KR20140018090A - A method for preparing hexaza[3.3.3]propellane compounds as key intermediates for new molecular explosives - Google Patents

Abstract

The present invention relates to a hexaza[3.3.3]propellane compound denoted by chemical formula I capable of being used as a major skeleton structure of a new molecular explosive, and a method for preparing the same. In the chemical formula I: R is a foreign atom selected from H, oxygen, nitrogen, sulfur, or halogen, or C-20 alkyl, cycloalkyl, arylalkyl, or aryl capable of including an unsaturated group; and X is H2, O, or S.

Description

Method for preparing hexaaza propane compound that can be used as a new molecular chemical intermediate {3.3.3] PROPELLANE COMPOUNDS AS KEY INTERMEDIATES FOR NEW MOLECULAR EXPLOSIVES

The present invention relates to a method for preparing a novel hexaaza [3.3.3] propane compound, which is a main skeleton of the hexanitrohexaaza [3.3.3] propane compound, which is a compound that can be used as a novel molecular chemical. It is about.

Among the high-density, multicyclic, insensitive molecular chemicals that have been developed in advanced countries such as the United States, the most explosive properties are the isowurtzitane-structured HNIW compound and the cubane-octane trocuban (ONC). It is known to be superior to HMX and RDX that are currently commercially available. Various researches on these compounds show that the compounds with high atomic density of the ring structure are advantageous for the explosive properties, but existing synthesis methods of HNIW or ONC compounds have a complicated process or a low yield. Therefore, in order to develop compounds with high ring tension and high atomic density, such as HNIW and ONC, the tricyclic compound propane structure was designed. Especially, [3.3.3] propane has a ring tension energy of 28 kcal / mol. The potential energy was also relatively high, but the production energy (ΔH _f (kcal / mol)) was -30 Kcal / mol, which was expected to be possible to synthesize. Therefore, azapropane compound substituted with many nitrogen atoms was designed. Compounds with azapropane structure are rarely applied as synthetic and high energy materials, and hexaaza [3.3.3] propane has not been synthesized or used yet.

An object of the present invention is hexaaza [3.3.3] pro, which is the main skeleton of hexanitrohexaaza [3.3.3] propane structure, which is a novel high-density, multicyclic, insensitive molecular chemical substance having high energy when applied as a molecular chemical. It is to provide a compound in which 6 nitrogen is substituted in the propane skeleton as a pellane compound and a method for producing the same.

The present invention provides a hexaaza [3.3.3] propane compound represented by the following general formula (I), which is a core structure of a novel high energy material that can be used as a molecular powder.

(I)

Wherein R is H, C ₁ -C ₂₀ alkyl, cycloalkyl, arylalkyl, or aryl, and the alkyl or aryl may include heteroatoms such as oxygen, nitrogen, sulfur, or an unsaturated group therein; X is H ₂ , O or S.

The present invention also provides a method for preparing a hexaaza [3.3.3] propane compound represented by the above formula (I), and in particular, the compounds (3), (4) and (5) shown in Scheme 1 below. It provides a method for producing a compound of hexaaza [3.3.3] propane structure represented by (6) and (7).

[Reaction Scheme 1]

In Scheme 1, Y is O or S; R ¹ and R ² are generally not particularly limited as long as they are organic functional groups that can be applied as protecting groups of amines. For example, C ₁ to C may include heteroatoms such as oxygen, nitrogen, sulfur, halogen, or unsaturated groups. ₂₀ alkyl, cycloalkyl, arylalkyl or aryl.

In the method for preparing the hexaaza [3.3.3] propane compound represented by the formula (I) according to the present invention, as shown in Scheme 1, in particular, X among the compounds of formula (I) is O or Provided is a method for preparing a compound having a hexaaza [3.3.3] propane structure represented by Compound (3) shown in Scheme 1, including the case of S.

In Scheme 1, as the compound (2), for example, glycoluril diamine (Y is O prepared by reacting potassium iron cyanide (K ₃ Fe (CN) ₆ ) and ammonium hydroxide from uric acid) ) Can be used.

Compound (3) which is one of the compounds of the hexaaza [3.3.3] propane structure according to the present invention can be prepared by introducing a carbonyl group into the compound (2) using an R-CO-X reagent. In the R-CO-X reagent, R is H, or C ₁ ~ C ₂₀ alkyl, cycloalkyl, alkoxy, arylalkyl or aryl which may include heteroatoms such as oxygen, nitrogen, sulfur, chlorine or unsaturated groups. X represents C ₁ -C ₂₀ alkyl, cycloalkyl, alkoxy, arylalkyl which may include heteroatoms or unsaturated groups such as oxygen, nitrogen, sulfur and the like, which are not equal to or equal to Cl, Br, I, H, or R Or aryl. Specific types of R-CO-X reagents corresponding to the above definitions may be arbitrarily selected and used by those skilled in the art. For example, formates such as benzyl chloroformate; Carbonates such as dietary butyl dicarbonate; Ureas such as diimidazole carbonyl; Carbamates; Phosgenes such as oxalic chloride; Aldehydes such as formaldehyde may be mentioned.

The introduction of the carbonyl group may be carried out by conventional reaction conditions known in the art, but may be carried out by, for example, one hour or more at a temperature of room temperature or reflux condition, and is commonly used if necessary. Any suitable base or acid coagent may be used.

In the method for preparing the hexaaza [3.3.3] propane compound represented by the formula (I) according to the present invention, as shown in Scheme 1, in particular, X among the compounds of formula (I) is O, A process for the preparation of hexaaza [3.3.3] propane structured compounds represented by compounds (4), (5), (6) and (7), including the case of S or H, is provided.

Compound (3) having a hexaaza [3.3.3] propelane structure synthesized in Scheme 1 above can convert the protecting group relatively freely, as described below, according to the necessity. The synthesis of various compounds represented by compounds (4), (5), (6) and (7) as shown in Scheme 1 is possible, as described in more detail below.

In preparing the compounds shown in Scheme 1, the preparation of compounds (4), (5), (6) and (7) from compound (3) comprises the following steps: bound to nitrogen from compound (3) Compound (4) is prepared by removing organic functional groups (R ¹ ), ie deprotecting nitrogen; Reacting the compound (4) thus prepared with another organic compound (R ² -X) to protect nitrogen to prepare compound (5); Compound (6) was prepared by reducing Y (carbonyl or thiocarbonyl) of Compound (5) with [M] -H _n ; Compound (7) is prepared by removing organic functional groups (R ² ) bound to nitrogen from compound (6), ie deprotecting nitrogen.

More specifically, in the preparation of the compounds shown in Scheme 1, the preparation of compound (4) from compound (3) is carried out by deprotection of nitrogen to remove organic functional groups R ¹ bonded to the nitrogen of compound (3). Is performed. The deprotection may be carried out under the conditions of an organic or inorganic acid containing a suitable hydrochloric acid, sulfuric acid, nitric acid, acetic acid, trifluoroacetic acid, or the like, depending on the functional group (R ¹ group) present in the compound (3), or sodium hydroxide solution, Metal catalysts such as copper, cesium, iron, haloaluminum, samarium, magnesium, ytterbium, titanium, tin, or the like under organic or inorganic base conditions such as ammonia solution, hydride, tertiary amine or neutral conditions, or It can be carried out using a nonmetallic catalyst. The deprotection conditions and suitable catalyst are not particularly limited and may be appropriately selected and implemented by those skilled in the art according to the functional group to be removed.

In the preparation of the compounds represented by the above Scheme 1, the preparation of the compound (5) from the compound (4), by reacting the R ² -X compound providing a protecting group with the compound (4), the amine of the compound (4) It can be carried out by introducing a protecting group to the group. In R ² -X, R ² is not particularly limited as long as it is a general amine protecting group, but C ₁ -C ₂₀ alkyl, cycloalkyl, which may include heteroatoms such as oxygen, nitrogen, sulfur, halogen, or unsaturated groups Arylalkyl or aryl, wherein X represents a C ₁ to C ₂₀ group which may include heteroatoms or unsaturated groups such as oxygen, nitrogen, sulfur, halogen, etc., which may or may not be equal to Cl, Br, I, H, or R ² ; Alkyl, cycloalkyl, alkoxy, arylalkyl or aryl. As the base used in the introduction of the protecting group, an organic or inorganic base such as sodium hydride, sodium hydroxide, lithium hydroxide, butyllithium, potassium carbonate, sodium carbonate, sodium bicarbonate and lithium dialkylamine may be used. The protecting group introduction conditions and the base are not particularly limited and may be appropriately selected and implemented by those skilled in the art.

On the other hand, in compound (5) shown in Scheme 1, Y may be O or S, as shown in Scheme 2, when Y in compound (5) is O (carbonyl group), Y is Lawesson's reagent Similar cases are well known that, when used under reflux conditions, they can be substituted with S (thiocarbonyl group). R ² is identical to the definition for R ² in R ² -X described in connection with the preparation of compound (5) in Scheme 1 above. This substitution step is not particularly limited, and conventional substitution methods may be used, and such methods may be appropriately performed by those skilled in the art. For example, Lawesson's reagent can be used to substitute reflux in a suitable solvent such as benzene.

[Reaction Scheme 2]

In the preparation of the compounds shown in Scheme 1, the preparation of the compound (6) from the compound (5) is carried out by reducing Y, which is a carbonyl group or a thiocarbonyl group, using [M] -H _n as shown in Scheme 1. Wherein M is selected from the group consisting of metals such as aluminum and boron, and n is an integer of 1 to 4. Specific examples of the reducing agent [M] -H _n are boron hydride, lithium borohydride, sodium borohydride, aluminum hydride, sodium aluminum hydride, lithium aluminum hydride, sodium borohydride, sodium borohydride, sodium borohydride It is any one selected from the group consisting of alkyl aluminum and Raney nickel. It may be used alone to perform the reduction process, or may be used together with any one selected from the group consisting of iodine, sulfuric acid, titanium chloride, aluminum chloride, tin chloride, zinc, triethylether tetrafluoroborate, and the like. The reduction process can be carried out.

In the preparation of the compounds represented by Scheme 1, the preparation of compound (7) from compound (6) is carried out in a manner similar to that described above in connection with the preparation of compound (4) from compound (3). Can be carried out by deprotection. The deprotection step may be carried out under the conditions of an organic or inorganic acid containing appropriate hydrochloric acid, sulfuric acid, nitric acid, acetic acid, trifluoro acetic acid, or the like, depending on the functional group (R ₂ group) present in the compound (6), or sodium hydroxide solution. Metal catalysts such as copper, cesium, iron, haloaluminum, samarium, magnesium, ytterbium, titanium, tin and the like under organic or inorganic base conditions such as ammonia solution, hydride, tertiary amine, or neutral conditions Or a deprotection process to remove the functional groups using a nonmetallic catalyst. The deprotection conditions and suitable catalyst are not particularly limited and may be appropriately selected and implemented by those skilled in the art according to the functional group to be removed.

The structure of the synthesized hexaazatricyclo [3.3.3] undecane compounds can be confirmed through instrumental analysis such as NMR and X-ray diffraction analysis.

According to the present invention, there is provided a method for synthesizing a hexaaza [3.3.3] propelane compound having a core structure of a hexanitrohexaazapropelone compound, which is a novel high-density, multicyclic, insensitive molecular chemical substance. The aza [3.3.3] propane compound can be freely converted to its protecting group as necessary, so that it is advantageous to smoothly synthesize it by introducing appropriate protecting group according to the situation in order to introduce nitro group or synthesize other similar compounds. In addition, when used as the basic skeleton of the high-energy molecular powder, there is an advantage that the potential energy is higher than the conventional molecular powder. In addition, the lifetime of the molecular powder compound of the present invention is expected to be at least 20 years, such as the life of conventional molecular powder materials.

1, 2 and 3 are X-ray diffraction analysis results for the compounds obtained in Examples 1, 2 and 4, respectively.

Hereinafter, the present invention will be described in more detail by way of specific examples. However, the present invention is not limited by the following examples.

Reagents and Materials

Potassium iron cyanide (K ₃ Fe (CN) ₆ ), dietary butyl dicarbonate (BoC ₂ O), triethylamine (TEA), N, N -dimethylamino pyridine (DMAP), benzyl bromide, allyl bromide, sodium hydride (NaH) and lithium aluminum hydride (LAH) used a reagent from Sigma-Aldrich. Solvents of trifluoroacetic acid, ammonium hydroxide, acetone, ethanol, tetrahydrofuran, dimethyl sulfoxide, dimethyl formamide, and methyl chloride were used from OCI and Grand Tablet.

Example  One

2,4,6,8,9,11- Hexa - N - Boc -3,7,10- Trioxo -2,4,6,8,9,11- Hexaaza [3.3.3] propane  Synthesis of 3 '

As shown in the reaction scheme, glycoluril diamine (2 ') (0.5 g, 2.90 mmol) and dietary butyl dicarbonate (6.7 mL, 29.04 mmol) were dissolved in dimethyl sulfoxide (2 mL). Dimethylamino pyridine (1.42 g, 11.62 mmol) was added slowly and stirred at room temperature for 6 hours or more. After the reaction, the mixture was extracted with diethyl ether, distilled under reduced pressure, and purified using silica gel column chromatography (eluent: hexane: ethyl acetate = 4: 1). A white solid compound (1.88 g, yield 81%) was obtained, which was crystallized with methylene chloride and analyzed by crystal structure using X-ray diffraction analysis. The results are shown in FIG. 1 to confirm that the compound 3 'was synthesized. It was.

NMR analysis results:

¹ H NMR (CDCl ₃ ) δ 1.54 (s, 54H)

¹³ C NMR (CDCl ₃ ) δ 147.6, 144.4, 85.2, 83.2, 27.8

IR (KBr) ν _max : 2938, 2936, 2045, 1802, 1775, 1628, 1475, 1458 cm ^-1

Elemental analysis:

Calculations: C-52.62, H-6.81, N-10.52

Found: C-52.57, H-7.06, N-10.12

Example  2

3,7,10- Trioxo -2,4,6,8,9,11-hexaaza [3.3.3] Propane Synthesis of 4 '

As shown in the above scheme, to the compound (3 ') (1.0 g, 1.25 mmol) synthesized in Example 1 was slowly added dropwise trifluoro acetic acid at room temperature until no bubbles formed and stirred for 1 hour, Trifluoro acetic acid was removed by distillation under reduced pressure. Ethanol (20 mL) was added dropwise to form a precipitate, which was filtered off and washed with acetone sufficiently. The filtered precipitate was dried to give a white solid (0.25 ㅎ, yield: 99%). The solid was recrystallized using dimethyl sulfoxide to obtain needle-shaped colorless crystals. The structure was confirmed by X-ray diffraction analysis. The results are shown in FIG. 2, and thus compound 4 'was synthesized. .

NMR analysis results:

_{^{1 H NMR (DMSO- d 6)}} δ 8.06 (s, 6H)

_{^{13 C NMR (DMSO- d 6)}} δ 159.4, 85.2

IR (KBr) ν _max : 3217, 2830, 1748, 1688, 1524, 1473 cm ^-1

HRMS (FAB): Calcd for C ₅ H ₇ N ₆ 0 ₃ [M] +: 199.0574, found: 199.0584.

Elemental analysis:

Calculation: C-30.31, H-3.05, N-42.41

Found: C-30.70, H-3.33, N-42.39

Example  3

2,4,6,8,9,11- Hexa - N Benzyl-3,7,10 Trioxo -2,4,6,8,11- Hexaaza [3.3.3] propane  Synthesis of 5 '

As shown in the above scheme, compound (4 ') (0.7 g, 3.53 mmol) synthesized in Example 2 was added to a mixture of N, N-dimethylformamide (4 mL) and dimethyl sulfoxide (1 mL) under nitrogen atmosphere. After melting, benzyl bromide (3.4 mL, 28.28 mmol) was added, and the reaction temperature was lowered to 0 ° C. or lower and stirred. After 5 minutes sodium hydride (1.13 g, 28.28 mmol) was added. The reaction temperature was slowly raised to room temperature and further stirred for 6 hours. After the reaction was completed, the temperature was lowered to 0 ° C., and an aqueous ammonium chloride solution was added thereto, followed by extraction with diethyl ether. The organic layer was distilled under reduced pressure, and then purified by silica gel chromatography (eluent: hexane: ethyl acetate = 4: 1), to obtain a white solid (1.28 g, yield 49%). Synthesized.

NMR analysis results:

¹ H NMR (CDCl ₃ ) δ 7.32-7.27 (m, 18H), 7.12-7.09 (m, 12H), 4.32 (s, 12H)

¹³ C NMR (CDCl ₃ ) δ 157.3, 136.8, 128.8, 127.7, 126.6, 89.5, 45.8

IR (KBr) ν _max : 3086. 3059. 2693, 2927, 1718, 1472, 1450, 1421cm ^-1

HRMS (FAB +): Calcd for C ₄₇ H ₄₂ N ₆ O ₃ [M] +: 739.3391. Found: 739.3395

Elemental analysis:

Calculations: C-76.40, H-5.73, N-11.37

Found: C-76.24, H-5.89, N-11.57

Example  4

2,4,6,8,9,11- Hexa - N Benzyl-2,4,6,8,11 Hexaaza [3.3.3] propane  Synthesis of 6 '

As shown in the reaction scheme, anhydrous tetrahydrofuran (7 mL) was slowly added to a vitreous reactor containing LAH (0.46 g, 12.20 mmol) under nitrogen atmosphere, and then the temperature was lowered to 0 ° C or lower. Compound (5 ') (0.5 g, 0.68 mmol) synthesized in Example 3 was slowly added and stirred. After 40 minutes, the temperature was slowly raised to room temperature (20 ° C) and stirred at 40 ° C for 12 hours. After the reaction, the temperature was lowered to 0 ° C. or lower and stirred. After 5 minutes, ethyl acetate (15 mL) was slowly added and stirred for 30 minutes. The solution was filtered sequentially using a pad of celite and a pad of silica gel, and then distilled under reduced pressure to obtain a white solid (0.38 g, yield: 81%). This was crystallized with methylene chloride to synthesize compound (6 ') as shown in the above scheme. This structure was confirmed by X-ray diffraction analysis, and the results are shown in FIG. 3, whereby it was confirmed that the compound (6 ′) was synthesized.

NMR analysis result;

¹ H NMR (CDCl ₃ ) δ 7.18-7.41 (m, 30H), 4.16 (s, 12H), 3.75 (s, 6H)

¹³ C NMR (CDCl ₃ ) δ 140.2, 128.3, 128.1, 126.7, 108.9, 76.5, 52.2

Elemental analysis:

Calculations: C-81.00, H-6.94, N-12.06

Found: C-81.01, H-6.99, N-11.92

Claims (5)

A method for producing a hexaaza [3.3.3] propane compound represented by the following compound (3), comprising introducing a carbonyl group into the following compound (2) using an R-CO-X compound:

In the structural formula of the compound (2), Y is O or S;

In the structural formula of the compound (3), R ¹ represents C ₁ to C ₂₀ alkyl, cycloalkyl, arylalkyl or aryl which may include a heteroatom or an unsaturated group selected from oxygen, nitrogen, sulfur and halogen, and Y Is O or S;
Among the R-CO-X compounds, R is C ₁ ~ C ₂₀ Alkyl, cycloalkyl, alkoxy, arylalkyl or aryl which may include heteroatoms or unsaturated groups selected from H, oxygen, nitrogen, sulfur and halogen. Wherein X is a C ₁ to C ₂₀ alkyl, cycloalkyl, which may include heteroatoms or unsaturated groups selected from oxygen, nitrogen, sulfur, and halogen, equal or not equal to Cl, Br, I, H, or R , Alkoxy, arylalkyl or aryl. Represented by the following compound (4), comprising carrying out a deprotection process of removing a protecting group of a hexaaza [3.3.3] propane compound represented by the following compound (3) using a metal catalyst or a non-metal catalyst Method for preparing hexaaza [3.3.3] propane compound:

In the structural formula of the compound (3), R ¹ represents C ₁ to C ₂₀ alkyl, cycloalkyl, arylalkyl or aryl which may include a heteroatom or an unsaturated group selected from oxygen, nitrogen, sulfur and halogen, and Y Is O or S;

In the formula, Y is O and S. In the hexaaza [3.3.3] propane compound represented by the following compound (5), R ² -X (wherein R ² may include a heteroatom or an unsaturated group selected from oxygen, nitrogen, sulfur and halogen) C ₁ to C ₂₀ alkyl, cycloalkyl, arylalkyl or aryl; X is a heteroatom selected from oxygen, nitrogen, sulfur and halogen, which is not equal to or equal to Cl, Br, I, H, or R ² or Reacting a C ₁ to C ₂₀ alkyl, cycloalkyl, alkoxy, arylalkyl or aryl compound which may include an unsaturated group in the presence of a base, thereby introducing a protecting group to the amine group of the following compound (4) A process for producing a hexaaza [3.3.3] propane compound represented by the following compound (5):

Wherein Y is O, S;

Wherein R ² is C ₁ to C ₂₀ alkyl, cycloalkyl, arylalkyl or aryl which may include heteroatoms or unsaturated groups selected from oxygen, nitrogen, sulfur and halogen; Y is O or S. In the hexaaza [3.3.3] propane compound represented by the following compound (5), Y is selected from the group consisting of [M] -H _n ( _wherein M is made of aluminum and boron, and n is 1 to 4). A method for producing a hexaaza [3.3.3] propane compound represented by the following compound (6), which comprises reducing the same by using an integer of

Wherein R ² is C ₁ to C ₂₀ alkyl, cycloalkyl, arylalkyl or aryl which may include heteroatoms or unsaturated groups selected from oxygen, nitrogen, sulfur and halogen; Y is O or S;

Wherein R ² is C ₁ to C ₂₀ alkyl, cycloalkyl, arylalkyl or aryl which may contain heteroatoms or unsaturated groups selected from oxygen, nitrogen, sulfur and halogen. With the following compound (7) which comprises carrying out the deprotection process of removing the protecting group R < ² > of the hexaaza [3.3.3] propane compound represented by following compound (6) using a metal catalyst or a nonmetal catalyst. Method for preparing the indicated hexaaza [3.3.3] propane compound:

Wherein R ² is C ₁ to C ₂₀ alkyl, cycloalkyl, arylalkyl or aryl which may contain heteroatoms or unsaturated groups selected from oxygen, nitrogen, sulfur and halogen.

.

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