JP3034185B2 - Method for producing dianthraquinone-N, N'-dihydroazine - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION The present invention relates to 1-aminoanthraquinone and its condensate, dianthraquinone-N, N '.
-To a process for producing dihydroazine. Dianthraquinone-N, N'-dihydroazine has long been known as a vat dye having excellent lightfastness, and a high-purity dye capable of dyeing cotton or the like into a reddish clear blue. It is. It is also an important compound as a pigment, and furthermore, 3,3'-dichlorodianthraquinone-
It is also an important compound as an intermediate for the production of N, N'-dihydroazine.

[0002]

2. Description of the Related Art Various methods have been disclosed as methods for producing dianthraquinone-N, N'-dihydroazine. A method of condensing 2-aminoanthraquinone with an alkaline condensing agent in the presence of an oxidizing agent without using an organic solvent, as described in PB reports BIOS 987 and FIAT1313, has long been known.

[0003] Also, 1-aminoanthraquinone (hereinafter, referred to as 1-aminoanthraquinone)
Abbreviated as "1-AAQ". Is also known to be dissolved or suspended in an organic solvent.
Organic phosphates such as hexamethyl phosphorotriamide described in JP-A-51-17222,
Alternatively, a method of producing the compound using an alkaline condensing agent in an organic nitrogen oxide such as pyridine-N-oxide, or in the presence of an organic sulfone or sulfoxide compound described in Japanese Patent Publication No. 40-1280. There is a method of producing using a condensing agent. However, in these methods, the yield of dianthraquinone-N, N'-dihydroazine obtained is extremely low, and it is difficult to say that the method is industrially advantageous.

[0004] As a method of solving these problems,
1,3-dimethyl-2-imidazolidinone (hereinafter referred to as “D
MI ”. ) In the presence of 1-AAQ with an alkaline condensing agent to produce the desired product in high yield and high quality (see JP-A-60-1169 and JP-A-60-1169). 62-25167).

[0005] However, even in these methods,
The resulting dianthraquinone-N, N'-dihydroazine contains several unidentified impurities, and these impurities tend to darken the color of the dyed product.
In order to remove these impurities, purification such as hydrosulfite treatment was required.

[0006]

SUMMARY OF THE INVENTION An object of the present invention is to provide an industrially advantageous method for obtaining high-yield and high-quality dianthraquinone-N, N'-dihydroazine containing very few of these impurities. To provide.

[0007]

Means for Solving the Problems The present inventors have made intensive studies to achieve the above object, and as a result, have reached the present invention. That is, the present invention relates to a mixed solvent in which the weight ratio between the aprotic polar solvent and water is 80:20 to 99: 1.
This is a method for producing dianthraquinone-N, N'-dihydroazine by suspending AAQ and reacting by adding an alkaline condensing agent thereto.

In the method of the present invention, the weight ratio of the aprotic polar solvent to water is from 80:20 to 99: 1. When the ratio of the aprotic polar solvent to water is out of the above range, the amount of by-products of impurities that cause dark color increases, and the quality of the product decreases, and the yield also decreases.

In the method of the present invention, first, 1-AAQ as a raw material is recrystallized in a mixed solvent of an aprotic polar solvent and water, and the weight ratio of the aprotic polar solvent to water is within the above range. , It becomes a regular crystal. The weight ratio of aprotic polar solvent to water is preferably 85:15 to 98.5: 1.5, more preferably 92: 8 to 98: 2, optimally 94: 6 to 96: 4, In this case, the most stable needle-like crystals are formed. If the weight ratio of the aprotic polar solvent to water is out of the range of 80:20 to 99: 1, the number of amorphous crystals increases, and as a result, it is considered that the yield and the like are adversely affected.

The aprotic polar solvent used in the method of the present invention includes DMI or 1,3,6-trimethylhexahydro-1,3,6-triazocin-2-one (hereinafter referred to as "TMA"). Is abbreviated). The amount of the aprotic polar solvent used is usually 0.1 to 10.0 parts by weight, preferably 0.2 to 5.0 parts by weight, more preferably 1.0 to 1 part by weight of 1-AAQ of the raw material. ~ 3.
0 parts by weight.

If the amount of the aprotic polar solvent is extremely small, the viscosity during the condensation reaction tends to increase, and the quality of dianthraquinone-N, N'-dihydroazine tends to decrease.

In the present invention, by adding a phase transfer catalyst to the solution in which the 1-AAQ is suspended, the reaction can proceed more gently. The phase transfer catalyst is not particularly limited as long as it is a compound having a function of easily reacting a substance in one phase with a substance in the other phase in a heterogeneous reaction composed of two or more phases. But, among others, quaternary ammonium salts, ethylene glycol compounds, organic phosphorus compounds, crown ether compounds,
A calixarene compound or a phosphonium salt compound is preferred. These can be used alone or as a mixture of two or more compounds.

Among the phase transfer catalysts used, the quaternary ammonium salt is a compound represented by the following general formula (1).

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In the formula, R ¹ , R ² , R ³ and R ⁴ are the same or independently and represent an unsubstituted or substituted alkyl group and an unsubstituted or substituted aryl group. Examples of unsubstituted or substituted alkyl groups include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl , Chloromethyl, hydroxyethyl, methoxypropyl, aminomethyl, methylcarbonylmethyl, benzyl, phenethyl group and the like, and as the unsubstituted or substituted aryl group, phenyl, methoxyphenyl, ethoxyphenyl, tolyl, chlorophenyl, fluorophenyl, Examples include a hydroxyphenyl, aminophenyl, nitrophenyl group and the like. Examples of the counter ion X ⁻ include fluorine ion, chlorine ion, bromine ion, iodine ion, hydrogen sulfate ion, sulfate ion, phosphate ion, hydrogen phosphate ion, cyanide ion, periodate ion, acetate ion, and toluene sulfone. Acid ion,
Examples thereof include trifluoromethanesulfonic acid ion and hydroxyl ion.

Among the phase transfer catalysts used, the ethylene glycol-based compound is a compound represented by the following general formula (2).

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In the formula, R ⁵ and R ⁶ are the same or independently a hydrogen atom or an alkyl group, and m represents an integer of 2 to 5.

The alkyl group in the general formula (2) includes methyl, ethyl, propyl, butyl, hexyl, dodecyl and the like. Particularly preferred examples of the ethylene glycol-based compound include diethylene glycol monomethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoethyl ether, diethylene glycol diethyl ether, diethylene glycol monobutyl ether, and pentaethylene glycol monomethyl ether.

Among the phase transfer catalysts used, the organic phosphorus compound is a phosphine, phosphine oxide or phosphine sulfide compound represented by the following general formula (3), (4) or (5).

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In the formula, R ⁷ , R ⁸ and R ^{9 each} independently or independently represent an unsubstituted or substituted alkyl group, an unsubstituted or substituted alkoxy group, an unsubstituted or substituted aryl group.

In the formulas (3), (4) and (5), examples of the unsubstituted or substituted alkyl group include methyl, ethyl and
Propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl,
Heptadecyl, octadecyl, nonadecyl, icosyl,
Chloromethyl, hydroxyethyl, methoxypropyl,
Examples include aminomethyl, methylcarbonylmethyl, benzyl, and phenethyl groups, and examples of unsubstituted or substituted alkoxy groups include methoxy, ethoxy, propoxy, butoxy, pentoxy, chloromethoxy, hydroxyethoxy, methoxybutoxy, and aminopropoxy groups. And an unsubstituted or substituted aryl group includes phenyl,
Examples include methoxyphenyl, ethoxyphenyl, tolyl, chlorophenyl, fluorophenyl, hydroxyphenyl, aminophenyl, and nitrophenyl groups.

Among the phase transfer catalysts used, the crown ether compound may be a crown ether compound in which part or all of the ethylene portion is replaced by phenylene.
The ethylene or phenylene moiety may be substituted, and examples of the substituent in the case of substitution include alkyl groups such as methyl, ethyl and propyl groups, alkoxy groups such as methoxy and ethoxy groups, hydroxy groups, and methyl groups. Alkylcarbonyl groups such as carbonyl and ethylcarbonyl groups, alkoxycarbonyl groups such as hydroxycarbonyl group, methoxycarbonyl and ethoxycarbonyl groups, alkylamino groups such as amino group, methylamino and ethylamino group, nitro group, fluorine, chlorine and bromine And iodine and the like. Further, a part of or all of the oxygen atoms may be replaced with nitrogen, sulfur or phosphorus atoms. As crown ether compounds, 12-
Crown-4, 15-crown-5, 18-crown-
Those having a skeleton such as 6, 21-crown-7, 24-crown-8 are preferable.

Among the phase transfer catalysts used, the calixarene compound has a structure represented by the following general formula (6).

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In the formula, R represents a hydrogen atom or an unsubstituted or substituted alkyl group, and n represents an integer of 2 to 10. In the formula (6), as the unsubstituted or substituted alkyl group,
Methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, icosyl, chloromethyl, hydroxyethyl,
Examples include methoxypropyl, aminomethyl, methylcarbonylmethyl, benzyl, and phenethyl groups.

Among the phase transfer catalysts used, the phosphonium salt compound is a compound represented by the following general formula (7).

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In the formula, R ¹⁰ , R ¹¹ , R ¹² , and R ¹³ are the same or independently represent an unsubstituted or substituted alkyl group and an unsubstituted or substituted aryl group. Examples of unsubstituted or substituted alkyl groups include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl,
Undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, icosyl, chloromethyl, hydroxyethyl, methoxypropyl, aminomethyl, methylcarbonylmethyl, benzyl, phenethyl and the like; unsubstituted or substituted aryl groups Examples include phenyl, methoxyphenyl, ethoxyphenyl, tolyl, chlorophenyl, fluorophenyl, hydroxyphenyl, aminophenyl, nitrophenyl and the like. Examples of the counter ion X ⁻ include fluorine ion, chlorine ion, bromine ion, iodine ion, hydrogen sulfate ion, sulfate ion, phosphate ion, hydrogen phosphate ion, cyanide ion, periodate ion, acetate ion, and toluene sulfone. Examples thereof include an acid ion, trifluoromethanesulfonic acid ion, and hydroxyl ion.

Of these phase transfer catalysts, the quaternary ammonium compound, organic phosphorus compound, crown ether compound, calixarene compound and phosphonium salt compound are usually used in an amount of 0.001 to 1-AAQ.
~ 20.0 mol%, preferably 0.01 ~
It is in the range of 10.0 mol%. In the case of an ethylene glycol-based compound, it is usually 0.1 to 10 based on 1-AAQ.
0 mol% is used. If the amount of the phase transfer catalyst used is extremely small, the catalytic effect is reduced, and if it is too large, it tends to be economically disadvantageous. The addition method is generally added at the start of the condensation reaction, but is not particularly limited as long as the phase transfer catalyst is present in the reaction system during the reaction.

Examples of the alkaline condensing agent used in the method of the present invention include alkali metal hydroxides such as potassium hydroxide and sodium hydroxide, and alkali metal salts such as potassium carbonate and sodium carbonate. Among them, potassium hydroxide is preferable. These can be used in the form of a solid or an aqueous solution.

The amount of the alkaline condensing agent used is 0.1 to 40.0 mole ratio, preferably 0.5 to 10.0 mole ratio, more preferably 0.8 to 10.0 mole ratio with respect to 1-AAQ of the raw material.
8.0 molar ratio.

The reaction temperature is usually 80 to 150 ° C., preferably 120 to 140 ° C., more preferably 130 to 135 ° C.
It is. If the reaction temperature is too low, the reaction rate will be low, and if it is too high, the reaction rate will be high. However, the quality of dianthraquinone-N, N'-dihydroazine may be reduced, which is not preferable.

[0030]

EXAMPLES The present invention will be further described below with reference to examples, but the present invention is not limited to the following examples unless it exceeds the gist. In the examples, “yield” indicates the yield relative to 1-AAQ of the raw material.
In the examples, staining and determination methods were performed as follows. 1. The obtained dye compound is dissolved in water, sodium hydroxide and hydrosulfite are added, and the mixture is left at 65 ° C. for 15 minutes to perform reduction. Add more water and bring back to room temperature (dye concentration approx. 2% by weight / solution). 2. A cotton thread is immersed in this solution, the temperature is raised to 60 ° C., and the temperature is maintained at this temperature for dyeing.
0 g). 3. The cotton thread is taken out, squeezed, and treated in the order of oxidation, washing with water, soaping and drying. 4. A cotton thread similarly dyed with a dianthraquinone-N, N'-dihydroazine compound synthesized by a method shown in a comparative example described later is used as a standard, and the dyeability is determined by comparing with the cotton thread. However, with respect to the dianthraquinone-N, N'-dihydroazine compound, a compound having a high purity is stained with a clear reddish blue, and a compound containing more impurities is stained with a greenish dark blue.

Example 1 242.1 g of 90 g (0.404 mol) of 1-AAQ
DMI of (2.69 weight times / 1-AAQ) and 9.9 g
In a mixture of water. Next, 2.0 g (0.018 mol) of a 50% aqueous potassium hydroxide solution was added. This is heated to 100 ° C. and kept for 1 hour. Air (40
(0 ml / min), 85.2 g (0.759 mol) of a 50% aqueous solution of potassium hydroxide was added dropwise over 3 hours at the same temperature. After the completion of the dropwise addition, the temperature was raised to 130 ° C., and the reaction was carried out over 12 hours while distilling off water in the system. After cooling to 70 ° C., 63 g of water was charged into the reaction mixture, and the mixture was stirred for 1 hour. After filtration, washing with water and drying, the desired product, dianthraquinone-N, N'-dihydroazine, is 86.4.
g was obtained. The yield was 96.0%. As a result of the dyeing test, the product was dyed in a clear reddish blue compared to the standard.

Example 2 236.7 g of DMI (2.63 weight times / 1-
AAQ) and 15.3 g of water, except that the reaction time was 10 hours. 86.0 g of the desired product, dianthraquinone-N, N'-dihydroazine, was obtained. The yield was 95.6% based on 1-AAQ. As a result of the dyeing test, the product was dyed in a clear reddish blue compared to the standard.

Example 3 As a solvent, 232.2 g of DMI (2.58 times by weight / 1-
AAQ) and 19.8 g of water, and the reaction was carried out in the same manner as in Example 1 except that the reaction time was changed to 11 hours. 86.4 g of the desired product, dianthraquinone-N, N'-dihydroazine, was obtained. The yield was 96.0% based on 1-AAQ. As a result of the dyeing test, the product was dyed in a clear reddish blue compared to the standard.

Example 4 214.2 g of DMI (2.38 weight times / 1-
AAQ) and 37.8 g of water, and the reaction time was 13.5.
The procedure was performed in the same manner as in Example 1 except that the time was changed. 84.8 g of the desired product, dianthraquinone-N, N'-dihydroazine
I got The yield was 94.2% based on 1-AAQ. As a result of the dyeing test, the product was dyed in a clear reddish blue compared to the standard.

Example 5 248.2 g of DMI (2.76 weight times / 1-
AAQ) and 3.8 g of water, and the same procedure as in Example 1 was carried out except that the reaction time was 7.5 hours. 85.5 g of the desired product, dianthraquinone-N, N'-dihydroazine, was obtained. The yield was 95.0% based on 1-AAQ. As a result of the dyeing test, the product was dyed in a clear reddish blue compared to the standard.

Example 6 246.6 g of DMI (2.74 weight times / 1-
AAQ) and 5.4 g of water were used in the same manner as in Example 1. 86.1 g of the desired product, dianthraquinone-N, N'-dihydroazine, was obtained. The yield was 95.6% based on 1-AAQ. As a result of the dyeing test, the product was dyed in a clear reddish blue compared to the standard.

Example 7 40.0 g (0.179 mol) of 1-AAQ was added to TMA11.
It was suspended in a mixture of 3 g and 5.9 g of water, and 1.3 g (0.012 mol) of a 50% aqueous potassium hydroxide solution was added. This was heated to 98 to 100 ° C., and 38.0 g of a 50% aqueous potassium hydroxide solution was added at the same temperature while passing air through.
(0.339 mol) was added dropwise over 2 hours. After the completion of the dropwise addition, the temperature was raised to 129 to 130 ° C., and the reaction was carried out over 14 hours while partially removing the water in the system. 68 ~
After cooling to 70 ° C., 150 g of warm water was charged into the reaction mixture, and the crystal portion was collected by filtration and washed with water. The cake was dried to obtain 38.3 g of the desired product, dianthraquinone-N, N'-dihydroazine. The yield was 96.0%. As a result of the dyeing test, the product was dyed in a clear reddish blue compared to the standard.

Example 8 40.0 g (0.179 mol) of 1-AAQ was added to TMA11.
It was suspended in a mixture of 3 g and 5.9 g of water, and 20.0 g (0.350 mol) of 98% potassium hydroxide was added. This mixture was heated to 98 to 100 ° C. and reacted for 4 hours while passing air. After cooling to 68 to 70 ° C, 150 g of warm water was charged into the reaction mixture, and the crystal portion was collected by filtration and washed with water. The filter cake was dried to obtain 36.8 g of the desired dianthraquinone-N, N'-dihydroazine. The yield was 93%. As a result of the dyeing test, the product was dyed in a clear reddish blue compared to the standard.

Example 9 222 g of TMA, 11.7 g of water, 20.0 g of potassium tert-butoxide (0.179 g) instead of KOH
Mol), and heated at 80 to 82 ° C, and reacted for 6 hours, to obtain 36.6 g of the desired dianthraquinone-N, N'-dihydroazine, in the same manner as in Example 8. The yield was 92%. As a result of the dyeing test, the product was dyed in a clear reddish blue compared to the standard.

Example 10 40.0 g (0.179 mol) of 1-AAQ was added to DMI1
The suspension was suspended in a mixture of 13 g and 5.9 g of water, and 0.14 ml (0.00036 mol) of a 40% benzyltrimethylammonium hydroxide methanol solution and 2.5 g of a 50% aqueous KOH solution (0.1 g) were added to the suspension. 022 mol) was added. The obtained mixture is heated to 98 to 100 ° C. and 38.0 g of a 50% aqueous KOH solution is passed while passing air.
(0.339 mol) was added dropwise over 2 hours. After completion of the dropwise addition, the temperature was raised to 129 to 130 ° C., and the reaction was carried out over 4 hours while partially removing the water in the system. 68-70
After cooling to 0 ° C., 150 g of warm water was charged into the reaction mixture,
The crystal part was collected by filtration and washed with water. The filter cake was dried to obtain 37.6 g of the desired product, dianthraquinone-N, N'-dihydroazine. The yield was 95%. As a result of the dyeing test, the product was dyed in a clear reddish blue compared to the standard.

Examples 11 to 56 In the same manner as in Example 10, various phase transfer catalysts were added to synthesize dianthraquinone-N, N'-dihydroazine, and a dyeing test was performed in the same manner. The reaction conditions and results are shown in Table 1. All conditions other than those shown in Table 1 are the same as in Example 10.

Comparative Example The procedure of Example 1 was repeated except that 252.0 g (2.8 times / 1-aminoanthraquinone) of DMI was used alone as a solvent. 81.0 g of the desired product, dianthraquinone-N, N'-dihiroazine, was obtained. The yield was 90.0%.

[0043]

[Table 1]

[0044]

[Table 2]

[0045]

[Table 3]

[0046]

[Table 4]

[0047]

[Table 5]

[0048]

[Table 6]

[0049]

[Table 7]

[0050]

According to the method of the present invention, dianthraquinone-N, N'-dihydroazine, which is an industrially useful compound, as a blue vat dye and pigment is obtained in a stable and high-quality and high yield. An industrially useful method that can be obtained can be provided.

Continuation of the front page (56) References JP-A-60-1169 (JP, A) JP-A-62-25167 (JP, A) JP-A-55-142053 (JP, A) JP-A-54-93021 (JP) JP-A-51-17222 (JP, A) JP-A-6-65511 (JP, A) JP-A-6-80648 (JP, A) JP-A-7-233330 (JP, A) 40-1280 (JP, B1) (58) Field surveyed (Int. Cl. ⁷ , DB name) C09B 5/48 C09B 5/44

Claims (9)

(57) [Claims] 1. A suspension of 1-aminoanthraquinone in a mixed solvent having a weight ratio of aprotic polar solvent to water of 80:20 to 99: 1, and adding an alkaline condensing agent to the suspension. And producing a dianthraquinone-N, N'-dihydroazine. 2. The method according to claim 1, wherein the weight ratio of the aprotic polar solvent to water is 85:15 to 98.5: 1.5. 3. The method according to claim 2, wherein the weight ratio of the aprotic polar solvent to water is 92: 8 to 98: 2. 4. The method according to claim 1, wherein the weight ratio of the aprotic polar solvent to water is from 94: 6 to 96: 4. 5. The aprotic polar solvent is 1,3-dimethyl-2-imidazolidinone or 1,3,6-trimethylhexahydro-1,3,6-triazocin-2-one. the method of. 6. The method according to claim 1, wherein the solution in which 1-aminoanthraquinone is suspended contains a phase transfer catalyst. 7. The quaternary ammonium salt as a phase transfer catalyst,
7. The method according to claim 6, wherein the method is one or a mixture of two or more selected from the group consisting of an ethylene glycol compound, an organic phosphorus compound, a crown ether compound, a calixarene compound, and a phosphonium salt compound. 8. A quaternary ammonium salt, wherein the phase transfer catalyst is:
8. The organic phosphorus compound, crown ether compound, calixarene compound, and phosphonium salt compound selected from the group consisting of 0.001 to 20.0 mol% based on 1-aminoanthraquinone as a raw material. the method of. 9. The method according to claim 6 , wherein the phase transfer catalyst is an ethylene glycol-based compound, and its use amount is 0.1 to 100 mol% based on 1-aminoanthraquinone as a raw material.