The method of obtaining hexanitrohexaazaisowurtzitane

 

(57) Abstract:

Describes how to obtain hexanitrohexaazaisowurtzitane formula VI W(NO2)6where W represents a hexavalent balance hexaazatetracyclo formula II and NO2is a nitrogroup, nitration allstargame derivatives hexaazatetracyclo, wherein the nitration is subjected to one of allstargame derivatives hexaazatetracyclo selected from the group consisting of the compounds of formula I WAn(NO2)(6-n)where n is an integer of 4 or 5; A are identical or different and represent a1-10-acyl group; W and NO2have the meanings defined above; a compound of formula III WAn(NO)(6-n)where W, A and n are defined above, and NO represents nitrosourea; a compound of formula IV WAm(NO2)(6-m)where W and A have the meanings defined above; m is an integer of 4 to 6; N represents a hydrogen atom, nitric acid in the presence of a catalyst for the nitration, and at least one compound selected from the group consisting of performancecounterid, represented by formula IX RfSO2NHSO2Rf, where N is the ima is Yes; S is a sulfur atom; O is an oxygen atom and N represents a nitrogen atom, phosphorus pentoxide, sulfur trioxide, nitrogen pentoxide and polyphosphoric acid is used as catalyst for the nitration. The technical result is to simplify the process and obtain the desired products in high yields. 12 c. and 18 C.p. f-crystals.

The invention relates to hexanitrohexaazaisowurtzitane and how to obtain it.

Art

As compounds containing patterns hexaazatetracyclo, various known derivatives hexaazatetracyclo containing arylmethyl group. These compounds are prepared by condensation of arylmethylidene and glyoxal (J. Org. Chem., v. 55, 1459-1466, 1990). Tetraacetylethylenediamine known as hexaazatetracyclo containing acyl group. It is the precursor hexanitrohexaazaisowurtzitane, which is a material for explosives (The Militarily Critical Technologies List, Office of the Under Secretary of Defense for Acquisition, . 12-22, October 1992; and Tetrahedron, v. 51, No. 16, 4711-4722, 1995). In addition, the known derivatives hexaazatetracyclo containing ethyl group, such as tetraacetylethylenediamine and such is intoxicatingly group (JP-A-6-321962). Known benzyl - and/or solvent derived hexaazatetracyclo other than the above tetraacetylethylenediamine, tetraacetylethylenediamine.

The above derivatives hexaazatetracyclo containing acyl group, an easily replaceable by nitro groups, useful as precursors derived printresizebutton for high explosives. However, using the above derivatives as precursors of nitro compounds is accompanied by several problems. For example, as in the nitration derivatives hexaazatetracyclo containing benzyl group, produces by-products, such as reduction of compounds, isolation and purification hexanitrohexaazaisowurtzitane representing the target compound of the present invention, is complicated. On the other hand, hydrochloric acid, strong acid, which is formed in the process of obtaining trimethylsilylethynyl contains hexaazatetracyclo causes decomposition hexabenzylhexaazaisowurtzitane, which is a starting compound in this way. It is also reported that hexanitroethane the person receiving it is missing (Tetrahedron, v. 51, No. 16, 4711-4722, 1995). In addition, we know that" hard to get hexanitrohexaazaisowurtzitane by nitration tetraacetylethylenediamine (Tetrahedron, v. 51, No. 16, 4711-4722, 1995).

Thus, the long overdue need to develop a method of obtaining hexanitrohexaazaisowurtzitane with high yield by using derivatives hexaazatetracyclo containing acyl group.

It is also an object of the present invention to provide hexanitrohexaazaisowurtzitane with high yield by using derivatives hexaazatetracyclo.

Description of the invention

Applicants have achieved the above objectives and implemented other objectives of the present invention through the development of a commercially viable method of producing hexanitrohexaazaisowurtzitane.

The present invention provides a derivative of gecause isovorticity containing nitrogroup, and the way to obtain this derivative, which is represented by the following General formula (I):

WAnN(6-n)(I)

where n represents an integer of 4 or 5, A is an acyl group containing 1-10 carbon atoms, and each acyl group is the same and entry balance hexaazatetracyclo the following formula (II):

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In addition, the present invention provides a derived hexaazatetracyclo containing nitrosourea, and the way to obtain this derivative, which is represented by the following General formula (III):

WAnNS(6-n)(III)

where n represents an integer of 4 or 5, A is an acyl group containing 1-10 carbon atoms, and each acyl group is the same or different from one or more other groups, NS represents nitrosopropane, W represents a hexavalent balance hexaazatetracyclo the following formula (II):

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Acceptable acyl group A in the above formulas (I) and (III) may be any acyl group, while it contains 1-10 carbon atoms. The acyl group may be an acetyl, formyl, propionyl, butyryl, isobutyryl, valeryl, hexanoyl, 2-phenylacetyl or similar groups. Preferably, A may represent an acyl group containing 1-5 carbon atoms, such as formyl, acetyl, propionyl, butyryl, valeryl and similar groups, and more preferably, A may represent an acyl group containing 2-4 carbon atoms, such as acetyl, propionyl, butyryl and similar groups. In the archives of other groups.

Each of the derived hexaazatetracyclo may take the form of any of various isomers, differing by the provisions of its acyl, nitro - and microsorum. However, any such isomers may be used in accordance with the present invention.

Below is a description of the methods of obtaining derivatives hexaazatetracyclo formulas (I) and (III).

Derived hexaazatetracyclo containing nitrogroup, the General formula (I), which gives hexanitrohexaazaisowurtzitane, can be obtained by nitration of compounds WAmH(6-in), as shown in the following reaction scheme (1):

WAmH(6-m)---> WAnN(6-n), (1)

where m is an integer of 4-6, n represents an integer of 4 or 5, A is an acyl group containing 1-10 carbon atoms, and each acyl group is the same or different from one or more of the other H represents a hydrogen atom, N represents a nitro-group, W represents a hexavalent balance hexaazatetracyclo.

At the same time, derived hexaazatetracyclo containing nitrosourea, the General formula (III) can be obtained by nitrotyrosine connection WAnH(6 is de n represents an integer of 4 or 5, A represents an acyl group containing 1-10 carbon atoms, and each acyl group is the same or different from one or more of the other H represents a hydrogen atom, NS represents nitrosopropane, W represents a hexavalent balance hexaazatetracyclo.

Any allstargame derived hexaazatetracyclo represented by the formula WAnH(6-n)or WAmH(6-m)in the above reaction scheme (1) or (2) may be used as the source material, regardless of its way to get. However, it is preferable to use compounds WAnH(6-n)or WAmH(6-m)who receive rehabilitation diarylethylenes WB6in the presence of Alliluyeva agent with additional recovery diarylethylenes of the obtained product in the absence of Alliluyeva agent, for example as described in PCT publication N WO96/23792. In more detail, the method of obtaining the above-mentioned starting compounds is described below.

Acyl groups derived hexaazatetracyclo WAnH(6-n)and WAmH(6-m)which are the starting compounds in reactions (1) and (2 is new or different from one or more others. Examples of acyl groups include acetyl, formyl, propionyl, butyryl, isobutyryl, valeryl, hexanoyl, 2-phenylacetyl and similar groups. Preferred acyl groups are groups containing 1-5 carbon atoms, such as formyl, acetyl, propionyl, butyryl, valeryl and similar groups, and more preferred acyl groups are groups containing 2-4 carbon atoms, such as acetyl, propionyl, butyryl and similar groups.

Each of these derivatives hexaazatetracyclo may take the form of any of various isomers, differing by the provisions of the acyl groups and hydrogen atoms. However, any such isomers may be used in accordance with the present invention.

Derivative represented by the formula WAmH(6-m)include WA4H2THAT WA5H1and WA6that can be used individually or as a mixture of two or more.

As nitrouse agent in the nitration reaction (1) can be used any nitrouse agent capable of netravati connection WAmH(6-m). Examples of such nitrous agents include nitric acid, cityregional nitrogen, mixtures of nitric acid with accelerator or more agents. Among the above nitrouse agents nitric acid may be partially or completely replaced by a metal nitrate, such as silver nitrate or the like, or nitroview salt, such as nitrosoethylurea or similar. The use of nitric acid, camerahouse or nitrogen pentoxide is preferred because of the increased selectivity of the nitration reaction (1).

Accelerators nitration are compounds that increase ELECTROPILOT nitronium ions. Examples of accelerators that may be used in accordance with the present invention, typically include:

A. Organic acid having a "PERFLUORO"-patterns, such as triperoxonane acid and the like, a strong organic or inorganic acid Bronsted, typical examples of which include sulfuric acid, fuming sulfuric acid, performancemonitoring, polyphosphoric acid, triftoratsetata and the like;

B. the Anhydrides of carboxylic acids, such as triperoxonane anhydride, acetic anhydride and the like;

C. Oxides, such as patikis phosphorus, pathiakis nitrogen and sulfur trioxide and the like; and

D. Lewis Acid, such as salts of rare earth metals performanance above accelerators nitration can be used as a mixture of two or more accelerators. Described in paragraphs A-C of accelerators nitration are preferred strong acid Bronsted on item A and oxides on paragraph C, as they increase the rate of nitration. More preferred are the strong acid Bronsted, if they have the same acidity or higher acidity than triperoxonane acid (for example, from the point of view of the RCA). Particularly preferred accelerators nitration on items A-C are sulfuric acid, triperoxonane acid, poly phosphoric acid, pathiakis phosphorus and sulfur trioxide.

The above performancemonitoring represented by the following formula (IX):

RfSO2NHSO2Rf' (IX)

where Rf and Rf' represent performanceline group containing 1-8 carbon atoms, S represents a sulfur atom, O represents an oxygen atom, N represents a nitrogen atom, H represents a hydrogen atom.

Performanceline group of perftoruglerodov can be linear or branched and can be used one or more of these imides. Examples of imides include bis(trifloromethyl)imide, bis(nonoperational)imide, bis(heptadecafluorooctyl)imide and under who are the salt of rare-earth metals perftoruglerodov acids of the formula (X):

M(RfSO3)3, (X)

where Rf represents performanceline group containing 1-8 carbon atoms, S represents a sulfur atom, O represents an oxygen atom, M represents a rare earth element.

Examples of salts of rare earth elements perftoruglerodov acids include Tris(cryptomelane)lanthanum (III), Tris(cryptomelane)ytterbium (III), Tris(cryptomelane)europium (III), Tris(cryptomelane)yttrium (III), Tris(cryptomelane)scandium (III), Tris(cryptomelane) praseodymium (III) and the like.

You can also use salts of rare earth elements of perftoruglerodov the following formula (XI):

M(RfSO2NSO2Rf')3, (XI)

where Rf and Rf' represent performanceline group containing 1-8 carbon atoms, S represents a sulfur atom, O represents an oxygen atom, N represents a nitrogen atom, M represents a rare earth element.

Performanceline group of perftoruglerodov can be linear or branched and can be used one or more of these imides.

Salts of rare earth elements of perftoruglerodov are acids is increased.

Examples of salts of rare earth elements perftoruglerodov, which are Lewis acids containing a rare earth element include Tris(bis(trifloromethyl)imide lanthanum (III), Tris(bis(trifloromethyl)imide ytterbium (III), Tris(bis(trifloromethyl)imide yttrium (III), Tris(bis(nonoperational)imide)ytterbium (III), Tris(bis(nonoperational)imide)yttrium (III), Tris(bis(nonoperational)imide)lanthanum (III), Tris(bis(heptadecafluorooctyl)imide)lanthanum (III), Tris(bis(heptadecafluorooctyl)imide)ytterbium (III), Tris(bis(heptadecafluorooctyl)imide)yttrium (III) and similar compounds.

Rare earth salt of perftoruglerodov are salts of perftoruglerodov and rare earth elements. Any item may be acceptable if it is a rare earth element, but preferred examples of the rare earth elements include lanthanum, ytterbium, yttrium and the like.

The above accelerators nitration are homogeneous or heterogeneous, and may be used any of them. For example, it is preferable to use the following accelerators nitration, as they can be easily, the strong acid Bronsted, such as zeolites and the like;

F. Solid organic Lewis acid, such as salts of rare earth metals of perftoruglerodov having alkyl fluoride groups with long chain;

G. Liquid performancelevel acid and oligocarbonate acid having a "PERFLUORO"-patterns that are not homogeneous soluble in the reaction systems.

Typical examples of the above zeolites, which can be used in accordance with the present invention include analcime, bikitaite, brewsterite, chabazite, clinoptilolite, bashiardes, edingtonite, epistilbite, erionite, tasit, Ferreira, gismondine, gmelinite, gonnardite, chabazite, heulandite, diatomaceous earth, laumontite, levanic, lost, mesolite, mordenite, natrolite, omega, paulinha, filipcic, scolecite, sodalities, stilbite, thomsonite and yugawaralite. Examples of synthetic zeolite compounds, which can also be used in accordance with the present invention, include "A", "N", "Lb", "P", "T", "X", "ZX-4", "ZX-5", "ZSM-5 and ZSM-11", "MCM-22", "tasit" "Linde type L" and the like.

As strong acids Branstad can also be used insoluble polymers containing altgroup, and containing sulfopropyl cation exchange resins are also strongly acidic solid catalysts that can be allocated at the end of the reaction for reuse. Examples of insoluble polymers containing sulfopropyl, and containing sulfopropyl cation exchange resins include, polyarilensulphone acid, fluoropolymers containing sulfopropyl, and the like. Preferred examples of insoluble polymers containing sulfopropyl are fluoropolymers containing sulfopropyl, repeating the link represented by the following General formula (XII):

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cation-exchange resin and the like. Preferred examples of insoluble polymers containing sulfopropyl, and cation exchange resins include Nafion-NR50 (a trade mark of the company DuPont) and the like.

Nitration in accordance with reaction (1) can be carried out in the presence of a solvent, although it may be carried out without solvent. Can be used any solvent, if he does not have a negative impact on the nitration of the original connection. Examples of solvents that can be used include halides such as dichloromethane, chloroform and the like; polar solvents, that is drofuran, diethyl ether and the like; esters such as ethyl acetate, methyl acetate, ethylpropane and the like; ketones, such as acetone, methyl ethyl ketone, utilizability and the like. These solvents can be used individually or as a mixture of two or more solvents.

The method in accordance with the reaction scheme (1) is conducted at a temperature in the range from -20 to 80oC and preferably from 0 to 60oC. the reaction Time varies from 0.5 to 10 hours, preferably from 1 to 8 hours.

The number nitrouse agent, which is used when carrying out the reaction (1) is typically in the range of from 2.0 to 500, preferably from 3.0 to 400, based on the molar relationship of the agent to WAmH(6-m). The number of accelerator nitration used to carry out the reaction is from 1.0 to 500, preferably from 1.5 to 300, based on molar relationships accelerator to WAmH(6-m).

In the nitrosation reaction in accordance with reaction scheme (2) as a starting compound can be used any allstargame derived hexaazatetracyclo formula WAnH(6-n)regardless of how you obtain it. However, it is preferable to use the UB> in the presence of Alliluyeva agent and additional recovery diarylethylenes of the obtained product in the absence of Alliluyeva agent, for example as described in PCT publication N WO96/23792. In more detail this process will be described below.

In the nitrosation reaction in accordance with reaction scheme (2) as starting compound, which are WA4H2and WA5H1can be used individually or as a mixture of two compounds. Connection WA4H2and WA5H1can be mixed with each other in any proportion and easily converted into nitroso compounds, as they may be respectively nitrotyrosine the same way.

As an agent in the method in accordance with the reaction scheme (2) can be used any nitrotyrosine agent capable of nitrotyrosine connection WAnH(6-n)obtaining WAnHS(6-n). For example, can be used nitrotyrosine agents, such as nitrous acid, cityregional nitrogen, salt microzone, nitrosylchloride and the like, which nitrosonium ions are strongly electrophilic. Nitrous acid may be used alone or as a mixture, sostojanija acid or the like. Preferably can be used in salt microzone, such as nitrosodimethylamine, nitrosoperoxycarbonate and such as salts of such fluoride ions are negative and increase ELECTROPILOT ions microzone. The number nitrotyrosine agent that can be added in accordance with the present invention, varies from 1 to 200 moles, preferably from 3 to 150 moles, and more preferably from 4 to 100 moles per mole WAnH(6-n).

Usually the nitrosation reaction (2) is carried out in the presence of a solvent, although it is possible its implementation and without solvent. Can be used any solvent, if he does not have a negative impact on the nitrosation. Examples of solvents that can be used include halides such as dichloromethane, chloroform, carbon tetrachloride and the like; polar solvents such as acetonitrile, sulfolane, dimethylformamide, dimethylacetamide and the like; carboxylic acids such as acetic acid, propionic acid and the like; anhydrides of carboxylic acids, such as acetic anhydride, propionic anhydride and the like; ethers such as tetrahydrofuran, diethyl ether and the like; with the ketone, utilizability and the like; water, pyridine, etc., These solvents can be used individually or as a mixture of two or more solvents.

The nitrosation reaction in accordance with reaction scheme (2) can be carried out at temperatures in the range from -50 to 200oC, preferably from -30 to 150oC and more preferably from -20 to 100oC.

Besides containing nitrogroup derivatives hexaazatetracyclo formula (I) can also be obtained by nitration WAnNS(6-n)obtained in accordance with reaction scheme (2) by using nitrouse agent, as shown in the following reaction scheme (3):

WAnNS(6-n)---> WAnN(6-n), (3)

where n represents an integer of 4 or 5, A is an acyl group containing 1-10 carbon atoms, and each acyl group is the same or different from one or more of the other NS represents nitrosourea, N represents a nitro-group, W represents a hexavalent hexaazatetracyclo the rest.

As source material in the nitration reaction scheme (3) is used WA4NS2and WA5NS1, SUB>5NS1can Mitrovitsa equally, the mixture can consist of these compounds in any ratio. Mixtures containing WA4NS1H1which can be formed by carrying out reaction according to scheme (2), and WA4H2and WA5H1that is not reacted during the course of performing such reactions can be used as starting materials in the reaction according to scheme (3).

For the method in accordance with the reaction scheme (3) can be used in the same nitrouse agent, solvent and reaction conditions, including reaction temperature, etc. that described above for the reaction of nitration in accordance with the reaction scheme (1).

Connection WAnH(6-n)that is a starting material in the above reaction schemes (1) and (2) may be obtained in accordance with the method, according to the following reaction scheme (4):

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Stage 1): recovery diarylethylene in the presence Alliluyeva agent

Stage 2): recovery diarylethylene in the absence Alliluyeva agent,

where m takes integer values 4-6, A represents an acyl group containing 1-10 carbon atoms, a being is arylmethyl group, H represents a hydrogen atom, and W represents a hexavalent, hexaazatetracyclo the rest.

That is, the connection WAmH(6-m)can be obtained by reconstruction diarylethylene WB6in the presence of Alliluyeva agent with obtaining WAmB(6-m)(stage 1), and then by restorative diarylethylene get WAmB(6-m)(stage 2).

In stage 1) of reaction scheme (4) recovery diarylethylene WB6with allermuir agent is usually carried out in the presence of a reducing agent by contact with catalyst recovery. In this case, can be used any combination of reducing agent and catalyst, if this combination can diarylethylene WB6. As reducing agents may be used hydrogen, formic acid and the like, it is preferable to use hydrogen. Examples of catalysts that may be used include platinum group metals and their derivatives. Preferably can be used in Pd and its derivatives, such as Pd(OAc)2, PdCl2Pd(NO3)2, PdO, Pd(OH)2Pd3Pb1Pd3Te1and under the Pd and its derivatives, such as Pd(OAc)2, PdCl2and similar. These catalysts can be used as they are, or deposited on carriers such as activated carbon, silica, alumina, silica - alumina, zeolite, activated clay and the like. Before use in the reaction, the catalysts may be subjected to recovery processing. If the solid catalysts, acidic surface sites can be inactivated by sililirovanie or acylation, although their surface acidity can be modified by adsorption of alkaline materials such as NaOH and the like. The amount of catalyst may depend on restoring activity, but usually the catalyst may be used in amounts of from 0.0001 to 20, preferably from 0.001 to 10, based on the mass ratio of metal content in the catalyst to WB6.

In stage 1) of reaction scheme (4) can be used any allerease agent, if he is able to allievate secondary amines. Examples alleluya agents include esters of carboxylic acids N-hydroxysuccinimide, such as N-acetoxystyrene, N-propionylcarnitine, N-(2-phenylacetate)succinimide and the like; angeri is midride and anhydride of formic acid and the like; illimitably, such as acetylimidazole, propylimidazol and the like; mixtures of panelbased and anhydrides of carboxylic acids, such as mixtures of panelbased and acetic anhydride and the like. Among these alleluya agents, esters of carboxylic acids N-hydroxysuccinimide (esters of N-hydroxysuccinimide), such as N-acetoxystyrene, N-propionylcarnitine and the like are preferable, since these esters enhance selective education WA6. These alleluya agents can be used alone or as a mixture of two or more compounds. The mixture of esters of carboxylic acids N-hydroxysuccinimide, such as N-acetoxystyrene, N-propionylcarnitine and the like, and anhydrides of carboxylic acids, such as acetic anhydride, propionic anhydride and the like, especially preferred as the compounds not only increase the speed of the reaction in stage 1) of reaction scheme (4), but also increase selective education WA4H2and WA5H1.

In stage 1) of reaction scheme (4) number Alliluyeva agent depends on his reaction method and reaction conditions, and is in the range from 4 to 100, and preferably in the interval is-hydroxysuccinimide ester and carboxylic acid anhydride as Alliluyeva agent, the amount of carboxylic acid anhydride is in the range from 0.01 to 100, preferably from 0.1 to 10, based on molar relationships anhydride to air.

As the solvent used in stage 1) of reaction scheme (4), may be used any solvent, if it dissolves WB6and if it does not adversely affect the reaction. Examples of such solvents include aromatic compounds such as benzene, toluene, ethylbenzene, xylene, cumene, cimen, diisopropylphenol, phenethyl ether and the like; amide compounds such as dimethylacetamide and the like; cyclic, linear and branched ethers, such as tetrahydrofuran, dioxane, tetrahydropyran, diethyl ether, DIPROPYLENE ether, diisopropyl ether, diethyl ether of ethylene glycol, dimethyl ether of diethylene glycol and the like; and aliphatic alcohols, such as methanol, ethanol, propanol, isopropyl alcohol, tert. -butyl alcohol and the like. These solvents may be used independently or as a mixture of two or more solvents. Of these aromatic compounds such as benzene, toluene, ethylbenzene, xylene and the like, can be used preferably since they increases the of solvent may depend on its dissolving ability and reaction temperature, but a solvent may be used in the range from 0.1 to 100, preferably from 1 to 100, based on the mass relations of the specified solvent to WB6.

In stage 1 of the reaction scheme (4) the reaction pressure is usually in the range from 0.01 to 100 MPa and preferably in the range from 0.1 to 30 MPa. If the reductant is hydrogen, then the higher the reaction pressure, the more in some cases increases the reaction rate. Therefore, the reaction pressure should be set in the range of preferably from 0.01 to 50 MPa and more preferably in the range from 0.1 to 20 MPa, based on the partial pressure of hydrogen. In addition, hydrogen can be inert gases such as nitrogen, argon, helium, etc.

The reaction temperature in stage 1 of the reaction scheme (4) is typically in the range of from -20 to 300oC and preferably from 0 to 200oC.

The reaction time in stage 1 of the reaction scheme (4) may vary depending on the catalyst, Alliluyeva agent, solvent, and reaction conditions that are used at this stage, but typically is in the range from 0.1 to 500 hours and preferably in the range from 1 to 200 hours.

At the stage of alzavano as WAmB(6-m)used for rehabilitation diarylethylene, regardless of the method of receipt.

In stage 2 in the reaction scheme (4) can be used any way, if he is able to provide diarylethylene connection WAmB(6-m). Diarylethylene usually carried out in the presence of a reducing agent by contacting the specified agent with the catalyst recovery.

As the reducing agent can be hydrogen, hydrazine, formic acid and similar compounds, and preferably is hydrogen. As catalysts may be used platinum metals and their derivatives. Preferably can be used in Pd and its derivatives, such as Pd(OAc)2, PdCl2Pd(NO3)2, PdO, Pd(OH)2Pd3Pb1Pd3Te1and similar compounds, as well as EN and its derivatives, such as RuCl3and similar. It is most preferable to use Pd and its derivatives, such as Pd(OAc)2, PdCl2and similar. These catalysts can be used as they are or deposited on carriers such as activated carbon, silica, oxide of the AI, these catalysts may be subjected to recovery processing. If the solid catalysts, acidic surface sites can be inactivated by sililirovanie or acylation, although their surface acidity can be modified by adsorption of alkaline materials such as NaOH and the like.

In stage 2 of the reaction scheme (4) the amount of the catalyst may depend on restoring activity, but the catalyst may be used in amounts of from 0.0001 to 10 and preferably from 0.001 to 1, based on the mass relations of the metal content in the specified catalyst to WAmB(6-m).

As the solvent used in stage 2 of the reaction scheme (4), may be used any solvent, if it dissolves the connection WAmB(6-m)and if it does not adversely affect the reaction rehabilitation diarylethylene. Examples of solvents include carboxylic acids such as acetic acid, propionic acid, butyric acid and the like; amide compounds such as dimethylacetamide and the like compounds; and amines, such as N,N-dimethylaniline and the like. These solvents may be used alone or as a mixture of two or more solvents. Carboxylic Ki is the viewpoint of the reaction rate.

In stage 2 of the reaction scheme (4) the amount of solvent that must be used can vary depending on its dissolving ability and reaction temperature. The solvent may be used in the range from 1 to 500 and preferably in the range from 5 to 100 mass ratio of the specified solvent to the compound WAmB(6-m).

The reaction pressure in stage 2 of the reaction scheme (4) is usually in the range from 0.01 to 100 MPa and preferably in the range from 0.1 to 10 MPa. If the reducing agent is hydrogen, the reaction pressure at this stage should be set in the range of preferably from 0.01 to 50 MPa and more preferably from 0.1 to 10 MPa, based on the partial pressure of hydrogen. In addition to the hydrogen gas may be an inert gas, such as nitrogen, argon, helium, etc.

The reaction temperature in stage 2 of the reaction scheme (4) is typically in the range of from -20 to 300oC and preferably from 0 to 200oC.

The reaction time in stage 2 of the reaction scheme (4) may vary depending on the catalyst, Alliluyeva agent, solvent and other conditions that are used at this stage, CLASS="ptx2">

The following is a description of the method of obtaining hexanitrohexaazaisowurtzitane derived from hexaazatetracyclo General formula (I) or (III). Hexanitrohexaazaisowurtzitane easily obtained by nitration derivatives hexaazatetracyclo General formula (I) or (III).

First, as shown in the following reaction scheme (5), hexanitrohexaazaisowurtzitane can be obtained by nitration of a derivative of General formula (I):

WAnN(6-n)---> WN6, (5)

As the source of material used in the method of the reaction scheme (5), serve as connection WA4N2and WA5N1that can be used alone or as a mixture of two compounds. Source material rubs contain WA4N1H1THAT WA3N3THAT WA2N4and WA1N5that might be formed in the reaction described in scheme (1), and WA4N2THAT WA5N1and WA6that remain unreacted after the specified process. For the method of reaction scheme (5), can be used the same accelerators nitration reaction, the solvent and reaction conditions, including reaction temperature, etc. that were described above Dios agent, as described for the nitration reaction scheme (1), and as nitrouse agent, it is preferable to use a mixture of nitric acid and accelerator nitration, since the rate of nitration can be increased. When using nitrouse agent consisting of nitric acid and a catalyst for the nitration, the amount of nitric acid is usually in the range from 6.0 to 500 and preferably from 9 to 400, based on molar relationships nitric acid to WAmH(6-m). The reaction temperature is in the range from -20 to 140oC and preferably from 0 to 120oC. the reaction Time for the reaction scheme (5) is in the range from 0.5 to 120 hours, and preferably from 1 to 50 hours.

Secondly, as shown in the following reaction scheme (6), hexanitrohexaazaisowurtzitane can be obtained nitrated derivative hexaazatetracyclo containing nitrosourea, and represented by the General formula (III):

WAnNS(6-n)---> WN6, (6)

As the source material for nitration in accordance with the reaction scheme (6) can be WA4NS2and WA5NS1that can be used alone or as a mixture of two compounds. Source may (2), and WA4H1and WA5H1that remain unreacted. In the way described by the reaction scheme (6), can be used the same nitrouse agent, solvent, reaction temperature and other reaction conditions described for the reaction of nitration in accordance with the reaction scheme (1).

Instead of a stepwise reaction method, consisting of combinations, such as the reaction schemes (1) and (5), (2) and (6), or (2), (3) and (5), hexanitrohexaazaisowurtzitane can also be obtained using the one-stage method of nitration WAmH(6-m)under the same conditions described above for reaction scheme (5) or (6), as shown in the following reaction scheme (7):

WAmH(6-m)---> WN6, (7)

where m takes integer of 4-6, A represents an acyl group containing 1-10 carbon atoms, and each acyl group is the same or different from one or more of the other H represents a hydrogen atom, N represents a nitro-group, W represents a hexavalent hexaazatetracyclo the rest.

For the method according to reaction scheme (7), can be used the same source material, nitrouse agent, rastvoritelei method is usually in the range from -20 to 140oC and preferably from 0 to 120oC. the reaction Time of the method is 0.5 to 120 hours, and preferably from 1 to 50 hours.

Derivatives hexaazatetracyclo formulas (I) and (III), which can be obtained in accordance with the present invention, useful as precursors hexanitrohexaazaisowurtzitane, which is a highly explosive substance.

Examples

Hereinafter the present invention will be described in more detail using the following examples. However, these examples should not be construed as limiting the scope of invention.

Example 1 WA4H2---> WN6< / BR>
The reactor volume of 200 ml was placed in a water bath with a temperature of 0oC. In a reactor add 17,50 g of 97% sulfuric acid and then slowly dropwise with stirring using a mixer add 5,63 grams of 98% nitric acid. To the resulting mixture of 1.00 g tetraazacyclotetradecane. The resulting mixture was heated to 60oC and then conduct the reaction within 24 hours. Upon completion of the reaction, the resulting reaction solution was added dropwise into 250 g of ice water. The resulting mixture is left to stand and then filtered through a membrane filter, recip is isovorticity, yield 98%. The structure of the product analyzed as follows.

Data infrared (IR) absorption spectroscopy of a specimen prepared from the product in the form of tablets with KBr, confirm the IR absorption in the region 1605 cm-1that is attributed to the asymmetric stretching vibrations of the nitro groups, two bands of infrared absorption in the region 1325 cm-1and 1270 cm-1which are attributed to the symmetric stretching vibrations of the nitro groups, two bands of infrared absorption in the region 945 cm-1and 880 cm-1ascribed to deformation vibrations of the nitro group, and the band IR absorption in the region 3030 cm-1that is attributed to the stretching vibrations of marinovich groups hexaazatetracyclo skeleton (hereinafter referred to as W-skeleton).

Such characteristics of the infrared absorption spectrum identical characteristics hexanitrohexaazaisowurtzitane described in "Combustion and Flame 87", 145-151, 1991.

In addition, disappears band IR absorption in the region of 1680 cm-1that is attributed to the carbonyl groups (C=O) of acetyl groups contained in tetraazacyclotetradecane, which was used as the starting material.

From the above analysis, it is Ethan a nitro group.

In addition, the analysis was performed using high performance liquid chromatography in the same way as described in "INTERNATIONAL SYMPOSIUM ON ENERGETIC MATERIALS TECHNOLOGY PROCEEDINGS", 24-27 September 1995 , S. 76-81, where the properties and characteristics hexanitrohexaazaisowurtzitane. It is established that the retention time of the product coincides with the time given in this publication.

Moreover, EI-mass spectroscopy product contains a fragment ion peak 392 (original ion-NO2), and the peaks of ions 316, 213 and 46 (NO2). These peaks ions also identical to the peaks shown in the aforementioned publication "INTERNATIONAL SYMPOSIUM ON ENERGETIC MATERIALS TECHNOLOGY PROCEEDINGS", 24-27 September 1995, S. 76-81.

Example 2 WA5H1---> WN6< / BR>
The reactor volume of 200 ml was placed in a water bath with a temperature of 0oC. In a reactor add 15,56 g of 97% sulfuric acid and then into the reactor under stirring using a stirrer slowly added dropwise to 5.00 g of 98% nitric acid. To the resulting mixture of 1.00 g PENTAERYTHRITE. The resulting mixture was heated to 60oC, and then conduct the reaction within 24 hours. Upon completion of the reaction, the resulting reaction solution was added to 250 g of ice water. The mixture of the with 250 g of purified water, getting 1,14 g hexanitrohexaazaisowurtzitane, yield 98%.

As a result of structural analysis of solid substances in accordance with the order, as described in Example 1, we discovered that get hexanitrohexaazaisowurtzitane.

Example 3 WA6---> WN6< / BR>
The reactor volume of 200 ml was placed in a water bath with a temperature of 0oC. In a reactor add 14,00 g of 97% sulfuric acid, and then with stirring using a stirrer slowly added dropwise 4,50 g 98% nitric acid. To the resulting mixture of 1.00 g hexaazatetracyclo. The resulting mixture was heated to 60oC, and then conduct the reaction within 24 hours. Upon completion of the reaction, the resulting reaction solution was added dropwise into 250 g of ice water. The resulting mixture is left to stand and then filtered through a membrane filter, receiving solid. The solid is washed with 250 g of purified water, getting 1,02 g hexanitrohexaazaisowurtzitane, yield 98%.

Analysis of the structure of solids in accordance with the description of Example 1 acknowledges receipt hexanitrohexaazaisowurtzitane.

Example 4 WA4H2---> WN6< / BR>
The reactor volume of 200 ml was placed in a water bath with the pace of dobavlaut 6.11 g triperoxonane acid. To the resulting mixture of 1.00 g tetraazacyclotetradecane. The resulting mixture was heated to 100oC and then conduct the reaction for 3 hours. Upon completion of the reaction, the resulting reaction solution was subjected to evaporation with the solvent, obtaining a solid substance. Solid neutralize 10% aqueous solution of NaHCO3, washed with water and dried to extract solids. The solid is dissolved in acetonitrile and analyzed by high-performance liquid chromatography. The result of the analysis confirms receipt hexanitrohexaazaisowurtzitane with a yield of 20%.

In addition, analysis of the structure of solids in accordance with the description of Example 1 acknowledges receipt hexanitrohexaazaisowurtzitane.

Example 5 WA6---> WN6< / BR>
The reactor volume of 200 ml was placed in a water bath with a temperature of 0oC. In a reactor add 18,00 g 98% nitric acid and then with stirring using a mixer add 8,14 g triperoxonane acid. To the resulting solution was added to 1.00 g hexaazatetracyclo. The resulting mixture was heated to 100oC and then conduct the reaction for 3 hours. Upon completion of the reaction obtained by rasara NaHCO3, washed with water and dried to remove solids. The solid is dissolved in acetonitrile and analyzed by high-performance liquid chromatography. The results of the analysis indicate that the received hexanitrohexaazaisowurtzitane, yield 18%.

In addition, analysis of the structure of solids in accordance with the description of Example 1 acknowledges receipt hexanitrohexaazaisowurtzitane.

Example 6 WA4H2---> WN6< / BR>
The reactor volume of 200 ml was placed in a water bath with a temperature of 0oC. In the reactor type of 11.25 grams of 98% nitric acid, followed by stirring using a stirrer add 7,14 g of sulfuric anhydride. To the resulting solution was added to 1.00 g tetraazacyclotetradecane with the mixture. The resulting mixture was heated to 60oC and then conduct the reaction within 24 hours. Upon completion of the reaction, the resulting reaction solution was added to 250 g of ice water. The resulting mixture is left to stand and then filtered through a membrane filter, receiving solid, which was washed with 250 g of purified water. Obtain 1.29 g hexanitrohexaazaisowurtzitane, a yield of 99%.

Structural analysis of solids in accordance with the UB>6---> WN6< / BR>
The reactor volume of 200 ml was placed in a water bath with a temperature of 0oC. In a reactor add 18,00 g 98% nitric acid and then with stirring using a mixer add 5,71 g of sulfuric anhydride. To the resulting solution was added to 1.00 g hexaazatetracyclo with the mixture. The resulting mixture was heated to 60oC and then conduct the reaction within 24 hours. Upon completion of the reaction, the resulting reaction solution was added to 250 g of ice water. The resulting mixture is left to stand and then filtered through a membrane filter, receiving solid, which was washed with 250 g of purified water. Get 1,03 g hexanitrohexaazaisowurtzitane, a yield of 99%.

The structure of the solids analyzed in accordance with the description of Example 1. Data analysis confirms receipt hexanitrohexaazaisowurtzitane.

Example 8 WA4H2---> WN6< / BR>
The reactor volume of 200 ml was placed in a water bath with a temperature of 0oC. In a reactor add 22,50 grams of 98% nitric acid and then with stirring using a mixer add 12,67 g of phosphorus pentoxide. To the resulting solution was added to 1.00 g tetraazacyclotetradecane. The resulting mixture is heated added dropwise into 250 g of ice water. The resulting mixture is left to stand for sediment. The precipitate is filtered off from the resulting solution and washed with water to extract the sediment. The residue is dissolved in acetonitrile and analyzed by high-performance liquid chromatography. The data obtained confirm that you have received hexanitrohexaazaisowurtzitane, yield of 11%.

Analysis of the structure of the resulting sludge in accordance with the description of Example 1 confirms that the received hexanitrohexaazaisowurtzitane.

Example 9 WA6---> WN6< / BR>
The reactor volume of 200 ml was placed in a water bath with a temperature of 0oC. In a reactor add 18,00 g 98% nitric acid and then with stirring using a mixer add 10,14 g of phosphorus pentoxide. To the resulting solution was added to 1.00 g hexaazatetracyclo. The resulting mixture was heated to 100oC and then conduct the reaction for 3 hours. Upon completion of the reaction, the resulting reaction solution was added dropwise into 250 g of ice water. The resulting mixture is left to stand for sediment. The precipitate is extracted by filtration from the mixture and washed with water to precipitation. The residue is dissolved in acetonitrile and analyzed by visocosity, exit 9%.

Analysis of the structure of the resulting sludge in accordance with the description of Example 1 confirms that the received hexanitrohexaazaisowurtzitane.

Example 10 WA4H2---> WN6< / BR>
The reactor volume of 200 ml was placed in a water bath with a temperature of 0oC. In a reactor add 22,50 grams of 98% nitric acid and then with stirring using a stirrer type of 11.25 g of Nafion-NR50. To the resulting solution was added to 1.00 g tetraazacyclotetradecane. The resulting mixture was heated to 100oC and then conduct the reaction for 3 hours. Upon completion of the reaction, the resulting reaction solution was added dropwise into 250 ml of water. The resulting mixture is left to stand for sediment. The precipitate is extracted by filtration from the mixture, washed with 250 ml of purified water, extracted by filtering and add 50 ml of acetone. The resulting mixture is stirred and filtered to separate Nafion-NR50. The obtained filtrate evaporated in vacuum to remove the solvent, to obtain a solid reaction product. The obtained product is dissolved in acetonitrile and analyzed by high-performance liquid chromatography. Data analysis confirmed that the obtained hexanitrohexaazaisowurtzitane the Yong hexanitrohexaazaisowurtzitane.

Example 11 WA4H2---> WN6< / BR>
The reactor volume of 200 ml was placed in a water bath with a temperature of 0oC. In the reactor type of 20.00 g of 98% nitric acid and then with stirring using a mixer add 10 g of Nafion-NRSO. To the resulting solution was added to 1.00 g tetraazacyclotetradecane. The resulting mixture was heated to 100oC and then conduct the reaction for 3 hours. Upon completion of the reaction, the resulting reaction solution was added dropwise into 250 ml of oxen. The resulting mixture is left to stand for the formation of a precipitate. The precipitate was separated by filtration from the mixture, washed with 250 ml of purified water, filtered off and add 50 ml of acetone. The resulting mixture is stirred and filtered to separate Nafion-NR50. The obtained filtrate evaporated in vacuum to remove the solvent, to obtain a solid reaction product. The obtained product is dissolved in acetonitrile and analyzed by high-performance liquid chromatography. Data analysis confirmed that the obtained hexanitrohexaazaisowurtzitane, yield 55%.

Analysis of the structure of the product in accordance with the description of Example 1 confirms that the received hexanitrohexaazaisowurtzitane.

Example 12 WA4H2---> WN<98% nitric acid and then with stirring using a stirrer type of 11.25 g of Tris-(bis-(heptadecafluorooctyl)imila)of ytterbium (III). To the resulting solution was added to 1.00 g tetraazacyclotetradecane. The resulting mixture was heated to 100oC and then conduct the reaction for 3 hours. Upon completion of the reaction, the resulting reaction solution was added dropwise into 250 ml of water. The resulting mixture is left to stand for the formation of a precipitate. The precipitate is filtered off from the mixture, washed with 250 ml of purified water, isolated by filtration from the mixture obtained. To selected draught add 50 ml of acetone. The resulting mixture is stirred and filtered to separate Tris-(bis- (heptadecafluorooctyl)imide)of ytterbium (III). The obtained filtrate evaporated in vacuum to remove the solvent, to obtain a solid reaction product. The obtained product is dissolved in acetonitrile and analyzed by high-performance liquid chromatography. Data analysis confirmed that the obtained hexanitrohexaazaisowurtzitane, yield 17%.

Analysis of the structure of the product in accordance with the description of Example 1 confirms that the received hexanitrohexaazaisowurtzitane.

Example 13 WA5H1---> WN6< / BR>
The reactor volume of 200 ml was placed in a water bath with a temperature of 0oC. In the reactor type of 20.00 g of 98% nitric acid and then taken to the solution is added to 1.00 g PENTAERYTHRITE. The resulting mixture was heated to 100oC and then conduct the reaction for 3 hours. Upon completion of the reaction, the resulting reaction solution was added dropwise into 250 ml of water. The resulting mixture is left to stand for the formation of a precipitate. The precipitate is filtered off, washed with 250 ml of purified water, extracted by filtration from the mixture obtained. To selected draught add 50 ml of acetone. The resulting mixture is stirred and filtered to separate Tris-(bis-(heptadecafluorooctyl)imide) of ytterbium (III). The obtained filtrate evaporated in vacuum to remove the solvent, to obtain a solid reaction product which is dissolved in acetonitrile and analyzed by high-performance liquid chromatography. Data analysis confirmed that the obtained hexanitrohexaazaisowurtzitane, exit 13%. Analysis of the structure of the product in accordance with the description of Example 1 confirms that the received hexanitrohexaazaisowurtzitane.

Example 14 WA4H2---> WN6< / BR>
The reactor volume of 200 ml was placed in a water bath with a temperature of 0oC. In the reactor type of 20.00 g of 98% nitric acid and then with stirring using a mixer add 4 g of Tris-(bis-(heptadecafluorooctyl)imide)lanthanum (III)>
C and then conduct a reaction for 5 hours. Upon completion of the reaction, the resulting reaction solution was added dropwise into 250 ml of water. The resulting mixture is left to stand for the formation of a precipitate. The precipitate is filtered off from the resulting solution, washed with 250 ml of purified water, isolated by filtration from the mixture obtained. To selected draught add 50 ml of acetone. The resulting mixture is stirred and filtered to separate Tris-(bis- (heptadecafluorooctyl)imide)lanthanum (III). The obtained filtrate evaporated in vacuum to remove the solvent, to obtain a solid reaction product which is dissolved in acetonitrile and analyzed by high-performance liquid chromatography. Data analysis confirmed that the obtained hexanitrohexaazaisowurtzitane, yield of 11%.

Analysis of the structure of the product in accordance with the description of Example 1 confirms that the received hexanitrohexaazaisowurtzitane.

Example 15 WA4H2---> WN6< / BR>
The reactor volume of 200 ml was placed in a water bath with a temperature of 0oC. In the reactor type of 20.00 g of 98% nitric acid and then with stirring using a mixer add 8 g of Tris-(bis-(nonoperational)imide)yttrium (III). To polucen who eat carry out the reaction for 2 hours. Upon completion of the reaction, the resulting reaction solution was added dropwise into 250 ml of water. The resulting mixture is left to stand for the formation of a precipitate. The precipitate is filtered off, washed with 250 ml of purified water, isolated by filtration from the mixture obtained. To selected draught add 50 ml of acetone. The resulting mixture is stirred and filtered to separate Tris-(bis-(nonoperational)imide) yttrium (III). The obtained filtrate evaporated in vacuum to remove the solvent, to obtain a solid reaction product which is dissolved in acetonitrile and analyzed by high-performance liquid chromatography. Data analysis confirmed that the obtained hexanitrohexaazaisowurtzitane, yield 16%.

Analysis of the structure of the product in accordance with the description of Example 1 confirms that the received hexanitrohexaazaisowurtzitane.

Example 16 WA4H2---> WN6< / BR>
The reactor volume of 200 ml was placed in a water bath with a temperature of 0oC. In a reactor add 22,50 grams of 98% nitric acid and then with stirring using a stirrer type of 11.25 g of zeolite ZSM-5. To the resulting solution was added to 1.00 g tetraazacyclotetradecane. The resulting mixture was heated to 100oC and then proml water. The resulting mixture is left to stand for the formation of a precipitate. The precipitate is filtered off, washed with 250 ml of purified water and was isolated by filtration of the resulting mixture. To selected draught add 50 ml of acetone. The resulting mixture is stirred and filtered to separate the zeolite ZSM-5. The obtained filtrate evaporated in vacuum to remove the solvent, to obtain a solid reaction product which is dissolved in acetonitrile and analyzed by high-performance liquid chromatography. Data analysis confirmed that the obtained hexanitrohexaazaisowurtzitane, exit 15%.

Analysis of the structure of the product in accordance with the description of Example 1 confirms that the received hexanitrohexaazaisowurtzitane.

Example 17 WA5H1---> WN6< / BR>
The reactor volume of 200 ml was placed in a water bath with a temperature of 0oC. In the reactor type of 20.00 g of 98% nitric acid and then with stirring using a mixer add 5 g of mordenite. To the resulting solution was added to 1.00 g PENTAERYTHRITE. The resulting mixture was heated to 100oC and then carry out the reaction for 6 hours. Upon completion of the reaction, the resulting reaction solution was added dropwise into 250 ml of water. Poluchennuyu by filtration from the mixture obtained. To selected draught add 50 ml of acetone. The resulting mixture is stirred and filtered to separate the mordenite. The obtained filtrate evaporated in vacuum to remove the solvent, to obtain a solid reaction product which is dissolved in acetonitrile and analyzed by high-performance liquid chromatography. Data analysis confirmed that the obtained hexanitrohexaazaisowurtzitane, yield 8%.

Analysis of the structure of the product in accordance with the description of Example 1 confirms that the received hexanitrohexaazaisowurtzitane.

Example 18 WA4H2---> WN6< / BR>
The reactor volume of 200 ml was placed in a water bath with a temperature of 0oC. In the reactor type of 20.00 g of the solution of nitric acid containing 10 mol.% N2O5to which add a 1.00 g tetraazacyclotetradecane. The resulting mixture was heated to 100oC and then conduct the reaction for 3 hours. Upon completion of the reaction, the resulting solution was evaporated to remove the solvent to obtain a solid product. The obtained solid product is neutralized 10% aqueous solution of NaHCO3, washed with purified water and dried, get a solid substance that is dissolved in acetonitrile and analyzed by wurtzite, output 15%.

In addition, analysis of the structure of solids in accordance with the description of Example 1 confirms that the received hexanitrohexaazaisowurtzitane.

Example 19 WA6---> WN6< / BR>
The reactor volume of 200 ml was placed in a water bath with a temperature of 0oC. In the reactor type of 20.00 g of the solution of nitric acid containing 10 mol.% N2O5and then, while stirring with a stir bar added to 1.00 g hexaazatetracyclo. The resulting mixture was heated to 100oC and then conduct the reaction for 3 hours. Upon completion of the reaction of the reaction solution to remove the solvent, to obtain a solid product. The obtained solid product is neutralized 10% aqueous solution of NaHCO3, washed with purified water and dried, to obtain a solid product, which was dissolved in acetonitrile and analyzed by high-performance liquid chromatography. Data analysis confirm the receipt hexanitrohexaazaisowurtzitane, yield 5%.

In addition, analysis of the structure of the solid product in accordance with the description of Example 1 confirms that the received hexanitrohexaazaisowurtzitane.

Example 20 WA4H2--> WN6< / BR>
The reactor volume with stirring using a mixer add 30,17 g of polyphosphoric acid. To the resulting solution was added to 1.00 g tetraazacyclotetradecane. The resulting mixture was heated to 100oC and then conduct the reaction for 3 hours. Upon completion of the reaction, the resulting reaction solution is added to a chemical beaker containing 250 ml of ice water. The resulting mixture was stirred for dissolving compounds derived from polyphosphoric acid obtained insoluble solid product is extracted by filtration from the mixture, washed with water and produce. The obtained solid product is dissolved in acetonitrile and analyzed by high-performance liquid chromatography. Data analysis confirm the receipt hexanitrohexaazaisowurtzitane, yield 16%.

In addition, analysis of the structure of the obtained solid product in accordance with the description of Example 1 confirms that the received hexanitrohexaazaisowurtzitane.

Example 21 WA6---> WN6< / BR>
The reactor volume of 200 ml was placed in a water bath with a temperature of 0oC. In a reactor add 18,00 g 98% nitric acid and then with stirring using a mixer add 24,14 g of polyphosphoric acid. To the resulting solution was added to 1.00 g hexaazatetracyclo. The mixture reacts at 10h, containing 250 ml of ice water. The resulting mixture was stirred for dissolving compounds derived from polyphosphoric acid, insoluble solid product is filtered off, washed with water and was isolated by filtration. Selected solid product is dissolved in acetonitrile and analyzed by high-performance liquid chromatography. Data analysis confirm the receipt hexanitrohexaazaisowurtzitane, exit 9%.

In addition, analysis of the structure of the solid product in accordance with the description of Example 1 confirms that the received hexanitrohexaazaisowurtzitane.

Example 22 WA4H2---> WN6< / BR>
The reactor volume of 200 ml was placed in a water bath with a temperature of 0oC. In a reactor add 22,50 grams of 98% nitric acid and then with stirring using a mixer add 75,00 g triperoxonane anhydride. To the resulting solution was added to 1.00 g tetraazacyclotetradecane. The resulting mixture was heated to 100oC and then conduct the reaction for 3 hours. Upon completion of the reaction, the obtained reaction solution to remove the solvent, to obtain a solid product, which is washed with 10% aqueous solution of NaHCO3and water. The obtained solid about the analysis confirm the receipt hexanitrohexaazaisowurtzitane, yield 8%.

In addition, analysis of the structure of the solid product in accordance with the description of Example 1 confirms that the received hexanitrohexaazaisowurtzitane.

Example 23 WA6---> WN6< / BR>
The reactor volume of 200 ml was placed in a water bath with a temperature of 0oC. In a reactor add 18,00 g 98% nitric acid and then with stirring using a mixer add 60,00 g triperoxonane anhydride. To the resulting solution was added to 1.00 g hexaazatetracyclo. The resulting mixture was heated to 100oC and then conduct the reaction for 3 hours. Upon completion of the reaction from the reaction solution by evaporation to remove the solvent to obtain a solid product. The product is washed with 10% aqueous solution of NaHCO3and water. The solid product is dissolved in acetonitrile and analyzed by high-performance liquid chromatography. Data analysis confirm the receipt hexanitrohexaazaisowurtzitane, the yield of 3%.

In addition, analysis of the structure of the solid product in accordance with the description of Example 1 acknowledges receipt hexanitrohexaazaisowurtzitane.

Example 24 WA4NS2---> WN6< / BR>
The reactor volume of 200 ml is placed in a water is remesiana with the help of a mixer add 4,80 g 98% nitric acid. To the resulting solution was added to 1.00 g dinitrosopentamethylenetetramine. The resulting mixture was heated to 60oC and then conduct the reaction within 24 hours. Upon completion of the reaction, the resulting reaction solution was added dropwise into 250 g of ice water. The resulting mixture is left to stand and then filtered to obtain a solid product. The solid product is washed with 250 ml of purified water, get 1,09 g hexanitrohexaazaisowurtzitane, yield 98%.

Analysis of the structure of the solid product in accordance with the description of Example 1 confirms that the received hexanitrohexaazaisowurtzitane.

Example 25. WA5NS1---> WN6< / BR>
The reactor volume of 200 ml was placed in a water bath with a temperature of 0oC. In a reactor add accounted for 14.45 g of 97% sulfuric acid and then slowly dropwise with stirring using a mixer add with 4.64 g of 98% nitric acid. To the resulting solution was added to 1.00 g moneytransferlicensecontract08. The resulting mixture was heated to 60oC and then conduct the reaction within 24 hours. Upon completion of the reaction, the resulting reaction solution was added to 250 g of ice water. The resulting mixture is left to stand and then filtered to obtain a solid p="ptx2">

Structural analysis of the solid product in accordance with the description of Example 1 confirms that the received hexanitrohexaazaisowurtzitane.

Example 26 WA5NS1---> WN6< / BR>
The reactor volume of 200 ml was placed in a water bath with a temperature of 0oC. In a reactor add 18,58 grams of 98% nitric acid and then with stirring using a stirrer type of 8.40 g triperoxonane acid. To the resulting solution was added to 1.00 g moneytransferlicensecontract08. The resulting mixture was heated to 100oC and then conduct the reaction for 3 hours. Upon completion of the reaction from the reaction solution by evaporation to remove the solvent to obtain a solid product, which neutralize 10% aqueous solution of NaHCO3and extracted by filtration from the mixture obtained. Extracted solid product is washed with water, dissolved in acetonitrile and analyzed by high-performance liquid chromatography. Data analysis confirm the receipt hexanitrohexaazaisowurtzitane, yield 8%.

In addition, analysis of the structure of the solid product in accordance with the description of Example 1 confirms that the received hexanitrohexaazaisowurtzitane.

Example 27 WAOr add 19,19 grams of 98% nitric acid and then with stirring using a mixer add 10,80 g of phosphorus pentoxide. To the resulting solution was added to 1.00 g dinitrosopentamethylenetetramine. The resulting mixture was heated to 100oC and then conduct the reaction for 3 hours. Upon completion of the reaction of the reaction solution to remove the solvent, then add 20 ml of water and filtered. Get a solid product that neutralize 10% aqueous solution of NaHCO3and was isolated by filtration of the resulting mixture. The extracted solid product is washed with water, dried, dissolved in acetonitrile and analyzed by high-performance liquid chromatography. Data analysis confirm the receipt hexanitrohexaazaisowurtzitane, yield 7%.

In addition, analysis of the structure of the solid product in accordance with the description of Example 1 confirms that the received hexanitrohexaazaisowurtzitane.

Example 28 WA4NS2---> WN6< / BR>
The reactor volume of 200 ml was placed in a water bath with a temperature of 0oC. In a reactor add 19,19 grams of 98% nitric acid and then with stirring using a mixer add 25,73 g of polyphosphoric acid. To the resulting solution was added to 1.00 g dinitrosopentamethylenetetramine. The resulting mixture was heated to 100oC and then carried out the reaction of the speaker 20 ml of water. The resulting mixture is stirred and filtered receive insoluble solid product. The obtained solid product is washed with water, dried, dissolved in acetonitrile and analyzed by high-performance liquid chromatography. Data analysis confirm the receipt hexanitrohexaazaisowurtzitane, yield of 11%.

In addition, analysis of the structure of the solid product in accordance with the description of Example 1 confirms that the received hexanitrohexaazaisowurtzitane.

Example 29 WA5NS1---> WN6< / BR>
The reactor volume of 200 ml was placed in a water bath with a temperature of 0oC. In a reactor add 19,19 grams of 98% nitric acid and then with stirring using a mixer add 63,96 g triperoxonane anhydride. To the resulting solution was added to 1.00 g moneytransferlicensecontract08. The resulting mixture was heated to 100oC and then conduct the reaction for 3 hours. Upon completion of the reaction of the reaction solution to remove the solvent, to obtain a solid product, which is washed with 10% aqueous solution of NaHCO3and water, dried, dissolved in acetonitrile and analyzed by high-performance liquid chromatography. Data analysis confirmed poluchaetstya with the description of Example 1 confirms, that obtained hexanitrohexaazaisowurtzitane.

Example 30 WA5NS1---> WN6< / BR>
The reactor volume of 200 ml was placed in a water bath with a temperature of 0oC. In the reactor type of 20.00 g of the solution of nitric acid containing 10 mol.% N2O5. Then, while stirring with a stir bar added to 1.00 g moneytransferlicensecontract08. The resulting mixture was heated to 100oC and then conduct the reaction for 3 hours. Upon completion of the reaction of the reaction solution is evaporated the solvent to obtain a solid product, which neutralize 10% aqueous solution of NaHCO3, washed with purified water and dried. Produce a solid product, which was dissolved in acetonitrile and analyzed by high-performance liquid chromatography. The data obtained confirm the receipt hexanitrohexaazaisowurtzitane, yield 5%. In addition, analysis of the structure of the solid product in accordance with the description of Example 1 confirms that the received hexanitrohexaazaisowurtzitane.

Example 31 WA4NS2---> WN6< / BR>
The reactor volume of 200 ml was placed in a water bath with a temperature of 0oC. In a reactor add 9,59 grams of 98% nitric acid and then when premarinandinterstitialcystitis. The resulting mixture was heated to 60oC and then conduct the reaction within 24 hours. Upon completion of the reaction, the reaction solution is added to 250 g of ice water. The resulting mixture is left to stand and then filtered through a membrane filter, get a solid product. The solid product is washed with 250 g of purified water, obtain 1.1 g hexanitrohexaazaisowurtzitane, a yield of 99%.

In addition, analysis of the structure of the solid product in accordance with the description of Example 1 confirms that the received hexanitrohexaazaisowurtzitane.

Example 32 WA5NS1---> WN6< / BR>
The reactor volume of 200 ml was placed in a water bath with a temperature of 0oC. In a reactor add 18,58 grams of 98% nitric acid and then with stirring using a mixer add 9,29 g Nafion-NR50. To the resulting solution was added to 1.00 g moneytransferlicensecontract08. The resulting mixture was heated to 100oC and then conduct the reaction for 3 hours. Upon completion of the reaction, the resulting reaction solution was added dropwise into 250 ml of water. The resulting mixture is left to stand for the formation of a precipitate. The precipitate was separated by filtration, washed with 250 ml of purified water and was isolated by filtration. To selected draught add the mandate under vacuum to remove solvent, get a solid reaction product. The obtained product is dissolved in acetonitrile and analyzed by high-performance liquid chromatography. Data analysis confirm the receipt hexanitrohexaazaisowurtzitane, yield 49%.

In addition, analysis of the structure of the obtained product in accordance with the description of Example 1 confirms that the received hexanitrohexaazaisowurtzitane.

Example 33 WA4NS2---> WN6< / BR>
The reactor volume of 200 ml was placed in a water bath with a temperature of 0oC. In a reactor add 18,58 grams of 98% nitric acid and then with stirring using a mixer add 9,29 g of Tris-(bis-(heptadecafluorooctyl)imide)yttrium (III). To the resulting solution was added to 1.00 g dinitrosopentamethylenetetramine. The resulting mixture was heated to 100oC and then conduct the reaction for 3 hours. Upon completion of the reaction, the resulting reaction solution was added dropwise into 250 ml of water. The resulting mixture is left to stand for the formation of a precipitate. The precipitate was separated by filtration from the mixture, washed with 250 ml of purified water and was isolated by filtration. To selected draught add 50 ml of acetone. The resulting mixture is stirred and filtered the DMA to remove solvent, get a solid reaction product which is dissolved in acetonitrile and analyzed by high-performance liquid chromatography. Data analysis confirm the receipt hexanitrohexaazaisowurtzitane, output 10%.

Analysis of the structure of the product in accordance with the description of Example 1 confirms that the received hexanitrohexaazaisowurtzitane.

Example 34 WA4NS2---> WN6< / BR>
The reactor volume of 200 ml was placed in a water bath with a temperature of 0oC. In a reactor add 18,58 grams of 98% nitric acid and then with stirring using a mixer add 3,29 g of Tris-(bis-(heptadecafluorooctyl)imide)europium 50 (III). To the resulting solution was added to 1.00 g dinitrosopentamethylenetetramine. The resulting mixture was heated to 100oC and then conduct a reaction for 8 hours. Upon completion of the reaction, the reaction solution is added dropwise into 250 g of water. The resulting mixture is left to stand for the formation of a precipitate. The precipitate is filtered off from the mixture, washed with 250 ml of purified water and was isolated by filtration. To selected draught add 50 ml of acetone to obtain a mixture. The mixture is stirred and filtered to separate Tris-(bis-(heptadecafluorooctyl reaction, which is dissolved in acetonitrile and analyzed by high-performance liquid chromatography. The data confirm the receipt hexanitrohexaazaisowurtzitane, yield 6%.

Analysis of the structure of the product in accordance with the description of Example 1 confirms that the received hexanitrohexaazaisowurtzitane.

Example 35 WA4NS2---> WN6< / BR>
The reactor volume of 200 ml was placed in a water bath with a temperature of 0oC. In a reactor add 18,58 grams of 98% nitric acid and then with stirring using a mixer add the 4.29 g of Tris-(bis-(nonoperational)imide)of ytterbium (III). To the resulting solution was added to 1.00 g dinitrosopentamethylenetetramine. The resulting mixture was heated to 90oC and then carry out the reaction for 4 hours. Upon completion of the reaction, the reaction solution is added dropwise into 250 ml of water. The resulting mixture is left to stand for forming

the precipitate. The precipitate is filtered off from the mixture, washed with 250 ml of purified water and was isolated by filtration of the resulting mixture. To selected draught add 50 ml of acetone. The resulting mixture is stirred and filtered to separate Tris-(bis-(nonoperational)imide) of ytterbium (III). The filtrate is evaporated in VA is serout using high-performance liquid chromatography. Data analysis confirm the receipt hexanitrohexaazaisowurtzitane, yield 18%.

In addition, analysis of the structure of the product in accordance with the description of Example 1 acknowledges receipt hexanitrohexaazaisowurtzitane.

Example 36 WA4N2---> WN6< / BR>
The reactor volume of 200 ml was placed in a water bath with a temperature of 0oC. In a reactor add 13,80 g of 97% sulfuric acid and then slowly dropwise with stirring using a mixer add 4.44 g of 98% nitric acid. To the resulting solution was added to 1.00 g dinitrotetraaminecobalt. The resulting mixture was heated to 60oC and then conduct the reaction within 24 hours. Upon completion of the reaction, the reaction solution is added to 250 g of ice water. The resulting mixture is left to stand and filtered through a membrane filter to obtain a solid product. The obtained solid product is washed with 250 ml of purified water, obtain 1.01 g hexanitrohexaazaisowurtzitane, yield 98%.

Structural analysis of the obtained solid product in accordance with the description of Example 1 also confirms that the received hexanitrohexaazaisowurtzitane.

Example 37 WA5N1---> WN6< / BR>
The reactor volume is edleno dropwise with stirring using a stirrer type of 4.46 g of 98% nitric acid. To the resulting solution was added to 1.00 g mononitrobenzene. The resulting mixture was heated to 60oC and then conduct the reaction within 24 hours. Upon completion of the reaction, the reaction solution is added to 250 g of ice water. The resulting mixture is left to stand and then filtered through a membrane filter for the extraction of solid product. The solid product is washed with 250 ml of purified water, get 1,05 g hexanitrohexaazaisowurtzitane, yield 98%.

Structural analysis of the obtained solid product in accordance with the description of Example 1 also confirms that the received hexanitrohexaazaisowurtzitane.

Example 38 WA5N1---> WN6< / BR>
The reactor volume of 200 ml was placed in a water bath with a temperature of 0oC. In a reactor add 17,87 grams of 98% nitric acid and then with stirring using a stirrer type of 8.09 g triperoxonane acid. To the resulting solution was added to 1.00 g mononitrobenzene. The resulting mixture was heated to 100oC and then conduct the reaction for 3 hours. Upon completion of the reaction, the resulting reaction solution was evaporated to remove the solvent to obtain a solid product, which neutralize 10% podnimetsia in acetonitrile and analyzed by high-performance liquid chromatography. Data analysis confirm the receipt hexanitrohexaazaisowurtzitane, yield 6%.

In addition, analysis of the structure of the solid product in accordance with the description of Example 1 confirms that the received hexanitrohexaazaisowurtzitane.

Example 39 WA4N2---> WN6< / BR>
The reactor volume of 200 ml was placed in a water bath with a temperature of 0oC. In a reactor add 17,75 grams of 98% nitric acid and then with stirring using a stirrer type of 10.00 g of phosphorus pentoxide. To the resulting solution was added to 1.00 g dinitrotetraaminecobalt. The resulting mixture was heated to 100oC and then conduct the reaction for 3 hours. Upon completion of the reaction from the reaction solution by evaporation to remove the solvent, then add 20 ml of water and filtered, to obtain a solid product. The obtained solid product is neutralized 10% aqueous solution of NaHCO3. The resulting mixture was filtered to separation of the solid product. The solid product is washed with water, dried, dissolved in acetonitrile and analyzed by high-performance liquid chromatography. Data analysis confirm the receipt hexanitrohexaazaisowurtzitane, exit 9%.

In addition, the analysis StreamWriter.

Example 40 WA4N2---> WN6< / BR>
The reactor volume of 200 ml was placed in a water bath with a temperature of 0oC. In a reactor add 17,75 grams of 98% nitric acid and then with stirring using a mixer add 23,80 g of polyphosphoric acid. To the resulting solution was added to 1.00 g dinitrotetraaminecobalt. The resulting mixture was heated to 100oC and then conduct the reaction for 3 hours. Upon completion of the reaction, the reaction solution is added in chemical beaker containing 20 ml of water. The resulting mixture is stirred and filtered off the insoluble solid product. The solid product is washed with water, dried, dissolved in acetonitrile and analyzed by high-performance liquid chromatography. Data analysis confirm the receipt hexanitrohexaazaisowurtzitane, yield 12%.

In addition, analysis of the structure of the solid product in accordance with the description of Example 1 confirms that the received hexanitrohexaazaisowurtzitane.

Example 41 WA5N1---> WN6< / BR>
The reactor volume of 200 ml was placed in a water bath with a temperature of 0oC. In a reactor add 17,75 grams of 98% nitric acid and then with stirring using a mixer add 59,57 Ana. The resulting mixture was heated to 100oC and then conduct the reaction for 3 hours. Upon completion of the reaction of the reaction solution is evaporated solvent. The obtained solid product is washed with 10% aqueous solution of NaHCO3and water, dried, dissolved in acetonitrile and analyzed by high-performance liquid chromatography. The data obtained confirm the receipt hexanitrohexaazaisowurtzitane, the yield of 3%.

In addition, analysis of the structure of the solid product in accordance with the description of Example 1 confirms that the received hexanitrohexaazaisowurtzitane.

Example 42 WA5N1---> WN6< / BR>
The reactor volume of 200 ml was placed in a water bath with a temperature of 0oC. In the reactor type of 20.00 g of the solution of nitric acid containing 10 mol.% N2O5and then, while stirring with a stir bar added to 1.00 g mononitrobenzene. The resulting mixture was heated to 100oC and then conduct the reaction for 3 hours. Upon completion of the reaction of the reaction solution to remove the solvent, to obtain a solid product, which neutralize 10% aqueous solution of NaHCO3, washed with purified water and dried to highlight solid produmannye analysis confirm receipt hexanitrohexaazaisowurtzitane, yield 6%.

In addition, analysis of the structure of the solid product in accordance with the description of Example 1 confirms that the received hexanitrohexaazaisowurtzitane.

Example 43 WA4N2---> WN6< / BR>
The reactor volume of 200 ml was placed in a water bath with a temperature of 0oC. In a reactor add to 8.94 g of 98% nitric acid and then with stirring using a mixer add 5,67 g of sulfuric anhydride. To the resulting solution was added to 1.00 g dinitrotetraaminecobalt. The resulting mixture was heated to 60oC and then conduct the reaction within 24 hours. Upon completion of the reaction, the resulting reaction solution was added to 250 g of ice water. The resulting mixture is left to stand and then filter for the extraction of solid product, which is washed with 250 g of purified water. Obtain 1.06 g hexanitrohexaazaisowurtzitane, a yield of 99%.

In addition, structural analysis of the solid product in accordance with the description of Example 1 also confirms that the received hexanitrohexaazaisowurtzitane.

Example 44 WA4N2---> WN6< / BR>
The reactor volume of 200 ml was placed in a water bath with a temperature of 0oC. In a reactor add 17,87 grams of 98% nitric acid and then when Illegalisation. The resulting mixture was heated to 100oC and then conduct the reaction for 3 hours. Upon completion of the reaction, the reaction solution is added dropwise into 250 ml of water. The resulting mixture is left to stand for the formation of a precipitate. The precipitate was separated by filtration, washed with 250 ml of purified water and was isolated by filtration of the resulting mixture. To selected draught add 50 ml of acetone, the resulting mixture is stirred and filtered to separate Nafion-NR50. The obtained filtrate evaporated in vacuum to remove the solvent, to obtain a solid reaction product which is dissolved in acetonitrile and analyzed by high-performance liquid chromatography. Data analysis confirm the receipt hexanitrohexaazaisowurtzitane, yield 68%.

In addition, analysis of the structure of the solid product in accordance with the description of Example 1 confirms that the received hexanitrohexaazaisowurtzitane.

Example 45 WA4N2---> WN6< / BR>
The reactor volume of 200 ml was placed in a water bath with a temperature of 0oC. In a reactor add 17,75 grams of 98% nitric acid and then with stirring using a mixer add 8,87 g of Tris-(bis-(heptadecafluorooctyl)imila)of ytterbium (III). To the resulting rectum conduct the reaction for 3 hours. Upon completion of the reaction, the reaction solution is added dropwise into 250 ml of water. The resulting mixture is left to stand for the formation of a precipitate. The precipitate is filtered off, washed with 250 ml of purified water and was isolated by filtration. To selected draught add 50 ml of acetone. The resulting mixture is stirred and filtered to separate Tris- (bis-(heptadecafluorooctyl) imide) of ytterbium (III). The obtained filtrate evaporated in vacuum to remove the solvent, to obtain a solid reaction product which is dissolved in acetonitrile and analyzed by high-performance liquid chromatography. Data analysis confirmed that the obtained hexanitrohexaazaisowurtzitane, yield 18%.

Analysis of the structure of the product in accordance with the description of Example 1 confirms that the received hexanitrohexaazaisowurtzitane.

Example 46 WA4N2---> WN6< / BR>
The reactor volume of 200 ml was placed in a water bath with a temperature of 0oC. In a reactor add 17,75 grams of 98% nitric acid and then with stirring using a stirrer type of 4.57 g of Tris-(bis-(heptadecafluorooctyl)imide)samarium (III). To the resulting solution was added to 1.00 g dinitrotetraaminecobalt. The resulting mixture nagley dropwise into 250 ml of water. The resulting mixture is left to stand for the formation of a precipitate. The precipitate is filtered off, washed with 250 ml of purified water and was isolated by filtration. To selected draught add 50 ml of acetone. The resulting mixture is stirred and filtered to separate Tris- (bis-(heptadecafluorooctyl)imide)samarium (III). The obtained filtrate evaporated in vacuum to remove the solvent, to obtain a solid reaction product which is dissolved in acetonitrile and analyzed by high-performance liquid chromatography. Data analysis confirmed that the obtained hexanitrohexaazaisowurtzitane, yield 8%.

Analysis of the structure of the product in accordance with the description of Example 1 confirms that the received hexanitrohexaazaisowurtzitane.

Example 47 WA4F2---> WN6< / BR>
The reactor volume of 200 ml was placed in a water bath with a temperature of 0oC. In a reactor add 7.50 g of 97% sulfuric acid and then slowly dropwise with stirring using a mixer add 24,11 grams of 98% nitric acid. To the resulting solution was added to 1.00 g deformalisation. The resulting mixture was heated to 100oC and then carry out the reaction for 15 hours. Upon completion of the reaction reacciones filter. Get a solid product, which is washed with 250 ml of purified water, obtain 0.87 g hexanitrohexaazaisowurtzitane, yield 78%.

Structural analysis of the solid product in accordance with the description of Example 1 acknowledges receipt hexanitrohexaazaisowurtzitane.

Example 48 WA4H2---> WA4NS2< / BR>
In a reactor with a volume of 200 ml add to 3.36 g tetraazacyclotetradecane and 100 ml of 50% acetic acid to obtain a mixture, which is then slowly added dropwise under stirring at 0oC add 20 ml of 4M aqueous solution of sodium nitrite. The resulting mixture was heated to 30oC and then carry out the reaction for 4 hours. To the resulting reaction solution was added 500 ml of chloroform. The resulting solution was intensively stirred and then allowed to stand for. The organic phase is separated from the solution and the solvent is evaporated. Get to 3.73 g dinitrosopentamethylenetetramine, yield 95%.

Below are the results of structural analysis of the product.

Range1H NMR (solvent: CDCl3standard - TMS, - dimensionless value of the chemical shift in M. D.): 2,05 (s, 6H, COCH3), 2,17 (s, 6H, COCH3), 5,46 (m, 2H, CH), 6,62 (m, 2H, CH), 7,30 (s, 2H, CH)of the obtained product are: the absorption band in the region 1670 cm-1that is attributed to the carbonyl groups (C=O) of acetyl groups, and two absorption bands in the regions 1380 cm-1and 1350 cm-1ascribed to nitrosopropane.

In addition, two absorption bands in the region between 3300 and 3400 cm-1ascribed to the NH-groups tetraazacyclotetradecane, completely disappear.

Example 49 WA4H2---> WA4NS2< / BR>
In a reactor with a volume of 200 ml add to 3.36 g tetraazacyclotetradecane and 100 ml of 35% hydrochloric acid and cooled to 0oC. To the resulting mixture is slowly added dropwise under stirring at 0oC add 20 ml of 4M aqueous solution of sodium nitrite. The resulting mixture was heated to 30oC and stirred for 4 hours. To the reaction solution was added 500 ml of chloroform. The resulting solution was intensively stirred and then allowed to stand for. The organic phase is separated from the solution and evaporated the solvent. Get 3,49 g dinitrosopentamethylenetetramine, yield 89%.

Product structure analyze analogous to Example 48. Data analysis confirm the receipt dinitrosopentamethylenetetramine.

Example 50 WA4H2---&g the red acid and cooled to 0oC. the resulting reaction solution slowly with stirring and at 0oC is blown into approximately 20 g of camerahouse nitrogen, and then stirred at 0oC for 1 hour. Upon completion of the reaction, the resulting reaction solution was evaporated the solvent in vacuo, get a solid product, which is washed with water and dried. Get to 3.73 g dinitrosopentamethylenetetramine, yield 95%.

The structure of the obtained product analyze analogous to Example 48. Data analysis confirm the receipt dinitrosopentamethylenetetramine.

Example 51 WA4H2---> WA4NS2< / BR>
In a reactor with a volume of 200 ml add to 3.36 g tetraazacyclotetradecane and 100 ml of pyridine and cooled to 0oC. To the resulting solution was slowly added dropwise with stirring and at 0oC add 10 ml of 4.8 M solution of nitrosylchloride in acetic anhydride, and then stirred for 1 hour. Upon completion of the reaction, the resulting reaction solution was added to 100 g of ice water with sediment. The precipitate is filtered off, washed with water and dried. Get 2,75 g dinitrosopentamethylenetetramine, yield 70%.

Product structure azithomycin.

Example 52 WA5H1---> WA5NS1< / BR>
In a reactor with a volume of 200 ml type of 3.78 g PENTAERYTHRITE and 100 ml of 50% acetic acid and cooled to 0oC. To the resulting mixture is slowly added dropwise with stirring and at 0oC add 20 ml of 4M aqueous solution of sodium nitrite. The resulting mixture was heated to 30oC and then stirred for 4 hours. To the resulting reaction solution was added 500 ml of chloroform, the solution rapidly stirred and then allowed to stand for. The organic phase is separated from the solution and evaporated in a vacuum solvent. Get 3,79 g moneytransferlicensecontract08, yield 93%.

Product structure analyze analogous to Example 48. Data analysis confirm the receipt moneytransferlicensecontract08.

Example 53 WA4NS2---> WA4N2< / BR>
In the reactor volume 100 ml type of 20.00 g of 98% nitric acid and 0,93 g dinitrosopentamethylenetetramine. The reaction is carried out at room temperature for 5 hours. Upon completion of the reaction of nitric acid evaporated in vacuo from the resulting reaction solution, and then washed with water and dried. Portonovo analysis of the product.

Range 1H NMR (solvent DMSO-d6standard - TMS, - dimensionless value of the chemical shift in M. D.): 2,10 (s, 12H, COCH3), to 6.75 (m, 2H, CH) and 7.35 (4H, CH, singlet at 7,35 memorial plaques with peaks on the shoulder on the side of the weak magnetic field).

The IR spectrum of the product confirmed the IR absorption in the region of 1680 cm-1ascribed to the stretching vibrations of carbonyl groups (C=O) of acetyl groups, and two bands of infrared absorption in the areas of 1570 cm-1and 1300 cm-1which are attributed to the stretching vibrations of the nitro groups, which confirms the presence of nitro and acetyl groups in the product.

EI-mass spectroscopy of the product shows the molecular ion peak m/z 426.

When determining the temperature of decomposition of the product at a heating rate of 10oC/min to a maximum temperature equal to 314oC.

Example 54 WA4NS2---> WA4N2< / BR>
The reactor volume of 200 ml was placed in a water bath with a temperature of 0oC. In the reactor, add 20 ml of N2O4and 0.4 g dinitrosopentamethylenetetramine. The reaction is carried out at 10oC for 5 hours. At the end of the reaction solution is evaporated the solvent to obtain a solid product, which neutralize 10%to 92%.

Analysis of the structure of the product in accordance with the description of Example 53 acknowledges receipt dinitrotetraaminecobalt.

Example 55 WA5NS1---> WA5N1< / BR>
The reactor volume of 200 ml was placed in a water bath with a temperature of 0oC. In the reactor, add 30 ml of 97% nitric acid and 0.96 g moneytransferlicensecontract08. The reaction is carried out at room temperature for 5 hours. At the end of the reaction solution is evaporated the solvent to obtain a solid product, which is washed with water and dried. Get mononitrotoluenes, yield 90%.

Analysis of the structure of the product in accordance with the description of Example 53 confirms that the received mononitrotoluenes.

Example 56 WA4NS2---> WA4N2< / BR>
The reactor volume of 200 ml was placed in a water bath with a temperature of 0oC. In the reactor was added 81 g of 97% sulfuric acid and slowly dropwise with stirring using a mixer add to 22.5 g 97% nitric acid. To the resulting solution was added 0.4 g dinitrosopentamethylenetetramine. The resulting mixture was stirred at 20oC for 30 minutes. On okoncane the ing liquid phase removed from the solution and the remaining solution was added 20 g of ice and then filtered. The obtained solid product is washed with 10% aqueous solution of NaHCO3and purified water, dried, dissolved in acetonitrile and analyzed by high-performance liquid chromatography. Get dinitrotetraaminecobalt, a yield of 20%.

Analysis of the structure of the solid product in accordance with the description of Example 53 acknowledges receipt dinitrotetraaminecobalt.

Example 57 WA4NS2---> WA4N2< / BR>
The reactor volume of 200 ml was placed in a water bath with a temperature of 0oC. In the reactor type of 6.95 g of the solution of nitric acid containing 10 mol.% N2O5and then, while stirring with a stir bar added to 1.00 g dinitrosopentamethylenetetramine. The reaction is carried out at 25oC for 1 hour. Upon completion of the reaction, the reaction solution is evaporated to remove solvent to obtain a solid product. The obtained solid product is neutralized 10% aqueous solution of NaHCO3and was isolated by filtration of the resulting mixture. The filtered solid product is washed with water, dried, dissolved in acetonitrile and analyzed by high-performance liquid chromatography data which confirm recip is oduct in accordance with the description of Example 53 also confirms, that obtained dinitrotetraaminecobalt.

Example 58 WA4NS2---> WA4N2< / BR>
The reactor volume of 200 ml was placed in a water bath with a temperature of 0oC. In a reactor add 18,22 g 97% nitric acid and then with stirring using a mixer add to 5.21 g triperoxonane acid. To the resulting solution was added 0.4 g dinitrosopentamethylenetetramine. The reaction is carried out at 60oC for 1 hour. Upon completion of the reaction of the reaction solution is evaporated the solvent to obtain a solid product, which neutralize 10% aqueous solution of NaHCO3and was isolated by filtration of the resulting mixture. Selected solid product is washed with water, dried, dissolved in acetonitrile and analyzed by high-performance liquid chromatography. Data analysis shows that the received dinitrotetraaminecobalt, yield 42%.

In addition, analysis of the structure of the solid product in accordance with the description of Example 53 acknowledges receipt dinitrotetraaminecobalt.

Example 59 WA4NS2---> WA4N2< / BR>
The reactor volume of 200 ml was placed in a water bath with a temperature of 0o< g phosphorus pentoxide. To the resulting solution was added 0.4 g dinitrosopentamethylenetetramine. The resulting mixture was stirred at 30oC for 30 minutes. Upon completion of the reaction of the reaction solution is evaporated the solvent, then add 20 ml of water and filtered. Get a solid product, which is washed with water, dried, dissolved in acetonitrile and analyzed by high-performance liquid chromatography. Data analysis shows that the received dinitrotetraaminecobalt, yield 56%. In addition, analysis of the structure of the solid product in accordance with the description of Example 53 acknowledges receipt dinitrotetraaminecobalt.

Example 60 WA4NS2---> WA4N2< / BR>
The reactor volume of 200 ml was placed in a water bath with a temperature of 0oC. In a reactor add 20,16 g 97% nitric acid and then with stirring using a mixer add 44,33 g of polyphosphoric acid. To the resulting solution was added 0.4 g dinitrosopentamethylenetetramine. The reaction is carried out at 40oC for 40 minutes. Upon completion of the reaction, the reaction solution was poured in chemical beaker containing 20 ml of water. The resulting mixture is stirred and filtered,enjoy using high-performance liquid chromatography. Data analysis shows that the received dinitrotetraaminecobalt, yield 56%.

In addition, analysis of the structure of the solid product in accordance with the description of Example 53 acknowledges receipt dinitrotetraaminecobalt.

Example 61 WA4NS2---> WA4N2< / BR>
The reactor volume of 200 ml was placed in a water bath with a temperature of 0oC. In a reactor add 18,22 g 97% nitric acid and then with stirring using a mixer add 60,73 g triperoxonane anhydride. To the resulting solution was added 0.4 g dinitrosopentamethylenetetramine. The reaction is carried out at 30oC for 1 hour. Upon completion of the reaction of the reaction solution is evaporated the solvent to obtain a solid product, which neutralize 10% aqueous solution of NaHCO3, washed with water, dried, dissolved in acetonitrile and analyzed by high-performance liquid chromatography. Data analysis shows that the received dinitrotetraaminecobalt, yield 72%. In addition, analysis of the structure of the solid product in accordance with the description of Example 53 acknowledges receipt dinitrotetraaminecobalt.

oC. In the reactor is added 20 g of a solution of nitric acid containing 10 mol.% N2O5and then add 0.4 g hexaazatetracyclo. The reaction is carried out at 60oC for 8 hours. Upon completion of the reaction the organic components extracted from the reaction solution with chloroform 4 times in portions of 200 ml Of the obtained mixture of chloroform evaporated in vacuum, get a solid product which was washed with 10% aqueous solution of NaHCO3and receive the mixture of nitro compounds. The resulting mixture was dissolved in acetonitrile and analyzed by high-performance liquid chromatography data which confirm the receipt dinitrotetraaminecobalt as a main component, yield 43%.

In addition, analysis of the component structure in accordance with the description of Example 53 confirms that the received dinitrotetraaminecobalt.

Example 63 WA4H2---> WA4N2< / BR>
The reactor volume of 200 ml was placed in a water bath with a temperature of 0oC. In the reactor is added 20 g of a solution of nitric acid containing 10 mol.% N2O5and then add 0.4 g tetraazacyclotetradecane. The reaction is carried out at 60o3
and receive the mixture of nitro compounds. The mixture is dissolved in acetonitrile and analyzed by high-performance liquid chromatography data which confirm the receipt dinitrotetraaminecobalt as a main component, yield 40%.

In addition, analysis of the component structure in accordance with the description of Example 53 confirms that the received dinitrotetraaminecobalt.

Example 64 WBN6---> WA4BN2< / BR>
In the above formula, A represents an acetyl group, BN represents a benzyl group, W represents a hexavalent balance hexaazatetracyclo formula (V).

In the autoclave of 300 ml download 1,89 g hexabenzylhexaazaisowurtzitane, 1.70 g of 10% Pd-C, 5 g N-acetoxystyrene, 160 ml of ethylbenzene or 3.24 g of acetic anhydride, and the rod for mixing. The atmosphere in the autoclave was replaced with gaseous hydrogen and increase the internal pressure to 5 MPa by additional supply of hydrogen gas under pressure. The reaction is carried out for 20 hours and filtered through filter paper to remove Pd-C. The solid on the filter paper was washed with 200 ml of chloroform to extract the residual reaction product. The obtained filtrate is mixed with the resulting solution of chloroform. The solvent is evaporated, get a solid product, which was dissolved in 200 ml of chloroform. To the resulting solution was added 200 ml of 28% aqueous ammonia and the mixture was intensively stirred for 30 minutes. As a result, the organic phase is separated N-acetoxystyrene. The chloroform is evaporated from the organic phase, obtain 1.39 g of white solid product, which is recrystallized from etilbenzene solution. Obtain 1.20 g of white solid, yield 87%. The obtained solid product analyzed using FD-mass spectrum, spectra1H-NMR,13C-NMR and13C1H COSY. The obtained data confirm that the solid product is tetraacetylethylenediamine. Below are the results of the analysis.

In FD-mass spectrum of the product is present peak at 517 (M+H)+.

Range1H-NMR (solvent: CDCl3standard - TMS, - dimensionless value of the chemical shift in M. D.): 1,94 (s, 6H, COCH3), of 2.15 (s, 6H, COCH3), 4,06 (d, 2H, CH

Range13C-NMR (solvent: CDCl3standard - TMS, - dimensionless value of the chemical shift in M. D.): 20,737 (CH3), 22,111 (CH3), 56,428 (CH2), 69,679 (CH), 70,592 (CH), 128,056 (Ph), 128,673 (Ph), 128,928 (Ph), 136,742 (Ph) and 168,263 (CO). This spectrum confirms the presence of acetyl groups, phenyl groups and methylene groups, benzyl groups, as well as marinovich groups of the W skeleton.

Range1H13C COSY indicates13C, connected with1N.

Example 65 WA4BN2---> WA4N2< / BR>
In the above formulas, a represents an acetyl group, BN is a benzyl group, H is a hydrogen atom, W is a hexavalent balance hexaazatetracyclo formula (V).

In the autoclave of 300 ml upload to 3.67 g tetraacetylethylenediamine, 1,60 g Pd(OAc)2and 150 ml of acetic acid, and the rod for mixing. The atmosphere in the autoclave was replaced with gaseous nitrogen and then in the autoclave serves hydrogen gas so as to raise the internal pressure to 0.5 MPa. The reaction is carried out for 15 hours under stirring with a magnetic stirrer. Upon completion of the reaction, the resulting mixture is then removed from the autoclave. The mixture Phi is Dogo substances. The solid is washed with 100 ml of ethyl acetate, get 2,33 g tetraazacyclotetradecane in the form of a white solid product, a yield of 99%. The results of the analysis of the obtained product are presented below.

Range1H-NMR (solvent: D2O, standard TMS, is a dimensionless value of the chemical shift in M. D.): 1,98 (s, 6H, COCH3), from 2.00 (s, 6H, CH3), from 5.29 (ush, 2H, CH), 5,50 (ush, 2H, CH), 6.35mm (m, 2H, CH). This spectrum confirms the presence of 4 acetyl groups and marinovich groups of the W skeleton.

The IR spectrum of the product there are two absorption bands in the region 3300-3400 cm-1which are attributed to the stretching vibrations of the secondary amines (N-H groups) and the absorption band at 1660 cm-1that is attributed to the stretching vibrations of carbonyl groups (C=O) of acetyl groups. These data confirm the presence of acetyl and NH-groups in W-skeleton.

Industrial application

Derivatives hexaazatetracyclo of the present invention are useful for obtaining hexanitrohexaazaisowurtzitane, which is a highly explosive substance.

1. The method of obtaining hexanitrohexaazaisowurtzitane formula VI

W(NO2)6,

where W represents the u,

nitration allstargame derivatives hexaazatetracyclo, wherein the nitration is subjected to one of allstargame derivatives hexaazatetracyclo selected from the group consisting of the compounds of formula I

WAn(NO2)(6-n),

where n is an integer of 4 or 5;

A are identical or different and are a C1-10-acyl group;

W and NO2have the meanings given above,

the compound of formula III

WAn(NO)(6-n),

where W, A and n are defined above;

NO is a nitroso group,

the compound of formula IV

WAmH(6-m),

where W and A have the meanings defined above;

m is an integer of 4 to 6;

H represents a hydrogen atom,

nitric acid in the presence of a catalyst for the nitration, and at least one compound selected from the group consisting of performancecounterid, represented by formula IX

RfSO2NHSO2Rf',

where H has the meaning given above;

Rf and Rf' represent performanceline group containing 1 to 8 carbon atoms;

S represents a sulfur atom;

O is an atom clipsporno acid, used as a catalyst for the nitration.

2. The method of obtaining hexanitrohexaazaisowurtzitane General formula VI nitration allstargame derivatives hexaazatetracyclo, wherein the nitration is subjected to one of allstargame derivatives hexaazatetracyclo selected from the group consisting of compounds of formulas I, III and IV, with nitric acid in the presence of a catalyst for the nitration, where the accelerator nitration is used, the carboxylic acid anhydride.

3. The method according to p. 2, wherein said carboxylic acid anhydride is triperoxonane anhydride.

4. The method of obtaining hexanitrohexaazaisowurtzitane formula VI nitration allstargame derivatives hexaazatetracyclo, wherein the nitration is subjected to one of the derivatives of hexaazatetracyclo selected from the group consisting of compounds of formulas I, III and IV, with nitric acid in the presence of a catalyst for the nitration, where the accelerator nitration using Lewis acid.

5. The method according to p. 4, which specified the Lewis acid is one of the salts of the rare earth element perftoruglerodov acids of the formula X
CLASS="ptx2">

6. The method according to p. 4, which specified the Lewis acid is one of the salts of the rare earth element perftoruglerodov formula XI

M(RfSO2NSO2Rf')3,

where M, Rf, Rf', S, N and O are defined above.

7. The method of obtaining hexanitrohexaazaisowurtzitane formula VI nitration allstargame derivatives hexaazatetracyclo, wherein the nitration is subjected to one of allstargame derivatives hexaazatetracyclo selected from the group consisting of compounds of formulas I, III and IV, with nitric acid in the presence of a catalyst for the nitration, where the accelerator nitration use strong acidic solid catalyst.

8. The method according to p. 7, wherein said solid strong acid catalyst is a strong acid solid catalyst Branstad.

9. The method according to p. 8, wherein said solid acid catalyst Branstad is a polymer containing the sulfonic acid group.

10. The method according to p. 8, wherein said solid acid catalyst Branstad is a zeolite.

11. The method of obtaining hexanitrohexaazaisowurtzitane General formula VI, which is rucenim allstargame derived hexaazatetracyclo formula I and nitration derivative of the formula I with nitric acid in the presence of a catalyst for the nitration, where at least one connection selected from the group consisting of performancecounterid formula IX, phosphorus pentoxide, sulfur trioxide, nitrogen pentoxide and polyphosphoric acid is used as the accelerator nitration.

12. The method of obtaining hexanitrohexaazaisowurtzitane formula VI, which includes the nitration nitrous agent allstargame derived hexaazatetracyclo formula IV with getting allstargame derived hexaazatetracyclo formula I and nitration derivative of the formula I with nitric acid in the presence of a catalyst for the nitration, where the accelerator nitration is used, the carboxylic acid anhydride.

13. The method according to p. 12, wherein said carboxylic acid anhydride is triperoxonane anhydride.

14. The method of obtaining hexanitrohexaazaisowurtzitane formula VI, which includes the nitration nitrous agent allstargame derived hexaazatetracyclo formula IV with getting allstargame derived hexaazatetracyclo formula I and nitration derivative of the formula I with nitric acid in the presence of a catalyst for the nitration, where as a catalyst for the nitration of ispolzuetsya rare earth element perftoruglerodov acids of formula X.

16. The method according to p. 14, in which this Lewis acid is one of the salts of the rare earth element perftoruglerodov formula XI.

17. The method of obtaining hexanitrohexaazaisowurtzitane formula VI, which includes the nitration nitrous agent allstargame derived hexaazatetracyclo formula IV with getting allstargame derived hexaazatetracyclo formula I and nitration derivative of the formula I with nitric acid in the presence of a catalyst for the nitration, where the accelerator nitration use strong acidic solid catalyst.

18. The method according to p. 17, wherein said solid strong acid catalyst is a strong acid solid catalyst Branstad.

19. The method according to p. 18, wherein said solid acid catalyst Branstad is a polymer containing the sulfonic acid group.

20. The method according to p. 18, wherein said solid acid catalyst Branstad is a zeolite.

21. The method of obtaining hexanitrohexaazaisowurtzitane General formula VI, which includes the nitrosation nitrotyrosine agent allstargame proizvodnog the III and nitration derivative of the formula III nitric acid in the presence of a catalyst for the nitration, where at least one connection selected from the group consisting of performancecounterid formula IX, phosphorus pentoxide, sulfur trioxide, nitrogen pentoxide and polyphosphoric acid is used as the accelerator nitration.

22. The method of obtaining hexanitrohexaazaisowurtzitane formula VI, which includes the nitrosation nitrotyrosine agent allstargame derived hexaazatetracyclo formula IV with getting allstargame derived hexaazatetracyclo formula III and nitration derivative of the formula III nitric acid in the presence of a catalyst for the nitration, where the accelerator nitration is used, the carboxylic acid anhydride.

23. The method according to p. 22, wherein said carboxylic acid anhydride is triperoxonane anhydride.

24. The method of obtaining hexanitrohexaazaisowurtzitane formula VI, which includes the nitrosation nitrotyrosine agent allstargame derived hexaazatetracyclo formula IV with getting allstargame derived hexaazatetracyclo formula III and nitration derivative of the formula III nitric acid in the presence of a catalyst for the nitration, where the accelerator is n, which defaults to one of the salts of the rare earth element perftoruglerodov acids of formula X.

26. The method according to p. 24, which specified the Lewis acid is one of the salts of the rare earth element perftoruglerodov formula XI.

27. The method of obtaining hexanitrohexaazaisowurtzitane formula VI, which includes the nitrosation nitrotyrosine agent allstargame derived hexaazatetracyclo formula IV with getting allstargame derived hexaazatetracyclo formula III and nitration derivative of the formula III nitric acid in the presence of a catalyst for the nitration, where the accelerator nitration use strong acidic solid catalyst.

28. The method according to p. 27, wherein said solid strong acid catalyst is a strong acid solid catalyst Branstad.

29. The method according to p. 28, wherein said solid acid catalyst Branstad is a polymer containing the sulfonic acid group.

30. The method according to p. 28, wherein said solid acid catalyst Branstad is a zeolite.

 

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