JP2844125B2 - Hexaazaisoulitanium derivative and method for producing the same - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a hexaazaisowurtzitane derivative having an acyl group and a method for producing the same.

In the hexaazaisowurtzitane derivative having an acyl group of the present invention, an NA group (A: acyl group) or N-
Include H group, the N-A group and N-H groups can be converted by various nitration methods N-NO _2.

Therefore, the hexaazaisowurtzitane derivative having an acyl group of the present invention is useful as a precursor of a polynitrated hexaazaisowurtzitane derivative used as an explosive or an additive for explosives. In particular, the hexaazaisowurtzitane derivative having an acyl group of the present invention can be used for explosive product mechanical properties, detonation rate, detonation pressure, burning rate, pressure index,
It is useful as a precursor of a polynitrated hexaazaisowurtzitane derivative, which is useful as an additive for controlling explosive performance such as sensitivity and heat resistance. In addition, hexanitrohexaazaisowurtzitane (hereinafter referred to as "HNW") is regarded as a promising next-generation high explosive material, but the hexaazaisowurtzitane derivative of the present invention is useful as a precursor thereof. is there.

In addition, the hexaazaisowurtzitanium derivative of the present invention utilizes the reactivity of the N—A group (A: acyl group) and the N—H group contained in the substance to form a highly active compound in the main chain or side chain. It can be derived into highly polar polymers containing acyl groups in density. This highly polar polymer is useful as a highly hydrophilic polymer or a high dielectric constant polymer.

The hexaazaisowurtzitane derivative of the present invention can be used as a polyfunctional crosslinking agent by utilizing its reactivity.

Further, the hexaazaisowurtzitane derivative of the present invention can be used as it is as an additive such as a polymer modifier.

<Background Art> Compounds having a hexaazaisowurtzitane (hereinafter abbreviated as “W”) skeleton related to the present application include, in addition to HNW, (1) hexakis (arylmethyl) hexaazaisowurtzitane (Hereinafter abbreviated as "HBW") (2) Tetraacetyldibenzylhexaazaisowurtzitane (hereinafter abbreviated as "TADBW")] (3) Hexaazaisowurtzitane having a carbamyl group (hereinafter abbreviated as "HCW") [ JP-A-6-321962] is known.

It is known that HBW of (1) can be obtained by condensing glyoxal with various arylmethylamines. [J. Org. Chem., Vol. 55, 1459-1466 (1990)] Also, there is a report that TADBW of (2) is useful as a raw material for explosives [The Militarily Critical Technol.
ogies List, Offioe of the Under Secretary of
Defense for Acquisition, 12-22, October (199
2)], however, is not shown how or how it can be converted into gunpowder. Nothing is said about the manufacturing method of TADBW.

As for the characteristics of HNW, International
Symposium on Energetic Materials Technology
PROCEEDINGS, SEPTEMBER 24-27, 76-81 (1995); COM
BUSTION AND FLAME 87,145-151 (1991), etc., but no report on the production method.

Therefore, the present inventors, in order to find a method for producing a polynitrated hexaazaisosoultitanium derivative such as HNW, HBW
Attempts to nitrate W and TADBW under various nitration conditions failed to obtain a substantially sufficient amount of polynitrated hexaazaisowurtzitanium derivatives from HBW and TADBW. Furthermore, HBW and TADBW contain a benzyl group, and under nitration conditions, nitrated aromatics having a high affinity for various nitro compounds are produced as by-products. There is also a problem that it is difficult to separate and purify the derivative.

It is difficult to obtain HCW of (3) in high yield. The reason is that hydrochloric acid, which is a strong acid, is generated during the production of the substance,
It is considered to induce the decomposition of HBW as a raw material.

As described above, the compounds having a W skeleton of the above (1), (2) and (3) are all used as precursors for industrially and advantageously producing polynitronitrated hexaazaisowurtzitane derivatives having HNW or a similar structure. Is not suitable.

<Disclosure of the Invention> In order to establish an industrially advantageous production method of a polynitrated hexaazaisowurtzitane derivative, the present inventors have developed a structure of a precursor that can be easily converted to a polynitrated hexaazaisowurtzitane derivative. The search and the synthesis method were studied diligently.

As a result, the N-acyl group bond and N-
Hexaacylhexaazaisowurtzitanium derivatives containing only H bonds have been found to be useful as precursors of polynitrated hexaazaisowurtzitane derivatives, and furthermore, industrially advantageous high yield production of the precursors We found a method and completed the present invention.

Another object of the present invention is to develop a new type of functional material containing a high-polarity functional group such as an N-acyl group or an NH group at a high density.

That is, the present invention provides a hexaazaisowurtzitane derivative having an acyl group represented by the general formula (1) and a method for producing the same.

WA _n H _(6-n) (1) wherein n is an integer of 4 to 6, 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) It represents a hexavalent hexaazaisowurtzitane residue. ] The hexaazaisowurtzitane derivative having an acyl group of the present invention is represented by the general formula (1).

As the acyl group A in the present invention, any acyl group having 1 to 10 carbon atoms can be used, which is stable under the conditions of the reductive dearylmethyl reaction used in the present invention. It may have a substituent. Usually, as the acyl group A, acetyl, propionyl, butyryl, isobutyryl, valeryl, hexanoyl, 2-phenylacetyl and the like are used, and preferably, an acyl group having 2 to 5 carbon atoms, for example, acetyl, propionyl, butyryl, valeryl And more preferably 2 to 3 carbon atoms.
For example, acetyl, propionyl and the like are used. The n acyl groups of the formula (1) may be the same or different.

The hexaazaisowurtzitane derivative WA _n H _(6-n) having an acyl group represented by the formula (1) of the present invention may be an acyl group or a hydrogen atom depending on the number of n, even if n is the same. A plurality of isomers can be taken depending on the substitution position of

For example, a typical structure of the compound represented by WA ₄ H ₂ is a structure represented by the formula (3), but a structural isomer thereof may be used.

In the hexaazaisowurtzitane derivative WA _n H _(6-n) having an acyl group of the present invention, n is an integer of 4 to 6,
Preferably they are 4 and 6.

As one of preferred structures of the hexaazaisowurtzitane derivative having an acyl group of the present invention, a derivative in which n is 6 in the formula (1), that is, the following formula (4) WA ₆ (4) Represents an acyl group having 1 to 10 carbon atoms, and W represents a hexavalent hexaazaisowurtzitanium residue. Hexacylhexaazaisowurtzitane shown below. This compound is preferable because it has a simple structure and can be easily purified into a high-purity substance. The hexaacetyl compound can be purified by sublimation, making it easier to obtain high-purity WA from the reaction product.
There is also the advantage that ₆ can be obtained.

As a preferred structure, among the hexaazaisowurtzitanium derivatives represented by the formula (1), hexaacylhexaazaisowurtzitanium in which n is 4 is exemplified. Since this compound contains a highly reactive NH group, only this portion is preferable because it can be selectively reacted. For example, by selectively nitrating this NH group, a dinitrated hexaazaisowurtzitanium derivative can be easily obtained in high yield.

In the hexaazaisowurtzitane compound having an acyl group of the present invention, high-density> NA groups (A: acyl groups) and>
Contains N-H groups, these groups are all be transformed into> N-NO ₂ by various nitration methods.

Hereinafter, a synthesis example of the hexaazaisowurtzitane derivative represented by the formula (1) will be described.

The WA ₆ of the present invention can also be obtained by acylating WA _n H _(6-n) with an acylating agent as represented by the following reaction formula (5).

[In the formula, n represents an integer of 4 to 5, A represents an acyl group having 1 to 10 carbon atoms, H represents a hydrogen atom, and W represents a hexavalent hexaazaisowurtzitanium residue. WA _n H used in the reaction represented by the formula (5)
_(6-n) is one of the substances not described in the literature synthesized for the first time by the present inventors, and the method for producing this substance will be described later.

As the acylating agent used in the reaction (5), any acylating agent can be used as long as it can acylate a secondary amine. Usually, acyl halides such as acetyl chloride, acetyl bromide and propionyl chloride; N-acetoxy Succinimide, N-propionyloxysuccinimide, N-
N- such as (2-phenylacetoxy) succinimide
Carboxylic acid esters of hydroxysuccinimide; carboxylic anhydrides such as acetic anhydride, propionic anhydride, butyric anhydride, and acetic acid-formic acid mixed acid anhydrides; and acylimidazoles such as acetylimidazole and propionylimidazole. Of these acylating agents, preferably, acyl halides such as acetyl chloride and propionyl chloride can be used.

The solvent used in the reaction (5) may be any solvent that dissolves WA _n H _(6-n) and does not adversely affect the reaction. For example, carboxylic acids such as acetic acid, propionic acid and butyric acid; aprotic polar solvents such as dimethylsulfoxide and dimethylacetamide; and carboxylic anhydrides such as acetic anhydride and propionic anhydride. Preferably, carboxylic anhydrides such as acetic anhydride and propionic anhydride are used. The above solvents may be used alone or in combination of two or more.

The reaction temperature in the reaction (5) is usually -10 to 300
° C, preferably in the range of 0 to 150 ° C.

The WA ₆ of the present invention is obtained by reductive dearylmethylation of WA _n B _(6-n) as represented by the following reaction formula (6),
It can also be obtained by acylation.

[In the formula, n represents an integer of 4 to 5, A represents an acyl group having 1 to 10 carbon atoms, B represents an arylmethyl group represented by the following formula (15), and W represents a hexavalent hexaazaisowurtzitanium residue. This WA _n B _(6-n) is referred to herein as formula (VII).

WA _n B _(6-n) used in the reaction (6) may be prepared by any method. This WA _n B
_{Since (6-n)} can be produced from WB _{6 as} described later, WA _n B _(6-n) produced by that method or an existing substance may be used.

In the step of 1) reductive dearylmethylation of the reaction (6), any method may be used as long as it allows the dearylmethylation reaction of WA _n B _(6-n) to proceed. Usually, it is carried out by contacting a reducing catalyst in the presence of a reducing agent.

Usually, hydrogen, hydrazine, formic acid and the like are used as the reducing agent, and preferably, hydrogen is used. As the catalyst, a metal belonging to the platinum group or a derivative thereof is usually used. Preferably, Pd (OAc) ₂ , PdCl ₂ , Pd (N
O ₃ ) ₂ , PdO, Pd (OH) 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, More preferably, Pd
(OAc) _2, Pd compounds such as PdCl _2, Pd alloys and metallic Pd are used. These catalysts can be used as they are, or activated carbon, silica, alumina, silica-alumina,
It can be used by being supported on various carriers such as zeolite and activated clay. Before the reaction, the catalyst may be subjected to a reduction treatment. In the case of a solid catalyst, a treatment such as silylation or acylation is performed to inactivate surface acid sites.
Alternatively, the acidity of the solid surface can be changed by adsorbing an alkaline substance such as NaOH. The amount of the catalyst may vary depending on the reduction activity of the catalyst, but is usually 0.0001 to 10, preferably 0.001 to 1, expressed as a weight ratio of the catalyst metal used to WA _n B _(6-n) . Used in range.

The solvent used in the step of 1) reductive dearylmethylation in the reaction of (6) may be any solvent that dissolves WA _n B _(6-n) and does not adversely affect the reaction. For example, acetic acid,
Carboxylic acids such as propionic acid and butyric acid; amide compounds such as dimethylacetamide; amine compounds such as N, N-dimethylaniline. These solvents can be used alone or in combination of two or more. It is preferable to use a carboxylic acid such as acetic acid or propionic acid from the viewpoint of the reaction rate.

The amount of the solvent may vary depending on the solubility of the solvent used and the reaction temperature, but is expressed in terms of a weight ratio to the used WA _n B _(6-n) , and is usually in the range of 1 to 500, preferably 5 to 100. used.

Reaction pressure is usually 0.1 to 1000, preferably 1 to 100 kg
in the range of f / cm ^2, when using hydrogen as the reducing agent is represented by the partial pressure of hydrogen, preferably 0.1~500kgf / cm
² , more preferably in the range of 1 to 100 kgf / cm ² . In addition to hydrogen, an inert gas such as nitrogen, argon, and helium may be present.

The reaction temperature is usually -20 to 300C, preferably 0 to 2C.
It is in the range of 00 ° C.

The reaction time may vary depending on conditions such as the catalyst and solvent used, but is usually 0.1 to 500 hours, preferably 1 to 500 hours.
200 hours.

In the reaction of (6), WA _n H _(6-n) [n is an integer of 4 to 5] is synthesized by the step of 1) reductive dearylmethylation, and it is acylated in the following 2) acylation step. I do.

The reaction conditions such as the acylating agent, the solvent, and the reaction temperature used in the 2) acylation step of the reaction (6) may be the same as those described in the reaction (5) and the reaction conditions. it can.

WA ₆ of the present invention, as represented by the following reaction formula (7), the WB ₆ was reductively de-arylmethyl in the presence acylating agent, reductive de-arylmethyl and in the absence acylating agent , Followed by acylation.

[Wherein A represents an acyl group having 1 to 10 carbon atoms, B represents an arylmethyl group, and W represents a hexavalent hexaazaisowurtzitanium residue. This WB ₆ is referred to herein as equation (VI).

In the reaction (7), 1) the step of reductive dearylmethylation in the presence of an acylating agent is usually carried out by contacting with a reducing catalyst in the presence of a reducing agent. Such a reducing agent and a catalyst, was allowed to proceed for de-arylmethyl reaction WB _6, the acylating agent in the reaction system so long as it does not deactivate, it can be used in any combination.
As the reducing agent, hydrogen, formic acid and the like are usually used, and preferably, hydrogen is used. As the catalyst, the same catalyst as described in the step of 1) reductive dearylmethyl in the reaction (6) can be used.

The amount of catalyst may vary depending on the reducing activity of the catalyst, the catalyst metal to be used, expressed by weight relative to the WB _6, usually 0.0001, preferably used in the range of 0.001 to 10.

As the acylating agent used in the step of reductive dearylmethylation in the presence of the acylating agent in the reaction (7), any acylating agent capable of acylating a secondary amine can be used. N-hydroxysuccinimide carboxylate such as acetoxysuccinimide, N-propionyloxysuccinimide, N- (2-phenylacetoxy) succinimide; acetic anhydride, propionic anhydride, butyric anhydride, acetic acid-formic acid Carboxylic acid anhydrides such as mixed acid anhydrides; acylimidazoles such as acetylimidazole and propionylimidazole; When N-hydroxysuccinimide carboxylic acid esters such as N-acetoxysuccinimide and N-propionyloxysuccinimide are used among these acylating agents, WA _n B _(6-n) (n is Integer of 4 to 5]. Therefore, carboxylic acid esters of N-hydroxysuccinimide are preferably used. These acylating agents can be used alone or in combination of two or more. In particular, when a carboxylic acid ester of N-hydroxysuccinimide such as N-acetoxysuccinimide or N-propionyloxysuccinimide and a carboxylic anhydride such as acetic anhydride or propionic anhydride are used in combination, It is particularly preferable because the reaction rate in step (1) of (7) is improved and the selectivity of WA _n B _(6-n) [n is an integer of 4 to 5] is improved.

The amount of the acylating agent, the reactivity varies depending on the reaction method and reaction conditions, expressed in molar ratio to the arylmethyl groups of WB _6, usually, 0.1 to 100, preferably,
Used in the range of 1-50. When the carboxylic acid ester of N-hydroxysuccinimide and the carboxylic acid anhydride are used as a mixture as the acylating agent, the amount of the carboxylic acid anhydride is represented by the molar ratio to the carboxylic acid ester of N-hydroxysuccinimide. Usually, it is used in the range of 0.01 to 100, preferably 0.1 to 10.

The solvent used in the reductive de-arylmethyl at 1) the presence acylating agent reaction (7) step, to dissolve the WB _6, it may be any solvent which does not adversely influence the reaction. For example, benzene, toluene, ethylbenzene, xylene,
Aromatic compounds such as cumene, cymene, diisopropylbenzene, phenylethyl ether; cyclic or linear or branched ethers such as tetrahydrofuran, dioxane, tetrahydropyran, diethyl ether, dipropyl ether, diisopropyl ether; methanol, ethanol, propanol And aliphatic alcohols such as isopropyl alcohol and t-butyl alcohol. These solvents can be used alone or in combination of two or more. Among the above solvents, benzene, toluene, ethylbenzene, the use of aromatic compounds such as xylene, preferably to improve the reaction rate of de arylmethyl the WB _6.

The amount of the solvent is may also vary depending on the solubility and the reaction temperature of the solvent used, expressed by weight relative to the WB ₆ used is usually 0.1 to 100, preferably used in the range of 1 to 100.

Reaction pressure is usually 0.1 to 1000, preferably 1 to 300 kg
in the range of f / cm ^2, in the case of using hydrogen as a reducing agent, and optionally to improve the reaction rate higher pressures, expressed at a partial pressure of hydrogen, preferably 0.1～500Kgf /
cm ² , more preferably in the range of 1 to 200 kgf / cm ² . In addition to hydrogen, an inert gas such as nitrogen, argon, and helium may be present.

The reaction temperature is generally -20 to 300 ° C, preferably 0 to 200 ° C.
It is in the range of ° C.

The reaction time may vary depending on conditions such as a catalyst, an acylating agent and a solvent to be used, but is usually in the range of 0.1 to 500 hours, preferably 1 to 200 hours.

In the step (1) of the reaction (7), in the step of reductive dearylmethylation in the presence of an acylating agent, WA _n B _(6-n) [n is an integer of 4 to 5]
And use it in the next step.

A catalyst, a reducing agent, a solvent, used in the step of 2) reductive dearylmethylation in the absence of an acylating agent in the reaction of (7);
The reaction conditions such as the reaction temperature and the reaction pressure can be the same as those used in the above 1) step of reductive dearylmethylation in the presence of an acylating agent. Alternatively, the same ones and reaction conditions as described in the step (1) of the reaction (6) 1) Reductive dearylmethyl can also be used.

The reaction mixture obtained by removing the acylating agent from the reaction solution obtained in the step (1) of the reaction (7) 1) dearylmethylation in the presence of the acylating agent is used for 2) dearyllation in the absence of the acylating agent. It can also be used as a reactant in the methyl step. At this time, without separating the reducing catalyst and the solvent,
Subsequent use in the step of reductive dearylmethyl in the absence of an acylating agent is preferred.

In the step (2) of the reaction (7) in the step of reductive dearylmethylation in the absence of an acylating agent, WA _n H _(6-n) [n is an integer of 4 to 5] is synthesized. ) Used in the acylation step.

The reaction conditions such as the acylating agent, the solvent, and the reaction temperature used in the 3) acylation step of the reaction (7) are the same as those described in the reaction (5) and the reaction conditions. Can also.

The step (3) of the acylation of the reaction (7) includes the step (2) of (7).
The reaction solution obtained in the step of reductive dearylmethylation in the absence of an acylating agent can be used as it is, or a solution from which a reduction catalyst and / or a solvent has been removed can be used as a starting material.

The WA ₆ of the present invention has a WA _n as represented by the reaction formula (8).
It can also be obtained by reductive dearylmethylation of B _(6-n) in the presence of an acylating agent.

[In the formula, n represents an integer of 4 to 5, A represents an acyl group having 1 to 10 carbon atoms, B represents an arylmethyl group, and W represents a hexavalent hexaazaisowurtzitane residue. The reaction conditions of the reaction (8) such as a reducing agent, a catalyst, an acylating agent, a solvent, and a reaction temperature and a reaction pressure are as follows.
And the same as those described later can be used.

The WA ₆ of the present invention has a WB ₆ as expressed by the following equation (9).
Can be obtained by reductive dearylmethylation in the presence of an acylating agent.

[In the formula, B represents an arylmethyl group, A represents an acyl group having 1 to 10 carbon atoms, and W represents a hexavalent hexaazaisowurtzitanium residue. The reaction conditions and the like for the reaction (9) can be the same as those described above in the step (1) of the reaction (7), 1) Reductive dearylmethylation in the presence of an acylating agent.

It is one of the preferred structure of the hexa-A Zai Seoul titanium derivative having an acyl group of the present invention WA _n H _(6-n) is, WA _n B as represented by the following formula _{(10) (6-n)} By reductive dearylmethylation in the absence of an acylating agent.

[In the formula, n represents an integer of 4 to 5, A represents an acyl group having 1 to 10 carbon atoms, B represents an arylmethyl group, and W represents a hexavalent hexaazaisowurtzitane residue. The reaction (10) can be performed under the same conditions as described in the step (1) of the reaction (6), 1) Reductive dearylmethyl.

The WA _n H _(6-n) of the present invention is obtained by subjecting WB ₆ to 1) reductive dearylmethylation in the presence of an acylating agent and then 2) absence of an acylating agent as represented by the following formula (11). Also obtained by reductive dearylmethylation below.

[In the formula, n represents an integer of 4 to 5, A represents an acyl group having 1 to 10 carbon atoms, B represents an arylmethyl group, H represents a hydrogen atom, and W represents a hexavalent hexaazaisowurtzitanium residue. The step of 1) reductive dearylmethylation in the presence of the acylating agent in the reaction (11) is described in the step of 1) reductive dearylmethylization in the presence of the acylating agent in the reaction (7). The same reaction conditions as described above can be used.

In the step (1) of the reaction (11) in the step of reductive dearylmethylation in the presence of an acylating agent, WA _n B _(6-n) [n is an integer of 4 to 5] is synthesized, and the following 2) Used in the process.

The step of the 2) reductive dearylmethyl reaction in the absence of the acylating agent in the reaction (11) is the same as the step of 2) the reductive dearylmethyl reaction in the absence of the acylating agent in the reaction (7). The same reaction conditions and the like as described can be used.

WA _n B _(6-n) used as a raw material for synthesizing the hexaazaisowurtzitanium derivative having an acyl group of the present invention is obtained by converting WB ₆ in the presence of an acylating agent as represented by the following formula (12). Obtained by reductive dearylmethylation.

[In the formula, n represents an integer of 4 to 5, A represents an acyl group having 1 to 10 carbon atoms, B represents an arylmethyl group, H represents a hydrogen atom, and W represents a hexavalent hexaazaisowurtzitanium residue. The reaction (12) can be carried out under the same reaction conditions as described in the step (1) of the reaction (7), ie, the step of reductive dearylmethylation in the presence of an acylating agent.

In the reductive dearylmethyl reaction in the presence of the acylating agent of the present invention, a reaction in which the formed N-acyl group is further reduced and converted to an N-alkyl group also occurs. N
- as hexa A wood Seoul representative titanium derivative having an alkyl group include WA ₄ R _2.

WA ₄ R ₂ is represented by WA _n B _(6-n) as represented by the following equation (13 _).
By reductive dearylmethylation in the presence of an acylating agent.

[In the formula, n is an integer of 4 to 5, A is an acyl group having 1 to 10 carbon atoms, B is an arylmethyl group, R is an alkyl group having 1 to 10 carbon atoms, and W is hexavalent hexaazaisowurtzitanium. Represents a residue. In the reaction (13), the reaction can be allowed to proceed under conditions in which the acylation is added to the reaction conditions in the step (1) of the reductive dearylmethylation of the reaction (6).

For acylation, the same acylating agent and conditions as described in the step (1) of the reaction (7), 1) Reductive dearylmethylation in the presence of an acylating agent, and the like can be used.

The conditions such as the solvent, catalyst, acylating agent, reaction temperature, and reaction pressure of the reaction (13) are the same as those in the step (1) of the reaction (7), 1) reductive dearylmethyl in the presence of the acylating agent. And conditions can also be used.

WA ₄ R ₂ can also be obtained by reductive dearylmethylation of WB ₆ in the presence of an acylating agent as represented by the following formula (14).

[In the formula, A represents an acyl group having 1 to 10 carbon atoms, B represents an arylmethyl group, R represents an alkyl group having 1 to 10 carbon atoms, and W represents a hexavalent hexaazaisowurtzitane residue. In the reaction (14), the same reaction conditions as described in the step (1) of the reaction (7) 1) Reductive dearylmethylation in the presence of an acylating agent can be used.

WB or WA _n B _(6-n) [n used as a raw material for synthesizing the hexaazaisowurtzitane derivative having an acyl group of the present invention
Is an integer of 4 to 5], and the arylmethyl group represented by B represents a methyl group substituted by an aryl group (Ar), and usually has 7 to 21 carbon atoms. Representative structures of arylmethyl group B, the general formula _{(15) -CH 2 Ar (15} ) [Ar represents an aromatic group having 6 to 20 carbon atoms] is a substituent represented by. The number of carbon atoms in Ar is usually 6 to 20, preferably 6 to 10, particularly preferably 6 to 10.
It is. Ar is, for example, phenyl; tolyl (o
-, M-, p-substituted), ethylphenyl (o-, m-
-, P-substituted), xylyl and other alkylphenyl groups; methoxyphenyl (o-, m-, p-substituted) and ethoxyphenyl (o-, m-, p-substituted) , Butoxyphenyl (o-, m-, p-substituted)
And the like; naphthyl groups and various substituted naphthyl groups; and the like, preferably phenyl groups and various alkoxyphenyl groups. Each of the six arylmethyl groups may be the same or different.

The compound represented by the formula (1) of the present invention can be produced by various methods, and specific examples of the production method have been described above.

The greatest feature of the process for the preparation of compounds represented by the aforementioned formula (1) is to use the process of reductive de-arylmethyl of the WB ₆ in the presence of an acylating agent.

 This reaction is represented by the following reaction formula (16).

[In the formula, p is an integer of 1 to 5, n is an integer of 4 to 6, B is an arylmethyl group, A is an acyl group having 1 to 10 carbon atoms, H is a hydrogen atom, and W is a hexavalent hexaazide. Represents a soul titanium residue. The mixing ratio of WA _p B _(6-p) and WA _n H _(6-n) in the reaction (16) is represented by the molar ratio of WA _p B _(6-p) to WA _n H _(6-n) . Express 0.0
The range is from 01 to 1000, preferably from 0.01 to 100.

This WA _p B _(6-p) is herein referred to as formula (VIII).

For the reaction of (16), the same reaction conditions and the like as described in the reaction (12) can be used.

That is, by reductive de-arylmethyl the WB ₆ in the presence of an acylating agent, 1) Formation of N-H bonds by reductive elimination of the arylmethyl group and 2) formation of N- acyl groups by their acylation Is important in producing the hexaazaisowurtzitane derivative represented by the formula (1) of the present invention.

In the equation (16), not only WA _p B _(6-p) [p is an integer of 1 to 5] is generated from WB ₆ but also WA _n H
_{(6-n) is} also generated.

Hereinafter, first, the estimated reaction path of the equation (16) will be briefly described, and then, the usefulness and utilization of this reaction will be described.

Formula (17) shows the detailed reaction route estimated from the substance confirmed to be formed in the reaction of (16). Note that, depending on the reaction conditions, as a side reaction, the N-acyl group formed is reduced to form an N-alkyl group. The product is also shown in the formula (17).

[Wherein A is an acyl group having 1 to 10 carbon atoms, B is an arylmethyl group, R is an alkyl group having 1 to 10 carbon atoms, H is a hydrogen atom, and W is a hexavalent hexaazaisowurtzitanium residue. Express. Here, when the N-acyl group is reduced to an N-alkyl group, the product is not reduced to WA _n H _(6-n) , WA ₆ and reduced WA _n R _(6-n) . Are mixed, and these individual compounds are represented by the following formula (V).

WA _t Q _(6-t) (V) wherein t is an integer of 4 to 6, A is an acyl group having 1 to 10 carbon atoms, and Q is each independently a hydrogen atom and / or 1 to 10 carbon atoms.
And W represents a hexavalent hexaazaisowurtzitanium residue represented by the following formula (2). ] At that time, inclusions containing no WA ₆ in the manufacturing process, i.e., represents what the above equation for each t = 4 to 5 containing no t = 6 in (V) as the following formula (XII).

WA _n Q _(6-n) (XII) In the reaction of (16), the composition ratio of the obtained product changes according to the reaction time when performing a batch reaction, or according to the contact time when performing a continuous reaction. The composition ratio can also vary depending on the type of catalyst and solvent used, the reaction temperature, the reaction time, and the like. Therefore, by appropriately setting the reaction conditions, the production ratio of these products can be appropriately changed.

The usefulness of the reaction (16) will be described below. In order to obtain a hexa A wood Seoul titanium derivative having an acyl group of the present invention from WB _6, WH _n B in the absence of an acylating agent by reductive de-arylmethyl the WB _{6 (6-n)} [n:. 1 to 6 integer)
And the acylation thereof is attempted, the W skeleton is decomposed, and the desired product cannot be obtained in high yield. This is because hexaazaisowurtzitane derivatives containing secondary amines such as WHB ₅ , WH ₂ B ₄ and WH ₃ B ₃ obtained by dearylmethylation in the absence of an acylating agent of WB ₆ are structurally Guessed for instability. On the other hand, by using the method of the present invention for reductive dearylmethylation in the presence of an acylating agent, a hexaazaisowurtzitane derivative having an acyl group can be synthesized without decomposition of the skeleton. This decomposition of the skeleton can be suppressed to unstable secondary amine with an aryl methyl group such as WHB ₅ and WH ₂ B ₄ to generate the initial stage of the reaction is stabilized immediately acylated in the reaction system, de It is believed that arylmethyl and acylation could continue to proceed.

See back, hexamethylene A wood Seoul titanium derivative having an acyl group of the present invention represented by the general formula (1), as described above, reductive de-aryl methylation reaction with an acylating agent in the presence of WB ₆ However, if the reaction is to be completed as in this case, many types of products are formed at the same time, and side reactions become remarkable. Therefore, the present inventors have studied to find a method for obtaining WA _n H _(6-n) [n is an integer of 4 to 6] industrially advantageously, with high selectivity, and with high yield. (12), (1
By carrying out each of the reactions (0) and (5) in that order, particularly good results were obtained.

Hereinafter, each reaction of the formulas (12), (10), and (5) will be described in more detail.

I. Reaction (12): In order to obtain WA _n B _(6-n) in a high yield in the above-mentioned reaction (12), 1) the reaction should be carried out so that the dearylmethylation reaction is stopped halfway. Adjust the type and amount of reagents. 2) Monitor the progress of the reaction by gas chromatography or liquid chromatography and stop the reaction at an appropriate time. 3) Also a good solvent for WB ₆ , but WA WA _n formed by the dearylmethylation reaction of WB ₆ using a solvent that is a poor solvent for _n B _(6-n) (eg, an aromatic compound such as ethylbenzene or toluene) Various methods such as a method of precipitating B _(6-n) from the reaction solution can be adopted.

Among the above methods 1), 2) and 3), the method 3) is particularly useful industrially because the operation is easy.

In the reaction of (12), side reactions are suppressed to reduce WA _n B _(6-n)
In order to increase the selectivity of N, a carboxylic acid ester of N-hydroxysuccinimide such as N-acetoxysuccinimide is further used as an acylating agent.
It is effective to employ a mixture of a carboxylic acid ester of hydroxysuccinimide and a carboxylic anhydride such as acetic anhydride in order to improve the yield and the selectivity. The reason for the effect of improving the selectivity of WA _n B _(6-n) by the carboxylic acid ester of N-hydroxysuccinimide is not clear, but such carboxylic acid ester and carboxylic acid anhydride as those of carboxylic acid anhydride are not clear. This is probably due to differences in reactivity with other acylating agents and substrate selectivity due to steric restrictions.

The effect of improving the remarkable selectivity of more than WA _n B such by N- hydroxy carboxylic acid ester of the succinic acid imide as _(6-n) are those for the first time been found by the present inventors, WA _n B It is extremely important to economically synthesize _(6-n) .

II. Reaction (10): When WA ₆ is synthesized by reductive dearylmethylation of WA _n B _(6-n) obtained in reaction (12) in the presence of an acylating agent, N-acyl Since side reactions such as formation of N-alkyl group bond by reduction of group bond occur, high selectivity
It is difficult to form a WA _6.

On the other hand, in the reductive dearylmethylation reaction of WA _n B _{(6-n) in} the absence of an acylating agent as in the reaction (10), side reactions such as formation of an N-alkyl compound may occur. The present inventors have found that the reaction is suppressed and the reaction proceeds at a high selectivity. From this reaction solution, high-purity WA _n B _(6-n) can be obtained in a high yield by a simple simple operation, so this reaction method is extremely useful as a method for synthesizing WA _n H _(6-n). Useful.

As described above, in the reductive dearylmethylation reaction of WB _{6 in} the absence of an acylating agent, the resulting WH _n B
_(6-n) [n: an integer of 1 to 6] is unstable in the reaction system,
It is difficult to isolate in high yield. On the other hand, as described above, WA _n H _(6-n) [n is an integer of 4 to 5] is a stable compound and can be synthesized in high yield.

WA _n B _(6-n) [n is an integer of 1 to 6] and WA _n H
_(6-n) It is not clear why there is a difference in the properties of [n is an integer of 4 to 5], but the properties of the acyl group A and the arylmethyl group B are different from those of the hexaazaisowurtzitanium in each compound. It is considered that this affects the stability of the skeleton.

WA _n B _(6-n) [n is an integer of 1 to 6] and WA _n H
The difference in characteristics of _(6-n) [n is an integer of 4 to 5] has been confirmed for the first time by the present inventors. Also WA _n H
_(6-n) [n: an integer of 4 to 5] represented by the hexaazaisowurtzitane compound is a compound not described in known literature,
First synthesized according to the present invention.

III. Reaction (5): WA _n H _(6-n) [n is an integer of 4 to 5]
As described above in <Technical Field>, it is useful as a functional material such as a precursor of a polynitrated hexaazaisowurtzitanium derivative or a raw material of a high-polarity polymer. It can be easily converted to WA _6.

WA _{6 is} also a compound synthesized for the first time according to the present invention and not described in known literature, and is useful as various functional materials like WA _n H _(6-n) described above.

Hexaazaisowurtzitane derivative WA _n H _(6-n) having an acyl group represented by the general formula (1) of the present invention [n is 4 to
[Integer of 6] is used as a starting material, and a polynitrated hexaazaisowurtzitane derivative can be obtained by combining it with a nitration reaction.

Hereinafter, an example of nitrating the NH group and the NA group of WA _n H _(6-n) [n is an integer of 4 to 6] of the present invention and converting it into an N-NO ₂ group will be described.

N _- H in WA _n H _(6-n) [N is an integer of 4 to 5] of the present invention
The group can be converted into an N-NO ₂ group by various nitration methods, but preferably is performed in a two-stage method as represented by the following formula (18) because the yield is improved because the yield is improved.

That is, as shown in reaction (18), first, WA _n H
_(6-n) after the N-H group is converted to N-NO groups to nitrosation, by nitrating the N-NO groups to N-NO ₂ group, in high yield WA _n (NO ₂ ) _(6-n) is obtained.

Wherein n is an integer of 4 to 5, A is an acyl group having 1 to 10 carbon atoms, H is a hydrogen atom, (NO) is a nitroso group, (NO ₂ ) is a nitro group, and W is a hexavalent hexaa Represents the Xysoulitanium residue. This WA _n (NO) _(6-n) is here referred to as equation (IX), and WA _n (NO ₂ ) _(6-n) is here referred to as equation (X).

As the nitrosating agent used in the nitrosation step of the reaction (18), WA _n H _(6-n) is nitrosated, and WA _n (NO)
Any substance that produces _(6-n) may be used, but usually a mixture of sodium nitrite and an acid, nitrous oxide, nitrosyl chloride and the like are used.

The reaction temperature is usually -50 to 200C, preferably -30 to 100.
° C, more preferably in the range of -20 to 50 ° C.

The oxidizing agent used in the nitration step of the reaction (18) may be any oxidizing agent that oxidizes a nitroso group to generate a nitro group. Usually, nitric acid, hydrogen peroxide and the like are used. Of these oxidants, nitric acid is preferably used. These oxidizing agents may be used alone or in combination of two or more.

The reaction temperature is usually -50 ° C to 200 ° C, preferably -30 ° C.
To 150 ° C, more preferably -20 ° C to 60 ° C.

NA in WA _n H _(6-n) [n is an integer of 4 to 6] of the present invention
Group, can be readily converted into N-NO ₂ group. As an example,
For example, WA ₆ can be converted to a polynitrated hexaazaisowurtzitane derivative such as WA ₄ (NO ₂ ) ₂ by nitration with various nitrating agents.

Further, as shown in reaction equation (19), WA _n E
Various hexaazaisowyritanium titanium derivatives represented by _(6-n) can be nitrated to obtain hexanitrohexaazaisowurtzitanium [W (NO ₂ ) ₆ ].

[In the formula, n represents an integer of 4 to 6, A represents an acyl group having 1 to 10 carbon atoms, E represents a nitroso group or a nitro group, and W represents a hexavalent hexaazaisowurtitanium residue. This W (NO ₂ ) ₆ is referred to herein as formula (XI).

The _{WA n E (6-n)} N-A group in the nitrating agent to be converted to N-NO ₂ group, as long as it can convert the N-A group to N-NO ₂ group. Examples thereof include various nitrating agents containing nitric acid, and more specifically, nitrating agents containing a strong protonic acid such as a nitric acid / sulfuric acid system or a nitric acid / trifluoroacetic acid system. Can be

The reaction temperature is usually -50 to 120 ° C, preferably -20.
~ 60 ° C.

The reaction time is generally 0.1 to 500 hours, preferably 1 to 500 hours.
200 hours.

As described above, the NH and NA groups in the W skeleton are functional groups that can be easily converted to nitro groups.
_n H _(6-n) [N is an integer of 4-6] Various polynitro hexa- A wood Seoul titanium derivative as an intermediate can be produced in high yield.

These polynitrated hexaaza soul soul titanium derivatives are additives or high-performance explosives that control explosive performance such as mechanical properties, detonation speed, detonation pressure, burning rate, pressure index, sensitivity, heat resistance, etc. of explosive products. Useful as

 An example of its usefulness is shown below.

For example, WA ₄ (NO ₂ ) ₂ is: 1) a polynitramine group-containing cyclic group such as HNW, cyclotetramethylenetetranitramine (hereinafter “HMX”) and cyclotrimethylenetrinitramine (hereinafter “RDX”). It has the same structure as a high-performance explosive that takes a structure, and is superior to HNW, HMX and RDX in heat resistance. [When added to explosive products, the heat resistance of the product is not significantly reduced. 2) Unlike nitramine compounds such as HNW, HMX, and RDX, they have good affinity with binder components such as polyurethane because they have NA groups in addition to N-nitro groups in the skeleton.

It has such a property.

Taking advantage of these properties, this WA ₄ (NO ₂ ) ₂ is added to explosives composed of nitramine compounds (HNW, HMX, RDX, etc.) and binders such as polyurethane, to bond solid components (nitramine compounds) and binders. Performance can be improved.

This WA ₄ (NO ₂ ) ₂ can be easily derived into HNW by nitration, and is therefore useful as a raw material for HNW. Also HNW
Is highly useful as an oxidizing agent for high-performance explosives and smokeless propellants because of its high density and high energy.

Tetra acyl hexa A wood Seoul titanium WA ₄ H of the present invention
By reacting ₂ with a dicarboxylic acid derivative such as dicarboxylic acid halide or dicarboxylic acid diester, a highly polar polymer having a hexaazaisowurtzitane skeleton in the main chain can be obtained.

The acylating agent having a specific functional group is used as an acylating agent when synthesizing the acyl _- containing hexaazaisowurtzitane derivative WA _n H _(6-n) [n is an integer of 4 to 6] of the present invention. Thereby, a crosslinkable polyacylhexaazaisowurtzitane can be obtained.

WA _n H _(6-n) [n is an integer of 4 to 6] of the present invention can be used as it is as an additive such as a polymer modifier.

<Brief Description of the Drawings> FIG. 1 is a system diagram showing a production process of a product of the present invention. As can be seen from the system diagram, hexamethylene A wood Seoul titanium derivative _{WA t Q (6-t)} (W is a hexavalent hexa A wood Seoul titanium residue having an acyl group of the present invention, Q is each independently hydrogen Atom and / or alkyl group having 1 to 10 carbon atoms, t is an integer of 4 to 6) is WB ₆ (W is the above group, B is 7 carbon atoms)
~ 21 arylmethyl group) directly, or a hexaazaisowurtzitane derivative WA _n B _(6-n) having an acyl group and an arylmethyl group (W and B are as described above, and n is 4)
5 integer), or _{WA p B (6-p)} (W, B are as above, p is is produced via an integer of 1 to 5).

Hexaazaisowurtzitane derivative WA _t Q _(6-t) having this acyl group (W, A, Q and t are as described above)
Is WA _n (NO) _(6-n) directly or having a nitroso group
(W and A are as described above, n is an integer of 4 to 5) and / or a nitro group-containing WA _n (NO ₂ ) _(6-n) (W and A are as described above and n is 4 to 5) Via an integer) and can be converted easily and in high yield to W (NO ₂ ) ₆ (W is as defined above).

〔Example〕

Next, the present invention will be described in more detail with reference to Examples.
The present invention is not limited in any way by these examples.

 Each measurement was performed as follows.

(1) ¹ H-NMR JNM-FX-200 manufactured by JEOL Ltd. was used.

(2) ¹³ C-NMR JNM-GX-400 manufactured by JEOL Ltd. was used.

(3) ¹³ C- ¹ H COSY ( ¹³ C- ¹ H shift correlation NMR) JNM-GX-400 manufactured by JEOL Ltd. was used. ¹³
A method for measuring the interaction of the C and ¹ H. If either ¹³ C or ¹ H can be assigned by this measurement, the ¹³ C
Alternatively, the chemical shift of ¹ H or ¹³ C to which ¹ H is bound is found.

(4) EI (Electron Impact)-Mass Spectrum Model HP5790B manufactured by Hewlett-Packard Company was used.

(5) GC (Gas Chromatography)-Mass Spectrum 1) A model HP5890A manufactured by Hewlett-Packard Company was used.

2) Column: metal capillary column 0.25mm id
× 15m Ultra ALLOY (HT), Filmthickness 1.15μm 3) Temperature: column; 100 ° C to 340 ° C (20 min), <20 ° C
/ min temperature rise> Injection port; 340 ° C, GC / MS connection part; 340 ° C 4) Carrier gas: He Total Flow; 100ml / min, Colu
mnpressure; 100kPa (6) FD (Field Desorption)-Mass spectrum Using JEOL HX-110 model manufactured by JEOL Ltd.
A few μg of a sample was dissolved in about 10 μl of methanol, and several μl of the solution was applied on an emitter for measurement.

(7) Infrared absorption spectrum Measured by the KBr method using an instrument FT / IR-5M manufactured by JASCO Corporation.

(8) Differential Scanning Calorimeter (DSC) An instrument DSC-220C manufactured by Seiko Electronic Industry Co., Ltd. was used.

(9) High Performance Liquid Chromatography The measurement was performed using the following apparatus and conditions.

1) Equipment: WATERS 610 Isocratic System 600 Controller 600E Pump 486 Tunable Absorbance Detector 2) Column: WATERS Micro Bonder Sphere Particle Size 5 microns Filler C18 Pore Size 100 Angstrom Column Size 3.9mm x 15cm 3) Mobile phase liquid: acetonitrile / water (60/40) 4) Flow rate: 0.5 ml / min 5) Column temperature: 40 ° C. Example 1 [Method for obtaining WA ₆ by acetylation of WA ₄ H ₂ ] Tetraacetylhexaazai Seoul Titanium 1.0g (2.98
mmol) in 100 ml of acetic anhydride and 5 g of acetyl chloride (63.
7 mmol) and stirred for 1 hour. Thereafter, the solvent was distilled off under reduced pressure, and the residue was dissolved in ethyl acetate. Hexane was added to the solution to precipitate a precipitate, and 1.16 g of hexaacetylhexaazaisowurtzitanium as a white solid (93% yield)
I got

Put this hexaacetylhexaazaisosoultitanium into a sublimation purification tool, immerse it in an oil bath at 270 ° C,
It was confirmed that sublimation could be achieved at a reduced pressure.

The analysis results of hexaacetylhexaazaisowurtzitane are shown below. ¹ H-NMR (solvent CDCl ₃ , tetramethylsilane (hereinafter “TM
S ”) standard, measurement temperature 60 degrees), δ (ppm) 2.05 (s, 6H, COCH ₃ ), 2.14 (s, 6H, COCH ₃ ), 2.41 (s, 6)
H, COCH ₃ ), 6.42 (s, 2H, CH), 6.48 (d, 2H, CH), 6.94 (d,
2H, CH).

^{The 1} H-NMR spectrum confirmed six acetyl groups and six hydrogen atoms on the W skeleton. ¹³ C-NMR (solvent CDCl ₃ , TMS standard), δ (ppm) 20.74 (CH ₃ ), 21.55 (CH ₃ ), 61.09 (CH), 66.55 (C
H), 72.17 (CH), 167.60 (C = O), 168, 31 (C =
O), 168.79 (C = O).

^{By 13} C-NMR, the methyl group carbon and the carbonyl carbon of the acetyl group, and the W skeleton carbon were confirmed.

The ¹³ C- ¹ H COSY, were assigned to ¹³ C bound of ¹ H.

EI-mass spectrum [m indicates the molecular weight of the parent molecule. ] 420 (5%, m / z ), 377 (5%, [m-COCH 3] / z), 335
(10%), 295 (15%), 208 (12%), 165 (10%), 123
(12%), 43 (100%, COCH ₃ ).

From the EI-mass spectrum, the parent ion peak of hexaacetylhexaazaisowurtzitane [420] and the ion peak of a molecule in which one acetyl group is removed from the parent molecule [37]
7] and an acetyl group ion peak [43].

As a result of measuring the infrared absorption spectrum (IR) by the KBr method, 1
At around 660 cm ⁻¹ , absorption of stretching vibration of the carbonyl group of the acetyl group (C ＝ O) was confirmed.

Example 2 [Method for synthesizing WA ₆ from WA ₄ B ₂ ] Tetraacetyldibenzylhexaazaisowurtzitane
3.67 g (7.11 mmol), Pd (OAc) ₂ 1.6 g (7.11 mmol), 150 ml of acetic acid, and a rotor were placed in a 300 ml microbomb,
It was replaced with nitrogen. After that, 5kgf / c of hydrogen was added to the micro cylinder.
The pressure was increased to m ² -G, and the mixture was stirred with a stirrer for 15 hours. The reaction solution was taken out from the micro-bomb, the catalyst was filtered, and the solvent was distilled off under reduced pressure, and the residue was washed with 100 ml of residual solid ethyl acetate and taken out. This white solid was dissolved in 200 ml of acetic anhydride, and 5 g (63.7 mmol) of acetyl chloride was added thereto, followed by stirring for 1 hour. Thereafter, the solvent was distilled off under reduced pressure and recrystallized from toluene to obtain 2.09 g (yield 70%) of hexaacetylhexaazaisowurtzitane as a white solid.

Example 3 [A method of performing the acetylation step without removing the product in the reductive dearylmethyl step from the solution when synthesizing WA ₆ from WA ₄ B ₂ ] The same operation as in Example 2 was performed. 5 g (63.7 mmol) of acetyl chloride was added to the reaction solution containing the reducing catalyst and the solvent obtained by reductive dephenylmethylation of tetraacetyldibenzylhexaazaisowurtzitanium, and the mixture was stirred for 3 hours. After filtration, the solvent was distilled off under reduced pressure, and the remaining solid was recrystallized from toluene to obtain 1.92 g (64% yield) of hexaacetylhexaazaisowurtzitane as a white solid.

Example 4 [Method for synthesizing WA ₆ from WB ₆ ] 1.89 g of hexabenzylhexaazaisowurtzitane (2.6 g
6 mmol), 1.70 g (1.60 mg atom) of 10% Pd-C, 5.0 g (31.8 mmol) of N-acetoxysuccinimide, 160 ml of ethylbenzene, 3.24 g (31.8 mmol) of acetic anhydride, and a rotor having a content of 300 ml. It was placed in a cylinder and the inside of the cylinder was replaced with hydrogen. Thereafter, hydrogen was injected into the cylinder to 10 kgf / cm ² -G, placed in a 60 ° oil bath, and stirred with a stirrer for 40 hours. After cooling the reaction solution to room temperature, the reaction solution was taken out of the bomb, and the precipitated WA _n B _(6-n) [n is 4 or 5] and the reducing catalyst were taken out by filtration. Put in a cylinder, hydrogen 5kgf / cm
^The pressure was increased to ^2- G, and the mixture was stirred for 20 hours. After completion of the reaction, 5 g (63.7 mmol) of acetyl chloride was added to the reaction solution, and the mixture was stirred for 1 hour. Thereafter, the solvent was distilled off from the reaction solution under reduced pressure, and 200 ml of chloroform was added to dissolve the solid containing WA ₆ as a main component.
The catalyst was filtered, the filtrate was evaporated under reduced pressure, and the residual solid was recrystallized from toluene to obtain 0.50 g (yield: 45%) of hexaacetylhexaazaisowurtzitanium as a white solid.

Example 5 [Method for synthesizing WA _n H _(6-n) and WA ₆ from WB ₆ ] The reductive debenzylation reaction of hexabenzylhexaazaisowurtzitane in the presence of an acetylating agent is the same as in Example 4. After the completion of the reaction, the reaction solution was taken out of the cylinder, the precipitated solid content and the reducing catalyst were filtered, and the solid on the filter paper was washed with 200 ml of chloroform. The filtrate (reaction solution and chloroform washing solution) was evaporated, and the remaining solid was dissolved in 200 ml of chloroform.
Then, N-acetoxysuccinimide was decomposed and removed to the aqueous phase side by adding vigorous stirring for 30 minutes. The chloroform layer was taken out, the solvent was distilled off, and the white solid obtained was dissolved in 50 ml of acetic acid, 0.6 g (2.66 mmol) of Pd (OAc) ₂ was added, and the mixture was placed in a 100 ml microbomb and hydrogen was added at 5 kgf / cm ² -G.
And the mixture was stirred for 20 hours. The yield of hexaacetylhexaazaisowurtzitanium at this point was analyzed by gas chromatography and found to be 0.3%. Thereafter, 5 g (63.7 mmol) of acetyl chloride was added, and the mixture was stirred for 1 hour. The solvent was distilled off under reduced pressure, and 200 ml of chloroform was added to the remaining solid.
The catalyst was removed by filtration, and the remaining solid after evaporating the solvent from the filtrate was recrystallized from toluene to obtain 0.39 g (yield 35%) of hexaacetylhexaazaisowurtzitane. This result indicates that hexaazaisowurtzitane compounds having secondary amines such as tetraacetylhexaazaisowurtzitane and pentaacetylhexaazaisowurtzitane were formed in the reaction solution before adding acetyl chloride. ing.

Example 6 [Method of synthesizing WA ₄ Et ₂ (Et: ethyl group) from WA ₄ B ₂ ] Tetraacetyldibenzylhexaazaisowurtzitane
0.50 g (0.97 mmol), 0.21 g (0.19 mg atom) of 10% Pd—C, 2.37 g (23.3 mmol) of acetic anhydride, 50 ml of acetic acid, and a rotator were placed in a 100 ml microbomb and replaced with hydrogen.
Then, pressurize hydrogen to 50kgf / cm ² -G and stir with a stirrer.
Stir for 5 hours. After completion of the reaction, the reaction solution was taken out of the micro-bomb, the catalyst was removed by filtration, and the filtrate was evaporated, and the residual solid was purified by a reprecipitation method using a chloroform / hexane system to obtain diethyl tetraethyl as a white solid. Acetyl hexaaza soul soul titanium was obtained. Table 1 shows the reaction conditions and the yield.

The analysis results of diethyltetraacetylhexaazaisowurtzitane are shown below.

EI-mass spectrum 392 (1%, m / z), 278 (1%), 236 (10%), 193
(25%), 138 (30%), 109 (45%), 97 (20%), 81
(81%), 69 (60%), 56 (20%), 43 (100%, COC
_{H 3), 29 (20%} , CH 2 CH 3), 28 (52%), 15 (20%, CH
₃ ).

From the EI-mass spectrum, a parent ion peak [392] of tetraacetyldiethylhexaazaisowurtzitanium, an acetyl group ion peak [43], and an ethyl group ion peak [29] were confirmed. ¹ H-NMR spectrum (solvent CDCl ₃ , TMS standard), δ (ppm) 1.25 (t, 6 H, CH _{3 of} ethyl group) 2.14 (s, 12 H, COCH ₃ ), 2.
90 (m, 4H, CH _{2 of} ethyl group), 5.20 (d, 2H, CH), 5.74 (d, 2
H, CH), 6.40 (s, 2H, CH).

^{From the 1} H-NMR spectrum, an ethyl group, an acetyl group, and a methine group of a W skeleton were confirmed.

Examples 7 to 12 [Synthesis of WA ₆ and WA ₄ R ₂ by Reductive Dearylmethylation of WA ₄ B ₂ in the Presence of Acylating Agent, and Change of Their Formation Ratio by Reaction Conditions] The reaction was carried out in the same manner as in Example 6, except that the kind, amount, solvent, catalyst type, amount of catalyst, hydrogen pressure and reaction time were changed. The reaction conditions and product yields are shown in Table 1.

Table 1 shows that hexaacetylhexaazaisowurtzitanium and diethyltetraacetylhexaazaisowurtzitanium can be synthesized using various catalysts.

Example 13 [Synthesis of hexaazaisowurtzitane derivatives having various acetyl groups such as WA ₄ B ₂ and WA ₅ B by reductive dearylmethylation of WB ₆ in the presence of an acylating agent] The hydrogen pressure was set to 50 kgf. / cm ² , reaction temperature is room temperature, reaction time is 2
A reductive debenzylation reaction of hexabenzylhexaazaisowurtzitane in the presence of an acetylating agent was performed in the same manner as in Example 4 except that the time was changed to 00 hours.

After completion of the reaction, the reaction product was analyzed by GC-mass spectrum, and as products, tetraacetyldibenzylhexaazaisowurtzitane, pentaacetylbenzylhexaazaisowurtzitane, hexaacetylhexaazaisowurtzitane, ethylpentaacetyl The formation of hexaazaisowurtzitane and diethyl teraacetylhexaazaisowurtzitane was confirmed. As a result of analyzing the yield by gas chromatography, tetraacetyldibenzylhexaazaisowurtzitane was 70%, and pentaacetylbenzylhexaazaisowurtzitane was 6.2%. It was confirmed that 0.9% of hexaacetylhexaazaisowurtzitanium, 1.3% of ethylpentaacetylhexaazaisowurtzitanium, and 1.1% of diethyltetraacetylhexaazaisowurtzitanium were produced. The EI- of these products
The mass spectrum is shown below.

Pentaacetylbenzylhexaaza soul titanium EI
- mass spectrum 468 (2%, m / z ), 425 (3%, [m-COCH 3] / z),
255 (12%), 91 (66%, CH ₂ Ph), 43 (100%, COC
H _3).

EI- of ethylpentaacetylhexaazaisosoultitanium
Mass spectrum 406 (1%, m / z ), 363 (1%, [m-COCH 3] / z),
278 (2%), 236 (5%), 193 (10%), 109 (12
%), 43 (100%, COCH ₃ ), 29 (15%, CH ₂ CH ₃ ), 15
(8%, CH _3).

EI of diethyltetraacetylhexaazaisosoul titanium
Mass spectra 392 (1%, m / z), 278 (1%), 236 (10%), 193
(25%), 138 (30%), 109 (45%), 97 (20%), 81
(81%), 69 (60%), 56 (20%), 43 (100%, COC
_{H 3), 29 (20%} , CH 2 CH 3), 28 (52%), 15 (20%, CH
₃ ).

EI- mass spectrum 420 of hexa acetyl hexamethylene A wood Seoul titanium (5%, m / z) , 377 (5%, [m-COCH 3] / z),
335 (10%), 295 (15%), 208 (12%), 165 (10
%), 123 (12%) , 43 (100%, COCH 3).

Example 14 (In the case of using only a carboxylic anhydride without using a carboxylic acid ester of N-hydroxysuccinimide as an acylating agent in the reductive dearylmethyl step in the presence of an acylating agent of WB ₆ Reaction of acetic anhydride without using N-acetoxysuccinimide
The reaction was carried out in the same manner as in Example 13 except that 32.4 g was used. During the reaction, the reaction solution was sampled, and the components were analyzed by FD-mass spectrum. As a result, diacetyltetrabenzylhexaazaisowurtzitanium (M ⁺ 61
2), it was found that triacetyltribenzylhexaazaisowurtzitane (M ⁺ 564) was produced as an intermediate. Ethyl diacetyltribenzylhexaazaisowurtzitane (M ⁺
550), ethyltriacetyldibenzylhexaazaisowurtzitane (M ⁺ 502), and diethyldiacetyldibenzylhexaazaisowurtzitane (M ⁺ 488).

The yield of the product after the reaction was determined by gas chromatography, which was 13% for triacetyltribenzylhexaazaisowurtzitane, 3.1% for ethyldiacetyltribenzylhexaazaisowurtzitanium, and 3.1% for tetraacetyldibenzylhexaazaisowurtzitanium. 7.5%, Ethyl triacetyl dibenzyl hexa aza soul soul titanium 32%, Diethyl diacetyl dibenzyl hexa aza soul soul titanium 30%,
Pentaacetylbenzylhexaaza soul titanium 1.6
%, Ethyltetraacetylbenzylhexaazaisowurtzitane 1.1%, Diethyltriacetylbenzylhexaazaisowurtzitane 6.2%, Hexaacetylhexaazaisowyltitanium 0.5%, Ethylpentaacetylhexaazaisowurtzitane 1.2%, Diethyltetraacetyl Hexaazaisoul titanium 1.1%.

From these results, when the carboxylic acid ester of N-hydroxysuccinimide is not used as the acylating agent,
It turns out that the generation of an alkyl group by the reduction reaction of an acyl group is remarkable.

Example 15 [Reaction when N-acetoxysuccinimide is used alone as an acylating agent in the reductive dearylmethyl step in the presence of an acylating agent of WB ₆ ] N-acetoxy was used without using acetic anhydride. Succinimide
The reaction was carried out in the same manner as in Example 13 except that 7.5 g was used. During the reaction, sample the reaction solution,
Analysis of the components FD- in mass spectrum, penta benzyl hexa A wood Seoul titanium ( "M ⁺ H] + 619), acetyl penta benzyl hexamethylene A wood Seoul titanium (M ⁺ 66
0), diacetyltetrabenzylhexaazaisowurtzitane (M ⁺ 612) and triacetyltribenzylhexaazaisowurtzitane (M ⁺ 564) were found to be intermediates. After the reaction was completed, the yield of the product by gas chromatography was 74% for diacetyltetrabenzylhexaazaisowurtzitane, 15% for triacetyltribenzylhexaazaisowurtzitanium, and 3% for tetraacetyldibenzylhexaazaisowurtzitanium. there were.

From this result, when used in the reductive de-arylmethyl steps with an acylating agent in the presence of WB _6, the carboxylic acid ester of N- hydroxysuccinimide alone as an acylating agent, WA ₄ B ₂ earlier acyl It is understood that the formation of an alkyl group by the reduction reaction of the group can be suppressed. But N
It can also be seen that the reaction rate is lower than when using a mixture of a carboxylic acid ester of hydroxysuccinimide and a carboxylic anhydride.

Example 16 [Method of Synthesizing WA ₄ H ₂ from WA ₂ B ₂ ] Tetraacetyldibenzylhexaazaisowurtzitane
3.67 g (7.11 mmol), 1.60 g (7.11 mmol) of Pd (OAc) ₂ , 150 ml of acetic acid, and a rotor were placed in a 300 ml microbomb,
It was replaced with nitrogen. After that, 5kgf / c of hydrogen was added to the micro cylinder.
The pressure was increased to m ² -G, and the mixture was stirred with a stirrer for 15 hours. The reaction solution was taken out of the microbomb, the catalyst was filtered, and the solvent was distilled off under reduced pressure, and the residue was washed with 100 ml of residual ethyl acetate.
White solid tetraacetylhexaaza soul titanium 1.67
g (yield 71%) was obtained.

The analysis results of tetraacetylhexaazaisosoultitanium are shown below. ¹ H-NMR (solvent D ₂ O, TMS standard), δ (ppm) 1.98 (s, 6H, COCH ₃ ), 2.00 (s, 6H, COCH ₃ ), 5.29 (m, 2
H, CH), 5.50 (m, 2H, CH), 6.35 (m, 2H, CH).

¹ H-NMR confirmed four acetyl groups and a methine group in the W skeleton.

As a result of measuring the infrared absorption spectrum (IR), 3300 to 34
Absorption of stretching vibration of two secondary amines (N—H groups) of 00 cm ⁻¹ was confirmed. Also, stretching vibration of the carbonyl (C ＝ O) group of the acetyl group was confirmed at around 1660 cm ⁻¹ . From these, it is found that an acetyl group and an NH group exist as substituents of the W skeleton.

Example 17 [Reaction for synthesizing WA ₄ H ₂ from WA ₄ B ₂ using a different catalyst from Example 16 and changing the reaction temperature] Tetraacetyldibenzylhexaazaisowurtzitane
1.20 g (2.33 mmol), 10% Pd-C 0.496 g (0.466 mmo
l), acetic acid 60 ml, and a rotor were placed in a 300 ml microbomb, and the atmosphere was replaced with nitrogen. Then, add hydrogen to the micro cylinder
It was press-fitted to 3 kgf / cm ² -G, put in a 40 ° C. oil bath, and stirred with a stirrer for 5 hours. The reaction solution was taken out from the microbomb, the catalyst was filtered off, and the solvent was distilled off under reduced pressure. The remaining solid was washed with 100 ml of ethyl acetate to obtain 0.57 g of tetraacetylhexaazaisowurtzitanium as a white solid (yield 73%). Was.

As a result, in this embodiment, almost the same as in Embodiment 16
It can be seen that WA ₂ H ₂ can be synthesized.

Example 18 [Production of WA _n H _(6-n) in Reductive Dearylmethyl Step in the Presence of Acylating Agent of WB ₆ ] Reductive Deprotection of Hexabenzylhexaazaisowurtzitane in the Presence of Acetylating Agent Benzyl reaction, reaction time 20
The procedure was performed in the same manner as in Example 4 except that the time was set to 0 hours. After the reaction was completed, the reaction solution was analyzed by gas chromatography. As a result, only 0.8% of hexaacetylhexaazaisowurtzitanium was produced, but tetraacetylhexaazaisowurtzitanium was present by high performance liquid chromatography. It was confirmed that. After adding acetyl chloride to the above reaction solution and stirring for one hour, hexaacetylhexaazaisowurtzitanium was confirmed by 5% gas chromatography. This also indicates that tetraacetylhexaazaisowurtzitane and pentaacetylhexaazaisowurtzitane are present in the reaction system.

Example 19 [Method for obtaining WA ₄ B ₂ by reductive dearylmethylation reaction in the presence of an acylating agent for WB ₆ ] 1.89 g (2.6 g) of hexabenzylhexaazaisowurtzitane
6 mmol), 1.70 g (1.60 mg atom) of 10% Pd-C, 5.0 g (31.8 mmol) of N-acetoxysuccinimide, 160 ml of ethylbenzene, 3.24 g (31.8 mmol) of acetic anhydride, and a rotor having a content of 300 ml. It was placed in a cylinder and the inside of the cylinder was replaced with hydrogen. Thereafter, hydrogen was injected into the cylinder to 50 kgf / cm ² -G and stirred with a stirrer for 20 hours. The reaction solution was taken out of the cylinder, the catalyst and the precipitated solid were filtered, and the solid on the filter paper was washed with 200 ml of chloroform. The filtrate (reaction solution and washing solution of chloroform) was evaporated, and the remaining solid was dissolved in 200 ml of chloroform.
Was added and stirred vigorously for 30 minutes. By this operation, N-
The acetoxysuccinimide is removed from the organic layer. Take out the chloroform layer, evaporate the solvent, and obtain 1.29 g of a white solid.
I got This is recrystallized from ethylbenzene to give a white solid
1.03 g (yield 75%) was obtained. The analysis of this compound FD- Mass spectrum, subjected to structural analysis by ¹ H and ^{13 C-NMR, 13 C- 1} H COSY, was confirmed to be tetra acetyl dibenzyl hexa A wood Seoul titanium. The analysis results of tetraacetyldibenzylhexaazaisowurtzitane are shown below.

FD-mass spectrum 517 ([M + H] ⁺ ). ¹ H-NMR spectrum (solvent CDCl ₃ , TMS standard) δ (ppm) 1.94 (s, 6H, COCH ₃ ), 2.15 (s, 6H, COCH ₃ ), 4.06 (d, 2
H, CH ₂ ) 4.29 (d, 2H, CH ₂ ), 5.09 (d, 2H, CH), 5.70 (d, 2
H, CH), 6.42 (s, 2H, CH), 7.3-7.5 (m, 10H, Ph).

¹ H-NMR spectrum confirmed four acetyl groups, two benzyl groups, and six methine groups in the W skeleton. ¹³ C-NMR (solvent CDCl ₃ , TMS standard) δ (ppm) 20.737 (CH ₃ ), 22.111 (CH ₃ ), 56.428 (CH ₂ ), 69.679
(CH), 70.592 (CH), 128.056 (Ph), 128.673 (Ph), 12
8.928 (Ph), 136.742 (Ph), 168.263 (CO).

^{The 13} C-NMR spectrum confirms an acetyl group, a phenyl group and a methylene group of a benzyl group, and a methine group in the W skeleton.

By ¹ H- ¹³ C COZY, was assigned to ¹³ C bound of ¹ H.

Example 20 [Method of nitrosating WA ₄ H ₂ to synthesize WA ₄ (NO) ₂ , and then oxidizing it to synthesize WA ₄ (NO ₂ ) ₂ ] 0.336 g (1 m
mol) and 10 ml of 50% acetic acid into a 100 ml reaction vessel and cool to 0 ° C. While stirring at 0 ° C., 2 ml of a 4 mol / l sodium nitrite aqueous solution is slowly added dropwise. Thereafter, the temperature is raised to 30 ° C. and the mixture is stirred for 4 hours. 50 ml of chloroform is added to the reaction solution and stirred vigorously. After standing, the organic layer is taken out and the solvent is distilled off under reduced pressure to obtain 0.373 g (yield 95%) of dinitrosotetraacetylhexaazaisowurtzitane.

30 ml of 100% nitric acid is placed in a 100 ml reaction vessel, and 0.9262 g of dinitrosotetraacetylhexaazaisole titanium is added to the reaction vessel.
(2.35 mmol) and stir at room temperature for 5 hours. afterwards,
The nitric acid is distilled off under reduced pressure to obtain 0.955 g (95% yield) of dinitrotetraacetylhexaazaisowurtzitane.

The analysis results of dinitrosotetraacetylhexaazaisowurtzitane are shown below. ¹ H NMR (solvent CDCl ₃ , TMS standard) δ (ppm) 2.05 (s, 6H, COCH ₃ ), 2.17 (s, 6H, COCH ₃ ), 5.46 (m,
2H, CH), 6.62 (m, 2H, CH), 7.30 (s, 2H, CH) ¹ HNMR spectra show that 4 acetyl groups and 6 W
The methine group of the skeleton was confirmed.

As a result of measuring an infrared absorption (IR) spectrum, 1670 cm ⁻¹
Absorption of carbonyl group of acetyl group (C = O), 15
At around 00 cm ^−1, around 1380 cm ⁻¹ , and around 1350 cm ⁻¹ , absorptions considered to be derived from nitroso groups were confirmed.

In addition, the absorption of the NH group confirmed by tetraacetylhexaazaisowurtzitane completely disappeared.

The analysis results of dinitrotetraacetylhexaazaisowurtzitane are shown below. ¹ H NMR (solvent DMSO-d ₆ , TMS standard) δ (ppm) 2.10 (s, 12 H, COCH ₃ ), 6.75 (m, 2 H, CH), 7.35 (7.35 pp
m has a peak top of a singlet and a peak with a shoulder on the low magnetic field side, 4H, CH) As a result of measuring an infrared absorption spectrum (IR), 1680 cm ⁻¹
The absorption of the stretching vibration of the carbonyl (C = O) group of the acetyl group was confirmed near, and the absorption of the stretching vibration of the nitro group was confirmed near 1570 cm ^{-1 and} around 1300 cm ^-1 . From this, W
It turns out that a nitro group and an acetyl group exist as a substituent of a skeleton.

As a result of measuring the FD-mass spectrum, a parent ion peak at m / z 426 was confirmed.

The decomposition temperature was measured using a differential scanning calorimeter (DS) using Seiko Denshi Kogyo DSC 220C.
C) (heating rate: 10 ° C./min), the exothermic peak top temperature was around 314 ° C. This temperature is higher than the exothermic peak top temperature of HNW (around 250 ° C.), indicating that dinitrotetraacetylhexaazaisowurtzitane is a nitramine compound having excellent heat resistance.

Example 21 [Method for nitrating WA ₆ to synthesize WA ₄ (NO ₂ ) ₂ ] 5 ml of acetic anhydride is placed in a 100 ml reaction vessel and cooled to 0 ° C. Thereafter, 5 ml of 100% nitric acid is slowly added dropwise at 0 ° C. while stirring. Thereafter, 0.5 g of dinitrogen pentoxide is added. Then, 0.1 g of hexaacetylhexaazaisosoul titanium (0.
238 mmol).

Thereafter, 0.5 g of dinitrogen pentoxide is added four times every hour.
After the reaction solution was quenched with ice water, the liquid component was distilled off under reduced pressure, and the remaining solid was analyzed by high performance liquid chromatography to confirm the formation of dinitrotetraacetylhexaazaisowurtzitanium.

Example 22 [Reaction for nitrating WA ₄ (NO ₂ ) ₂ to synthesize W (NO ₂ ) ₆ ] A 200 ml reaction vessel was immersed in a bath at 0 ° C., 25 ml of sulfuric acid was added, and 25 ml of 100% nitric acid was slowly added thereto. Drip. 0.2 g (0.457 mmol) of dinitrotetraacetylhexaazaisowurtzitanium is added to the mixed acid, and the mixture is stirred at 0 ° C. for 8 hours and then at room temperature for 67 hours. After completion of the reaction, the organic component in the reaction solution was extracted with chloroform (200 ml × 2 times), and the chloroform phase was evaporated under reduced pressure to obtain a 10% solid.
After washing with NaHCO ₃ water, hexanitrohexaazaisowoulitanium 0.06 g was obtained (30% yield). The structure of the product was confirmed by the following analysis.

As a result of measuring the infrared absorption (IR) spectrum by the KBr method, 1
Absorption of anti-symmetric stretching vibration of nitro group around 605cm ^-1 , 1325c
m ^-1 and near 1270 cm ^-1 near the two absorption symmetric stretching vibration of nitro groups, the absorption of the bending of the nitro group of two in the vicinity of 945 cm ^-1 and near 880 cm ^-1, W skeleton around 3030 cm ^-1 The absorption of stretching vibration of the methine group was confirmed.

These characteristic absorptions are described in the literature [COMBUSTION AND FLAME
87: 145-151 (1991)], which is consistent with the characteristic absorption of the IR spectrum of hexanitrohexaazaisowurtzitane. The absorption of the carbonyl group (C ＝ O) of the acetyl group of dinitrotetraacetylhexaazaisowurtzitanium used as a raw material around 1680 cm ⁻¹ completely disappeared.

From this result, it is understood that the acetyl group of dinitrotetraacetylhexaazaisowurtzitanium was converted to a nitro group, and hexanitrohexaazaisowurtzitanium was formed.

In addition, the literature reported about various characteristics of HNW [Inter
national Symposium on Energetic Materials Tec
hnology PROCEEDINGS, SEPTEMBER 24-27, 76-81 (1
995)], the product was analyzed under the same conditions as in the high performance liquid chromatography described above, and showed the same retention time as the literature.

Further, as a result of measuring the EI-mass spectrum, 392 (parent ion-NO ₂ ), 316, ₂
Ion peaks of 13, 46 (NO ₂ ) were confirmed. These ion peaks are also described in the above document [International Sympo
sium on Energetic Materials Technology PROCEE
DINGS, SEPTEMBER 24-27, 76-81 (1995)].

Comparative Example 1 [the WB ₆ after reductive de-arylmethyl absence acylating agent, the acylation reaction] hex benzyl hexamethylene A wood Seoul titanium 3.0 g (4.24
mmol), 0.476 g (2.12 mmol) of Pd (OAc) ₂ , 75 ml of tetrahydrofuran (THF), 75 ml of ethanol, and a rotor in a 300 ml microbomb, and after replacing the inside of the bomb with hydrogen, hydrogen was added at 10 kgf / cm ² -G. And stirred at room temperature for 300 hours. At this time, WB by gas chromatography
As a result of measuring the amount of toluene generated by the dearylmethyl reaction of No. ₆ , it was found that almost 100% of the benzyl group had been eliminated. Then, the reaction solution was taken out, the reduction catalyst was removed, the solvent was distilled off under reduced pressure, and 100 ml of acetic anhydride was added as an acetylating agent.
However, gas chromatography did not confirm any hexaazaisowurtzitane derivative having an acyl group.

This is, W skeleton when a WB ₆ to reductive de-arylmethyl absence acylating agent suggesting that decomposition.

Comparative Example 2 [the WB ₆ after reductive de-arylmethyl with an acylating agent in the absence, the reaction acylating] Other possible without the addition of the acylating agent, hexa benzyl hexa A in the same manner as in Example 19 After performing reductive dearylmethylation in the absence of an acylating agent of zysoulitoltitanium, and after completion of the reaction, the same amount of the acylating agent used in Example 19 was added to the reaction solution, and the mixture was stirred under a nitrogen atmosphere for 5 hours. Thereafter, the reaction solution was treated in the same manner as in Example 19, but the presence of tetraacetyldibenzylhexaazaisowurtzitane could not be confirmed.

<Industrial Applicability> According to the present invention, a precursor of a polynitrated hexaazaisosoultitanium derivative useful as an explosive raw material and an additive for an explosive product, a raw material of a highly polar polymer, a high-density crosslinking agent,
And a hexaazaisowurtzitane derivative having an acyl group, which is useful as a polymer additive.

Claims (53)

(57) [Claims] 1. A hexaazaisowurtzitane derivative having an acyl group represented by the following formula (V): WA _t Q _(6-t) (V) wherein t is an integer of 4 to 6, A is an acyl group having 1 to 10 carbon atoms, and Q is each independently a hydrogen atom and / or 1 to 10 carbon atoms.
The alkyl group W leaves a hexavalent hexaazaisowurtzitanium residue represented by the following formula (2). ] 2. The derivative of claim 1, wherein t is 6. 3. The derivative of claim 1, wherein t is 4. 4. A method for producing a hexaacylhexaazaisowurtzitane represented by the following formula (4), wherein a hexaazaisowurtzitane derivative represented by the following formula (1) is acylated with an acylating agent. WA ₆ (4) wherein A is an acyl group having 1 to 10 carbon atoms, and W is the following formula (2)
Represents a hexavalent hexaazaisowurtzitane residue represented by ] WA _n H _(6-n) (1) wherein n is an integer of 4 to 5, H is a hydrogen atom, A and W
Represents a group defined above. ] 5. The method for producing hexaacylhexaazaisowurtzitane according to claim 4, wherein n is 4. 6. A hexaazaisulfurium derivative represented by the following formula (1) obtained by subjecting a hexaazaisowurtzine derivative represented by the following formula (VII) to reductive dearylmethylation in the absence of an acylating agent: A method for producing a hexaacylhexaazaisowurtzitane represented by the following formula (4), comprising synthesizing a titanium derivative and then acylating the hexaazaisowurtzitane derivative represented by the formula (1) with an acylating agent. WA ₆ (4) wherein A is an acyl group having 1 to 10 carbon atoms, and W is the following formula (2)
Represents a hexavalent hexaazaisowurtzitane residue represented by ] WA _n B _(6-n) (VII) wherein n is an integer of 4 to 5, B is an arylmethyl group having 7 to 21 carbon atoms, and A and W represent the groups defined above. WA _n H _(6-n) (1) wherein n is an integer of 4 to 5, H is a hydrogen atom, A and W
Represents a group defined above. ] 7. The method for producing hexaacylhexaazaisowurtzitane according to claim 6, wherein n is 4. 8. A hexakis (arylmethyl) hexaazaisowurtzitanium represented by the following formula (VI) is subjected to reductive dearylmethylation in the presence of an acylating agent to obtain the following formula (VII)
Synthesizes a hexaazaisowurtzitane derivative represented by
Next, the hexaazaisowurtzitane derivative represented by the formula (VII) is reductively dearylmethylated in the absence of an acylating agent to synthesize a hexaazaisowurtzitane derivative represented by the following formula (1). Then, a method for producing a hexaacylhexaazaisowurtzitane represented by the following formula (4), wherein the hexaazaisowurtzitane derivative represented by the general formula (1) is acylated with an acylating agent. WA ₆ (4) wherein A is an acyl group having 1 to 10 carbon atoms, and W is the following formula (2)
Represents a hexavalent hexaazaisowurtzitane residue represented by ] WB ₆ (VI) [wherein, B represents an arylmethyl group having 7 to 21 carbon atoms, and W represents a group defined above. WA _n B _(6-n) (VII) wherein n is an integer of 4 to 5, and B, A and W represent the groups defined above. WA _n H _(6-n) (1) wherein n is an integer of 4 to 5, H is a hydrogen atom, A and W
Represents a group defined above. ] 9. In the formulas (1) and (VII), n is 4
The method for producing hexaacylhexaazaisowurtzitane according to claim 8, wherein 10. An acylating agent for hexakis (arylmethyl) hexaazaisowurtzitane represented by the formula (VI)
The acyl acylating agent of a hexaazaisowurtzitane derivative represented by the general formula (1) is an acyl halide, which is a carboxylic acid ester of -hydroxysuccinimide. Production method. 11. An acylating agent for hexakis (arylmethyl) hexaazaisowurtzitanium represented by the formula (VI)
The hexoxy succinimide is a mixture of a carboxylic acid ester and a carboxylic anhydride, and the acylating agent for the hexaazaisowurtzitanium derivative represented by the formula (1) is an acyl halide. A method for producing acylhexaazaisosoultitanium. 12. The hexakis (arylmethyl) hexaazaisowurtzitanium acylating agent represented by the formula (VI) is a carboxylic anhydride, and the hexaazaisowurtzitanium derivative represented by the general formula (1) The method for producing hexaacylhexaazaisowurtzitane according to claim 8 or 9, wherein the acylating agent is an acyl halide. 13. A hexaazaisoulate represented by the following formula (1) obtained by subjecting a hexaazaisowurtzitane derivative represented by the following formula (VII) to reductive dearylmethylation in the absence of an acylating agent: A method for producing a soul titanium derivative. WA _n H _(6-n) (1) wherein n is an integer of 4 to 5, 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) Represents a hexavalent hexaazaisowurtzitane residue. ] WA _n B _(6-n) (VII) wherein n is an integer of 4 to 5, B is an arylmethyl group having 7 to 21 carbon atoms, and A and W represent the groups defined above. ] 14. The method for producing a hexaazaisowurtzitane derivative according to claim 13, wherein n in the formulas (1) and (VII) is 4. 15. A reductive dearylmethylation of hexakis (arylmethyl) hexaazaisowurtzitanium represented by the following formula (VI) in the presence of an acylating agent, and represented by the following formula (VII) The following formula (1) is obtained by synthesizing a hexaazaisowurtzitane derivative and then subjecting the hexaazaisowurtzitane derivative represented by the formula (VII) to reductive dearylmethylation in the absence of an acylating agent. A method for producing the represented hexaazaisowurtzitane derivative. WA _n H _(6-n) (1) wherein n is an integer of 4 to 5, 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) Represents a hexavalent hexaazaisowurtzitane residue. ] WB ₆ (VI) [wherein, B represents an arylmethyl group having 7 to 21 carbon atoms, and W represents a group defined above. WA _n B _(6-n) (VII) wherein n is the integer described above, and B, A and W represent the groups defined above. ] 16. The method for producing a hexaazaisowurtzitane derivative according to claim 15, wherein n in the formulas (1) and (VII) is 4. 17. An acylating agent for hexakis (arylmethyl) hexaazaisowurtzitanium represented by the formula (VI)
17. The method for producing a hexaazaisowurtzitane derivative according to claim 15, which is a carboxylic acid ester of hydroxysuccinimide. 18. An acylating agent for hexakis (arylmethyl) hexaazaisowurtzitane represented by the formula (VI)
17. The method for producing a hexaazaisowurtzitane derivative according to claim 15, which is a mixture of a carboxylic acid ester of hydroxysuccinimide and a carboxylic anhydride. 19. The process for producing a hexaazaisowurtzitane derivative according to claim 15 or 16, wherein the acylating agent of hexakis (arylmethyl) hexaazaisowurtitanium represented by the formula (VI) is a carboxylic anhydride. 20. Reductive dearylmethylation of hexakis (arylmethyl) hexaazaisowurtzitanium represented by the following formula (VI) in the presence of an acylating agent to give the following formula (VI)
The following formula (VII) comprising synthesizing a hexaazaisowurtzitane derivative represented by the formula (I) and separating the hexaazaisowurtzitane derivative represented by the formula (VII)
A method for producing a hexaazaisoulitanium derivative represented by the formula: WA _n B _(6-n) (VII) wherein n is an integer of 4 to 5, A is an acyl group having 1 to 10 carbon atoms, B is an arylmethyl group having 7 to 21 carbon atoms, and W is It represents a hexavalent hexaazaisowurtzitanium residue represented by (2). ] WB ₆ (VI) wherein A, B and W represent the groups defined above. ] 21. The method according to claim 2, wherein n in the formula (VII) is 4.
A method for producing a hexaazaisowurtzitane derivative. 22. The acylating agent for hexakis (arylmethyl) hexaazaisowurtzitane represented by the formula (VI)
22. The method for producing a hexaazaisowurtzitane derivative according to claim 20 or 21, which is a carboxylic acid ester of hydroxysuccinimide. 23. The acylating agent for hexakis (arylmethyl) hexaazaisowurtzitane represented by the formula (VI)
22. The method for producing a hexaazaisowurtzitane derivative according to claim 20, which is a mixture of a carboxylic acid ester of hydroxysuccinimide and a carboxylic anhydride. 24. The process for producing a hexaazaisowurtzitane derivative according to claim 20 or 21, wherein the acylating agent for hexakis (arylmethyl) hexaazaisowurtzitane represented by the formula (VI) is a carboxylic anhydride. (25) A hexakis (arylmethyl) hexaazaisowurtzitanium represented by the following formula (VI) is subjected to reductive dearylmethylation in the presence of an acylating agent to give a compound of the formula (VIII)
Synthesizes a hexaazaisowurtzitane derivative represented by
Next, a hexaazaisowurtzitane derivative represented by the following formula (V), which is obtained by further subjecting the hexaazaisowurtzitane derivative represented by the formula (VIII) to reductive dearylmethylation in the presence of an acylating agent, Alternatively, a method for producing a mixture of the same with a hexaazaisowurtzitane derivative represented by the following formula (VIII): WA _t Q _(6-t) (V) wherein t is an integer of 4 to 6, A is an acyl group having 1 to 10 carbon atoms, and Q is each independently a hydrogen atom and / or 1 to 10 carbon atoms.
And W represents a hexavalent hexaazaisowurtzitanium residue represented by the following formula (2). ] _{WA p B (6-p)} (VIII) wherein, p is an integer of 1 to 5, B represents an arylmethyl group, A and W are as defined above group of 7 to 21 carbon atoms. WB ₆ (VI) wherein A, B and W represent the groups defined above. ] 26. An acylating agent for a hexakis (arylmethyl) hexaazaisowurtzitanium represented by the formula (VI) and an acylating agent for a hexaazaisowurtzitane derivative represented by the formula (VIII) are N- 26. The production method according to claim 25, which is a carboxylic acid ester of hydroxysuccinimide. 27. An acylating agent for hexakis (arylmethyl) hexaazaisowurtitanium represented by the formula (6) and an acylating agent for a hexaazaisowurtzitane derivative represented by the formula (VIII) are N- 26. The production method according to claim 25, which is a mixture of a carboxylic acid ester of hydroxysuccinimide and a carboxylic anhydride. 28. An acylating agent for hexakis (arylmethyl) hexaazaisowurtitanium represented by the formula (VI) and an acylating agent for a hexaazaisowurtzitane derivative represented by the formula (VIII) are carboxylic acid 26. The production method according to claim 25, which is an anhydride. 29. A hexaazaisowurtzitane derivative having a nitroso group represented by the following formula (IX). WA _n (NO) _(6-n) (IX) [wherein, n is an integer of 4 to 5, A is an acyl group having 1 to 10 carbon atoms, NO is a nitroso group, and W is represented by the following formula (2). Represents the hexavalent hexaazaisowurtzitane residue to be formed. ] 30. A hexaazaisowurtzitane derivative having a nitro group represented by the following general formula (X). WA _n (NO ₂ ) _(6-n) (X) wherein n is an integer of 4 to 5, A is an acyl group having 1 to 10 carbon atoms, NO ₂ is a nitro group, and W is the above formula (2) Represents a hexavalent hexaazaisowurtzitane residue represented by ] 31. The following formulas (1), (4), (IX),
A method for producing hexanitrohexaazaisowurtzitane represented by the following formula (XI), wherein the hexaazaisowurtzitane derivative represented by (X) is nitrated with a nitrating agent. W (NO ₂ ) ₆ (XI) [wherein, NO ₂ represents a nitro group, and W represents a hexavalent hexaazaisowurtzitanium residue represented by the following formula (2). ] WA ₆ (4) WA _n H _(6-n) (1) WA _n (NO) _(6-n) (IX) WA _n (NO ₂ ) _(6-n) (X) [Equation (4), ( 1), (IX) and (X), n is an integer of 4 to 5, A is an acyl group having 1 to 10 carbon atoms, H is a hydrogen atom, B is
The arylmethyl group, NO is a nitroso group, NO ₂ represents a nitro group, W represents a hexavalent hexa A wood Seoul titanium residue represented by the formula (2). ] 32. The method according to claim 31, wherein the nitrating agent of the hexaazaisowurtzitane derivative represented by the formula (1), (4), (IX) or (X) is a nitrating agent containing a strong protonic acid. Method. 33. The method according to claim 32, wherein the strong protic acid is one selected from the group consisting of sulfuric acid and trifluoroacetic acid. 34. Hexakis (arylmethyl) hexaazaisowurtzitane represented by the following formula (VI) is subjected to reductive dearylmethylation in the presence of an acylating agent, and is represented by the following formula (VII). A hexaazaisowurtzitanium derivative is synthesized and subjected to reductive dearylmethylation in the absence of an acylating agent to obtain a hexaazaisowurtzitanium derivative represented by the following formula (1). A method for producing hexanitrohexaazaisosoultitanium represented by the following formula (XI): W (NO ₂ ) ₆ (XI) [wherein, NO ₂ represents a nitro group, and W represents a hexavalent hexaazaisowurtzitanium residue represented by the following formula (2). ] WB ₆ (VI) [wherein, B represents an arylmethyl group having 7 to 21 carbon atoms, and W represents a group defined above. WA _n B _(6-n) (VII) wherein n is an integer of 4 to 5, A is an acyl group having 1 to 10 carbon atoms, and B and W represent the groups defined above. WA _n H _(6-n) (1) [wherein, H is a hydrogen atom, n is the integer described above, and A and W represent the groups defined above. ] 35. The method according to claim 34, wherein the nitrating agent of the hexaazaisowurtzitanium derivative represented by the formula (1) is a strong protonic acid-containing nitrating agent. 36. The method according to claim 35, wherein the strong protic acid is one selected from the group consisting of sulfuric acid and trifluoroacetic acid. 37. Nitrosation of a hexaazaisowurtzitane derivative represented by the following formula (1) to give the following formula (IX)
Synthesizes a hexaazaisowurtzitane derivative represented by
It is nitrated to give a hexaazaisowurtzitanium derivative represented by the following formula (X), and then the derivative is nitrated to form a hexanitrohexaazaisowurtzitanium represented by the following formula (XI): Production method. W (NO ₂ ) ₆ (XI) [wherein, NO ₂ represents a nitro group, and W represents a hexavalent hexaazaisowurtzitanium residue represented by the following formula (2). ] WA _n H _(6-n) (1) [wherein, n is an integer of 4 to 5, A is an acyl group having 1 to 10 carbon atoms, H is a hydrogen atom, and W is a group defined above. WA _n (NO) _(6-n) (IX) [wherein, NO represents a nitroso group, n represents the above integer, and A, H and W represent the groups defined above. WA _n (NO ₂ ) _(6-n) (X) [wherein, NO ₂ is a nitro group, n is the above integer, and A, H and W represent the groups defined above]. ] 38. The process according to claim 37, wherein the nitrosating agent of the hexaazaisowurtzitanium derivative represented by the formula (1) is a mixture of sodium nitrite and an acid. 39. The method according to claim 37, wherein the nitrosating agent of the hexaazaisowurtzitanium derivative represented by the formula (IX) is nitric acid. 40. The method according to claim 37, wherein the nitrating agent of the hexaazaisowurtzitane derivative represented by the formula (IX) is hydrogen peroxide or a mixture of hydrogen peroxide and nitric acid. 41. The method according to claim 37, wherein the nitrating agent of the hexaazaisowurtzitanium derivative represented by the formula (X) is a nitrating agent containing a strong protonic acid. 42. The method according to claim 41, wherein the strong protonic acid is one selected from the group consisting of sulfuric acid and trifluoroacetic acid. 43. A method for producing a hexaazaisowurtzitane derivative represented by the following formula (IX), wherein a hexaazaisowurtzitane derivative represented by the following formula (1) is nitrosated with a nitrosating agent. WA _n (NO) _(6-n) (IX) [wherein n is an integer of 4 to 5, A is an acyl group having 1 to 10 carbon atoms, NO is a nitroso group, and W is represented by the following formula (2). Represents the hexavalent hexaazaisowurtzitane residue to be formed. ] WA _n H _(6-n) (1) [wherein, H is a hydrogen atom, n is the integer described above, and A and W represent the groups defined above. ] 44. The method according to claim 43, wherein the nitrosating agent of the hexaazaisowurtzitanium derivative represented by the formula (1) is a mixture of sodium sulfite and an acid. 45. A method for producing a hexaazaisowurtzitane derivative represented by the following formula (X), wherein a hexaazaisowurtzitane derivative represented by the following formula (IX) is nitrated with a nitrating agent. WA _n (NO ₂ ) _(6-n) (X) wherein n is an integer of 4 to 5, A is an acyl group having 1 to 10 carbon atoms, NO ₂ is a nitro group, and W is a compound represented by the following formula (2) Represents a hexavalent hexaazaisowurtzitane residue represented by ] WA _n (NO) _(6-n) (IX) [wherein, NO represents a nitroso group, n represents the above integer, and A, H, and W represent the groups defined above. ] 46. The method according to claim 45, wherein the nitrating agent of the hexaazaisowurtzitanium derivative represented by the formula (IX) is nitric acid. 47. The method according to claim 45, wherein the nitrosating agent of the hexaazaisowurtzitanium derivative represented by the formula (IX) is hydrogen peroxide or a mixture of hydrogen peroxide and nitric acid. 48. A process for producing a hexaazaisowurtzitane derivative represented by the following formula (X), wherein a hexaazaisowurtzitane derivative represented by the following formula (1) is nitrated with a nitrolating agent. WA _n (NO ₂ ) _(6-n) (X) wherein n is an integer of 4 to 5, A is an acyl group having 1 to 10 carbon atoms, NO ₂ is a nitro group, and W is a compound represented by the following formula (2) Represents a hexavalent hexaazaisowurtzitane residue represented by ] WA _n H _(6-n) (1) [wherein, H is a hydrogen atom, n is the integer described above, and A and W represent the groups defined above. ] 49. The method according to claim 48, wherein the nitrating agent of the hexaazaisowurtzitane derivative represented by the formula (1) is nitric acid or a mixture of nitric acid and nitrous oxide. 50. A method for producing a hexaazaisowurtzitanium derivative represented by the following formula (X), wherein a hexaacylhexaazaisowurtzitanium represented by the following formula (4) is nitrated with a nitrating agent: . WA _n (NO ₂ ) _(6-n) (X) wherein n is an integer of 4 to 5, A is an acyl group having 1 to 10 carbon atoms, NO ₂ is a nitro group, and W is a compound represented by the following formula (2) Represents a hexavalent hexaazaisowurtzitane residue represented by ] WA ₆ (4) wherein A and W represent the groups defined above. ] 51. The method according to claim 50, wherein the nitrating agent is a mixture of nitric acid and nitrous oxide. 52. Hexakis (arylmethyl) hexaazaisowurtzitanium represented by the following formula (VI) is subjected to reductive dearylmethylation in the presence of an acylating agent to give the following formula (XI)
A method for synthesizing a hexaazaisowurtzitane derivative represented by the formula (I) and then separating the derivative, thereby producing a hexanitrohexaazaisowurtzitane represented by the following formula (XII). WA _n Q _(6-n) (XII) wherein n is an integer of 4 to 5, A is an acyl group having 1 to 10 carbon atoms, and Q is each independently a hydrogen atom and / or 1 to 10 carbon atoms.
W represents a hexavalent hexaazaisowurtzitanium residue represented by the following formula (2) except that all are hydrogen atoms. ] WB ₆ (VI) [wherein, B represents an arylmethyl group having 7 to 21 carbon atoms, and W represents a group defined above. ] 53. A hexaazaisulfurium derivative represented by the following formula (XII), which is reductively dearylmethylated in the presence of an acylating agent of a hexaazaisowurtzine derivative represented by the following formula (VII): A method for producing a hexaazaisowurtzitanium derivative represented by the following formula (XII), in which a titanium derivative is synthesized and then separated. WA _n Q _(6-n) (XII) wherein n is an integer of 4 to 5, A is an acyl group having 1 to 10 carbon atoms, and Q is each independently a hydrogen atom and / or 1 to 10 carbon atoms.
W represents a hexavalent hexaazaisowurtzitanium residue represented by the following formula (2) except that all are hydrogen atoms. ] WA _n B _(6-n) (VII) [wherein, B is an arylmethyl group having 7 to 21 carbon atoms, n is the integer described above, and A and W represent the groups defined above. ]