CN1241568A

CN1241568A - Hexaaxaisowurtzitane derivative and method for producing the same

Info

Publication number: CN1241568A
Application number: CN 99108921
Authority: CN
Inventors: 儿玉保; 东條正弘; 池田正纪
Original assignee: Asahi Kasei Kogyo KK
Current assignee: Asahi Kasei Corp
Priority date: 1995-02-01
Filing date: 1999-06-30
Publication date: 2000-01-19

Abstract

Disclosed is an acyl group-containing hexaazaisowurtzitane derivatives represented by the general formula WAn(NO2)(6-n), wherein n represents an integer of 4 to 6; A independently represents C1-C10 acyl; NO2 represents nitro; and W represents a hexavalent hexaazaisowurtzitane residue represented by formula (II). Also disclosed is a method for producing the above-mentioned acyl group-containing hexaazaisowurtzitane derivative. The derivatives can be used not only as raw materials for explosives but also as an additive for propellants and explosives.

Description

Hexaazaisowurtzitane derivative containing acyl and nitro and preparation method thereof

The invention relates to an acyl and nitro hexaazaisowurtzitane (hexaazaisowurtzitane) derivative and a preparation method thereof. More specifically, the present invention relates to acyl group-and nitro group-containing hexaazaisowurtzitane derivatives represented by the following formula (VIII):

WA_n(NO₂)_(6-n)(VIII)

in which n represents an integer from 4 to 5, A independently of one another represents C₁-C₁₀Acyl radical, NO₂Represents a nitro group, W represents a hexavalent residue of a hexaazaisowurtzitane of the following formula (II)

Acyl and nitro group-containing hexaazaisowurtzitane derivative WA_n(NO₂)_(6-n)[ hereinafter abbreviated as "ANW"]Not only can be used as hexanitrohexaazaisowurtzitane W (NO)₂)₆[ will be described in detail below]Can be used as an additive for modifying the properties of propellants and explosives (such as mechanical properties, explosion velocity, explosion pressure, combustion velocity, pressure index, sensitivity and heat resistance) and can also be used as a high-performance raw material for explosives. The present invention also relates to a process for producing the above acyl group-and nitro group-containing hexaazaisowurtzitane derivative from an acyl group-containing hexaazaisowurtzitane derivative or from a nitroso group-containing hexaazaisowurtzitane derivative derived from an acyl group-containing hexaazaisowurtzitane derivative.

The acyl-containing hexaazaisowurtzitane derivative has A high content of N-A group (wherein A represents an acyl group) and optionally N-H group(s), wherein each N-A group isAnd the N-H group can be converted to N-NO by various nitration processes₂A group.

Therefore, the acyl group-containing hexaazaisowurtzitane derivative is useful as a precursor of a polynitrohexaazaisowurtzitane derivative which is useful not only as a raw material for anexplosive but also as an additive for a propellant and an explosive. More specifically, the polynitrohexaazaisowurtzitane derivatives can be advantageously used as additives for propellants and explosives to improve various properties (such as mechanical properties, explosion speed, explosion pressure, combustion speed, pressure index, sensitivity and heat resistance). Furthermore, hexanitrohexaazaisowurtzitane W (NO)₂)₆(hereinafter often abbreviated as "HNW", which is a polynitrohexaazaisowurtzitane derivativeRepresentative) is likely to be the feedstock for a new generation of high explosive. As described above, the acyl group-containing hexaazaisowurtzitane derivative is useful as a precursor of this valuable polynitrohexaazaisowurtzitane derivative.

Further, the acyl group-containing hexaazaisowurtzitane derivative can be advantageously used for the preparation of A highly polar polymer having A high content of acyl group in the main chain and/or side chain thereof, by virtue of the respective reactivity of the N-A group (A represents an acyl group) and the N-H group contained therein. Such a highly polar polymer can be used not only as a highly hydrophilic polymer but also as a highly dielectric polymer.

In addition, the acyl group-containing hexaazaisowurtzitane derivative can be advantageously used as a polyfunctional crosslinking agent by virtue of the reactivity of the derivative.

Further, the acyl group-containing hexaazaisowurtzitane derivative is useful as various additives such as a polymer modifier and the like.

However, it is represented by the following formula (VIII): WA_n(NO₂)_(6-n)The acyl group-and nitro group-containing hexaazaisowurtzitane derivative represented by the following formula (wherein n, A and W are as defined above) and the process for producing the same are not known.

In the present specification, for the sake of convenience, the term "polynitrohexaazaisowurtzitane derivative" includes not only hexanitrohexaazaisowurtzitane but also ANW, which includes a compound having a single nitro group as well as a compound having two nitro groups.

In addition to the above-mentioned HNW, other known compounds having the same hexaazaisowurtzitane skeleton (hereinafter simply referred to as "W") as the acyl group-containing hexaazaisowurtzitane derivative include:

(1) hexakis (arylmethyl) hexaazaisowurtzitane (herein abbreviated as "HBW");

(2) tetraacetyldibenzylhexaazaisowurtzitane (abbreviated herein as "TADBW") and

(3) hexaazaisowurtzitane (abbreviated herein as "HCW") having trimethylsilylethoxycarbonyl group (see unexamined Japanese patent application laid-open Specification No. 6-321962).

It is known that HBW can be prepared by condensation of various arylmethylamines with glyoxal [ see J.org.chem., vol.55, 1459-.

TADBW has been reported to be useful as a feedstock for making explosives [ see The MilitariyCritical Technologies List, Office of The Under secret of defenses for acquisition, 12-22 (10.1992)]. However, this document neither reports on the process of converting TADBW into explosive and the chemical structure of the resulting explosive nor describes a process for producing TADBW.

The properties of HNW that are expected to be useful as feedstock for high explosive are described in International Symposium on Energetic Materials Technology, PROCEEDINGS, SEPTEMBER 24-27, 76-81 (1995): COMBUSTIONAND FLAME 87, 145-151(1991), etc., but no literature reports the preparation method of HNW.

At the beginning, in order to develop a method for producing a polynitrohexaazaisowurtzitane derivative such as HNW,the present inventors tried to nitrify HBW and TADBW under various nitrification conditions, but could not obtain a satisfactory amount of the polynitrohexaazaisowurtzitane derivative. Furthermore, HBW and TADBW have benzyl groups, and therefore, when HBW or TADBW is nitrated, a by-product, a nitroaromatic compound having high affinity for various nitro compounds, is inevitably formed. Therefore, it is difficult to separate the desired polynitrohexaazaisowurtzitane derivatives from the nitroaromatic by-products.

It is also difficult to produce HCW in high yield because hydrochloric acid, which is a strong acid, is generated when HCW is produced and can decompose the raw material HBW.

Therefore, none of the W skeleton-containing compounds HBW, TADBW and HCW is suitable for use as a precursor for the industrial production of polynitrohexaazaisowurtzitane derivatives.

Further, as described above, the following formula (VIII): WA_n(NO₂)_(6-n)(wherein n, A and W are as defined above) andnitrohexaazaisowurtzitane derivatives and processes for producing the same are unknown.

Accordingly, the present inventors have made extensive and intensive studies with a view to developing an advantageous industrial production process of a polynitrohexaazaisowurtzitane derivative, and have intended to develop a precursor which can be easily converted into a polynitrohexaazaisowurtzitane derivative, and also to develop a process for producing the precursor.

As a result, it has been unexpectedly found that hexaazaisowurtzitane derivatives having a polar group consisting of only N-acyl groups and optionally N-H groups are useful as precursors of polynitrohexaazaisowurtzitane derivatives. The present inventors have also found an advantageous industrial process for producing the above hexaazaisowurtzitane derivative in high yield. Further, the present inventors have also found that, as described above, ANW, i.e., an acyl group-and nitro group-containing hexaazaisowurtzitane-type structural alkane derivative, can be used not only as a precursor of HNW but also as an additive for modifying a propellant and an explosive and further as a high-performance raw material for an explosive, and found an industrially advantageous process for producing ANW in high yield. It has also been found that hexaazaisowurtzitane type structural alkanes having N-acyl, N-alkyl and optionally N-H groups can be advantageously used as multifunctional crosslinkers. The present invention has been completed based on the above findings.

An object of the present invention is to provide the above acyl group-and nitro group-containing hexaazaisowurtzitane derivative, and another object thereof is to provide a process for producing the same.

Accordingly, the present invention provides an acyl group-and nitro group-containing hexaazaisowurtzitane derivative represented by the following formula (VIII):

WA_n(NO₂)_(6-n)(VIII)

In order that the invention may be more readily understood, the main features and different preferred embodiments of the invention are listed below:

1. an acyl and nitro group-containing hexaazaisowurtzitane derivative represented by the following formula (VIII):

WA_n(NO₂)_(6-n)(VIII)

2. A process for producing an acyl and nitro group-containing hexaazaisowurtzitane derivative represented by the following formula (VIII):

WA_n(NO₂)_(6-n)(VIII)

The method comprises nitrifying a nitrosohexaazaisowurtzitane derivative represented by the following formula (VII):

WA_n(NO)_(6-n)(VII)

wherein NO represents a nitroso group, and n, A and W are as defined above.

3. The method according to item 2 above, wherein the nitrating agent is nitric acid.

4. The method according to item 2 above, wherein the nitro reagent is hydrogen peroxide or a mixture of hydrogen peroxide and nitric acid.

5. A process for producing an acyl and nitro group-containing hexaazaisowurtzitane derivative represented by the following formula (VIII):

WA_n(NO₂)_(6-n)(VIII)

The method comprises nitrating a hexaazaisowurtzitane derivative represented by the following formula (IV) with a nitrating agent:

WA_nH_(6-n)(IV)

wherein H represents a hydrogen atom, and n, A and W are as defined above.

6. The method according to item 5 above, wherein the nitrating agent is nitric acid or a mixture of nitric acid and dinitrogen pentoxide.

7. A process for producing an acyl and nitro group-containing hexaazaisowurtzitane derivative represented by the following formula (VIII):

WA_n(NO₂)_(6-n)(VIII)

in which n represents an integer from 4 to 5, A independently of one another represents C₁-C₁₀Acyl radical, NO₂Represents a nitro group, W represents a hexaazaisowurtzitane of the formula (II)Residue:

the method comprises nitrating a hexaacyl hexaazaisowurtzitane derivative represented by the following formula (III):

WA₆(III)

wherein A and W are as defined above.

8. The method according to item 7 above, wherein the nitrating agent is a mixture of nitric acid and dinitrogen pentoxide.

The acyl group-containing hexaazaisowurtzitane derivative represented by the following formula (I) is a useful precursor of polynitrohexaazaisowurtzitane derivative:

WA_tQ_(6-t)(I)

wherein t represents an integer of 4 to 6, and A independently represents C₁-C₁₀Acyl, Q independently of one another represent a hydrogen atom or C₁-C₁₀Alkyl, W represents the hexavalent residue of hexaazaisowurtzitane of the following formula (II)

As will be described in more detail below, the compounds of formula (I) above include compounds used in the process of the present invention as starting materials for the preparation of ANW.

As typical examples of the compounds of the above formula (I) and useful as starting materials for preparing ANW, the following discussion will be made with reference to acyl-containing hexaazaisowurtzitane derivatives represented by the following formula (I-a):

WA_tH_(6-t)(I-a)

wherein t represents an integer of 4 to 6, and A represents C₁-C₁₀Acyl, H represents a hydrogen atom, W represents a hexavalent residue of a hexaazaisowurtzitane of the following formula (II):

the acyl group A on the hexaazaisowurtzitane derivative is not particularly limited as long as it has 1 to 10 carbon atoms. The acyl group may be substituted with a substituent that is stable under the reductive dearylmethylation conditions employed in the methods described below. Examples of the acyl group include acetyl, propionyl, butyryl, isobutyryl, valeryl, hexanoyl and 2-phenylacetyl; preferably C therein₂-C₅Acyl groups such as acetyl, propionyl, butyryl and valeryl; more preferably C₂-C₃Acyl groups such as acetyl and propionyl. The acyl groups represented by At in the above formula (I-a) may be the same or different.

For the formula (I-a) WA_tH_(6-t)The acyl-containing hexaazaisowurtzitane derivative can exist in various isomers, and t of the isomers is a numerical phaseLikewise, the positions of the N-acyl and N-H groups are different.

For example, as formula (I-a) WA wherein t is 4_tH_(6-t)Formula WA₄H₂As examples of the compounds shown, compounds shown by the following formula (I-a') can be cited, but formula WA₄H₂The compound may be any structural isomer of the compound of the following formula (I-a'):

in acyl group-containing hexaazaisowurtzitane derivative WA_tH_(6-t)In the formula, t represents an integer of 4 to 6, preferably 4 or 6.

One preferable example of the acyl group-containing hexaazaisowurtzitane derivative of the present invention is a compound represented by the formula (I-a) wherein n is 6, namely, hexaacyl hexaazaisowurtzitane represented by the following formula (III):

WA₆(III)

in the formula: a represents C₁-C₁₀Acyl, and W represents the hexavalent residue of a hexaazaisowurtzitane-type structure alkane.

The hexaacyl hexaazaisowurtzitane compound of the above formula (III) has an advantage that it is easy to obtain a very pure product because of its simple structure. It should also be noted here that, among the compounds of formula (III), the hexaacetyl compound can be purified by sublimation, and therefore WA of high purity can be easily isolated from the reaction mixture₆(A is acetyl).

Another preferred example of the acyl group-containing hexaazaisowurtzitane derivative is a compound represented by the formula (I-a) wherein t is 4. The compound has the advantage that N-H groups contained therein can be selectively reacted due to their high reactivity. For example, a dinitrohexaazaisowurtzitane derivative can be easily obtained in high yield by selective nitration of N-H groups.

As described above, the acyl group-containing hexaazaisowurtzitane derivative has A high content of N-A group (A represents an acyl group) such as optional N-H group, and each of the N-A group and the N-H group can be nitrated by various kindsProcess for conversion to N-NO₂A group.

The following examples describe the preparation of acyl group-containing hexaazaisowurtzitane derivatives of the formula (I-a).

As a preferred example of the acyl group-containing hexaazaisowurtzitane derivative, a hexaacyl hexaazaisowurtzitane WA₆Can be prepared by reacting acyl group-containing hexaazaisowurtzitane derivative WA_nH_(6-n)(n is 4 or 6) by acylation with an acylating agent, as shown in the following formula (1):

in the formula: n represents an integer of 4 to 5, A represents C₁-C₁₀Acyl, H represents a hydrogen atom, and W represents a hexavalent residue of a hexaazaisowurtzitane-type structure alkane.

WA used in the reaction represented by the formula (1)_nH_(6-n)(n is 4 or 5) has not been disclosed in the prior art documents, and was synthesized for the first time by the present inventors. WA_nH_(6-n)The preparation method of (A) requires first discussing WA₆The preparation method of (1).

The acylating agent used in the reaction represented by formula (1) is not particularlylimited as long as it can acylate WA_nH_(6-n)The secondary amino group contained in (n is 4 or 5) may be used. Examples of acylating agents include: acyl halides such as acetyl chloride, acetyl bromide and propionyl chloride; carboxylic acid esters of N-hydroxysuccinimide, such as N-acetoxysuccinimide, N-propionyloxysuccinimide, and N- (2-phenylacetyloxy) succinimide; carboxylic anhydrides such as acetic anhydride, propionic anhydride, lactic anhydride and mixed anhydrides of acetic acid and formic acid; and acylimidazoles such as acetyl imidazole and propionyl imidazole. Among the above acylating agents, acid halides (such as acetyl chloride, propionyl chloride, etc.) are preferred.

The reaction solvent used in the reaction represented by formula (1) is not particularly limited as long as it can dissolve WA_nH_(6-n)(n is 4 or 5) and does not adversely affect the reaction. Examples of the solvent include: carboxylic acids such as acetic acid, propionic acid and lactic acid; aprotic polar solvents such as dimethyl sulfoxide and dimethylacetamide; and carboxylic acid anhydrideSuch as acetic anhydride and propionic anhydride. Preferred are carboxylic anhydrides (e.g., acetic anhydride, propionic anhydride, etc.). The above solvents may be used alone or in combination.

The reaction temperature of the reaction represented by the formula (1) is generally from-10 ℃ to 300 ℃, preferably from 0 ℃ to 150 ℃.

WA obtained by the reaction of formula (1)₆Can be isolated by conventional methods. For example, WA may be obtained by distilling off the solvent from the reaction mixture after the reaction is complete₆Isolation (see, e.g., example 1). In addition, WA can also be prepared by conventional method₆And (5) purifying. Examples of the purification method include: separating the WA at 270 ℃ and a low pressure of 100mmHg₆Sublimation (see,e.g., reference example 1); separating the WA in toluene₆Recrystallization (see, for example, reference example 2); and separating the WA₆Reprecipitation in chloroform.

Compound WA₆It can also be prepared as follows: formula WA_nB_(6-n)The acyl-containing and arylmethyl-containing hexaazaisowurtzitane derivative is subjected to reduction dearylmethylation, and then acylated by an acylating reagent, wherein the acylation is shown in the following formula (2)

Wherein n represents an integer of 4 to 5, and A represents C₁-C₁₀Acyl group, B represents an arylmethyl group represented by the following formula (XIII), H represents a hydrogen atom, and W represents a hexavalent residue of hexaazaisowurtzitane.

In the reaction represented by the above formula (2), with respect to the starting compound WA_nB_(6-n)The source and the preparation method of (b) are not particularly limited. For example, a hexaazaisowurtzitane (WB) having a hexaazaisowurtzitane structure obtained by the following method₆) Prepared WA_nB_(6-n)Also, commercially available WA may be used_nB_(6-n)。

In the process represented by the above formula (2), the reductive dearylmethylation (step a) can be carried out by any conventional method as long as it can carry out WA_nB_(6-n)The reduction dearylmethylation reaction is carried out. Generally, by subjecting WA to_nB_(6-n)Is contacted with a reduction catalyst in the presence of a reducing agent,to carry out reductive dearylmethylation (step a).

The reducing agent is usually hydrogen, hydrazine, formic acid or the like, and hydrogen is preferred. The reduction catalyst generally uses a catalyst containing a platinum group metal or a derivative thereof. Preferred examples of the reducing catalyst include Pd compounds [ e.g., Pd (OAc)]₂、PdCl₂、Pd(NO₃)₂、PdO、Pd(OH)₂、Pd₃Pb₁And Pd₃Te₁]Pd alloys and metallic Pd and Ru compounds (e.g. RuCl)₃) Ru alloy and Ru metal, more preferably Pd compound [ e.g. Pd (OAc)]₂、PdCl₂Etc. of]Pd alloy and metallic Pd. These reduction catalysts can be used directly. In addition, these reduction catalysts can be used after being supported on various supports such as activated carbon, silica, alumina, silica-alumina, zeolite and activated clay. These catalysts may be subjected to a reduction treatment before use. When the catalyst supported on a carrier is used, the acidity of the surface of the carrier can be controlled by deactivating the acidic sites on the surface of the carrier by a method such as silylation or acylation, or by treating the carrier so that a basic substance (e.g., NaOH) is adsorbed on the surface of the carrier. The amount of reducing catalyst used depends on the reducing activity of the catalyst. However, with the metal in the catalyst and WA_nB_(6-n)The weight ratio of (A) represents that the catalyst is used in an amount of usually 0.0001 to 10, preferably 0.001 to 1.

The solvent used in the reductive dearylmethylation (step a) of the process represented by the above formula (2) is not particularly limited as long as the solvent can dissolve WA_nB_(6-n)And does not adversely affect the reaction. Examples of the solvent include: carboxylic acids such as acetic acid, propionic acid and lactic acid; amides such as dimethylacetamide; and amines, such as N, N-dimethylaniline. The above solvents may be used alone or in combination. In order to achieve a high reaction rate, it is preferable to use a carboxylic acid (e.g.,acetic acid or propionic acid, etc.) as a solvent.

The amount of the solvent used depends on the dissolving power of the solvent and the reaction temperature. With a solvent and WA_nB_(6-n)The weight ratio of (A) to (B) means that the amount of the solvent used is usually 1 to 500, preferably 5 to 100.

Formula (A), (B) and2) the reaction pressure for the reductive dearylmethylation (step a) in the process shown is generally from 0.1 to 1000kgf/cm²Preferably 1 to 100kgf/cm². When hydrogen is used as the reducing agent, the reaction pressure is preferably from 0.1 to 500kgf/cm in terms of the hydrogen partial pressure²More preferably 1 to 100kgf/cm². In addition to hydrogen, inert gases such as nitrogen, argon and helium may be present in the reaction system.

The reaction temperature for the reductive dearylmethylation (step a) in the process represented by the formula (2) is generally from-20 ℃ to 300 ℃, preferably from 0 ℃ to 200 ℃.

The reaction time for the reductive dearylmethylation (step a) in the process represented by formula (2) depends on the kind of catalyst, solvent, and the like. The reaction time is usually 0.1 to 500 hours, preferably 1 to 200 hours.

Compound WA WAs synthesized by reductive dearylmethylation (step a) in the method represented by formula (2)_nH_(6-n)(wherein n is 4 or 5). Then, the synthesized WA_nH_(6-n)Acylation in the process represented by the formula (2) (step b) is carried out.

The acylating agent, solvent and reaction conditions (e.g., reaction temperature) used in the acylation in the process represented by formula (2) (step b) are as described for the acylation reaction represented by formula (1).

The WA obtained₆The separation and purification can be carried out by the method mentioned in the reaction represented by the above formula (1).

As an example of the acyl group-containing hexaazaisowurtzitane derivative, WA₆It can also be prepared as follows: WB is reacted in the presence of an acylating agent₆Reductive dearylmethylation to provide a first reaction product, followed by reductive dearylmethylation of the first reaction product in the absence of an acylating agent to provide a second reaction product, followed by acylation of the second reaction product, as shown in formula (3) below:

wherein n represents an integer of 4 to 5, and A represents C₁-C₁₀Acyl, B is arylmethyl, and W is a hexavalent residue of a hexaazaisowurtzitane.

In the process of the formula (3), reductive dearylmethylation in the presence of an acylating agent (step a) is carried out by reacting WB with a reducing agent in the presence of an acylating agent₆By contact with a reducing catalyst. The reducing agent and the catalyst are not particularly limited as long as they promote WB₆The reduction of (2) is sufficient to remove arylmethylation without deactivating the acylating agent in the reaction system. As the reducing agent, hydrogen gas, formic acid or the like is generally used, and hydrogen gas is preferred. The reduction catalyst is as described in the reductive dearylmethylation (step a) of the process represented by the above formula (2).

The amount of catalyst used depends on the reducing activity of the catalyst. With the metal in the catalyst and WB₆The amount of this procatalyst used is usually 0.0001 to 20, preferably 0.001 to 10, by weight.

In the process represented by the formula (3), when reductive dearylmethylation is carried out in the presence of an acylating agent, the acylating agent used is not particularly limited as long as it can acylate WB₆By reductive dearylmethylation of the secondary amino group formed. Examples of acylating agents include: carboxylic acid esters of N-hydroxysuccinimide, such as N-acetoxysuccinimide, N-propionyloxysuccinimide, and N- (2-phenylacetyloxy) succinimide; carboxylic acid anhydrides such as acetic anhydride, propionic anhydride, lactic anhydride and mixed anhydrides of acetic acid and formic acid; and acylimidazoles such as acetyl imidazole and propionyl imidazole. The acylating agent is preferably a carboxylic acid anhydride of N-hydroxysuccinimide (e.g., N-acetoxysuccinimide, N-propionyloxysuccinimide, etc.) because they can enhance the formation of WA_nB_(6-n)(wherein n is 4 or 5). These acylating agents may be used alone or in admixture thereof. The acylating agent is particularly preferably a mixture of a carboxylic acid ester of N-hydroxysuccinimide (e.g., N-acetoxysuccinimide or N-propionyloxysuccinimide, etc.) and a carboxylic acid anhydride (e.g., acetic anhydride or propionic anhydride, etc.), since this not only enhances the process of step a [ formula (3)]]The reaction rate of reductive dearylmethylation of (A) and the formation of WA is also increased_nB_(6-n)(wherein n is 4 or 5).

The amount of the acylating agent used depends on the reactivity of the acylating agent, the type of reaction and the reaction conditions.With acylating agents and WB₆The molar ratio of arylmethyl groups in (b) means that the acylating agent is used in an amount of usually 0.1 to 100, preferably 1 to 50. When a mixture of a carboxylic acid ester of N-hydroxysuccinimide and a carboxylic acid anhydride is used as the acylating agent, the amount of the carboxylic acid anhydride to be used is usually 0.01 to100, preferably 0.1 to 10, in terms of the molar ratio of the carboxylic acid anhydride to the N-hydroxysuccinimide.

In the process represented by the formula (3), when reductive dearylmethylation is carried out in the presence of an acylating agent (step a),

in the process represented by formula (3), when WA has been formed in a significant amount_nB_(6-n)When it is used, the reaction solvent is not particularly limited as long as the solvent can dissolve WB₆And does not adversely affect the reaction. Examples of the solvent include: aromatic compounds such as benzene, toluene, ethylbenzene, xylene, cumene, cymene, diisopropylbenzene and phenylethyl ether; cyclic, straight chain or branched ethers such as tetrahydrofuran, dioxane, tetrahydropyran, diethyl ether, dipropyl ether and diisopropyl ether; and aliphatic alcohols such as methanol, ethanol, propanol, isopropanol and tert-butanol. These solvents may be used alone or in combination. Among the above solvents, aromatic compounds (e.g., benzene, toluene, ethylbenzene, xylene, etc.) are preferable, because use of these solvents can increase WB₆The reductive dearylmethylation reaction rate.

The amount of the solvent used depends on the dissolving power of the solvent and the reaction temperature. With a solvent and WB₆The weight ratio of (A) to (B) means that the amount of the solvent used is usually 0.1 to 100, preferably 1 to 100.

In the process of the formula (3), the reaction pressure for reductive dearylmethylation (step a) in the presence of an acylating agent is usually from 0.1 to 1000kgf/cm²Preferably 1 to 300kgf/cm². When hydrogen is used as the reducing agent, the reaction rate increases with an increase in the reaction pressure in some cases. The reaction pressure is preferably 0.1 to 500kgf/cm in terms of hydrogen partial pressure²More preferably 1 to 200kgf/cm². In addition to hydrogen, inert gases such as nitrogen, argon and helium may be present in the reaction system.

In the process of formula (3), the reaction temperature for reductive dearylmethylation (step a) in the presence of the acylating agent is generally from-20 ℃ to 300 ℃, preferably from 0 ℃ to 200 ℃.

In the process represented by formula (3), when WA has been formed in a significant amount_nB_(6-n)At this point, the reductive dearylmethylation reaction (step a) is terminated. More specifically, the progress of the dearylmethylation reaction is monitored by gas chromatography or liquid chromatography when the desired amount of WA has been formed_nB_(6-n)When this occurs, the reaction is terminated.

The reaction time depends on the type of catalyst, acylating agent, solvent, and the like. The reaction time is usually 0.1 to 500 hours, preferably 1 to 200 hours.

Synthesis of Compound WA by reductive dearylmethylation of step a in the Process of formula (3) (in the presence of acylating agent)_nB_(6-n)(wherein n is 4 or 5). Then in step b of the process represented by formula (3), the synthesized WA_nB_(6-n)Reductive dearylmethylation (in the absence of an acylating agent).

In process step b of formula (3), the catalyst, reducing agent and reaction conditions (reaction temperature and reaction pressure, etc.) used to carry out the reductive dearylmethylation (in the absence of the acylating agent) are as described for the reductive dearylmethylation (in the presence of the acylating agent) in step a. In addition, catalysts, reducing agents, solvents and reaction conditions used in the reductive dearylmethylation in step a of the process represented by formula (2) can also be used.

The acylating agent is removed from the reaction mixture obtained in step a of the process of formula (3) by reductive dearylmethylation (in the presence of the acylating agent), and in step b of the process of formula (3) the obtained mixture from which the acylating agent has been removed is reductively dearylmethylated (in the absence of the acylating agent). In this case, it is preferred not to remove the reducing catalyst and solvent used in the reductive dearylmethylation of step a, but to leave them in the reaction mixture obtained in the reductive dearylmethylation of step a and to use them in situ in the reductive dearylmethylation of step b.

In step b of the process of formula (3), reductive dearylmethylation (in the absence of acylating agent) gives WA_nH_(6-n)(wherein n is 4 or 5), and then subjecting it toAcylation in step c of the process of formula (3).

In step c of the process represented by formula (3), the acylating agent, solvent and reaction conditions (reaction temperature, etc.) used for the acylation are as described in the acylation reaction represented by formula (1) above.

In step c of the process of formula (3), the reaction mixture obtained in step b of the process of formula (3) by reductive dearylmethylation (in the absence of an acylating agent) may be acylated in situ with an acylating agent. Alternatively, the reduction catalyst and/or the solvent may be removed from the reaction mixture obtained in step b, and then the acylation may be performed in step c.

WA₆It is also possible to use WA by reacting WA in the presence of an acylating agent_nB_(6-n)Reduced dearylmethylation as shown in the following formula (4):

Reducing agents, reduction catalysts, acylating agents, solvents, reaction conditions (such as reaction temperature and pressure, etc.) which may be used are as described in the reaction shown in formula (9) (see below).

WA₆It is also possible to prepare WB by reacting WB with an acylating agent in the presence of an acylating agent₆Reduced dearylmethylation as shown in the following formula (5):

wherein B represents an arylmethyl group, A represents C₁-C₁₀Acyl, W represents the hexavalent residue of hexaazaisowurtzitane-type structure alkanes.

The reducing agent, the reduction catalyst, the acylating agent, the solvent, the reaction conditions, and the like which can be used in the reaction represented by formula (5) are as described in step a of the method represented by formula (3).

Another example of an acyl group-containing hexaazaisowurtzitane derivative is represented by the formula WA_nH_(6-n)(wherein n is 4 or 5) by subjecting WA to an acylation reaction in the presence of an acylating agent_nB_(6-n)(wherein n is 4 or 5) by reductive dearylmethylation, as shown in the following formula (6):

The reducing agent, the reduction catalyst, the solvent, the reaction conditions, and the like which can be used in the reaction represented by formula (6) are as described in step a of the method represented by formula (2).

WA obtained by the reaction of formula (6)_nH_(6-n)Can be isolated by conventional methods. The separation can be carried out, for example, by the following method: after the reduction dearylmethylation reaction is finished, filtering and removing the catalyst from the reaction mixture to obtain a filtrate; from the filtrate obtained, the solvent was distilled off (see, for example, reference example)5)。

Acyl-containing hexaazaisowurtzitane derivative WA_nH_(6-n)(wherein n is 4 or 5) can also be prepared as follows: a) WB is reacted in the presence of an acylating agent₆Reductive dearylmethylation, followed by b) reductive dearylmethylation of the product obtained in the absence of an acylating agent, as shown in formula (7) below: a) b)

wherein n represents an integer of 4 to 5, and A represents C₁-C₁₀Acyl, B represents an arylmethyl group, H represents a hydrogen atom, and W represents a hexavalent residue of a hexaazaisowurtzitane-type structure alkane.

In step a of the process represented by formula (7), the reducing agent, the reducing catalyst, the acylating agent, the solvent, the reaction conditions, and the like which can be used for the reductive dearylmethylation (in the presence of the acylating agent) are as described in stepa of the process represented by formula (3).

Is shown in formula (7)In step a of the process, WA is synthesized by reductive dearylmethylation (in the presence of an acylating agent)_nB_(6-n)(wherein n is 4 or 5), and then in step b of the process represented by formula (7), subjecting the synthesized WA_nB_(6-n)Reductive dearylmethylation (in the absence of an acylating agent).

In step b of the process of formula (7), the reducing agent, reduction catalyst, solvent, reaction conditions, etc. that can be used to perform reductive dearylmethylation (in the absence of an acylating agent) are as described in step b of the process of formula (3).

The WA obtained_nH_(6-n)The isolation can be carried out by the method mentioned in the reaction represented by the above formula (6).

As a synthetic acyl-containing hexaazaisowurtzitane derivative WA_nH_(6-n)Starting material of, WA_nB_(6-n)Can be prepared by reacting WB in the presence of an acylating agent₆Reductive dearylmethylationAnd is prepared as shown in the following formula (8):

wherein n represents an integer of 4 to 5. A represents C₁-C₁₀Acyl, B is arylmethyl, and W is a hexavalent residue of a hexaazaisowurtzitane.

The reducing agent, reduction catalyst, acylating agent, solvent, reaction conditions, and the like that can be used in the reaction represented by formula (8) are as described in step a of the method represented by formula (3).

WA obtained by the reaction represented by the formula (8)_nB_(6-n)Can be isolated by conventional methods. For example, the separation can be carried out by the following method: filtering the reaction mixture obtained by reduction dearylmethylation by using filter paper, and filtering out precipitate and catalyst; treating the precipitate on the filter paper with chloroform, and dissolving the precipitate; evaporating the solvent and chloroform from the filtrate to obtain a solid residue; dissolving the solid residue in chloroform to obtain a solution; adding ammonia water into the obtained solution; separating the resulting mixture into an aqueous phase and a chloroform phase; separating the chloroform phase; the solvent was distilled off from the chloroform phase (see, for example, reference example 19).

In the reductive dearylmethylation in the presence of the aforementioned acylating agent, a side reaction occurs in which the N-acyl group formed in the main reaction is further reduced to an N-alkyl group.

Thus, as described above, by reductive dearylmethylation in the presence of an acylating agent, there is also provided an N-alkyl hexaazaisowurtzitane derivative represented by the following formula (XII):

WA_nQ_(6-n)(XII)

wherein n represents an integer of 4 to 5, A independently represents C₁-C₁₀Acyl, Q independently of one another represent a hydrogen atom or C₁-C₁₀Alkyl groups, but not all Q's, are simultaneously hydrogen atoms, and W represents the hexavalent residue of a hexaazaisowurtzitane of formula (II)

As described above, the N-alkyl group-containing hexaazaisowurtzitane derivative can be advantageously used as a polyfunctional crosslinking agent.

Examples of the N-alkyl-containing hexaazaisowurtzitane derivative include diethyl tetraacetyl hexaazaisowurtzitane derivatives obtained in reference examples 6 to 12 (WA)₄R₂) Ethyl pentaacetyl hexaazaisowurtzitane (WA) obtained in reference examples 13 and 14₅R₁) And watch [ formula (12)]Monoalkyltetraacetylhexaazaisowurtzitane (WA)₄RH)。

The N-alkyl hexaazaisowurtzitane derivative can be prepared by subjecting WA to acylation in the presence of an acylating agent_nB_(6-n)Reduced dearylmethylation as shown in the following formula (9):

wherein n represents an integer of 4 to 5, and A represents C₁-C₁₀Acyl, B represents an arylmethyl group, Q independently represents a hydrogen atom or C₁-C₁₀The alkyl group, but not all Q groups are hydrogen atoms at the same time, and W represents a hexavalent residue of a hexaazaisowurtzitane-structure alkane.

The reductive dearylmethylation reaction of formula (9) can be carried out under the same reaction conditions as the reductive dearylmethylation reaction of step a of the process of formula (2), except that the reaction of formula (9) is carried out in the presence of an acylating agent.

In the reductive dearylmethylation reaction of formula (9) (in the presence of an acylating agent), the acylating agent that may be used is as described in step a of the process of formula (3).

The solvent, the reduction catalyst, the acylating agent, the reaction conditions (such as reaction temperature and pressure), and the like which can be used in the reaction represented by formula (9) are as described in step a of the process represented by formula (3).

WA obtained by the reaction represented by the formula (9)_nQ_(6-n)Can be isolated by conventional methods. The separation can be carried out, for example, by the following method: filtering the catalyst from the reaction mixture to obtain a filtrate; the solvent was distilled off from the filtrate (see, for example, reference example 6).

WA_nQ_(6-n)It is also possible to prepare WB by reacting WB with an acylating agent in the presence of an acylating agent₆Reductive dearylmethylationAnd is prepared as shown in the following formula (10):

As the solvent, the reduction catalyst, the acylating agent, the reaction conditions, and the like to be used in the reaction of formula (10), those mentioned in step a of the method of formula (3) above can be used.

The WA obtained_nQ_(6-n)The separation can be carried out by the method mentioned in the above formula (9).

WBs each useful as a starting material for the synthesis of an acyl group-containing hexaazaisowurtzitane derivative₆And WA_nB_(6-n)(wherein n is 4 or 5), the arylmethyl group represented by B is an aryl-substituted methyl group and usually has 7 to 20 carbon atoms. A representative structure of arylmethyl groups is represented by the following formula (XII)I) Shown in the figure:

-CH₂Ar (XIII)

wherein Ar represents C₆-C₂₀An aromatic group.

The number of carbon atoms of Ar in the above formula (XIII) is usually 6 to 20, preferably 6 to 10, and most preferably 6. Examples of Ar include: a phenyl group; alkylphenyl groups such as tolyl (o-, m-and p-isomers), ethylphenyl (o-, m-and p-isomers) and xylyl groups; alkoxyphenyl, such as methoxyphenyl (o-, m-, and p-isomer), ethoxyphenyl (o-, m-, and p-isomer), and butoxyphenyl (o-, m-, and p-isomer); and unsubstituted and substituted naphthyl. Among them, phenyl and alkoxyphenyl are preferred. In each WB₆And WA_nB_(6-n)(wherein n is 4 or 5) the arylmethyl groups may be the same or different.

Formula (I) WA_tQ_(6-t)(wherein t is an integer of 4 to 6) can be synthesized by the above-mentioned methods.

The most characteristic feature of the process for producing the acyl group-containing hexaazaisowurtzitane derivative of the formula (I) is that WB₆The reductive dearylmethylation of (a) is carried out in the presence of an acylating agent.The reaction is represented by the following formula (11):

wherein p represents an integer of 1 to 5, t represents an integer of 4 to 6, B represents an arylmethyl group, A represents C₁-C₁₀Acyl, Q independently of one another represent a hydrogen atom or C₁-C₁₀Alkyl groups, but not all Q groups, are not simultaneously hydrogen atoms, and W represents the hexavalent residue of a hexaazaisowurtzitane-type structure alkane.

In the reaction mixture obtained by the reaction of the above formula (11), WA_pB_(6-n)And WA_tQ_(6-t)The molar ratio of (A) is usually 0.001 to 1,000, preferably 0.01 to 100.

As the solvent, the reduction catalyst, the acylating agent, the reaction conditions and the like to be used in the reaction of formula (11), those mentioned above in the reaction of formula (8) can be used.

By reacting WB in the presence of an acylating agent₆When the acyl group-containing hexaazaisowurtzitane derivative represented by the formula (I-a) is produced by reductive dearylmethylation, it is important that a) arylmethyl group B is reduced and eliminated to form an N-H group, and B) acylation of the N-H group to form an N-acyl group is performed sequentially.

The above formula (11) shows that not only WB₆To obtain WA_pB_(6-p)(wherein p represents an integer of 1 to 5) and is derived from WA_pB_(6-p)Further reaction to give WA_nH_(6-n)。

In the reaction represented by the formula (11), when a reaction mixture [ containing WA]having a desired composition is obtained_pB_(6-p)And WA_tQ_(6-t)]When this is the case, the reductive dearylmethylation reaction is terminated. More specifically, the reaction is terminated when the progress of the dearylmethylation reaction is monitored by gas chromatography or liquid chromatography to obtain a reaction mixture having a desired composition.

The following first illustrates the proposed route for the reaction of formula (11) and then the use of the reaction of formula (11).

The route of the reaction of formula (11) is illustrated in detail in the table of the following formula (12). Since the N-alkyl group can be formed by the reduction (side reaction) of the N-acyl group which occurs depending on the reaction conditions, the N-alkyl group-containing hexaazaisowurtzitane derivative by-product is also shown in the table of formula (12)As described in (1). In the table of formula (12), A represents C₁-C₁₀Acyl, B represents arylmethyl, R represents C₁-C₁₀Alkyl, H represents a hydrogen atom and W represents the hexavalent residue of a hexaazaisowurtzitane-type structure alkane. Watch [ type (12)]

When the reaction of formula (11) is carried out in a discontinuous manner, the proportion of the reaction product obtained varies with the reaction time. When the reaction of formula (11) is carried out in a continuous manner, the proportion of the reaction product obtained varies with the contact time. In addition, the proportion of the reaction product obtained may vary depending on the kinds of the catalyst and the solvent used, the reaction temperature, etc. Therefore, in the reaction of formula (11), the proportion of the reaction product can be changed in a desired proportion by appropriately selecting the reaction conditions.

The application of the reaction of formula (11) is described in detail below.

When trying to make WB first₆Reducing dearylmethylation in the absence of an acylating agent to obtain WH_nB_(6-n)(wherein n represents an integer of 1 to 6), and acylating the resultant WH_nB_(6-n)To obtain an acyl group-containing hexaazaisowurtzitane derivative, the desired product cannot be obtained in a high yield due to decomposition of the W skeleton. The reason for this is presumed to be from WB₆Secondary amino group-containing hexaazaisowurtzitane derivatives (e.g. WHB) formed by reductive dearylmethylation in the absence of acylating agent₅，WH₂B₄And WH₃B₃) The structure of (2) is unstable. In contrast, by using the WB thereof₆The process for reductive dearylmethylation of the formula (11) in the presence of an acylating agent can synthesize an acyl group-containing hexaazaisowurtzitane derivative without decomposition of the Wskeleton. The reason for this is believed to be that in the reaction of formula (11), unstable secondary amino group-containing hexaazaisowurtzitane derivatives (e.g., WHB)₅And WH₂B₄) They are formed at an early stage of the reaction) is immediately acylated and thus stabilized in the reaction system, and thus decomposition of the W skeleton can be suppressed, thereby further performing dearylmethylation and acylation.

As described above, the acyl group-containing hexaazaisowurtzitane derivative represented by the formula (I-a) can be obtained by reacting WB with₆The one-step synthesis of reductive dearylmethylation is carried out in the presence of an acylating agent. However, when trying to complete the reaction in one step, many reaction products are formed at a time and side reactions obviously occur. The present inventors have studied to develop a method capable of solving these problems and of advantageously producing WA on an industrial scale with high selectivity and high yield_tH_(6-t)(wherein t is an integer of 4 to 6). As a result, it was found that excellent results were obtained by carrying out the reactions of the above-mentioned formulae (8), (6) and (1) in the stated order.

The respective reactions of the formulae (8), (6) and (1) are described in more detail below.

I. A reaction of formula (8):

to produce WA in high yield in the reaction of the above formula (8)_nB_(6-n)Various methods may be used. Examples of such methods include:

1) a process in which the type and amount of reactants are selected so that the reductive dearylmethylation reaction can be terminated prior to completion;

2) a process in which the reductive dearylmethylation reaction is monitored by gas chromatography or liquid chromatography and the reaction is terminated at an appropriate time; and

3) one of them is WB₆Is a good solvent of (A) but is WA_nB_(6-n)A poor solvent (e.g. an aromatic compound such as ethylbenzene or toluene) to the WB₆WA produced by reductive dearylmethylation_nB_(6-n)Precipitating from the reaction mixture.

Among the methods 1), 2) and 3), the method 3) is most advantageous industrially from the viewpoint of easy operation.

In the reaction of formula (8), to suppress side reactions to improve WA_nB_(6-n)It is advantageous to use as acylating agent a mixture of a carboxylic ester of N-hydroxysuccinimide, such as N-acetoxysuccinimide or a carboxylic ester of N-hydroxysuccinimide, with a carboxylic anhydride, such as acetic anhydride. When such an acylating agent is used, not only can WA be improved_nB_(6-n)Can improve WA_nB_(6-n)The yield of (a). When using carboxylic acid esters of N-hydroxysuccinimide as acylating agents, WA_nB_(6-n)The reason for the improved selectivity of (A) is not clear. However, it is believed that the carboxylic acid ester of N-hydroxysuccinimide and other acylating agents such as carboxylic acid anhydride on WA_nB_(6-n)Due to the differences in reactivity of the acylating agent and its substrate specificity due to steric hindrance, including specific three-dimensional structure and volume.

WA is significantly improved when a carboxylic acid ester of N-hydroxysuccinimide is used as the acylating agent_nB_(6-n)The fact of selectivity ofThe first discovery by the present inventors. This finding is industrially advantageous for the synthesis of WAs_nB_(6-n)Is important.

Reaction of formula (6):

WA produced when in the reaction of formula (8)_nB_(6-n)The reductive dearylmethylation of (a) is carried out in the presence of an acylating agent to synthesize WA₆In the case, side reactions such as the formation of N-alkyl groups due to the reduction of N-acyl groups may occur, and thus it is difficult to synthesize WA with high selectivity₆。

In contrast, when WA is carried out in the absence of an acylating agent as shown in formula (6)_nB_(6-n)In the reductive dearylmethylation of (2), the formation of side reactions such as N-alkyl groups is suppressed, and thus the reductive dearylmethylation proceeds with high selectivity. This phenomenon has been discovered by the present inventors. From the reaction mixture obtained from the reductive dearylmethylation of formula (6), WA of high purity can be obtained in high yield by simple separation operation_nH_(6-n). Thus, the reaction of formula (6) is coupled to the synthesis of WA_nH_(6-n)Is very useful.

When WB is carried out in the absence of an acylating agent as described above₆When the reduction dearylmethylation of (2) is carried out, the WH produced_nB_(6-n)(wherein n represents an integer of 1 to 6) is unstable in the reaction system, and thus it is difficult to obtain WH in a high yield_nB_(6-n). In contrast, WA, as described above_nH_(6-n)(wherein n is an integer of 4 to 5) is stable in the reaction system, and thus WA can be synthesized in high yield_nH_(6-n)。

WH_nB_(6-n)(wherein n represents an integer of 1 to 6) and WA_nH_(6-n)The reason why (wherein n represents an integer of 4 to 5) have different properties from each other is not clear. It is believed, then, that the difference inproperties between arylmethyl B and acyl A results in WH_nB_(6-n)And WA_nH_(6-n)The hexaazaisowurtzitane skeleton has different stabilities.

WH described above_nB_(6-n)(wherein n represents an integer of 1 to 6) and WA_nH_(6-n)(wherein n represents an integer of 4 to 5)The difference in performance of (a) was first discovered by the present inventors. Also, formula WA_nH_(6-n)(wherein n represents an integer of 1 to 6) have not been disclosed in any literature, and have been synthesized for the first time by the method described in detail above.

Reaction of formula (1):

WA as described above in the "prior art" herein_nH_(6-n)(wherein n represents an integer of 4 to 5) can be advantageously used as a material for various functional materials such as a precursor of polynitrohexaazaisowurtzitane derivative and a material for highly polar polymers. If necessary, WA_nH_(6-n)(wherein n represents an integer of 4 to 5) can be easily converted into WA by carrying out the reaction of the formula (1)₆。

WA₆Has not been disclosed in any literature and was synthesized by the present inventors for the first time. WA₆Can also be advantageously used as various functional materials, such as WA_nH_(6-n)(wherein n represents an integer of 4 to 5).

The method for preparing the ANW of the present invention is described in detail below.

As mentioned above, the formula (I-a) WA_tH_(6-t)(wherein t represents an integer of 4 to 6) is used as a raw material in the nitration reaction to obtain a polynitrohexaazaisowurtzitane derivative.

The following description is provided for the WA_tH_(6-t)(wherein t represents an integer of 4 to 6) to convert its N-H group and N-A group into N-NO₂Method for radical synthesisFor example.

WA_nH_(6-n)(wherein N represents an integer of 4 to 5) the N-H group can be converted to N-NO by various nitration methods₂A group. For example, WA can be easily converted in one step_nH_(6-n)(wherein n is an integer of 4 to 5) to WA_n(NO₂)_(6-n)(wherein n is an integer of 4 to 5). However, from improving the required WA_n(NO₂)_(6-n)From the viewpoint of yield, it is preferable to carry out a reaction comprisingThe two-step process shown in formula (13) proceeds from the N-H group to N-NO₂And (4) converting the groups.

Illustratively, WA is reacted as shown in the following reaction formula (13)_nH_(6-n)Nitrosation of the N-H group to an N-NO group and nitration of the N-NO group to an N-NO group₂Group, thereby obtaining WA_n(NO₂)_(6-n)。

Wherein n represents an integer of 4 to 5, A represents C₁-C₁₀Acyl, H represents a hydrogen atom, (NO) represents a nitroso group, (NO)₂) Represents a nitro group, and W represents a hexavalent residue of a hexaazaisowurtzitane-type structure alkane.

As the nitrosating agent used in the process of formula (13), any nitrosating agent may be used as long as it can nitrosate WA_nH_(6-n)Production of WA_n(NO)_(6-n)And (4) finishing. Mixtures of sodium nitrite and acid are typically used; dinitrogen tetroxide; nitrosyl chloride and the like as nitrosating agents.

The temperature of the nitrosation reaction is generally inthe range-50 ℃ to 200 ℃, preferably-30 ℃ to 100 ℃, more preferably-20 ℃ to 50 ℃.

As the oxidizing agent used in the nitration reaction in the process of formula (13), any oxidizing agent can be used as long as it can oxidize a nitroso group to produce a nitro group. Examples of common oxidizing agents include nitric acid and hydrogen peroxide. Among them, nitric acid is preferred. These oxidizing agents may be used alone or in combination.

The oxidation reaction temperature is generally in the range of-50 ℃ to 200 ℃, preferably-30 ℃ to 150 ℃, more preferably-20 ℃ to 60 ℃.

In addition, nitric acid or a mixture of nitric acid and dinitrogen pentoxide is used (see, for example, the reference examples)21) By nitration, WA_tH_(6-t)(wherein t represents an integer of 4 to 6) can be easily converted into N-NO₂A group. For example, WA₆Can be converted into polynitrohexaazaisowurtzitane derivatives such as WA by various nitration methods using nitrating agents such as a mixture of nitric acid and dinitrogen pentoxide₄(NO₂)₂。

Further, as shown in the following reaction formula (14), formula WA_nE_(6-n)Various hexaazaisowurtzitane derivatives can be nitrated to obtain hexanitrohexaazaisowurtzitane [ W (NO)₂)₆]。

Wherein n represents an integer of 4 to 6, and A represents C₁-C₁₀Acyl, E represents a nitroso or nitro group, and W represents a hexavalent residue of a hexaazaisowurtzitane-type structure alkane.

As ready to be used for WA_nE_(6-n)N-NO converted from the N-A group of (2)₂Nitrating agent for the group, any nitrating agent may be used, provided that it is capable of converting the N-A group to N-NO₂The group is just needed. For example, various nitrating reagents containing nitric acid may be used. Illustrative examples of nitrating agents include mixtures of nitrate sources (e.g., nitric acid) and strong protic acids (e.g., sulfuric acid or trifluoroacetic acid), more specifically nitric/sulfuric acid mixtures or nitric/trifluoroacetic acid mixtures.

The temperature of the reaction of formula (14) is generally in the range of-50 ℃ to 120 ℃, preferably-20 ℃ to 60 ℃.

The reaction time of the reaction of formula (14) is generally in the range of 0.1 to 500 hours, preferably 1 to 200 hours.

As described above, the N-H group and the N-A group of the W skeleton are functional groups which can be easily converted into nitro groups. Thus, by using WA_tH_(6-t)(wherein t represents an integer of 4 to 6) as an intermediate, and various polynitrohexaazaisowurtzitane derivatives can be produced in high yield.

As described above, the present invention provides a process for producing a hexanitrohexaazaisowurtzitane represented by the following formula (IX):

W(NO₂)₆(IX)

in the formula (II) NO₂Represents a nitro group, W represents a hexavalent residue of a hexaazaisowurtzitane of the following formula (II)

The method comprises nitrating at least one compound selected from the group consisting of compounds represented by formula (III), formula (IV), formula (VII), and formula (VIII) with a nitrating agent:

WA₆(III)

wherein A independently of one another represents C₁-C₁₀Acyl, W is as described above;

WA_nH_(6-n)(IV)

wherein n represents an integer of 4 to 5, H represents a hydrogen atom, A and W are as defined above;

WA_n(NO)_(6-n)(VII)

wherein NO represents a nitroso group, n, A and W are as defined above;

WA_n(NO₂)_(6-n)(VIII)

in the formula, n, A, NO₂And W is as described above.

The polynitrohexaazaisowurtzitane derivatives prepared from the acyl group-containing hexaazaisowurtzitane derivatives are advantageously used for modifying properties of propellants and explosives, such as mechanical properties, initiation speed, initiation pressure, burning rate, pressure index, sensitivity, heat resistance and the like, and as raw materials for high-performance explosives.

The following is a description of the advantages of polynitrohexaazaisowurtzitane derivatives prepared from acyl group-containing hexaazaisowurtzitane derivatives.

For example, WA₄(NO₂)₂Has the following advantageous properties:

1)WA₄(NO₂)₂has a molecular structure similar to that of high-performance explosives having a cyclic structure containing a polynitroamine group, such as HNW, cyclotetramethylene tetranitramine (hereinafter abbreviated as "HMX") and cyclotrimethylene trinitroamine (hereinafter abbreviated as "RDX"), and has more excellent heat resistance than HNW, HMX and RDX. [ even when WA is used₄(NO₂)₂Additives as propellants and explosivesWithout the risk of significantly reducing the thermal resistance of the propellant and explosive]。

2) In contrast to the above-mentioned nitroamine compounds (i.e., HNW, HMX and RDX), WA₄(NO₂)₂Not only has N-nitro groups but also has N-A groups in the backbone, so that it has good affinity for adhesives such as polyurethane.

By combining WA with the above advantageous properties₄(NO₂)₂The adhesion between the solid component (i.e., the nitramine compound) and the adhesive can be improved by addition to propellants and explosives comprising the nitramine compound (e.g., HNW, HMX, RDX, or the like) and the adhesive, such as polyurethane.

WA₄(NO₂)₂Can be easily converted into HNW by nitration, and thus it can be used as a raw material for producing HNW. HNW has high density and high energy, and thus it is useful as an oxidizer for high explosive and smokeless propellants.

By reacting tetraacylhexaazaisowurtzitane WA₄H₂By reacting with a dicarboxylic acid derivative such as dicarboxylic acid halide or dicarboxylic acid diester, a highly polar polymer having a hexaazaisowurtzitane skeleton in its main chain can be obtained.

Synthesis of acyl-containing hexaazaisowurtzitane derivative WA using acylating agent having specific functional group_nH_(6-n)(wherein n represents an integer of 4 to 6), a crosslinkable polyacylhexaazaisowurtzitane can be obtained.

WA_nH_(6-n)(wherein n represents an integer of 4 to 6) may be used as such as an additive, such as a polymer modifier.

A flow chart showing the preferred method employed in the preparation method according to the present invention is given below.

Scheme table preferred method adopted in preparation method related to the inventionMeaning of symbols in tables

W: hexavalent residues of hexaazaisowurtzitanes

B: arylmethyl group

A： C₁-C₁₀Acyl radical

Q: hydrogen atom and/or C₁-C₁₀Alkyl radical

NO: nitroso group

NO₂: nitro radical

As can be seen from the above-mentioned flow chart, the acyl group-containing hexaazaisowurtzitane derivative WA_tQ_(6-t)(wherein W is a hexavalent residue of hexaazaisowurtzitane-type alkane, and Q is independently a hydrogen atom or C₁-C₁₀Alkyl, t is an integer of 4 to 6) may be substituted with hexakis (arylmethyl) hexaazaisowurtzitane WB₆(wherein W is as defined above and B is C₇-C₂₁Arylmethyl) or via hexaazaisowurtzitane derivative WA containing acyl and arylmethyl_nB_(6-n)(wherein W and B are as defined above and n is 4 or 5). The acyl group-containing hexaazaisowurtzitane derivative WA_tQ_(6-t)(wherein W, A, Q and t are as defined above) can be easily converted into hexanitrohexaazaisowurtzitane W (NO) in high yield₂)₆(wherein W is as defined above) and the conversion may be carried out directly or via WA which is a nitroso-containing hexaazaisowurtzitane derivative_n(NO)_(6-n)(wherein W and A are as defined above and n is 4 or 5) and/or a nitro group-containing hexaazaisowurtzitane derivative WA of the present invention_n(NO₂)_(6-n)(wherein W and A are as defined above and n is 4 or 5).

Examples

The present invention will be described in more detail below with reference to reference examples, examples and comparative examples, which should not be construed as limiting the scope of the present invention.

Various measurements were made as follows.

(1)¹H-NMR：

JNM-FX-200(JEOL LTD., manufactured and sold by Japan) was used.

(2)¹³C-NMR：

JNM-GX-400(JEOL LTD., manufactured and sold by Japan) was used.

(3)¹³C-¹H COSY(¹³C-¹H shift related NMR):

JNM-GX-400 was used. In the method, measurement is made¹³C and¹the interaction between H. By using the method, in determining¹³C or¹H, after the peak of interest, it can be determined that H is attached to it¹³C of¹H or is connected with¹Of H¹³Chemical shift of C.

(4) EI (electron impact) -mass spectrometry:

HP 5790B (manufactured and sold by Hewlett Packard Company, u.s.a.) was used.

(5) GC (gas chromatography praseodymium) -mass spectrum:

1) HP 5890A (manufactured and sold by Hewlett Packard Company, u.s.a.) was used.

2) Column: metal capillary column, 0.25mm (inner diameter) × 15m, Ultra a (HT) (column used under high temperature conditions), film thickness coated on inner wall of capillary: 0.15. mu.M.

3) Temperature: column: the temperature was increased from 100 ℃ to 340 ℃ at a ramp rate of 20 ℃/min and maintained at 340 ℃ for 20 min.

Injecting a hole: 340 deg.C

GC/MS connection: 340 deg.C

4) Carrier gas: helium (helium flow rate introduced into the apparatus: 100 ml/min; column pressure: 100kPa)

(6) FD (field Desorption) -Mass Spectrometry

JEOL HX-110(JEOL LTD., manufactured and sold by Japan) was used. And a few. mu.g of the sample was dissolved in about 10. mu.l of methanol to thereby obtain a solution. Mu.l of the resulting solution was coated on an emitter and measured.

(7) Infrared absorption spectrum

The measurement was performed by KBr pellet method using FT/IR-5M (manufactured and sold by Japan Spectroscopic Co., Ltd., Japan).

(8) Differential Scanning Calorimeter (DSC)

DSC-220 (manufactured and sold by Seiko Instruments Inc., Japan) was used.

(9) High performance liquid chromatography

The measurement was performed under the following conditions by using the following instrument.

1) The instrument comprises the following steps: 610 ISOCRATIC SYSTEM (Waters assoc.co., u.s.a. manufactured and sold)

① 600 controller

② 600E pump

③ 486 adjustable absorption detector

2) Column: mu-Bondasphere (Waters Assoc. Co., U.S.A. make and sell)

① particle size 5 μ M

② Filler C18

③ Aperture 100 u

④ column size 3.9mm x d15cm

3) Mobile phase liquid:

acetonitrile/water: 64/40

4) Flow rate: 0.5ml/min

5) Column temperature: 40 deg.C

Reference example 1[ from WA₄H₂Acetylation synthesis of WA₆]

1.0g (2.98mmol) of tetraacetylhexaazaisowurtzitane was dissolved in 100ml of acetic anhydride. To the resulting solution was added 5g (63.7mmol) of acetyl chloride, and the resulting mixture was stirred for 1 hour to effect a reaction, and then, the solvent was distilled off from the resulting reaction mixture under reduced pressure to obtain a residue. The resulting residue was dissolved in ethyl acetate. To the resultant solution was added hexane to obtain a precipitate which was 1.16g of white hexaacetylhexaazaisowurtzitane (yield: 93%).

The obtained hexaacetylhexaazaisowurtzitane-type structural alkane was put into a sublimator, and then the instrument was immersed in an oil bath at 270 ℃. It was confirmed that hexaacetylhexaazaisowurtzitane was sublimable under reduced pressure of 100 mmHg.

The analysis results of hexaacetylhexaazaisowurtzitane type structure alkane are as follows.

¹Results of H-NMR [ solvent: CDCl₃(ii) a The standard is as follows: tetramethylsilane (hereinafter often referred to as "TMS");measuring the temperature: 60 ℃; unit: delta (ppm)]：2.05(s，6H，COCH₃)，2.14(s，6H，COCH₃)，2.41(s，6H，COCH₃) 6.42(s, 2H, CH), 6.48(d, 2H, CH) and 6.94(d, 2H, CH).

By passing¹H-NMR confirmed 6 hydrogen atoms and 6 acetyl groups of the W skeleton.

¹³Results of C-NMR [ solvent: CDCl₃(ii) a The standard is as follows: TMS; unit: delta (ppm)]：

20.74(CH₃)，21.55(CH₃) 61.09(CH), 66.55(CH), 72.17(CH), 167.60(C ═ O), 168.31(C ═ O) and 169.79(C ═ O).

By passing¹³C-NMR was conducted to identify the carbon atom of the methyl group and the carbon atom of the carbonyl group which are the acetyl groups and the carbon atom of the W skeleton.

By passing¹³C-¹HCOSY, can be surely connected to the other end of the cable¹Each determined by H-NMR¹Of H¹³C。

EI-spectrum results [ m represents the molecular weight of the parent molecule]: 420 (5%, m/z), 377 (5%, m minus COCH)₃Molecular weight/z) of 335 (10%), 295 (15%), 208 (12%), 165 (10%), 123 (12%) and 43 (100%, COCH)₃)。

By EI-mass spectrometry, a parent ion peak (420) of hexaacetylhexaazaisowurtzitane, an ion peak (377) ascribed to a residual molecule having a structure in which an acetyl group is removed from the parent molecule, and an ion peak (43) ascribed to an acetyl group can be determined.

The results of the infrared absorption spectrum obtained by KBr method showed that the absorption spectrum was 1660^-1There is an absorption peak in the vicinity, wherein the absorption peak is attributed to stretching vibration of carbonyl group (C ═ O) of acetyl group.

Reference example 2[ from WA₄B₂Synthesis of WA₆]

3.67g (7.11mmol) of tetraacetyldibenzylhexaazaisowurtzitane, 1.6g (7.11mmol) of Pd (OAc) as a reduction catalyst₂And 150ml of acetic acid were added to a 300ml miniature high pressure vessel together with a stirring element. The vessel was purged with nitrogen. Then hydrogen is introducedGas was introduced into the vessel so that the internal pressure thereof became 5kgf/cm²-G, and then the contents of the vessel are stirred for 15 hours to effect the reaction. The resulting reaction mixture was removed from the vessel and filtered to remove the catalyst. Then, the resultant filtrate was distilled under reduced pressure to distill off the solvent, thereby obtaining a solid residue. The solid residue obtained is washed with 100ml of ethyl acetate. The resulting white solid residue was dissolved in 200ml of acetic anhydride. To the resultant solution was added 5g (63.mmol) of acetyl chloride, and the resultant mixture was stirred for 1 hour. Then, the solvent was distilled off from the mixture under reduced pressure. The resultant residue was recrystallized from toluene, thereby obtaining 2.09g of a white hexaacetylhexaazaisowurtzitane (yield: 70%).

Reference example 3[ from WA₄B₂Synthesis of WA₆In which the reaction mixture resulting from reductive dearylmethylation is acetylated in situ without removal of catalyst and solvent]

Reductive dearylmethylation of tetraacetyldibenzylhexaazaisowurtzitane was carried out in substantially the same manner as in reference example 2, to thereby obtain a reaction mixture containing a reducing catalyst and a solvent. To the reaction mixture was added 5g (63.7mmol) of acetyl chloride (acetylating agent) and the resultant mixture was stirred for 3 hours to effect a reaction. The resulting reaction mixture was filtered to remove the catalyst. The resultant filtrate was distilled under reduced pressure to distill off the solvent. The resulting solid residue was recrystallized from toluene, thereby obtaining 1.92g of white hexaacetylhexaazaisowurtzitane (yield: 64%).

Reference example 4[ from WB₆Synthesis of WA₆)

1.89g (2.66mmol) of hexabenzylhexaazaisowurtzitane, 1.70g (1.60 mg-atom) of Pd-C (Pd content: 10%) as a reduction catalyst,5.0g (31.8mmol) of N-acetoxysuccinimide (acetylating agent), 160ml of ethylbenzene and 3.24g (31.8mmol) of acetic anhydride (acetylating agent) were charged together with a stirring element into a 300ml miniature high pressure vessel. The vessel was purged with hydrogen. Then, hydrogen gas was introduced into the vessel so that the internal pressure thereof became 10kg/cm²G, then the vessel is immersed in an oil bath at 60 ℃. The contents of the vessel were then stirred for 40 hours to effect the reaction. The resulting reaction mixture was cooled to room temperature. Then, withdrawing WA-containing material from the vessel in the form of a precipitate_nB_(6-n)(wherein n is 4 or 5) and filtering to filter off precipitate and reduce the catalyst. The resulting precipitate, the recovered reduction catalyst and 50ml of acetic acid as a solvent were charged into a 300ml mini-sized high-pressure vessel. Hydrogen gas was introduced into the vessel so that the internal pressure thereof became 5kg/cm²-G, the contents of which are stirred for 20 hours to effect the reaction. After the completion of the reaction, 5g (63.7mmol) of acetyl chloride was added to the resultant reaction mixture and the mixture was stirred for 1 hour. The resultant mixture was distilled under reduced pressure to distill off the solvent, thereby obtaining a solid residue. 200ml of chloroform WAs added to the resulting solid residue, which would consist mainly of WA₆The solid residue of the composition was dissolved in chloroform. The resulting solution was filtered to remove the catalyst. The resultant filtrate was distilled under reduced pressure, thereby distilling off the solvent. The resultant residue was recrystallized from toluene to obtain 0.50g of white hexaacetylhexaazaisowurtzitane (yield: 45%).

Reference example 5[ from WB₆Synthesis of WA_nH_(6-n)And WA₆]

Reductive debenzylation of hexabenzylhexaazaisowurtzitane in the presence of acetylating agent in substantially the same manner as in reference example 4, to obtain WA-containing_nB_(6-n)(wherein n is 4 or 5). After completion of the reaction, the reaction mixture containing the precipitate was taken out from the vessel and filtered using filter paper to filter out the precipitate and reduce the catalyst. The precipitate on the filter paper was treated in situ with 200ml of chloroform to dissolve the precipitate thereon. The filtrate (containing chloroform for treatment) was subjected to distillation to remove the solvents (ethylbenzene and chloroform). The resulting solid residue was dissolved in 200ml of chloroform to obtain a solution. To this solution was added 28% aqueous ammonia solution, and the resulting mixture was vigorously stirred for 30 minutes, thereby separating the reaction mixture into an aqueous phase and a chloroform phase, in which N-acetoxysuccinimide decomposed and entered the aqueous phase. Is divided intoThe chloroform phase was separated and distilled to evaporate the solvent (chloroform). The resulting white solid residue was dissolved in 50ml of acetic acid. To the resulting solution was added 0.6g (2.66mmol) of Pd (OAc) as a reduction catalyst₂. The solution containing the reduction catalyst was charged to a 100ml mini-bomb. Hydrogen is generatedGas was introduced into the vessel so that the internal pressure thereof became 5kgf/cm²-G, the contents of which are stirred for 20 hours to effect the reaction. (the yield of hexaacetylhexaazaisowurtzitane at this time was 0.3%, as determined by gas chromatography). 5g (63.7mmol) of acetyl chloride was added to the reaction mixture, and the resultant mixture was stirred for 1 hour. Then, the solvent (acetic acid) was distilled off from the mixture to obtain a solid residue. 200ml of chloroform was added to the resulting solid residue. The resulting solution was filtered to remove the catalyst. The resultant filtrate was distilled to distill off the solvent, thereby obtaining a solid residue. The resulting solid residue was recrystallized from toluene, thereby obtaining 0.39g of hexaacetylhexaazaisowurtzitane (yield: 35%). This indicates that hexaazaisowurtzitane compounds having a secondary amino group such as tetraacetylhexaazaisowurtzitane and pentaacetylhexaazaisowurtzitane had been formed before the addition of acetyl chloride and that such compounds having a secondary amino group had been converted into hexaacetylhexaazaisowurtzitane by the addition of acetyl chloride.

Reference example 6[ by WA₄B₂Synthesis of WA₄Et₂(wherein Et represents ethyl)]

0.50g (0.97mmol) of tetraacetyldibenzylhexaazaisowurtzitane, 0.21g (0.19 mg-atom) of Pd-C (Pd content: 10%) as a reduction catalyst, 2.37g (23.3mmol) of acetic anhydride (acetylating agent) and 50ml of acetic acid were charged together with a stirring element into a 100ml minivessel under high pressure. The vessel was purged with hydrogen. Then, hydrogen gas was introduced into the vessel so that the internal pressure thereof became 50kgf/cm²-G. The contents of the vessel were then stirred for 15 hours to effect reaction. After completion of the reaction, the resultant reaction mixture was taken out of the vessel and filtered to filter off the reduction catalyst. Distilling the resulting filtrate to distill offSolvent (acetic acid). The resulting solid residue was reprecipitated with a mixture of chloroform and hexane to perform purification, thereby obtaining a white diethyltetraacetylhexaazaisowurtzitane. The reaction conditions and yields are shown in table 1.

The analysis results of diethyl tetraacetyl hexaazaisowurtzitane type structural alkane were as follows:

EI-mass spectrum result:

392(1％，m/z)，278(1％)，236(10％)，193(25％)，138(30％)，109(45％)，97(20％)，81(81％)，69(60％)，56(20％)，43(100％，COCH₃)，29(20％，CH₂CH₃) 28 (52%) and 15 (20%, CH)₃)。

The parent ion peak (302) of tetraacetyldiethylhexaazaisowurtzitane, the ion peak (43) of acetyl group and the ion peak (29) of ethyl group were identified by EI-mass spectrometry

¹Results of H-NMR spectrum [ solvent: CDCl₃(ii) a The standard is as follows: TMS; unit delta (ppm)]1.25(t, 6H, CH for ethyl)₃)，2.41(s，12H，COCH₃) 2.90(m, 4H, CH for ethyl)₂) 5.20(d, 2H, CH), 5.74(d, 2H, CH) and 6.40(s, 2H, CH).

Methine, ethyl and acetyl groups of the W skeleton are available¹And (5) identifying an H-NMR spectrum.

Reference examples 7 to 12[ from WA in the Presence of an acylating agent₄B₂Synthesis of WA by reductive dearylmethylation₆And WA₄R₂And observing WA produced according to the change of reaction conditions₆And WA₄R₂Change of the ratio of the amounts of]

In reference examples 7 to 12, reactions were carried out in substantially the same manner as in reference example 6 except that the type and amount of the acylating agent, the type of the solvent, the type and amount of the catalyst, the hydrogen pressure and the reaction time were different. The reaction conditions and the yields of the reaction products are shown in table 1.

As shown in Table 1, various catalysts can be used to prepare hexaacetoxyhexaazaisowurtzitane and diethyltetraacetylhexaazaisowurtzitane.

TABLE 1

Reference to Examples	Acylating agent (amount)^*1	Catalyst (quantity)^*2	Hydrogen pressure (kgf/cm²-G)	Reaction time (hours)	Yield of^*5
					Yield of^*5		WA₆ (％)	WA₄Et² (％)
					6	Ac₂O(12)	WA₆ (％)	WA₄Et² (％)	10％Pd-C(10)	50	15	0.2	92.0
7	Ac₂O(12)	10％Pd-C(10)	5	10	6	Ac₂O(12)	4.3	46.8	10％Pd-C(10)	50	15	0.2	92.0
7	Ac₂O(12)	10％Pd-C(10)	5	10	8	Ac₂O(12)	4.3	46.8	10％Pd-C(1)	5	531	15.1	5.1
9	Ac₂O(12)	PdO(112)	50	40	8	Ac₂O(12)	2.7	15.1	10％Pd-C(1)	5	531	15.1	5.1
9	Ac₂O(12)	PdO(112)	50	40	10	Ac₂O(12)	2.7	15.1	10％Pd-C^*4	50	17	1.8	55.0
11	Ac₂O(6)+NAS(6)^*3	10％Pd-C(10)	50	16	10	Ac₂O(12)	4.5	35.3	10％Pd-C^*4	50	17	1.8	55.0
11	Ac₂O(6)+NAS(6)^*3	10％Pd-C(10)	50	16	12	Ac₂O(12)	4.5	35.3	5％Pd-Al₂O₃(10)	50	15	3.7	45.4

^*1The numbers in parentheses indicate the acylating agent and the WB used₆An equimolar amount, e.g. 12 equivalents, of benzyl (E) means 23.3, mmol.^*2The number in parentheses indicates the number based on WB used₆Mole% of catalyst of benzyl groups.^*3NAS stands for N-acetoxysuccinimide.^*410% Pd-C was treated with acetic anhydride before use.^*5The yield was measured by gas chromatography.^*6In table 1, Ac represents an acetyl group, and Et represents an ethyl group.

Reference example 13[ by WB in the Presence of acylating agent₆The reduction dearylmethylation of (A) to synthesize hexaazaisowurtzitane (WA) containing different acetyl groups₄B₂And WA₅B]

To harmonize with ginsengDearylmethylation of hexabenzylhexaazaisowurtzitane in the presence of an acylating agent was carried out in substantially the same manner as in example 4 except that the reaction was carried out under the following conditions: the pressure in the high-pressure reactor was 50kgf/cm²-G, the reaction temperature is room temperature and the reaction time is 200 hours.

After the reaction was completed, the reaction product in the reaction mixture was analyzed by gas chromatography. As a result, it was found that the reaction mixture contained the following compounds: tetraacetyldibenzylhexaazaisowurtzitane, pentaacetylbenzylhexaazaisowurtzitane, hexaacetylhexaazaisowurtzitane, ethylpentaacetylhexaazaisowurtzitane and diethyltetraacetylhexaazaisowurtzitane. The yields of the above-mentioned compounds were analyzed by gas chromatography. The results are as follows: tetraacetyldibenzylhexaazaisowurtzitane: 70 percent; penta-acetyl benzyl hexaazaisowurtzitane: 6.2 percent; hexaacetylhexaazaisowurtzitane: 0.9 percent; ethyl pentaacetyl hexaazaisowurtzitane: 1.3 percent; and diethyl tetraacetyl hexaazaisowurtzitane: 1.1 percent.

EI mass spectra results for these compounds are as follows.

EI mass spectrum results of pentaacetyl benzyl hexaazaisowurtzitane structure alkanes:

468(2％，m/z)，425(3％，[m-COCH₃molecular weight of (2)]/z)，255(12％)，91(66％，CH₂ph) and 43 (100%, COCH)₃)。

EI mass spectrum results of ethyl pentaacetyl hexaazaisowurtzitane structure alkanes: 406 (1%, m/z), 363 (1%, [ m-COCH)₃Molecular weight of (2)]/z，278(2％)，236(5％)，193(10％)，109(12％)，43(100％，COCH₃)，29(15％，CH₂CH₃) And 15 (8%, CH)₃)。

EI mass spectra results of diethyl tetraacetyl hexaazaisowurtzitane structure alkanes:

EI mass spectrum results of hexaacetylhexaazaisowurtzitane structure:

420(5％，m/z)，377(5％，[m-COCH₃molecular weight of (2)]Z), 335 (10%), 295 (15%), 208 (12%), 165 (10%), 123 (12%) and 43 (100%, COCH)₃)。

Reference example 14 WB with carboxylic acid anhydride alone and without N-hydroxysuccinimide carboxylate as acylating agent₆By reductive dearylmethylation of]

Reductive debenzylation was carried out in substantially the same manner as in reference example 13, except that only 32.4g of acetic anhydride was used as the acylating agent and N-acetoxysuccinimide was not used. During the reaction, a sample of the reaction mixture was removed. The sample composition was analyzed by FD mass spectrometry. As a result, it was found that this sample contained the intermediate compound: diacetyl tetrabenzyl hexaazaisowurtzitane (M)⁺612) And triacetyl tribenzyl hexaazaisowurtzitane (M)⁺564). In addition, it was also found that this sample contained, as a compound having at least one acetyl group reduced: ethyl diacetyl tribenzyl hexaazaisowurtzitane (M)⁺550) Ethyl triacetyl dibenzylhexaazaisowurtzitane (M)⁺502) And diethyl diacetyldibenzylhexaazaisowurtzitane (M)⁺488)。

After the reaction was completed, the reaction mixture was analyzed by gas chromatography for the yield of the reaction product in the final reaction mixture. As a result, it was found that the yield of each reaction product was as follows:

triacetyl tribenzyl hexaazaisowurtzitane: 13 percent; ethyl diacetyl tribenzyl hexaazaisowurtzitane: 3.1 percent; tetraacetyldibenzylhexaazaisowurtzitane: 7.5 percent; ethyl triacetyl dibenzyl hexaazaisowurtzitane: 32 percent; diethyl diacetyldibenzylhexaazaisowurtzitane: 30 percent; penta-acetyl benzyl hexaazaisowurtzitane: 1.6 percent; ethyl tetraacetyl benzyl hexaazaisowurtzitane: 1.1 percent; diethyl triacetyl benzyl hexaazaisowurtzitane: 6.2 percent; hexaacetylhexaazaisowurtzitane: 0.5 percent; ethyl pentaacetyl hexaazaisowurtzitane: 1.2 percent; and diethyl tetraacetyl hexaazaisowurtzitane: 1.1 percent.

The above results show that acyl groups are significantly reduced to alkyl groups when carboxylic acid esters of N-hydroxysuccinimide are not used as acylating agents.

Reference example 15[ WB when using N-acetoxysuccinimide alone as acylating agent₆By reductive dearylmethylation of]

Reductive debenzylation was carried out in substantially the same manner as in reference example 13, except that 7.5g of N-acetoxysuccinimide was used as the acylating agent without acetic anhydride. During the reaction, a sample of the reaction mixture was taken and the composition of the sample was analyzed by FD mass spectrometry. As a result, it was found that this sample contained the intermediate compound: pentabenzylhexaazaisowurtzitane ([ M + H) ([ M + H])]⁺619) Acetyl pentabenzyl hexaazaisowurtzitane (M)⁺660) Diacetyl tetrabenzyl hexaazaisowurtzitane (M)⁺612) And triacetylbenzylhexaazaisowurtzitane (M)⁺564). After the reaction was completed, the yield of each reaction product was analyzed by gas chromatography. The results are as follows: diacetyl tetrabenzyl hexaazaisowurtzitane: 74 percent; triacetyl tribenzyl hexaazaisowurtzitane: 15 percent; and tetraacetylbenzyl hexaazaisowurtzitane: 3 percent.

The above results indicate that when in WB₆When only the carboxylic ester of N-hydroxysuccinimide is used as the acylating agent in the reductive dearylmethylation of (2), WB is the reaction product₆To WA_nB_(6-n)(where n is an integer from 1 to 5) in a sequential dearylmethylation process, WA_nB_(6-n)(wherein n is an integer of 1 to 4) reduction of acyl groupThe conversion into alkyl groups can be inhibited. However, the results also show that the reaction rate of the abovereaction is smaller than that of the reaction carried out using a mixture of a carboxylic ester of N-hydroxysuccinimide and a carboxylic anhydride as an acylating agent.

Reference example 16[ by WA₄B₂Synthesis of WA₄H₂]

3.67g (7.11mmol) of tetraacetyldibenzylhexaazaisowurtzitane, 1.60g (7.11mmol) of Pd (OAc)₂As a reduction catalyst and 150ml of acetic acid as a solvent were fed together with stirring elements into a 300ml miniature high-pressure reactor, which was purged with nitrogen. Hydrogen was fed into the reactor so that the pressure in the reactor became 5kg/cm²G, stirring the contents of the reactor for 15 hours to effect the reaction. The reaction mixture was taken out of the reactor and filtered to filter off the catalyst. The obtained filtrate was subjected to distillation under reduced pressure to distill off the solvent. The resulting solid residue was washed with 100ml of ethyl acetate to obtain 1.67g of white tetraacetylhexaazaisowurtzitane (yield: 71%).

The analysis results of the tetraacetylhexaazaisowurtzitane obtained were as follows.

¹Results of H-NMR spectrum [ solvent: d₂O, standard: TMS, unit: delta (ppm)]

1.98(s，6H，COCH₃)，2.00(s，6H，COCH₃) 5.29(m, 2H, CH), 5.50(m, 2H, CH) and 6.35(m, 2H, CH).

Methine and 4 acetyl groups of the W skeleton can be used¹And H-NMR identification.

The infrared absorption spectrum result shows that the fluorescence intensity is 3300-3400cm^-1In the range of 2 absorption peaks, each of which is caused by the stretching vibration of the secondary amino group (N-H group) at 1600cm^-1There is also an absorption peak in the vicinity, which is considered to be caused by a stretching vibration of the carbonyl group (C ═ O) of the acetyl group. The above results indicate that the W skeleton has acetyl and N-H group substituents.

Reference example 17[ use of a catalyst different from that in reference example 16 at a reaction temperature different from that in reference example 16 with WA₄B₂Synthesis of WA₄H₂]

1.20g (2.33mmol) of tetraacetyldibenzylhexaazaisowurtzitane, 0.496g (0.466mmol) of Pd-C (Pd content: 10%) as a reaction catalyst and 60ml of acetic acid as a solvent were charged together with a stirring element into a 300ml miniature high-pressure reactor, which was purged with nitrogen. Hydrogen was fed to the reactor so that the pressure in the reactor became 3kgf/cm²G, then the reactor is immersed in an oil bath at 40 ℃. The contents of the reactor were stirred for 5 hours to effect a reaction. The reaction mixture was taken out of the reactor and filtered to filter off the catalyst. The obtained filtrate was subjected to distillation under reduced pressure to distill off the solvent. The resulting solid residue was washed with 100ml of ethyl acetate to obtain 0.57g of white tetraacetylhexaazaisowurtzitane.

The above results show that WA can be prepared as in reference example 16 even when a catalyst different from that of reference example 16 is used and the reaction is carried out at a temperature different from that of reference example 16₄H₂。

Reference example 18[ WB in the presence of acylating agent₆Formation of WA during reductive dearylmethylation of_nH_(6-n)Confirmation of (2)]

Reductive debenzylation of hexabenzylhexaazaisowurtzitane in the presence of an acylating agent was carried out in substantially the same manner as in reference example 4 except that the reaction time was 200 hours. After the reaction was completed, the reaction mixture was analyzed by gas chromatography. As a result, it was found that the yield of hexaacetylhexaazaisowurtzitane was only 0.8%. On the other hand, tetraacetylhexaazaisowurtzitane (WA) WAs identified by high performance liquid chromatography₄H₂) Are present. Acetyl chloride was added to the above reaction mixture, and the reaction mixture was stirred for 1 hour toThe reaction is carried out. The resulting reaction mixture was analyzed by gas chromatography. The analysis result showed that the yield of hexaacetylhexaazaisowurtzitane was 5%. This also indicates that WA WAs present before the addition of acetyl chloride_nH_(6-n)Such as tetraacetylhexaazaisowurtzitane and pentaacetylhexaazaisowurtzitaneWurtzite-type structural alkanes are present.

Reference example 19[ starting from WB in the presence of acylating agent₆Synthesis of WA by reductive dearylmethylation₄B₂]

1.89g (2.66mmol) of hexabenzylhexaazaisowurtzitane, 1.70g (1.6 mg atom) of Pd-C (Pd content: 10%) as a reduction catalyst, 5.0g (31.8mmol) of N-acetoxysuccinimide (acylating agent), 160ml of ethylbenzene (solvent) and 3.24g (31.8mmol) of acetic anhydride (acylating agent) were charged together with a stirring member into a 300ml miniature autoclave reactor, which was purged with nitrogen. Hydrogen was fed to the reactor so that the pressure in the reactor became 50kg/cm²G, stirring the contents of the reactor for 20 hours to effect a reaction. The reaction mixture was removed from the reactor and filtered with filter paper to filter off the precipitate and reduce the catalyst. The precipitate on the filter paper was treated in situ with 200ml chloroform to dissolve the precipitate. The filtrate (containing chloroform for treatment) was subjected to distillation to distill off the solvent. The resulting solid residue wasdissolved in 200ml of chloroform to obtain a solution. To this solution was added 200ml of 28% aqueous ammonia solution, and the resulting mixture was vigorously stirred for 30 minutes to separate the reaction mixture into an aqueous phase and a chloroform phase, in which N-acetoxysuccinimide was decomposed and transferred to the aqueous phase. The chloroform phase was separated and subjected to distillation to distill off the solvent, obtaining 1.29g of a white solid residue. The obtained white solid residue was crystallized from ethylbenzene to obtain 1.03g of white tetraacetyldibenzylhexaazaisowurtzitane (yield: 75%). From the following FD-Mass Spectrometry,¹H-NMR、¹³C-NMR and¹³C^-1as a result of H COSY, it was confirmed that the white substance obtained by recrystallization was tetraacetyldibenzylhexaazaisowurtzitane. The above analysis results are as follows:

FD-Mass Spectrometry: 517([ M + H)]⁺)。

¹H-NMR spectrum [ solvent: CDCl₃(ii) a The standard is as follows: TMS, unit: delta (ppm)]：

1.94(s，6H，COCH₃)，2.15(s，6H，COCH₃)，4.06(d，2H，CH₂)，4.29(d，2H，CH₂)，5.09(d，2H，CH)，5.70(d，2H，CH)，6.42(s, 2H, CH) and 7.3-7.5(m, 10H, Ph).

By using¹H-NMR can identify 6 methines, 4 acetyl and 2 benzyl of the W skeletonAnd (4) a base.

¹³C-NMR [ solvent: CDCl₃(ii) a The standard is as follows: TMS; unit: delta (ppm)]：20.737(CH₃)，22.111(CH₃)，56.428(CH₂) 69.679(CH), 70.592(CH), 128.056(Ph), 128.673(Ph), 128.928(Ph), 136.742(Ph) and 168.263 (CO).

By using¹³C-NMR can identify methylene groups of methine, acetyl and phenyl and benzyl groups of the W skeleton.

By using¹H-¹³C COSY to identify bonds to¹Each identified by H-NMR¹On H¹³C。

Example 1

[ by mixing WA₄H₂Nitrosation to prepare WA₄(NO)₂And oxidizing WA₄(NO)₂Synthesis of WA₄(NO₂)₂]

0.336g (1mmol) of tetraacetylhexaazaisowurtzitane and 10ml of 50% acetic acid as a solvent were charged into a 100ml reactor. The resulting mixture was cooled and maintained at 0 ℃. While the mixture was stirred at 0 deg.C, 2ml of an aqueous solution of sodium nitrite (sodium nitrite concentration: 4mol/l) was gradually added dropwise thereto. The resulting mixture was then heated to 30 ℃ and then stirred for 4 hours to effect nitrosation. To the resulting reaction mixture was added 50ml of chloroform. The reaction mixture was stirred vigorously and then allowed to stand, and the reaction mixture separated into an organic phase and an inorganic phase. The organic phase was separated and the solvent was distilled off from the organic phase under reduced pressure to obtain 0.373g of dinitrosotetraacetyl hexaazaisowurtzitane (yield: 95%).

30ml of 100% nitric acid (oxidant) was added to a 100ml reactor. 0.9262g (2.35mmol) of the dinitrosotetraacetyl hexaazaisowurtzitane mentioned above was then fed into the reactor. The resulting mixture was stirred at room temperature for 5 hours to effect nitration reaction. The resulting reaction mixture was subsequently distilled under reduced pressure to distill off nitric acid, yielding 0.955g of dinitrotetraacetylhexaazaisowurtzitane (yield: 95%).

The analysis results of the dinitroso tetraacetyl hexaazaisowurtzitane obtained were as follows.

¹H-NMR result [ solvent: CDCl₃(ii) a The standard is as follows: TMS; unit:delta (ppm)]：

2.05(s，6H，COCH₃)，2.17(s，6H，COCH₃) 5.46(m, 2H, CH), 6.62(m, 2H, CH) and 7.30(s, 2H, CH).

By using¹H-NMR can identify 6 methines and 4 acetyl groups of W.

Infrared absorption Spectroscopy (IR) results showed at 1670cm^-1There is an absorption peak nearby, wherein the absorption peak is caused by carbonyl (C ═ O) of acetyl group, and is about 1500cm^-1、1380cm^-1And 1350cm^-1There are absorption peaks in the vicinity, each of which is caused by a nitroso group.

The IR results showed that the absorption peak due to the N-H group identified in the IR spectrum of tetraacetylhexaazaisowurtzitane structure alkane disappeared completely.

The analysis results of dinitrotetraacetylhexaazaisowurtzitane type structural alkane are as follows:

¹H-NMR result [ solvent: DMSO-d₆(ii) a The standard is as follows: TMS; unit delta (ppm)]；

2.10(s，12H，COCH₃) 6.75(m, 2H, CH) and 7.35 (the peak has a single peak at 7.35ppm and a shoulder on the low magnetic field side of the single peak, 4H, CH).

The infrared absorption spectrum result shows that 1680cm^-1There is an absorption peak near the peak, which is caused by the stretching vibration of the carbonyl group (C ═ O) of the acetyl group, at 1570cm^-1And 1300cm^-1There are absorption peaks in the vicinity, each peak being caused by the stretching vibration of the nitro group. This indicates that nitro groups and acetyl groups are present as substituents on the W skeleton of dinitrotetraacetylhexaazaisowurtzitane.

The presence of the parent ion peak (m/z426) can be identified by FD-mass spectrometry.

The decomposition temperature of dinitrotetraacetylhexaazaisowurtzitane-type structural alkane was measured by differential scanning calorimetry (temperature rising rate 10 ℃/min) using a DSC 200C manufactured and sold by Seiko Instruments Inc., Japan. As a result, it was found that the peak temperature was about 314 ℃ which was higher than that of HNW (about 250 ℃). This indicates that dinitrotetraacetylhexaazaisowurtzitane is a nitroamine compound having excellent heat resistance.

Example 2

[ Nitrification of WA₆Synthesis of WA₄(NO₂)₂]

5ml of acetic anhydride were added to a 100ml reactor, cooled and maintained at 0 ℃.5ml of 100% nitric acid (nitrating agent) was gradually added dropwise to the reactor with stirring at 0 ℃. To the resulting mixture was added 0.5g of dinitrogen pentoxide (nitrating agent), followed by 0.1g (0.238mmol) of hexaacetylhexaazaisowurtzitane-type structural alkane, and then 0.5g of dinitrogen pentoxide. This addition of 0.5g of dinitrogen pentoxide was repeated 4 times at 1-hour intervals. The resulting mixture was quenched with water and ice. The liquid component of the mixture was distilled off under reduced pressure, and the resulting solid residue was analyzed by high performance liquid chromatography. As a result, it was confirmed that the solid residue was dinitrotetraacetylhexaazaisowurtzitane.

Reference example 20

[ Nitrification of WA₄(NO₂)₂Synthesis of W (NO)₂)₆]

A200 ml reactor was immersed in a bath at 0 ℃.25 ml of sulfuric acid was added to the reactor, and then 25ml of 100% nitric acid was added dropwise to the reactor to obtain a mixture acid (nitrating agent). 0.2g (0.457mmol) of dinitrotetraacetylhexaazaisowurtzitane was added to the mixed acid, and the resulting mixture was stirred at 0 ℃ for 8 hours. The mixture was then stirred at room temperature for another 67 hours to effect a reaction. After the reaction was completed, 200ml of chloroform was added to the reaction mixture, and the organic matter in the reaction mixture was extracted into a chloroform phase (this extraction operation was repeated 2 times). The chloroform phase was distilled under reduced pressure to distill off the solvent. The solid residue obtained is taken up in 10% NaHCO₃The aqueous solution was washed to obtain 0.06g of hexanitrohexaazaisowurtzitane (yield: 30%). The analysis results of the hexanitrohexaazaisowurtzitane obtained were as follows.

The infrared absorption spectrum by the KBr method has the following absorption peaks: at 1605cm^-1An absorption peak is arranged nearby and is caused by the asymmetric stretching vibration of the nitro; at 1325cm^-1Nearby and 1270cm^-1Absorption peaks are nearby and are caused by symmetric stretching vibration of nitro groups; at 945cm^-1Near and 880cm^-1Absorption peaks are nearby and are caused by bending vibration of nitro groups; and at 3030cm^-1There is an absorption peak in the vicinity, which is caused by the stretching vibration of the methine group on the W skeleton.

These infrared absorption peaks are characterized in comparison to the infrared absorption peaks disclosed in COMBUSTION AND FLAME 87: 145-151(1991) the infrared absorption peak characteristics of hexanitrohexaazaisowurtzitane are consistent. The above infrared absorption spectrum results also revealed that the carbonyl group (C ═ O) of the acetyl group of dinitrotetraacetylhexaazaisowurtzitane (used as a raw material) causes a difference of 1680cm^-1The nearby absorption peak disappeared completely.

The above results indicate that the acetyl group of the dinitrotetraacetylhexaazaisowurtzitane is replaced by the nitro group to form the hexanitrohexaazaisowurtzitane.

The results of Hexanitrohexaazaisowurtzitane (HNW) analyzed by high performance liquid chromatography under the same conditions as disclosed in International Symposium on environmental materials Technology proceeding, September 24-27, 76-81(1995) (in which the characteristics of various HNWs are reported) indicate that the HNWs obtained have the same retention time as the HNWs disclosed in the publication.

EI-Mass Spectroscopy results showed the presence of the following fragmentation peaks, such as ion peak [ molecular weight of HNW (parent ion) minus NO₂Molecular weight of (2)]316, 213 and 46 (NO)₂) Wherein the ion peak is dissociated from HNW disclosed in International Symposium on environmental Materials technologies, September 24-27, 76-81(1995) aboveThe sub-peaks are identical.

Comparative example 1[ WB in the absence of acylating agent₆Acylation reaction after reductive dearylmethylation]

3.0g (4.24mmol) of hexabenzylhexaazaisowurtzitane, 0.476g (2.12mmol) of Pd (OAc)₂75ml of Tetrahydrofuran (THF) and 75ml of ethanol are introduced into a 300ml miniaturised high-pressure reactor with stirring elements. The reactor was purged with nitrogen. Then, hydrogen gas was supplied into the reactor to adjust the internal pressure to 10kgf/cm²-G. The contents of the reactor were then stirred at room temperature for 300 hours to effect a reaction. After the reaction was completed, WB was measured by gas chromatography₆The amount of toluene formed by dearylmethylation. As a result, it was found that almost 100% of the benzyl groups were removed. The reaction mixture was removed from the reactor and the reducing catalyst was removed from the reaction mixture. The solvent was distilled off from the reaction mixture under reduced pressure. To the residue was added 100ml of acetic anhydride (acylating agent), followed by 10ml of acetyl chloride. However, the results of gas chromatography showed that no acyl group-containing hexaazaisowurtzitane derivative was formed.

The above results show that WB is carried out in the absence of an acylating agent₆The decomposition of the W structure occurs during the reductive dearylmethylation of (2).

Comparative example 2[ WB in the absence of acylating agent₆Acylation reaction is carried out after reduction dearylmethylation]

Reductive dearylmethylation of hexabenzylhexaazaisowurtzitane in the absence of an acylating agent was carried out in substantially the same manner as in reference example 19 except that the acylating agent was not used. After the reaction was completed, the same acylating agent in the same amount as in reference example 19 was added to the reaction mixture. The reaction mixture was stirred under a nitrogen atmosphere for 5 hours to effect a reaction. The resulting reaction mixture was treated in the same manner as in reference example 19. However, the presence of tetraacetyldibenzylhexaazaisowurtzitane was not identified in the reaction mixture.

According to the present invention, an acyl group-and nitro group-containing hexaazaisowurtzitane derivative can be produced. The acyl and nitro hexaazaisowurtzitane derivative can be used as a precursor of HNW, is a very useful additive, can be used for modifying the properties of a propellant and an explosive, such as mechanical properties, initiation speed, initiation pressure, combustion rate, pressure index, sensitivity, heat resistance and the like, and can be used as a raw material of a high-performance explosive. Further, according to the process of the present invention, there is provided a process forproducing an acyl group-and nitro-hexaazaisowurtzitane derivative, which can easily produce an acyl group-and nitro-hexaazaisowurtzitane derivative in a high yield.

Claims

WA_n(NO₂)_(6-n)(VIII)

WA_n(NO₂)_(6-n)(VIII)

WA_n(NO)_(6-n)(VII)

wherein NO represents a nitroso group, and n, A and W are as defined above.

3. A process according to claim 2, wherein the nitrating agent is nitric acid.

4. The method of claim 2, wherein the nitro reagent is hydrogen peroxide or a mixture of hydrogen peroxide and nitric acid.

WA_n(NO₂)_(6-n)(VIII)

WA_nH_(6-n)(IV)

wherein H represents a hydrogen atom, and n, A and W are as defined above.

6. A process according to claim 5, wherein the nitrating agent is nitric acid or a mixture of nitric acid and dinitrogen pentoxide.

WA_n(NO₂)_(6-n)(VIII)

in which n represents an integer from 4 to 5, A independently of one another represents C₁-C₁₀Acyl radical, NO₂Represents nitro, W represents hexanitrogenof the following formula (II)Hexavalent residues of heterowurtzite-structure alkanes:

WA₆(III)

wherein A and W are as defined above.

8. A process according to claim 7, wherein the nitrating agent is a mixture of nitric acid and dinitrogen pentoxide.