JPH10287676A - Production of hexaazaisowurtzitane derivative - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject compound as the precursor of a compound capable of being used as a raw material for high performance gunpowder in a high yield by removing by-product components inhibiting a reductive arylmethyl-removing reaction with an organic solvent. SOLUTION: This method for producing a highly pure hexaazaisowurtzitane derivative comprises removing by-product components from a crude hexabenzylhexaazalsowurtzitane of formula I (B is benzyl; W is a hexaazalsowurtzitane residue of formula II) synthesized from glyoxal and benzylamine with an organic solvent. The hexabenzylhexaazaisowurtzitane can be subjected to a reductive arylmethyl-removing reaction in the presence of an acylating agent to obtain the hexabenzylhexaazaisowurtzitane derivative having an acyl group in a short time in good reproducibility. The by-product components are preferably components other than the hexabenzylhexaazaisowurtzitane detected by liquid chromatography.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a method for producing a hexaazaisowurtzitane derivative which is a precursor of hexanitrohexaazaisowurtzitane used for improving the performance of conventional explosive compositions.

[0002]

2. Description of the Related Art As a method for producing hexanitrohexaazaisowurtzitane, which is a high-performance explosive material, hexakis (arylmethyl) hexaazaisowurtzitane is subjected to reductive dearylmethylation in the presence of an acylating agent to obtain tetraacyl. Bis (arylmethyl) hexaazaisowurtzitane, pentaacylarylmethylhexaazaisowurtzitane,
There is a report that a precursor is a hexaazaisowurtzitane derivative having an arylmethyl group, an acyl group, a hydrogen atom, or the like, such as hexaacylhexaazaisowurtzitanium (The)
Military Critical Techn
logosList, Office of the
e Under Secretary of Defen
se for Acquisition, 12-22,
October (1992), Tetrahedron
Vol. 51, No. 16, 4711-4722 (199)
5), PCT-JP96-00189).

A process for producing hexakis (arylmethyl) hexaazaisowurtzitane for producing these hexaazaisowurtzitane derivatives can be obtained by condensing various arylmethylamines and glyoxal (J. Org.Chem., Vol.
59-1466 (1990)). Purification by the production method described in this document recrystallizes with acetonitrile, but there is no detailed description of the purification method, analysis method, and purity, and it cannot be said that the product was purified by recrystallization. The solubility of a by-product component detected by liquid chromatography in acetonitrile is low, and purification can be performed only under extremely dilute conditions. The by-product component inhibits the reductive dearylmethyl reaction.

[0004]

The object of the present invention is achieved by benzylamine and glyoxal, which inhibit the reaction of hexabenzylhexaazaisowurtzitanium in the reductive dearylmethyl reaction in the presence of an acylating agent. An object of the present invention is to provide a method for producing a hexaazaisowurtzitane derivative in high yield by removing a by-product component contained in hexabenzylhexaazaisowurtzitanium.

[0005]

Means for Solving the Problems The present inventors remove an by-product component contained in crude hexabenzylhexaazaisowurtzitanium, which inhibits a reductive dearylmethyl reaction, with an organic solvent, and removes the by-product component. It has been found that high-purity hexabenzylhexaazaisowurtitanium containing no component can be produced, and the compound is dearylmethylated in the presence of an acylating agent to obtain a hexaazaisowurtzitanium derivative having an acyl group. Was successfully produced in high yield, and the present invention was completed.

That is, the present invention is detected by liquid chromatography which is a by-product in the production of hexabenzylhexaazaisowurtzitanium represented by the following general formula (1) obtained by the condensation reaction of benzylamine and glyoxal. This is a method of obtaining highly pure hexabenzylhexaazaisowurtzitane by removing and purifying by-product components including by-product components with an organic solvent, and further subjecting this to reductive deprotection in the presence of an acylating agent. The present invention provides a method for producing a hexaazaisowurtzitane derivative having an acyl group represented by the following general formula (2) in a high yield by arylmethylation.

WB ₆ (1) [wherein B represents a benzyl group, and W represents a hexaazaisowurtzitanium residue represented by the following formula (3). WA _n B _m H _(6-nm) (2) wherein n is an integer of 4 to 6, m is an integer of 0 to 2, A is an acyl group having 1 to 10 carbon atoms, B is a benzyl group, H represents a hydrogen atom, and W represents a hexaazaisowurtzitanium residue represented by the following formula (3). ]

[0008]

Embedded image

In the general formula (2), as the acyl group, any acyl group having 1 to 10 carbon atoms can be used. Usually, formyl, acetyl, propionyl, butyryl, isobutyryl, valeryl, hexanoyl, 2-phenylacetyl, trifluoroacetyl, pentafluoropropionyl and the like are used, preferably an acyl group having 1 to 5 carbon atoms, for example, formyl, acetyl, Propionyl, butyryl, valeryl, trifluoroacetyl, and the like are used, and more preferably, they have 1 to 1 carbon atoms.
An acyl group of 4, for example, formyl, acetyl, propionyl, butyryl, trifluoroacetyl and the like are used. The most preferred example is acetyl.

According to the production method of the present invention, any acid catalyst may be used in the production of the hexaazaisowurtzitane derivative as long as it is hexabenzylhexaazaisowurtzitane obtained by the condensation reaction of benzylamine and glyoxal. May be used. Hexabenzylhexaazaisowurtitanium synthesized from glyoxal and benzylamine used in the present invention can be synthesized by any method as long as it is hexabenzylhexaazaisowurtzitanium obtained by a condensation reaction of glyoxal and benzylamine. It may be done.

The solvent used in the condensation reaction between glyoxal and benzylamine may be any solvent that does not adversely affect the reaction. Preferred examples include nitriles such as acetonitrile, polopionitrile, butyronitrile, alcohols such as methanol, ethanol, propanol and butanol, N, N-dimethylacetamide, N, N-dimethylformamide,
1,3-dimethyl-2-imidazolidone, N-methyl-
Amides such as 2-pyrrolidone, N, N-diethylnipecotamide, water and the like can be used. These may be used alone or as a mixture of two or more solvents. More preferably, acetonitrile, propionitrile, nitriles such as butyronitrile, methanol,
Alcohols such as ethanol, propanol and butanol, water, and the like may be used alone or as a mixed solvent of two or more kinds. The most preferred example is a mixed solvent of acetonitrile and water.

The glyoxal used in the condensation reaction between glyoxal and benzylamine may be glyoxal in an aqueous solution or 100% glyoxal. In the case of an aqueous solution, the weight ratio is 10 to 1
A range of 00% can be used, but preferably 10 to
90%, 20 to 6 in the case of industrial production
A range of 0% is preferred. The glyoxal has a purity of 80% or more, preferably 90% or more, and more preferably 95% or more of the components in the case of an aqueous solution, out of the water.

The concentration of glyoxal used in the condensation reaction of glyoxal and benzylamine is expressed as a weight ratio to the solvent, from 0.001 to 0.5, preferably from 0.01 to 0.5.
The range is from 0.05 to 0.4, and more preferably from 0.005 to 0.2. The benzylamine used in the condensation reaction between glyoxal and benzylamine is benzylamine having a purity of 90% or more, preferably 95% or more, and more preferably 99% or more. The concentration of benzylamine used in the condensation reaction of glyoxal and benzylamine is in the range of 0.1 to 100, preferably 0.5 to 50, and more preferably 1 to 10 in terms of the molar ratio of glyoxal.

The acid catalyst used in the condensation reaction of glyoxal and benzylamine may be any acid as long as it is a Bronsted acid, but carboxylic acids such as formic acid, acetic acid, propionic acid and butyric acid, sulfuric acid, Mineral acids such as nitric acid can be used. Preferred examples are formic acid, acetic acid and propionic acid. The concentration of the acid catalyst used in the condensation reaction of glyoxal and benzylamine is represented by a molar ratio to gliaxal and is 0.0001 to 10, preferably 0.001 to 1, more preferably 0.1 to 0.5. Range. The reaction temperature of the condensation reaction between glyoxal and benzylamine may be any temperature as long as it is between the freezing point and the boiling point of the solvent, but is preferably in the range of -10 to 30 ° C. In the general formula (2), there are positional isomers depending on the number of n and m, but any isomer may be used.

The component contained in crude hexabenzylhexaazaisowurtzitanium obtained by the condensation reaction of benzylamine and glyoxal, which inhibits the reductive dearylmethyl reaction, is a by-product detected by liquid chromatography. Or by-products that are not detected by liquid chromatography, but according to the production method of the present invention, by-products that are not detected by liquid chromatography while removing by-product components detected by liquid chromatography In the production method according to the present invention, hexabenzylhexaazaisowurtzitanium of extremely high purity can be produced, and further, a hexaazaisowurtzitanium derivative containing an acyl group can be obtained in a high yield. be able to.

The by-product components detected by the liquid chromatography described above are components other than hexabenzylhexaazaisowurtzitane detected under the analysis conditions shown in Table 1 below. The analysis conditions of the liquid chromatography described here were all measured under the conditions shown in Table 1. FIG. 1 shows an example of analysis by liquid chromatography according to the present invention. In FIG. 1, the peak at a retention time of 2.4 minutes is hexabenzylhexaazaisowurtzitane, and the peak at a retention time of 2.2 minutes is a main by-product detected by liquid chromatography.

[0017]

[Table 1]

The above retention times are not critical, as is generally known in liquid chromatography analysis. Generally, in liquid chromatography analysis, it is known that the retention time varies somewhat depending on the conditioning of the analytical column, the degree of deterioration of the analytical column, the equipment used, and the use environment. By-products detected by liquid chromatography analysis according to the present invention are components detected in a shorter time than the retention time of hexabenzylhexaazaisowurtitanium under the liquid chromatography analysis conditions shown in Table 1. According to our experiments,
A chart as shown in FIG. 1 is obtained. In this figure, by-products detected by liquid chromatography are components having a retention time of 2.2 minutes.

The structure of the by-product detected by the liquid chromatography is unknown, and it is not clear how the reductive dearylmethyl reaction is inhibited. By using high-purity hexabenzylhexaazaisowurtzitanium, which has been purified by removing the by-products of the reductive dearylmethyl reaction in the presence of the acylating agent, the reaction proceeds in a short time with good reproducibility, A hexaazaisowurtzitane derivative containing an acyl group can be obtained in a yield.

As described in the prior art section, a method for producing crude hexabenzylhexaazaisowurtzitanium by the condensation reaction of benzylamine and glyoxal has been described in the literature for various arylamines (J. Or.).
g. Chem. , Vol. 55,1459-1466
(1990)). According to this document, crude hexabenzylhexaazaisowurtzitane is suspended in cold acetonitrile, filtered, and then recrystallized with acetonitrile, but the concentration and crystallization temperature are not described, and impurities are removed. Conditions cannot be specified. We have:
After obtaining crude hexabenzylhexaazaisowurtzitane by the method described in the above literature, for example, 16.68 g of crude hexabenzylhexaazaisowurtzitane was recrystallized using 1 l of acetonitrile. The obtained acetonitrile recrystallized hexabenzylhexaazaisowurtzitanium contained 0 to 15% by weight of a by-product. Acetonitrile recrystallized hexabenzylhexaazaisowurtzitanium obtained by this method was used to produce a hexaazaisowurtzitanium derivative having an acyl group by a reductive dearylmethyl reaction with a Pd catalyst in the presence of an acylating agent. Although the time required for the reaction fluctuated within an extremely large range depending on the purification conditions, and a long time was required, hexabenzylhexaazaisowurtzitanium decomposed the bone nucleus by acidic protons produced as a by-product after acylation. The hexaazaisowurtzitane derivative having an acyl group was obtained only in an extremely low yield.

In the production method according to the present invention, by-products other than hexabenzylhexaazaisowurtzitanium, which inhibit reductive dearylmethyl reaction in the presence of an acylating agent and are detected by liquid chromatography, By recrystallizing the crude hexabenzylhexaazaisowurtitanium at a concentration that does not exceed the solubility of the product components, it is possible to extract hexabenzylhexaazaisowurtzitanium of extremely high purity, By the arylmethyl reaction, a hexaazaisowurtzitane derivative having an acyl group can be obtained in a very short time and with good reproducibility in a high yield.

The production method of the present invention is intended to reduce the by-product component in crude hexabenzylhexaazaisowurtzitanium detected by liquid chromatography from a concentration that does not exceed the solubility of the by-product in the organic solvent at the crystallization temperature. It is possible to obtain extremely high-purity hexabenzylhexaazaisowurtzitanium which is taken out by recrystallization,
Further, this is a process for producing an acyl group-containing hexaazaisowurtzitanium in a high yield by reductive dearylmethylation in the presence of an acylating agent.

The solvent used in this production method is a combination of one or more organic solvents, and is a solvent having a solubility ratio P of 0.1 to 20 represented by the following general formula (4). Any combination of organic solvents may be used. P = H / I (4) wherein H is the solubility (g / l) of hexabenzylhexaazaisowurtzitanium dissolved in the organic solvent, and I is the impurity detected by liquid chromatography analysis dissolved in the organic solvent. Indicates the solubility (g / l) of the component. ]

The above-mentioned solubility is measured by a general method, but it is difficult to measure the solubility of a by-product containing a by-product component detected by liquid chromatography. According to the method of the present inventors, the dissolved amount of by-products including by-product components detected by liquid chromatography can be calculated from the dissolved amount of by-product components detected by liquid chromatography. it can. That is, an excessive amount of crude hexabenzylhexaazaisowurtzitane is added to a certain amount of an organic solvent, and the mixture is stirred while being kept at a constant temperature in a thermostat,
The undissolved solids are removed to obtain only a clear solution, and liquid chromatography analysis is performed. The amount of hexabenzylhexaazaisowurtzitane dissolved in this solution is calculated by liquid chromatography analysis. Further, if the organic solvent is distilled off from the transparent solution using a rotary evaporator, only the solid component dissolved in the transparent solution is obtained, and the hexabenzylhexaazaisomer is calculated from the weight of the solid component. By subtracting the amount of titanium dissolved, the amount of by-products other than hexabenzylhexaazaisowurtzitane contained in the transparent solution can be calculated. This dissolved amount had a good proportional relationship with the detection area of the by-product component detected by the liquid chromatography analysis of the transparent solution described above by the liquid chromatography analysis. Therefore, if the by-product component detected by liquid chromatography is analyzed by liquid chromatography, the amount of by-product component detected by liquid chromatography and the amount of by-product not detected by liquid chromatography are dissolved at the same time. It became possible to calculate.

In the present invention, the solubility of a by-product containing a by-product component detected by liquid chromatography analysis in an organic solvent was determined by the above-described method. In the present invention, the solubility of by-products including by-product components detected by liquid chromatography analysis dissolved in an organic solvent refers to the solubility determined by the above method. As the solvent, toluene, aromatic hydrocarbons such as benzene, tetrahydrofuran, diethyl ether, dipropyl ether, ethers such as dibutyl ether,
Nitriles such as acetonitrile, propionitrile, butyronitrile, N, N-dimethylacetamide;
N, N-dimethylformamide, 1,3-dimethyl-2
-Imidazolidone, N-methyl-2-pyrrolidone, N,
Amides such as N-diethylnipecotamide, alcohols such as methanol, ethanol, propanol, butanol, pentanol, hexanol, heptanol, octanol, ethyl formate, ethyl acetate, methyl acetate, methyl acetate, propyl acetate, butyl acetate, propion Methyl acid,
Ethyl propionate, propyl propionate, butyl propionate, methyl butyrate, ethyl butyrate, propyl butyrate,
Esters such as butyl butyrate, and halogenated hydrocarbons such as dichloromethane, chloroform and 1,2-dichloroethane. These solvents may be used alone or in combination of two or more.

In order to increase the purification yield from the crude crystals, it is preferable to use an organic solvent having a small value of the solubility ratio P represented by the formula (4). Preferred examples include alcohols, nitriles, esters, and amides, and these solvents may be used alone or as a mixture of two or more. More preferably, ethanol and ethyl acetate, ethanol and N, N-dimethylacetamide, acetonitrile and ethyl acetate, acetonitrile and N, N-
A combination of dimethylacetamide is most preferable, and a mixed solvent of ethanol and ethyl acetate is most preferable.
Table 2 shows the solubility of hexabenzylhexaazaisowurtzitane and the solubility of impurity components in each temperature and each organic solvent.

[0027]

[Table 2]

As a recrystallization method, crystallization can be performed by a general recrystallization method. For example, by heating to a temperature not exceeding the boiling point of the organic solvent, dissolving the crude crystals, and then cooling and crystallizing, or when using a mixed solvent, dissolve in a good solvent and gradually add a poor solvent. A crystallization method can also be used. In the case of heating, it is preferable to dissolve at a temperature not exceeding 130 ° C., because there is a risk of lowering the yield due to thermal decomposition of hexabenzylhexaazaisowurtzitane. In either method, high-purity hexabenzylhexaazaisowurtzitanium can be obtained by dissolving the crude crystal once and then crystallization.

The concentration of the recrystallization must be such that the by-product component detected by liquid chromatography can be sufficiently dissolved at the crystallization temperature. Literature (J. Org. Chem., Vol. 55, 1)
The crude crystal obtained by the method described in No. 459-1466 (1990)) contains 0-15% of impurities expressed in terms of weight ratio as a result of additional tests by the present inventors. That is, it is necessary to select a temperature and an amount of the solvent that can sufficiently dissolve this amount.

The precipitation of the crystals is completed between one hour and several days. During this time, the liquid may be stirred or left standing. When left to stand, relatively large acicular crystals are obtained, and when stirred, fine crystals are often obtained. Usually, the yield of hexabenzylhexaazaisowurtzitanium crystallized in most cases within a few hours does not change, but during crystallization and crystallization, it is necessary to keep the liquid temperature constant to obtain the yield and purity. Is extremely important in the reproducibility of The liquid temperature at this time must be equal to or higher than the freezing point of the organic solvent and kept constant.

After the precipitation of the crystals, the crystals can be taken out of the suspension by a general method. For example, any method such as a method by centrifugation, a method by suction filtration, and a method by pressure filtration may be used. The hexabenzylhexaazaisowurtzitanium purified as described above is subjected to the production of a hexaazaisowurtzitane derivative having an acyl group by a reductive dearylmethyl reaction in the presence of an acylating agent.

The solvent used in the step of the reductive dearylmethyl reaction in the presence of the acylating agent is a solvent that dissolves hexabenzylhexaazaisowurtzitane and that does not adversely affect the reaction. Any solvent may be used as long as it is used. Preferred solvents include aromatic hydrocarbons such as benzene, toluene and ethylbenzene, ethers such as tetrahydrofuran, N, N-dimethylacetamide, N, N-dimethylformamide,
1,3-dimethyl-2-imidazolidone, N-methyl-
Amides such as 2-pyrrolidone, N, N-diethylnipecotamide, methanol, ethanol, propanol,
Alcohols such as butanol, pentanol, hexanol, heptanol, octanol, ethyl formate,
Ethyl acetate, methyl acetate, propyl acetate, butyl acetate,
Esters such as methyl propionate, ethyl propionate, propyl propionate, butyl propionate, methyl butyrate, ethyl butyrate, propyl butyrate, and butyl butyrate can be used. More preferred are N, N-dimethylacetamide and N, N-dimethylformamide. These solvents may be used alone or as a mixture of two or more.

The concentration of hexabenzylhexaazaisowurtzitane in the reductive dearylmethylation step in the presence of the acylating agent is usually 0.00% in terms of the weight ratio to the solvent.
It is in the range of 1-1, preferably 0.005-0.3, more preferably 0.01-0.2. As the reducing agent used in the step of the reductive dearylmethyl reaction in the presence of the acylating agent, hydrogen and formic acid are usually used. Preferably it is hydrogen. The amount of the reducing agent to be used is expressed in a molar ratio to the arylmethyl group of hexabenzylhexaazaisowurtitanium of 1.0 to 1000, preferably 1.
It is used in the range of 0 to 100, more preferably 1.0 to 50. When hydrogen is used as the reducing agent, 0.01 to 1000, preferably 0.1 to 1000, expressed as hydrogen partial pressure.
1 to 30, more preferably 0.1 to 15 kgf / c
It is used in the range of m ^2. In addition to hydrogen, an inert gas such as nitrogen, argon, and helium may be present.

The reduction catalyst used in the step of the reductive dearylmethyl reaction in the presence of the acylating agent may be any catalyst capable of reductive dearylmethylation of the arylmethyl group of hexabenzylhexaazaisowurtzitane. Such a material can be used, but usually a metal belonging to the platinum group or a derivative thereof is used. Preferably, Pd (OA
c) ₂ , Pd (OAc) ₂ , Pd (NO ₃ ) ₂ , Pd
P such as O, PdCl ₂ , Pd ₃ Pb ₁ , Pd ₃ Te ₁
d compounds, Pd alloys and Pd metals; R such as RuCl ₃
A u compound, a Ru alloy, a Ru metal and the like are used, and more preferably, a Pd compound such as Pd (OAc) ₂ and PdCl ₂ , a Pd alloy and a Pd metal are used.

These catalysts can be used as they are, or can be used by being supported on various carriers such as activated carbon, silica, alumina, silica-alumina, zeolite, activated clay, zirconia, titania, and ion exchange resins. it can. When a catalyst is used, the surface acid sites may be deactivated by performing a treatment such as silylation or acylation on these carriers, or an activation treatment for increasing the surface acid sites. Or NaO
By adsorbing an alkaline substance such as H, the acidity of the surface of the short body can be changed. When a heterogeneous reduction catalyst is used, it may be used in a fixed bed or in a fluidized bed.

The acylating agent used in the step of the reductive dearylmethylation reaction in the presence of the acylating agent is any one that can acylate a secondary amine to form an N-acyl bond. Usually, acetic anhydride, propionic anhydride, formic anhydride, butyric anhydride, carboxylic anhydrides such as anhydrides of acetic acid-formic acid mixture, N-acetoxysuccinimide, N-propionylsuccinimide, N-
N- such as (2-phenylacetoxy) succinimide
Examples thereof include carboxylic acid esters of hydroxysuccinimide, acylimidazoles such as acetylimidazole and propionylimidazole. Among these acylating agents, carboxylic anhydrides such as acetic anhydride, propionic anhydride, and an anhydride of an acetic acid-formic acid mixture are preferably used. More preferably, it is acetic anhydride.

The amount of the acylating agent varies depending on its reactivity and reaction method, but it is usually from 0.67 to 100, preferably from 0.67 to 100, expressed as a molar ratio to the arylmethyl group of hexabenzylhexaazaisowurtitanium. Is 0.67 ~
10, more preferably in the range of 0.67 to 3. The reaction temperature of the reductive dearylmethyl reaction step in the presence of the acylating agent is usually the freezing point of the solvent used to 200 ° C.
Preferably, it is 30 to 180 ° C, more preferably 40 to 180 ° C.
C. to 165.degree.

The process for producing hexaazaisowurtzitanium having an acyl group according to the present invention comprises the steps of: removing a by-product that inhibits a dearylmethyl reaction contained in crude hexabenzylhexaazaisowurtzitanium obtained from glyoxal and benzylamine; By using high-purity hexabenzylhexaazaisowurtzitane which has been removed by using an organic solvent having a solubility ratio P in the range of 0.1 to 20, the reductive dearylmethyl reaction can be carried out in the presence of an acylating agent. Can be carried out in a short time with good reproducibility, and an industrially advantageous hexaazaisowurtzitane derivative having an acyl group can be produced.

[0039]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples. <Synthesis of crude hexabenzylhexaazaisowurtzitane>
In a 3 l separable flask equipped with a cooling tube, a dropping funnel, a thermometer, and a stirring rod, 1.1 l of acetonitrile, 100 ml of distilled water, and 120 ml of benzylamine (1.1 mol)
1) 4.6 ml (0.11 mol) of 90% formic acid is added, and the internal temperature is kept at 0 ° C. using a thermostat. 57 ml (0.50 mol) of a 40% aqueous glyoxal solution is placed in a dropping funnel and slowly dropped over 1 hour. After completion of the dropwise addition, the mixture is allowed to warm to room temperature with stirring. Then at room temperature 2
Stir for 0 hours. A white solid precipitates out of the yellow solution. The white solid is filtered off with suction and washed with 500 ml of acetonitrile previously cooled to 0.degree. At this time, the yellow liquid is washed away, and white needle-like crystals are obtained.
The white crystals obtained are recrystallized from 5 l of acetonitrile. 106 g of white needle crystals of crude hexabenzylhexaazaisowurtzitane are obtained (yield: about 90%). The purity by liquid chromatography was 96.2%.

[0040]

Comparative Example 1 16.58 g of crude hexabenzylhexaazaisowurtzitane (purity: 96.2%) and 1 l of acetonitrile were placed in a 2 l beaker, and kept at 90 ° C. in a thermostat while stirring with a stirrer to remove all the crude crystals. Allow to dissolve. After dissolution,
The temperature of the thermostat is lowered to 20 ° C., and the crystals are crystallized while stirring for 4 hours. Filter with suction and dry the crystals to obtain white crystals. The obtained white crystals had a yield of 15.18 g and a purity of 97.2%.

[0041]

EXAMPLE 1 3.9 g of crude hexabenzylhexaazaisowurtzitane (purity: 96.2%) and 1 liter of acetonitrile were placed in a 2 liter beaker, and stirred in a thermostat while stirring with a stirrer.
Keep at 0 ° C. to dissolve all crude crystals. After dissolution, the temperature of the thermostat is lowered to 20 ° C., and the crystals are crystallized while stirring for 4 hours. Filter with suction and dry the crystals to obtain white crystals. The obtained white crystals had a yield of 2.8 g and a purity of 100%.
Met.

[0042]

Example 2 50 g of crude hexabenzylhexaazaisowurtzitanium (purity 96.2%) and 1 l of ethyl acetate were placed in a 2 l beaker, and the mixture was kept at 60 ° C. in a thermostat while stirring with a stirrer to dissolve all the crude crystals. Let it. After melting, add 1
The temperature is lowered to 5 ° C., and the crystals are crystallized while stirring for 4 hours. Filter with suction and dry the crystals to obtain white crystals. The obtained white crystals had a yield of 23.3 g and a purity of 100%.

[0043]

Example 3 25 g of crude hexabenzylhexaazaisowurtzitane (purity 96.2%), 500 ml of ethyl acetate and 500 ml of ethanol were placed in a 2 l beaker, and the mixture was kept at 60 ° C. in a thermostat while stirring with a stirrer. Is completely dissolved. After dissolution, the temperature of the thermostat is lowered to 15 ° C., and the crystals are crystallized while stirring for 4 hours. Filter with suction and dry the crystals to obtain white crystals. The obtained white crystals had a yield of 20.
0 g and 100% purity. <Production example of tetraacetyldibenzylhexaazaisosoul titanium>

[0044]

Comparative Example 2 In a 100 ml autoclave, hexabenzylhexaazaisowurtzitane prepared in Comparative Example 1 was used.
1 g, 10% Pd-C (a catalyst in which Pd is supported on activated carbon in a divalent state) 3.15 g, acetic anhydride 1.84 g, N,
Add 30 ml of N-dimethylacetamide and cover the autoclave. After purging the autoclave with nitrogen,
It is replaced with hydrogen and adjusted so that the hydrogen pressure becomes 1.1 kgf / cm ² . Stirring is started at a stirring speed of 700 rpm or more, and heating is started so that the reaction temperature becomes 60 ° C.
During the reaction, the internal pressure of the autoclave is 1.1 kgf / cm ²
Replenish hydrogen continuously so that it is maintained at. The reaction was stopped after a reaction time of 4 hours, the reaction solution was taken out, and the catalyst was separated by filtration. The yield of tetraacetyldibenzylhexaazaisowurtzitane was 10.5%.

[0045]

Example 4 The same operation as in Comparative Production Example was performed except that the hexabenzylhexaazaisowurtzitanium obtained in Example 3 was used. The yield of tetraacetyldibenzylhexaazaisowurtzitanium was 55%, and the yield of pentaacetylbenzylhexaazaisowurtzitanium was 9%.

[0046]

According to the method for purifying hexabenzylhexaazaisowurtzitane of the present invention, high-purity hexabenzylhexaazaisowurtzitanium can be obtained, and by using these, hexaazaisowurtzitane having an acyl group can be obtained. Can be industrially advantageously carried out in the presence of an acylating agent for the production of

[Brief description of the drawings]

FIG. 1 is a diagram showing an example of analysis by liquid chromatography shown in the present invention.

 ────────────────────────────────────────────────── ─── Continuing on the front page (72) Inventor Tamotsu Kodama 1 at 2 Samejima, Fuji City, Shizuoka Prefecture Asahi Kasei Corporation

Claims (8)

[Claims] 1. A hexaazaisowurtzitane characterized by removing and purifying by-product components from crude hexabenzylhexaazaisowurtzitanium represented by the following general formula (1) synthesized from glyoxal and benzylamine. A method for producing a derivative. WB ₆ (1) [wherein, B represents a benzyl group, and W represents a hexaazaisowurtzitanium residue represented by the following formula (3). ] 2. The method for producing a hexaazaisowurtzitane derivative according to claim 1, wherein the by-product component is a component other than hexabenzylhexaazaisowurtzitane detected by liquid chromatography. 3. The method for producing a hexaazaisowurtzitanium derivative according to claim 1, wherein the by-product component is a by-product containing a by-product component detected by liquid chromatography. 4. The method according to claim 1, wherein the removal and purification is performed by a combination of at least one organic solvent having a solubility ratio P represented by the following formula (4) having a value of 0.1 to 20. A method for producing a hexaazaisowurtzitane derivative as described above. P = H / I (4) wherein H is the solubility (g / l) of hexabenzylhexaazaisowurtzitanium dissolved in the organic solvent, and I is the impurity detected by liquid chromatography analysis dissolved in the organic solvent. Indicates the solubility (g / l) of the component. ] 5. The method according to claim 1, wherein the organic solvent is an organic solvent composed of at least one selected from aromatic hydrocarbons, ethers, nitriles, amides, esters, and alcohols. A method for producing the hexaazaisowurtzitane derivative according to claim 4. 6. The method according to claim 4, wherein the organic solvent is a combination of an organic solvent containing ethyl acetate and ethyl alcohol. 7. The process for producing a hexaazaisowurtzitane derivative according to claim 4, wherein the organic solvent is used in a concentration that does not exceed the solubility of the by-product component in the organic solvent at the crystallization temperature. Method. 8. An acyl group represented by the following general formula (2), wherein the hexabenzylhexaazaisowurtzitanium according to claim 1 is subjected to reductive dearylmethylation in the presence of an acylating agent. A method for producing a hexaazaisoulitanium derivative. WA _n B _m H _(6-nm) (2) [wherein, n is an integer of 4 to 6, m is an integer of 0 to 2, A is an acyl group having 1 to 10 carbon atoms, B is a benzyl group, H Represents a hydrogen atom, and W represents a hexaazaisowurtzitanium residue represented by the following formula (3). ]