JPS6020420B2 - Manufacturing method of azo compound - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing azo compounds, and more particularly to a method for producing metallizable azo compounds and their metal anchor salts.

The compound according to the present invention has the following general formula 1: [In the above formula, R represents a nitro group, and 02 and R3 are
Each independently represents 1OH or -NZ, and R
4, R5 and R6 each represent a hydrogen atom, R7 represents -SQM, or R7 represents a hydrogen atom,
One of R4 and R5 represents a nitro group, and the other represents -SQ
M group, R6 represents a hydrogen atom, R8 represents the following formula W, (in the above formula, R9 represents a hydrogen atom or a (C, ~4) alkoxy group, R and o represent a hydrogen atom, a nitro group, or - S
03M, R, . represents a hydrogen atom or a chlorine atom.

However, R9, R mountain and R, . one or two of which are hydrogen atoms, M represents a hydrogen ion or a non-chromogenic cation], and is metallized. Kamo〈 is a non-metallized form.

The metallization of the compound of formula 1 is a 1:1 type or a 1:2 type metal salt. The 1:2 type metal salt according to the present invention is a salt of a compound of formula 1 or a rust salt of a compound of formula 1 and another metallizable azo compound. The present invention provides compounds of formula 1 and its 1:
The present invention provides a method for producing tsuba salts of type 1 and type 1:2, which method comprises: '1} In order to obtain a compound represented by formula 1, the following formula m: [in the above formula, R4, The diazo derivative of the compound represented by R5, R6 and R7 are the same as defined above] and the diazo derivative as R8 are combined in a desired order with the following formula 0: [in the above formula, R,, R2 ．．
R3 and M are the same as defined above]; (1) wherein at least one of the complex salt-forming compounds is a compound of formula 1:
In order to obtain metal salts of type 1 or 1:2 type, the metal-supplying compound is combined with the compound of formula 1 above and, if necessary, with other metallizable azo compounds, in the case of different azo compounds. a metal-supplying compound, either simultaneously or in any desired order;
(1) reacting the diazo compound of the amine of formula m and the diazo conductor as R8 with 1 of the compound of formula b to obtain a 1:1 type steel rust salt of the compound of formula 1;
: Coupling with type 1 steel tsuba salt, ■ Formula 1 above
In order to obtain a 1:1 type steel tsuba salt of the compound, the diazo derivative as R8 was converted into the following formula:
, R4, R5, R6. Coupling with a 1:1 type steel fin salt of a compound represented by R and M are the same as those specified above; '51 At least one metallizable component corresponds to the above formula 1. 1:2 as if it were a thing
In order to obtain iron, chromium or cobalt salts of the type m, a diazo compound of an amine of the formula m and a diazo derivative as R8 are combined, one of the metallizable constituents of which corresponds to the formula m. and coupling with a 1:2 iron, chromium or cobalt salt, the others being the same or different, or {6} 2
In order to obtain iron, chromium or cobalt rust salts of the 1:2 type, or mixtures thereof, in which at least one of the species salt-forming azo compounds is a compound of formula 1 above, the diazo derivative as R8 is A 1:2 type iron, chromium or cobalt rust salt or coupling with a mixture thereof.

In the above method of the present invention, when a mixture is used as a starting compound, it goes without saying that the resulting compound can also be obtained as a mixture.

If R8 is a group of a diazo moiety, the diazo moiety with the higher coupling energy is coupled last.

R8 is preferably a radical of the diazo component which has a higher coupling energy than the diazo derivative of formula m, and therefore the introduction of the group R8 is preferably carried out in the last coupling reaction. Coupling can be performed by conventional methods.

The coupling of a diazo derivative of a compound of formula m with a compound of formula 0 or a rust salt containing a compound of formula 0 is suitably carried out at a temperature of 0 to 25 qo, preferably 4 to 5°C.
This reaction is preferably carried out in an aqueous medium with at least 5 baits. The coupling between the diazo derivative as R8 and the rust salt containing the compound of Shikihata or the compound of Shikihata is from 0 to
Suitably it is carried out at a temperature of 2yo, preferably 4-5°C.

This reaction is preferably carried out in an aqueous medium at a pH of 4-9. Coupling promoters may also be used.
Examples of suitable coupling promoters include urea, pyridine and cellosolve. Formation of metal salts can be carried out by known methods.

For example, iron rust salts are formed using iron salts. PH is 3.
It is preferably 5 to 6, more preferably 4 to 4.5. Suitable reaction temperatures range from 95 qC to reflux temperature or even higher temperatures when treated under pressure, for example up to 120°C. Cobalt and chromium salts are formed under similar temperature conditions. For the formation of cobalt rust salts, the pH is advantageously between 4 and 10, and for the formation of chromium rust salts it is advantageously between 2 and 10. The reaction is carried out in an aqueous, water-organic or organic medium. Preferred organic solvents are such that they have a boiling point above 100°C, are miscible with water, and in which the compound to be rusted and the metal salt are soluble. Examples of suitable solvents include:
Alcohols, ether alcohols and amides such as cellosolve, methylcellosolve, formamide and dimethylformamide. Preferably, the organic solvent is used in the production of chrome salt. Copper salts are formed in an aqueous medium under neutral to alkaline conditions, preferably between 7.5 and 10 degrees centigrade.

This reaction is advantageously carried out in the presence of excess ammonia. Suitable reaction temperatures are above 70 DEG C., preferably from 80 to 100 q0, or if desired under pressure. Preferably, the amount of copper compound used is such as to provide at least 1 mole of copper per mole of azo dye. The term "excess ammonia" means an excess of the amount that would be equally trapped by the copper, preferably an amount sufficient to dissolve each copper salt. Examples of suitable metal-donating compounds include:

For copper: cupric chloride, acetate, formate or sulfate For iron: ferrous sulfate or nitrate, ferric sulfate or nitrate or for ferric chromium chloride: chromium trioxide, For dichromic fluoride, sulfate, formate or acetate, ammonium chromium sulfate, potassium chromium sulfate, sodium or potassium chromate or sodium dichromate or cobalt: monochromic cobalt formate, acetate, sulfate or chloride. In the preparation of cobalt cobalt chlorides or cobalt acetates of the 1:2 type, it is advantageous to use at least 1 mol (preferably not more than 2 mol) of metal per 2 mol of azo compound.

* When producing asymmetrical 1:2 tsuba salts, in particular 1:2 chromium, the corresponding 1:1 metal complexes are first prepared and then these complexes are reacted with other metallizable azo dyes. Therefore, it is advantageous to obtain the desired asymmetric 1:2 metal salt.

According to the invention, there is also provided a metal salt mixture comprising salts of different metals.

Such complex salts are formed by reacting the azo dye with a different metal-donating compound, preferably forming a salt of one metal, and then converting any uncomplexed azo compound that may be present in the reaction mixture to the other metal. Produced by reacting with a feed compound. The term "halogen" means chlorine, bromine, fluorine or iodine, with chlorine being preferred.

The other metallizable azo compound may be any metallizable compound, but it is an aromatic substituted by a metallizable group, such as hydroxyl or amino, in the position ortho to the azo group. Preferred are azo compounds in which the group nucleus is placed on either side of the azo group.

Examples of such other metallizable azo compounds include:
The following formula V: [In the above formula, R'2 and R'3 each independently represent 1OH or 1NH2, and A is the hydroxyl group shown in the formula at the ortho position with respect to the azo group. like,
otherwise unsubstituted represents a substituted benzene or naphthalene group, R4,3R5,R6,R
7 and R8 represent the same as defined above, n represents 0 or 1, and m represents 1 or 2.

However, the sum of m+n is 2, and when this compound is a trisazo compound, it preferably has at least one sulfo group. Preferred as other metallizable compounds are the compounds of the formula 0 described above or the compounds of the following formula: [In the above formula, R4, R
5, R6, R7 and R8 represent the same as defined above, Y represents a hydrogen atom, chlorine atom, -SQM or nitro group, Y2 represents a chlorine atom, S03M or a nitro group, M represents the same as defined above. Z represents the same thing].

Accordingly, a 1:2 type salt of a compound of formula 1 or of a compound of formula 1 with another metallizable azo compound may be used with a diazo derivative of the amine of formula m mentioned above or a Z mixture thereof and, if necessary, , a diazo derivative as R8, or a mixture thereof, according to the following formula K: [In the above formula, x each independently represents -NH- or -0-, and Me represents iron, cobalt, nickel or chromium. . The diazo derivative as 0,
It can be produced by coupling using 1, 2 or 3 moles (provided that the molar ratio of the diazonium compound to the compound of formula K is 4:1 or less).

Examples of compounds of formula K include compounds represented by the following formula There are compounds obtained exclusively from compounds of formula 0, especially compounds obtained from two identical compounds of formula 2.

Diazo derivatives of compounds of formula m or mixtures thereof are of formula K
and, if necessary, a diazo derivative as R8 or a mixture thereof in a molar ratio of 1:1 to 2:1. . Preferred among the compounds of formula 1 are those in which R8 is a group of a diazo component, and R
Further preferred are compounds in which 8 is a diazo group of formula W as described above. In compounds of formula 1, it is preferred that any alkoxy groups have 1 or 2 carbon atoms.

Preferably R2 and R3 are -OH. R7 is -S
In the case of a 03M group, this one S03M group is preferably in the meta position relative to the azo group. Compounds in which at least one of R4, R5, R6 and R7 is a group other than a hydrogen atom are preferred. Particularly preferred are compounds and salts in which up to three of R4, R5, R6 and R7 are hydrogen atoms. The trisazo compound of formula 1 has at most 3 -S0
3M and the disazo compound preferably has at most 2 -S03M.

Compounds of formula 1 having at least two water-dropping groups are preferred. Preferably, M is a hydrogen ion, an alkali metal cation or a non-pupillary or imitation ammonium ion.

Examples of substituted ammonium ions include (C,~3)alkylammonium and hydroxy(C2~3)alkylammonium ions, such as triethylammonium, tetramethylammonium, mono, di- or trietanol asmonium and mono, di- Or there is tri-isopropanol ammonium ion. Examples of alkali metal cations are lithium, sodium or potassium ions, with sodium and potassium ions being preferred alkali metal cations, the former being particularly preferred. Preferred compounds of formula 1 are:
In formula 1, R is -NQ, R2 and R3 are both -OH, and R4, R5, R6 and R7 are each a hydrogen atom or an electron-withdrawing substituent as described above (provided that R4 , R5 and R8, if they are other than hydrogen atoms, they are in the ortho or para position with respect to the ami/group,
R7 shall be in the ortho position to the amino group)
These are compounds in which R8 is a group of a diazo component, preferably a group of formula W as described above, and M is the same as defined above.

A particularly preferred compound of formula 1 is the following formula lb: [wherein R
``8 represents the group of the diazo component of the above-mentioned formula W, R',
and R'' and R... each represent a hydrogen atom, the R side represents -S03M, or the R side represents a hydrogen atom, one of R' and R'' represents a nitro group, and the other represents -S03M R''' represents a hydrogen atom].

A preferred metal key salt is the 1:1 Sezurin salt of the compound of Formula 1, Formula 1
a 1:2 iron, cobalt and chromium fin salt of a compound of formula 1 with another metallizable compound, or a 1:2 iron, cobalt and chromium rust salt of a compound of formula 1 with another metallizable compound; , the 1:2 salts of compounds of formula 1, especially the iron and cobalt mirror salts, are preferred.

Furthermore, the mixed metal salt is preferably a mixture of iron and cobalt salts. When R8 in a compound of formula 1 or skin is a group of a diazo component and such compound of formula 1 is keyed with another compound of formula 1 or a compound of formula 1, the azo group of the group as R8 It should be understood that a hydroxyl or carboxy group in the ortho position is used with the hydroxyl group as R2 to form a metal salt bond.

The negative charge of the metal atoms in the 1:2 type metal salt is compensated by hydrogen ions or non-chromogenic cations.

As such a non-chromogenic cation, those mentioned above for M are suitable. The ions that compensate for the charge of the metal may be the same as M or different, but preferably the same. The free acid form or the ammonium salt form is preferred, and the free acid form is particularly preferred. Compounds of formula m and W are known or can be prepared in conventional manner from available starting materials.

Azo compounds of formula V can be prepared in conventional manner from known or available starting materials.

Compounds of the formula 0' in which R is hydrogen are known.
The compound of formula 0 is a diazo derivative of an amine represented by the following formula M: where R and M are the same as defined above. ]
It can be produced by coupling with a compound represented by Z.

This coupling reaction is carried out in a conventional manner.

P of at least 7.5 in a basic, preferably aqueous medium
Coupling in H is carried out using a thin Z contact.
The reaction temperature is 0-25°C, preferably 4-500°C.
It is prepared by adding alkali metal hydroxides or carbonates or ammonia or amines. When R2 and R3 are the same, the coupling is of the following formula:
It was discovered that this occurs along the path indicated by the arrow in 2. If R2 and R3 are different, mixtures are obtained which can be separated in the usual manner. According to the invention there is therefore also provided a mixture of compounds of formula 1 and their fin salts obtained using a mixture of compounds of formula (b). Although such a mixture may be separated into individual components by a known method, it is preferable to use the mixture as it is without separation. The metal key salts and mixtures thereof according to the present invention are useful as water-soluble dyes.

These can be used to dye substrates that can be dyed with anionic dyes. Examples of suitable substrates include paper and especially leather. Any type of leather is suitable and can be dyed in the usual manner. The rust salt according to the present invention exhibits remarkable dyeing ability for leather with low affinity. A highly concentrated brown dyeing is obtained which exhibits outstanding fastness to sunlight, hard water, washing, perspiration, alkalis, acids and buffing. Paper can be dyed with the salt according to the invention in the usual manner, in stock or in sheet form.

The following examples serve to further explain the invention.

In the examples, "parts" and "%" are expressed by weight. Example 1 29.5 parts of a diazo derivative of 1-amino-2-hydroxy-4-sulfo-6-nitronaphthalene (nitrodiazooxide acid sodium salt) was added to a diazo derivative at 0° C.
It was added to a solution of 11 parts of 1,3-dihydroxybenzene in 20 parts of water and 35 parts of soda ash.

Coupling was completed after 2 hours.

26.4 parts of the diazo derivative of 4-teramine-2-sulfodiphenylamine in the solution of the obtained monoazo dye,
The mixture was allowed to run for 1 hour at a pH of 9.5 for 30 minutes. 13.8 parts of a diazo derivative of 1-amino-4-nitrobenzene was added to the resulting disazo dye solution over a period of 30 minutes, and the mixture was stirred for 3 hours. The resulting trisazo dye solution was heated to 95°C for 1 hour, then 1 part of crystalline iron trichloride was added and the mixture was held at this temperature for a total of 4.5 hours for 1 hour.

After cooling to 20° C., the dye was separated from the oven.

This dye was dried as a black-brown powder and dyed leather a dark brown color.

The dyeings had remarkable fastness to sunlight, washing, perspiration, hard water, acids and alkalis. Example 2 0 The procedure of Example 1 was repeated, but this time 14 parts of crystalline cobalt sulfate was used instead of 1 part of crystalline iron chloride used in Example 1, and the reaction was carried out at pH 9 by adding sodium hydroxide. carried out.

After salting out, the dye was obtained in the form of the sodium salt, or by addition of the free acid, the dye in the form of the free taic acid was obtained. This dye dyes the leather a grayish-brown color, and this dyeing is exposed to sunlight, hard water,
It had remarkable fastness to washing, sweat, acids and alkalis. Example 3 (Reference Example) In place of the 14 parts of cobalt sulfate used in Example 2, a corresponding amount of nickel sulfate was used and the reaction was carried out at a pH of 3.5-5.

The dye obtained dyed the leather dark brown and the dyeing had similar fastness properties. Example 4 The trisazo dye obtained as described in Example 1 was dissolved in formamide, heated to 120 DEG C. and 25 parts of chromium alum were added.

After the formation of the key salt, the dye was precipitated by pouring it into a 20% saline solution and heating in an 8U oven. This dye was dried as a black-brown powder and dyed leather a deep reddish-brown color. The dye can also be obtained in free acid form by precipitation with addition of acid. Example 5 A trisazo beam prepared as described in Example 1 was heated to 80°C and treated for 1 hour at 80°C with the addition of 25 parts of crystalline copper sulphate in the presence of a slight excess of ammonia. .

After cooling to 20 qo, the product was precipitated by pouring it into common salt, separated in an oven, and dried.

The product obtained was in the form of an ammonium salt, a black powder, which dyed the leather a brownish-gray color. Dyed products are exposed to sunlight, washed,
It had remarkable fastness to sweat, hard water, acids and alkalis. Examples 6 to 25 In analogy to what has been described in the previous examples, metallizable azo dyes of the formula:

These dyes are listed in Table 1 below by indicating the groups R,2-,6. These 1:2 cobalt compound and 1:1 copper tsuba compound dye leather grayish brown;
Chromium compounds stain bright reddish brown. Table 1 Examples 26-37 Metallizable azo dyes of the following formula were able to be produced in a similar manner to the previous examples.

These dyes are listed by the groups R, 2-, 6 as shown in Table 2 below. These 1:2 copalt rust compounds and 1:
1 Steel rust compound imparts a gray-brown stain to leather; 1
: Dichromium complex compounds give a reddish-brown coloring. table
2 Examples 38 to 49 A metallizable azo dye represented by the following formula was able to be produced by the same operations as in the previous examples.

These dyes are shown in Table 3 below by the groups R,2-,6. These 1:2 cobalt rust compounds and 1:1 copper rust compounds dye leather grayish brown, and the 1:2 chromium complex compounds dye leather fat reddish brown. Table 3 Example 50 29.5 parts of a diazo derivative of 1-amino-2-hydroxy-4-sulfo-6 nitronaphthalene was dropped on a rope at 0°C.
, to a solution of 11 parts of 1,3-dihydroxybenzene in 200 parts of water and 35 parts of soda ash.

Coupling was completed after 2 hours.

26.4 parts of a diazo mystery conductor of 4-amino-2-sulfodiphenylamine was added to the obtained solution of the mo/azo dye.
At pen 9.5, the mixture was flown for 30 minutes and sailed for 1 hour. 12. to the obtained disazo dye. The diazo derivative of 1-amino-2-methoxybenzene in the group part,
It was added at pH 9 and rinsed for 1 hour at 5°C. After coupling, 95 to 100 qo of the obtained trisazo dye
7 parts of crystalline cobalt sulfate were added. The pH was adjusted to 9 and the temperature was maintained at 95-100°C for 1 hour. After all the cobalt was dissolved, the pH of the reaction mixture was adjusted to 4-5, then 6.5 parts of iron chloride was added, and the mixture was kept at 95-100°C for another hour. . After coupling, the dye was precipitated using common salt and dried. A mixture of 1:2 cobalt and 1:2 iron rust salts of trisazo dyes was obtained, which dyed leather in a medium dark brown color with remarkable fastness properties. Example 51 Me is Fe, Co or Cr.

Dye 1 29.5 parts of a diazo derivative of 1-amino-2-hydroxy-4-sulfo-6-nitronaphthalene was added to
20$ with 35 parts of soda ash added at 15qo
to a solution of 11 parts of 1,3-dihydroxybenzene in 1 part of water.

Coupling was completed after 2 hours.

26.4 parts of a diazo derivative of 4-amino-2-sulfodiphenylamine was added to the solution of the obtained monoazo dye, and the pH
9.5 for 3 minutes and this mixture
The mixture was incubated for 1 hour until no diazo compound was detected. 12. In the obtained disazo dye. A portion of the diazo derivative of 1-amino-2-methoxybenzene was introduced at shaft 9. The reaction was carried out at 0°C. This mixture was stirred for 1 hour, and after coupling, the resulting trisazo dye was combined with Dye 0 below. This dye was manufactured as follows.

19. A diazo derivative of 1-amino-2-hydroxy-3,5-dinitrobenzene was prepared at pH 9 and at a temperature of 0 to 0.
To the monoazo dye obtained by coupling with 11 parts of 1,3-dihydroxybenzene at 5° C., 26.4 parts of the diazo derivative of 4-amino-2-sulfodiphenylamine are added in solution 9 and this mixture is was concentrated for 2 hours at 0-5°C.

Once the coupling was complete, dyes 1 and 2 were heated to 95° C. and 27 parts of iron chloride m (crystals) were added.

The pH was adjusted to 4.5 with hydrochloric acid and the mixture was heated to 95°C for 1 hour.
Holds time. The product was precipitated by adding common salt and was separated in a furnace. When dry, the dye turned into a dark brown powder and dyed the leather a deep reddish-brown color. In place of the iron chloride 0 used above, the corresponding 0b and Cr rust salts could be prepared using cobalt and chromium donating compounds and under the conditions described in Examples 1, 2 and 3.

*Example 52 By the same operation as described in Example 1, a dye of the following formula was obtained, which was metallized by the same operation as described in Examples 1 and 2 to form 1:2 cobalt and 1:2 iron key salts. Obtained.

Application example A: 10 parts of freshly tanned and neutralized chromium fur removed.
In a dyeing machine, treated for 30 minutes in a solution consisting of 560 parts of water and 1 part of the dye obtained in Example 1, and in the same bath 2 parts of anion fat, the main component of which is sulfonated whale oil. Three powders were treated with liquid, dried and finished in the usual manner.

Leather was obtained which was uniformly dyed in a dark grayish brown color. Application example B 10 calf suede hides were treated in a dyeing container with 1000 parts of water and 2 parts of ammonia for 4 hours, and 50 parts of 55q0 of water, 2 parts of ammonia and Example 1 Dyeing was carried out in a new bath containing the solution dye of No. 1 obtained in .

For exhaustion of the dye, 4 parts of formic acid (485%) were added gradually and dyeing was continued until the dye was completely fixed. This was washed with water, dried, and finished in the usual manner. This suede skin exhibited a dark brown uniform staining after buffing the suede skin. Application example C: Chromium-tanned lambskin of 10 pieces and 1 piece of dye obtained in Example 1 were added to 55 pieces of 100 pieces in a dyeing container.
The dye was fixed on the leather by treating it for 45 minutes in a solution consisting of o0 water and 1.5 parts of anionic whale brain oil emulsion, and adding 5 parts of formic acid (85%) in portions over 30 seconds to fix the dye on the leather.

After normal drying and finishing treatments, a uniform dark gray-brown dyed leather was obtained. Application Example D Buffing was carried out by spraying, pouring and pouring a solution of 2 parts of the dye obtained in Example 1 in 847 parts of water, 15 parts of ethyl glycol and 3 parts of formic acid (85%). It was applied to the dehaired side of composite tanned cowhide.

This leather was dried and finished under gentle conditions. The leather was dyed grayish brown and had remarkable fastness. By substituting the dye of Example 1 with the same amount of the dye of Examples 2 to 51 and following the procedure of Examples A to O above, leather dyeings with similar properties were obtained.

The hues of these dyeings are indicated in the corresponding production examples. Table 4 below shows the cylindrical coordinates (L, C and Ho) of the transmission colors of exemplary dyes in water-dimethylformamide solutions in the color space according to CIELAB. The transmission was measured spectroscopically in the visible range of light (40 meters to 70 meters) at regular intervals. The length of the passage was 1 enemy. Each coordinate is under the D65 light source, loo visibility standard observer data (FieldSnendard○widerver
Data) was expressed in CIELAB units. The dye solvent was a mixture of 76 parts dimethylformamide, 21 parts water and 3 parts orthophosphoric acid. The concentration of the dye solution was chosen so that the transmission maximum was 25.1%. Furthermore, Table 4 below shows the maximum absorption wavelength of the same dye solutions measured at the same time.

Claims (1)

[Claims] 1 The following general formula I: ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the above formula, R_1 represents a nitro group, R_2 and R
_3 each independently represents -OH or -NH_2, R_4, R_5 and R_6 each represent a hydrogen atom, R_7 represents -SO_3M, or R^7 represents a hydrogen atom, and 1 of R_4 and R_5 one represents a nitro group, the other represents a -SO_3M group, and R
_6 represents a hydrogen atom, R_8 is the following formula IV, ▲ mathematical formula,
There are chemical formulas, tables, etc. ▼ (In the above formula, R^9 is a hydrogen atom or (C_1_~_4)
It represents an alkoxy group, R_1_0 represents a hydrogen atom, a nitro group or -SO_3M, and R_1_1 represents a hydrogen atom or a chlorine atom. However, one or two of R^9, R_1_0 and R_1_1 are hydrogen atoms), and M represents a hydrogen ion or a non-color-forming cation. in the form metallized with copper, chromium, cobalt or iron or in non-metallized form, in order to obtain the compound represented by the above formula I, the following formula III: ▲ mathematical formula, chemical formula, table etc. ▼ [In the above formula, R_4, R_5, R_6 and R_7 represent the same thing as defined above] and the diazo derivative as R^8 in a desired order, Formula II below: ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [In the above formula, R_1, R_2. R_3 and M are the same as defined above]. 2. When producing the compound described in claim 1, 1:1 type or 1:2 type copper, chromium, cobalt, such that at least one of the complex salt-forming compounds is a compound of the formula I above, is used. or in order to obtain a metal complex salt of iron, the metal-supplying compound is combined with the compound of formula I above and, if necessary, with another metallizable azo compound, either simultaneously or in the desired order in the case of different azo compounds. with a metal-supplying compound,
A method comprising reacting. 3. When producing the compound according to claim 1, in order to obtain a 1:1 type copper complex salt of the compound of formula I, a diazo compound of the amine of formula III and R_8
A method comprising coupling a diazo derivative as a compound of formula II with a 1:1 copper complex of the compound of formula II. 4 When producing the compound described in claim 1, in order to obtain a 1:1 type copper complex salt of the compound of formula I, the diazo derivative as R^8 is converted to the following formula VIII: ▲ mathematical formula, chemical formula , tables, etc. ▼ [In the above formula, R_1, R_2, R_3, R_4, R_5
, R_6. R_7 and M are the same as defined above] A method comprising coupling with a 1:1 copper complex of a compound represented by 5. When producing the compound described in claim 1, at least one of the metallizable components has the formula I
In order to obtain iron, chromium or cobalt complexes of the 1:2 type, which correspond to a 1:2 iron, chromium or cobalt complex salt, one of which corresponds to the formula II and the others are the same or different. . 6. When producing the compound described in claim 1, a 1:2 iron, chromium or cobalt complex salt is used, in which at least one of the two complex-forming azo compounds is a compound of formula I. or to obtain a mixture thereof, R_
The diazo derivative as 8 is a 1:2 type of iron such that one of the two complex-forming azo compounds is a compound of the formula VIII and the others are the same or different. A method comprising coupling with a chromium or cobalt complex salt or a mixture thereof.