JP2976018B2 - Method for producing hexaazaisowurtzitane having acyl group - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a hexaazaisowurtzitane having an acyl group, which is a nitrating precursor of hexanitrohexaazaisowurtzitane used for improving the performance of conventional explosive compositions. The present invention relates to a method for producing derivatives.

[0002]

2. Description of the Related Art As a method for producing hexaazaisowurtzitane having an acyl group, hexakis (arylmethyl)
Hexaazaisowurtzitane is subjected to reductive dearylmethylation in the presence of an acylating agent to give tetraacylbis (arylmethyl) hexaazaisowurtzitane, pentaacylarylmethylhexaazaisowurtzitane, hexaacylhexaazaisowurtzitane, There is known a method for producing hexaazaisowurtzitane derivatives having an acyl group such as tetraacyldialkylhexaazaisowurtzitanium and an arylmethyl group, an alkyl group, a hydrogen atom and the like [Tetra
hedronVol. 51, No16, 4711-47
22 (1995), PCT-JP 96-00189).
Solvents used in the production methods described in these documents and patent applications are carboxylic anhydrides such as acetic anhydride,
Carboxylic acids such as acetic acid, aromatic compounds such as benzene, toluene, and xylene, ether compounds such as tetrahydrofuran and dioxane, and alcohol compounds such as methanol and ethanol are used. In these solvents, N
The acid skeleton by-produced after acylation of the -H group with an acylating agent increases the acidity of the reaction solution, and the skeleton of hexaazaisowurtzitane derivatives containing a large amount of arylmethyl groups in the initial stage of the reaction, which is liable to cause skeletal decomposition by protons Easy to induce decomposition. As a method for synthesizing tetraacylhexaazaisowurtzitanium, hexakis (arylmethyl)
There is no example of direct derivation from hexaazaisoul titanium.

[0003]

SUMMARY OF THE INVENTION An object of the present invention is to change the acidity of a reaction solvent in the reductive dearylmethylation of hexakis (arylmethyl) hexaazaisowurtzitane in the presence of an acylating agent in a reaction solvent. It is an object of the present invention to provide a method for producing tetraacylhexaazaisowurtzitanium in one step from hexakis (arylmethyl) hexaazaisowurtzitanium in a high yield by suppressing skeletal decomposition.

[0004]

DISCLOSURE OF THE INVENTION The present inventors have prepared a compound having an amide group as a reaction solvent for a reductive dearylmethylation reaction of hexakis (arylmethyl) hexaazaisowurtzitane in the presence of an acylating agent. By using a highly active catalyst, hexakis (arylmethyl) hexaazaisowurtzitane was successfully derived in one step to tetraacylhexaazaisowurtzitanium in high yield, and the present invention was completed.

That is, the present invention provides a method for synthesizing WA _n H _(6-n) in one step by reductive dearylmethylation of WB ₆ represented by the following general formula (1) in the presence of an acylating agent. To provide. WB ₆ → WA _n H _(6-n) (1) wherein n is an integer of 4 to 5, B is an arylmethyl group having 7 to 21 carbon atoms, A is an acyl group having 1 to 10 carbon atoms, W Represents a hexavalent hexaazaisowurtzitanium residue represented by the following formula (2). ]

[0006]

Embedded image The reaction involves 1) reductive dearylmethylation in the presence of an acylating agent in a reaction solvent, and in one step WA _n H
_(6-n) is synthesized.

As the solvent having an amide group used in the reaction of the reaction formula (1), any solvent having an amide group that dissolves WB ₆ and does not adversely affect the reaction can be used. it can. Preferably, N, N-
Examples include dimethylacetamide, N, N-dimethylformamide, 1,3-dimethyl-2-imidazolidone, N-methyl-2-pyrrolidone, N, N-diethylnipecotamide and the like. More preferably, N, N-dimethylacetamide and N, N-dimethylformamide are mentioned. These solvents having an amide group may be used alone or in combination of two or more.

[0008] The concentration of WB ₆ in the reaction of reaction formula (1) are expressed by weight relative to the solvent, typically 0.001
1, preferably 0.005 to 0.3, more preferably 0.01 to 0.2. As the reducing agent used in the reaction of the reaction formula (1), hydrogen and formic acid are usually used. Preferably, hydrogen is used. The amount of the reducing agent used is 0.1 to 10,000, preferably 0.67 to 10,000 in terms of the molar ratio of WB _{6 to} the arylmethyl group.
1000, more preferably in the range of 2 to 50.

When hydrogen is used as the reducing agent, the partial pressure of hydrogen is 0.01 to 100, preferably 0.1 to 100.
1 to 30, more preferably 0.1 to 15 kgf / c
It is used in the range of m ^2. In addition to hydrogen, an inert gas such as nitrogen, argon, and helium may be present. As the reduction catalyst used in the reaction of the reaction formula (1), any catalyst can be used as long as it reduces the arylmethyl group of WB ₆ by reductive dearylmethyl, but usually, a metal belonging to the platinum group, or And derivatives thereof, and preferably Pd (OAc) ₂ , PdCl ₂ , Pd (N
O ₃ ) ₂ , PdO, Pd (OH) ₂ , Pd ₃ Pb ₁ , P
Pd compounds such as d ₃ Te _1, Pd alloys and metallic Pd; Ru compounds such as RuCl _3, Ru alloys and Ru
A metal or the like is used, and more preferably, Pd (OA
c) _2, Pd compounds such as PdCl _2, Pd alloys and metallic Pd are used.

These catalysts may be used as they are, or may be activated carbon, silica, alumina, silica-alumina,
It can be used by being supported on various carriers such as zeolite, activated clay, zirconia, and titania. Before the reaction, the catalyst may be subjected to a reduction treatment. When the catalyst is used by being supported on a carrier, these carriers may be subjected to a treatment such as silylation or acylation to deactivate the surface acid sites or to increase the surface acid sites. Alternatively, the acidity of the surface of the carrier can be changed by adsorbing an alkaline substance such as NaOH.

[0011] Among these catalysts, Pd ²⁺ is carried on activated carbon and Pd-C produced by reducing the Pd ²⁺ has a very high activity, so that it is most preferable as the catalyst of the present invention.
When a heterogeneous reduction catalyst is used, it may be used as a fixed bed or as a fluidized bed. As the acylating agent used in the reaction of the reaction formula (1), any one can be used as long as it can acylate a secondary amine to form an N-acyl bond. Usually, acetic anhydride and propionic anhydride are used. Carboxylic acid anhydrides such as, formic anhydride, butyric anhydride, acetic acid-formic acid mixed acid anhydride; N-acetoxysuccinimide, N-propionyloxysuccinimide,
N such as-(2-phenylacetoxy) succinimide
-Carboxylic acid esters of hydroxysuccinimide; and acylimidazoles such as acetylimidazole and propionylimidazole. Of these acylating agents, preferably, acetic anhydride, propionic anhydride,
Carboxylic anhydrides such as anhydrides of acetic acid-formic acid mixed acids are used. More preferably, it is acetic anhydride.

[0012] The amount of the acylating agent, the reactivity, also differ depending on the reaction method, expressed by a molar ratio to the arylmethyl groups of WB _6, usually, from 0.67 to 100, preferably 0.67 to 10, more preferably 0.67 to
3 range. The reaction temperature of the reaction formula (1) is usually from the freezing point of the solvent used to 200 ° C., preferably from 30 to 1
It is used at a temperature of 80 ° C, more preferably 40 to 165 ° C. If the reaction is carried out at a relatively low temperature of 40 to 80 ° C., the skeleton decomposition can be relatively suppressed even if WB ₆ remains in the solvent for a long time. By reacting at a high temperature of
The improvement in the solubility of WB ₆ enables a reaction under high concentration conditions, and the resulting WA _n B _(6-n) can be separated from the catalyst while being dissolved in the solvent and taken out.
Reaction at a high temperature (100 to 165 ° C) is also a preferred method.

When the solvent having an amide group of the present invention is used in the reaction of the reaction formula (1), the decomposition of the skeleton can be relatively suppressed even if the reaction is carried out at a high temperature of 100 to 165 ° C. Of course, skeletal decomposition is suppressed even when the reaction is carried out in a temperature range of 40 to 80 ° C. This skeletal decomposition suppression effect
Derived from the weak basicity of the solvent having an amide group. That is, in the reductive de-arylmethyl reaction in the presence of an acylating agent, acidic protons are generated after acylation with secondary acylating agent of the amine, but the acidic protons promotes skeletal decomposition of WB _6, a reaction solvent As the acid proton generated by using a solvent having a weakly basic amide group as neutralized to maintain the acidity in the reaction system low,
Decomposition of the skeleton is relatively suppressed even under high temperature conditions.

The structures of the raw material WB ₆ and the products WA _n B _(6-n) and WA _n H _(6-n) used in the present invention will be described below. The arylmethyl group represented by B in the reaction formula (1) refers to a methyl group substituted with an aryl group (Ar), and usually has 7 to 21 carbon atoms. Representative structures of the arylmethyl group B include:
It is a substituent represented by the general formula (3).

-CH ₂ Ar (3) [Ar represents an aromatic group having 6 to 20 carbon atoms. The number of carbon atoms in Ar is usually from 6 to 20, preferably from 6 to
10, particularly preferably 6. Ar is, for example, phenyl; tolyl (o-, m-, p-substituted);
Various alkylphenyl groups such as ethylphenyl (o-, m-, p-substituted) and xylyl; methoxyphenyl (o-, m-, p-substituted), ethoxyphenyl (o
-, M-, p-substituted), butoxyphenyl (o-,
m-, p-substituted products), etc .; naphthyl group and various substituted naphthyl groups; and phenyl group and various alkoxyphenyl groups are preferably used. The _six arylmethyl groups in WB6 may be the same or different.

In the reaction formula (1), the acyl group has 1 to 1 carbon atoms.
Any acyl group of 0 can be used. Usually, formyl, acetyl, propionyl, butyryl, isobutyryl, valeryl, hexanoyl, 2-
Phenylacetyl or the like is used, preferably having 1 carbon atom.
To 5 acyl groups, for example, formyl, acetyl, propionyl, butyryl, valeryl and the like are used, and more preferably an acyl group having 1 to 3 carbon atoms, for example, formyl,
Acetyl, propionyl and the like are used.

In the reaction formula (1), WA ₄ H ₂ and WA ₅ H ₁
The hexaazaisowurtzitane derivative represented by the formula (I) can take a plurality of isomers depending on the difference in the substitution position of an acyl group and a hydrogen atom, and the reaction product obtained by the production method of the present invention is a mixture of these isomers. Either may be used. WA _n B _(6-n) in the present invention is represented by the following formulas (4-1) to (4-6).
And the isomers having the steric structures represented by the following formulas (5-1) to (5-2) and their enantiomeric structures.

[0018]

Embedded image

[0019]

Embedded image [In the formula, A represents the acyl group, H represents a hydrogen atom, and W represents the hexaazaisowurtzitanium residue. WA ₄ H ₂ and WA ₅ H ₁ in the reaction formula (1) of the present invention.
In the above formula, the hexaazaisowurtzitanium derivative represented by the formula (1) may have an isomer in which the B group is replaced by a hydrogen atom (H) and an enantiomer structure thereof.

[0020] The reaction of the present invention, by reductive de-arylmethyl the WB ₆ in the presence of an acylating agent, 1) generating a second N-H bond by reductive elimination of the arylmethyl group) acylated Is a reaction in which the formation of an N-acyl group proceeds simultaneously. Further, depending on the reaction conditions, formation of an N-alkyl group by reduction of the generated N-acyl group occurs as a side reaction. Equation (6) shows a reaction route estimated from a substance confirmed to be formed in this reaction.

[0021]

Embedded image

Therefore, the substance represented by the formula (6) may be contained in the reaction product represented by the reaction formula (1) of the present invention. By employing the production method using the compound having an amide group of the present invention as a solvent, a hexaazaisowurtzitanium derivative having an acyl group can be industrially advantageously produced in high yield.

[0023]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, which should not be construed as limiting the present invention. (Example 1) 2.1 g of hexabenzylhexaazaisowurtzitane in a 100 ml autoclave, 10% Pd-C
(A catalyst prepared by supporting Pd ²⁺ on activated carbon and subjecting it to a reduction treatment) 3.15 g, 1.84 g of acetic anhydride, N, N
-Add 30 ml of dimethylacetamide and cover. After the inside of the autoclave is replaced with nitrogen, the inside of the autoclave is replaced with hydrogen, and hydrogen is maintained at 1.1 kgf / cm ² . 700 stirring
Starting at rpm or higher, the temperature is raised to 60 ° C., and then the reaction is carried out for 3 hours (while maintaining the hydrogen pressure at 1.1 kgf / cm ² ).

1 ml of the reaction solution (a solution in which the catalyst was dispersed in a slurry state) was sampled, the liquid component was distilled off under reduced pressure, and tetrahydrofuran (THF) / water (1/1) was added to the remaining solid.
1) Add 1 ml of the solution, stir, dissolve tetraacetylhexaazaisowurtzitanium and pentaacetylhexaazaisowurtzitanium, filter the catalyst through a 0.2 micrometer filter, and analyze by high performance liquid chromatography. . As a result, it was confirmed that tetraacetylhexaazaisowurtzitane was produced at a yield of 68% and pentaacetylhexaazaisowurtzitane was produced at a yield of 19%.

[0025]

According to the method of the present invention using a solvent having an amide group and a highly active catalyst, hexakis (arylmethyl) hexaazaisowurtzitane can be converted to hexaazaisowurtzitane having an acyl group in one step. Xysoultitanium derivatives can be industrially advantageously produced in high yield.

──────────────────────────────────────────────────続 き Continuing from the front page (72) Inventor Nobuto Miyake 3-13-1 Ushidori, Kurashiki-shi, Okayama Asahi Kasei Kogyo Co., Ltd. (56) References International Publication 96/23792 (WO, A1) (58) Field (Int. Cl. ⁶ , DB name) C07D 487/22 CA (STN) REGISTRY (STN)

Claims (1)

(57) [Claims] 1. A catalyst containing Pd in the presence of an acylating agent in a reaction solvent which is a compound having an amide group and comprising hexakis (arylmethyl) hexaazaisowurtzitanium as represented by the following reaction formula (1). A process for producing tetraacylhexaazaisowurtzitane and pentaacylhexaazaisowurtzitane directly in a single step by reductive dearylmethylation in the presence of hexaazaisowurtzitane having an acyl group. WB ₆ → WA ₄ H ₂ + WA ₅ H ₁ (1) wherein B is an arylmethyl group having 7 to 21 carbon atoms, A is an acyl group having 1 to 10 carbon atoms, H is a hydrogen atom, and W is It represents a hexavalent hexaazaisowurtzitanium residue represented by (2). ]