ~ ,.:
- . ... . . .
:-, , : -... .. :

~0~51 No. Monoazo dyé Disazo dye ,~ r ~ N--N~) . ~

11. ~N=N- ~ ~ N--N--~) . H03S ~ S03 _ _ .

01~ ~10 ¦ 1 2, I ~ ~ I K (~

L~ ~ ~)03H

_ 14 -- :
.:.

10~38C~Sl 1~.Monoazo dye Disazo dye OH 1~0 .
I 1'0 (NN~ =N~

. OH HO

¦ U21~

- 15 _ . - . -. .
.:
' ,,' ~ILO~t~30~1 .
No. Monoazo dye Disazo dye OH HO
16. ~ ~2 ¢r-N=N~

N~ SO3H

OH HO
17. I r ~ ~N=N~
L L
.
OH HO

18 . ~ N=N S ~ rN=N
~L

- , . .- ~. , .

t . ~ , : . , ~ ` ~ ` - .

~ -- - --= - - ~
No. Monoa~o dye Disazo dye OH HO

. OH HO
¦ CH3 H ~N=N~

OH HO (~--N--N

_ 17 -, . .

, ~ ,.

. :. . - .

, , . . . . ~ .

~a~sosl l ~ --- - -- ~
No. Monoazo dye Dlsa~ ~ye OH . HO
OH HO ~)--N~N ~g 22. I ~ rN~ N

.

OH }10 OH HO ~N~NII) 23 . (~N =N a~ N U
02N CH3 ~SO31~

.~ ~I r;~

. ..

3OSl , _ _ No. Monoazo dye Disazo dye . . . _ HO I S~ N--N
25. ~ 02N~ ~N=N~ ; N

. _ .

OH HO (~--N--N~
26. 2 ~N=N- ~ N~SO3H

.

OH HO~11--N--N--/( ~

_ 19 -, .

5l No. Monoazo dye Disazo dye . 0'11 }~O

~ ; Nb; ([~

.

, 0~ ~0 0~ UO ~ ~ N ~

_ .

OH HO
~''1`~

, _ 20 -. . .

.
.. . .
~. ~

8{~51 , No. Monoazo dye Disazo dye OH HO

I l . ~ 0 OH HO

32. ~N=N-- ~ n OH HO

, - - . ~- - ~ ,.

-. . .. -., ~ . ~

l~BOSl __ No. Monoazo dye Disa~o- dye _ ___ , OH . HO

34. ~ ~ N=N ~ (~ =N

OH HO

35.~2N ~ ( N-~-O--3H~) ~ _ Oll HO

~ ~
.' , _ . , - , '` ~ . ~ . . .
' 0~1 - -No. Monoazo dye Disazo dye OH HO

7. ~ N=U~ ~U--U-~

OH HO
OH 110 ~--N~N~
L ~ o~n ~) N

:

_ 23 -::: : . ~ : .,:
- ,: - ~ :. , :

sl - -- ~
No. Monoazo dye Disazo dy~
. .

--N=N~ ~N~

. .

OH HO
¦ H HO ¦ ~--N=N~
41. 02N ~ `rN=N~ ~--SO 11 OH HO
¦ O H3 HO I ~N=N~

2 O :113 ~ ~ SO3H
_ . .
':
.
- 24 _ .. . . ~, --; :
... . .

, )5~

_ ~_ _ No. Monoazo dye Disazo dye Ol~ HO

43 ~ N=N~ N--N~

2 N C~cl3H

_ , OH HO
L~

_ 25 -.

:
.: ,.
- ~ :. . . ~ .. :: -. :

., ~
- . : .: . ~ .

No. Monoazo dye - Disazo dye .
. _ ___ .
OH QH OHOH
46. k~N N~ N=N~

OH OH OHOH
7 J ~ N=N

j ~r ~ .

.~ `

_ 26 -.

. ~

Nc~. Monoazo dye Di.sazo dye .. . i ~ _ OH H(i .
. OH HO ~N=N~J~
49 HN ~ U = N~

_~

OH OH

, ~ ~ J~ ¦

., _ 27 --.

:: ;. .

:
, ..
.

QS~

, . _ _ ~
No, Monoazo dye Disazo dye , . ._~

OH OH OH OH
52. 2~ =N~ (N~N= N~U) . ._ -OH OH

¦O O ¦ ÇJ N=N~) ¦
53' 2N~ - N=N~ I ~bO3H

. . _ _ _ OHOH

54. 0~ N=N~) , _ 28 -. . , . :
,. ~
, .

~3~51 No. Monoazo dye Disazo dye .
_ .
OH OH
OH Ol~ ¢r N = N ~--2 ~--N=ll~ I N~

. .. ~ _ OH O}l OH O~ (~N=N--~) ~.
56. 02N ~ N=ll J ) N U

: . . _ ___ . ._. ___ N = N~

: , . . :
~: ~ :: .. .-- :- . :: , , . :
- : :~

0~1 No. Monoazo dye Dlsazo dye __ .. . . .. .

OH OH

58 . ~2N ~ r ~

I I ~
. OH OH
~ r ~i ~

_ 30 -.'. 1.

.
.

~ , _ . _ No. Monoa~o dye Di a~A ~, _ _ . - 0~1 01-1 0~011 . OU OH (~N=~ N=N-~) 6~ . S03~ HO 3S

. _ . _ ' OH 011 OU- OHOli OH

¦ 61. ¦ 2N~) =N~ N=N~) +(~N=N~

. N~ N~S03H

_ .

_ 31 -. .

.

, ~ ~3 Dyeing Procedure for Wool 100 parts of wool yarn are put at 50C into a dyebath which contains 2 parts of the dye of Example 2, 4 parts of ammonium sulphate and 2 parts of a levelling agent in 4000 parts of r water. The liquor is brought to the boil in the course of 45 minutes and kept thereat for a further 45 minutes. The goods are then removed from the bath~ thoroughly rinsed with cold water and dried A level black dyeing is obtained.

Dyeing Procedure for Leather 100 parts of clothing velours leather (dry weight) are wet back at 50C for 2 hours in a solution of 1000 parts of water and 2 parts of 24% ammonia and subsequently dyed for 1 hour at 60C in a solution of 1000 parts of water, 2 parts of 24% ammonia and 6 parts of the dye of Example 1. A
solution of 40 parts of water and 4 parts of fonnic acid (85%) is then added and dyeing is continued for a further 30 minutes. The leather is then thoroughly rinsed and, if appropriate, treated for 30 minutes at 50C with 2 parts of a dicyandiamine/formaldehyde condensation product. Other kinds of velour leather as well as glove leather can be dyed black in the same manner.

. ~, . . .
. .

Claims (16)

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:

1. Chromium complex dyes of the formula (1) wherein X1 represents a halogen atom, a C1-C5-alkyl group, a C1-C2-alkoxy group, a nitro group, a C2-C3-alkanoyl-amino or C2-C3-alkoxycarbonylamino group, Me? represents a cation, and Ar represents the radical of an aromatic diazo component which carries one to three SO3H and/or COOH groups, and is optionally further substituted by halogen, C1-C5-alkyl, C1-C2-alkoxy or nitro.

2. Chromium complex dyes according to claim 1, wherein Ar carries one to three SO3H groups or one SO3H and one COOH
group.

3. Chromium complex dyes according to claim 1 or 2, wherein Ar represents a naphthalene or benzene ring which carries one to three sulpho groups and can be optionally further sub-stituted by chlorine, nitro, C1-C5-alkyl or C1-C2-alkoxy.

4. Chromium complex dyes according to claim 1 or 2, wherein Ar carries one or two sulpho groups.

5. Chromium complex dyes according to claim 1 or 2, wherein X1 represents a hydrogen or chlorine atom, a nitro or methyl group.

6. Chromium complexes according to claim 1 or 2, wherein X1 represents a hydrogen atom and the nitro group is in the para-position to the azo group.

7. Chromium complexes according to claim 1 or 2, wherein the nitro group is in the ortho-position to the oxygen atom and X1 is a nitro group which is in the para-position to the oxygen atom.

8. A process for the manufacture of chromium complex dyes of the formula (1) wherein X1 represents a halogen atom, a C1-C5-alkyl group, a C1-C2-alkoxy group, a nitro group, a C2-C3-alkanoyl-amino or C2-C3-alkoxycarbonylamino group, Me? represents a cation, and Ar represents the radical of an aromatic diazo component which carries one to three SO3H and/or COOH groups, and is optionally further substituted by halogen, C1-C5-alkyl, C1-C2-alkoxy or nitro, which process comprises reacting an azo dye of the formula (2) or a disazo dye of the formula (3) with a chromium donor to give the 1:1 chromium complex and subsequently reacting this latter with the non-metallised dye of the formula (3) or (2) to give the 1:2 chromium complex.

9. A process according to claim 8, wherein the 1:1 chromium complex of the monoazo dye of the formula (1) is prepared first.

10. A process according to claim 8, wherein the starting material is a dye of the formula (3), in which Ar carries one to three SO3H groups or one SO3H and one COOH group.

11. A process according to claims 8 to 10, wherein the starting material is a dye of the formula (3), in which Ar is a naphthalene or benzene ring which contains one to three sulpho groups and which can optionally be further substituted by chlorine, nitro, C1-C5-alkyl or C1-C2-alkoxy.

12. A process according to claim 8 or 9, wherein Ar carries one or two sulpho groups.

13. A process according to claim 8 or 9, wherein the starting material is a dye of the formula (2), in which X1 represents a hydrogen or chlorine atom, a nitro or methyl group.

14. A process according to claim 8 or 9, wherein the starting material is a dye of the formula (2), in which X1 is a hydrogen atom and the nitro group is in the para-position to the azo group.

15. A process according to claim 8 or 9, wherein the starting material is a dye of the formula (2), in which the nitro group is in the ortho-position to the hydroxyl group and X1 is in the para-position to the hydroxyl group.

16. A process for dyeing and printing nitrogen-containing material which comprises the use of a dye defined according to claim 1.

17. The dyed or printed material obtained according to

claim 16.