RU2485108C1 - 3-(trinitromethyl-onn-azoxy)-4-nitraminofurazans and methods for production thereof - Google Patents

Abstract

FIELD: chemistry.

SUBSTANCE: invention relates to organic chemistry, specifically to novel 3-(trinitromethyl-ONN-azoxy)-4-nitraminofurazans of general formula I

. In formula I, R is Me,

or

. The invention also relates to methods of producing compounds of formula I.

EFFECT: obtaining compounds which can be used as oxidants for rocket fuel and explosive compositions.

3 cl, 1 tbl, 3 ex

Description

The present invention relates to the field of organic chemistry, namely to the chemistry of nitro compounds, in particular, to new 3- (trinitromethyl-ONN-azoxy) -4-nitraminofurazans of the general formula I not described in the literature and to methods for their preparation. The compounds of formula I can find application as oxidizing agents for rocket fuels and explosive compositions.

Nitraminofurazans of the general formula (II) are described in the literature:

Where

when R ¹ = N

R = Me [A.B.Sheremetev, N.S. Aleksandrova, “Reactions of 3-amino-4-methylfurazan with nitrating agents”, Izv. AN Ser. Chem., 2005, 54, 1665], R ² = OMe (according to the structural base of SciFieder CAS American Chemical Society),

for lithium salt (R ¹ = H → Li) [V.A. Petrosyan, V.A. Frolovsky, “Electrosynthesis of diazene oxides upon oxidation of nitraminanions to Pt in CH ₃ CN in the presence of nitrobenzene”. Izv. AN Ser. Chem., 2000, 49, 1427], R ² = NO ₂ [I.V. Tselinsky, S.F. Melnikova, S.N. Vergizov, “Nitration of methylenebis (aminofurazanov)”, Zh. organ. Chemistry, 1995, 31, 8, 1234],

R ² = N ₃ [MAIlyushin, IVTselinskii, “The influence of the structure of the salts of azoles upon the processes of their thermal and laser initiation”, Central European Journal of Energetic Materials, 2006, 3, 1-2, 39],

R ² = NHNO ₂ (according to the structural base of SciFieder CAS American Chemical Society),

R ² = N (O) = NBu ^t [V.P. Zelenov, A.A. Lobanova, S.V. Sysolyatin, “The effect of substrate and electrophile ionization upon receipt of 1,2,3,4-tetrazine-1,3 -dioxides ”, Current problems of theoretical chemistry, materials of reports of international scientific, technical and methodological conferences, Kazan, Russian Federation, Dec. 22-24, 2004, 337],

R ² = N (O) = NAc [V.P. Zelenov, A.A. Lobanova, S.V. Sysolyatin, “The effect of ionization of the substrate and electrophile upon receipt of 1,2,3,4-tetrazine-1,3- Dioxides ”, Current problems of theoretical chemistry, materials of reports of international scientific, technical and methodological conferences, Kazan, Russian Federation, Dec. 22-24, 2004, 337],

(по данным структурной базы SciFieder CAS American Chemical Society),

(according to the structural base of SciFieder CAS American Chemical Society),

[K.Yu.Suponitsky, K.A. Lysenko, M.Yu. Antipin, N.S. Aleksandrova, A.B.Sheremetev, T.S. Novikova, “4,4'-Bis (nitramino) azofurazan and its salt. The study of molecular and crystalline structures based on x-ray structural analysis and quantum-mechanical data ”, Izv. AN Ser. Chem., 2009, 58, 2065],

(по данным структурной базы SciFieder CAS American Chemical Society),

(according to the structural base of SciFieder CAS American Chemical Society),

for trisodium salt [A.V. Sergeevsky, T.V. Romanova, S.F. Melnikova, I.V. Tselinsky, “Reactivity of 3,5-bis (4-amino-1,2,5-oxadiazole-3 -yl) -1,2,4-triazole ", Zh. organ. Chemistry, 2005, 270],

[A.V. Sergeevsky, T.V. Romanova, S.F. Melnikova, I.V. Tselinsky, “Reactivity of 3,5-bis (4-amino-1,2,5-oxadiazol-3-yl) -1,2,4-triazole ", Zh. organ. Chemistry, 2005, 270].

When R ¹ = Me

R ² = Me [RSStepanov, LAKruglyakova, AMAstachov, Thermal decomposition of some 4-substituted 3-methylfurazans, International Annual Conference of ICT, 2008, 39th, 50/1],

R ² = OMe, NMeNO ₂ (according to the structural base of SciFieder CAS American Chemical Society).

R ² = Me [RLWilier, RS Day, R. Gilardi, G. Clifford, Synthesis and properties of methylenebis [nitraminofurazans], J. Heterocycl. Chem., 1992, 29, 7, 1835],

R ² = COOH [ABSheremetev, ILYudin, NNMakhova, IVOvchinnikov, DB Lempert, “Synthesis of organic high nitrogen compounds as pyrotechnic gas-generating ingredients”, International Annual Conference of ICT, 2002, 33rd, Energetic Materials, 128/1],

R ² = NO ₂ [RLWiller, RS Day, R. Gilardi, G. Clifford, Synthesis and properties of methylenebis [nitraminofurazans], J. Heterocycl. Chem., 1992, 29, 7, 1835],

R ² = N ₃ [I.V. Tselinsky, S.F. Melnikova, S.N. Vergizov, “Nitration of methylene bis (aminofurazanov)”, Zh. organ. Chemistry, 1995, 31, 8, 1234],

[A.Gunasekaran, T.Jayachandran, J.H.Boyer, M.L.Trudell, «A convenient synthesis of diaminoglyoxime and diaminofurazan: useful precursors for the synthesis of high density energetic materials», J.Heterocycl. Chem., 1995, 32, 4, 1405].

[A. Gunasekaran, T. Jayachandran, JH Boyer, MLTrudell, “A convenient synthesis of diaminoglyoxime and diaminofurazan: useful precursors for the synthesis of high density energetic materials”, J. Heterocycl. Chem., 1995, 32, 4, 1405].

The described structurally similar nitraminofurazans are characterized by a low percentage of active oxygen, as a result of which they have a negative oxygen balance, which prevents their use as oxidizing agents for rocket fuels and explosive compositions. In addition, nitraminofurazans with R ¹ = H are unstable, due to the presence of a mobile acidic NH proton.

The present invention is the search for new compounds with a high content of active oxygen and the development of methods for their preparation.

The problem is achieved by new 3-trinitromethyl-ONN-azoxy) nitraminofurazans not described in the literature of general formula (I):

где

Where

или

,R = Me

or

,

and methods for their preparation.

The proposed compounds of formula (I) differ from the known nitraminofurazans in the presence of both a nitraminofurazan fragment and an azoxytrinitromethyl group saturated with active oxygen.

получают путем обработки 3-(динитрометил-ONN-азокси)-4-(N-алкиламино)фуразанов общей формулы (III)The proposed 3- (trinitromethyl-ONN-azoxy) -4-nitraminofurazans of the general formula I, where R = Me or

obtained by treating 3- (dinitromethyl-ONN-azoxy) -4- (N-alkylamino) furazans of general formula (III)

, азотной кислотой в присутствии уксусного ангидрида в среде неполярного органического растворителя по следующей схеме:where R = Me or

, nitric acid in the presence of acetic anhydride in a non-polar organic solvent, according to the following scheme:

As an organic non-polar solvent, for example, methylene chloride is used. The process is carried out at room temperature, in an excess of nitric acid, for example, at a molar ratio of nitric acid:

acetic anhydride 1: 0.18.

, получают путем взаимодействия аммониевой соли 3-(динитрометил-ONN-азокси)-4-аминофуразана с газообразным хлором в среде инертного органического растворителя, с последующей обработкой полученного 3-(хлородинитрометил-ONN-азокси)-4-аминофуразана формальдегидом в присутствии серной кислоты в среде полярного органического растворителя, и образующийся при этом N,N-бис[(3-(хлородинитрометил-ONN-азокси)фуразан-4-ил]метилендиамин подвергают взаимодействию с азотной кислотой в присутствии уксусного ангидрида в среде неполярного органического растворителя, полученный N,N-бис[(3-(хлородинитрометил-ONN-азокси)фуразан-4-ил]метилендинитрамин обрабатывают йодидом калия в среде водного спирта, с последующим подкислением полученной при этом соответствующей дикалиевой соли, и образующийся N,N-бис[(3-(динитрометил-ONN-азокси)фуразан-4-ил]метилендинитрамин подвергают взаимодействию с азотной кислотой в присутствии трифторуксусного ангидрида в среде неполярного органического растворителя.The proposed 3- (trinitromethyl-ONN-azoxy) -4-nitraminofurazan of the general formula I, where R =

, obtained by reacting the ammonium salt of 3- (dinitromethyl-ONN-azoxy) -4-aminofurazan with chlorine gas in an inert organic solvent, followed by treating the obtained 3- (chlorodinitromethyl-ONN-azoxy) -4-aminofurazan with formaldehyde in the presence of sulfuric acid in a polar organic solvent, and the resulting N, N-bis [(3- (chlorodinitromethyl-ONN-azoxy) furazan-4-yl] methylenediamine is reacted with nitric acid in the presence of acetic anhydride in a non-polar organic solution The resulting N, N-bis [(3- (chlorodinitromethyl-ONN-azoxy) furazan-4-yl] methylene dinitramine obtained is treated with potassium iodide in aqueous alcohol, followed by acidification of the corresponding corresponding dipotassium salt, and N, N- bis [(3- (dinitromethyl-ONN-azoxy) furazan-4-yl] methylene dinitramine is reacted with nitric acid in the presence of trifluoroacetic anhydride in a non-polar organic solvent.

The process proceeds as follows:

As an inert organic solvent in the chlorination stage of the ammonium salt of 3- (dinitromethyl-ONN-azoxy) -4-aminofurazan, for example, methylene chloride is used. The process is carried out at room temperature.

The reaction of 3- (chlorodinitromethyl-ONN-azoxy) -4-aminofurazan with formaldehyde is preferably carried out using sulfuric acid at a concentration of 70-85%, and, for example, ethyl acetate is used as a polar organic solvent. The process is carried out at room temperature.

As an organic non-polar solvent in the nitration step of N, N-bis [(3- (chlorodinitromethyl-ONN-azoxy) furazan-4-yl] methylenediamine, for example, methylene chloride is used. The process is carried out at room temperature.

Ethanol is used as the alcohol in the reduction stage of N, N-bis [(3- (chlorodinitromethyl-ONN-azoxy) furazan-4-yl] methylene dinitramine as potassium iodide. The process is carried out at room temperature. The acidification is carried out, for example, with hydrogen chloride gas in diethyl ether as an inert organic solvent.

As an organic non-polar solvent in the nitration step of N, N-bis [(3- (dinitromethyl-ONN-azoxy) furazan-4-yl] methylene dinitramine, for example, methylene chloride is used. The process is carried out at room temperature, in an excess of nitric acid, for example , with a molar ratio of nitric acid: trifluoroacetic anhydride of 1: 0.25.

As components (energy fillers, oxidizing agents) of rocket fuels and explosive compositions, energy-intensive organic compounds are used, which are usually nitramines, such as RDX, HMX and the recently proposed CL-20. The disadvantage of these explosives are low oxygen balance (KB) and the enthalpy of formation (ΔH _f °).

The present invention provides a new class of substances - 3- (trinitromethyl-ONN-azoxy) -4-nitraminofurazans of the general formula (I) having both a nitraminofurazan moiety and a trinitromethyl azoxy group in their structure, and characterized by a combination of a large positive CB and a significantly higher ΔH _f ° in comparison with nitramines of similar purpose (see table). Such compounds can be used as oxidizing agents for rocket fuels and explosive compositions.

Thus, the invention meets the criteria of "novelty", "inventive step" and "industrial applicability".

Table Characterization of 3- (trinitromethyl-ONN-azoxy) -4-nitraminofurazanofurazan as oxidizing agents in comparison with similar nitramines Like Formula ΔH _f °, kcal / kg  wt.% active oxygen KB α (oxidizer excess ratio) Ia C ₄ H ₃ N ₉ O ₁₀ +373 ¹ 47.5 +2.37 1.05 Ib C ₈ H ₄ N ₁₈ O ₂₀ +413 ¹ 47.6 + 4.76 1,11 Ic C ₇ H ₂ N ₁₈ O ₂₀ +424 ¹ 48.6 +12.16 1.33 RDX C ₃ H ₆ N ₆ O ₆ +100 ² 43,2 -21.6 0.67 octogen C ₄ H ₈ N ₈ O ₈ +61 ² 43,2 -21.6 0.67 CL-20 C ₆ H ₆ N ₁₂ O ₁₂ +255 ³ 43.8 -11.0 0.80 ¹ enthalpy of formation ΔH _f ° according to the program HyperChem Release 7.5 Professional (semi-empirical method РМ3) ² E.Yu. Orlova, Chemistry and technology of high explosives. Chemistry, Leningrad, 1973, 688 pp. ³ JPAgraval, RD Hodgson, Organic Chemistry of Explosives, Wiley, Southern Gate, 2007, 384 p.

The present invention is characterized by the following examples. The starting compounds are described in the article: O.A. Lukyanov, V.V. Parakhin, G.V. Pokhvisneva, T.V. Ternikova, “3-amino-4- (α-nitroalkyl-ONN-azoxy) furazans and some of them derivatives. " Izv. AN Ser. Chem., 2012.

Example 1

To a mixture of CH ₂ Cl ₂ (1.0 ml) and Ac ₂ O (0.55 ml, 5.86 mmol) with stirring at a temperature of 0-5 ° C was added HNO ₃ (1.34 ml, 1.52 g / cm ³ ). After 15 minutes with stirring at 0 ° C, a solution of 3- (dinitromethyl-ONN-azoxy) -4- (N-methylamino) furazan (50 mg, 0.202 mmol) in CH ₂ Cl ₂ (2.0 ml) was added and the resulting the reaction mass was stirred at 20 ° C for 5 days, poured onto ice, the product was extracted with CH ₂ Cl ₂ (5 × 10 ml), the organic phase was separated, dried over MgSO ₄ , after removal of the solvent in vacuum, the product was purified by preparative thin layer chromatography (PTLC) ) on silica gel (eluent - ethyl acetate-hexane, 1: 4, two broaches). Received 40 mg (59%) of 3- (trinitromethyl-ONN-azoxy) -4- (N-methylnitramino) furazan, white crystals, so pl. 57.0-58.0 ° C. Found (%): C, 14.54; H, 0.89; N, 37.07. C ₄ H ₃ N ₉ O ₁₀ (337.12). Calculated (%): C, 14.24; H, 0.89; N, 37.39. IR spectrum (KBr), ν / cm ^-1 : 1616 (very sec., N-NO ₂ ); 1576 (s, C-NO ₂ ); 1528 (s., N = N → O); 1280 (v. S., Br., N = N → O and N-NO ₂ ); 796 (s, N-NO ₂ ). ¹ H NMR Spectrum (CDCl ₃ , δ, ppm): 3.94 (s, 3H, Me). ¹³ C NMR Spectrum (CDCl ₃ , 75 MHz, δ, ppm): 40.1 (Me); 118.3 (C (NO ₂ ) ₃ ); 149.3 (C-NNO ₂ ); 150.0 (CN = N → O). ¹⁴ N NMR spectrum (CDCl ₃ , 22 MHz, δ, ppm): - 74.3 (N → O, Δν _0.5 = 138 Hz); - 48.7 (C ( NO ₂ ) ₃ , Δν _0.5 = 21 Hz); - 40.8 (N- NO ₂ , Δν _0.5 = 48 Hz).

Example 2

To a mixture of CH ₂ Cl ₂ (0.5 ml) and Ac ₂ O (0.44 ml, 4.70 mmol) with stirring at a temperature of 0-5 ° C was added HNO ₃ (1.09 ml, 1.52 g / cm ³ ). After standing for 15 minutes with stirring and 0 ° C, a solution of N, N'-bis- [3 - ((dinitromethyl-ONN-azoxy) furazan-4-yl] ethylenediamine (40 mg, 0.081 mmol) in CH ₂ Cl ₂ ( 1.0 ml) and the resulting reaction mass was stirred at 20 ° C for 5 days, poured into ice, the product was extracted with CH ₂ Cl ₂ (5 × 10 ml), the organic phase was separated, dried over MgSO ₄ , after removing the solvent in vacuo purified by PTLC on silica gel (eluent: ethyl acetate-hexane, 1: 4, two stretches). 34 mg (62%) of N, N'-bis [3- (trinitromethyl-ONN-azoxy) furazan-4-yl] ethylene dinitramine was obtained white crystal M.p. 117,0-118,0 ° C (from CHCl ₃ -hexane) Found (%):. C, 14.47; H, 0.40; N, 37.30 C ₈ H ₁₈ N ₄ O ₂₀ (672.23). Calculated (%): C, 14.29; H, 0.60; N, 37.50. IR spectrum (KBr), ν / cm ^-1 : 1604 (ref. , N-NO ₂ ); 1580 (s., C-NO ₂ ); 1532 (cf., N = N → O); 1286 (very sec., N = N → O); 1264 (s., N -NO ₂ ); 795 (s, N-NO ₂ ). ¹ H NMR spectrum (CDCl ₃ , δ, ppm): 4.85 (s, 4H, 2CH ₂ ). ¹³ C NMR spectrum (acetone -d ₆ , 75 MHz, δ, ppm): 50.8 (2CH ₂ ); 118.1 (2C (NO ₂ ) ₃ ); 150.1 (2C-NNO ₂ ); 150.6 (2C-N = N → O). ¹⁴ N NMR spectrum (acetone-d ₆ , 22 MHz, δ, ppm): - 78.2 (2N → O, Δν _0.5 = 162 Hz); - 47.9 (2C ( NO ₂ ) ₃ , Δν _0.5 = 18 Hz); - 41.0 (2N- NO ₂ , Δν _0.5 = 45 Hz).

Example 3

After suspension of the ammonium salt of 3- (dinitromethyl-ONN-azoxy) -4-aminofurazana (890 mg, 3.56 mmol) in CH ₂ Cl ₂ (125.0 mL) was passed Cl ₂ for 10 min at 20 ° C , the precipitate was filtered off, the mother liquor was evaporated in vacuo, the product was purified by silica gel column chromatography (eluent, benzene-acetone, 6: 1). Received 850 mg (89%) of 3- (chlorodinitromethyl-ONN-azoxy) -4-aminofurazan, bright yellow crystals, so pl. 99.0-102.0 ° C with decomp. (from hexane). Found (%): C, 13.27; H, 0.90; Cl, 13.60; N, 36.32. C ₃ H ₂ ClN ₇ O ₆ (267.54). Calculated (%): C, 13.47; H, 0.75; Cl, 13.25; N, 36.65. IR spectrum (KBr), ν / cm ^-1 : 3460 (s, NH ₂ ); 3345 (vp, NH ₂ ); 1620 (v.s., NH ₂ ); 1583 (s, C-NO ₂ ); 1517 (o.s., N = N → O); 1412 (s, C-NO ₂ ); 1292 (s., N = N → O); 787 (s, N-NO ₂ ). ¹ H NMR Spectrum (CDCl ₃ , δ, ppm): 4.58 (br s, 2H, NH ₂ ); (acetone-d ₆ , δ, ppm): 6.22 (br s, 2H, NH ₂ ). ¹³ C NMR spectrum (acetone-d ₆ , 75 MHz, δ, ppm): 125.7 (C (NO ₂ ) ₂ Cl); 146.7 (C-NH ₂ ); 152.5 (CN = N → O). ¹⁴ NMR spectrum (acetone-d ₆ , 22 MHz, δ, ppm): - 71.8 (N → O, Δν _0.5 = 44 Hz); - 34.9 (C ( NO ₂ ) ₂ CL, Δν _0.5 = 24 Hz).

To a solution of 3-chlorodinitromethyl-ONN-azoxy) -aminofurazan (850 mg, 3.18 mmol) in ethyl acetate (12.7 ml) with stirring at a temperature of 0-3 ° C, a 75% aqueous solution of H ₂ SO _{4 was} first added (22 , 4 ml), then paraform (67 mg, 2.23 mmol), the resulting suspension was stirred for 2.5 h and poured into ice, the product was extracted with CH ₂ Cl ₂ (7 × 70 ml), the organic phase was separated, washed with water (4 × 50 ml), 5% aqueous solution of Na ₂ CO ₃ (50 ml) and water (4 × 50 ml), the organic layer was dried over MgSO ₄ , after removal of the solvent in vacuo, the product was purified by PTLC on silica gel (eluent - ethylace athexane, 1: 3, three broaches) and received 836 mg (96%) of N, N-bis [(3- (chlorodinitromethyl-ONN-azoxy) furazan-4-yl] methylenediamine, light orange crystals, t. mp 154.5-156.0 ° C (from CCl ₄ ). Found: m / z 568.9398 [M + Na] ⁺ . C ₇ H ₄ Cl ₂ N ₁₄ O _12. Calculated: m / z 568, 9402 [M + Na] ⁺ . IR spectrum (KBr), ν / cm ^-1 : 3375 (s, NH); 1613 (ppm, br., N-H); 1581 (ppm, C- NO ₂ ); 1516 (r.s., N = N → O); 1387 (s., C-NO ₂ ); 1279 (s., N = N → O); 789 (s, N-NO ₂ ). ¹ H NMR spectrum (acetone-d ₆ , δ, ppm): 4.95 (t, 2H, CH ₂ , J = 6.0 Hz); 7.13 (br s, 2H, 2NH). ¹³ C NMR spectrum (acetone-d ₆ , 75 MHz, δ, ppm): 53.5 (CH ₂ ); 126.4 (2C (NO ₂ ) ₂ Cl); 146.9 (2C-NH); 153.7 (2C-N = N → O). ¹⁴ N NMR spectrum (acetone-d ₆ , 22 MHz, δ, ppm): - 70.4 (2N → O, Δν _0.5 = 136 Hz); - 32.1 (2C ( NO ₂ ) ₂ Cl, Δv _0.5 = 24 Hz).

To a mixture of CH ₂ Cl ₂ (75.0 ml) and Ac ₂ O (4.18 ml, 44.28 mmol), HNO ₃ (10.26 ml, 1.52 g /) was added with stirring at a temperature of 0-5 ° C. cm ³ ). After holding for 15 min with stirring and 0 ° C, N, N-bis [(3- (chlorodinitromethyl-ONN-azoxy) furazan-4-yl] methylenediamine (836 mg, 1.53 mmol) was added and the resulting reaction mass was stirred at a temperature 0-5 ° C for 40 min, poured into ice, the product was extracted with CH ₂ Cl ₂ (6 × 50 ml), the organic phase was separated, washed with 3% aqueous NaHCO ₃ solution (50 ml) and water (4 × 50 ml) , dried over MgSO ₄ , after removing the solvent in vacuo, the product was purified by PTLC on silica gel (eluent: ethyl acetate-hexane, 1: 4, three broaches). 740 mg (76%) of N, N-bis [(3- (chlorodinitromethyl) was obtained -ONN-azoxy) fur bonded-4-yl] metilendinitramina, colorless crystals, m.p. 132,5-134,0 ° C with decomposition (from C ₂ H ₅ OH-H ₂ O) Found (%):.. C, 13,33 ; H, 0.23; Cl, 10.98; N, 34.92. C ₇ H ₂ Cl ₂ N ₁₆ O ₁₆ (637.09). Calculated (%): C, 13.19; H, 0, 31; Cl, 11.15; N, 35.16. IR spectrum (KBr), ν / cm ^-1 : 3022 (b.p., CH ₂ ); 2995 (b.p., CH ₂ ); 1620 (rpm, N-NO ₂ ); 1590 (rpm, C-NO ₂ ); 1534 (s, N = N → O); 1280 (rpm, N = N → O) ; 788 (cf. N-NO ₂ ). ¹ H NMR Spectrum (CDCl ₃ , δ, ppm): 6.53 (s, 2H, CH ₂ ); (acetone-d ₆ , δ, ppm): 6.91 (s, 2H, CH ₂ ). ¹³ C NMR spectrum (acetone-d ₆ , 75 MHz, δ, ppm): 66.4 (CH ₂ ); 127.4 (2C (NO ₂ ) ₂ Cl); 149.1 (2C-NNO ₂ ); 151.5 (2C-N = N → O). ¹⁴ N NMR spectrum (acetone-d ₆ , 22 MHz, δ, ppm): - 61.5 (2N → O, Δν _0.5 = 162 Hz); - 43.8 (2N- NO ₂ , Δν _0.5 = 45 Hz); - 33.3 (2C ( NO ₂ ) ₂ Cl, Δν _0.5 = 18 Hz).

To a solution of N, N-bis [(3- (chlorodinitromethyl-ONN-azoxy) furazan-4-yl] methylene dinitramine (740 mg, 1.16 mmol) in ethanol (28.0 ml) at 20 ° C was slowly added with stirring KI solution (505 mg, 3.04 mmol) in water (2.3 ml), after holding for 30 minutes, the solvent was evaporated in vacuo, the product was purified by PTLC on silica gel (eluent - benzene-acetone, 1: 1.5) Received 740 mg (99%) of the dipotassium salt of N, N-bis [(3- (dinitromethyl-ONN-azoxy) furazan-4-yl] methylene dinitramine, light yellow crystals, mp 144.0-146.0 ° C dec NMR ¹ H (acetone-d _6, δ, ppm). 6.61 (s, 2H, CH ₂₎ to a solution of dipotassium. oli N, N-bis [(3- (dinitromethyl-ONN-azoxy) furazan-4-yl] metilendinitramina (740 mg, 1.15 mmol) in Et ₂ O (320,0 ml) at 20 ° C and stirring was passed HCl for 20 min while cooling in a water bath, the precipitate was filtered off, the mother liquor was dried over MgSO ₄ , the solvent was evaporated in vacuo to give 594 mg (91%) N, N-bis [(3- (dinitromethyl-ONN-azoxy) furazan -4-yl] methylene dinitramine, white crystals, mp. 120.0-121.0 ° C with decomp. (from CH ₂ Cl ₂ -hexane). Found: m / z 566.9915 [MH]. C ₇ H ₄ N ₁₆ O ₁₆ . Calculated: m / z 566.9918 [MH]. IR spectrum (KBr), ν / cm ^-1 : 3020 (conc., CH ₂ ); 2992 (vol. CH ₂ ); 1308 (cf. N-NO ₂ ) 1608 (very strong, N-NO ₂ ); 1598 (s, C-NO ₂ ); 1532 (s., N = N → O); 1282 (s., N = N → O). ¹ H NMR Spectrum (acetone-d ₆ , δ, ppm): 6.85 (s, 2H, CH ₂ ); 9.47 (br s, 2H, 2CH). ¹³ C NMR spectrum (acetone-d ₆ , 75 MHz, δ, ppm): 66.3 (CH ₂ ); 115.4 (2C (NO ₂ ) ₂ Cl); 149.0 (2C-NNO ₂ ); 152.0 (2C-N = N → O). ¹⁴ N NMR spectrum (acetone-d ₆ , 22 MHz, δ, ppm): - 65.8 (2N → O, Δv _0.5 = 136 Hz); - 44.1 (2N- NO ₂ , Δν _0.5 = 68 Hz); - 34.9 (2C ( NO ₂ ) ₂ Cl, Δv _0.5 = 23 Hz).

To a mixture of CH ₂ Cl ₂ (20.8 ml) and (CF ₃ CO) ₂ O (7.27 ml, 52.3 mmol), HNO ₃ (8.78 ml, 1) was added with stirring at a temperature of 0-5 ° C. 52 g / cm ³ ). After holding for 15 min with stirring and 0 ° C, N, N-bis [(3- (dinitromethyl-ONN-azoxy) furazan-4-yl] methylene dinitramine (594 mg, 1.05 mmol) was added and the resulting reaction mass was stirred at a temperature 20 ° C for 7.0 h, poured into ice, the product was extracted with CH ₂ Cl ₂ (7 × 100 ml), the organic phase was separated, washed with water (4 × 300 ml), dried over MgSO ₄ , after removal of the solvent in vacuo, the product was purified by PTLC on silica gel (eluent: ethyl acetate-hexane, 1: 5, 3 broaches). 454 mg (66%) of N, N-bis [(3- (trinitromethyl-ONN-azoxy) furazan-4-yl] methylene dinitramine was obtained, white crystal s, m.p. 117,0-118,0 ° C (from C ₂ H ₅ OH-H ₂ O) Found (%): C, 13.01; H, 0.21; N, 38.68. C ₇ H ₂ N ₁₈ O ₂₀ (658.20) Calculated (%): C, 12.77; H, 0.31; N, 38.30. Found: m / z 611.9768 [M-NO ₂ ]. C ₇ H ₂ N ₁₈ O _20. Calculated: m / z 611.9758 [M-NO ₂ ]. IR spectrum (KBr), ν / cm ^-1 : 1643 (s, N-NO ₂ ) ; 1606 (r.s., C-NO ₂ ); 1530 (sr., N = N → O); 1279 (rs., N = N → O); 798 (s., N-NO ₂ ) NMR spectrum ¹ H (CDCl ₃ , δ, ppm): 6.54 (s, 2H, CH ₂ ); (acetone-d ₆ , δ, ppm): 6.91 (s, 2H, CH ₂ ). ¹³ C NMR spectrum (acetone-d ₆ , 75 MHz, δ, ppm): 66.3 (CH ₂ ); 118.7 (2C (NO ₂ ) ₃ ); 149.4 (2C-NNO ₂ ); 151.4 (2C-N = N → O). ¹⁴ N NMR spectrum (acetone-d ₆ , 22 MHz, δ, ppm): - 77.2 (2N → O, Δν _0.5 = 162 Hz); - 47.9 (2C ( NO ₂ ) ₃ , Δν _0.5 = 18 Hz); - 44.4 (2N- NO ₂ , Δν _0.5 = 45 Hz).

Claims (3)

1. 3- (Trinitromethyl-ONN-azoxy) -4-nitraminofurazans of the general formula I:

,
where R = Me

or

. 2. The method of producing compounds according to claim 1 of general formula I,
where R = Me or

,
consisting in the fact that 3- (dinitromethyl-ONN-azoxy) -4- (N-alkylamino) furazans of the general formula III:

,
where R = Me or

,
subjected to interaction with nitric acid in the presence of acetic anhydride in a non-polar organic solvent. 3. The method of producing compounds according to claim 1 of General formula I,
where R =

,
consisting in the fact that the ammonium salt of 3- (dinitromethyl-ONN-azoxy) -4-aminofurazan is reacted with gaseous chlorine in an inert organic solvent, followed by treatment of the obtained 3- (chlorodinitromethyl-ONN-azoxy) -4-aminofurazan with formaldehyde sulfuric acid in a polar organic solvent, and the resulting N, N-bis [(3- (chlorodinitromethyl-ONN-azoxy) furazan-4-yl] methylenediamine is reacted with nitric acid in the presence of acetic anhydride in a non-polar or of the organic solvent, obtained N, N-bis [(3- (chlorodinitromethyl-ONN-azoxy) furazan-4-yl] methylene dinitramine is treated with potassium iodide in aqueous alcohol, followed by acidification of the corresponding corresponding dipotassium salt, and N, N bis [(3- (dinitromethyl-ONN-azoxy) furazan-4-yl] methylene dinitramine is reacted with nitric acid in the presence of trifluoroacetic anhydride in a non-polar organic solvent.