RU2768870C1 - 3-amino-4-{ [4-(nitro-nno-azoxy)furazan-3-yl]-nno-azoxy} furazan and method for its preparation - Google Patents

Abstract

FIELD: chemical industry.SUBSTANCE: invention relates to a new 3-amino-4-{[4-(nitro-NNO-azoxy)furazan-3-yl]-NNO-azoxy}furazan of formula I, which can be used as an oxidizer or an energy-intensive filler for mixed solid rocket fuels. The invention also relates to a method for producing 3-amino-4-{[4-(nitro-NNO-azoxy)furazan-3-yl]azoxy}furazans.EFFECT: expansion of the range of rocket fuels.3 cl, 1 tbl, 3 ex

Description

The present invention relates to the field of organic chemistry, namely, to the chemistry of energy-intensive heterocyclic compounds, specifically, to a new, not described in the literature, 3-amino-4-{[4-(nitro-NNO-azoxy)-furazan-3-yl] -NHO-azoxy}furazan, formulas:

and how to get it.

The compound of formula I can find application as an oxidizer or energy-intensive filler of mixed solid rocket propellants (STRT). The literature describes structurally similar high-energy azoxyfurazans (according to the SciFinder CAS database of the American Chemical Society) with the general formula:

where Χ=Ν(O)=Ν-ΝO ₂ (IIa), ΝO ₂ (IIb),

(N.E. Leonov, M.S. Klenov, O.V. Anikin, A.M. Churakov, Y.A. Strelenko, A.A. Voronin, D.B. Lempert, N.V. Muravyev, IV Fedyanin, S. E. Semenov, V. A. Tartakovsky, "Synthesis of New Energetic Materials Based on Furazan Rings and Nitro-NNO-azoxy Groups", ChemistrySelect, 2020, 5, 12243-12249). Compound IIa is liquid, and compound IIb is low-melting (mp 65-66°C), which makes it impossible to use them as energy-intensive fillers for STRT.

A structural analogue of 3-amino-4-[(4-nitrofurazan-3-yl)-NNO-azoxy]furazan is also known, formula:

(T.S. Novikova, T.M. Mel'nikova, O.V. Kharitonova, V.O. Kulagina, NS Aleksandrova, A.V. Sheremetev, T.S. Pivina, L.I. Khmel'nitskii, S.S. Novikov, "An Effective Method for the Oxidation of Aminofurazans to Nitrofurazans" Mendeleev Commun., 1994, 4, 138-140; AK Zelenin, ED Stevens, ML Trudell, "Synthesis and Structure of 4-[(4-Nitro-1,2, 5-oxadiazol-3-yl)-NNO-azoxyl]-1,2,5-oxadiazol-3-amine", Struct. Chem., 1997, 8, 373-377). Compound III crystallizes only as a solvate with ethanol and water molecules, is characterized by a relatively low enthalpy of formation and a low oxidant excess coefficient (α), which makes the use of this compound as a component of STRT ineffective.

Substituted azoxyfurazans of the general formula are also known:

или

where

or

claimed in the patent (RU 2747110 C1, 04/27/2021) as oxidizers and energy-intensive fillers of mixed solid rocket fuels. However, compounds IVa,b,d are characterized by a relatively low enthalpy of formation, and compounds IVa,c have a low oxidant excess coefficient (α<0.5), which limits the effectiveness of their use as components of STRT.

, оптимального коэффициента избытка окислителя (α>0.6) и температуры плавления выше 100°С, что обеспечит эффективность его применения в качестве окислителя или энергоемкого наполнителя СТРТ, а также разработка способа его получения. Поставленная техническая задача достигается новым неописанным в литературе 3-амино-4-{[4-(нитро-NNO-азокси)фуразан-3-ил]-ΝΝΟ-азокси}фуразаном формулы:The technical objective of the proposed invention is to find a compound of the azoxyfurazans series, characterized by a combination of high enthalpy of formation

, optimal oxidant excess coefficient (α>0.6) and melting temperature above 100°C, which will ensure the efficiency of its use as an oxidizing agent or energy-intensive filler of STRT, as well as the development of a method for its production. The set technical task is achieved by a new undescribed in the literature 3-amino-4-{[4-(nitro-NNO-azoxy)furazan-3-yl]-NΝΟ-azoxy}furazan of the formula:

and how to get it.

и коэффициент избытка окислителя (α=0.67), а наличие аминогруппы в соединении I обеспечивает его оптимальную температуру плавления 114°С. Соединении I может представить интерес в качестве окислителя или энергоемкого наполнителя смесевых твердых ракетных топлив.The proposed compound of formula I contains in its molecule an explosophoric nitro-NNO-azoxy group, which can significantly increase the enthalpy of formation

and the excess coefficient of the oxidizing agent (α=0.67), and the presence of an amino group in compound I provides its optimum melting point of 114°C. Compound I may be of interest as an oxidizing agent or an energy-intensive filler for mixed solid propellants.

Also proposed is a method for obtaining 3-amino-4-{[4-(nitro-NNO-azoxy)furazan-3-yl]-NNO-azoxy}furazan of formula I, which consists in the fact that 3-substituted 4-{[4-( nitro-NNO-azoxy)furazan-3-yl]-NNO-azoxy}furazan of the general formula:

where X=Ν(O)=Ν-ΝO ₂ or ΝO ₂ ,

subjected to interaction with a saturated aqueous solution of ammonia in an aprotic organic solvent, followed by isolation of the target product.

The process of obtaining the target product I proceeds according to the following scheme:

where X=N(O)=N-ΝO ₂ (IIa), ΝO ₂ (IIb).

As an aprotic organic solvent, for example, methylene chloride, chloroform are used. The process is carried out at a temperature mainly from 0 to 25°C.

и коэффициенту избытка окислителя (α) значительно превосходит такие штатные энергоемкие наполнители смесевых твердых ракетных топлив, как гексоген (RDX) и октоген (НМХ), а также известные энергоемкие соединения III и IVa,б,г (см. Таблицу). Также соединение I значительно превосходит известное энергоемкое соединение IVв по коэффициенту избытка окислителя (α) (см. Таблицу).Compound I by enthalpy of formation

and oxidizer excess factor (α) is significantly superior to such standard energy-intensive fillers of mixed solid rocket fuels as hexogen (RDX) and octogen (HMX), as well as known energy-intensive compounds III and IVa,b,d (see Table). Also, compound I significantly exceeds the well-known energy-intensive compound IVc in terms of the excess oxidant coefficient (α) (see Table).

и коэффициент избытка окислителя (α=0.67) и аминогруппу, наличие которой обеспечивает его оптимальную температуру плавления 114°С и делает его пригодным для применения в качестве окислителя или энергоемкого наполнителя СТРТ. Благодаря сочетанию высокой энтальпии образования, высокой плотности, оптимального содержания кислорода и наличия в своем составе водорода соединение формулы I может представить интерес в качестве энергоемкого компонента смесевых твердых ракетных топлив.The technical result of the present invention is the creation of a new type of compound 3-amino-4-{[4-(nitro-NNO-azoxy)furazan-3-yl]-NNO-azoxy}furazan of formula I, having in its structure an explosophoric nitro-NNO- azoxy group, which provides high enthalpy of formation

and an excess ratio of an oxidizing agent (α=0.67) and an amino group, the presence of which provides its optimum melting point of 114°C and makes it suitable for use as an oxidizing agent or an energy-intensive filler for STRT. Due to the combination of high enthalpy of formation, high density, optimal oxygen content and the presence of hydrogen in its composition, the compound of formula I may be of interest as an energy-intensive component of mixed solid propellants.

Starting 3-(nitro-NNO)-azoxy)-4-{[4-(nitro-NNO-azoxy)furazan-3-yl]-NNO-azoxy}furazan (IIa) and 3-nitro-4-{[4 -(nitro-NNO-azoxy)furazan-3-yl]-NNO-azoxy}furazan (IIb) was obtained from 3-amino-4-(tert-butyl-NNO-azoxy)furazan according to published methods (N.E. Leonov , M. S. Klenov, O. V. Anikin, A. M. Churakov, A. A. Strelenko, A. A. Voronin, D. B. Lempert, N. V. Muravyev, IV Fedyanin, S. E. Semenov, V.A. Tartakovsky, "Synthesis of New Energetic Materials Based on Furazan Rings and Nitro-NNO-azoxy Groups", ChemistrySelect, 2020, 5, 12243-12249).

The invention is illustrated by the following non-limiting examples.

Example 1

Preparation of 3-amino-4-{[4-(nitro-NNO-azoxy)furazan-3-yl]-NNO-azoxy}furazan (I) from 3-(nitro-NNO-azoxy)-4-{[4- (nitro-NNO-azoxy)furazan-3-yl]-NNO-azoxy}furazan (IIa).

Saturated aqueous ammonia (25%) (2 ml) was added dropwise with stirring to a solution of 3-(nitro-NNO-azoxy)-4-{[4-(nitro-NNO-azoxy)furazan-3-yl]-NNO -azoxy}furazan (IIa) (0.36 g, 1.0 mmol) in methylene chloride (10 mL) at 25°С. The reaction mixture was stirred at 25° C. for 30 min, then water (20 ml) was added. The organic layer was separated, the aqueous layer was extracted with methylene chloride (5 × 10 ml). The combined organic layer was washed with water (20 ml), saturated aqueous sodium chloride solution (20 ml), dried over magnesium sulfate and concentrated in vacuo. The residue was purified by column chromatography on silica gel (eluent - petroleum ether-AcOEt (10:1, then 5:1)). 123 mg (43%) of 3-amino-4-{[4-(nitro-NNO-azoxy)furazan-3-yl]-NNO-azoxy}furazan (I) was obtained as yellow crystals, m.p. 114°C (dec.). DSC (5°C⋅min ^-1 ): _Tc.dec. =114°C. Elemental analysis for C ₄ H ₂ N ₁₀ O ₆ : Found: H, 0.74; C, 16.82; N, 48.85. C ₄ H ₂ N ₁₀ O ₆ . Calculated: H, 0.70; C, 16.79; N, 48.95. High Resolution Mass Spectrum (ESI): Found: m/z: 309.0050 [M+Na] ⁺ . C ₄ H ₂ N ₁₀ O ₆ . Calculated: m/z: 309.0051 [M+Na] ⁺ . IR spectrum (KBr), ν/cm ^-1 : 3453 s, 3319 cp, 3260 w, 3302 w, 1641 s, 1625 s, 1582 w, 1549 w, 1514 s, 1497 m, 1480 s, 1459 w, 1433 w, 1408 w, 1361 w, 1321 w, 1280 s, 1213 w, 1153 w NMR ¹ H (acetone-d ₆ , δ, ppm, 600.1 MHz): 6.67 (br. s, 2 Η, ΝΗ ₂ ). ^13C NMR (acetone-d ₆ , δ, ppm, 150.9 MHz): 149.8 (C(3) or C(3')), 152.0 (C(3) or C(3')), 153.0 ( br., C(4) or C(4')), 153.6 (br., C(4) or C(4')). NMR 14Ν (acetone-d ₆ , δ, ppm, 43.4 MHz): -42 (N(O)=N-ΝO ₂ , Δν _1/2 =20 Hz), -59 (N(O)=N , Δν _1/2 =55 Hz), -66 (N(O)=N-ΝO ₂ , Δν _1/2 =30 Hz), -339 (ΝΗ2, Δν _1/2 =725 Hz). NMR ¹⁵ N (acetone-d ₆ , δ, ppm, 60.8 MHz): 38.5, 34.7, 34.4, 2.5 (nitrogen atoms of furazan cycles), - 41.3 (N(O)=N-NO ₂ ), - 58.8 (N(O)=N), - 65.7 (N(O)=Ν-ΝO ₂ ), - 337.3 (NH ₂ ).

Example 2

Preparation of 3-amino-4-{[4-(nitro-NNO-azoxy)furazan-3-yl]-NNO-azoxy}furazan (I) from 3-nitro-4-{[4-(nitro-NNO-azoxy )furazan-3-yl]-NNO-azoxy}furazan (IIb).

Saturated aqueous ammonia solution (25%) (5 ml) was added dropwise with stirring to a solution of 3-nitro-4-{[4-(nitro-NNO-azoxy)furazan-3-yl]-NNO-azoxy}furazan (IIb ) (0.82 g, 2.6 mmol) in methylene chloride (50 mL) at 25°C. The reaction mixture was stirred at 25° C. for 30 min, then water (50 ml) was added. The organic layer was separated, the aqueous layer was extracted with methylene chloride (4×25 ml). The combined organic layer was washed with water (50 ml), saturated aqueous sodium chloride solution (50 ml), dried over magnesium sulfate and concentrated in vacuo. The residue was purified by column chromatography on silica gel (eluent - petroleum ether-AcOEt (10:1, then 5:1)). 282 mg (38%) of 3-amino-4-{[4-(nitro-NNO-azoxy)furazan-3-yl]-NNO-azoxy}furazan (I) was obtained as yellow crystals, m.p. 114°C (dec.). The product is identical (m.p., IR, NMR ¹ H and ¹³ C) to compound I obtained in example 1.

Example 3

Preparation of 3-amino-4-{[4-(nitro-NNO-azoxy)furazan-3-yl]-NNO-azoxy}furazan (I) from 3-nitro-4-{[4-(nitro-NNO-azoxy )furazan-3-yl]-NNO-azoxy}furazan (IIb).

Similar to example 2, but the process is carried out in chloroform at 0°C for 1.5 hours. 148 mg (20%) of 3-amino-4-{[4-(nitro-NNO-azoxy)furazan-3-yl]-NNO-azoxy}furazan (I) was obtained as yellow crystals, m.p. 114°C (dec.). The product is identical (mp, IR, NMR ¹ H and ¹³ C) to compound I obtained in example 1.

Claims (7)

1. 3-Amino-4-{[4-(nitro-NNO-azoxy)furazan-3-yl]-NNO-azoxy}furazan formula

. 2. 3-Amino-4-{[4-(nitro-NNO-azoxy)furazan-3-yl]-NNO-azoxy}furazan of formula I according to claim 1 as an oxidizing agent or energy-intensive filler of mixed solid rocket fuels. 3. The method of obtaining 3-amino-4-{[4-(nitro-NNO-azoxy)furazan-3-yl]azoxy}furazan of formula I according to claim 1, which consists in the fact that 3-substituted 4-{[4 -(nitro-NNO-azoxy)furazan-3-yl]-NNO-azoxy}furazan of the general formula

where X=Ν(O)=Ν-ΝO ₂ or NO ₂ , subjected to interaction with a saturated aqueous solution of ammonia in an aprotic organic solvent, followed by isolation of the target product.