JP3034054B2 - Method for producing hexanitrohexaazaisoulitanium - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to hexanitrohexaazaisowurtzitane and a method for producing the same.

(Background technology)

As a compound having a hexaazaisowurtzitanium skeleton, hexaazaisowurtzitane derivatives having various arylmethyl groups obtained by condensing arylmethylamine and glyoxal are known [J. Org. Chem., vol.55, 1459-1466 (1990)]. As a hexaazaisowurtzitane compound having an acyl group,
Tetraacetyldibenzylhexaazaisowurtzitanium is known, and it has been reported that this compound is a precursor of hexanitrohexaazaisowurtzitane which is a raw material for explosives [The Militarily Critical Technologies L.
ist, Office of the Under Secretary of Defense
for Acquisition, 12-22, October (1992), Tetrahe
dron Vol.51, No16, 4711-4722 (1995)]. Further, hexaazaisowurtzitane derivatives having an ethyl group such as tetraacetyldiethylhexaazaisowurtzitanium are also known (Tetrahedron Vol. 51, No. 16, 4711-4722 (1992)).
5)) and hexaazaisowurtzitane having a trimethylsilylethyloxycarbonyl group are also known (JP-A-6-321962). Further, in addition to compounds having an acetyl group, such as the above-mentioned tetraacetyldibenzylhexaazaisowurtzitanium and tetraacetyldiethylhexaazaisowurtzitanium, hexaazaisowurtzitane derivatives having a benzyl group and / or an ethyl group are also available. It is known.

Hexaazaisowurtzitane having an acyl group easily substituted with a nitro group is useful as a precursor of a high-density nitro compound as a raw material for explosives. However, obtaining a nitro compound as a precursor of the above-described compound has the following problems. For example, a hexaazaisoulitoltitanium derivative having a benzyl group generates a nitrated aromatic compound as a by-product when it is nitrated, so that the target hexanitrohexaazaisowurtzitane is separated and purified. It is complicated. In addition, during the production of hexaazaisowurtzitane having a trimethylsilylethyloxycarbonyl group, hydrochloric acid, which is a strong acid, is generated, which induces the decomposition of hexabenzylhexaazaisowurtzitane, which is a raw material. Furthermore, there is a report that hexaacetylhexaazaisowurtzitanium can be obtained by nitrating tetraacetyldibenzylhexaazaisowurtzitanium, but there is no description of a specific production method thereof (Tetrahedron Vos).
l.51, No16, 4711-4722 (1995)). It has been reported that it is difficult to produce hexanitrohexaazaisowurtzitanium by nitrating tetraacetyldiethylhexaazaisowurtzitanium (Tetrahedron Vol. 51, No. 16, No. 4).
711-4722 (1995)).

Therefore, there has been a demand for a method for producing hexanitrohexaazaisowurtzitanium in high yield using a hexaazaisowurtzitanium derivative having an acyl group.

[Disclosure of the Invention]

The present inventors have found an industrially advantageous method for synthesizing hexanitrohexaazaisowurtzitanium, and have completed the present invention.

An object of the present invention is to produce hexanitrohexaazaisowurtzitanium in high yield using a hexaazaisowurtzitanium derivative.

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

WA _n N _(6-n) (I) wherein n is 4 or 5, A is an acyl group having 1 to 10 carbon atoms, each acyl group may be the same or different, and N is nitro. The group W represents a hexavalent hexaazaisowurtzitanium residue represented by the following formula (II). ] Further, the present invention provides a hexaazaisowurtzitane derivative having a nitroso group represented by the general formula (III) and a method for producing the same.

WA _n NS _(6-n) (III) wherein n is 4 or 5, A is an acyl group having 1 to 10 carbon atoms, each acyl group may be the same or different, and NS is nitroso. The group W represents a hexavalent hexaazaisowurtzitanium residue represented by the following formula (II). ] As the acyl group A in the above formulas (I) and (III), any acyl group having 1 to 10 carbon atoms can be used. As the acyl group A, acetyl, formyl, propionyl, butyryl, isobutyryl, valeryl, hexanoyl, 2-phenylacetyl and the like are used. Preferably, an acyl group having 1 to 5 carbon atoms, for example, formyl, acetyl, propionyl, butyryl, valeryl and the like are used, and more preferably, an acyl group having 2 to 4 carbon atoms such as acetyl, propionyl, butyryl and the like are used. The n acyl groups in the formula may be the same or different.

These hexaazaisowurtzitanium derivatives can take a plurality of isomers depending on the substitution position of the acyl group, nitroso group and nitro group, and the present invention may have any of these structures.

Hereinafter, a method for producing the hexaazaisowurtzitane derivative of the above formulas (I) and (III) will be described.

First, in order to produce a hexaazaisoisotitanium derivative having a nitro group of the general formula (I) and hexanitrohexaazaisowurtzitanium from the derivative, as shown in the reaction formula (1), _It suffices to nitrate _m H _(6-m) .

WA _m H _(6-m) → WA _n N _(6-n) (1) wherein m is an integer of 4 to 6, n is an integer of 4 to 5, and A is an acyl group having 1 to 10 carbon atoms. Wherein each acyl group may be the same or different, H is a hydrogen atom, N is a nitro group,
W represents a hexavalent hexaazaisowurtzitane residue. In addition, in order to produce hexaazaisowurtzitanium having a nitroso group represented by the general formula (III), WA _n H _(6-n) is nitrosated as shown in a reaction formula (2). Good.

WA _n H _(6-n) → WA _n NS _(6-n) (2) wherein n is an integer of 4 to 5, A is an acyl group having 1 to 10 carbon atoms, and each acyl group is H may be the same or different, H represents a hydrogen atom, NS represents a nitroso group, and W represents a hexavalent hexaazaisowurtzitanium residue. WA _n H which is a raw material of the above reaction formulas (1) and (2)
Derivatives prepared by any method may be used for _(6-n) and WA _m H _(6-m) . For example, as described in WO 96/23792, after reductive de-arylmethyl the WB ₆ in the presence of an acylating agent, is prepared by reductive de-aryl methylation in the absence acylating agent WA _n H
_It is preferable to use _(6-n) and WA _m H _(6-m) . This manufacturing method will be described later in detail.

The acyl group of the hexaazaisowurtzitane derivative, WA _n H _(6-n) or WA _m H _(6-m) , which is a raw material of the reaction formulas (1) and (2), is an acyl group having 1 to 10 carbon atoms. It is. Each acyl group may be the same or different. As the acyl group, acetyl, formyl, propionyl, butyryl, isobutyryl, valeryl, hexanoyl, 2-phenylacetyl and the like are used, and preferably an acyl group having 1 to 5 carbon atoms such as formyl, acetyl, propionyl, butyryl, valeryl and the like are used. And more preferably an acyl group having 2 to 4 carbon atoms, for example, acetyl, propionyl, butyryl and the like.

In addition, these hexaazaisoulitanium derivatives
A plurality of isomers can be taken depending on the substitution position of the acyl group and the hydrogen atom, and the present invention can be used with any of these structures.

WA _m H _(6-m) includes WA ₄ H ₂ , WA ₅ H _1, and WA ₆ , and any one of them may be used alone, or a mixture of two or more may be used. Good.

As the nitrating agent used in the nitration step of the reaction formula (1), any nitrating agent capable of nitrating WA _m H _(6-m) may be used. For example, only nitric acid,
Examples include nitrous oxide, a mixture of nitric acid and a nitration accelerator, and nitrous oxide. These nitrating agents may be used as a mixture of two or more. Among the above nitrating agents, nitric acid may be partially or entirely replaced with a metal nitrate such as silver nitrate or a nitronium salt such as nitronium tetrafluoroborate. The use of nitric acid, nitrous oxide, or nitrous oxide is preferred because the selectivity of the nitration reaction can be increased.

The nitration accelerator enhances the electrophilicity of the nitronium ion, and is usually A. an organic acid having a perfluoro structure such as trifluoroacetic acid, sulfuric acid, fuming sulfuric acid, perfluoroalkylsulfonylimide, polyphosphoric acid, trifluorofluoride, etc. Organic or inorganic strong Bronsted acids such as methanesulfonic acid; B. carboxylic anhydrides such as trifluoroacetic anhydride and acetic anhydride; C. diphosphorus pentoxide, dinitrogen pentoxide, sulfur trioxide and the like Oxides; D. Lewis acids such as rare earth salts of penfluoroalkylsulfonylimides and rare earth salts of perfluoroalkylsulfonates; and the like. These nitration accelerators may be used as a mixture of two or more. Among the above nitration accelerators A to C, the strong Bronsted acid of A. and the oxide of C. are preferred because they increase the rate of the nitration reaction. The strong Bronsted acid of A. is more preferably an acid having an acidity equal to or stronger than trifluoroacetic acid (for example, an acidity represented by pKa). A. ~
Among C., sulfuric acid, trifluoroacetic acid, polyphosphoric acid, diphosphorus pentoxide, and sulfur trioxide are particularly preferable.

The perfluoroalkylsulfonylimide is represented by the following formula (IX).

RfSO ₂ NHSO ₂ Rf ′ (IX) [wherein, Rf and Rf ′ represent a perfluoroalkyl group having 1 to 8 carbon atoms, S is a sulfur atom, O is an oxygen atom, N is a nitrogen atom, and H is a hydrogen atom. Represents The perfluoroalkyl group of the perfluoroalkylsulfonylimide may be a linear perfluoroalkyl group or a branched perfluoroalkyl group, and may be obtained by simultaneously using one or more kinds of perfluoroalkylsulfonylimide. Is also good. Examples of perfluoroalkylsulfonylimide include, for example, bis- (trifluoromethylsulfonyl) imide, bis- (nonafluorobutylsulfonyl) imide, bis- (heptadecafluorooctylsulfonyl) imide and the like.

Further, a rare earth salt of perfluoroalkylsulfonic acid represented by the following formula (X) can also be used as a nitration accelerator.

M (RfSO ₃ ) ₃ (X) [wherein, Rf represents a C 1-8 perfluoroalkyl group, S represents a sulfur atom, O represents an oxygen atom, and M represents a rare earth element. Examples of rare earth salts of perfluoroalkylsulfonic acids include, for example, tris- (trifluoromethylsulfone)
Lanthanum [III], tris- (trifluoromethylsulfone) yttrium [III], tris- (trifluoromethylsulfone) europium [III], tris- (trifluoromethylsulfone) ytterbium [III],
Tris- (trifluoromethylsulfone) scandium [III] and tris- (trifluoromethylsulfone) praseodymium [III].

Further, a compound represented by the following formula (XI) can be used as the rare earth salt of perfluoroalkylsulfonylimide.

M (RfSO ₂ NSO ₂ Rf ′) ₃ (XI) wherein Rf and Rf ′ each represent a C 1-8 perfluoroalkyl group, S is a sulfur atom, O is an oxygen atom, N is a nitrogen atom, M represents a rare earth element. The perfluoroalkyl group of the perfluoroalkylsulfonylimide may be a linear perfluoroalkyl group or a branched perfluoroalkyl group, and may be obtained by simultaneously using one or more kinds of perfluoroalkylsulfonylimide. Is also good.

Rare earth salts of perfluoroalkylsulfonylimides are water-stable Lewis acids, and this Lewis acid catalyst is
After the reaction, it can be recovered and reused.

Examples of rare earth salts of perfluoroalkylsulfonylimide include, for example, tris- [bis- (trifluoromethylsulfonyl) imide] lanthanum [III], tris-
[Bis- (trifluoromethylsulfonyl) imide] ytterbium [III], tris- (bis- (trifluoromethylsulfonyl) imide] yttrium [III],
Tris- [bis- (nonafluorobutylsulfonyl) imide] ytterbium [III], tris- [bis- (nonafluorobutylsulfonyl) imide] yttrium [III], tris- [bis- (nonafluorobutylsulfonyl) imido lanthanum [ III], Tris- [bis-
(Heptadecafluorooctylsulfonyl) imide] lanthanum [III], tris- [bis- (heptadecafluorooctylsulfonyl) imide] ytterbium [II
I] and a Lewis acid catalyst containing a rare earth element such as tris- [bis- (heptadecafluorooctylsulfonyl) imide] yttrium [III].

The rare earth salt of perfluoroalkylsulfonylimide is a salt of perfluoroalkylsulfonylimide and a rare earth element, and any element may be used as long as it is a rare earth element. Preferred examples of the rare earth element include lanthanum, ytterbium, Yttrium and the like are preferred.

The accelerator can be used either homogeneously or heterogeneously. For example, it is preferable to use the following because the recovery of the accelerator is facilitated.

E. Inorganic solid Brönsted acid such as Nafion-NR50 (trade name, DuPont) and zeolite; F. Inorganic solid such as rare earth such as perfluoroalkylsulfonylimide having long-chain fluoroalkyl group Lewis acid; G. Liquid perfluoroalkanesulfonic acid which does not dissolve uniformly in the reaction system, orgosulfonic acid having a perfluoro skeleton; typical examples of the above zeolite include analium (anal)
cime), bicatite (bikataite), brewsterite (brewsterite), chabazite (chabazite), clinoptilobite (clinoptilobite), bachiardite (bachiardite), agingtonite (edingtonite),
Epistilbite, erionite (eri
onite), faujasite, ferrierite, gismondine,
Gmelinite, gonnardite
ite), harmontome, heulandite, kieselguhr, laumontite, levinite
e), losod, mesolite, mordenite, natrolite,
Omega (omega), Paulingite (paulingite), phillipsite (philipsite), scolesite (scolec)
ite), sodalite hydrate, stilbite, tomsonit
e), yugawaralite, and "A", "N-
A "," ^Lb "," P "," T "," X "," ZX-4 ",
"ZX-5N," ZSM-5 "," ZSM-11 "," MCM-22 ",
"Faujasiten, Linde Type L" and the like are used.

As the strong Bronsted acid, an insoluble polymer substance having a sulfonic acid group and a cation exchange resin having a sulfonic acid group can also be used.

Insoluble polymer substances having sulfonic acid groups and cation exchange resins having sulfonic acid groups are also strongly acidic solid catalysts that can be recovered and reused after the reaction. Examples of the insoluble polymer substance having a sulfonic acid group and the cation exchange resin having a sulfonic acid group include polyethylene sulfonic acid, a fluorine-containing polymer having a sulfonic acid group, and the like. Preferably, the following general formula (XII) And a sulfonic acid group-containing insoluble polymer such as a fluorinated polymer having a sulfonic acid group having a repeating unit represented by the following formula: and a cation exchange resin. Preferred examples of the insoluble polymer substance having a sulfonic acid group and the cation exchange resin include Nafion-NR50 (trade name, manufactured by DuPont) and the like.

The nitration step of the reaction (1) can be performed without a solvent, or can be performed in a solvent. As the solvent, any solvent can be used as long as it does not adversely affect the nitration of the above raw materials. For example, halides such as dichloromethane and chloroform; polar solvents such as acetonitrile, sulfolane, dimethylformamide, and dimethylacetamide; ether compounds such as THF and diethyl ether; ester compounds such as ethyl acetate, methyl acetate, and ethyl propionate; acetone, methyl ethyl ketone And ketone compounds such as ethyl isobutyl ketone. One of these solvents may be used alone, or a mixture of two or more solvents may be used.

The step of the reaction formula (1) is performed at -20 to 80 ° C, preferably 0 to 80 ° C.
Perform at 60 ° C. The reaction time is 0.5 to 10 hours, preferably 1 to 8 hours.

The amount of the nitrating agent used in the step of the reaction formula (1) is
Expressed as a molar ratio to WA _m H _(6-m) , usually 2.0 to 50
0, preferably 3.0-400. The amount of the nitration promoter is expressed as a molar ratio with respect to WA _m H _(6-m) from 1.0 to 50.
0, preferably 1.5 to 300 can be used.

WA _n H _{(6-n) as} a starting material for the nitrosation step represented by the reaction formula (2) of the present invention may be produced by any method. For example, as described in WO 96/23792, after reductive de-arylmethyl the WB ₆ in the presence of an acylating agent, is prepared by reductive de-aryl methylation in the absence acylating agent WA _n H
_It is preferable to use _(6-n) . This manufacturing method will be described later in detail.

The raw materials for the nitrosation step of reaction formula (2) include WA ₄ H ₂ and WA ₅ H ₁ , and either one of them may be used or a mixture of two may be used. WA ₄ H2 and WA ₅
Since H ₁ can be nitrosated by the same method, it can be easily converted into a nitroso compound by mixing at any ratio.

Scheme (2) The step nitrosating agent used _{in, WA n H (6-n} ) WA by nitrosating the _n NS _(6-n)
Any material can be used as long as it can be manufactured. For example, sulfurous acid, dinitrogen tetroxide, a nitrosonizing agent such as a nitrosonium salt or nitrosyl chloride, which has enhanced electrophilicity of nitrosonium ions, etc. can be used.Nitrous acid may be used as it is, but sodium nitrite, A mixture of nitrite such as potassium nitrite and an acid such as acetic acid and hydrochloric acid can also be used. As the nitrosonium salt, those in which a fluoride such as nitrosonium tetrafluoroborate or nitrosonium hexafluorophosphate is an anion are preferable because the electrophilicity of the nitrosonium ion is further enhanced. The addition amount of the nitrosating agent is 1 mol per mol of WA _n H _(6-n).
200200 mol, preferably 3-150 mol, more preferably 4-100 mol.

The nitrosation step of the reaction formula (2) may be solvent-free,
Usually, the reaction is carried out in a solvent. Any solvent can be used as long as it does not adversely affect the reaction. For example, halides such as dichloromethane, chloroform and carbon tetrachloride; acetonitrile, sulfolane,
Polar solvents such as dimethylformamide and dimethylacetamide; carboxylic acids such as acetic acid and propionic acid; acetic anhydride;
Carboxylic anhydrides such as propionic anhydride; ether compounds such as THF and diethyl ether; ester compounds such as ethyl acetate, methyl acetate and ethyl propionate; ketone compounds such as acetone, methyl ethyl ketone and ethyl isobutyl ketone; water and pyridine are used. Is done. These solvents may be used alone or in combination of two or more.

The nitrosation step in the reaction formula (2) may be performed at a temperature in the range of −50 to 200 ° C., preferably −30 to 150 ° C., and more preferably −20 to 100 ° C.

As shown in the reaction formula (3), the nitro group of the formula (I) can be obtained by nitrating WA _n NS _(6-n) obtained by the formula (2 ₎ with a nitrating agent. Hexaazaisoulitanium derivatives can be produced.

WA _n NS _(6-n) → WA _n N _(6-n) (3) wherein n is an integer of 4 to 5, A is an acyl group having 1 to 10 carbon atoms, and each acyl group is NS may be the same or different, NS represents a nitroso group, N represents a nitro group, and W represents a hexavalent hexaazaisowurtzitanium residue. The raw materials for the nitration step of reaction formula (3) include WA ₄ NS ₂ and
WA ₅ NS ₁ may be used, but either one may be used or two types may be used as a mixture. WA ₄ NS ₂ and
Since WA ₅ NS ₁ can be nitrated in the same manner, the raw materials may contain these in any ratio.
Also, WA ₄ NS ₁ H ₁ , which may be generated by the reaction formula (2),
A mixture containing unreacted and remaining WA ₄ H ₂ and WA ₅ H ₁ may be used as a raw material.

The reaction conditions such as the nitrating agent of the reaction formula (3), the solvent and the reaction temperature of the present invention can be the same as those described in the nitration step of the reaction formula (1) and the reaction conditions. .

WA _n H used as a raw material in the above reaction formulas (1) and (2)
_(6-n) is obtained by the following reaction formula (4).

Wherein m is an integer of 4 to 6, A is an acyl group having 1 to 10 carbon atoms, each acyl group may be the same or different, B is an arylmethyl group, H is a hydrogen atom, and W is It represents a hexavalent hexaazaisowurtzitane residue. That is, WB ₆ is 1) reductively dearylmethylated in the presence of an acylating agent to synthesize WA _m B _(6-m) , and 2)
It is obtained by reductive dearylmethylation of A _m B _(6-m) .

The step of 1) reductive dearylmethylation in the presence of the acylating agent in the reaction (4) is usually carried out by contacting with a reducing catalyst in the presence of a reducing agent. As the reducing agent and catalyst to be used in this case, if as it can proceed the de-arylmethyl reaction of WB _6, it can be used in any combination. As a reducing agent,
Hydrogen, formic acid and the like can be used, and hydrogen is preferably used. As the catalyst, for example, a metal belonging to the platinum group or a derivative thereof is used, and preferably, Pd (OA
c) ₂ , PdCl ₂ , Pd (NO ₃ ) ₂ , PdO, Pd (OH) ₂ , Pd ₃ P
b ₁ , Pd derivatives such as Pd ₃ Te ₁ and Pd metal; Ru such as RuCl ³
Derivatives and Ru metal are used, and more preferably, Pd derivatives such as Pd (OAc) ₂ and PdCl ₂ and Pd metal are used. These catalysts may be used as they are, or may be used by being supported on various carriers such as activated carbon, silica, alumina, silica-alumina, zeolite and activated clay. These catalysts may be subjected to a reduction treatment before the reaction. In the case of a solid catalyst, treatment such as silylation or acylation can be used to inactivate surface acid sites, or to change the acidity of the solid surface by adsorbing an alkaline substance such as NaOH. . The amount of the catalyst may vary depending on the reduction activity of the catalyst, etc.
Expressed as the weight ratio of catalyst metal to WB ₆ , typically 0.000
It can be used in the range of 1 to 20, preferably 0.001 to 10.

As the acylating agent used in the step (1) of (4), any one can be used as long as it can acylate a secondary amine, and N-acetoxysuccinimide and N-propionyloxysuccinic acid can be used. Imide, N- (2
Carboxylic acid esters of N-hydroxysuccinimide such as -phenylacetoxy) succinimide; carboxylic anhydrides such as acetic anhydride, propionic anhydride, butyric anhydride, and acetic acid-formic acid mixed acid anhydride; acetylimidazole, propionylimidazole Acylimidazole; phenyl bromide such as phenyl bromide and acetic anhydride; and carboxylic anhydride. When N-hydroxysuccinimide carboxylic acid ester (N-hydroxysuccinimide ester) such as N-acetoxysuccinimide and N-propionyloxysuccinimide is used among these acylating agents, WA ₆ This is preferred because the selectivity of is improved. One of these acylating agents may be used alone, or two or more of them may be used in combination. In particular, N-acetoxysuccinimide, N-
A carboxylic acid ester of N-hydroxysuccinimide such as propionyloxysuccinimide, and acetic anhydride;
When a carboxylic anhydride such as propionic anhydride is mixed and used, the reaction rate in the step (1) of the reaction (4) is improved, and the selectivity of WA ₄ H ₂ and WA ₅ H ₁ is also improved. Particularly preferred.

The amount of the acylating agent to be added varies depending on the reaction method and reaction conditions, 4 to 100 expressed by a molar ratio to the arylmethyl groups of WB _6, preferably, be used in the range of 4.5 to 50 it can. When an N-hydroxysuccinimide ester and a carboxylic anhydride are used as a mixture as an acylating agent, the amount of the carboxylic anhydride is represented by a molar ratio of the N-hydroxysuccinimide to the carboxylic ester. , 0.01 to 100, preferably 0.1 to 10.

The solvent used in step 1) of (4), or by dissolving the WB _6, it may be any solvent which does not adversely influence the reaction.
For example, aromatic compounds such as benzene, toluene, ethylbenzene, xylene, cumene, cymene, diisopropylbenzene, and phenylethyl ether; amide compounds such as dimethylacetamide; tetrahydrofuran, dioxane, tetrahydropyran, diethyl ether, dipropyl ether, diisopropyl ether; Cyclic or linear or branched ethers such as ethylene glycol diethyl ether, diethylene glycol diethyl ether and diethylene glycol dimethyl ether; aliphatic ketones such as aliphatic alcohols such as methanol, ethanol, propanol, isopropyl alcohol and t-butyl alcohol; No. One of these solvents may be used alone, or two or more thereof may be used as a mixture. Of the above solvents, benzene,
Toluene, ethylbenzene, preferably to improve the reaction rate of the aromatic de arylmethyl of using the WB ₆ compounds such as xylene.

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

Reaction pressure is usually 0.01-100, preferably 0.1-30MP
When hydrogen is used as the reducing agent, the reaction rate may increase as the pressure increases in some cases, and therefore, expressed as a partial pressure of hydrogen, 0.01 to 50 MPa, more preferably 0.1 to 50 MPa. It is good to set in the range of 20MPa. In addition to hydrogen, an inert gas such as nitrogen, argon, and helium may be present.

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

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

As the WA _m B _(6-m) used in the 2) reductive dearylmethylation step of the reaction (4), any obtained by any method can be used.

In the step (2) of (4), any method may be used as long as the method allows the dearylmethylation reaction of WA _m B _(6-m) to proceed. Usually, it is carried out by contacting with a reducing catalyst in the presence of a reducing agent.

As the reducing agent, hydrogen, hydrazine, formic acid and the like can be used, and preferably, hydrogen is used. As the catalyst, a metal belonging to the platinum group or a derivative thereof is used. Preferably, Pd (OAc) ₂ , PdCl ₂ , Pd (NO ₃ ) ₂ , P
Pd derivatives such as dO, Pd (OH) ₂ , Pd ₃ Pb ₁ , Pd ₃ Te ₁ and
Pd metal; Ru derivatives such as RuCl ³ and Ru metals are used, and more preferably Pd derivatives such as Pd (OAc) ₂ and PdCl ₂ and Pd metals are used. These catalysts may be used as they are, or may be used after being supported on various carriers such as activated carbon, silica, alumina, silica-alumina, zeolite, and activated clay. Before the reaction, the catalyst may be subjected to a reduction treatment. In the case of a solid catalyst,
By performing a treatment such as silylation or acylation, the acidity of the solid surface can be changed by inactivating the surface acid sites or by adsorbing an alkaline substance such as NaOH.

The amount of the catalyst used may vary depending on the reduction activity of the catalyst and the like, but is expressed as a weight ratio of the catalyst metal used to WA _m B _(6-m) , 0.0001 to 10, preferably 0.001 to 1
Can be used in the range.

The solvent used in step (2) of (4) is WA _m B _(6-m)
Or any solvent which does not adversely affect the reductive dearylmethylation reaction. Examples thereof include carboxylic acids such as acetic acid, propionic acid and butyric acid; amide compounds such as dimethylacetamide; amine compounds such as N, N-dimethylaniline. These solvents may be used alone or as a mixture of two or more. It is preferable to use a carboxylic acid such as acetic acid or propionic acid from the viewpoint of the reaction rate.

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

Reaction pressure is usually 0.01-100, preferably 0.1-10MP
a, and when hydrogen is used as the reducing agent,
Expressed as a partial pressure of hydrogen, the pressure is preferably in the range of 0.01 to 50 MPa, more preferably 0.1 to 10 MPa. In addition to hydrogen, an inert gas such as nitrogen, argon, and helium may be present.

The reaction temperature is usually -20 to 30C, preferably 0 to 20C.
It is in the range of 0 ° C.

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

Next, a method for producing hexanitrohexaazaisowurtzitane from the hexaazaisowurtzitane derivative represented by the general formulas (I) and (III) will be described. Formula (I) (II
By using the nitration step, hexanitroisazaitolosetitanium derivative (I) can easily produce hexanitrohexaazaisowurtzitane.

First, as shown in the following formula (5), hexanitrohexaazaisowurtzitane can be produced by nitrating the general formula (I).

WA _n N _(6-n) → WN ₆ (5) WA ₄ N ₂ and WA ₅ N ₁ may be mentioned as raw materials for the nitration step in the reaction formula (5). Alternatively, a mixture of both may be used. WA ₄ N ₁ H which may be formed in the step of reaction formula (1) is contained in the raw material.
_{1, WA 3 N 3, WA} 2 N 4, WA 1 N 5, remaining as an unreacted WA
₄ H ₂ , WA ₅ H ₁ , and WA ₆ may be included. Reaction formula (5)
The reaction conditions of the nitration accelerator, the solvent, and the reaction temperature used in the step (b) can be the same as those described in the nitration step of the reaction formula (1), and the reaction conditions. As the nitrating agent, those similar to those described in the step of the reaction formula (1) can be used. However, if a mixture of nitric acid and a nitration accelerator is used as the nitrating agent, the rate of the nitration reaction can be increased. Is preferred because it can be accelerated. When using a nitrating agent obtained by mixing nitric acid and a nitration accelerator, the amount of the nitrating agent is expressed as a molar ratio to WA _m H _(6-m) , and the amount of the nitric acid is usually 6.0 to 500. , Preferably 9-400
Used in. The reaction temperature is usually -20 to 140
C., preferably at 0-120.degree. The reaction time may be 0.5 to 120 hours, preferably 1 to 50 hours.

Also, as shown in the following formula (6), hexanitrohexaazaisowurtzitane can be produced by nitrating the general formula (III).

WA _n NS _(6-n) → WN ₆ (6) As a raw material for the nitration step of the reaction formula (6), WA ₄ N
S ₂ and WA ₅ N ₁ may be mentioned, but either one of them may be used as a raw material or a mixture of two kinds may be used as a raw material. Further, in this raw material, WA ₄ NS ₁ H ₁ which may be generated in the step of the reaction formula (2), WA ₄ H ₂ , W remaining without reacting
A ₅ H ₁ may be contained. As the reaction conditions such as the nitrating agent, the solvent, and the reaction temperature used in the step of the reaction formula (6), those usable in the nitration step of the reaction formula (1) and the reaction conditions can be used.

Further, even if the reaction is not performed stepwise as in the reaction steps (1) and (5), or the reaction steps (2) and (6), and the reaction steps (2), (3) and (5), As shown in the following reaction formula (7), hexanitrohexaazaisowurtzitanium is synthesized by nitrating WA _m H _(6-m) under the same conditions as in reaction formulas (5) and (6) throughout. You can also.

WA _m H _(6-n) → WN ₆ (7) wherein n is an integer of 4 to 5, A is independently the same or different acyl group having 1 to 10 carbon atoms, and H is a hydrogen atom , N represents a nitro group, and W represents a hexavalent hexaazaisowurtzitanium residue. With respect to the raw material, nitrating agent and solvent of the reaction formula (7),
The same as in the nitration step of reaction formula (1),
And reaction conditions can be used. The reaction is carried out usually at -20 to 140C, preferably at 0 to 120C. The reaction time may be 0.5 to 120 hours, preferably 1 to 50 hours.

The hexaazaisowurtzitane derivatives of formulas (I) and (III) obtained in the present invention are useful as a precursor for obtaining hexanitrohexaazaisowurtzitane, which is a high-performance explosive.

〔Example〕

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples.

[Example 1] WA ₄ H ₂ → WN ₆ 200 ml reaction vessel was immersed in a water bath at 0 ° C, and 97%
17.50 g of sulfuric acid was added, and 5.63 g of 98% nitric acid was slowly added dropwise while stirring with a stirrer. 1.00 g of tetraacetylhexaazaisowurtzitanium was added to the mixed acid, the temperature was raised to 60 ° C., and the mixture was reacted for 24 hours after the temperature was raised. After the reaction is completed, 250 g of ice water
The reaction solution was added dropwise thereto, and the mixture was allowed to stand, and then filtered with a membrane filter. The obtained solid was washed with 250 g of purified water,
Hexanitrohexaazaisosoul titanium 1.28 g was obtained (98% yield).

 The structural analysis of the product was performed as follows.

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

These absorption properties are described in the literature [COMBUSTION AND FLA
ME 87: 145-151 (1991)], which is consistent with the characteristic absorption of the IR spectrum of hexanitrohexaazaisosoultitanium.

The carbonyl group of the acetyl group of tetraacetylhexaazaisowurtzitanium (C =
O) absorption around 1680 cm ^-1 has been eliminated.

From this result, it was found that the acetyl group of tetraacetylhexaazaisowurtzitanium was converted to a nitro group, and hexanitrohexaazaisowurtzitanium was formed.

In addition, a document that reports on various properties of hexanitrohexaazaisosoul titanium [International Sympo
sium on Energetic Material Technology PROCEED
INGS, SEPTEMBER 24-27, 76-81 (1995)], the above product was analyzed under the same conditions as in the high performance liquid chromatography, and showed the same retention time as that in the literature.

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

[Example 2] WA ₅ H ₁ → WN ₆ 200 ml reaction vessel was immersed in a water bath at 0 ° C, and 97%
15.56 g of sulfuric acid was added, and while stirring with a stirrer, 5.00 g of 98% nitric acid was slowly added dropwise. 1.00 g of pentaacetylhexaazaisowurtzitanium was added to the mixed acid, the temperature was raised to 60 ° C., and the mixture was reacted for 24 hours. After the reaction is completed, 250 g of ice water
The reaction solution was added dropwise thereto, and the mixture was allowed to stand, and then filtered with a membrane filter. The obtained solid was washed with 250 g of purified water,
1.14 g of hexanitrohexaazaisosoul titanium was obtained (yield 98%).

Structural analysis of the product was performed in the same manner as in Example 1, and it was found that hexanitrohexaazaisowurtzitane was synthesized.

[Example 3] WA ₆ → WN _{6 A} 200 ml reaction vessel was immersed in a water bath at 0 ° C, and 97%
14.00 g of sulfuric acid was added, and while stirring with a stirrer, 4.50 g of 98% nitric acid was slowly added dropwise. 1.00 g of hexaacetylhexaazaisowurtzitanium was added to the mixed acid, the temperature was raised to 60 ° C., and after the temperature was raised, the reaction was carried out for 24 hours. 250g of ice water after reaction
The reaction solution was added dropwise thereto, and the mixture was allowed to stand, and then filtered with a membrane filter. The obtained solid was washed with 250 g of purified water,
1.02 g of hexanitrohexaazaisosoul titanium was obtained (98% yield).

Structural analysis of the product was performed in the same manner as in Example 1, and it was found that hexanitrohexaazaisowurtzitane was synthesized.

Example 4 WA ₄ H ₂ → WN _{6 A} 200 ml reaction vessel was immersed in a water bath at 0 ° C., and 98%
22.50 g of sulfuric acid was added, and while stirring with a stirrer, 6.11 g of trifluoroacetic acid was added. To the solution was added 1.00 g of tetraacetylhexaazaisowurtzitane, the temperature was raised to 100 ° C., and the reaction was performed for 3 hours after the temperature was raised. After completion of the reaction, the reaction solution was distilled off, and the obtained solid was neutralized with 10% aqueous NaHCO ₃ , washed with water and dried to collect a solid. The solid was dissolved in acetonitrile and analyzed by high performance liquid chromatography to confirm that hexanitrohexaazaisowurtzitane was produced at a yield of 20%.

Structural analysis of the product was performed in the same manner as in Example 1, and it was found that hexanitrohexaazaisowurtzitane was synthesized.

[Example 5] WA ₆ → WN _{6 A} 200 ml reaction vessel was immersed in a water bath at 0 ° C, and 98%
18.00 g of sulfuric acid was added, and while stirring with a stirrer, 8.14 g of trifluoroacetic acid was added. To the solution was added 1.00 g of hexaacetylhexaazaisowurtzitane, the temperature was raised to 100 ° C., and the reaction was performed for 3 hours after the temperature was raised. After completion of the reaction, the reaction solution was distilled off, and the obtained solid was neutralized with 10% aqueous NaHCO ₃ , washed with water and dried to collect a solid. The solid was dissolved in acetonitrile and analyzed by high performance liquid chromatography to confirm that hexanitrohexaazaisowurtzitane was produced at a yield of 18%.

Structural analysis of the product was performed in the same manner as in Example 1, and it was found that hexanitrohexaazaisowurtzitane was synthesized.

Example 6 WA ₄ H ₂ → WN _{6 A} 200 ml reaction vessel was immersed in a water bath at 0 ° C.
11.25 g of sulfuric acid was added, and while stirring with a stirrer, 7.14 g of sulfuric anhydride was added. To the solution was added 1.00 g of tetraacetylhexaazaisosoul titanium, and the temperature was raised to 60 ° C.
The reaction was performed for 24 hours after the temperature was raised. After completion of the reaction, the reaction solution was added to 250 g of ice water, allowed to stand, and then filtered through a membrane filter. The obtained solid was washed with 250 g of purified water to obtain 1.29 g of hexanitrohexaazaisosoul titanium (yield 99
%).

Structural analysis of the product was performed in the same manner as in Example 1, and it was found that hexanitrohexaazaisowurtzitane was synthesized.

[Example 7] WA ₆ → WN _{6 A} 200 ml reaction vessel was immersed in a water bath at 0 ° C, and 98%
18.00 g of sulfuric acid was added, and 5.71 g of sulfuric anhydride was added while stirring with a stirrer. To the solution, 1.00 g of hexaacetylhexaazaisosoul titanium was added, and the temperature was raised to 60 ° C.
The reaction was performed for 24 hours after the temperature was raised. After completion of the reaction, the reaction solution was added to 250 g of ice water, allowed to stand, and then filtered through a membrane filter. The obtained solid was washed with 250 g of purified water to obtain 1.03 g of hexanitrohexaazaisosoul titanium (yield 99
%).

Structural analysis of the product was performed in the same manner as in Example 1, and it was found that hexanitrohexaazaisowurtzitane was synthesized.

Example 8 WA ₄ H ₂ → WN _{6 A} 200 ml reaction vessel was immersed in a water bath at 0 ° C., and 98%
22.50 g of sulfuric acid was added, and 12.67 g of diphosphorus pentoxide was added while stirring with a stirrer. To the solution was added 1.00 g of tetraacetylhexaazaisowurtzitane, the temperature was raised to 100 ° C., and after the temperature was raised, the mixture was reacted for 3 hours. After the reaction, 250 ml of ice water
The reaction solution was dropped into the mixture, and after standing, the precipitated solid was filtered. Then, the filtrate was washed with water to recover the solid. The recovered solid was dissolved in acetonitrile and analyzed by high-performance liquid chromatography, yielding 11 g of hexanitrohexaazaisowurtzitane.
Confirmed that it was generated by.

Structural analysis of the product was performed in the same manner as in Example 1, and it was found that hexanitrohexaazaisowurtzitane was synthesized.

Example 9 WA ₆ → WN _{6 A} 200 ml reaction vessel was immersed in a water bath at 0 ° C.
18.00 g of sulfuric acid was added, and 10.14 g of diphosphorus pentoxide was added while stirring with a stirrer. To the solution was added 1.00 g of hexaacetylhexaazaisosoul titanium, and the temperature was raised to 100 ° C.
After the temperature was raised, the reaction was performed for 3 hours. After completion of the reaction, the reaction solution was added dropwise to 250 ml of ice water, and after standing, the precipitated solid was filtered. The filtrate was washed with water to collect a solid. The collected solid was dissolved in acetonitrile, dissolved in acetonitrile and analyzed by high performance liquid chromatography, and it was confirmed that hexanitrohexaazaisowurtzitanium was produced in a yield of 9 g.

Structural analysis of the product was performed in the same manner as in Example 1, and it was found that hexanitrohexaazaisowurtzitane was synthesized.

Example 10 WA ₄ H ₂ → WN _{6 A} 200 ml reaction vessel was immersed in a water bath at 0 ° C., and 98%
Add 22.50 g of sulfuric acid and stir with a stirrer.
11.25 g of NR50 was added. 1.00 g of tetraacetylhexaazaisowurtzitane was added to the solution, the temperature was raised to 100 ° C., and after the temperature was raised, the mixture was reacted for 3 hours. After completion of the reaction, the reaction solution was dropped into 250 ml of water, allowed to stand, the precipitated solid was filtered, and the filtrate was washed with 250 ml of purified water. 50 ml of filtered solid acetone
And stirred, filtered, and filtered as Nafion-
NR50 was recovered. Filtration is performed by evaporating under reduced pressure with an evaporator.
The reaction product solid was recovered. This solid was dissolved in acetonitrile and analyzed by high performance liquid chromatography, and it was confirmed that hexanitrohexaazaisowurtzitanium was produced at a yield of 70%.

Structural analysis of the product was performed in the same manner as in Example 1, and it was found that hexanitrohexaazaisowurtzitane was synthesized.

[Example 11] WA ₄ H ₂ → WN _{6 A} 200 ml reaction vessel was immersed in a water bath at 0 ° C, and 98%
Add 20.00 g of sulfuric acid and stir with a stirrer.
10 g of -NR50 were added. To the solution was added 1.00 g of tetraacetylhexaazaisosoul titanium, and the temperature was raised to 100 ° C.
After the temperature was raised, the reaction was performed for 3 hours. After the completion of the reaction, the reaction solution was added dropwise to 250 ml of water, allowed to stand, the precipitated solid was filtered, and the filtrate was washed with 250 ml of purified water. The filtered solid was added to 50 ml of acetone, filtered after stirring, and filtered as Nafion-NR.
50 were collected. Filtration was performed by evaporating under reduced pressure with an evaporator to collect a reaction product solid. This solid was dissolved in acetonitrile and analyzed by high performance liquid chromatography to confirm that hexanitrohexaazaisowurtzitane was produced at a yield of 55%.

Structural analysis of the product was performed in the same manner as in Example 1, and it was found that hexanitrohexaazaisowurtzitane was synthesized.

[Example 12] WA ₄ H ₂ → WN _{6 A} 200 ml reaction vessel was immersed in a water bath at 0 ° C, and 98%
22.50 g of sulfuric acid is added, and tris- [bis- (heptadecafluorooctylsulfonyl) is stirred with a stirrer.
[Imide] 11.25 g of ytterbium (III) was added.
Add tetraacetylhexaazaisoulitanium 1.
After adding 00 g, the temperature was raised to 100 ° C., and after the temperature was raised, the reaction was carried out for 3 hours.
After completion of the reaction, the reaction solution was dropped into 250 ml of water, allowed to stand, the precipitated solid was filtered, and the filtrate was washed with 250 ml of purified water. The filtered solid was added with 50 ml of acetone, stirred and filtered,
Tris- [bis- (heptadecafluorooctylsulfonyl) imide] ytterbium [III] was recovered as a filtrate. Filtration was performed by evaporating under reduced pressure with an evaporator to collect a reaction product solid. This solid was dissolved in acetonitrile and analyzed by high performance liquid chromatography to confirm that hexanitrohexaazaisowurtzitane was produced at a yield of 17%.

Structural analysis of the product was performed in the same manner as in Example 1, and it was found that hexanitrohexaazaisowurtzitane was synthesized.

[Example 13] WA ₅ H ₁ → WN _{6 A} 200 ml reaction vessel was immersed in a water bath at 0 ° C., and 98%
Add 20.00 g of sulfuric acid, and stir with a stirrer. Tris- [bis- (heptadecafluorooctylsulfonyl)]
10 g of [imido] ytterbium [III] was added. 1.00 g of pentaacetylhexaazaisoul titanium in the solution
Was added, the temperature was raised to 100 ° C., and after the temperature was raised, the reaction was performed for 3 hours. After completion of the reaction, the reaction solution was dropped into 250 ml of water, allowed to stand, the precipitated solid was filtered, and the filtrate was washed with 250 ml of purified water. To the filtered solid, 50 ml of acetone was added, and the mixture was stirred and filtered, and tris- [bis- (heptadecafluorooctylsulfonyl) imide] ytterbium [III] was recovered as a filtered fraction. Filtration was performed by evaporating under reduced pressure with an evaporator to collect a reaction product solid. This solid was dissolved in acetonitrile and analyzed by high performance liquid chromatography, and it was confirmed that hexanitrohexaazaisowurtzitane was produced at a yield of 13%.

Structural analysis of the product was performed in the same manner as in Example 1, and it was found that hexanitrohexaazaisowurtzitane was synthesized.

Example 14 WA ₄ H ₂ → WN _{6 A} 200 ml reaction vessel was immersed in a water bath at 0 ° C.
Add 20.00 g of sulfuric acid, and stir with a stirrer. Tris- [bis- (heptadecafluorooctylsulfonyl)]
4 g of [imido] lanthanum [III] was added. To the solution was added 1.00 g of tetraacetylhexaazaisosoul titanium, and 9
The temperature was raised to 0 ° C., and the reaction was performed for 5 hours after the temperature was raised. After the reaction,
The reaction solution was added dropwise to 250 ml of water, allowed to stand, the precipitated solid was filtered, and the filtrate was washed with 250 ml of purified water. 50 ml of acetone was added to the filtered solid, and the mixture was stirred and filtered, and tris- [bis- (heptadecafluorooctylsulfonyl) imide] lanthanum [III] was collected as a filtrate. Filtration was performed by evaporating under reduced pressure with an evaporator to collect a reaction product solid. This solid was dissolved in acetonitrile and analyzed by high performance liquid chromatography to confirm that hexanitrohexaazaisowurtzitane was produced at a yield of 11%.

Structural analysis of the product was performed in the same manner as in Example 1, and it was found that hexanitrohexaazaisowurtzitane was synthesized.

[Example 15] WA ₄ H ₂ → WN _{6 A} 200 ml reaction vessel was immersed in a water bath at 0 ° C, and 98%
Add 20.00 g of sulfuric acid, and stir with a stirrer. Tris- [bis- (nonafluorobutylsulfonyl) imide]
8 g of yttrium [III] was added. To the solution was added 1.00 g of tetraacetylhexaazaisosoul titanium, and 100
C., and reacted for 2 hours after the temperature was raised. After the reaction,
The reaction solution was dropped into 250 ml, and the mixture was allowed to stand and the precipitated solid was filtered.
The filtrate was washed with 250 ml of purified water. 50 ml of acetone was added to the filtered solid, and the mixture was stirred and filtered, and tris- [bis- (nonafluorobutylsulfonyl) imide] yttrium [III] was recovered as a filtrate. Filtration was performed by evaporating under reduced pressure with an evaporator to collect a reaction product solid. This solid was dissolved in acetonitrile and analyzed by high performance liquid chromatography to confirm that hexanitrohexaazaisowurtzitane was produced at a yield of 16%.

Structural analysis of the product was performed in the same manner as in Example 1, and it was found that hexanitrohexaazaisowurtzitane was synthesized.

[Example 16] WA ₄ H ₂ → WN _{6 A} 200 ml reaction vessel was immersed in a water bath at 0 ° C, and 98%
22.50 g of sulfuric acid was added, and 11.25 g of zeolite ZSM-5 was added while stirring with a stirrer. 1.00 g of tetraacetylhexaazaisowurtzitane was added to the solution, the temperature was raised to 100 ° C., and after the temperature was raised, the mixture was reacted for 3 hours. After the reaction, water 250m
The reaction mixture was added dropwise to the mixture, and the mixture was allowed to stand. The precipitated solid was filtered, and the filtrate was washed with 250 ml of purified water. Acetone 5 on the filtered solid
It was added to 0 ml, stirred, filtered, and the zeolite ZSM-5 was recovered as a filtrate. Filtration was performed by evaporating under reduced pressure with an evaporator to collect a reaction product solid. This solid was dissolved in acetonitrile and analyzed by high performance liquid chromatography. Hexanitrohexaazaisowurtzitane yielded 15%.
Confirmed that it was generated by.

Structural analysis of the product was performed in the same manner as in Example 1, and it was found that hexanitrohexaazaisowurtzitane was synthesized.

Example 17 WA ₅ H ₁ → WN _{6 A} 200 ml reaction vessel was immersed in a water bath at 0 ° C., and 98%
20.00 g of sulfuric acid was added, and 15 g of mordenite was added while stirring with a stirrer. 1.00 g of pentaacetylhexaazaisole titanium was added to the solution, and the temperature was raised to 100 ° C.
After the temperature was raised, the reaction was performed for 6 hours. After completion of the reaction, the reaction solution was dropped into 250 ml of water, allowed to stand, the precipitated solid was filtered, and the filtrate was washed with 250 ml of purified water. Acetone (50 ml) was added to the filtered solid, and the mixture was stirred and filtered, and mordenite was collected as a filtrate. Filtration was performed by evaporating under reduced pressure with an evaporator to collect a reaction product solid. This solid was dissolved in acetonitrile and analyzed by high performance liquid chromatography to confirm that hexanitrohexaazaisowurtzitane was produced at a yield of 8%.

Structural analysis of the product was performed in the same manner as in Example 1, and it was found that hexanitrohexaazaisowurtzitane was synthesized.

Example 18 WA ₄ H ₂ → WN _{6 A} 200 ml reaction vessel was immersed in a water bath at 0 ° C., and N ₂ O ₅
Was added to 20.00 g of a nitric acid solution containing 10 mol%, and the mixture was heated to 100 ° C., and reacted for 3 hours after the temperature was raised. After completion of the reaction, the reaction solution was distilled off, and the obtained solid was neutralized with 10% aqueous NaHCO ₃ , washed with purified water and dried, and the solid was recovered. The solid was dissolved in acetonitrile and analyzed by high performance liquid chromatography. Hexanitrohexaazaisowurtzitane yielded 15%.
Confirmed that it was generated by.

Structural analysis of the product was performed in the same manner as in Example 1, and it was found that hexanitrohexaazaisowurtzitane was synthesized.

Example 19 WA ₆ → WN _{6 A} 200 ml reaction vessel was immersed in a water bath at 0 ° C., and N ₂ O ₅
Was added, and while stirring with a stirrer, 1.00 g of hexaacetylhexaazaisowurtzitanium was added, the temperature was raised to 100 ° C., and the temperature was raised, followed by a reaction for 3 hours. After completion of the reaction, the reaction solution was distilled off, and the obtained solid was neutralized with 10% aqueous NaHCO ₃ , washed with purified water and dried, and the solid was recovered. The solid was dissolved in acetonitrile and analyzed by high performance liquid chromatography to confirm that hexanitrohexaazaisowurtzitane was produced at a yield of 5%.

Structural analysis of the product was performed in the same manner as in Example 1, and it was found that hexanitrohexaazaisowurtzitane was synthesized.

[Example 20] WA ₄ H ₂ → WN _{6 A} 200 ml reaction vessel was immersed in a water bath at 0 ° C, and 98%
22.50 g of nitric acid was added, and 30.17 g of polyphosphoric acid was added while stirring with a stirrer. 1.00 g of tetraacetylhexaazaisowurtzitane was added to the solution, the temperature was raised to 100 ° C., and after the temperature was raised, the mixture was reacted for 3 hours. After the reaction is completed, the reaction solution is
The mixture was placed in a beaker containing 0 ml, stirred to dissolve the compound derived from polyphosphoric acid, and the insoluble solid was filtered and washed with water to collect the solid. The recovered solid was dissolved in acetonitrile and analyzed by high performance liquid chromatography to confirm that hexanitrohexaazaisowurtzitane was produced at a yield of 16%.

Structural analysis of the product was performed in the same manner as in Example 1, and it was found that hexanitrohexaazaisowurtzitane was synthesized.

[Example 21] WA ₆ → WN _{6 A} 200 ml reaction vessel was immersed in a water bath at 0 ° C., and 98%
18.00 g of nitric acid was added, and 24.14 g of polyphosphoric acid was added while stirring with a stirrer. To the solution, 1.00 g of hexaacetylhexaazaisowurtzitane was added, and reacted at 100 ° C. for 3 hours. After completion of the reaction, the reaction solution was placed in a beaker containing 250 ml of ice water, stirred to dissolve the compound derived from polyphosphoric acid, and the insoluble solid was filtered and washed with water to collect the solid. The recovered solid was dissolved in acetonitrile and analyzed by high performance liquid chromatography, and it was confirmed that hexanitrohexaazaisowurtzitane was produced at a yield of 9%.

Structural analysis of the product was performed in the same manner as in Example 1, and it was found that hexanitrohexaazaisowurtzitane was synthesized.

Example 22 WA ₄ H ₂ → WN _{6 A} 200 ml reaction vessel was immersed in a water bath at 0 ° C., and 98%
22.50 g of nitric acid was added, and while stirring with a stirrer, 75.00 g of trifluoroacetic anhydride was added. Add 1.00 g of tetraacetylhexaazaisole titanium to the solution, and add
, And reacted for 3 hours after the temperature was raised. After completion of the reaction, the reaction solution was distilled off, and the obtained solid was washed with 10% aqueous NaHCO ₃ , washed with water, dissolved in acetonitrile, and analyzed by high performance liquid chromatography to obtain hexanitrohexaazaisowurtzitanium. It was confirmed that it was produced at 8%.

Structural analysis of the product was performed in the same manner as in Example 1, and it was found that hexanitrohexaazaisowurtzitane was synthesized.

[Example 23] WA ₆ → WN _{6 A} 200 ml reaction vessel was immersed in a water bath at 0 ° C, and 98%
18.00 g of nitric acid was added, and while stirring with a stirrer, 60.00 g of trifluoroacetic anhydride was added. Add 1.00 g of hexaacetylhexaazaisosoul titanium to the solution, and add
, And reacted for 3 hours after the temperature was raised. After distilling off the reaction solution, the obtained solid was washed with 10NaHCO ₃ water, washed with water, dissolved in acetonitrile and analyzed by high performance liquid chromatography, and the yield of hexanitrohexaazaisowurtzitanium was 3%.
Confirmed that it was generated by.

Structural analysis of the product was performed in the same manner as in Example 1, and it was found that hexanitrohexaazaisowurtzitane was synthesized.

[Example 24] WA ₄ H ₂ → WN _{6 A} 200 ml reaction vessel was immersed in a water bath at 0 ° C, and 97%
4.92 g of nitric acid was added, and 4.80 g of 98% nitric acid was slowly added dropwise while stirring with a stirrer. 1.00 g of dinitrosotetraacetylhexaazaisowurtzitanium was added to the mixed acid, the temperature was raised to 60 ° C., and after the temperature was raised, reacted for 24 hours. After completion of the reaction, the reaction solution was added dropwise to 250 g of ice water, allowed to stand, and then filtered. The obtained solid was washed with 250 g of purified water to obtain 1.09 g of hexanitrohexaazaisowurtzitanium (yield 98
%).

Structural analysis of the product was performed in the same manner as in Example 1, and it was found that hexanitrohexaazaisowurtzitane was synthesized.

[Example 25] WA ₅ NS ₁ → WN _{6 A} 200 ml reaction vessel was immersed in a water bath at 0 ° C., and 97%
4.45 g of nitric acid was added, and 4.64 g of 98% nitric acid was slowly added dropwise while stirring with a stirrer. 1.00 g of mononitrosopentaacetylhexaazaisowurtzitanium was added to the mixed acid, the temperature was raised to 60 ° C., and after the temperature was raised, the reaction was carried out for 24 hours. After the completion of the reaction, the reaction solution was added to 250 g of ice water, allowed to stand, and then filtered. The obtained solid was washed with 250 g of purified water to obtain 1.08 g of hexanitrohexaazaisowurtzitanium (yield 98
%).

Structural analysis of the product was performed in the same manner as in Example 1, and it was found that hexanitrohexaazaisowurtzitane was synthesized.

[Example 26] WA ₅ NS ₁ → WN ₆ 200 ml reaction vessel was immersed in a water bath at 0 ° C., and 98%
18.58 g of nitric acid was added, and 8.40 g of trifluoroacetic acid was added while stirring with a stirrer. 1.00 g of mononitrosopentaacetylhexaazaisowurtzitanium was added to the solution, the temperature was raised to 100 ° C., and after the temperature was raised, the mixture was reacted for 3 hours. After completion of the reaction, the reaction solution was distilled off, and the obtained solid was neutralized with 10 NaHCO ₃ aqueous solution and filtered. The filtrate was washed with water, dried, dissolved in acetonitrile, and analyzed by high performance liquid chromatography. As a result, it was confirmed that hexanitrohexaazaisowurtzitanium was produced in a yield of 8%.

Structural analysis of the product was performed in the same manner as in Example 1, and it was found that hexanitrohexaazaisowurtzitane was synthesized.

[Example 27] WA ₄ NS ₂ → WN _{6 A} 200 ml reaction vessel was immersed in a water bath at 0 ° C, and 98%
19.19 g of nitric acid was added, and 10.80 g of diphosphorus pentoxide was added while stirring with a stirrer. Add 1.00 g of dinitrosotetraacetylhexaazaisosoul titanium to the solution,
, And reacted for 3 hours after the temperature was raised. After completion of the reaction, the reaction solution was distilled off, 20 ml of water was added, and the mixture was filtered. The obtained solid was neutralized with 10 NaHCO ₃ aqueous solution and filtered. The filtrate was washed with water, dried, dissolved in acetonitrile, and analyzed by high performance liquid chromatography. As a result, it was confirmed that hexanitrohexaazaisowurtzitanium was produced in a yield of 7%.

Structural analysis of the product was performed in the same manner as in Example 1, and it was found that hexanitrohexaazaisowurtzitane was synthesized.

Example 28 WA ₄ NS ₂ → WN _{6 A} 200 ml reaction vessel was immersed in a water bath at 0 ° C., and 98%
19.19 g of nitric acid was added, and 25.73% of polyphosphoric acid was added while stirring with a stirrer. Add 1.00 g of dinitrosotetraacetylhexaazaisosoul titanium to the solution,
, And reacted for 3 hours after the temperature was raised. After completion of the reaction, the reaction solution was placed in a beaker containing 20 ml of water, stirred and dissolved, and the insoluble solid was filtered, washed with water, dried, dissolved in acetonitrile, and analyzed by high performance liquid chromatography. It was confirmed that hexanitrohexaazaisoulitanium was produced at 11%.

Structural analysis of the product was performed in the same manner as in Example 1, and it was found that hexanitrohexaazaisowurtzitane was synthesized.

Example 29 WA ₅ NS ₁ → WN _{6 A} 200 ml reaction vessel was immersed in a water bath at 0 ° C., and 98%
19.19 g of nitric acid was added, and 63.96% of trifluoroacetic anhydride was added while stirring with a stirrer. Mononitrosopentaacetylhexaazaisoul titanium 1.00
g was added, the temperature was raised to 100 ° C., and after the temperature was raised, the reaction was performed for 3 hours. After distilling off the reaction solution, the obtained solid was washed with 10% NaHCO ₃ water and water, dried, dissolved in acetonitrile and analyzed by high performance liquid chromatography. As a result, hexanitrohexaazaisomer was obtained in a yield of 2%. It was confirmed that titanium was generated.

Structural analysis of the product was performed in the same manner as in Example 1, and it was found that hexanitrohexaazaisowurtzitane was synthesized.

Example 30 WA ₅ NS ₁ → WN _{6 A} 200 ml reaction vessel was immersed in a water bath at 0 ° C., and N ₂ O ₅
Was added, and while stirring with a stirrer, 1.00 g of mononitrosopentaacetylhexaazaisowurtzitanium was added, the temperature was raised to 100 ° C., and the reaction was performed for 3 hours. After completion of the reaction, the reaction solution was distilled off, and the obtained solid was neutralized with 10% aqueous NaHCO ₃ , washed with purified water and dried, and the solid was recovered. The solid was dissolved in acetonitrile and analyzed by high performance liquid chromatography to confirm that hexanitrohexaazaisowurtzitane was produced at a yield of 5%.

Structural analysis of the product was performed in the same manner as in Example 1, and it was found that hexanitrohexaazaisowurtzitane was synthesized.

[Example 31] WA ₄ NS ₂ → WN _{6 A} 200 ml reaction vessel was immersed in a water bath at 0 ° C, and 98%
9.59 g of nitric acid was added, and 6.09 g of sulfuric anhydride was added while stirring with a stirrer. 1.00 g of dinitrosotetraacetylhexaazaisoulitanium was added, the temperature was raised to 60 ° C., and the reaction was performed for 24 hours after the temperature was raised. After completion of the reaction, the reaction solution was added to 250 g of ice water, allowed to stand, and then filtered through a membrane filter. The obtained solid was washed with 250 g of purified water to obtain 1.10 g of hexanitrohexaazaisowurtzitanium (yield 98
%).

 The product was subjected to structural analysis in the same manner as in Example 1 and identified.

[Example 32] WA ₅ NS ₁ → WN ₆ 200 ml reaction vessel was immersed in a water bath at 0 ° C.
Add 18.58 g of nitric acid and stir with a stirrer.
-9.29 g of NR50 was added. To the solution was added 1.00 g of mononitrosopentaacetylhexaazaisosoul titanium,
C., and reacted for 3 hours after the temperature was raised. After the reaction,
The reaction solution was dropped into 250 ml, and the mixture was allowed to stand and the precipitated solid was filtered.
The filtrate was washed with 250 ml of purified water. 50 ml of acetone was added to the filtered solid, and the mixture was stirred and filtered.
fion-NR50 was recovered. The filtrate was distilled off under reduced pressure by an evaporator to collect a reaction product solid. This solid was dissolved in acetonitrile and analyzed by high performance liquid chromatography, and it was confirmed that hexanitrohexaazaisowurtzitanium was produced in a yield of 49%.

Structural analysis of the product was performed in the same manner as in Example 1, and it was found that hexanitrohexaazaisowurtzitane was synthesized.

[Example 33] WA ₄ NS ₂ → WN _{6 A} 200 ml reaction vessel was immersed in a water bath at 0 ° C, and 98%
18.58 g of sulfuric acid is added, and tris- [bis- (heptadecafluorooctylsulfonyl) is added while stirring with a stirrer.
9.29 g of [imide] ytterbium [III] were added. 1.00 g of dinitrosotetraacetylhexaazaisowurtzitanium was added to the solution, the temperature was raised to 100 ° C., and after the temperature was raised, the reaction was carried out for 3 hours. After completion of the reaction, the reaction solution was dropped into 250 ml of water, allowed to stand, the precipitated solid was filtered, and the filtrate was washed with 250 ml of purified water. 50 ml of acetone was added to the filtered solid, and the mixture was stirred and filtered. Tris- [bis- (heptadecafluorooctylsulfonyl) imide] yttrium [II
I] was recovered. Filtration is performed by evaporating under reduced pressure with an evaporator.
The reaction product solid was recovered. This solid was dissolved in acetonitrile and analyzed by high performance liquid chromatography to confirm that hexanitrohexaazaisowurtzitane was produced at a yield of 10%.

Structural analysis of the product was performed in the same manner as in Example 1, and it was found that hexanitrohexaazaisowurtzitane was synthesized.

Example 34 WA ₄ NS ₂ → WN _{6 A} 200 ml reaction vessel was immersed in a water bath at 0 ° C., and 98%
18.58 g of sulfuric acid is added, and tris- [bis- (heptadecafluorooctylsulfonyl) is added while stirring with a stirrer.
3.29 g of [imido] europium [III] were added. 1.00 g of dinitrosotetraacetylhexaazaisowurtzitanium was added to the solution, the temperature was raised to 100 ° C., and after the temperature was raised, the reaction was carried out for 8 hours. After completion of the reaction, the reaction solution was dropped into 250 ml of water, allowed to stand, the precipitated solid was filtered, and the filtrate was washed with 250 ml of purified water. The filtered solid was added to 50 ml of acetone, stirred, filtered, and tris- [bis- (heptadecafluorooctylsulfonyl) imide] europium [III] was collected as a filtrate. Filtration was performed by evaporating under reduced pressure with an evaporator to collect a reaction product solid. This solid was dissolved in acetonitrile and analyzed by high performance liquid chromatography to confirm that hexanitrohexaazaisowurtzitane was produced at a yield of 6%.

Structural analysis of the product was performed in the same manner as in Example 1, and it was found that hexanitrohexaazaisowurtzitane was synthesized.

Example 35 WA ₄ NS ₂ → WN _{6 A} 200 ml reaction vessel was immersed in a water bath at 0 ° C., and 98%
18.58 g of sulfuric acid is added, and while stirring with a stirrer, tris- [bis- (nonafluorobutylsulfonyl) imide] is added.
4.29 g of ytterbium [III] was added. Add dinitrosotetraacetylhexaazaisoulitanium 1.00 to the solution
g was added, the temperature was raised to 90 ° C., and after the temperature was raised, the reaction was carried out for 4 hours. After completion of the reaction, the reaction solution was dropped into 250 ml of water, allowed to stand, the precipitated solid was filtered, and the filtrate was washed with 250 ml of purified water. 50 ml of acetone was added to the filtered solid, and the mixture was stirred and filtered, and tris- [bis- (nonafluorobutylsulfonyl) imide] ytterbium [III] was recovered as a filtrate.
Filtration was performed by evaporating under reduced pressure with an evaporator to collect a reaction product solid. This solid was dissolved in acetonitrile and analyzed by high performance liquid chromatography to confirm that hexanitrohexaazaisowurtzitane was produced at a yield of 18%.

Structural analysis of the product was performed in the same manner as in Example 1, and it was found that hexanitrohexaazaisowurtzitane was synthesized.

[Example 36] WA ₄ N ₂ → WN _{6 A} 200 ml reaction vessel was immersed in a water bath at 0 ° C, and 97%
13.80 g of sulfuric acid was added, and while stirring with a stirrer, 4.44 g of 98% nitric acid was slowly added dropwise. . 1.00 g of dinitrotetraacetylhexaazaisowurtzitanium was added to the mixed acid, the temperature was raised to 60 ° C., and after the temperature was raised, the reaction was carried out for 24 hours. After the completion of the reaction, the reaction solution was added to 250 g of ice water. After leaving still, it was filtered through a membrane filter. The obtained solid is purified water
Wash with 250g, Hexanitrohexaaza soul titanium
1.01 g was obtained (98% yield).

Structural analysis of the product was performed in the same manner as in Example 1, and it was found that hexanitrohexaazaisowurtzitane was synthesized.

[Example 37] WA ₅ N ₁ → WN _{6 A} 200 ml reaction vessel was immersed in a water bath at 0 ° C., and 97%
13.81 g of sulfuric acid was added, and 4.46 g of 98% nitric acid was slowly added dropwise while stirring with a stirrer. . 1.00 g of mononitropentaacetylhexaazaisowurtzitanium was added to the mixed acid, the temperature was raised to 60 ° C., and the reaction was performed for 24 hours. After completion of the reaction, the reaction solution was added to 250 g of ice water, allowed to stand, and then filtered through a membrane filter. The obtained solid is purified water
Wash with 250g, Hexanitrohexaaza soul titanium
1.05 g was obtained (98% yield).

Structural analysis of the product was performed in the same manner as in Example 1, and it was found that hexanitrohexaazaisowurtzitane was synthesized.

Example 38 WA ₅ N ₁ → WN _{6 A} 200 ml reaction vessel was immersed in a water bath at 0 ° C., and 97%
17.87 g of sulfuric acid was added, and while stirring with a stirrer, 8.09 g of trifluoroacetic acid was added. To the solution was added 1.00 g of mononitropentaacetylhexaazaisosoul titanium, and 1
The temperature was raised to 00 ° C., and after the temperature was raised, the reaction was performed for 3 hours. After the reaction,
After evaporating the reaction solution, the obtained solid was neutralized with 10% aqueous NaHCO ₃ and filtered. The filtrate was washed with water, dried, dissolved in acetonitrile, and analyzed by high performance liquid chromatography. As a result, it was confirmed that hexanitrohexaazaisowurtzitane was produced in a yield of 6%.

Structural analysis of the product was performed in the same manner as in Example 1, and it was found that hexanitrohexaazaisowurtzitane was synthesized.

[Example 39] WA ₄ N ₂ → WN _{6 A} 200 ml reaction vessel was immersed in a water bath at 0 ° C, and 98%
17.75 g of sulfuric acid was added, and 10.00 g of diphosphorus pentoxide was added while stirring with a stirrer. 1.00 g of dinitrotetraacetylhexaazaisowurtzitanium was added to the solution, the temperature was raised to 100 ° C., and after the temperature was raised, the reaction was carried out for 3 hours. After completion of the reaction, the reaction solution was distilled off, 20 ml of water was added, and the mixture was filtered.
Neutralized with 10% aqueous NaHCO ₃ and filtered. The filtrate was washed with water, dried, dissolved in acetonitrile, and analyzed by high performance liquid chromatography. As a result, it was confirmed that hexanitrohexaazaisowurtzitanium was produced in a yield of 9%.

Structural analysis of the product was performed in the same manner as in Example 1, and it was found that hexanitrohexaazaisowurtzitane was synthesized.

[Example 40] WA ₄ N ₂ → WN ₆ 200 ml reaction vessel was immersed in a water bath at 0 ° C, and 98%
17.75 g of sulfuric acid was added, and 23.80 g of polyphosphoric acid was added while stirring with a stirrer. 1.00 g of dinitrotetraacetylhexaazaisowurtzitanium was added to the solution, the temperature was raised to 100 ° C., and after the temperature was raised, the reaction was carried out for 3 hours. After completion of the reaction, the reaction solution was placed in a beaker containing 20 ml of water, stirred and dissolved,
The insoluble solid was filtered, washed with water, dried, dissolved in acetonitrile, and analyzed by high performance liquid chromatography. As a result, it was confirmed that hexanitrohexaazaisowurtzitanium was produced at a yield of 12%.

Structural analysis of the product was performed in the same manner as in Example 1, and it was found that hexanitrohexaazaisowurtzitane was synthesized.

[Example 41] WA ₅ N ₁ → WN _{6 A} 200 ml reaction vessel was immersed in a water bath at 0 ° C., and 98%
17.75 g of sulfuric acid was added, and while stirring with a stirrer, 59.57 g of trifluoroacetic anhydride was added. 1.00 g of mononitropentaacetylhexaazaisowurtzitanium was added to the solution, the temperature was raised to 100 ° C., and the reaction was performed for 3 hours after the temperature was raised. After the reaction solution was distilled off, the obtained solid was washed with 10% aqueous NaHCO ₃ and water, dried, dissolved in acetonitrile, and analyzed by high performance liquid chromatography. As a result, hexanitrohexaazaisoul was obtained in a yield of 3%. It was confirmed that titanium was generated.

Structural analysis of the product was performed in the same manner as in Example 1, and it was found that hexanitrohexaazaisowurtzitane was synthesized.

Example 42 WA ₅ N ₁ → WN _{6 A} 200 ml reaction vessel was immersed in a water bath at 0 ° C., and N ₂ O ₅
Was added, and while stirring with a stirrer, 1.00 g of mononitropentaacetylhexaacetylsexaazaisoisotitanium was added, the temperature was raised to 100 ° C, and the reaction was performed for 3 hours after the temperature was raised. After completion of the reaction, the reaction solution was distilled off, and the obtained solid was neutralized with 10% aqueous NaHCO ₃ , washed with purified water and dried, and the solid was recovered. The solid was dissolved in acetonitrile and analyzed by high performance liquid chromatography. Hexanitrohexaazaisowurtzitane yielded 6%.
Confirmed that it was generated by.

Structural analysis of the product was performed in the same manner as in Example 1, and it was found that hexanitrohexaazaisowurtzitane was synthesized.

Example 43 WA ₄ N ₂ → WN _{6 A} 200 ml reaction vessel was immersed in a water bath at 0 ° C.
8.94 g of sulfuric acid was added, and 5.67 g of sulfuric anhydride was added while stirring with a stirrer. 1.00 g of dinitrotetraacetylhexaazaisowurtzitane was added, the temperature was raised to 60 ° C, and the reaction was performed for 24 hours after the temperature was raised. After the completion of the reaction, the reaction solution was added to 250 g of ice water, allowed to stand, and then filtered. The obtained solid is purified water
Wash with 250g, Hexanitrohexaaza soul titanium
1.06 g was obtained (98% yield).

 Structural analysis of the product was performed in the same manner as in Example 1 and identified.

[Example 44] WA ₄ N ₂ → WN _{6 A} 200 ml reaction vessel was immersed in a water bath at 0 ° C, and 98%
Add 17.87 g of nitric acid and stir with a stirrer.
8.94 g of NR50 was added. 1.00 g of dinitrotetraacetylhexaazaisowurtzitanium was added to the solution, the temperature was raised to 100 ° C., and after the temperature was raised, the reaction was carried out for 3 hours. After the reaction, water 250m
The reaction mixture was added dropwise to the mixture, and the mixture was allowed to stand. The precipitated solid was filtered, and the filtrate was washed with 250 ml of purified water. Acetone 5 on the filtered solid
0 ml was added, and the mixture was stirred and filtered.
-NR50 was recovered. The filtrate was distilled off under reduced pressure by an evaporator to collect a reaction product solid. This solid was dissolved in acetonitrile and analyzed by high performance liquid chromatography to confirm that hexanitrohexaazaisowurtzitane was produced in a yield of 68%.

Structural analysis of the product was performed in the same manner as in Example 1, and it was found that hexanitrohexaazaisowurtzitane was synthesized.

[Example 45] WA ₄ N ₂ → WN _{6 A} 200 ml reaction vessel was immersed in a water bath at 0 ° C, and 98%
Add 17.75 g of sulfuric acid, and stir with a stirrer. Tris- [bis- (heptadecafluorooctylsulfonyl)
8.87 g of [imide] ytterbium [III] was added. 1.00 g of dinitrotetraacetylhexaazaisowurtzitanium was added to the solution, the temperature was raised to 100 ° C., and after the temperature was raised, the reaction was carried out for 3 hours. After completion of the reaction, the reaction solution was dropped into 250 ml of water, allowed to stand, the precipitated solid was filtered, and the filtrate was washed with 250 ml of purified water. The filtered solid was added to 50 ml of acetone, stirred, filtered, and tris- [bis- (heptadecafluorooctylsulfonyl) imide] ytterbium [III] was collected as a filtered fraction. Filtration was performed by evaporating under reduced pressure with an evaporator to collect a reaction product solid. This solid was dissolved in acetonitrile and analyzed by high performance liquid chromatography to confirm that hexanitrohexaazaisowurtzitane was produced at a yield of 18%.

Structural analysis of the product was performed in the same manner as in Example 1, and it was found that hexanitrohexaazaisowurtzitane was synthesized.

[Example 46] WA ₄ N ₂ → WN _{6 A} 200 ml reaction vessel was immersed in a water bath at 0 ° C, and 98%
Add 17.75 g of sulfuric acid, and stir with a stirrer. Tris- [bis- (heptadecafluorooctylsulfonyl)
4.57 g of [imide] samarium [III] was added. Add dinitrotetraacetylhexaazaisoulitanium to the solution
1.00 g was added, the temperature was raised to 100 ° C., and after the temperature was raised, the reaction was performed for 3 hours. After completion of the reaction, the reaction solution was dropped into 250 ml of water, allowed to stand, the precipitated solid was filtered, and the filtrate was washed with 250 ml of purified water.
The filtered solid was added to 50 ml of acetone, stirred and filtered, and tris- [bis- (heptadecafluorooctylsulfonyl) imide] samarium [III] was filtered off.
Was recovered. Filtration was performed by evaporating under reduced pressure with an evaporator to collect a reaction product solid. This solid was dissolved in acetonitrile and analyzed by high performance liquid chromatography to confirm that hexanitrohexaazaisowurtzitane was produced at a yield of 8%.

Structural analysis of the product was performed in the same manner as in Example 1, and it was found that hexanitrohexaazaisowurtzitane was synthesized.

Example 47 WA ₄ F ₂ → WN _{6 A} 200 ml reaction vessel was immersed in a water bath at 0 ° C., and 97%
7.50 g of sulfuric acid was added, and 24.11 g of 98% nitric acid was slowly added dropwise while stirring with a stirrer. 1.00 g of diformyltetraacetylhexaazaisowurtzitanium was added to the mixed acid, the temperature was raised to 100 ° C., and after the temperature was raised, the mixture was reacted for 1.5 hours. After completion of the reaction, the reaction solution was added to 250 g of ice water, allowed to stand, and then filtered through a membrane filter. The obtained solid is purified water
Wash with 250g, Hexanitrohexaaza soul titanium
0.87 g was obtained (78% yield).

The structure of the product was analyzed in the same manner as in Example 1.
Hexanitrohexaazaisosoul titanium was found to be synthesized.

(Example 48) WA ₄ H ₂ → WA ₄ NS ₂ Tetraacetylhexaazaisosoul titanium 3.36 g and 50
% Acetic acid (100 ml) was placed in a 200 ml reaction vessel, and a 4 mol / sodium sulfite aqueous solution (20 ml) was slowly added dropwise while stirring at 0 ° C. Thereafter, the temperature was raised to 30 ° C., and the reaction was performed for 4 hours after the temperature was raised. 500 ml of chloroform was added to the reaction solution, and the mixture was vigorously stirred and extracted. After standing, the organic layer was taken out and the solvent was distilled off. As a result, it was confirmed that dinitrosotetraacetylhexaazaisowurtzitane was produced in 3.73 g (yield 95%). The analysis results of dinitrosotetraacetylhexaazaisowurtzitane are shown below.

¹ H NMR (solvent CDCl ₃ , TMS standard) δ (ppm) 2.05 (s, 6H, C
OCH ₃ ), 2.17 (s, 6H, COCH ₃ ) 5.45 (m, 2H, CH), 6.62
(M, 2H, CH), 730 (s, 2H, CH) ¹ H
Acetyl groups and 6 methine groups of the W skeleton were confirmed.

As a result of measuring an infrared absorption (IR) spectrum, 1670 cm ⁻¹
Near the carbonyl group of the acetyl group (C = O) absorption, 1500
cm around ^-1 was confirmed absorption that may have derived from nitroso group near 1380 cm ^-1 and near 1350 cm ^-1.

The two absorptions derived from NH between 3300 and 3400 cm ⁻¹ , which were confirmed by tetraacetylhexaazaisowurtzitanium, were completely eliminated.

(Example 49) WA ₄ H ₂ → WA ₄ NS ₂ Tetraacetylhexaazaisosoul titanium 3.36 g and 35
100 ml of% hydrochloric acid is placed in a 200 ml reaction vessel and cooled to 0 ° C.
While stirring at 0 ° C., 20 ml of a 4 mol / sodium sulfite aqueous solution was slowly added dropwise. Thereafter, the temperature was raised to 30 ° C., and after the temperature was raised, the mixture was stirred for 4 hours. 500 ml of chloroform was added to the reaction solution, followed by vigorous stirring. After standing, the organic layer was taken out and the solvent was distilled off under reduced pressure. As a result, it was confirmed that dinitrosotetraacetylhexaazaisowurtzitane was produced in 3.49 g (89% yield).

Structural analysis of the product was performed in the same manner as in Example 48, and it was found that dinitrosotetraacetylhexaazaisowurtzitanium was synthesized.

Example 50 WA ₄ H ₂ → WA ₄ NS ₂ 3.36 g of tetraacetylhexaazaisowurtzitanium and 100 ml of acetic acid were placed in a 200 ml reaction vessel and cooled to 0 ° C. 0 ° C
About 20 g of dinitrogen tetroxide gas was slowly blown into the reaction solution while stirring, and then stirred at 0 ° C. for 1 hour. After completion of the reaction, the solvent was distilled off under reduced pressure, washed with water and dried, whereby it was confirmed that dinitrosotetraacetylhexaazaisowurtzitane was produced in 3.73 g (yield 95%).

Structural analysis of the product was carried out in the same manner as in Example 48, and it was found that dinitrosotetraacetylazaisowurtzitanium was synthesized. .

Example 51 WA ₄ H ₂ → WA ₄ NS ₂ 3.36 g of tetraacetylhexaazaisowurtzitanium and 100 ml of pyridine were placed in a 200 ml reaction vessel and cooled to 0 ° C.
While stirring at 0 ° C., 10 ml of 4.8 M nitrosyl chloride in acetic anhydride was slowly added dropwise. Thereafter, the mixture was stirred for 1 hour. After the completion of the reaction, the reaction solution is poured into 100 g of ice water. The precipitated solid was collected by filtration, washed with water, and dried to give 2.75 g of dinitrosotetraacetylhexaazaisowurtzitanium (yield 7
0%).

Structural analysis of the product was performed in the same manner as in Example 48, and it was found that dinitrosotetraacetylhexaazaisowurtzitanium was synthesized. .

(Example 52) WA ₅ H ₁ → WA ₅ NS ₁ Pentaacetylhexaazaisosoul titanium 3.78 g and 50
100 ml of 100% acetic acid is placed in a 200 ml reaction vessel and cooled to 0 ° C.
While stirring at 0 ° C., 20 ml of a 4 mol / sodium nitrite aqueous solution was slowly added dropwise. Thereafter, the temperature was raised to 30 ° C., and after the temperature was raised, the mixture was stirred for 4 hours. 500 ml of chloroform was added to the reaction solution, followed by vigorous stirring. After standing, the organic layer was taken out, and the solvent was distilled off under reduced pressure. As a result, it was confirmed that mononitrosopentaacetylhexaazaisowurtzitanium was produced in 3.79 g (93% yield).

Structural analysis of the product was performed in the same manner as in Example 48, and it was found that mononitrosopentaacetylhexaazaisowurtzitane was synthesized. .

Example 53] _{WA 4 NS 2 → WA 4 N} 2 100ml reaction vessel was charged with 98% nitric acid 20.00 g, it dinitroso tetraacetyl hexamethylene A wood Seoul titanium 0.93g
Was added and reacted at room temperature for 5 hours. Thereafter, the nitric acid was distilled off under reduced pressure, washed with water and dried, and it was confirmed that 0.96 g of dinitrotetraacetylhexaazaisowurtzitanium was produced (yield 95%).

The analysis results of dinitrosotetraacetylhexaazaisowurtzitane are shown below.

¹ HNMR (solvent DMSO-d _6, TMS standard) δ (ppm) 2.10 (s , 1
2H, COCH ₃ ) 6.75 (m, 2H, CH), 7.35 (singlet peak at 7.35 ppm, peak 4H, CH with a shoulder on the low magnetic field side) As a result of confirming the infrared absorption spectrum (IR), 1680cm ^-1
From the carbonyl group of the acetyl group (C = O) in the vicinity, the absorption of stretching vibration is confirmed, 1570 cm ^-1 and around 1300cm
Absorption of stretching vibration of the nitro group was confirmed near ^-1 . This indicates that a nitro group and an acetyl group are present.

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

As a result of confirming the decomposition temperature, the peak top temperature was 314 ° C. at a heating rate of 10 ° C./min.

Example 54 WA ₄ NS ₂ → WA ₄ N _{2 A} 200 ml reaction vessel was immersed in a water bath at 0 ° C., and N ₂ O ₄
Was added thereto, and 0.4 g of dinitrosotetraacetylhexaazaisowurtzitanium was added thereto and reacted at 10 ° C. for 5 hours. After completion of the reaction, the solid obtained by distilling off the reaction solution was removed.
It was neutralized with 10NaHCO ₃ water, washed with water, and it was confirmed that dinitrotetraacetylhexaazaisowurtzitanium was produced in a yield of 92%.

The structure of the product was analyzed in the same manner as in Example 53, and it was found that dinitrotetraacetylhexaazaisowurtzitanium was synthesized.

[Example 55] WA ₅ NS ₁ → WA ₅ N _{1 A} 200 ml reaction vessel was immersed in a water bath at 0 ° C., and 97%
30 ml of nitric acid was added, and 0.96 g of mononitrosopentaacetylhexaazaisowurtzitanium was added thereto, and the mixture was reacted at room temperature for 5 hours. After completion of the reaction, the solid obtained by distilling the reaction solution was washed with water and dried to confirm that mononitropentaacetylhexaazaisowurtzitane was produced in a yield of 90%.

Structural analysis of the product was performed in the same manner as in Example 53, and it was found that mononitropentaacetylhexaazaisowurtzitane was synthesized.

[Example 56] WA ₄ NS ₂ → WA ₄ N _{2 A} 200 ml reaction vessel was immersed in a water bath at 0 ° C, and 97%
Add 81 g of sulfuric acid, and stir with a stirrer.
2.5 g was slowly added dropwise. 0.4 g of dinitrosotetraacetylhexaazaisowurtzitanium was added to the mixed acid, and 20
Stirred at C for 30 minutes. After completion of the reaction, the reaction solution was allowed to stand to precipitate a white solid, the supernatant was removed, and 20 g of ice was added, followed by filtration. The filtrate is washed with 10% aqueous NaHCO ₃ and purified water,
After drying, dissolved in acetonitrile and analyzed by LC,
It was confirmed that dinitrotetraacetylhexaazaisowurtzitane was produced at a yield of 20%.

The structure of the product was analyzed in the same manner as in Example 53, and it was found that dinitrotetraacetylhexaazaisowurtzitanium was synthesized.

Example 57 WA ₄ NS ₂ → WA ₄ N _{2 A} 200 ml reaction vessel was immersed in a water bath at 0 ° C., and N ₂ O ₅
Was added, and while stirring with a stirrer, 1.00 g of dinitrosotetraacetylhexaazaisowurtzitanium was added, followed by reaction at 25 ° C. for 1 hour.
After completion of the reaction, the reaction solution was distilled off, and the obtained solid was washed with 10NaHC.
Neutralized with O ₃ water and filtered. The filtrate was washed with water, dried, dissolved in acetonitrile and analyzed by LC. As a result, it was confirmed that dinitrotetraacetylhexaazaisowurtzitanium was produced in a yield of 70%.

The structure of the product was analyzed in the same manner as in Example 53, and it was found that dinitrotetraacetylhexaazaisowurtzitanium was synthesized.

Example 58 WA ₄ NS ₂ → WA ₄ N _{2 A} 200 ml reaction vessel was immersed in a water bath at 0 ° C., and 97%
18.22 g of sulfuric acid was added, and while stirring with a stirrer, 5.21 g of trifluoroacetic acid was added. Add 0.4 g of dinitrosotetraacetylhexaazaisowurtzitanium to the solution and add 60 g
The reaction was performed at a temperature of 1 ° C for 1 hour. After completion of the reaction, the reaction solution was distilled off, and the obtained solid was neutralized with 10% aqueous NaHCO ₃ and filtered. The filtrate was washed with water, dried, dissolved in acetonitrile, and analyzed by LC. As a result, it was confirmed that dinitrotetraacetylhexaazaisowurtzitane was produced in a yield of 42%.

The structure of the product was analyzed in the same manner as in Example 53, and it was found that dinitrotetraacetylhexaazaisowurtzitanium was synthesized.

[Example 59] WA ₄ NS ₂ → WA ₄ N _{2 A} 200 ml reaction vessel was immersed in a water bath at 0 ° C, and 98%
17.64 g of sulfuric acid was added, and 3.98 g of diphosphorus pentoxide was added while stirring with a stirrer. Add 0.4 g of dinitrosotetraacetylhexaazaisowurtzitanium to the solution,
For 30 minutes. After completion of the reaction, the reaction solution was distilled off, and water 20
After adding ml, the mixture was filtered, washed with water, dried, dissolved in acetonitrile, and subjected to LC analysis. As a result, it was confirmed that dinitrotetraacetylhexaazaisowurtzitanium was produced in a yield of 56%.

The structure of the product was analyzed in the same manner as in Example 53, and it was found that dinitrotetraacetylhexaazaisowurtzitanium was synthesized.

Example 60 WA ₄ NS ₂ → WA ₄ N _{2 A} 200 ml reaction vessel was immersed in a water bath at 0 ° C.
% Nitric acid 20.16 g was added, and 44.33 g of polyphosphoric acid was added while stirring with a stirrer. Add 0.4 g of dinitrosotetraacetylhexaazaisowurtzitanium to the solution, and add
And reacted for 40 minutes. After the completion of the reaction, the reaction solution was placed in a beaker containing 20 ml of water, stirred and dissolved, and the insoluble solid was filtered, washed with water, dried and dissolved in acetonitrile, and LC
As a result of the analysis, it was confirmed that dinitrotetraacetylhexaazaisowurtzitanium was produced at a yield of 56%.

The structure of the product was analyzed in the same manner as in Example 53, and it was found that dinitrotetraacetylhexaazaisowurtzitanium was synthesized.

Example 61 WA ₄ NS ₂ → WA ₄ N _{2 A} 200 ml reaction vessel was immersed in a water bath at 0 ° C., and 97%
18.22 g of nitric acid was added, and 60.73 g of trifluoroacetic anhydride was added while stirring with a stirrer. 0.4 g of dinitrosotetraacetylhexaazaisowurtzitanium was added to the solution and reacted at 30 ° C. for 1 hour. After completion of the reaction, the reaction solution was distilled off, and the obtained solid was neutralized with 10% aqueous NaHCO ₃ , washed with water,
After drying and dissolving in acetonitrile and performing LC analysis, dinitrotetraacetylhexaazaisowurtzitane yielded 72%.
It was confirmed that it was generated by.

The structure of the product was analyzed in the same manner as in Example 53, and it was found that dinitrotetraacetylhexaazaisowurtzitanium was synthesized.

Example 62 WA ₆ → WA ₄ N _{2 A} 200 ml reaction vessel was immersed in a water bath at 0 ° C., and N ₂ O ₅
Of nitric acid solution containing 10 mol%, and 0.4 g of hexaacetylhexaazaisowurtzita was added thereto, and the mixture was heated at 60 ° C.
And reacted for 8 hours. After completion of the reaction, the organic component in the reaction solution was extracted with chloroform (200 ml × 4 times), and the solid obtained by distilling off chloroform under reduced pressure was washed with 10% aqueous NaHCO _{3 to} remove various nitrated mixtures. Obtained. This solid was dissolved in acetonitrile and analyzed by high performance liquid chromatography, and it was confirmed that the main component, dinitrotetraacetylhexaazaisowurtzitanium, was analyzed with a yield of 43%.

The structure of the product was analyzed in the same manner as in Example 53, and it was found that dinitrotetraacetylhexaazaisowurtzitanium was synthesized.

Example 63 WA ₄ H ₂ → WA ₄ N _{2 A} 200 ml reaction vessel was immersed in a water bath at 0 ° C., and N ₂ O ₅
Of nitric acid solution containing 10 mol%, 0.4 g of tetraacetylhexaazaisowurtzitane is added thereto,
And reacted for 8 hours. After completion of the reaction, the organic component in the reaction solution was extracted with chloroform (200 ml × 4 times), and the solid obtained by distilling off chloroform under reduced pressure was washed with 10% aqueous NaHCO _{3 to} remove various nitrated mixtures. Obtained. This solid was dissolved in acetonitrile and analyzed by high performance liquid chromatography to confirm that the main component, dinitrotetraacetylhexaazaisowurtzitanium, was analyzed in a yield of 40%.

The structure of the product was analyzed in the same manner as in Example 53, and it was found that dinitrotetraacetylhexaazaisowurtzitanium was synthesized.

[Example 64] WBN ₆ → WA ₄ BN _{2 wherein} A represents an acetyl group, BN represents a benzyl group, and W represents a hexavalent hexaazaisowurtzitanium residue represented by the formula (V). Hexabenzylhexaazaisoul titanium 1.89g, 10
% Pd-C 1.70 g, N-acetoxysuccinimide 5.0
g, 160 ml of ethylbenzene, 3.24 g of acetic anhydride, and a rotator were placed in a 300-ml micro-bomb, and the inside of the bomb was replaced with hydrogen. Thereafter, hydrogen was injected into the cylinder up to 5 MPa and reacted with a stirrer for 20 hours. The reaction solution was taken out of the cylinder, the catalyst was filtered, and the solid on the filter paper was washed with 200 ml of chloroform. The filtrate (reaction solution and chloroform washing solution) was evaporated, and the remaining solid was dissolved in 200 ml of chloroform. 200 ml of 28% aqueous ammonia was added thereto.
Reacted for 0 minutes. By this operation, N-acetoxysuccinimide is removed from the organic layer. The chloroform layer was taken out and the solvent was distilled off to obtain 1.39 g of a white solid. This was recrystallized from ethylbenzene to give 1.20 g of white solid (yield 8
7%). The analysis of this solid was performed using the FD-mass spectrum, ¹
Structural analysis was performed using H, ¹³ C-NRM, and ¹³ C- ¹ H COSY to confirm that the substance was tetraacetyldibenzylhexaazaisowurtzitane. The analysis results of tetraacetyldibenzylhexaazaisowurtzitane are shown below.

 FD-mass spectrum 517 ([M + H] +).

¹ H-NMR spectrum (solvent CDCl ₃ , TMS standard) δ (ppm)
1.94 (s, 6H, COCH ₃ ), 2.15 (s, 6H, COCH ₃ ), 4.06 (d, 2H, C
_{H 2), 4.29 (d,} 2H, CH 2), 5.09 (d, 2H, CH), 5.70 (d, 2H, C
H), 6.42 (s, 2H, CH), 7.3 to 7.5 (m, 10H, Ph).

¹ H-NMR spectrum confirmed four acetyl groups, two benzyl groups, and six methine groups in the W skeleton.

¹³ C-NRM (solvent CDCl ₃ , TMS standard) δ (ppm) 20.737
_{(CH 3), 22.111 (CH} 3), 56.428 (CH 2), 69.678 (CH), 7
0.592 (CH), 128.056 (Ph), 128.673 (Ph), 128.928 (Ph), 136.742 (Ph), 168.263 (CO).

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

By ¹ H- ¹³ C COZY, it was identified by ¹³ C bound of ¹ H.

[Example 65] WA ₆ BN ₂ → WA ₄ H ₂ [In the formula, A is an acetyl group, BN is a benzyl group, H is a hydrogen atom, and W is a hexavalent hexaazaisowurtzitanium residue represented by the formula (V). Represents a group. ] Tetraacetyldibenzylhexaazaisosoultitanium
3.67g, Pd (OAc) ₂ 1.60g, acetic acid 150ml, and rotor 300m
l Placed in a micro cylinder and replaced with nitrogen. Thereafter, hydrogen was injected into the microbomb to a pressure of 0.5 MPa, and reacted with a stirrer for 15 hours. Remove the reaction solution from the micro cylinder and
The catalyst was filtered, and the solvent was distilled off under reduced pressure. The remaining solid was washed with 100 ml of ethyl acetate to obtain 2.33 g (99% yield) of white fixed tetraacetylhexaazaisowurtzitanium.

The analysis results of tetraacetylhexaazaisosoultitanium are shown below.

¹ H-NMR (solvent C ₂ O, TMS standard), δ (ppm) 1.98 (s, 6
H, COCH ₃ ), 2.00 (s, 6H, CH ₃ ), 5.29 (br, 2H, CH), 5.50
(Br, 2H, CH), 6.35 (m, 2H, CH).

¹ H-NMR confirmed four acetyl groups and a methine group in the W skeleton. As a result of measuring an infrared absorption spectrum (IR), absorption of stretching vibration of two secondary amines (N—H groups) at 3300 to 3400 cm ⁻¹ was confirmed. At 1660 cm ⁻¹ , stretching vibration of the carbonyl (C ＝ O) group of the acetyl group was confirmed. From these, acetyl group and N—H are substituted as substituents of the W skeleton.
It can be seen that the group is present.

[Industrial applicability]

INDUSTRIAL APPLICABILITY The present invention is useful as a method for producing hexanitrohexaazaisowurtzitane, which is a high-performance explosive.

──────────────────────────────────────────────────続 き Continued on the front page (56) References Patent 2844125 (JP, B2) (58) Fields investigated (Int. Cl. ⁷ , DB name) C07D 487/22 CA (STN) REGISTRY (STN)

Claims (35)

(57) [Claims] (1) The following general formula (I), (III) or (I)
In the method for producing hexanitrohexaazaisowurtzitanium, which is obtained by nitrating a hexaazaisowurtzitanium derivative represented by V) with nitric acid in the presence of a nitration promoter, the following general formula (IX) is used as a nitration promoter. Wherein at least one selected from the group consisting of perfluoroalkylsulfonylimide, diphosphorus pentoxide, sulfur trioxide, dinitrogen pentoxide, and polyphosphoric acid represented by the following formula (VI) is used: A method for producing the represented hexanitrohexaazaisosoultitanium. WA _n N _(6-n) (I) wherein n is an integer of 4 to 5, A is each independently the same or different acyl group having 1 to 10 carbon atoms, N is a nitro group, and W is It represents a hexavalent hexaazaisowurtzitane residue represented by the following formula (II). WA _n NS _(6-n) (III) wherein n is an integer of 4 to 5, A is each independently the same or different acyl group having 1 to 10 carbon atoms, NS is a nitroso group, W is
Represents a hexavalent hexaazaisowurtzitanium residue represented by the following formula (II). WA _m H _(6-m) (IV) [wherein, m is an integer of 4 to 6, A is each independently the same or different acyl group having 1 to 10 carbon atoms, H is a hydrogen atom, W is Represents a hexavalent hexaazaisowurtzitanium residue represented by the following formula (II). WN ₆ (VI) [wherein, N represents a nitro group, and W represents a hexavalent hexaazaisowurtzitanium residue represented by the following formula (II). ] RfSO ₂ NHSO ₂ Rf ′ (IX) [wherein, Rf and Rf ′ represent a perfluoroalkyl group having 1 to 8 carbon atoms, S is a sulfur atom, O is an oxygen atom, N is a nitrogen atom, and H is a hydrogen atom. Represents ] 2. The compound represented by the following general formula (I), (III) or (I)
In the method for producing hexanitrohexaazaisowurtzitanium, which is obtained by nitrating the hexaazaisowurtzitanium derivative represented by V) with nitric acid in the presence of a nitration promoter, a carboxylic anhydride is used as the nitration promoter. A method for producing hexanitrohexaazaisowurtzitanium represented by the following formula (VI): WA _n N _(6-n) (I) wherein n is an integer of 4 to 5, A is each independently the same or different acyl group having 1 to 10 carbon atoms, N is a nitro group, and W is It represents a hexavalent hexaazaisowurtzitane residue represented by the following formula (II). WA _n NS _(6-n) (III) wherein n is an integer of 4 to 5, A is each independently the same or different acyl group having 1 to 10 carbon atoms, NS is a nitroso group, W is
Represents a hexavalent hexaazaisowurtzitanium residue represented by the following formula (II). WA _m H _(6-m) (IV) [wherein, m is an integer of 4 to 6, A is each independently the same or different acyl group having 1 to 10 carbon atoms, H is a hydrogen atom, W is Represents a hexavalent hexaazaisowurtzitanium residue represented by the following formula (II). WN ₆ (VI) [wherein, N represents a nitro group, and W represents a hexavalent hexaazaisowurtzitanium residue represented by the following formula (II). ] 3. The method according to claim 2, wherein the carboxylic anhydride is trifluorosulfuric anhydride. 4. A compound represented by the following general formula (I), (III) or (I)
The use of a Lewis acid as a nitration accelerator in a process for producing hexanitrohexaazaisowurtzitane, in which a hexaazaisowurtzitanium derivative represented by V) is nitrated with nitric acid in the presence of a nitration accelerator, A method for producing hexanitrohexaazaisosoultitanium represented by the following formula (VI): WA _n N _(6-n) (I) wherein n is an integer of 4 to 5, A is each independently the same or different acyl group having 1 to 10 carbon atoms, N is a nitro group, and W is It represents a hexavalent hexaazaisowurtzitane residue represented by the following formula (II). WA _n NS _(6-n) (III) wherein n is an integer of 4 to 5, A is each independently the same or different acyl group having 1 to 10 carbon atoms, NS is a nitroso group, W is
Represents a hexavalent hexaazaisowurtzitanium residue represented by the following formula (II). WA _m H _(6-m) (IV) [wherein, m is an integer of 4 to 6, A is each independently the same or different acyl group having 1 to 10 carbon atoms, H is a hydrogen atom, W is Represents a hexavalent hexaazaisowurtzitanium residue represented by the following formula (II). WN ₆ (VI) [wherein, N represents a nitro group, and W represents a hexavalent hexaazaisowurtzitanium residue represented by the following formula (II). ] 5. The method according to claim 4, wherein the Lewis acid is a rare earth salt of perfluoroalkylsulfonic acid represented by the following general formula (X). M (RfSO ₃ ) ₃ (X) [wherein, Rf represents a C 1-8 perfluoroalkyl group, S represents a sulfur atom, O represents an oxygen atom, and M represents a rare earth element. ] 6. The method according to claim 4, wherein the Lewis acid is a rare earth salt of perfluoroalkylsulfonylimide represented by the following formula (XI). M (RfSO ₂ NSO ₂ Rf ′) ₃ (XI) wherein Rf and Rf ′ each represent a C 1-8 perfluoroalkyl group, S is a sulfur atom, O is an oxygen atom, N is a nitrogen atom, M represents a rare earth element. ] 7. The method according to claim 1, wherein a strongly acidic solid catalyst is used as a nitration accelerator. 8. The method for producing hexanitrohexaazaisowurtzitane according to claim 7, wherein the strongly acidic solid catalyst is a Lewis acid catalyst. 9. The method for producing hexanitrohexaazaisowurtzitane according to claim 7, wherein the strongly acidic solid catalyst is a strong Bronsted acid catalyst. 10. The method according to claim 9, wherein the strong Bronsted acid catalyst is a polymer having a sulfonic acid group. 11. The method according to claim 9, wherein the strong Bronsted acid catalyst is zeolite. 12. A hexaazaisowurtzitanium derivative represented by the general formula (IV) is nitrated with a nitrating agent to produce a hexaazaisowurtzitanium derivative represented by the general formula (I). A method for producing hexanitrohexaazaisowurtzitane of the general formula (VI), wherein the derivative is nitrated with nitric acid in the presence of a nitration accelerator. WA _m H _(6-m) (IV) [wherein, m is an integer of 4 to 6, A is each independently the same or different acyl group having 1 to 10 carbon atoms, H is a hydrogen atom, and W is It represents a hexavalent hexaazaisowurtzitane residue represented by the following formula (II). WA _n N _(6-n) (I) wherein n is an integer of 4 to 5, A is each independently the same or different acyl group having 1 to 10 carbon atoms, N is a nitro group, W is Represents a hexavalent hexaazaisowurtzitanium residue represented by the following formula (V). WN ₆ (VI) [wherein, N represents a nitro group, and W represents a hexavalent hexaazaisowurtzitanium residue represented by the following formula (II). ] 13. A nitration accelerator represented by the following general formula (I)
13. The method according to claim 12, wherein at least one selected from the group consisting of perfluoroalkylsulfonylimide represented by X), diphosphorus pentoxide, sulfur trioxide, dinitrogen pentoxide and polyphosphoric acid is used. For producing hexanitrohexaazaisowurtzitane. RfSO ₂ NHSO ₂ Rf ′ (IX) [wherein, Rf and Rf ′ represent a perfluoroalkyl group having 1 to 8 carbon atoms, S is a sulfur atom, O is an oxygen atom, N is a nitrogen atom, and H is a hydrogen atom. Represents ] 14. The method for producing hexanitrohexaazaisowurtzitanium according to claim 12, wherein a carboxylic anhydride is used as the nitration accelerator. 15. The method for producing hexanitrohexaazaisowurtzitane according to claim 14, wherein the carboxylic anhydride is trifluoroacetic anhydride. 16. The method for producing hexanitrohexaazaisowurtzitane according to claim 12, wherein a Lewis acid is used as the nitration accelerator. 17. The method according to claim 16, wherein the Lewis acid is a rare earth salt of perfluoroalkylsulfonic acid represented by the following general formula (X). M (RfSO ₃ ) ₃ (X) [wherein, Rf represents a C 1-8 perfluoroalkyl group, S represents a sulfur atom, O represents an oxygen atom, and M represents a rare earth element. ] 18. The method according to claim 16, wherein the Lewis acid is a rare earth salt of perfluoroalkylsulfonylimide represented by the following formula (XI). M (RfSO ₂ NSO ₂ Rf ′) ₃ (XI) wherein Rf and Rf ′ each represent a C 1-8 perfluoroalkyl group, S is a sulfur atom, O is an oxygen atom, N is a nitrogen atom, M represents a rare earth element. ] 19. The method for producing hexanitrohexaazaisowurtzitanium according to claim 12, wherein the nitration accelerator is a solid catalyst having strong acidity. 20. The method for producing hexanitrohexaazaisowurtzitane according to claim 19, wherein the strongly acidic solid catalyst is a Lewis acid catalyst. 21. The method according to claim 19, wherein the strongly acidic solid catalyst is a strong Bronsted acid catalyst. 22. The method according to claim 21, wherein the strong Bronsted acid catalyst is a polymer having a sulfonic acid group. 23. The method for producing hexanitrohexaazaisowurtzitane according to claim 21, wherein the strong Bronsted acid catalyst is zeolite. 24. A hexaazaisowurtzitanium derivative represented by the general formula (III) is produced by nitronating a hexaazaisowurtzitanium derivative represented by the general formula (IV) with a nitrosating agent, In the presence of a nitration accelerator,
Formula (VI) characterized by nitration using nitric acid
The method for producing hexanitrohexaazaisowurtzitane represented by the formula: WA _m H _(6-m) (III) wherein m is an integer of 4 to 6, A is each independently the same or different acyl group having 1 to 10 carbon atoms, H is a hydrogen atom, and W is It represents a hexavalent hexaazaisowurtzitane residue represented by the following formula (II). WA _n NS _(6-n) (I) wherein n is an integer of 4 to 5, A is each independently the same or different acyl group having 1 to 10 carbon atoms, NS is a nitroso group, W is
Represents a hexavalent hexaazaisowurtzitanium residue represented by the following formula (V). WN ₆ (VI) [wherein, N represents a nitro group, and W represents a hexavalent hexaazaisowurtzitanium residue represented by the following formula (II). ] 25. A nitro value promoter represented by the following general formula (I)
25. The method according to claim 24, wherein at least one selected from the group consisting of perfluoroalkylsulfonylimide, diphosphorus pentoxide, sulfur trioxide, dinitrogen pentoxide and polyphosphoric acid represented by X) is used. For producing hexanitrohexaazaisowurtzitane. RfSO ₂ NHSO ₂ Rf ′ (IX) [wherein, Rf and Rf ′ represent a perfluoroalkyl group having 1 to 8 carbon atoms, S is a sulfur atom, O is an oxygen atom, N is a nitrogen atom, and H is a hydrogen atom. Represents ] 26. The method according to claim 24, wherein a carboxylic anhydride is used as a nitration accelerator. 27. The method for producing hexanitrohexaazaisowurtzitane according to claim 26, wherein the carboxylic anhydride is trifluoroacetic anhydride. 28. The method according to claim 24, wherein a Lewis acid is used as the nitration accelerator. 29. The method according to claim 28, wherein the Lewis acid is a rare earth salt of perfluoroalkylsulfonic acid represented by the following general formula (X). M (RfSO ₃ ) ₃ (X) [wherein, Rf represents a C 1-8 perfluoroalkyl group, S represents a sulfur atom, O represents an oxygen atom, and M represents a rare earth element. ] 30. The method according to claim 28, wherein the Lewis acid is a rare earth salt of perfluoroalkylsulfonylimide represented by the following formula (XI). M (RfSO ₂ NSO ₂ Rf ′) ₃ (XI) wherein Rf and Rf ′ each represent a C 1-8 perfluoroalkyl group, S is a sulfur atom, O is an oxygen atom, N is a nitrogen atom, M represents a rare earth element. ] 31. The method for producing hexanitrohexaazaisowurtzitane according to claim 24, wherein the nitration accelerator is a solid catalyst having strong acidity. 32. The method for producing hexanitrohexaazaisowurtzitanium according to claim 31, wherein the strongly acidic solid catalyst is a Lewis acid catalyst. 33. The method according to claim 31, wherein the strongly acidic solid catalyst is a strong Bronsted acid catalyst. 34. The method according to claim 33, wherein the strong Bronsted acid catalyst is a polymer having a sulfonic acid group. 35. The method for producing hexanitrohexaazaisowurtzitane according to claim 33, wherein the strong Bronsted acid catalyst is zeolite.