JPS5965064A - Preparation of 1,4-diamino-2,3-dicyanoanthraquinone - Google Patents

Abstract

PURPOSE:To prepare the titled compound economically in an industrial scale, by reacting 1,4-diamino-2,3-dihalogenoanthraquinone with a sulfonating agent in an aqueous medium in the presence of a quaternary ammonium compound, and reacting the product with a cyanizing agent without separating from the reaction system. CONSTITUTION:1,4-Diamino-2,3-dihalogenoanthraquinone is made to react with a sulfonating agent such as sodium sulfite in an aqueous medium in the presence or absence of an inert organic solvent, in the presence of a quaternary ammonium compound of formula I (R1 and R2 are 1-24C alkyl, etc.; R3 and R4 are 1-10C alkyl; X is anion residue) or formula II (R5 is 1-24C alkyl; R6 is H or methyl) and/or a quaternary phosphonium compound of formula III (R7- R10 are 1-24C alkyl, etc.) to obtain 1,4-diaminoanthraquinone-2,3-disulfonic acid or its salt. Without separating the product from the reaction system, the compound is made to react with a cyanizing agent such as sodium cyanide to obtain the objective compound.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel method for producing 1,4-diamino-2,3-dicyanoanthraquinone, which is an anthraquinone intermediate particularly useful in the dye industry.

1. An industrially advantageous method for producing 1.4-diamino-2,3-dicyanoanthraquinone! , a method of reacting an aqueous solution of 1,4-diaminoanthraquinone-2,3-disulfonic acid with a cyano compound is known (German Patent No. 935669, U.S. Patent No. 3203751, Japanese Patent Publication No. 17648/1983, 1972-77251. etc.).

Mako, the method for producing 1,4-diaminoanotraquinone-2,3-disulfonic acid, which is the raw material for this method, is as follows:
1. After converting 4-noamino-2,3-dihalogenoanthraquinone into a boric acid compound, this compound was diluted with +l in an aqueous medium.
[The method of heating reaction with alkali metal sulfate is public η1< osF 1975886, USP27955
98, Special Publication No. 49-2828).

However, these known methods are limited to 1,4-diamino-
Using 2,3-dihalogenoanthraquinone as a starting material,
It requires three steps: boration, sulfonation, and cyanation, and has the following disadvantages, particularly due to the use of sulfuric acid from many companies in the first step.

(1) When proceeding to the sulfonation step, a large amount of neutralizing agent or ionic agent is required, and a large amount of water or cooling energy is required to remove the heat of neutralization, and the cost thereof is enormous.

(2) Since the sulfonation step is diluted with a large amount of water and contains a large amount of inorganic salts, it is not economically advantageous to directly proceed with the cyanation step.

Therefore, it is necessary to isolate it once using 1,4-diaminoanthraquinone-2°8-disulfonic acid.

At that time, wastewater containing a large amount of inorganic salts is discharged, which is unfavorable from an environmental standpoint.

(3) The boric acid compound of 1,4-diamino-2,3-dihalogenoanthraquinone obtained in the first step 4jN is heated or , extremely unstable to alkalis,
Even during sulfonation, the proportion of hydrolysis returning to the starting material is small, and as a result, the yield of 1,4-diaminoanthraquinone-2,3-disulfonic acid is not always satisfactory.

- It is also known to carry out the oxidation in a hot bath medium. In other words, there is a method (■ as fJ medium), a method using nor, and ■ a method using acetic anhydride (hereinafter referred to as 2L).
SP 197588 (i), a method using nitrobenocene (Japanese Patent Application Laid-Open No. 55-69558) is known.

However, in (1), the order during wastewater treatment is not resolved.
(2) is an example of an explosion of a mixture of acetic anhydride and boric acid.
New, Aug, 2'0°1973, t'42)
It is not industrially useful because it has been reported that In addition, (2) is economically disadvantageous because the reaction is not completed unless boric acid is used in large quantities (6 to 8 molar ratio to the raw material). In addition, in these methods, 1,4-diamino-2゜3-
It is necessary to once isolate diaminoanthraquinone using a boric acid compound, and a complicated process is required to recover the used solvent.

As described above, the method of using an organic solvent for boric oxidation is not satisfactory enough to replace the method of using sulfuric acid, and does not completely solve the problem.

In order to overcome the drawbacks of the present invention, a (ir; Hl-t).

As a result of extensive research into a method for directly converting the halogen atom of 4-diamino-2,3-dihalogenoanthraquinone into a sulfonic acid group, it was surprisingly discovered that the reaction could be carried out using a quaternary ammonium compound and/or a quaternary ammonium compound in an aqueous medium. In the presence of phosphoryl compounds, 1,4-diamino-
2,3-Siba "1-chenoandraquinone reacts directly with a sulfonating agent such as an alkali metal sulfite salt (7).

] 4-cya epsilonanoanotraquinone-28-disulfonic acid is obtained all at once, and without isolation, it can be easily converted to 1,4-diamino-28-disulfonic acid by subsequent reaction with a cyanating agent.
It was discovered that 2,3-dicyanoanthraquinone could be obtained and the present invention was completed.

In addition, the present invention provides a method for preparing a 1,4-diamino-2-3-dihalogenoanthraquinone in an aqueous medium in the presence or absence of an inert rJ solvent as a quaternary ammonium compound and/or a quaternary phosphonium compound. In the presence of the compound, sul d
711 characterized by reacting with a cyanating agent to form 1,4-diaminoanthraquinone-2゜3-disulfonic acid, and reacting this compound with a cyanating agent without isolating it.
．． 4- Shea Shiba No 2.8- Dicyano An!・This is a method for producing laquinone.

Conventionally, 1,4-diamino-2,3-15-10 anthraquinone's β-position nitrogen atom +! Because it is strongly bonded, it is necessary to form a boric acid compound of this substance and activate the gen atom in order to exchange it with the sulfuric acid group. (D.R.T. Patent No. 93566≦)).

Therefore, the skewer that is directly substituted with the sulfonic acid group without going through the boric acid compound has an unexpected force.

Next, the present invention will be explained in detail.

First, the sulfonation reaction will be explained using LN.

1,4-? used in the present invention? raremino-2,3-
Dihalogenoanthraquinone and [no Cl, 1,4-diamino-2,3-dichloroanthraquinone and 1.4
-Diamino-2,3-jib mouth!・Anthraquinones are included.

Examples of the quaternary ammonium compound used in the present invention include quaternary ammonium compounds represented by general formula (I) or (It).

(In the formula, R+, R2 is an alkyl group having 1 to 24 carbon atoms or an optionally substituted benzyl group, 1L
g, R4 is an alkyl group having 1 to 10 carbon atoms, X is an anionic residue, ) L6 (in the formula, R6 is an alkyl group having 1 to 24 carbon atoms,) La is a hydrogen atom or a methyl group, and X is The above meaning remains. ) In addition to chlorine, bromine, and iodine, examples of the anion residue in the general formula include sulfate, phosphate, acetate, methyl sulfate, ethyl sulfate, and hydrogen sulfate residues.

Specific examples of quaternary ammonium compounds include the following compounds.

Tetramethylammonilla! - Chloride, tetraethylammonium chloride, tetra-n-propylammonium chloride, tetra-n-butylammonium chloride, tetramethylammonium!・Methyl sulfur v1 salt, tetraethylammonium ethyl sulfate, triethylpropylammonium chloride, octyltrimethylammonium chloride, dodecyltrimethylammonium chloride, hexadecyltrimethylammonium chloride, octadecyltrimethylammonium chloride, tetracosyltrimethylammonium chloride, dioctatecyl Tetraalkyl quaternary ammonium compounds such as dimethylammonium chloride, diheptadecyldimethylammonium chloride, trioctylmethylammonium cum chloride, benzyltrimethylammonium chloride, benzyltriethylammonium chloride, benzyltripropylammonium chloride, benzylethyldipropyl ammonium chloride, dodecyldimethylbenzylammonium chloride, o, m or P-methoxybenzyltriethylammonium chloride, o, m, p-').

Benzyltrialkylammonium compounds and dibenzyldialkyl ammonium compounds such as robennrutriethylammonium chloride, ocdylbenzyldimethylammonium chloride, diethyldibenzylammonium chloride.

N-methylpyridinium chloride, N-ethylpyridinium chloride, N-butylpyridinium chloride, N-
Dotesylpyridinium chloride, N-octadecylpyridinium chloride, N-methylvicolinium chloride,
N-furkylpyridinium compounds such as N-butylpicolinium chloride and N-dodecylpicolinium chloride, and N-alkylpicolinium soups.

and corresponding promide iodides, sulfates, phosphates, hydrogen sulfates, acetates, methyl sulfates, ethyl sulfates, or mixtures thereof. Benzyltrialkylammonium compounds such as chloride are preferably used.

The amount of the quaternary ammonium compound used varies depending on the quaternary ammonium compound used, but in general, the ratio of the quaternary ammonium compound to the total of the quaternary ammonium compound and the aqueous medium is 2-90%. ,
80-9 for tetraalkylammonium compounds
0% by weight, preferably 40-80% by weight, in the case of benzyltrialkylammonium compounds 10-85% by weight, preferably 15-80% by weight of N-alkylpyridinium compounds or N-alkylbicoliniuno compounds. In the case of 2-60 double-jaw blades, preferably 5-50 double-jaw blades.

For example, in the case of benzyltriethylammonium chloride, the amount is 20 to 75% by weight, preferably 30 to 70% by weight. If the quaternary ammonium compound has stronger nbphilicity than this, the amount used may be even smaller;
If it is weak, it is preferable to use more than coil.

Examples of the quaternary phosphonium compounds used in the present invention include quaternary phosphonium compounds represented by the general formula @).

(In the formula, IL7. LLs , , Rs , 10 is an alkyl group having 1 to 24 carbon atoms, or 1 is a phenolic group) [7, and R7 may be a benzyl group, X represents an anionic residue, etc. In the general formula, anionic residues include chlorine, kenase, iodine pond, sulfate, phosphate, acetate, Vt (vti f
< The residue of liJ is raised.

Specific examples of quaternary phosphonilam compounds include tetramethylphosphonium chloride, 1traethylphosponium chloride, tetrabutylphosphonyl phosphonium chloride, octyltriethylphosphonium chloride, hexadecyltriedylphosphonium chloride, hexadecyl Tetrialkylbosphonium chloride compounds such as tributylphosphonium chloride, dodecyltrimethylposponium 20lide, 1-hethyleneethylphosphonium chloride, and tetrimethylphosphonium chloride.

Benzyl 1-realkylphosphonium compounds such as benzyltriethylphosphonium chloride and pencyltributylphosphonium chloride; methyltriphenylphosphonium compounds;
Alkyl triphenyl phosphonium compounds such as ram chloride and ethyl trinocol phosphonium chloride, tetraphenyl phosphonium chloride, and corresponding bromides, iodides, sulfates and phosphates of these chlorides,
The amount of the acetate or hydrogen sulfate quaternary phosphonium compound to be used varies depending on the quaternary phosphonium compound used, but in general, the amount of the quaternary phosphonium compound to the total of the quaternary phosphonium compound and the aqueous medium is 2-
80 weight 1i 96', and in the case of a tetraalkylphosphonium compound, 2O-8 (1 drop%, preferably 2
5-75% by weight, in the case of benzyltrialkylphosphonium compounds 5-75% by weight, preferably 10-7
0 wt 1%, in the case of alkyltriphenylphosphonium compounds 2-6 (l r++it”, preferably 5
-50 city H1% Z).

For example, triphenylphosphonium 1j′;
, for [11550 wt., preferably 15-
The amount of sleep is 45%. If the lipophilicity of the 4th phosphor compound is stronger than this, the amount added should be smaller than this.
For example, in the case of tetra-raphenylphosphonium chloride, it is 2-40'? It is preferable to use more than 1 if the Km% is too heavy and the loading capacity is weak.

A quaternary phosphonium compound and a quaternary ammonium compound can also be used together.

4th absorption ammonium compound
The amount of the aqueous medium containing the class phosphonium compound "1" is t, 4.-diamino-2,8-cyhalogenoanthraginone, 2dL)4'j41.IN per iQ.

If the amount of aqueous medium is relatively small, η11 is preferred, adding an inert organic solvent to the system.

The inert organic solvent used in that case is preferably one that is immiscible with water;
, 2-dichlorobenzene, ■, 2゜4-trichlorobenzene, i, 3.5・-1・dichlorobenzene, l
, halogenated aromatic carbons such as 8.5-1" phosphorus, nitrobenzene, etc.,
The amount used is usually 2-20% per 1°4-diamino-2,3-dihalogenoanthraquinone! The quantity is double.

In the present invention, the quaternary ammonium compound is
When using a relatively poorly water-soluble class phosphonium compound, it is also possible to add a water-soluble organic solvent. Examples of these solvents include ethylene glycol, ethylene glycol monoalkyl ether, diethylene glycol monoalkyl ether, triethylene glycol, triethylene glycol monoalkyl ether, formamide, methylpormamide, dimethylformamide, N-alkylpyrrolidone, dimethyl sulfoxide, and sulfur. Shiran, hexamethyl phosphoric triamide,
methanol, ethanol, propatool, phthanol,
Mention may be made of pyridine, picoline, or mixtures thereof.

In the present invention, alkali metal sulfites such as sodium sulfite and potassium sulfite are used as the sulfonating agent. Alternatively, an alkali metal bisulfite such as sodium bisulfite or potassium bisulfite, or an ammonium salt of sulfite or hydrogen sulfite may be used. These uses, lt range from 2.0 to 1,4-diamino-2,3-dihalogenoanotraquinone. 5.0 molar ratio, preferably t
i < is a 2.2-4.0 molar ratio.

In the present invention, the pH of the reaction system for the sulfonation reaction can be varied within a fairly wide range. That is, the sulfonation reaction can be carried out in a pH range of 4-11.

If the pH is lower than this, sulfur dioxide gas will dissipate out of the system,
Sulfonation tends to be difficult to occur effectively. Also high IL
In the case of H region, l-amino-4-
This is not preferred because oxyanthraquinone-2,8-disulfonic acid is produced as a by-product.

The pH value of the reaction mixture may be controlled, if necessary, for example by adding a suitable buffer to the system. Examples of the H buffer include sodium carbonate, sodium phosphate,
Examples include sodium hydrogen carbonate, dipotassium phosphate, sodium dihydrogen phosphate, and potassium dihydrogen phosphate. Further, the reaction may be controlled by appropriately supplying a suitable alkali such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium acetate, etc. as it is or as an aqueous solution during the reaction.

The reaction usually proceeds at temperatures above 50'C, but at temperatures as low as 70'C-1
It is appropriate to carry out the reaction at 20°C. The reaction is usually j-4
Ends at 0:11U! do.

During the reaction, catalytic amounts of boric acid compounds such as orthoboric acid, metaboric acid, boric anhydride, sodium borate, J-fluoride or potassium borate may also be added. The appropriate amount of these is 1 molar ratio or less relative to the starting material.

Also, during the reaction, a catalytic amount of a copper compound, such as copper sulfate,
Cuprous chloride, cupric chloride, copper oxide, basic copper carbonate, copper acetate, etc. may also be added. The appropriate amount of these is 0.5 mol F based on the starting material.

After carrying out the sulfonation reaction in this way, the produced 1
, without isolating 4-diaminoanthraquinone-2°8-disulfonic acid, if necessary after clarifying filtration,
Continuing with Examples of Cyanation Next, the cyanation reaction will be explained.

The cyanation reaction is carried out by a method known per se, for example, as disclosed in JP-A-56
It can be carried out according to the method described in Japanese Patent No. 77251.

The amount of quaternary ammonium compound or quaternary phosphonium compound that should be present in the reaction system varies depending on the type of quaternary compound used, but generally the amount of quaternary compound relative to the total of quaternary compound and water is The proportion is 2-90% by weight, in the case of tetraalkylammonium compounds 10-90% by weight, preferably 15-80% by weight, and in the case of trialkylbenzylammonium compounds 2-90% by weight.
80% by weight, preferably 2.5-70% by weight, 2-50% by weight in the case of N-anoL-kylpyridinium compounds, preferably 5-40% by weight in the case of tetraalkylposponium compounds. is 10 to 70% by weight, preferably 15
~65% by weight, 2-70% by weight in the case of benzyltrialkylphosphoniuno compounds, preferably i, t2.5
601 m%, and in the case of alkyltriphenylphosphonium compounds, it is 1-50% by weight, preferably 2-40% by weight. For example, in the case of pencil triethylammonium chloride, 2-70%, preferably 2.5-
This is 60% of the vehicle volume. Therefore, if necessary, water is added to the reaction mixture after completion of sulfonation to adjust the concentration of the quaternary compound.

In the present invention, cyanating agents include, for example, cyanides of alkali metals, alkaline earth metals, and ammonia, specifically sodium cyanide, potassium cyanide,
Ammonium cyanide, magnesium cyanide, calcium cyanide or mixtures thereof are used. Among these, sodium cyanide and potassium cyanide are particularly preferably used. Cyanohydrins that produce cyanide ions in 1:1 of water, such as acetone cyanohydrin, can also be used.

The amount used is 2.0-10 molar ratio to 1,4-diamino-2,3-dihalogenoanthraquinone.

The cyanation reaction is preferably performed with p) i8 to 11, more preferably p) i8.5 to 10.50. ＞Perform within the range.

In the case of a lower pH range than this (this is outside the system -\ cyanide (L hydrogen liberation is seen, shea,] cyanogen O))
t-11 tends to be a loss. Also, high pH range Q)
In this case, it promotes the fourth-order hydrolysis of the intermediate and the main product IjQ product Q) during the reaction, so the desired Fl−L, <NaL)
.

The pEl value of the reaction mixture is determined by sufficient jltO
>Can be easily controlled by adding conventional buffers.

As a buffering agent, a compound such as sulfur (IZ anti-150) (IJJI l) is used as an example.

Also, during the reaction with cyanide, add a drop of a suitable acid or weak acid such as hydrochloric acid, sulfuric acid, phosphoric acid, acetic acid, propionic acid, etc. May be controlled.

It may be advantageous if a dehydrogenating agent is added. As dehydrogenating agents, organic nitro compounds such as nitrobenzene, nitrobenzene sulfonic acid, nitrophenol, organic or inorganic peracids such as peracetic acid, persulfuric acid,
Sodium, potassium, or ammonium salts such as perboric acid or perphosphoric acid, or -f-O are used. Furthermore, it is also possible to use a diaphragm. At this time, it is usually preferable to add ammonium molybutate or ammonium vanadate. In the present invention, the reaction temperature for cyanation is 40~] 00
"C1 is preferably 50 to 90'C.The reaction is fast on the product temperature side, but in order to prevent higher-order hydrolysis, pIi
It is preferable to set it as low as possible, and conversely, on the low temperature side, it is preferable to use the first stone as long as it does not exceed pJJ, 11 [7].

The reaction was completed in 220 hours/R. After the reaction is completed, the excess cyanating agent is removed with sodium hypoalite or hydrogen peroxide, and then filtered to obtain 1,4-diamino-2.
, 8-dicyano-anthraquinone is obtained.

The quaternary ammonium compound or quaternary phosphonium compound used in the present invention can be converted into a quaternary ammonium compound by using an alkali from the P solution.
is recovered as it is as a quaternary nium compound, or as quaternary ammonium hydroxide or quaternary phosphoniurium hydroxide using several solvents, and then back-extracted with acidic water. Can be reused.

According to the method of the present invention, 1,4-diaminoanthraquinone-2,3-disulponic acid is converted into a highly concentrated solution and (
7, it can be subsequently subjected to a cyanation reaction to yield 1,4-diamino-2,3-dicyanoanthraquinone without isolating it. The quaternary ammonium compound L) used in the sulfonation reaction is a quaternary ammonium compound.
The class phosphonium compound has the effect of increasing the yield and improving the purity of the target product during cyanation, and the yield and purity of the obtained 1,4-diamino-2,3-dicyanoanthraquinone. is 111%. Also, there is no problem during sulfuric acid treatment and wastewater treatment. Therefore, it is economically advantageous, and the commercial value of the present invention is high.

The present invention will now be described in detail by way of examples.

In the text, parts indicate weight products, and % indicates weight % v0 Example 1 1.4-Shealow 2.8-
Dichloroanotraquinone 5. Add part C) and 7.18 parts of anhydrous thorium sulfite, and add 28 parts of anhydrous thorium sulfite while stirring thoroughly.
The pH was adjusted to 9.2 using a % sulfur hydroxide aqueous solution. The mixture was then heated to 90-95”C (7,
The reaction was allowed to proceed until almost all of the starting material in the chromatography disappeared. During this time, the pH of system 113 (7) was adjusted to 9.0-9.2 using a 28% aqueous sodium hydroxide solution.
maintained.

Then 0.5 part of diatomaceous earth was added to the reaction mixture and the mixture was heated at 70°
The cake was washed with 28 parts of warm water and combined with Solution P.

After cooling the P washing solution to 25°C, sodium cyanide 3.2
The reaction mixture was heated to 60-65 pH while maintaining the pH in the system at 9.4-9.8 using 43% phosphoric acid aqueous solution.
The mixture was heated to 0.degree. C. and reacted until 1,4-diaminoanthraquinone-2,3-disulfonic acid disappeared by chromatography.

Next, excess sulfurium cyanide was decomposed with 35% hydrogen peroxide solution and filtered, and the cake was thoroughly washed with warm water and dried to obtain 1,4-diamino-2,3-dicyanoanthra. I got 4.2 copies of non-container.

This product was a single component when analyzed by chromatography, and the elemental analysis values were as follows. -2,3
- 5.0 parts of dichloroanthraquinone (': 50 parts of monochlorobenzene't ft ), and after charging 8.0 parts of anhydrous potassium sulfite with thorough stirring, the mixture was heated to 90-95°C and purified by chromatography. The reaction was allowed to proceed until most of the starting material disappeared.

During this time, the pH of the reaction system was 9.5 to 8.5.

Then, monochlorobenzene was distilled off from the reaction mixture by steam distillation, 0.5 part of diatomaceous earth was added, and the mixture was clarified and filtered at 70°C.

After cooling the furnace liquid to 25°C, 4.2 parts of potassium cyanide and 0.2 parts of sodium rn-nitrobenzenesulfonate A were added.
of the system and adjust the pH of the system to 9.0 using an 80% aqueous sulfuric acid solution.
The reaction mixture was heated to 65-70 °C while maintaining the temperature between 8 and 9.6 °C.
The reaction mixture was heated to 100 ml and reacted until 1,4-diaminoanthraquinone-2,3-disulfonic acid disappeared by chromatography.

Next, excess potassium cyanide was decomposed with a 12% sodium hypochlorite solution and filtered, and the cake was thoroughly washed with warm water and dried to obtain 4.2 parts of 1,4-diamino-2,8-dicyanoanthraquinone. I got it.

Similar results were obtained when benzyltrimethylammonium chloride was replaced with the corresponding bromide.

Example 3 1,4-diamino-2,3 was added to a mixture of 59.5 parts of dodecyltrimethylammonium chloride and 48.7 parts of water.
- Charge 6.45 parts of dibromoanthraquinone, and charge 5.7 parts of anhydrous bent sodium sulfate while stirring thoroughly;
Next, adjust the pH to 9.6 using 28% sodium hydroxide at 0°C. The mixture was heated to 80-85[deg.]C and reacted until almost all of the starting material disappeared by chromatography. During this time, the pf of the system was maintained at 9.2 to 9.6 using a 28% aqueous sodium hydroxide solution.

After cooling the reaction mixture to 25°C, 2.5 parts of sodium cyanide and 0.1 part of nitrobenzene were added to give a 50%
Using acetic acid aqueous solution, thread Q) p J'L is 9.5 to 9.8.
The reaction mixture was heated to 60-65 DEG C. and allowed to react until 1) 1,4-diaminoanthraquinone-2,3-disulfonic acid disappeared by chromatography.

Next, the same treatment as in Example 1 was carried out to obtain (■).

4-Diamino-2,8-dicyanoanthraquinone 4.1
I got the department.

Similar results were obtained when dodecyltrimethylammonium chloride was replaced with the corresponding bromide.

Example 4 Mixture number of 78.7 parts of tetra-tl-butylammonium bromide and 428 parts of water and 1°4-diamino-2
, 5.0 parts of 3-dichloroanthraquinone were charged and thoroughly stirred; 7.18 parts of anhydrous sodium sulfite and 0.9 parts of sodium phosphate were added, and the reaction mixture was heated to 90-95'C. ), and the reaction was allowed to proceed until almost all the starting material disappeared by chromatography.

After cooling the reaction mixture to 25°C, potassium cyanide 8.
The pH in the system was maintained at 9.4 to 9.8 degrees using an 80% aqueous sulfuric acid solution, the reaction mixture was heated to 60-65°C, and 1 part was determined by chromatography. .4-cyaminoanthraquinone-2,3-disulfone tolerance; The reaction was allowed to occur until it disappeared. Then, the same treatment as in Example 1 was carried out to add 4.0 parts of 1,4-diamino-2,3-dicyanoanthraquinone to f%f.

Example 5 1,4-diamino-2 was added to a mixture of 14 parts of N-butylpyridinium chloride, 82.6 parts of water, and 14 parts of pyridine.
After charging 5.0 parts of ,3-dichloroanthraquinone and 6.4 parts of anhydrous potassium sulfite with sufficient stirring, the reaction mixture a was heated to 95-100°C, and the starting material was determined by chromatography. The reaction was allowed to take place until it almost disappeared. During this time, the pH of the system showed g 9.5.

The reaction mixture was then cooled to 25°C, 3.2 parts of sodium cyanide was added, and the pI of the reaction system was maintained at 9.4 to 9.8 using a phosphoric acid water bath solution. 2711! to 60-65°C and chromatography to obtain 1,4-diaminoanthraquinone-2,3-
The reaction was allowed to proceed until the disulfonic acid disappeared. Thereafter, the same post-treatment as in Example 1 was carried out to obtain 1,4-diamino-2,3-
4.0 m of dicyanoanthraquinone was obtained.

Example 6 1°4-diamino-2,
5.0 parts of 3-dichloro
After charging the mixture, the mixture was heated to 90-95°C and reacted until most of the starting material disappeared by chromatography. During this time, the pfL of the system was 7.58.
．． I accept 5.

Next, 1,2-dichlorobenzene was distilled off from the mixture by steam distillation, and the distilled water was separated and used as a reaction solution. Subsequently, 0.5 part of diatomaceous earth was added to the reaction solution and filtered at 70''C, and the cake was washed with 16.3 parts of warm water and mixed with Okisin.

After cooling the P washing solution to 25°C, sodium cyanide 3.2
1 part and 0.1 part of nitrobenzene were heated to 60-65° C. while maintaining the I) K in the system at 9.49.8 using a 50% aqueous sulfuric acid solution, and the reaction mixture was heated to 60-65° C. and chromatographically determined.

The reaction was continued until 4-diaminoanthraquinone-2,3-disulfonic acid disappeared.

Subsequently, the same post-treatment as in Example 1 was carried out to obtain 4.2 parts of 1°4-diamino-2,3-dicyanoanthraquinone.

Example 5.0 parts of 1,4-diamino-2,3-dichloroanthraquinone was added to a mixture of 20 parts of methyl 1-riphenylphosponium bromide and 30 parts of water, and 8.0 parts of anhydrous potassium sulfite was added with thorough stirring. () and then 28%
The PI was adjusted to 9.2 using an aqueous potassium hydroxide solution. The mixture was heated to 100-105°C with thorough stirring and allowed to react until the starting material had almost completely disappeared by chromatography. During this time, I) H in the system was maintained at 9.0-9.2 using a 28% potassium hydroxide water bath.

After completion of the sulfonation reaction, a cyanation reaction was carried out in the same manner as in Example 1 to obtain 1.4-diamino-2,3-dicyanoanthraquinone 4. ] Get the part.

Example 8 To a mixture of 50 parts of hexatecyltriethylphosphonium chloride and 50 parts of water, 6.45 parts of 1,4-diamino-2,3-dibromo-Tonthraquinone was charged, and while stirring thoroughly, 5.0 parts of anhydrous sodium sulfite was added. 7 parts, and then reduce p It to 9 using 28% aqueous sodium hydroxide solution.
．． Adjusted to 4. While stirring thoroughly, heat the mixture to 85-9
The mixture was heated to 0°C and reacted until almost all the starting material disappeared by chromatography. During this period, the p It of the system was 9.4 to 8.3.

After the sulfonation reaction was completed, a cyanation reaction similar to that in Example 2 was carried out to obtain 4.1 parts of 1,4-diamino-2,3-dicyanoanthraquinone.

Example 9 In a mixture of 15 parts of tetrabutylphosphonium bromide and 15 parts of water, 5.0 parts of 1,4-diamino-2°3-dichloroanthraquinone and 5 parts of 1,2°4-trichlorobenzene were added.
After charging 8.0 parts of anhydrous potassium sulfite with thorough stirring, the mixture was heated to 110-115°C and reacted until almost all the starting material disappeared by chromatography.

Next, trichlorobenzene was distilled off by steam distillation, and then filtered at 80°C to remove insoluble matter, and then Example 1
A cyanation reaction was carried out in the same manner as 1,4-diamino-2
, 4.0 parts of 3-dicyanoanthraquinone were obtained.

Example 1O 5.0 parts of 1,4-diamino-2,3-dichloroanthraquinone was added to a mixture of 25 parts of benzyltriethylphosphonium bromide and 25 parts of water, and 7.18 parts of anhydrous sodium sulfite was added with sufficient stirring. After charging, the mixture was heated to 90-95'C and reacted until most of the starting material disappeared by chromatography.

During this period, the p1■ of the system was 9.5 to 8.5.

After the sulfonation reaction was completed, a cyanation reaction was carried out in the same manner as in Example 1 to obtain 4.2 parts of 1,4-diamino-2,3-dicyanoanthraquinone.

Example ti 5 parts of 1,4-diamino-2,3-dichloroanthraquinone in a mixture of 10 parts of phenylphosphonium chloride, 40 parts of water and 72110 parts of N,N-dimethylform
．． After charging 6.5 parts of anhydrous potassium sulfite with thorough stirring, the mixture was heated to 100-10
The mixture was heated to 5°C and allowed to incubate until almost all the starting material disappeared by chromatography.

After the sulfonation reaction was completed, a cyanation reaction was carried out in the same manner as in Example 2 to obtain 1,4-diamino-2,8-dicyanoane!・I received 4.0 copies of Laquinone.

Examples 12 to 15 In Example 1, various quaternary ammonium compounds shown in Table 1 were used in place of benzyltriethylammonium chloride, and the other conditions were the same as in Example 1. When the reaction was carried out, similar results were obtained. Obtained.

Table 1 Examples 16-18 In Example 2, benzyltrimethylammonium 20
The reaction was carried out using various quaternary ammonium compounds shown in Table 2 instead of lido, and other conditions were the same as in Example 2, and the same results were obtained.

2nd Example 19-21 In Example 5, the reaction was carried out using various quaternary ammonium compounds shown in Table 3 instead of N-butylpyridinium chloride, and the other conditions were the same as in Example 5. I got a similar result.

Table 3 Example 22 Penzyltriethylammoniuno^chloride 27,6
1,4-diamino-2,8 in a mixture of m, 5 parts of methyltriphenylphosphonium prod, and 32 parts and 6 parts of water.
- 5.0 parts of dichloroanthraquinone, 0.3 parts of boric acid,
0.2 parts of anhydrous cupric chloride and 2 parts of monochlorobenzene
After charging 7.18 parts of anhydrous sodium sulfite with thorough stirring, the mixture was heated to 90-95°C and reacted until almost all the starting material disappeared by chromatography.

After monochlorobenzene was then removed from the reaction mixture by steam distillation, a cyanation reaction was carried out in the same manner as in Example 1 to obtain 4.1 parts of 1,4-diamino-2,3-dicyanoanthraquinone.

Example 2B ■ to a mixture of 55.6 parts of penzyltriethylammonium chloride and 55.6 parts of water.

4-diamino-2,3-dichloroanthraquinone 5.0
After adding 5.9 parts of sodium hydrogen sulfite and 0.3 parts of boric acid with sufficient stirring, the mixture was heated to 90%
Heating to 95°C and chromatographically removing the starting material t
The reaction was allowed to proceed until most of '1 disappeared.

Next, a cyanation reaction was carried out in the same manner as in the example, and 1,4-
8.8 parts of diamino-2,3-dicyanoanthraquinone were obtained.

Supplementary Procedures (Spontaneous) Special 1 Go 1 Commissioner's Office Mr. Kazuo Wakasugi 1 Indication of Matter f' 1 1982 Patent Application No. 175568 Bow 2, Name of Invention 1,4-Diamino-2,3-dicyanoanthraquinone Manufacturing method 3 Supplement 1 [Relationship with the case of the person who performs 2 Patent applicant address 5-15 Kitahama, Higashi-ku, Osaka Name (20
9) Hijikata, Representative of Sumitomo Chemical Industries, Ltd.
Take 4 Agent Address: 5-15-5 Kitahama, Higashi-ku, Osaka City, Column 6 of the detailed description of the invention in the specification subject to amendment, Contents of the amendment (1) Lines 9-10 of Ward 2 of the specification: “ The production method is 1,4-diamino......" instead of "The production method is 1,4-diamino-2,8
-Dihalogenoanthraquinone is heat-treated with boric acid in sulfuric acid to produce 1,4-diamino...'' is corrected.

(2) From the bottom of No. 3 of the same, in the second line, the word "less than" is corrected to "not less."

(8) The phrase "residue of hydrogen sulfate" on page 8, lines 4-5 is corrected as follows.

"Residues of hydrogen sulfates, hydrogen phosphates, dihydrogen phosphates, carbonates, bicarbonates, sulfites, bisulfites, cyanates, cyanates, thiocyanates, nitrates, and hydroxyl groups" ( 4) In line e of the same No. toH, replace “sulfate” with “
, hydroxides, sulfates,” amended +F.

(5) "Ethyl sulfate, or" on page 9, line 7 of the same @
Correct the statement as follows.

[Ethyl (i11CIII2 salt, hydrogen phosphate, dihydrogen phosphate, carbonate, bicarbonate, sulfuric acid, bisulfite, cyanide, cyanate, thiocyanate, nitrate, or'' (6) On page 12, 4h, the phrase "residue of hydrogen sulfate" is corrected as follows.

[Residues of hydrogen sulfates, hydrogen phosphates, dihydrogen phosphates, carbonates, bicarbonates, dihydrogen sulfates, bisulfites, cyanates, cyanates, thiocyanates, nitrates, and hydroxyl groups.” (7) Same $13 page! In line 184, "sulfate" should be corrected to "hydroxide, sulfate".

(8) On page 13, lines 4-5, the phrase "hydrogen sulfate or" is corrected as follows.

"Hydrogen sulfate, hydrogen phosphate, dihydrogen phosphate, carbonate, hydrogen carbonate, sulfite, hydrogen sulfite, cyanide,
Anate, thiocyanate, nitrate, or " Procedural amendment (spontaneous) 1982 b) Knee 3 ft) Day 1, Case indication 1982 Patent application No. 175568 2, Title of the invention 1.4- Process for producing diamino-2,3-dicyanoanthraquinone 3゜Relationship with the case of the person making the amendment Patent applicant 5, Detailed description of the invention column 6 of the specification subject to amendment, Contents of the amendment (1) Description No. On page 5, line 13, the phrase ``phonic acid all at once'' is corrected to ``phonic acid or its salts all at once.''

(2) On page 6, line 4, the words "3-disulfonic acid and none" should be corrected to "8-disulfonic acid or its salts and none."

(8) On page 18, line 4, the phrase "3-disulfonic acid" is corrected to "8-disulfonic acid or a salt thereof."

(4) On page 22, line 15 of the same page, it says “phonic acid”.
[For fonic acid, 〈 is corrected to mean its salt or −1.

Claims (1)

[Claims] (Jljl, 4-diamino-2,3-dihalogenoanthraquinone in an aqueous medium, in the presence or absence of an inert organic solvent, in the presence of a quaternary ammonium compound and/or a quaternary phosphonium compound) 1 characterized in that the compound is reacted with a sulfonating agent to form 1,4-diaminoanthraquinone-2,3-disulfonic acid or a salt thereof, and then reacted with a cyanating agent without isolating this compound.
, 4-diamino-2゜3-dicyanoanthraquinone'
R1M 75 method.