JPH10291989A - Production of hexaazaisowurtzitane having acyl group - Google Patents

Abstract

PROBLEM TO BE SOLVED: To profitably obtain the subject compound useful for enhancing the performance of gunpowder, etc., by subjecting hexaazalsowurtzitane to a reductive arylmethyl-removing reaction in the presence of an acylating agent and subsequently subjecting the product to a reductive arylmethylatin reaction in the presence of an acylating agent. SOLUTION: This method for producing hexaazaiowurtzitane having acyl groups comprises subjecting a compound of the formula: WB6 s hexavalent hexaazaiowurtziane group of the formula; B is a 7-21C arylmethyl group) (e.g. hexabenzylhexaazaisowurtzitane) in the presence of an acylating agent (e.g. acetic anhydride) and 10% Pd-C catalyst and subsequently subjecting the synthesized compound of the formula: WA2 B4 (A is a 1-10C acyl group) (e.g. diacetyltetrabenzylhexaazaisowurtzitane) to a reductive arylmethylation reaction in the presence of an acylating agent, thereby profitably obtaining the objective hexaazaisowurtzitane of the formula: WAn B(6-n) [(n) is an integer of 4-6] used as a nitration precursor for hexanitrohexaazaisowurtzitane useful for enhancing the performance of gunpowder, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a hexaazaisowurtzitane having an acyl group, which is a nitrating precursor of hexanitrohexaazaisowurtzitane used for improving the performance of conventional explosive compositions. The present invention relates to a method for producing derivatives.

[0002]

2. Description of the Related Art As a method for producing hexaazaisowurtzitane having an acyl group, hexakis (arylmethyl) hexaazaisowurtzitane is subjected to reductive dearylmethylation in the presence of an acylating agent to give tetraacylbis (arylmethyl). ) An acyl group such as hexaazaisowurtzitane, pentaacylarylmethylhexaazaisowurtzitane, hexaacylhexaazaisowurtzitane, tetraacyldialkylhexaazaisowurtzitanium and an arylmethyl group, an alkyl group, a hydrogen atom, etc. There is known a method for producing hexaazaisowurtzitane derivatives having
etrahedronVol. 51, No16, 471
1-4722 (1995), PCT-JP96-001
89). In the production methods described in these documents and patents, hexakis (arylmethyl) hexaazaisowurtzitane is directly derived into tetraacylbis (arylmethyl) hexaazaisowurtzitane.

Hexakis (arylmethyl) hexaazaisowurtzitane is unstable to acids and heat, and in order to dissolve the product tetraacylbis (arylmethyl) hexaazaisowurtzitanium in a high concentration, High temperature conditions must be employed. That is, in order to allow the reaction to proceed while dissolving hexakis (arylmethyl) hexaazaisowurtzitanium in a solvent under a high concentration condition,
It is necessary to carry out under high temperature conditions in which the decomposition reaction of hexakis (arylmethyl) hexaazaisowurtzitanium is activated, which causes skeletal decomposition.

The solvents used in these documents and patents include carboxylic anhydrides such as acetic anhydride, carboxylic acids such as acetic acid, aromatic compounds such as benzene, toluene and xylene, and ethers such as tetrahydrofuran and dioxane. Compounds and alcohol compounds such as methanol and ethanol are used. In these solvents, an acidic proton produced as a by-product after acylation of the NH group with an acylating agent increases the acidity of the solution, and the proton-produced hexaazide containing many arylmethyl groups in the initial stage of the reaction, which is liable to cause skeletal decomposition by protons. It is easy to induce skeletal decomposition of soul titanium derivatives.

[0005]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a hexaazaisowurtzitanium derivative having an acyl group by subjecting hexakis (arylmethyl) hexaazaisowurtitanium to reductive dearylmethylation in the presence of an acylating agent. An object of the present invention is to provide a method for producing a hexaazaisowurtzitane derivative having an acyl group in a high yield by changing the acidity and reaction temperature of a solvent to suppress skeletal decomposition.

[0006]

Means for Solving the Problems The present inventors have developed a heat-labile hexakis (arylmethyl) hexaazaisowurtzitane at a low temperature and a heat-stable diacyltetrakis (arylmethyl) hexaazide. Conversion to soul-titanium and subsequent reaction under relatively high temperature conditions succeeded in synthesizing hexaazaisoulitanium having an acyl group in high yield, and using a compound having an amide group as a reaction solvent The present invention succeeded in producing hexaazaisowurtzitane having an acyl group at a high yield, and completed the present invention.

That is, the present invention relates to a process for reducing a hexakis (arylmethyl) hexaazaisowurtzitane (WB ₆ ) in the presence of an acylating agent to give a diacyl as shown in the following reaction formula (1). Synthesis of tetrakis (arylmethyl) hexaazaisowurtzitane (WA ₂ B ₄ ) [Step 1], and further reductive arylmethylation in the presence of an acylating agent to synthesize WA _n B _(6-n) [ Step 2] is to provide a method for producing hexaazaisowurtane having an acyl group. [In the formula, n is an integer of 4 to 6, B is an arylmethyl group having 7 to 21 carbon atoms, A is an acyl group having 1 to 10 carbon atoms, H is a hydrogen atom, and W is represented by the following formula (2). And represents a hexavalent aza soulitol titanium residue. ]

[0008]

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As the solvent used in the reaction in step 1 of the reaction formula (1), any solvent may be used as long as it dissolves WB ₆ and does not adversely affect the reaction. It is preferable to use a compound having an amide group having a property. More preferably, N, N-dimethylacetamide, N, N-dimethylformamide,
1,3-dimethyl-2-imidazolidone, N-methyl-
2-pyrrolidone, N, N-diethylnipecotamide and the like. Most preferably, N, N-dimethylacetamide and N, N-dimethylformamide are mentioned. These solvents having an amide group may be used alone or in combination of two or more. WB of reaction of reaction formula (1)
The concentration of ₆ is usually expressed as a weight ratio to the solvent, and is usually 0.1.
001 to 1, preferably 0.005 to 0.3, and more preferably 0.01 to 0.2.

As the reducing agent used in the reaction of Step 1 of the reaction formula (1), hydrogen and formic acid are usually used. Preferably, hydrogen is used. The amount of the reducing agent used is
0.1 to 10,000, preferably 0.67 to 1000, expressed as a molar ratio of WB ₆ to arylmethyl group,
More preferably, it is used in the range of 2 to 50. When hydrogen is used as the reducing agent, it is used in the range of 0.01 to 100, preferably 0.1 to 30, and more preferably 0.1 to 15 kgf / cm ² in terms of the partial pressure of hydrogen. You. In addition to hydrogen, an inert gas such as nitrogen, argon, and helium may be present.

As the reduction catalyst used in the reaction of step 1 of the reaction formula (1), any catalyst can be used as long as it can reductively remove the arylmethyl group of WB _6. A metal belonging to the group or a derivative thereof is used, and preferably Pd (OAc) ₂ , P
dCl ₂ , Pd (NO ₃ ) ₂ , PdO, Pd (O
H) ₂ , Pd compounds such as Pd ₃ Pb ₁ and Pd ₃ Te ₁ , Pd alloys and Pd metals; Ru compounds such as RuCl ₃ , Ru alloys and Ru metals and the like are used, and more preferably Pd (OAc) ₂ And Pd such as PdCl ₂
Compounds, Pd alloys and Pd metals are used.

These catalysts may be used as they are, or may be activated carbon, silica, alumina, silica-alumina,
It can be used by being supported on various carriers such as zeolite, activated clay, zirconia, and titania. Before the reaction, the catalyst may be subjected to a reduction treatment. When the catalyst is used by being supported on a carrier, these carriers may be subjected to a treatment such as silylation or acylation to deactivate the surface acid sites or to increase the surface acid sites. Alternatively, the acidity of the surface of the carrier can be changed by adsorbing an alkaline substance such as NaOH. Among these catalysts, Pd ²⁺ supported on activated carbon and subjected to a reduction treatment to form Pd—C has a very high activity, and is therefore most preferable as the catalyst of the present invention.
When a heterogeneous reduction catalyst is used, it may be used as a fixed bed or as a fluidized bed.

The acylating agent used in the reaction of step 1 of the reaction formula (1) can be any one which can acylate a secondary amine to form an N-acyl bond. Carboxylic anhydrides such as acetic anhydride, propionic anhydride, formic anhydride, butyric anhydride, and acetic acid-formic acid mixed acid anhydride; N-acetoxysuccinimide, N-propionyloxysuccinimide, N- (2-phenylacetoxy) ) N-hydroxysuccinimide carboxylic acid esters such as succinimide; and acylimidazoles such as acetylimidazole and propionylimidazole. Of these acylating agents, carboxylic anhydrides such as acetic anhydride, propionic anhydride and acetic acid-formic acid mixed acid anhydride are preferably used. More preferably, it is acetic anhydride.

The amount of the acylating agent, the reactivity, also differ depending on the reaction method, expressed by a molar ratio to the arylmethyl groups of WB _6, usually, from 0.67 to 100, preferably 0.67 to 10, more preferably 0.67 to
3 is used. The reaction temperature in step 1 of the reaction formula (1) is in the range of 20 to 60 ° C. This reaction is 2
By performing the reaction at a relatively low temperature of 0 to 60 ° C., even if WB ₆ remains in the solvent for a long time, the skeleton decomposition can be relatively suppressed, so that the reaction is preferably performed at a low temperature. As the solvent used in the reaction of Step 2 of the reaction formula (1), any solvent may be used as long as it dissolves WA ₂ B ₄ and does not adversely affect the reaction. It is preferable to use a compound having an amide group. More preferably, N, N-dimethylacetamide, N, N-dimethylformamide, 1,3-dimethyl-2-imidazolidone, N-methyl-2-pyrrolidone, N, N-diethylnipecotamide and the like can be mentioned. Most preferably, N,
N-dimethylacetamide and N, N-dimethylformamide are exemplified. Solvents having these amide groups are
You may use individually or in mixture of 2 or more types.

WA ₂ of the reaction in step 2 of reaction formula (1)
The concentration of B ₄ is usually expressed as a weight ratio to the solvent, and is usually 0.1%.
001 to 1, preferably 0.005 to 0.3, and more preferably 0.01 to 0.2. The reducing agent used in the reaction of Step 2 of the reaction formula (1) is usually
Hydrogen and formic acid are used. Preferably, hydrogen is used. The amount of the reducing agent used is 0.1 to 1000 in terms of a molar ratio to the arylmethyl group of WA ₂ B _4.
0, preferably 0.50 to 1000, and more preferably 2 to 50. When hydrogen is used as the reducing agent, the partial pressure of hydrogen is expressed as 0.01 to 10
0, preferably 0.1 to 30, more preferably
It is used in a range of 0.1 to 15 kgf / cm ² . In addition to hydrogen, an inert gas such as nitrogen, argon, and helium may be present.

As the reduction catalyst used in the reaction of step 2 of the reaction formula (1), any catalyst can be used as long as it can reductively remove the arylmethyl group of WA ₂ B _4. , A metal belonging to the platinum group, or
Its derivative is used, and preferably, Pd (OA
c) ₂ , PdCl ₂ , Pd (NO ₃ ) ₂ , PdO, Pd
Pd compounds such as (OH) ₂ , Pd ₃ Pb ₁ and Pd ₃ Te ₁ , Pd alloys and Pd metals; Ru such as RuCl ₃
Compounds, Ru alloys and Ru metals are used, and more preferably, Pd such as Pd (OAc) ₂ and PdCl ₂
d compounds, Pd alloys and Pd metals are used.

These catalysts may be used as they are, or may be activated carbon, silica, alumina, silica-alumina,
It can be used by being supported on various carriers such as zeolite, activated clay, zirconia, and titania. Before the reaction, the catalyst may be subjected to a reduction treatment. When the catalyst is used by being supported on a carrier, these carriers may be subjected to a treatment such as silylation or acylation to deactivate the surface acid sites or to increase the surface acid sites. Alternatively, the acidity of the surface of the carrier can be changed by adsorbing an alkaline substance such as NaOH. Among these catalysts, Pd ²⁺ supported on activated carbon and subjected to a reduction treatment to form Pd—C has a very high activity, and is therefore most preferable as the catalyst of the present invention.
When a heterogeneous reduction catalyst is used, it may be used as a fixed bed or as a fluidized bed.

As the acylating agent used in the reaction of step 2 of the reaction formula (1), any one can be used as long as it can acylate a secondary amine to form an N-acyl bond. Carboxylic anhydrides such as acetic anhydride, propionic anhydride, formic anhydride, butyric anhydride, and acetic acid-formic acid mixed acid anhydride; N-acetoxysuccinimide, N-propionyloxysuccinimide, N- (2-phenylacetoxy) ) N-hydroxysuccinimide carboxylic acid esters such as succinimide; and acylimidazoles such as acetylimidazole and propionylimidazole. Of these acylating agents, carboxylic anhydrides such as acetic anhydride, propionic anhydride and acetic acid-formic acid mixed acid anhydride are preferably used. More preferably, it is acetic anhydride.

The amount of the acylating agent varies depending on its reactivity and reaction method, but is usually expressed as a molar ratio to the arylmethyl group of WA ₂ B ₄ , usually 0.50 to 100,
Preferably 0.50 to 10, more preferably 0.50
Used in the range of ~ 3. The reaction temperature in Step 2 of the reaction formula (1) is in the range of 40 to 165 ° C. WA ₂ B ₄
Is superior to WB ₆ in thermal stability, so that the reaction in step 2 can employ relatively high temperature conditions. This allows the reaction to proceed under conditions in which the product WA ₄ B ₂ is dissolved at a high concentration. After removing the catalyst from the reaction solution of Step 1 of Reaction Formula (1), Step 2
It is a very preferable method to add a catalyst for the reaction and allow the reaction to proceed as it is.

In the present invention, as shown in the following reaction formula (3), WB ₆ is subjected to reductive dearylmethylation in the presence of an acylating agent to synthesize WA ₂ B ₄ [Step 1]. Is further subjected to reductive arylmethylation in the presence of an acylating agent to give W
Hex with A _n B _(6-n) to synthesize [Step 2], which was further reductive de-arylmethyl by synthesizing _{WA n H (6-n)} [ Step 3] acyl group, wherein the The present invention provides a method for producing Azai Soul Tan. [In the formula, n is an integer of 4 to 6, B is an arylmethyl group having 7 to 21 carbon atoms, A is an acyl group having 1 to 10 carbon atoms, H is a hydrogen atom, and W is represented by the following formula (2). And represents a hexavalent aza soulitol titanium residue. ]

[0021]

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The reaction conditions and the like in step 1 of the reaction formula (3) can be the same as the reaction conditions and the like in step 1 of the reaction formula (1). As the reaction conditions and the like in Step 2 of Reaction Formula (3), the same conditions as those in Step 2 of Reaction Formula (1) can be used. It is a very preferable method to remove the catalyst from the reaction solution in step 1 of the reaction formula (3), add the catalyst for step 2 and allow the reaction to proceed as it is. As the reducing agent used in the reaction in Step 3 of the reaction formula (3), hydrogen and formic acid are usually used. Preferably, hydrogen is used.

The amount of the reducing agent used is WA _n B
Expressed in a molar ratio to the arylmethyl group of _(6-n) ,
1.0 to 1000, more preferably 1.0 to 100
Used in the range. When hydrogen is used as the reducing agent, it is expressed as a partial pressure of hydrogen, which is 0.01 to 100, preferably 0.1 to 30, and more preferably 0.1 to 20.
It is used in the range of kgf / cm ² . In addition to hydrogen, an inert gas such as nitrogen, argon, and helium may be present.

The solvent used for the reaction in step 3 of the reaction formula (1) can be any mixture of a solvent having an amide group and water, as long as it does not adversely affect the reaction. Examples of the solvent having an amide group include N, N-dimethylacetamide, N, N-dimethylformamide, 1,3-dimethyl-2-imidazolidone, N-methyl-2-pyrrolidone, and N, N-diethylnipecotamide. And the like. Preferably, N, N-dimethylacetamide and N, N-dimethylformamide are mentioned. These solvents having an amide group may be used alone or in combination of two or more. The mixing ratio of the solvent having an amide group and water is represented by a weight ratio of water to the solvent having an amide group, and is usually 0.1 to 10, preferably,
The range is from 0.2 to 5, more preferably from 0.5 to 2. As the solvent, in addition to the solvent having an amide group and water, a carboxylic acid such as formic acid, acetic acid, or propionic acid may be contained. Expressed as a weight ratio with respect to 0.001 to 1, preferably 0.01 to 0.8,
More preferably, it is in the range of 0.1 to 0.5. A preferred carboxylic acid as the carboxylic acid contained in the solvent is acetic acid.

The reaction conditions such as the type of the reduction catalyst and the reaction temperature used in the reaction in step 3 of the reaction formula (3) can be the same as those in the reaction in step 2 of the reaction formula (1). The feature of the reaction represented by step 3 of the reaction formula (3) is that a solvent having an amide group and water are mixed and used as a reaction solvent. The role and effect of these two solvents will be briefly described below.

The solvent having an amide group is WA _n B _(6-n)
Can be used in combination with water since it is a solvent having a high affinity for water that dissolves the product WA _n H _(6-n) . Thus, when a solvent obtained by mixing a solvent having an amide group and water is used in the reaction of Step 3 of the reaction formula (3), the reaction proceeds while the raw materials and products are dissolved in the solvent at a high concentration. The catalyst activity can be prevented from lowering on the catalyst surface after the product is deposited, and the reaction can proceed with high activity. At the same time, it facilitates the separation of the heterogeneous catalyst and product.

When a mixed solvent of water and a solvent having an amide group is used, a component having a lower boiling point than water and a solvent having an amide group in the reaction solution after the reaction is removed by distillation or distillation under reduced pressure, and the mixture is placed in a kettle. product and solvent with the remaining amide groups WA _n H _(6-n) is cooled to a primary solution WA _n H
_(6-n) can be crystallized and removed by filtration or centrifugation. In this crystallization method, a distillation operation is performed on the reaction solution,
Since high purity WA _n H _(6-n) can be obtained only by performing a cooling operation and a separation operation (filtration or centrifugation),
This is the preferred method.

After completion of the reaction in step 1 of the reaction formula (3),
The catalyst for Step 1 is removed, the catalyst for Step 2 is added, and Step 2 is performed.
The method of removing the catalyst for the step 3, adding the catalyst for the step 3 and water, and carrying out the reaction of the step 3 is an industrially advantageous method because the operation of isolating individual intermediates can be omitted. Further, since there is no loss of the intermediate during the isolation operation, W
This is a method for producing WA _n H _(6-n) from B ₆ in high yield. The amount of water added between the reaction in step 2 and the reaction in step 3 of the reaction formula (3) is the mixing ratio of the solvent having an amide group and the water described in the solvent component in step 3 of the reaction formula (3). Quantity.

Furthermore, the present invention provides the following reaction formula (4)
WB ₆ is reductively dearylmethylated in the presence of an acylating agent to synthesize WA ₂ B ₄ [Step 1], which is further reductively methylated in the presence of an acylating agent to obtain WA _n. It is intended to provide a method for producing hexaazaisowurtane having an acyl group, which is characterized by synthesizing H _(6-n) [Step 2 ′]. [In the formula, n is an integer of 4 to 6, B is an arylmethyl group having 7 to 21 carbon atoms, A is an acyl group having 1 to 10 carbon atoms, H is a hydrogen atom, and W is represented by the following formula (2). And represents a hexavalent aza soulitol titanium residue. ]

[0030]

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The reaction conditions and the like in step 1 of reaction formula (4) can be the same as those in step 1 of reaction formula (1). As the reaction conditions and the like in Step 2 ′ of Reaction Formula (4), the same conditions as those in Step 2 of Reaction Formula (1) can be used. It is also possible to use a mixed solvent containing water as one component as the reaction solvent in step 2 ′. The time for adding water to the reaction in step 2 'may be any of 1) before the reaction, 2) during the reaction, and 3) after the reaction in step 2'.

The amount of water to be added is usually 0.1 to 10, preferably 0.2 to 5, more preferably 0.5 to 2, expressed as a weight ratio of water to the solvent having an amide group.
Range. As the solvent, in addition to the solvent having an amide group and water, a carboxylic acid such as formic acid, acetic acid, or propionic acid may be contained. 0.001 to 1, preferably 0.01 to
0.8, more preferably in the range of 0.1 to 0.5. A preferred carboxylic acid as the carboxylic acid contained in the solvent is acetic acid.

By using a mixed solvent containing water as one component as a solvent in step 2 ′ of the reaction formula (4), tetraacylhexaazaisowurtzitanium, one of the products, becomes soluble in the solvent. This is a preferred method because the separation from the catalyst becomes easy. Further, tetraacylhexaazaisowurtzitane has low solubility in a solvent having an amide group, and can be crystallized by distilling water from the reaction solution. During this crystallization, other by-products remain soluble in the solvent having an amide group, so that the tetraacylhexaazaisowurtzitane after crystallization is of high purity. After the completion of the reaction in Step 1 of Reaction Formula (4), the catalyst for Step 1 is removed, and Step 2 ′
The method for adding the catalyst for the process and performing step 2 ′ is described in WA
Since isolation procedure ₂ B ₄ can be omitted, it is industrially advantageous method. In addition, this method is capable of producing WA _n H _(6-n) from WB ₆ in high yield because the loss of the intermediate during the isolation operation is eliminated.

The structures of the raw material WB ₆ and the products WA _n B _(6-n) and WA _n H _(6-n) used in the present invention will be described below. The arylmethyl group represented by B in the formulas (1), (3) and (4) represents a methyl group substituted by an aryl group (Ar), and usually has 7 to 21 carbon atoms.
Is used. A typical structure of the arylmethyl group B is a substituent represented by the following general formula (5). —CH ₂ Ar (5) [Ar represents an aromatic group having 6 to 20 carbon atoms. The number of carbon atoms in Ar is usually from 6 to 20, preferably from 6 to
10, particularly preferably 6. Ar is, for example, phenyl; tolyl (o-, m-, p-substituted);
Various alkylphenyl groups such as ethylphenyl (o-, m-, p-substituted) and xylyl; methoxyphenyl (o-, m-, p-substituted), ethoxyphenyl (o
-, M-, p-substituted), butoxyphenyl (o-,
m-, p-substituted products), etc .; naphthyl group and various substituted naphthyl groups; and phenyl group and various alkoxyphenyl groups are preferably used. The _six arylmethyl groups in WB6 may be the same or different.

As the acyl group in formulas (1), (3) and (4), any acyl group having 1 to 10 carbon atoms can be used. Usually, formyl, acetyl, propionyl, butyryl, isobutyryl, valeryl, hexanoyl, 2-phenylacetyl and the like are used, preferably an acyl group having 1 to 5 carbon atoms, for example, formyl, acetyl, propionyl, butyryl, valeryl and the like are used. And more preferably an acyl group having 1 to 3 carbon atoms, for example, formyl, acetyl, propionyl and the like.

The hexaazaisowurtzitanium derivative represented by WA _n B _(6-n) in the formulas (1) and (3) has a plurality of isomers depending on the substitution position of the acyl group and the arylmethyl group. The WA _n B _(6-n) used in the production method of the present invention may have any of these structures. The following equations (6-1) to (6-6) and equation (7-
The isomers having the three-dimensional structures shown in 1) to (7-2) and their enantiomeric structures can be taken.

[0037]

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[0038]

Embedded image [In the formula, A represents the acyl group, B represents the arylmethyl group, and W represents the hexaazaisowurtzitanium residue. ]

Further, WA _n H in the equations (3) and (4)
_The hexaazaisowurtzitane derivative represented by _(6-n) is
A plurality of isomers can be obtained depending on the substitution position of the acyl group and the hydrogen atom, and WA _n H _(6-n) produced by the production method of the present invention may be any of these.
The specific structure is such that the arylmethyl group of the hexaazaisowurtzitane derivative represented by the formulas (6-1) to (6-6) and the formulas (7-1) to (7-2) is a hydrogen atom. The structure is replaced with

Next, the reactions represented by the reaction formulas (1), (3) and (4) will be briefly described. This reaction is
By reductive dearylmethylation of B ₆ in the presence of an acylating agent, 1) formation of an N—H bond by reductive elimination of an arylmethyl group and 2) formation of an N-acyl group by its acylation sequentially This is a reaction that is allowed to proceed. In addition, depending on the reaction conditions, N-
The formation of an alkyl group occurs as a side reaction. Equation (8) shows a reaction route estimated from a substance confirmed to be formed in this reaction.

[0041]

Embedded image [Wherein, B is an arylmethyl group having 7 to 21 carbon atoms, H is a hydrogen atom, A is an acyl group having 1 to 10 carbon atoms, R is an alkyl group having 1 to 10 carbon atoms, and W is a group represented by the formula (2). Represents the hexavalent hexaazaisowurtzitane residue shown. Therefore, the substance shown in the formula (8) may be included in the reaction products represented by the reaction formulas (1), (3), and (4) of the present invention.

[0042]

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. (Example 1) WB ₆ → WA ₂ B _{4 In a} 100 ml autoclave, 2.1 g of hexabenzylhexaazaisowurtzitanium and 10% of Pd-C (2% of Pd-C) were added.
3.15 g of a catalyst supported on activated carbon in a valence state and dried at a low temperature), 3.15 g, acetic anhydride 2.45 g, and N, N-dimethylacetamide 30 ml are put therein, and the autoclave is covered. After the inside of the autoclave is replaced with nitrogen, the inside of the autoclave is replaced with hydrogen, and the hydrogen pressure is adjusted to be 1.1 kgf / cm ² .

The stirring is started at a stirring speed of 700 rpm or more, and the temperature is raised so that the reaction temperature becomes 40 ° C. 40
After reacting at 1 ° C. for 1 hour, the reaction solution was sampled and analyzed by gas chromatography and high performance liquid chromatography. As a result, the yield of acetylpentabenzylhexaazaisowurtzitane was 8%, and the yield of diacetyltetrabenzylhexaazaisowurtzitane was 8%. It was confirmed that 65% of triacetyltribenzylhexaazaisowurtzitanium was produced at a yield of 8%.

Example 2 WA ₂ B ₄ → WA ₄ B ₂ + WA ₅ B ₁ (+ WA ₄ H ₂ +
WA ₅ H ₁₎ 100ml autoclave diacetyl tetrabenzyl hexamethylene A wood Seoul titanium 1.82 g, 10% Pd-
3.15 g of C, 0.92 g of acetic anhydride, and 30 ml of N, N-dimethylacetamide are added, and the autoclave is covered. After nitrogen substitution in the autoclave, hydrogen substitution,
The hydrogen pressure is adjusted to 2.0 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 130 ° C.
The reaction is carried out by continuously supplying hydrogen so that the hydrogen pressure at 130 ° C. becomes ² kgf / cm ² . After stirring at 130 ° C. for 2 hours, the reaction solution was sampled and analyzed by gas chromatography. As a result, the yield of tetraacetyldibenzylhexaazaisowurtzitanium was 60%, and the yield of pentaacetylbenzylhexaazaisowurtzitanium was 15%. It was confirmed that it was generated by. When the reaction solution was analyzed by high performance liquid chromatography, it was confirmed that tetraacetylhexaazaisowurtzitane was formed at a yield of 12% and pentaacetylhexaazaisowurtzitane at a yield of 9%. Was done.

Example 3 1.54 g of tetraacetyldibenzylhexaazaisowurtzitane in a 100 ml autoclave of WA ₄ B ₂ → WA ₄ H ₂ was added to 10% Pd-
3.15 g of C, 30 m of N, N-dimethylacetamide
1) Add 30 ml of water and cover the autoclave. After the inside of the autoclave is replaced with nitrogen, the inside of the autoclave is replaced with hydrogen, and the hydrogen pressure is adjusted to 3.3 kgf / cm ² . 70
Stirring was started at a stirring speed of 0 rpm or more, and the reaction temperature was 1
Start raising the temperature to 30 ° C. During the stirring, hydrogen is continuously supplied so that the pressure in the autoclave becomes 3.3 kgf / cm ² . After stirring at 130 ° C. for 1 hour, the reaction solution was sampled and analyzed by high performance liquid chromatography. As a result, it was confirmed that tetraacetylhexaazaisowurtzitane was produced in a yield of 82%.

(Embodiment 4) WB ₆ → WA ₂ B ₄ → WA ₄ B ₂ + WA ₅ B ₁ → WA ₄
H ₂ + WA ₅ H ₁ 100ml autoclave the hexamethylene benzyl hexa A wood Seoul titanium 2.1g, 10% Pd-C3.15
g, 1.84 g of acetic anhydride and 30 ml of N, N-dimethylacetamide, and the inside of the autoclave was replaced with nitrogen and then replaced with hydrogen to adjust the hydrogen pressure to 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 40 ° C. After stirring at 40 ° C. for 1 hour (at this point, diacetyltetrabenzylhexaazaisowurtzitane is produced as a main product), the reaction solution is taken out, the catalyst is filtered off, and 10% Pd—C 3 is added to the filtrate. .15 g is added and the slurry is placed in a 100 ml autoclave. After the autoclave was covered, the inside of the autoclave was replaced with nitrogen and then with hydrogen, and the inside of the autoclave became 2.0 kgf / c.
Adjust to ² m2.

The stirring is started at a stirring speed of 700 rpm or more, and the temperature is raised so that the reaction temperature becomes 130 ° C.
During the reaction, hydrogen is continuously supplied at 130 ° C. so as to maintain the hydrogen pressure or 2.0 kgf / cm ² . After stirring at 130 ° C. for 1 hour (at this point, tetraacetyldibenzylhexaazaisowurtzitane is formed as a main product), the reaction solution is taken out, the catalyst is filtered off, and 1% is added to the filtrate.
Add 3.15 g of 0% Pd-C, 30 ml of water, put it in an autoclave and cover it. After the inside of the autoclave was replaced with nitrogen, the inside of the autoclave was replaced with hydrogen.
/ Cm ² .

The stirring is started at a stirring speed of 700 rpm or more, and the temperature is raised so that the reaction temperature becomes 130 ° C.
During the reaction, the pressure in the autoclave is 3.3 kgf / cm
Continuously replenish hydrogen as maintained at ² . 130
After stirring at 1 ° C. for 1 hour, the reaction solution was sampled and analyzed by high performance liquid chromatography. As a result, tetraacetylhexaazaisowurtzitane was formed at a yield of 60% and pentaacetylhexaazaisowurtzitane at a yield of 15%. It was confirmed that.

Example 5 WB ₆ → WA ₂ B ₄ → WA ₄ H ₂ + WA ₅ H ₁ 2.1 g of hexabenzylhexaazaisowurtzitane in a 100 ml autoclave, 10% Pd-C 3.15
g, 1.84 g of acetic anhydride and 30 ml of N, N-dimethylacetamide, and the inside of the autoclave was replaced with nitrogen and then replaced with hydrogen to adjust the hydrogen pressure to 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 40 ° C. After stirring at 40 ° C. for 1 hour (at this point, diacetyltetrabenzylhexaazaisowurtzitane is produced as a main product), the reaction solution is taken out, the catalyst is filtered off, and 10% Pd-C is added to the filtrate. 3.15 g of (a catalyst in which Pd is supported on activated carbon in a divalent state and dried at a low temperature) is added, and the slurry is placed in a 100 ml autoclave. After closing the autoclave, the inside of the autoclave is replaced with nitrogen and then replaced with hydrogen, and the inside of the autoclave is adjusted to 1.1 kgf / cm ² .

The stirring is started at a stirring speed of 700 rpm or more, and the temperature is raised so that the reaction temperature becomes 60 ° C. During the reaction, hydrogen is continuously supplied at 60 ° C. so as to maintain the hydrogen pressure or 1.1 kgf / cm ² . After stirring at 60 ° C. for 3 hours, the reaction solution was sampled and analyzed by high performance liquid chromatography. As a result, it was found that tetraacetylhexaazaisowurtzitane was formed at a yield of 63% and pentaacetylhexaazaisowurtzitane at a yield of 18%. It was confirmed that.

Example 6 Thermal Stability of WB ₆ in Reaction Solution 2.1 g of hexabenzylhexaazaisowurtzitane, 4.1 ml of acetic anhydride, N, N
-30 ml of dimethylacetamide, 40, 60,
The remaining amount of hexabenzylhexaazaisowurtzitane (hereinafter abbreviated as 6B) was analyzed by high performance liquid chromatography when exposed to each temperature of 80, 110 and 130 ° C. for 1 hour. As a result, the residual amount of 6B at each temperature was 100
%, 98% at 60 ° C, 92% at 80 ° C, 0% at 110 ° C,
It was 0% at 130 ° C. These results indicate that 6B decomposes in DMAc in the presence of reactive acetic anhydride in a temperature atmosphere exceeding 40 ° C. That is, it is understood that in this reaction, the reaction using 6B as a starting material is preferably performed at 40 ° C. or lower.

Example 7 Thermal Stability of WA ₂ B _{4 in} a Reaction Solution The procedure of Example 6 was repeated except that hexabenzylhexaazaisowurtzitane was changed to diacetylhexaazaisowurtzitane. As a result of examining the thermal stability of tetrabenzylhexaazaisowurtzitanium, decomposition of diacetyltetrabenzylhexaazaisowurtzitanium could not be confirmed in the range of 40 to 130 ° C. That is, diacetyltetrabenzylhexaazaisowurtzitane is 130
It was found that the compound was stably present at a temperature of not more than ° C.

Example 8 Thermal stability of WA ₄ B _{2 in} a reaction solution Same as Example 6, except that hexabenzylhexaazaisowurtzitane was changed to tetraacetyldibenzylhexaazaisowurtzitane. As a result of examining the thermal stability of tetraacetyldibenzylhexaazaisowurtzitanium by the method,
No decomposition of tetraacetyldibenzylhexaazaisowurtzitanium was confirmed in the range of 40 to 130 ° C. That is, it was found that tetraacetyldibenzylhexaazaisowurtzitanium was thermally stable up to 130 ° C.

[0055]

Industrial Applicability According to the series of production methods of the present invention using a compound having an amide group as a solvent, an acyl group-containing hexaazaisowurtzitanium derivative can be industrially advantageously produced in high yield.

 ────────────────────────────────────────────────── ─── Continuing on the front page (72) Inventor Nobuto Miyake 3-13-1 Utsudori, Kurashiki-shi, Okayama Prefecture Asahi Kasei Corporation

Claims (7)

[Claims] Claims: 1. As represented by the following reaction formula (1),
Reductive dearylmethylation of B ₆ in the presence of an acylating agent
To synthesize A ₂ B ₄ [Step 1], which was further synthesizing reductive arylmethyl and WA _n B _(6-n) in the presence of an acylating agent having the Step 2] acyl group, wherein the A method for producing hexaazaisoultan. [In the formula, n is an integer of 4 to 6, B is an arylmethyl group having 7 to 21 carbon atoms, A is an acyl group having 1 to 10 carbon atoms, H is a hydrogen atom, and W is represented by the following formula (2). And represents a hexavalent aza soulitol titanium residue. ] 2. As represented by the following reaction formula (3), W
Reductive dearylmethylation of B ₆ in the presence of an acylating agent
A ₂ B ₄ was synthesized [Step 1], which was further subjected to reductive arylmethylation in the presence of an acylating agent to synthesize WA _n B _(6-n) [Step 2], which was further subjected to reductive dearylmethylation. And synthesizing WA _n H _(6-n) [Step 3]. A method for producing hexaazaisowurtane having an acyl group. [In the formula, n is an integer of 4 to 6, B is an arylmethyl group having 7 to 21 carbon atoms, A is an acyl group having 1 to 10 carbon atoms, H is a hydrogen atom, and W is represented by the following formula (2). And represents a hexavalent aza soulitol titanium residue. ] 3. As represented by the following reaction formula (4), W
Reductive dearylmethylation of B ₆ in the presence of an acylating agent
A ₂ B ₄ is synthesized [Step 1], and further subjected to reductive arylmethyl in the presence of an acylating agent to synthesize WA _n H _(6-n) [Step 2 ′]. A method for producing hexaazaisoultan having the same. [In the formula, n is an integer of 4 to 6, B is an arylmethyl group having 7 to 21 carbon atoms, A is an acyl group having 1 to 10 carbon atoms, H is a hydrogen atom, and W is represented by the following formula (2). And represents a hexavalent aza soulitol titanium residue. ] 4. The reaction for synthesizing WA ₂ B ₄ [Step 1] is carried out at 10 to 60 ° C.
3. The method for producing hexaazaisowurtane having an acyl group according to any one of 3. 5. The solvent used for the reaction [Step 1] for synthesizing WA ₂ B ₄ and the solvent used for the reaction [Step 2] for synthesizing WA _n B _(6-n) are compounds having an amide group. The method for producing hexaazaisowurtane having an acyl group according to claim 1, wherein 6. The solvent used for the reaction [Step 1] for synthesizing WA ₂ B ₄ and the solvent used for the reaction [Step 2] for synthesizing WA _n B _(6-n) are compounds having an amide group, 3. The acyl aza-isomer having an acyl group according to claim 2, wherein the solvent used in the reaction for synthesizing WA _n H _(6-n) [Step 3] is a mixture of a compound having an amide group and water. Production method of tongue. 7. The solvent used in the reaction [Step 1] for synthesizing WA ₂ B ₄ is a compound having an amide group,
Hex with A _n H solvent used in _(6-n) a synthesizing reaction [step 2 '] is an acyl group of claim 3, wherein the compound is a solvent containing as one component having an amide group Asai soul tan manufacturing method.