RU2828547C1 - Cyano-polynitro-2,4,6,8,10,12-hexaazaisowurtzitanes and methods for production thereof - Google Patents

Abstract

FIELD: organic chemistry.

SUBSTANCE: invention relates to organic chemistry, namely to polycyclic framework nitro compounds, specifically to novel cyano-polynitro-2,4,6,8,10,12-hexaazaisowurtzitans of general formula (I), which can be used as high-energy components of mixed solid rocket fuels. In formula (I) R=H (Ia), NO (Ib), CH₂C(NO₂)₃ (Ic), NO₂ (Id), CN (Ie).

EFFECT: invention also relates to methods of producing said compounds.

5 cl, 1 tbl, 5 ex

Description

The proposed invention relates to the field of organic chemistry, namely to the chemistry of polycyclic framework and nitro compounds, specifically to new, undescribed in the literature, energy-intensive cyano-polynitro-2,4,6,8,10,12-hexaazaisowurtzitanes of the general formula:

where R=H (Ia), NO (Ib), _CH2C ( _NO2 ) ₃ (Iv), _NO2 (Ig); CN (Id), and to methods for their production.

Compounds of formula I can find application as high-energy components of mixed solid rocket fuels. The literature presents energetic nitriles of the general formula:

Where

1) R ¹ =CH ₂ N(NO ₂ )CH ₂ CN, CH ₂ CH ₂ N(NO ₂ )CH ₂ CH ₂ CN [Y. Oyumi, A.L. Rheingold, T.B. Brill, "Thermal decomposition of energetic materials xviii. bis(cyanomethyl)nitramine and bis(cyanoethyl)nitramine", Propellants Explos. Pyrotech., 1987, 12, 1-7];

2)

[(a) Yu. M. Mikhailov, S. V. Chapyshev, V. V. Nedel'ko, "Synthesis, thermal stability, heats of formation, and explosive properties of cyano-substituted di-, tri-, and tetraazidopyridines", Russ. Chem. Bull., 2009, 58, 2097–2102; (b) S. V. Chapyshev, D. V. Korchagin, Yu. V. Ganin, E. N. Ushakov, "Synthesis, structure, and properties of high-energy tetraazidopyridine-4-carbonitrile", Chem. Heterocycl. Comp., 2017, 53, 786–790];

3)

[(a) F. Boneberg, A. Kirchner, T.M. Klapotke, D. G. Piercey, M.J. Poller, J. Stierstorfer, "A study of cyanotetrazole oxides and derivatives thereof, Chem. - Asian J, 2013, 8, 148-159; (b) Y. Dong, Y. Liu, W. Huang, Y. Tang," Assembling high nitrogen isomeric energetic molecules via a lithium-mediated concerted [2+3] reaction of two diazo compounds", Chem. Eng. J., 2022, 444, 136596];

4)

[(a)L.L. Fershtat, M.A. Epishina, A.S. Kulikov, I.V. Ovchinnikov, I.V. Ananyev, N.N. Makhova, "An efficient access to (1H-tetrazol-5-yl)furoxan ammonium salts via a two-step dehydration/[3+2]-cycloaddition strategy", Tetrahedron, 2015, 71, 6764-6775; (b) A.A. Larin, D.M. Bystrov, L.L. Fershtat, A.A. Konnov, N.N. Makhova, K.A. Monogarov, D.B. Meerov, I.N. Melnikov, A.N. Pivkina, V.G. Kiselev, N.V. Muravyev, “Nitro-, cyano-, and methylfuroxans, and their bis-derivatives: From green primary to melt-cast explosives”, Molecules, 2020, 25, 5836];

5)

[Z. Cheng, W. Yang, Q. Ma, Z.Q. Zhang, L. Yang, H. Yang, G. Fan, G. Cheng, "Constructing heat-resistant and insensitive energetic compounds with the introduction of cyano group into fused pyrazolotriazine skeleton", Cryst. Growth Des., 2021, 22, 334-340];

6)

[N.E. Leonov, F.M. Sidorov, M.S. Klenov, A.M. Churakov, Y.A. Strelenko, A.N. Pivkina, I.V. Fedyanin, D.B. Lempert, T.S. Kon'kova, Y.N. Matyushin V.A. Tartakovsky, "Synthesis and properties of novel energetic (cyano-NNO-azoxy)furazans", Mendeleev Commun., 2021, 31, 792-794].

In addition, energy-intensive 4(10)-substituted polynitro-2,4,6,8,10,12-hexaazaisowurtzitanes of the general formula have been described in the literature:

Where

1) R ² and R ³ =H, R ² =NO ₂ and R ³ =H [AJ Bellamy, A. MacCuish, P. Golding, M.F. Mahon, “The use of trifluoroacetyl as an N-and O-protecting group during the synthesis of energetic compounds containing nitramine and/or nitrate ester groups”, Propellants, Explos., Pyrotech, 2007, 32, 20-31];

2) R ² =NO ₂ and R ³ =C(O)N ₃ , R ² =R ³ =C(O)N ₃ [K. Dong, Yu. Wang, X. B. Gong, J. Zhang, Ch. H. Sun, SP Pang, "Formyl azido substituted nitro hexaazaisowurtzitane - synthesis, characterization and energetic properties", New J. Chem., 2013, 37, 3685-3691];

3) R ² =NO ₂ and R ³ =CH ₂ C(NO ₂ ) ₃ , R ² =R ³ =CH ₂ C(NO ₂ ) ₃ [O.A. Lukyanov, N.I. Shlykova, G.V. Pokhvisneva, T.V. Ternikova, S.V. Nikitin, G.A. Smirnov, Yu.V. Nelyubina, P.V. Dorovatovsky, T.S. Konkova, N.V. Muravyov, A.N. Pivkina, Optimization of key stages of synthesis and study of the main physicochemical properties of high-energy compounds - 4-(2,2,2-trinitroethyl)-2,6,8,10,12-pentanitrohexaazaisowurtzitane and 4,10-bis(2,2,2-trinitroethyl)-2,6,8,12-tetranitrohexaazaisowurtzitane", Izvestiya AN. Chemical Series, 2017, 66, 1066-1073];

4) R ² =NO ₂ and R ³ =CH ₂ C(NO ₂ ) ₂ F, R ² =CH ₂ C(NO ₂ ) ₃ and R ³ =CH ₂ C(NO ₂ ) ₂ F [O.A. Lukyanov, N.I. Shlykova, G.V. Pokhvisneva, T.V. Ternikova, K.A. Monogarov, D.B. Meerov, Yu.V. Nelyubina, P.V. Dorovatovsky, T.S. Konkova, Izvestiya AN. Chemical Series, 2019, 68, 110-115];

5) R ² =NO ₂ and R ³ =CH ₂ N ₃ , R ² =CH ₂ C(NO ₂ ) ₃ and R ³ =CH ₂ N ₃ , R ² =R ² =CH ₂ N ₃ [OA Luk' yanov, VV Parakhin, NI Shlykova, AO Dmitrienko, EK Melnikova, TS Kon'kova, KA Monogarov, DB Meerov, "Energetic N-azidomethyl derivatives of polynitro hexaazaisowurtzitanes series: CL-20 analogues having the highest enthalpy", New J. Chem ., 2020, 44, 8357-8365];

6) R ² =NO ₂ and R ³ =CH ₂ N(NO ₂ )H, CH ₂ N(NO ₂ )CH ₃ , CH ₂ N(NO ₂ )(CH ₂ ) ₂ NHNO ₂ , CH ₂ N(NO ₂ )(CH ₂ ) ₂ N(NO ₂ )CH ₃ [1. RU 2772602 C1, 05/23/2022; 2. VV Parakhin, GV Pokhvisneva, T.V. Ternikova, SV Nikitin, GA Smirnov, TS Kon'kova, DB Lempert, AN Pivkina, "Energetic alkylnitraMHHe-functionalized pentanitro hexaazaisowurtzitanes: towards advanced less sensitive CL-20 analogues", J. Mater. Chem. A, 2022, 10, 818-828].

7) R ² =H and R ² =NO and R ² =NO ₂ and R ² =CH ₂ N ₃ and R ² =CH ₂ C(NO ₂ ) ₃ and .

[1. RU 2786221 C1, 19.12.2022; 2. V.V. Parakhin, G.V. Pokhvisneva, S.V. Nikitin, G.A. Smirnov, T.S. Kon'kova, D.B. Lempert, A.N. Pivkina, "Linking polynitro hexaazaisowurtzitane cages via an N,N'-methylene bridge: a promising strategy for designing energetic ensembles of CL-20 derivatives and adjusting their properties", New J. Chem., 2023, 47, 2444-2455]. Polynitro-2,4,6,8,10,12-hexaazaisowurtzitanes of general formula III are characterized by a relatively high density, but at the same time they have a high sensitivity to friction, and most of them have a relatively low enthalpy of formation and heat of combustion.

The most promising polynitro-2,4,6,8,10,12-hexaazaisowurtzitane of general formula III, where R ² = R ³ = NO ₂ (2,4,6,8,10,12-hexanitro-2,4,6,8,10,12-hexaazaisowurtzitane (CL-20, GNIV)) is also described in the literature [A.T. Nielsen, A.P. Chafin, S. L. Christian, D. W. Moore, M. P. Nadler, R. A. Nissan, D. J. Vanderah, R. D. Gilardi, C. F. George, and J. L. Flippen-Anderson, "Synthesis of polyazapolycyclic caged polynitramine", Tetrahedron, 1998, 54, 11793-11812]. The known compound has a comparatively high density, but is characterized by a comparatively low enthalpy of formation and low heat of combustion, as well as high sensitivity to friction. The technical task of the present invention is to create new energy-intensive polynitro-2,4,6,8,10,12-hexaazaisowurtzitanes with higher values of the enthalpy of formation and heat of combustion and at the same time possessing high resistance to friction while maintaining high density and high thermal stability, as well as to develop methods for their production.

The set technical task is achieved by new cyano-polynitro-2,4,6,8,10,12-hexaazaisowurtzitanes of the general formula, not described in the literature:

where R=H (Ia), NO (Ib), _CH2C ( _NO2 ) ₃ (Iv), _NO2 (Ig), CN (Id), and methods for their production.

The proposed compounds of formula I differ from all known 2,4,6,8,10,12-hexaazaisowurtzitanes by the presence of a polynitro-2,6,8,10,12-hexaazaisowurtzitane nitramino framework and an explosophoric N-cyano group in one structure. The said combination provides both a high energy potential and resistance to external influences of these compounds.

The proposed cyano-polynitro-2,4,6,8,10,12-hexaazaisowurtzitane of formula I, where R=H (Ia), is obtained by sequentially treating 4-trifluoroacetyl-2,6,8,12-tetranitro-2,4,6,8,10,12-hexaazaisowurtzitane (IV) with trichloroacetyl isocyanate in an aprotic polar solvent, then with methanol in the presence of a strong inorganic acid, then with ethanol in the presence of sodium acetate to form 4-carbamoyl-2,6,8,12-tetranitro-2,4,6,8,10,12-hexaazaisowurtzitane (V), which is subjected to interaction with trifluoromethanesulfonic anhydride in the presence of a tertiary amine in an aprotic polar solvent, followed by isolation of the target product 4-cyano-2,6,8,12-tetranitro-2,4,6,8,10,12-hexaazaisowurtzitane (Ia).

At the stage of obtaining 4-carbamoyl-2,6,8,12-tetranitro-2,4,6,8,10,12-hexaazaisowurtzitane (V), for example, acetonitrile is used as the aprotic polar solvent, and for example, sulfuric acid is used as the strong inorganic acid. At the stage of obtaining 4-cyano-2,6,8,12-tetranitro-2,4,6,8,10,12-hexaazaisowurtzitane (Ia), for example, pyridine is used as the tertiary amine, and for example, acetonitrile is used as the aprotic polar solvent. The proposed cyano-polynitro-2,4,6,8,10,12-hexaazaisowurtzitane of formula I, where R=NO (Ib), is obtained by treating 4-trifluoroacetyl-2,6,8,12-tetranitro-2,4,6,8,10,12-hexaazaisowurtzitane (IV) with a nitrosating reagent in a polar organic solvent, followed by treatment with ethanol, resulting in the formation of 4-nitroso-2,6,8,12-tetranitro-2,4,6,8,10,12-hexaazaisowurtzitane (VI), which is subjected to sequential treatment with trichloroacetyl isocyanate in an aprotic polar solvent, and then with methanol in the presence of a strong inorganic acid, with the formation of 4-carbamoyl-10-nitroso-2,6,8,12-tetranitro-2,4,6,8,10,12-hexaazaisowurtzitane (VII), which is subjected to interaction with trifluoromethanesulfonic anhydride in the presence of a tertiary amine in an organochlorine solvent medium, followed by isolation of the target product 4-cyano-10-nitroso-2,6,8,12-tetranitro-2,4,6,8,10,12-hexaazaisowurtzitane (Ib).

At the stage of obtaining 4-nitroso-2,6,8,12-tetranitro-2,4,6,8,10,12-hexaazaisowurtzitane (VI), for example, the sodium nitrite/acetic acid system is used as a nitrosating reagent in a polar organic solvent. At the stage of obtaining 4-carbamoyl-10-nitroso-2,6,8,12-tetranitro-2,4,6,8,10,12-hexaazaisowurtzitane (VII), for example, acetonitrile is used as an aprotic polar solvent, and for example, sulfuric acid is used as a strong inorganic acid. At the stage of obtaining 4-cyano-10-nitroso-2,6,8,12-tetranitro-2,4,6,8,10,12-hexaazaisowurtzitane (Ib), for example, pyridine is used as a tertiary amine, and for example, dichloroethane (DCE) is used as an organochlorine solvent. The proposed cyano-polynitro-2,4,6,8,10,12-hexaazaisowurtzitanes of formula I, where R=CH ₂ C(NO ₂ ) ₃ (Ib), NO ₂ (Ig) or CN (Id), are obtained by sequential treatment of the corresponding polynitro-2,4,6,8,10,12-hexaazaisowurtzitane of the general formula:

where R ⁴ =CH ₂ C(NO ₂ ) ₃ (VIIIa), NO ₂ (VIIIb) or H (VIIIb), trichloroacetyl isocyanate in an aprotic polar solvent, and then methanol in the presence of a strong inorganic acid, to form 4-carbamoyl-polynitro-2,4,6,8,10,12-hexaazaisowurtzitane of the general formula:

where R ⁵ = CH ₂ C(NO ₂ ) ₃ (IXa), NO ₂ (IXб) or C(O)NH ₂ (IXb), which is subjected to interaction with trifluoromethanesulfonic anhydride in the presence of a tertiary amine in an aprotic polar solvent, followed by isolation of the target product of the general formula:

where R= _CH2C ( _NO2 ) ₃ (Ia), _NO2 (Ib) or CN (Ic).

At the stage of obtaining 4-carbamoyl-10-(2,2,2-trinitroethyl)-2,6,8,12-tetranitro-2,4,6,8,10,12-hexaazaisowurtzitane (IXa), 4-carbamoyl-2,6,8,10,12-pentanitro-2,4,6,8,10,12-hexaazaisowurtzitane (IXb) and 4,10-dicarbamoyl-2,6,8,12-tetranitro-2,4,6,8,10,12-hexaazaisowurtzitane (IXb), for example, acetonitrile is used as an aprotic polar solvent, and for example, sulfuric acid is used as a strong inorganic acid. At the stage of obtaining 4-cyano-10-(2,2,2-trinitroethyl)-2,6,8,12-tetranitro-2,4,6,8,10,12-hexaazaisowurtzitane (Ic), 4-cyano-2,6,8,10,12-pentanitro-2,4,6,8,10,12-hexaazaisowurtzitane (Ig) and 4,10-dicyano-2,6,8,12-tetranitro-2,4,6,8,10,12-hexaazaisowurtzitane (Id), for example, pyridine is used as a tertiary amine, and for example, acetonitrile is used as an aprotic polar solvent. The process of obtaining the target products Ia and Ib occurs according to the following scheme:

The process of obtaining target products Iв, Iг and Iд proceeds according to the following scheme:

High-energy components (energy fillers, oxidizers) of mixed solid rocket propellants are represented by energy-intensive organic compounds, which are usually regular explosives such as hexogen and octogen, as well as a promising high-energy compound - 2,4,6,8,10,12-hexanitro-2,4,6,8,10,12-hexaazaisowurtzitane (CL-20, GNIV), which is a standard among polynitro-2,4,6,8,10,12-hexaazaisowurtzitanes. The disadvantage of these energy-intensive compounds is their low enthalpy of formation and heat of combustion, as well as their high sensitivity to friction (see table).

The technical result of the proposed invention is the creation and development of methods for obtaining new, not described in the literature, high-energy compounds - cyano-polynitro-2,4,6,8,10,12-hexaazaisowurtzitanes of general formula I, which are a polynitro-2,6,8,10,12-hexaazaisowurtzitane nitramino framework containing an explosophoric cyano group, as well as additional energy-intensive functional groups, and characterized by a combination of high density and thermal stability, along with higher values of the enthalpy of formation and heat of combustion, as well as lower sensitivity to friction, in comparison with explosives of similar purpose (see Table). Namely, in terms of the enthalpy of formation and heat of combustion, all new Ia-d compounds (ΔH _obr = +1397-+1980 kJ⋅kg ^-1 and Q _crop =9.78-12.1 MJ⋅kg ^-1 ) significantly exceed all the most powerful standard energy-intensive compounds, including hexogen (ΔH _obr = +301 kJ⋅kg ^-1 and Q _crop =9.48 MJ⋅kg ^-1 ), octogen (ΔH _obr = +251 kJ⋅kg ^-1 and Q _crop =9.45 MJ⋅kg ^-1 ) and even the reference CL-20 (ΔH _obr = +857 kJ⋅kg ^-1 and Q _crop =8.21 MJ⋅kg ^-1 ). Moreover, the friction resistance of the new cyano derivatives Ig (F ₅₀ = 220 N) and Id (F ₅₀ = 210 N) is the highest among known polynitro-2,4,6,8,10,12-hexaazaisowurtzitanes and significantly exceeds the similar parameter of hexogen (F ₅₀ = 120 N), octogen (F ₅₀ = 112 N) and CL-20 (F ₅₀ = 48 N). Also, in terms of thermal stability, the new cyano-substituted samples Ig (T _dec = 223°C) and Id (T _dec = 238°C) are superior to hexogen (T _dec = 204°C) and CL-20 (T _dec = 212°C), and samples Ia, Ib and Ig have a higher density (d = 1.899-1.924 g⋅cm ^-3 ) compared to hexogen (d = 1.791 g⋅cm ^-3 ) and octogen (d = 1.897 g⋅cm ^-3 ). These compounds can find application as high-energy components of mixed solid rocket fuels. The present invention is characterized by the following examples. Starting compounds: 4-trifluoroacetyl-2,6,8,12-tetranitro-2,4,6,8,10,12-hexaazaisowurtzitane (IV) [AJ Bellamy, A. MacCuish, P. Golding, М.F. Mahon, "The use of trifluoroacetyl as an N-and O-protecting group during the synthesis of energetic compounds containing nitramine and/or nitrate ester groups", Propellants, Explos., Pyrotech., 2007, 32, 20-31], 4-(2,2,2-trinitroethyl)-2,6,8,12-tetranitro-2,4,6,8,10,12-hexaazaisowurtzitane (VIIIa) [O.A. Lukyanov, N.I. Shlykova, G.V. Pokhvisneva, T.V. Ternikova, S.V. Nikitin, G.A. Smirnov, Yu.V. Nelyubina, P.V. Dorovatovsky, T.S. Konkova, N.V. Muravyov, A.N. Pivkina, "Optimization of key stages of synthesis and study of the main physicochemical properties of high-energy compounds - 4-(2,2,2-trinitroethyl)-2,6,8,10,12-pentanitrohexaazaisowurtzitane and 4,10-bis(2,2,2-trinitroethyl)-2,6,8,12-tetranitrohexaazaisowurtzitane", Izvestiya AN. Chemical Series, 2017, 66, 1066-1073], 2,6,8,10,12-pentanitro-2,4,6,8,10,12-hexaazaisowurtzitane (VIIIb) [AJ Bellamy, A. MacCuish, P. Golding, MF Mahon, "The use of trifluoroacetyl as an N- and O-protecting group during the synthesis of energetic compounds containing nitramine and/or nitrate ester groups", Propellants, Explos., Pyrotech., 2007, 32, 20-31] and 2,6,8,12-tetranitro-2,4,6,8,10,12-hexaazaisowurtzitane (VIIIb) [AJ Bellamy, A. MacCuish, P. Golding, MF Mahon, "The use of trifluoroacetyl as an N-and O-protecting group during the synthesis of energetic compounds containing nitramine and/or nitrate ester groups", Propellants, Explos., Pyrotech., 2007, 32, 20-31] were obtained according to published methods.

Example 1

To a solution of 4-trifluoroacetyl-2,6,8,12-tetranitro-2,4,6,8,10,12-hexaazaisowurtzitane (IV) (0.500 g, 1.13 mmol) in MeCN (5 mL) was added dropwise a solution of trichloroacetyl isocyanate (1.30 g, 6.90 mmol) in MeCN (4 mL). The reaction mixture was kept at 20 °C with stirring for 24 h, and the solvent was removed in vacuo. To the residue were added MeOH (7 mL) and 92% H ₂ SO ₄ (0.2 mL), the resulting solution was kept at 20 °C with stirring for 24 h, and the solvent was removed in vacuo. The residue was dissolved in ethyl acetate (15 ml), the solution was washed with water (3×5 ml) until the washings were neutral, then the solution was dried over MgSO ₄ , and the solvent was removed in vacuo. A mixture of Et ₂ O and hexane, 1:1 (2 ml) was added to the residue, the resulting precipitate was filtered off, dried in air, then dissolved in EtOH (4 ml), and a solution of NaOAc (0.890 g, 10.9 mmol) in EtOH (8 ml) was added to the resulting solution. The reaction mixture was kept at 20 °C with stirring for 1 h, the separated precipitate was filtered off, washed with water (20 ml) and dried in air. 4-Carbamoyl-2,6,8,12-tetranitro-2,4,6,8,10,12-hexaazaisowurtzitane (V) (0.218 g, 50%) was obtained as a colorless powder, mp 210°C (decomp.). ¹ H NMR (300.1 MHz, acetone-d ₆ ): δ 5.71 (br s, 1H, NH), 6.32 (br s, 2H, NH ₂ ), 6.42 (d, JH _,H = 7 Hz, 2H, CH ^4.5 ), 7.33 (d, JH _,H = 8 Hz, 2H, CH ^2.3 ), 7.68 (s, 2H, CH ^1.6 ) ppm. ¹ H NMR (300.1 MHz, DMSO-d ₆ ): δ 6.30 (br s, 1H, NH), 7.10 (br s, 2H, NH ₂ ), 6.16 (br s, 2H, CH ^4.5 ), 6.93 (br s, 2H, CH ^2.3 ), 7.65 (s, 2H, CH ^1.6 ) ppm. ¹³ C NMR (75.5 MHz, DMSO-d ₆ ): δ 68.0 (CH ^2.3 ), 71.4 (CH ^4.5 ), 72.3 (CH ^1.6 ), 154.7 (C=O) ppm. ¹⁴ N NMR (21.7 MHz, DMSO-d ₆ ): δ -36 (Δν _1/2 = 365 Hz) (4 NO ₂ ) ppm. IR (KBr): ν ^~ 3460 (m) and 3310 (m) (NH ₂ ), 3210 (m) (NH), 3044 (m) (CH), 1708 (s) (C=O), 1587 (vs) and 1548 (s) (as NNO ₂ ), 1324 (s), 1288 (vs) and 1265 (vs) (sym NNO ₂ ) cm ^-1 . HRMS (ESI): m/z calculated for [C ₇ H ₉ N ₁₁ O ₉ +NH ₄ ⁺ ]: 409.0923; found [M+NH ₄ ] ⁺ : 409.0922.

Pyridine (0.17 mL, 2.10 mmol) was added dropwise to a solution of (CF ₃ SO ₂ ) ₂ O (0.34 mL, 2.00 mmol) in MeCN (4 mL). The resulting solution was kept at 20 °C with stirring for 10 min and added dropwise to a solution of 4-carbamoyl-2,6,8,12-tetranitro-2,4,6,8,10,12-hexaazaisowurtzitane (V) (0.200 g, 0.510 mmol) in MeCN (4 mL). The reaction mixture was kept at 20 °C with stirring for 4.5 h until compound V disappeared on TLC (eluent, ethyl acetate-hexane, 1:1), then diluted with water (20 mL). The product was extracted with ethyl acetate (2×15 ml), the extract was washed with water (3×5 ml). After drying over MgSO ₄ and removing the solvent in vacuo, 4-cyano-2,6,8,12-tetranitro-2,4,6,8,10,12-hexaazaisowurtzitane (Ia) was isolated from the residue by flash column chromatography (eluent, ethyl acetate). Et ₂ O (1 ml) was added to the crude product, the formed precipitate was filtered off and dried in air. The product Ia can be further purified by recrystallization from ethyl acetate under CCl atmosphere. 4-Cyano-2,6,8,12-tetranitro-2,4,6,8,10,12-hexaazaisowurtzitane (Ia) (0.169 g, 88%) was obtained as a colorless powder, DSC (5 °C⋅min ^-1 ): onset 173 °C, max 210 °C. Density (pycnometer, 26 °C): 1.902 g cm ^-3 . ¹ H NMR (600.13 MHz, acetone-d ₆ ): δ 5.96 (br s, 1H, NH), 6.56 (br s, 2H, CH ^4,5 ), 6.88 (d, J _H,H = 7 Hz, 2H, CH ^2,3 ), 7.81 (s, 2H, CH ^1,6 ) ppm. ¹³ C { ¹ H} NMR (150.9 MHz, acetone-d ₆ ): δ 71.6 (CH ^4.5 ), 72.5 (CH ^2.3 ), 72.7 (CH ^1.6 ), 111.1 (CN) ppm. ¹⁴ N NMR (43.37 MHz, acetone-d ₆ ): δ -40 (Δν _1/2 = 72 Hz) (2 N ^9.10 O ₂ ), -38 (Δν _1/2 = 75 Hz) (2 N ^7.8 O ₂ ) ppm. ¹⁵ N{ ¹ H} NMR ([INVGATED], 60.8 MHz, acetone-d ₆ ): δ -336.3 (N ² ), -182.6 (N ^1,3 ), -177.6 (N ^4,5 ), -172.0 (CN ¹¹ ), -39.9, (N ^7,8 ), -37.1, (N ^9,10 ) ppm. IR (KBr): ν ^~ 3388 (m) (NH), 3038 (m) (CH), 2243 (s) (CN), 1595 (vs) and 1555 (s) (ac NNO ₂ ), 1328 (vs), 1292 (vs) and 1269 (vs) (sym NNO ₂ ) cm ^-1 . HRMS (ESI): m/z calculated for [C ₇ H ₇ N ₁₁ O ₈ -H ⁺ ]: 372.0406; found [M-H] ⁺ : 372.0398.

Example 2

To a solution of 4-trifluoroacetyl-2,6,8,12-tetranitro-2,4,6,8,10,12-hexaazaisowurtzitane (IV) (0.50 g, 1.13 mmol) in AcOH (5 mL) was added portionwise NaNO ₂ (0.35 g, 5 mmol). The reaction mixture was kept at 20 °C with stirring for 4 h until compound IV disappeared on TLC (eluent, ethyl acetate-hexane, 1:1), and then diluted with water (30 mL). The resulting precipitate was filtered, washed with water and dried in air, then dissolved in EtOH (8 mL). The reaction mixture was kept at 20°C with stirring for 45 min, the resulting precipitate was filtered, washed with a mixture of EtOH and water, 1:1 (4 ml), then dried in air. 4-Nitroso-2,6,8,12-tetranitro-2,4,6,8,10,12-hexaazaisowurtzitane (VI) (0.311 g, 87%) was obtained as a colorless powder, mp 190°C (with sec.). ¹ H NMR (300.1 MHz, acetone-d ₆ ): δ 5.92 (br s, 1H, NH), 6.49 and 6.80 (2d, J _H,H =8 Hz, 2H, CH ^2.3 ), 7.84 (dd, J _H,H1 =16 Hz, J _H,H2= 2 Hz, 2H, CH ^4.5 ) and 7.96 (dd, J _H,H =8 Hz, J _H,H =2 Hz, 2H, CH ^4.5 ), 7.85 (d, J _H,H =6 Hz, 2H, CH ^1.6 ) ppm. ¹³ C NMR (75.5 MHz, acetone-d ₆ ): δ 68.0 (CH ^2.3 ), 71.4 (CH ^4.5 ), 72.3 (CH ^1.6 ), 154.7 (C=O) ppm. ¹⁴ N NMR (21.7 MHz, acetone-d ₆ ): δ -40 (Δν _1/2 = 61 Hz) (2 N ^7.8 O ₂ ) and -37 (Δν _1/2 = 59 Hz) (2 N ^9.10 O ₂ ) ppm. IR (KBr): ν ^~ 3466 (m) and 3401 (m) (NH), 3037 (m) (CH), 1604 (vs) and 1558 (vs) (ac NNO ₂ ), 1330 (vs), 1289 (vs) and 1266 (vs) (sym NNO ₂ ) cm ^-1 . Elemental analysis for C ₆ H ₇ N ₁₁ O ₉ (377.19): calcd: C, 19.10; H, 1.86; N, 40.85%; found: C, 19.43; H, 1.99; N, 40.60%. To a solution of 4-nitroso-2,6,8,12-tetranitro-2,4,6,8,10,12-hexaazaisowurtzitane (VI) (0.440 g, 1.17 mmol) in MeCN (5 mL) was added dropwise a solution of trichloroacetyl isocyanate (1.50 g, 8.00 mmol) in MeCN (4 mL). The reaction mixture was kept at 20 °C with stirring for 24 h, then the solvent was removed in vacuo. MeOH (7 mL) and 92% H ₂ SO ₄ (0.3 mL) were added to the residue, the resulting solution was kept at 20 °C with stirring for 24 h, and the solvent was removed in vacuo. The residue was dissolved in ethyl acetate (20 ml), washed with distilled water (3×5 ml) until the washings were neutral, dried over MgSO ₄ , and the solvent was removed in vacuo. 4-Carbamoyl-10-nitroso-2,6,8,12-tetranitro-2,4,6,8,10,12-hexaazaisowurtzitane (VII) was isolated from the residue by preparative TLC (eluent, ethyl acetate:hexane, 1:1). 4-carbamoyl-10-nitroso-2,6,8,12-tetranitro-2,4,6,8,10,12-hexaazaisowurtzitane (VII) (0.299 g, 61%) was obtained as a colorless powder, mp 168–169°C. 130-132°C (decomp.). ¹ H NMR (300.1 MHz, acetone-cd ₆ ): δ 6.51 (br s, 1H, NH ₂ ), 7.47 and 7.83 (2 dd, J _H,H1 = 8 Hz, J _H,H2 = 2 Hz, 2H, CH ^2,3 ), 7.92 and 8.12 (2 dd, J _H,H1 = 8 Hz, J _H,H2 = 2 Hz, 2H, CH ^4,5 ), 7.95 (s, 2H, CH ^1,6 ) ppm. ¹³ C NMR (75.5 MHz, acetone-d ₆ ): δ 61.1 and 71.5 (CH ^4.5 ), 70.6 and 73.2 (CH ^2.3 ), 74.9 and 75.1 (CH ^1.6 ), 155.3 (C=O) ppm. ¹⁴ N NMR (21.7 MHz, acetone-d ₆ ): δ -40 (1V _1/2 = 100 Hz) (4 NO ₂ ) ppm. IR (KBr): ν ^~ 3468 (s) and 3324 (s) (NH ₂ ), 3039 (w) (CH), 1708 (vs) (C=O), 1604 (vs) and 1555 (s) (ac NNO ₂ ), 1325 (s), 1290 (vs) and 1266 (vs) (sym NNO ₂ ) cm ^-1 . HRMS (ESI): m/z calcd for [C ₇ H ₈ N ₁₂ O ₁₀ +Na ⁺ ]: 443.0379; found [M+Na] ⁺ : 443,0386.

Pyridine (0.15 ml, 1.86 mmol) was added dropwise to an emulsion of (CF ₃ SO ₂ ) ₂ O (0.300 ml, 1.80 mmol) in dichloroethane (5 ml). The resulting solution was maintained at 20°C with stirring for 10 min, then added dropwise to a suspension of 4-carbamoyl-10-nitroso-2,6,8,12-tetranitro-2,4,6,8,10,12-hexaazaisowurtzitane (VII) (0.108 g, 0.257 mmol) in dichloroethane (5 ml) at 0-5°C with stirring. The reaction mixture was kept at 20 °C with stirring for 20 min until compound VII disappeared on TLC (eluent ethyl acetate-hexane, 1:1), then the solvent was removed in vacuo. The residue was dissolved in ethyl acetate (15 mL) and washed with water (3×5 mL). After drying the solution over MgSO ₄ and removing the solvent in vacuo, 4-cyano-10-nitroso-2,6,8,12-tetranitro-2,4,6,8,10,12-hexaazaisowurtzitane (Ib) was isolated from the residue by flash column chromatography (eluent ethyl acetate-hexane, 1:1). Et ₂ O (1 mL) was added to the crude product, the formed precipitate was filtered off and dried in air. 4-Cyano-10-nitroso-2,6,8,12-tetranitro-2,4,6,8,10,12-hexaazaisowurtzitane (Ib) (0.043 g, 42%) was obtained as a colorless powder. DSC (5 °C⋅min ^-1 ): onset 209 °C, max 229 °C. Density (pycnometer, 26 °C): 1.899 g cm ^-3 . ¹ H NMR (600.13 MHz, acetone-d ₆ ): δ 7.14 and 7.43 (br s, 2H, CH ^2,3 ), 8.02 and 8.24 (br s, 2H, CH ^4,5 ), 8.10 (s, 2H, CH ^1,6 ) ppm. ¹³ C{ ¹ H} NMR (150.9 MHz, acetone-d ₆ ): δ 60.3 and 72.6 (CH ^4.5 ), 73.9 and 74.6 (CH ^2.3 ), 72.6 (CH ^1.6 ), 110.2 (CN) ppm. ¹⁴ N NMR (43.37 MHz, acetone-d ₆ ): δ -42 (Δν _1/2 = 79 Hz) (4 NO ₂ ^cage ) ppm. ¹⁵ N NMR ([INVGATED], 60.8 MHz, acetone-d ₆ ): δ -185.8, -182.8, -182.2, -181.9 (N ^1,3 and N ^4,6 ), -170.5 (CN ¹¹ ), -172.8 (N ¹² O), -144.6 (N ⁵ ), -41.6, -41.4, -41.3, -41.0 (N ^7,8 and N ^9,10 ) ppm. IR (KBr): 3035 (m) (CH), 2247 (m) (CN), 1606 (vs) and 1565 (s) (ac NNO ₂ ), 1326 (s), 1289 (vs) and 1267 (vs) (sym NNO ₂ ) cm ^-1 . Elemental analysis for C ₇ H ₆ N ₁₂ O ₉ (402.20): calcd: C, 20.90; H, 1.50; N, 41.79%; found: C, 20.89; H, 1.37; N, 41.45%.

Example 3

To a solution of 4-(2,2,2-trinitroethyl)-2,6,8,12-tetranitro-2,4,6,8,10,12-hexaazaisowurtzitane (VIIIa) (0.600 g, 1.18 mmol) in MeCN (5 mL) was added dropwise a solution of trichloroacetyl isocyanate (1.33 g, 7.00 mmol) in MeCN (7 mL). The reaction mixture was kept at 20 °C with stirring for 6 h, and the solvent was removed in vacuo. To the residue were added MeOH (8 mL) and 92% H ₂ SO ₄ (0.4 mL), the resulting solution was kept at 20 °C with stirring for 15 h, and the solvent was removed in vacuo. The residue was dissolved in ethyl acetate (20 ml), washed with distilled water (3×5 ml) until the washings were neutral, then the solution was dried over MgSO ₄ and the solvent was removed in vacuo. A mixture of Et ₂ O and hexane, 1:1 (2 ml) was added to the residue, the resulting precipitate was filtered off and dried in air. 4-carbamoyl-10-(2,2,2-trinitroethyl)-2,6,8,12-tetranitro-2,4,6,8,10,12-hexaazaisowurtzitane (IXa) (0.63 g, 97%) was obtained as a colorless powder, mp 118-120°C. ¹ H NMR (300.1 MHz, acetone-d ₆ ): δ 5.51 (s, 1H, CH ₂ ), 6.42 (br s, 2H, NH ₂ ), 6.72 (d, J _H,H = 8 Hz, 2H, CH ^4.5 ), 7.44 (d, J _H,H = 8 Hz, 2H, CH ^2.3 ), 7.84 (s, 2H, CH ^1.6 ) ppm. ¹³ C NMR (75.5 MHz, acetone-d ₆ ): δ 55.4 (CH ₂ ), 70.2 (CH ^1.6 ), 74.2 (CH ^2.3 ), 78.0 (CH ^4.5 ), 127.9 (C(NO ₂ ) ₃ ), 155.0 (C=O) ppm. ¹⁴ N NMR (21.7 MHz, acetone-d ₆ ): δ -38 (Δν _1/2 = 113 Hz) (4 NNO ₂ ), -38 (Δν _1/2 = 33 Hz) (3 CNO ₂ ) ppm. IR (KBr): ν ^~ 3486 (vs) and 3419 (vs) (NH ₂ ), 3042 (w) (CH), 1707 (vs) (C=O), 1596 (brvs) (ac CNO ₂ and NNO ₂ ), 1292 (brs) and 1266 (s) (sym CNO ₂ and NNO ₂ ) cm ^-1 . HRMS (ESI): m/z calcd for [C ₉ H ₁₀ N ₁₄ O ₁₅ +Н ⁺ ]: 555.0523; found [M+H] ⁺ : 555.0511.

Pyridine (0.30 ml, 3.70 mmol) was added dropwise to a solution of (CF ₃ SO ₂ ) ₂ O (0.60 ml, 3.64 mmol) in MeCN (5 ml). The resulting solution was kept at 20 °C with stirring for 10 min, then added dropwise to a solution of 4-carbamoyl-10-(2,2,2-trinitroethyl)-2,6,8,12-tetranitro-2,4,6,8,10,12-hexaazaisowurtzitane (IXa) (0.300 g, 0.540 mmol) in MeCN (5 ml). The reaction mixture was kept at 20 °C with stirring for 2.5 h, then diluted with water (40 ml). The product was extracted with ethyl acetate (2×20 ml), the extract was washed with water (3×5 ml). After drying over MgSO ₄ and removing the solvent in vacuo, 4-cyano-10-(2,2,2-trinitroethyl)-2,6,8,12-tetranitro-2,4,6,8,10,12-hexaazaisowurtzitane (Ic) was isolated from the residue by flash column chromatography (eluent, ethyl acetate-hexane, 1:2). Et ₂ O (1 ml) was added to the crude product, the resulting precipitate was filtered off and dried in air. 4-Cyano-10-(2,2,2-trinitroethyl)-2,6,8,12-tetranitro-2,4,6,8,10,12-hexaazaisowurtzitane (Iв) (0.255 g, 88%) was obtained as a colorless powder, DSC (5 °C⋅min ^-1 ): onset 203 °C, max 220 °C. Density (pycnometer, 26 °C): 1.868 g cm ^-3 . ¹ H NMR (600.13 MHz, acetone-d ₆ ): δ 5.49 (s, 2H, CH ₂ ), 6.87 (d, J _H,H = 8 Hz, 2H, CH ^4.5 ), 7.07 (d, J _H,H = 7 Hz, 2H, CH ^2.3 ), 8.05 (s, 2H, CH ^1.6 ) ppm. ¹³ C { ¹ H} NMR (150.9 MHz, acetone-d ₆ ): δ 53.2 (CH ₂ ), 72.9 (CH ^1.6 ), 73.2 (CH ^2.3 ), 77.2 (CH ^4.5 ), 110.4 (CN), 126.3 (C(NO ₂ ) ₃ ) ppm. ¹⁴ N NMR (43.37 MHz, acetone-d ₆ ): δ -41 (Δν _1/2 = 126 Hz) (2 N ^7,8 O ₂ ), -39 (Δν _1/2 = 130 Hz) (2 N ^9,10 O ₂ ) ppm. ¹⁵ N{ ¹ H} NMR ([INVGATED], 60.8 MHz, acetone-d ₆ ): δ -335.7 (N ² ), -181.4 (N ^4.6 ), -178.3 (N ^1.3 ), -170.5 (CN ¹¹ ), -144.6 (N ⁵ ), -40.7 (N ^7.8 ), -38.5 (N ^9.10 ), -30.7 (C(N ¹² O ₂ ) ₃ ) ppm. IR (KBr): ν ^~ 3040 (w) (CH), 2247 (m) (CN), 1597 (brv) (ac CNO ₂ and NNO ₂ ), 1293 (brv) and 1268 (s) (sym CNO ₂ and NNO ₂ ) cm ^-1 . HRMS (ESI): m/z calcd for [C ₉ H ₈ N ₁₄ O ₁₄ +NH ₄ ⁺ ]: 559.0237; found [M+NH ₄ ] ⁺ : 559.0235.

Example 4

To a solution of 2,6,8,10,12-pentanitro-2,4,6,8,10,12-hexaazaisowurtzitane (VIIIb) (0.500 g, 1.27 mmol) in MeCN (6 mL) was added dropwise a solution of trichloroacetyl isocyanate (1.05 g, 5.60 mmol) in MeCN (3 mL). The reaction mixture was kept at 20 °C with stirring for 24 h, and the solvent was removed in vacuo. MeOH (10 mL) and 92% H ₂ SO ₄ (0.2 mL) were added to the residue, the resulting solution was kept at 20 °C with stirring for 24 h, then the solvent was removed in vacuo. The residue was dissolved in ethyl acetate (15 ml), washed with distilled water (3×5 ml) until the washings were neutral, then the solution was dried over MgSO ₄ and the solvent was removed in vacuo. Et ₂ O (1 ml) was added to the residue, the resulting precipitate was filtered off and dried in air. 4-carbamoyl-2,6,8,10,12-pentanitro-2,4,6,8,10,12-hexaazaisowurtzitane (IXb) (0.443 g, 80%) was obtained as a colorless powder, mp 202-204°C (decomp.) (from EtOH-H ₂ O). ¹ H NMR (300.1 MHz, DMSO-d ₆ ): δ 7.09 (br s, 2H, NH ₂ ), 7.39 (d, J _H ,H = 7 Hz, 2H, CH ^2.3 ), 7.79 (d, J _H,H = 7 Hz, 2H, CH ^4.5 ), 7.93 (s, 2H, CH ^1.6 ) ppm. ¹³ C NMR (75.5 MHz, DMSO-d ₆ ): δ 70.0 (CH ^2.3 ), 70.2 (CH ^4.5 ), 73.4 (CH ^1.6 ), 154.2 (C=O) ppm. ¹⁴ N NMR (21.7 MHz, DMSO-d ₆ ): δ -39 (Δν _1/2 = 431 Hz) (4 NO ₂ ) ppm. IR (KBr): ν ^~ 3487 (vs), 3449 (s), 3400 (s) and 3355 (m) (NH ₂ ), 3041 (vs) (CH), 1714 (vs) and 1687 (vs) (C=O), 1615 (vs), 1594 (vs) and 1571 (vs) (ac NNO ₂ ), 1332 (vs), 1295 (vs) and 1269 (vs) (sym NNO ₂ ) cm ^-1 . Elemental analysis for C ₈ H ₁₀ N ₁₂ O ₁₀ (434.24): calculated: C, 19.27; H, 1.85; N, 38.53%; found: C, 19.37; H, 1.85; N, 38.21%.

Pyridine (0.30 ml, 3.90 mmol) was added dropwise to a solution of (CF ₃ SO ₂ ) ₂ O (0.60 ml, 3.64 mmol) in MeCN (5 ml). The resulting solution was kept at 20 °C with stirring for 10 min and added dropwise to a solution of 4-carbamoyl-2,6,8,10,12-pentanitro-2,4,6,8,10,12-hexaazaisowurtzitane (IXb) (0.200 g, 0.870 mmol) in MeCN (3 ml). The reaction mixture was kept at 20 °C with stirring for 5 h, then diluted with water (20 ml). The product was extracted with ethyl acetate (2×15 ml), the extract was washed with water (3×5 ml). After drying over MgSO ₄ and removing the solvent in vacuo, 4-cyano-2,6,8,10,12-pentanitro-2,4,6,8,10,12-hexaazaisowurtzitane (Ig) was isolated from the residue by flash column chromatography (eluent, ethyl acetate:hexane, 1:2). Et ₂ O (1 ml) was added to the crude product, the formed precipitate was filtered off and dried in air. 4-cyano-2,6,8,10,12-pentanitro-2,4,6,8,10,12-hexaazaisowurtzitane (Ig) (0.112 g, 58%) was obtained as a colorless powder. Product Ig can be further purified by reprecipitation from MeCN with water. DSC (5°C⋅min ^-1 ): onset 223°C, max 241°C. Density (pycnometer, 26°C): 1.924 g cm ^-3 . ¹ H NMR (600.13 MHz, acetone- _d6 ): 7.30 (d, JH _{,H =} 8 Hz, 2H, ^CH2,3 ), 8.17 (s, 2H, ^CH1,6 ), 8.25 (d, JH,H =8 Hz, 2H, ^CH4,5 ) ppm. ¹ H NMR (300.1 MHz, DMSO-d ₆ ): 7.03 (d, J _H,H = 8 Hz, 2H, CH ^2,3 ), 7.81 (d, 2H, CH ^4,5 ), 8.01 (s, 2H, CH ^1,6 ) ppm. ¹³ C { ¹ H} NMR (150.9 MHz, acetone-d ₆ ): δ 72.2 (CH ^4,5 ), 74.9 (CH ^1,6 ), 75.2 (CH ^2,3 ), 111.4 (CN) ppm. ¹⁴ N NMR (43.37 MHz, acetone-a ₆ ): δ -42 (Δν _1/2 = 156 Hz) (5 NNO ₂ ) ppm. ¹⁵ N NMR ([INVGATED], 60.8 MHz, acetone-d ₆ ): δ -328.6 (N ² ), -199.3 (N ⁵ ), -182.4 (N ^1,3 ), -180.1 (N ^4,6 ), -171.1 (CN ¹¹ ), -43.3 (N ¹² ), -41.3 (N ^9,10 ), -41.0 (N ^7,8 ) ppm. IR (KBr): ν ^~ 3042 (s) (CH), 2248 (s) (CN), 1633 (vs), 1593 (vs) and 1571 (vs) (ac NNO ₂ ), 1329 (vs), 1292 (vs) and 1258 (vs) (sym NNO ₂ ) cm ^-1 . Elemental analysis for C ₇ H ₆ N ₁₂ O ₁₀ (418.20): calcd: C, 20.10; H, 1.45; N, 40.19; found: C, 20.48; H, 1.32; N, 39.85%.

Example 5

To a suspension of 2,6,8,12-tetranitro-2,4,6,8,10,12-hexaazaisowurtzitane (VIIIb) (0.560 g, 1.61 mmol) in MeCN (15 mL) was added dropwise a solution of trichloroacetyl isocyanate (3.00 g, 15.9 mmol) in MeCN (10 mL). The reaction mixture was kept at 20 °C with stirring for 24 h, then the solvent was removed in vacuo. MeOH (25 mL) and 92% H ₂ SO ₄ (0.3 mL) were added to the residue, the resulting solution was kept at 20 °C with stirring for 24 h, then the solvent was removed in vacuo. The residue was dissolved in ethyl acetate (50 ml), washed with distilled water (2×20 ml) until the washings were neutral, then the solution was dried over MgSO ₄ and the solvent was removed in vacuo. Et ₂ O (50 ml) was added to the residue, the resulting precipitate was filtered off, washed with Et ₂ O (2×20 ml) and dried in air. 4,10-dicarbamoyl-2,6,8,12-tetranitro-2,4,6,8,10,12-hexaazaisowurtzitane (IXw) (0.650 g, 93%) was obtained as a colorless powder, mp 245°C (decomp.). ¹ H NMR (300.1 MHz, acetone-d ₆ ): δ 6.51 (br s, 2H, NH ₂ ), 7.43 (d, J _H,H = 7 Hz, 2H, CH ^2.3 and CH ^4.5 ), 7.79 (s, 2H, CH ^1.6 ) ppm. ¹³ C NMR (75.5 MHz, acetone-d ₆ ): δ 68.7 (CH ^2.3 and CH ^4.5 ), 73.4 (CH ^1.6 ), 154.4 (C=O) ppm. ¹⁴ N NMR (21.7 MHz, acetone-d ₆ ): δ -38 (Δν _1/2 = 130 Hz) (4 NO ₂ ) ppm. IR (KBr): ν ^~ 3426 (vs), 3320 (vs) (NH ₂ ), 3268 (s) and 3205 (s) (NH ₂ ), 3040 (s) (CH), 1678 (brvs) (C=O), 1611 (vs) and 1557 (vs) (ac NNO ₂ ), 1323 (vs), 1288 (vs) and 1263 (vs) (sym NNO ₂ ) cm ^-1 . HRMS (ESI): m/z calcd for [C ₈ H ₁₀ N ₁₂ O ₁₀ +Н ⁺ ]: 435.0716; found [M+Н]+: 435.0707. ^1H NMR (300.1 MHz, acetone- _d6 ): δ 7.13 (s, 2H, CH ^2.3 and CH ^4.5 ), 8.10 (s, 2H, CH ^1.6 ) ppm. ^1H NMR (600.13 MHz, DMSO- _d6 ): δ 6.82 (s, 2H, CH ^2.3 and CH ^4.5 ), 7.93 (s, 2H, CH ^1.6 ) ppm. ¹³ C { ¹ H} NMR (150.9 MHz, DMSO-d ₆ ): δ 73.6 (CH ^2.3 , CH ^4.5 and CH ^1.6 ), 111.2 (2 CN) ppm. ¹⁴ N NMR (43.37 MHz, DMSO-d ₆ ): δ -24 (Δν _1/2 = 416 Hz) (4 NNO ₂ ) ppm. ¹⁵ N NMR ([INVGATED], 60.8 MHz, DMSO-d ₆ ): δ -328.6 (N ^2.5 ), -182.7 (N ^1.3 and N ^4.6 ), -171.6 (CN ¹¹ ), -40.8 (N ^7.8 and N ^9.10 ) ppm. IR (KBr): ν ^~ 3031 (vs) (CH), 2246 (vs) (CN), 1616 (vs), 1599 (s) and 1565 (vs) (ac NNO ₂ ), 1349 (vs), 1330 (vs), 1298 (vs) and 1264 (vs) (sym NNO ₂ ) cm ^-1 . Elemental analysis for C ₈ H ₆ N ₁₂ O ₈ (398.21): calcd: C, 24.13; H, 1.52; N, 42.21%; found: C, 24.12; H, 1.51; N, 42.21%.

Pyridine (0.28 ml, 3.60 mmol) was added dropwise to a solution of (CF ₃ SO ₂ ) ₂ O (0.58 ml, 1.22 mmol) in MeCN (9 ml). The resulting solution was kept at 20 °C with stirring for 5 min and added dropwise to a suspension of 4,10-dicarbamoyl-2,6,8,12-tetranitro-2,4,6,8,10,12-hexaazaisowurtzitane (IXb) (0.191 g, 0.440 mmol) in MeCN (9 ml). The reaction mixture was kept at 20 °C with stirring for 24 h, then the solvent was removed in vacuo. The residue was dissolved in ethyl acetate (50 ml), the solution was washed with water (2×20 ml). After drying the solution over MgSO ₄ and removing the solvent in vacuo, 4,10-dicyano-2,6,8,12-tetranitro-2,4,6,8,10,12-hexaazaisowurtzitane (Id) was isolated from the residue by flash column chromatography (eluent, ethyl acetate). Et ₂ O (50 mL) was added to the crude product, the resulting precipitate was filtered off and air-dried. 4,10-dicyano-2,6,8,12-tetranitro-2,4,6,8,10,12-hexaazaisowurtzitane (Id) (0.160 g, 91%) was obtained as a colorless powder. Product Ie can be further purified by recrystallization from MeCN-H ₂ O. DSC (5 °C min ^-1 ): onset 238 °C, max 249 °C (from MeCN-H ₂ O). Density (pycnometer, 26 °C): 1.858 g cm ^-3 . ¹ H NMR (300.1 MHz, acetone-d ₆ ): δ 7.13 (s, 2H, CH ^2,3 and CH ^4,5 ), 8.10 (s, 2H, CH ^1,6 ) ppm. ¹ H NMR (600.13 MHz, DMSO-d ₆ ): δ 6.82 (s, 2H, CH ^2,3 and CH ^4,5 ), 7.93 (s, 2H, CH ^1,6 ) ppm. ¹³ C{ ¹ H} NMR (150.9 MHz, DMSO-d ₆ ): δ 73.6 (CH ^2,3 , CH ^4,5 and CH ^1,6 ), 111.2 (2 CN) ppm. ¹⁴ N NMR (43.37 MHz, DMSO-d ₆ ): δ -24 (Δν _1/2 = 416 Hz) (4 NNO ₂ ) ppm. ¹⁵ N NMR ([INVGATED], 60.8 MHz, DMSO-d ₆ ): δ -328.6 (N ^2,5 ), -182.7 (N ^1,3 and N ^4,6 ), -171.6 (CN ¹¹ ), -40.8 (N ^7,8 and N ^9,10 ) ppm. IR (KBr): "v ^~ 3031 (vs) (CH), 2246 (vs) (CN), 1616 (vs), 1599 (s) and 1565 (vs) (ac NNO ₂ ), 1349 (vs), 1330 (vs), 1298 (vs) and 1264 (vs) (sym NNO ₂ ) cm ^-1 . Elemental analysis for C ₈ H ₆ N ₁₂ O ₈ (398.21): calcd: C, 24.13; H, 1.52; N, 42.21%; found: C, 24.12; H, 1.51; N, 42.21%.

Claims (11)

1. Cyano-polynitro-2,4,6,8,10,12-hexaazaisowurtzitanes of the general formula where R=H (Ia), NO (Ib), _CH2C ( _NO2 ) ₃ (Iv), _NO2 (Ig), CN (Id). 2. Cyano-polynitro-2,4,6,8,10,12-hexaazaisowurtzitanes of general formula I according to claim 1 as high-energy components of mixed solid rocket fuels. 3. A method for producing cyano-polynitro-2,4,6,8,10,12-hexaazaisowurtzitane of general formula I according to claim 1, where R=H (Ia), consisting in that 4-trifluoroacetyl-2,6,8,12-tetranitro-2,4,6,8,10,12-hexaazaisowurtzitane (IV) is subjected to sequential treatment with trichloroacetyl isocyanate in an aprotic polar solvent, then with methanol in the presence of a strong inorganic acid and ethanol in the presence of sodium acetate, the resulting 4-carbamoyl-2,6,8,12-tetranitro-2,4,6,8,10,12-hexaazaisowurtzitane (V) is subjected to interaction with trifluoromethanesulfonic anhydride in the presence of a tertiary amine in an aprotic polar solvent with subsequent isolation of the resulting 4-cyano-2,6,8,12-tetranitro-2,4,6,8,10,12-hexaazaisowurtzitane (Ia). 4. A method for producing cyano-polynitro-2,4,6,8,10,12-hexaazaisowurtzitane of general formula I according to claim 1, where R=NO (Ib), consisting in that 4-trifluoroacetyl-2,6,8,12-tetranitro-2,4,6,8,10,12-hexaazaisowurtzitane (IV) is subjected to successive treatment with a nitrosating reagent in a polar organic solvent, then with ethanol, the resulting 4-nitroso-2,6,8,12-tetranitro-2,4,6,8,10,12-hexaazaisowurtzitane (VI) is subjected to successive treatment with trichloroacetyl isocyanate in an aprotic polar solvent, then with methanol in the presence of a strong inorganic acid, the resulting 4-carbamoyl-10-nitroso-2,6,8,12-tetranitro-2,4,6,8,10,12-hexaazaisowurtzitane (VII) is reacted with trifluoromethanesulfonic anhydride in the presence of a tertiary amine in an organochlorine solvent, followed by isolation of the resulting 4-cyano-10-nitroso-2,6,8,12-tetranitro-2,4,6,8,10,12-hexaazaisowurtzitane (Ib). 5. A method for producing cyano-polynitro-2,4,6,8,10,12-hexaazaisowurtzitane of the general formula I according to claim 1, where R= _CH2C ( _NO2 ) ₃ (Iv), _NO2 (Ig) or CN (Id), consisting in that the corresponding polynitro-2,4,6,8,10,12-hexaazaisowurtzitane of the general formula where R ⁴ =CH ₂ C(NO ₂ ) ₃ (VIIIa), NO ₂ (VIIIb) or H (VIIIc), is subjected to sequential treatment with trichloroacetyl isocyanate in an aprotic polar solvent, then with methanol in the presence of a strong inorganic acid, and the resulting 4-carbamoyl-polynitro-2,4,6,8,10,12-hexaazaisowurtzitane of the general formula where R ⁵ = CH ₂ C(NO ₂ ) ₃ (IXa), NO ₂ (IXb) or C(O)NH ₂ (IXb), is subjected to interaction with trifluoromethanesulfonic anhydride in the presence of a tertiary amine in a medium of an aprotic polar solvent, followed by isolation of the resulting target product of general formula I, where R has the above-mentioned values.