JP2987056B2 - 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.

[0002]

BACKGROUND OF THE INVENTION The objective compound of the present invention, dianthraquinone-
N, N'-dihydroazine (6,15-dihydro-5,
9,14,18-anthrazine tetron; trade name Ind
anthrene Blue RS, Mikethre
n Blue RS) has been well known as a blue vat dye having excellent light fastness for a long time, and a high-purity dye can dye cotton or the like into a reddish clear blue. Also,
It is an important compound that is also used as a pigment, and is also an important compound as a production intermediate for 3,3′-dichlorodianthraquinone-N, N′-dihydroazine.

Various methods have been disclosed as methods for producing this dianthraquinone-N, N'-dihydroazine. Generally, BIOS 987 and F
As described in IAT1313, a method of condensing 2-aminoanthraquinone by alkali melting in the presence of an oxidizing agent has been known for a long time. In this method, dianthraquinone-N, N'-dihydroazine can be produced using only the raw materials, 2-aminoanthraquinone, oxidizing agent and alkaline condensing agent, without using a solvent. However, on the other hand, since the yield is low and the obtained product contains many impurities, purification operations such as hydrosulfite treatment cannot be avoided in order to use it as a dye or pigment. Therefore, the yield of the desired product, dianthraquinone-N, N'-dihydroazine, is extremely low, and it is difficult to say that the method is industrially suitable.

There is also known a method of condensing 1-aminoanthraquinone in an organic solvent in a dissolved or suspended state. In a phosphoric acid amide compound such as hexamethyl phosphorotriamide or an organic nitrogen oxide such as pyridine-N-oxide or quinoline-N-oxide as described in JP-A-51-17222, A method of condensing with an alkaline condensing agent,
This is a method of condensing with an alkaline condensing agent in the presence of an organic sulfone or sulfoxide compound as described in JP-A-1280. However, when a supplementary test of these prior art examples is conducted, dianthraquinone-N, N'-dihydroazine can be produced, but all have low yields of about 70 to 80% and are industrially suitable. Hard to say.

[0005] As a method for solving the problems of the prior art, the present applicant has reacted 1-aminoanthraquinone with an alkaline condensing agent in the presence of 1,3-dialkyl-2-imidazolidinone to obtain the desired dianthraquinone- N, N '
-An improved process of the prior art for producing dihydroazine with high yield and quality has already been filed. (Japanese Patent Laid-Open No. 60
JP-A-1169 and JP-A-62-25167. ) By this technology, dianthraquinone-N, N'-
The yield of dihydroazine is dramatically improved, and the dianthraquinone-N, N'-
It is now possible to obtain much better quality than dihydroazine. However, this method has a long reaction time of 10 to 15 hours, leaving room for improvement in terms of production efficiency, and its solution has been strongly desired. Further, the dianthraquinone obtained by these prior arts-
Each of N, N'-dihydroazines contains several kinds of impurities of unknown structure that cause dark color, and it was necessary to perform purification operations such as hydrosulfite treatment.

[0006]

DISCLOSURE OF THE INVENTION The present invention solves these problems of the prior art, obtains the desired compound in a high yield in a short time, and can be carried out simply without performing purification operations such as hydrosulfite treatment. An object of the present invention is to provide a method for obtaining high-quality dianthraquinone-N, N'-dihydroazine by only a water washing treatment.

[0007]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to solve the above problems, and as a result, have found an industrially extremely valuable method, and have completed the present invention. That is, the present invention provides a method for producing dianthraquinone-N, N'-dihydroazine by reacting 1-aminoanthraquinone with an alkaline condensing agent in the presence of 1,3-dialkyl-2-imidazolidinone. A method for producing dianthraquinone-N, N'-dihydroazine, comprising adding a catalyst.

The phase transfer catalyst used in the method of the present invention may be a heterogeneous reaction comprising two or more phases.
There is no particular limitation as long as the compound has a function of facilitating the reaction between the substance in one phase and the substance in the other phase. Among them, a quaternary ammonium compound, an ethylene glycol compound, an organic phosphorus compound, A crown ether compound, a calixarene compound, or a phosphonium salt compound is preferred. These can be used alone or as a mixture of two or more compounds.

[0009] Among the phase transfer catalysts used in the method of the present invention, the quaternary ammonium compound is a compound represented by the following general formula (1):

Embedded image In the formula, R ¹ , R ² , R ³ and R ⁴ are the same or independently an unsubstituted or substituted alkyl group, or an unsubstituted or substituted aryl group. Examples of the alkyl group which may be unsubstituted or substituted 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, and as an unsubstituted or optionally substituted aryl group, phenyl, methoxyphenyl, ethoxyphenyl, Tolyl, chlorophenyl, fluorophenyl, hydroxyphenyl, aminophenyl, nitrophenyl and the like can be mentioned. The counter ion X ⁻ is fluorine ion, chlorine ion, bromine ion, iodine ion, hydrogen sulfate ion, sulfate ion, phosphate ion, hydrogen phosphate ion, cyanide ion, periodate ion, acetate ion, toluene sulfonate ion. , Trifluoromethanesulfonic acid ion or hydroxyl ion.

Among the phase transfer catalysts used in the method of the present invention, the ethylene glycol compound is a compound represented by the following general formula (2):

Embedded image In the formula, R and R ′ are the same or independently a hydrogen atom and an alkyl group, and examples of the alkyl group include methyl, ethyl, propyl, butyl, hexyl, dodecyl and the like, and n is 2 to 5 Indicates an integer. Particularly preferred are 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 in the method of the present invention, the organic phosphorus compound is represented by the following general formula (3):
Phosphine, phosphine oxide or phosphine sulfide represented by (4) or (5),

Embedded image In the formula, R ¹ , R ² , and R ³ are the same or independently an unsubstituted or substituted alkyl group, an unsubstituted or substituted alkoxy group, or an unsubstituted or substituted Shows good aryl groups. Examples of the alkyl group which may be unsubstituted or substituted include methyl, ethyl, propyl, butyl, pentyl, hexyl, cyclohexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, Heptadecyl, octadecyl,
Nonadecyl, icosyl, chloromethyl, hydroxyethyl, methoxypropyl, aminomethyl, methylcarbonylmethyl, benzyl, phenethyl and the like, examples of unsubstituted or optionally substituted alkoxy groups include methoxy, ethoxy, propoxy, Butoxy, pentoxy, chloromethoxy, hydroxyethoxy, methoxybutoxy, aminopropoxy, methylcarbonylmethoxy, and the like.Examples of an unsubstituted or optionally substituted aryl group include phenyl, methoxyphenyl, ethoxyphenyl, and tolyl. , Chlorophenyl, fluorophenyl, nitrophenyl, hydroxyphenyl, aminophenyl and the like. These substituents may combine to form a ring.

In the phase transfer catalyst used in the method of the present invention, the crown ether compound may be one in which part or all of the ethylene group is replaced by a phenylene group. The ethylene group and the phenylene group may be unsubstituted or substituted.Examples of the substituent when substituted are methyl, ethyl,
Alkyl groups such as propyl, methoxy, alkoxy groups such as ethoxy, hydroxy groups, methylcarbonyl, alkylcarbonyl groups such as ethylcarbonyl, hydroxycarbonyl groups, methoxycarbonyl, alkoxycarbonyl groups such as ethoxycarbonyl, amino groups, methylamino, ethyl Examples thereof include an alkylamino group such as amino, a nitro group, and a halogen. Further, a part of or all of the oxygen atoms may be replaced with nitrogen, sulfur or phosphorus atoms. Among them, 12-crown-4, 15-crown-
5,18-crown-6,21-crown-7,24-
Those having a skeleton such as crown-8 are preferred.

Among the phase transfer catalysts used in the method of the present invention, the calixarene compound has the structure represented by the following general formula (6):

Embedded image In the formula, R represents a hydrogen atom or an unsubstituted or optionally substituted alkyl group, and n represents an integer of 2 to 10.
Examples of the alkyl group which may be unsubstituted or substituted 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 and the like can be mentioned.

Among the phase transfer catalysts used in the method of the present invention, the phosphonium salt compound is a compound represented by the following general formula (7):

Embedded image In the formula, R ¹ , R ² , R ³ and R ⁴ represent an unsubstituted or substituted alkyl group or an unsubstituted or substituted aryl group. Examples of the alkyl group which may be unsubstituted or substituted 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 can be mentioned. Examples of the unsubstituted or substituted aryl group include phenyl, methoxyphenyl, ethoxyphenyl, tolyl, chlorophenyl, fluorophenyl, nitrophenyl, aminophenyl, hydroxyphenyl and the like. Examples of the counter ion X ⁻ of the phosphonium salt include a fluorine ion, a chlorine ion, a bromine ion, an iodine ion, a hydrogen sulfate ion, a sulfate ion, a phosphate ion, a hydrogen phosphate ion and a cyanide ion.

In the process of the present invention, the phase transfer catalyst can be used in the form of a solid, an aqueous solution or a solution of an organic solvent which is inert to the raw materials. Of these phase transfer catalysts, the fourth
The quaternary ammonium compound, the organic phosphorus compound, the crown ether compound, the calixarene compound and the phosphonium salt compound are usually used in an amount of 0.001 to 20.0 mol%, preferably 0.01 to 1 mol%, based on 1-aminoanthraquinone.
It is used in the range of 0.0 mol%, and the ethylene glycol compound is usually used in an amount of 0.1 to 0.1-aminoanthraquinone.
Use 100 mol%. If the amount is extremely small, the catalytic effect tends to be small, and if it is too large, it tends to be economically disadvantageous. In addition, the addition method is generally added at the start of the condensation reaction, but it is sufficient that the phase transfer catalyst is present in the reaction system during the reaction, and is not particularly limited.

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. These can be used in the form of a solid or an aqueous solution. The alkaline condensing agent used in the method of the present invention is used in an amount of 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-aminoanthraquinone.
It is used in a range of 5.0 molar ratio. When the amount of the alkaline condensing agent used is extremely small, the reaction rate tends to be slow, and 1-aminoanthraquinone remains in the product, which may cause deterioration in quality.

The 1,3-dialkyl-2-imidazolidinone used in the method of the present invention is not particularly limited as long as it has an inactive alkyl group in the raw material and the product. Those in which the alkyl group is a methyl group are preferred because they are relatively easily available. 1,3-Dialkyl-2-imidazolidinone is usually used alone, but there is no problem to use it in combination with another solvent as long as it is inert to the raw materials and products. The amount of 1,3-dialkyl-2-imidazolidinone used in the method of the present invention is 0.01 to 10 with respect to 1-aminoanthraquinone.
Weight ratio, preferably in the range of 0.1 to 4.5 weight ratio. If this amount is extremely large, the amount of by-products tends to increase.

In the method of the present invention, an oxidizing agent such as air, oxygen, perborate, nitrate or chlorate may be used in order to make the reaction proceed smoothly. In particular, air and oxygen are preferred because they are easy to handle.

As a specific method of carrying out the method of the present invention,
1, 1-aminoanthraquinone dissolved or suspended
A method in which a predetermined amount of a phase transfer catalyst is added to 3-dialkyl-2-imidazolidinone, and a predetermined amount of an alkali condensing agent is added alone or in an aqueous solution under an air stream to cause a reaction. However, the order of charging the raw materials is not limited to this.

The reaction is carried out at 50 to 200 ° C., preferably at 70 ° C.
C. to 180.degree. C., more preferably 90 to 160.degree. If the reaction temperature is too low, the reaction rate tends to decrease. If the reaction temperature is too high, the reaction rate increases, but a side reaction or decomposition reaction of 1-aminoanthraquinone occurs, and conversely, dianthraquinone-N, N'-dihydroazine. Tends to decrease the yield and quality of the product.

The reaction time depends on the amount of the phase transfer catalyst and the reaction temperature and is not determined uniquely. However, the reaction is usually completed within 6 hours, and the dianthraquinone-N, N'-dihydroazine is obtained in high yield. Is obtained.

[0022]

EXAMPLES Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited to the following examples unless it exceeds the gist. In the description, the term “yield” indicates the yield based on 1-aminoanthraquinone. In addition, the staining and determination method are 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 for reduction. Add more water and bring to room temperature.
(Dye concentration is about 2% by weight / solution) 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. (Dye aqueous solution 1 per g of yarn
00g ratio) Take out the cotton thread, squeeze, and process in the order of oxidation → washing → soaping → drying. 4. A yarn dyed with a dianthraquinone-N, N'-dihydroazine compound synthesized by a method shown in a comparative example described below is used as a standard, and a comparison is made with this.
However, with respect to the dianthraquinone-N, N'-dihydroazine compound, a compound having a high purity shows a clear blue color with a reddish color, and a compound containing a large amount of impurities shows a dark blue color with a greenish tint.

Example 1 40.0 g (0.179 mol) of 1-aminoanthraquinone was added to 1,3-dimethyl-2-imidazolidinone 113
g of a 40% benzyltrimethylammonium hydroxide solution in methanol as a phase transfer catalyst.
15 g (0.00036 mol) and 2.5 g (0.022 mol) of a 50% aqueous potassium hydroxide solution were added. This is heated to 98-100 ° C and 50% while passing air.
An aqueous solution of potassium hydroxide (38.0 g, 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. 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 37.6 g of the desired dianthraquinone-N, N'-dihydroazine. The yield was 95%. As a result of a dyeing test, the color was reddish and clear blue as compared with the standard.

Examples 2 to 47 In the same manner as in Example 1, various phase transfer catalysts were added to synthesize dianthraquinone-N, N'-dihydroazine, and a dyeing test was performed in the same manner as in Example 1. Was performed. Table 1 shows the reaction conditions and the results. All conditions other than those shown in Table 1 are the same as those in the first embodiment.

[0025]

[Table 1]

[0026]

[Table 2]

[0027]

[Table 3]

[0028]

[Table 4]

[0029]

[Table 5]

[0030]

[Table 6]

[0031]

[Table 7]

COMPARATIVE EXAMPLE The reaction was carried out in the same manner as in Example 1 except that no phase transfer catalyst was added. The reaction took 12 hours, and 36.4 g of the desired dianthraquinone-N, N'-dihydroazine was obtained. The yield is 90% based on 1-aminoanthraquinone.
Met. When the cotton yarn was dyed according to the dyeing test method, a greenish dark blue color was exhibited.

[0033]

According to the method of the present invention, dianthraquinone-N, N'-dihydroazine, which is a compound which is industrially extremely useful as a blue vat dye and pigment, can be produced from 1-aminoanthraquinone in a short time and at a high yield. Can be obtained at Moreover, the obtained dianthraquinone-N, N'-dihydroazine can be easily isolated without performing a complicated purification operation, and is of high quality.

Continuation of front page (56) References JP-A-62-25167 (JP, A) JP-A-60-1169 (JP, A) JP-A-60-179462 (JP, A) JP-A-61-278567 (JP) , A) (58) Field surveyed (Int. Cl. ⁶ , DB name) C09B 5/48

Claims (2)

(57) [Claims] 1. A method for producing dianthraquinone-N, N'-dihydroazine by reacting 1-aminoanthraquinone with an alkaline condensing agent in the presence of 1,3-dialkyl-2-imidazolidinone, wherein a phase transfer catalyst is used. A process for producing dianthraquinone-N, N'-dihydroazine. 2. A phase transfer catalyst comprising: a quaternary ammonium compound, an ethylene glycol compound, an organic phosphorus compound,
Crown ether compounds, calixarene compounds,
The method according to claim 1, wherein the method is one selected from the group consisting of and a phosphonium salt compound, or a mixture of two or more.