JPS59159855A - Sulfonamide group-free and amino group-free metal complex dye - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides a free acid in the form of a compound of the general formula (where A is the residue of a penzole-based or naphthalene-based diazo component having a hydroxyl group or a carboxyl group adjacent to the azo bridge, 8 and K is a residue of a coupling component, D is a residue of an aromatic diazo component, and K and D each have a metallatable group at the 0-position relative to the azo group, provided that the compound of formula 1 has a total of The present invention relates to a metal complex compound dye containing no sulfonamide group or amine group, represented by the following formula (having 4 or 5 sulfone groups).

The dyes of formula 1 do not contain fiber-active groups, ie groups capable of forming chemical bonds with cellulosic or polyamide materials under normal dyeing conditions. Dyes of formula 1 have no sulfonamide groups, free amine groups or monoalkylamino groups.

Residue A preferably has a hydroxyl group in the o-position relative to the diazo group.

Residue B of the coupling moiety is preferably derived from the group of coupling moieties described below. Phenols, naphthols, pyrazolones, pyridones, acetoacetic amides especially anilides (all in the plural).

The residues Δ and B further carry one or several substituents, such as lower alkyl or alkoxy groups, chlorine, bromine, nitro, cyanogen, sulfone or acylamino groups.

Lower alkyl or alkoxy group means one having 1 to -6 carbon atoms, especially 1 to 2 carbon atoms, and acylamino group is lower, alkanoylamino group, alkoxycarbonylamino group or aroylamino group. .

A is derived from, for example, the amines listed below. Anthranyl 14-4 is 5-sulfoanthrani/l' acid, 2-amino-1- and droxypenzole, 4-chloro- and 4,6
-dichloro-2-amine-1-hydroxypenzole,
4- or 5-nitro-2-amine-1-hydroxypenzole, 4-chrono- and 4-methyl- and 4-acetylamino-6-21-rho-2-amino-1-hydroxypenzole, 6- Acetylamino- and 6-chloro-4
-nitro-2-amino-1-hydroxypenzole, 4
-cyano-2-amine-1-hydroxypenzole, 4
-methoxy-2-amino-1-hydroxypenzole,
4-methoxy-5-chloro-2-amino-1-, hydroxypenzole, 4-methyl-2-amino-1-hydroxypenzole, 4-chloro-5-ditlO-2-7 minnow 1-hydroxypenzole sol, 3.4,6-) dichloro-2-amino-1-hydroxypenzole, 6-acetylamino-4-cubenzole, 2-7minor 1-hydroxybenzo-4- or -5-sulfonic acid, 4 −
Nitro-2-7mi/-1-hydroxyben7'-ru-
6-sulfonic acid, 5-nitro- or 6-nitro-2-amino-1-hydroxybenzo-4-sulfonic acid, 4
-chlor-2-7 minnow 1-hydroxybenzo-6
-sulfonic acid, 1-amino-2-hydroxynaphthalene-4-sulfonic acid, 1-amino-2-hydroxy-6-
Nitronaphthalene-4-sulfonic acid, 2-amino-1-
Hydroxybenzo-4,6-disulfonic acid.

Instead of said amines having a hydroxyl group, corresponding methoxy compounds or corresponding compounds in which the hydroxyl group is tosylated can also be used, examples being anisidine, 4- or 5-chloroanisidine, 4- or 5-nitroanisidine. Carrot, anisidine-4- or -5-sulfonic acid, or tosylated 1-hydroxy-7-2-aminepenzole (in the case of metallization, a metquin group or -0-) syl group to the Kano I group be changed). Compounds having this group are particularly used when the corresponding 1-hydroxy-2-amine compound is difficult to couple with.

Preference is given to residues of 1-hydroxy-2-aminepenzole which are substituted by chlorine atoms, nitro groups and/or sulfone groups. In particular, A is preferably a residue of 1-hydroxy-2-amino-4-nitropenzole which optionally further has a sulfone group.

Preferred camplining components B are as follows. A lower alkyl group or alkoxy group, or phenols which may be substituted with an acylamino group (the acylamino group has the above-mentioned -N taste), resorcinol, a lower alkyl group or alkoxy group, a chlorine atom, an acylamino group, or Naphthols optionally substituted by sulfo/group (acylamino group has the above meaning)
.

a phenyl or naphthyl group optionally substituted by a chlorine atom, a nitro group, a lower alkyl or alkoxy group or a sulfone group in the 1-position, and a C4-C4-alkyl group, especially a methyl group, in the 1-position; 5-pyrazolones having the following.

acetoacetic anilide and benzoyl n7[7 nilide, which may optionally be substituted on the anilide nucleus by chlorine atoms, bromine atoms, lower alkyl or alkoxy groups or sulfonic groups, or 6-hydroxy-6-diatwo or 6-bitroxy-6-carbonamide-4-
Alkyl-2-pyridone, which is a lower optionally substituted alkyl group in the 1-position, e.g. methyl, ethyl,
substituted by an inglovir group, a β-hydroxyethyl group, a β-aminoethyl group or a γ-inoprofoxyfurovir group or by a group + C, and in the 4-position a lower a)v-kyl group, especially a methyl group ).

Examples of coupling components are as follows.

2-Twophthol, 1,6- or 1,5-dihydroxynaphthalene, 1-naphthol, 1-acetylaminortunaphthol, 1-glopionylamino-7-naphthol, 1-carbomethoxyamino-7-naphthol, 1
-carboethoxyamino-7-naphthol, 1-carbopropoxyamino-7-naphthol, 6-acetyl-2
-naphthol, 2-naphthol-6-1-4-1-5-
1-6-1-7- or -8-sulfonic acid, 1-naphthol-6-1-4- or -5-sulfonic acid, 4-methyl-
1-naphthol, 4-methoxy-1-7thol, 4-
Acetyl-1-naphthol, 5,8-dichloro-1-naphthol, 5-//D-1-f-phthol, 1-phenyl-3-methylhyrasole-5-oy, 1-phenyl-
5-pyrazole-6-carboxylic acid amide, 1-(2'-
13'- or 4'-methylphenyl) = 6-methylpyrazol-5-one, 1-(2'-13'-4ha4'-sulfophenyl)-6-methylpyrazol-5-one, 1
- (2'-chloro-5'-sulfophenyl) -3-
Methylpyrazol-5-one, i -(2'- or 4'
-methoxyphenyl)-6-methylpyrazol-5-one, 1-(2'-13'- or 4'-chlorophenyl)-6-methylpyrazol-5-one, 1-(2'-
16'-Also, 4'-nitrophenyl)-3-methylpyrazol-5-one, 1- (2!, 5'- or 6', 4
'-Dichlorophenyl)-3-methylpyrazole-5-
one, 1-(2',5'-dichloro-4'-sulfophenyl)-6-methylpyrazol-5-one, acej.
acetanilide, acetoacetanilide-4-sulfonic acid, acetoacetanilide, acetoacetate)
-o-toluicide, acetoaceto-〇-chloroanilide, acetoacetyl-m-xylidide, tetralol, 4-
Methylphenol, 6-dialkylaminephenol,
Especially 6-dimethylamine- and 6-diethylaminophenol-4-butylphenol, 4-7 milphenol, especially 4-1. - amylphenol, 2-isopropyl-4-methylphenol, 2- or 6-acetylamino-4-methylphenol, 2-methoxy7carponylamino-4-methylphenol, 2-ethoxycarbonylamino-4-methylphenol and - 6,4-dimethylphenol, resorcinol, 1-methyl-6~cyano-4~
Ethyl-6-hydroxypyridone, 1-methyl-6-noano-4-methyl-6-hydroxypyridone, 1-phenyl-3-carbonamido-4-methyl-6-hydroxypyridone.

Preferably, coupling component B is 1- or 2-
Naphthol, resorcinol, p-alkyl (Cs~co
)-phenol, 1-phenyl-6-methyl-5-pyrazolone or acetoacetanilide, in which case the phenyl group in the next two compounds is a C1-C4-alkyl group, a C1-C4-alkoxy group, a chlorine It may be substituted with an atom or a sulfone group.

Dyes of the formula D=N=NK(II) include, in particular, known metallizable dyes, such as the sulfonamide groups listed as mordant dyes in the Color Index;
Those containing no amino group or monoalkylamino group are used.

D is preferably the residue of 1-hydroxy-2-aminepenzole or 1-amino-2-hydroxynaphthalene, which is further substituted by nitro and/or sulfone groups.

K is preferably the residue of a coupling component described below.

1-naphthol or 2-naphthol optionally substituted by a sulfone group, phenol substituted in the p-position by an 01-co-alkyl group, 1- or 2-naphthylamine optionally substituted by a sulfone group, 1-phenyl -6-methyl-5-pyrazolone or acetoacetanilide (the phenyl groups in the latter two compounds are C1-c
It may be substituted with a 4-alkoxy group, a chlorine atom, or a sulfone group (.).

Particularly preferred °C dyes of the invention are in the free acid form of the following formula: In this formula, Δ' is 1-human.

The residue of xy-2-aminepenzole, which is 1
substituted with 1 or 2 chlorine atoms, nitro group or sulfone group, B'ba2-7thol, resorcinol,
p-alkyl (C, ~C6)-phenol, 1-phenyl-6-methyl-5-pyrazolone, or the residue of acetoacetanilide, of which the phenyl group in the latter two compounds is C, ~c4- alkyl M, c, ~c4-alkoxy group, optionally substituted by a chlorine atom or a sulfone group, K' optionally by a sulfone group (P) a residue of 1-naphthol or 2-naphthol,
Residues of phenol substituted in the p-position by a C4-c6-alkyl group, residues of 2-naphthylamine or 1-phenyl-6-methyl-5-pyrazolone or acetoacetanilide, optionally substituted by a sulfonic group. and the phenyl group in the latter two compounds is C7-C
4-7/l/ may be substituted by a coquine group, a chlorine atom or a sulfone group, where gon is a residue of 1-hydroxy-2-aminepenzole or 1-amino-2-hydro-synafthari/; , which is further substituted with a nitro group and/or a sulfone group.

Metallizable compounds of the following formula can be obtained by known methods, for example by diazotizing an amine of the formula % and then coupling in an alkaline p[() with a coupling component of the formula %. 2 to diazotize the amine groups of the naphthalene and 2 to couple with coupling component B, where A and B have the meanings given above.

The preparation of the 1=2-chromium complex compounds of the invention of formula 1 (which includes dyes of formula 1 and formula IV) can be carried out, for example, by first reacting the dye, preferably compound 1, with a chromium-donating agent to prepare 1: 1-complex compound. This is then reacted with other dyes to convert it into a 1:2-complex compound. The reaction is preferably carried out in a neutral to slightly alkaline medium, in an open or closed vessel, at elevated temperatures, for example from 50 DEG to 120 DEG C. It is possible to work in organic solvents such as alcohols or ketones, or in aqueous solutions. That-
In some cases, the reaction can be accelerated by adding a solvent such as alcohol, formamide, etc. Generally 1
=1=The complex compound and the metallizable dye are preferably reacted in chemical equivalents. An excess of metallizable dye is usually slightly less favorable than in the case of metal-free dyes.

It is also possible to react dye mixtures of formulas (II) and IV with chromium donors.

In another method of preparing the inventive 1=2-chromium complexes of formula I, they are first diazotized and coupled with the coupling component H--B. Part 17) In this case, A and B are formula 1
It has the meaning in the case of

A41. by the above method. The new o i'-complex compounds are preferably isolated in the form of their salts, especially alkali salts such as lithium salts, potassium salts, sometimes sodium salts or ammonium salts. It is suitable for dyeing various natural or synthetic polyamide materials, such as wool, silk, synthetic polyamides, polyurethanes, especially wool or leather.

The new dye has a deep color and good coverage. It has good fastness properties, such as wash-1 water-1 sweat-1 rub-5 diffusion-5 light-1 acid and alkali fastnesses, as well as good dyeing properties. Additionally, they are generally not sensitive to calcium salts in the dyebaths, which makes it possible to use unsoftened water. The fact that it dyes well on various types of leather, including leather tanned only with chromium salts and leather that has been post-tanned with vegetable or synthetic tanning agents, is that
Particularly noteworthy.

A deep brown to black color tone is obtained. Other formula I
The dye is eminently suitable for dyeing finished wool without felting.

Example 1 240 parts of 4-nitro-2-amine di-1-hydroxy-benzole-6-sulfonic acid was stirred in 2000 parts of water,
Cool to 5°C with hydrochloric acid and ice. 3.3 Add dropwise 320 parts by volume of N-sodium nitrite solution and stir for 2 hours at 7°C. After decomposing excess nitrous acid with amidosulfonic acid, the diazo solution was dissolved in 1-hydroxy-8-aminenaphthalene-3, which was dissolved in 2000 parts of water together with 40 parts of sodium hydroxide and 150 parts of sodium carbonate.
Pour into a solution of 619 parts of 6-disulfonic acid and cool at 10° with ice.
Make it C. Coupling ends after about 2 hours. Adjust the pH to 6 with hydrochloric acid.

3. Inject 610 parts by volume of 3N IJ solution. Then add ice, cool to 5°C, and adjust the pH with hydrochloric acid.
Set to 0.6. After the diazotization has ended, the diazotized azo dye is added to a solution of 146 parts of 2-naphthol in 2000 parts of water, 41 parts of sodium hydroxide and 600 parts of sodium carbonate.

The temperature of the coupling mixture is maintained at 15° C. by adding ice and filtered with suction after the end of the coupling.

A press cake containing a 1:1 chromium complex obtained from 684 parts of a monoazo dye from naphthalene-4-sulfonic acid and 2-hydroxynaphthalene and 52 parts of chromium is mixed. Heat to 70°C, add caustic Noda solution to maintain pH between 7 and 75, and heat until no starting material is detected by chromatography. Finished wool without spray drying the dye is dyed black with good fastness properties. The black leather dyeing also has good fastness properties and is very dark even on post-tanned leather.

When using a 1:1-chromium complex compound of the following azo dye, a dye having similar properties can be obtained. The value on the far right is λITlaX or melting point.

OHNH2 Example 2 Hydrochloric acid 2
Bring to 7°G using 75 parts by volume and ice. 3,3 to this
160 parts by volume of N-sodium nitrite solution are added dropwise and stirred for 2 hours. After decomposing excess nitrous acid, the diazo component solution was dissolved in 16 parts of 1-hydroquine-8-aminenaphthalene-3,,6-disulfonic acid, which was dissolved in 1000 parts of water together with 20 parts of sodium hydroxide and 75 parts of sodium carbonate.
0 parts of solution and bring to 10°C on ice. Coupling ends after 6 hours.

The pH is adjusted to 0.6 with hydrochloric acid, and 160 parts by volume of 6.6N sodium nitrite solution are added. This diazotization solution is
1000 parts of water, 20 parts of sodium hydroxide and carbonic acid)
Flow into a solution of 60 parts resorcin in 4250 parts IJ tau. - After stirring overnight, the coupling is completed. The dye precipitated by adding 1500 parts of sodium chloride is aspirated and filtered.

The obtained press cake was stirred in 2500 parts of water, and diazotized 1-amine-2-hydroxy-naphthalene-4 was added.
- 1:1 obtained from 192 parts of monoazo dye from sulfonic acid and 2-hydroxy-naphthalene and 25 parts of chromium.
- Press cake addition of chromium complex compound. When the pH is maintained at 7-Z5 with caustic soda solution, the reaction is
Ends after hours. 1000 parts of sodium chloride and 1250 parts of potassium chloride are added to dye the dye and the leather black, the dyeing having good fastness properties.

Similarly good dyes can be obtained by using the 1:1 chromium complex compound of ``Cise Dye Ne 1'' below. The rightmost number is λH1a
X or melting point 0 0HH2N Example 6 77 parts of 4-nitro-2-aminone enol was dissolved in 1000 parts of water.
1 part, along with hydrochloric acid and ice, and 160 parts by volume of a 6.6N sodium nitrite solution were added to diazotize. This diazotization 1) suspension was mixed with 160 parts of 1-hydroxy-8-aminenaphthalene-6,6-disulfonic acid in 1000 parts of water, 20 parts of sodium hydroxide and 70 parts of sodium carbonate.
part of the solution. Coupling will be completed in 2 hours. Adjust the pH to 6.5 with hydrochloric acid, add 160 parts by volume of 3.3N sodium nitrite solution, cool to 10°C with ice, and add □ drops of hydrochloric acid until the pH reaches 1.5. The diazotization is completed after 6 hours. Decompose excess nitrous acid with amidosulfonic acid. Add the diazo component solution to 600% water.
parts, 16 parts of sodium hydroxide and 150 parts of sodium carbonate
113 parts of 2=hydroxy-naphthalene-6-sulfonic acid in 1 part. Add ice to bring the temperature to 10℃
If held at , the coupling will be completed overnight.

The press cake obtained by suction filtration is added to 1°00 parts of water.
1 obtained from 192 parts of a monoazo dye phase from diazotized 1-amino-2-hydroxy-naphthalene-4-sulfonic acid and 2-hydroxynaphthalene and 26 parts of chromium:
It is added together with the 1-chromium complex compound. 7
Stir at 0'C for 4 hours, add 1) H with dilute caustic Noda solution and dye to a black tone with good fastness.

HLJ3? 0 mouths 110 Example 4 2-Hydroxy-1-amino-5-chlorobenzole 1
4.5 parts are stirred with 1[]0 parts of water. To this are added 15 parts by volume of concentrated hydrochloric acid, 100 parts of ice, and 7 parts of 26'jr sodium nitrite solution. After stirring for 2 hours at 5° C., the excess nitrous acid is destroyed with amidosulfonic acid and the diazotized mixture is dissolved in 100 parts by volume of 5% sodium hydroxide solution and 1-hydroxy-8-
60 parts of amino-naphthalene-6,6-disulfonic acid are added to the bath solution. After the coupling is complete, the solution is prepared with hydrochloric acid (T)H,6, and after stirring for half an hour, 60 parts by volume of 23% sodium nitrite solution are added. Then 200 parts of water and 7 parts of hydrochloric acid
Add 0 parts by volume and leave for 2 hours. After the coupling is completed, it is acidified and suctioned once. The isolated product was dissolved in 50 ml of water.
0 parts and heated to 70°C, then the diazotized 1:1-chromium complex compound of 5-nitro-2-aminephenol and 2-aminenaphthalene-5-sulfonic acid was completely reacted. Addition dyeing is carried out in an amount necessary to form an asymmetric 1:2-chromium complex.

Using 1=1-chromium complex compound of the listed compound (・, similarly, a chromium complex compound is obtained.The rightmost value is λ1118
X or melting point.

02N Example 5 5-chloro-2- in 2000 parts by volume of 2% caustic soda solution
Hydroxy-1-amine benzo-6-sulfonic acid 2
26% sodium nitrite solution to 2.35 parts of solution 30
Add parts by volume.

This mixture is gradually added at 0-5° C. to a mixture of 60 parts by volume of concentrated hydrochloric acid and 250 parts of ice.

After stirring the whole at 0 to 5°C, 60 parts of 1-amino-8-hydroxy-naphthalene-6-disulfonic acid,
(100 parts by volume of 4% caustic soda solution, 50 parts of ice, and carbonic acid)
Gradually add 65 parts of IJum to the mixture. After the coupling is completed, 80 parts by volume of concentrated hydrochloric acid and 2 parts of saturated saline
00 parts by volume are added to precipitate the coupling product and filtered off with suction.

The filter cake is dissolved in 500 parts of 1% sodium hydroxide solution and this solution is poured gradually, together with 60 parts by volume of 26% sodium nitrite solution, into a mixture of 70 parts by volume of concentrated hydrochloric acid, 600 parts of water and 400 parts of ice. After stirring for 2 hours at 0-5°C, 22% 2% caustic soda solution was added to the diazotized mixture.
1-phenyl-6-methyl-pyrazolone- in 0 parts by volume
(5) Add 19 parts of the solution and then gradually bring the pH to 6. The resulting disazo dye is filtered with suction zT+ and washed with dilute saline. The entire amount of dye obtained is stirred at 40° C. with 400 parts of water and 10 parts of 25% aqueous ammonia. Diazotized 4-nitro-2- is then obtained by known methods.
An equivalent of the 1=1-chromium complex compound of the dye from hydroxy-1-aminobenzo->2-aminenaphthalene-5-sulfonic acid is added. The reaction dissolves in a covering green color and dyes wool and leather to greenish-black tones.

When the compound in the first column of the table (1) is reacted with the disazo dye in the second column in a ratio of 1=1, a dye having similar properties is obtained. This dye dyes wool and leather in the shades shown in column 6 with good fastness properties. ′

Claims (1)

[Claims] 1. In the form of a free acid, the general formula (where A is the residue of a penzole-based or naphthalene-based diazo component having a hydroxyl group or carboxyl group at a position adjacent to the azo bridge, B and I) Residues of coupling components,■
) is a residue of an aromatic diazo component, and K and J] each have a metallizable group at the 'C-position with respect to the azo group.
, provided that a metal complex compound dye containing no sulfonamide group or amine group represented by the compound of formula 1 (having a total of 4 or 5 sulfone groups). 2. The following formula (where A' is the residue of 1-hydroxy-2-aminepenzole, which is substituted with one or two chlorine atoms, nitro group or sulfone group, and B' is 2 -naphthol, lucine, p-alkyl-CC, ~C6) -phenol, 1-phenyl-3-methyl-5-pyrazolone or the residue of acetoacetanilide, where the phenyl group in the last two compounds is C1 ~c4-alkyl group, c+ ~C4'
7/lzz may be substituted with an oxygen group, a chlorine atom or a sulfone group, K' is a 1-naphthol residue or a 2-naphthol residue which may be substituted with a sulfone group, 01 to C6 at the p-position - Phenol residue substituted with an alkyl group, 2-naphthylamine optionally substituted with a sulfone group, 1-phenyl-3-meth'f
a residue of 5-pyrazolone or acetoacetanilide,
The phenyl group in the last two compounds may be substituted by a C1-C4-alkoxy group, a chlorine atom or a sulfone group, and d is 1-hydroxy-2-aminepenzole or 1'amino-2-hydroxy - a residue of naphthalene which is further substituted by a nitro group and/or a sulfone group) according to claim 1. 3. Claim 1 A method of using the compound described in 1. for dyeing nitrogen-containing fibers or leather.