JPH08208655A - Production of hexaazaisowurtzitane derivative - Google Patents

Abstract

PURPOSE: To obtain a hexaazaisowurtzitane derivative containing an acyl group and useful as a precursor for high-density nitro compound which is a raw material for gunpowder, a high-density cross-linking agent, etc., by a specific method using a hexakis(arylmethyl)hexaazaisowurtzitane as a raw material. CONSTITUTION: A hexakis(arylmethyl)hexaazaisowurtzitane of the formula WB6 (B is arylmethyl; W is a hexavalent hexaazaisowurtzitane residue) is subjected to reductive dearylmethylation in the presence of an acylating agent (preferably a mixture of N-hydroxysuccinic acid imide ester with carboxylic acid anhydride) to provide an acyl substitution product of hexaazaisowurtzitane of the formula WBx A(6-x) and WAy R(6-y) [(x) and (y) are 1-5; A is a 1-10C acyl; B is an arylmethyl; R is an alkyl]. The reaction is usually carried out in the presence of a reducing agent and a catalyst, preferably under 0.5-200kgf/cm<2> G pressure at 0-200 deg.C for 1-200hr. Hydrogen is preferably used as the reducing agent and a Pd derivative or a Pd metal is preferably used as the catalyst.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a precursor of a high-density nitro compound, which is a raw material for explosives, a monomer of a polymer material, and a hexaazaisol titanium compound having an acyl group, which is useful as a high-density crosslinking agent, and its production. Regarding the method.

[0002]

2. Description of the Related Art As a compound having a hexaazaisosoul titanium skeleton, a compound in which six nitrogen atoms of a hexaazaisosoul titanium skeleton are substituted with various arylmethyl groups is known, and various arylmethylamines are known. And glyoxal are condensed with each other [J. Org. C
hem. , Vol. 55, 1459-1466 (199
0)]. Further, tetraacetyldibenzylhexaazaisoultitanium is known as a hexaazaisowurtzol titanium compound having an acyl group, and this is a precursor of hexanitrohexaazaisoultitanium, which is a raw material for chemicals. There is a report [The Military
Critical Technologies Lis
t, Office of the Under Se
creativity of Defense for Ac
question, 12-22, October (1
992)], but its manufacturing method is not shown.

[0003]

Hexaazaisourtitanium having an acyl group, which is a functional group that can be substituted with a nitro group, is useful as a precursor of a high-density nitro compound, which is a raw material for explosives, but is known. The only product is tetraacetyldibenzylhexaazaisourtitanium, and its manufacturing method is not shown. An object of the present invention is to provide a method for producing a hexaazaisosoul titanium derivative having an acyl group.

[0004]

The present inventors have accomplished the present invention by synthesizing a hexaazaisosoul titanium derivative having an acyl group. That is, the present invention is a method for producing a hexaazaisosoul titanium derivative represented by the general formulas (3) and (4). WB _X A _(6-X) (3) WA _y R _(6-y) (4) [wherein, x and y are integers of 1 to 5, A is an acyl group having 1 to 10 carbon atoms, and B is aryl. The methyl group and W represent a hexavalent hexaazaisosoul titanium residue represented by the following formula (2). ]

[0005]

Embedded image

The hexaazaisosoul titanium derivative having an acyl group of the present invention is represented by the above general formula (1). As the acyl group in the present invention, any acyl group having 1 to 10 carbon atoms can be used, and it has a functional group stable under the reductive dearylmethyl condition employed in the present invention. You can stay. Usually, formyl, acetyl, propionyl, butyryl, isobutyryl, valeryl, hexanoyl, 2-phenylacetyl, trifluoroacetyl, pentafluoropropionyl, heptafluorobutyryl and the like are used, preferably an acyl group having 1 to 5 carbon atoms, for example, Formyl, acetyl, propionyl, butyryl, valeryl, trifluoroacetyl and the like are used, and more preferably, an acyl group having 2 to 4 carbon atoms, for example, acetyl, propionyl, butyryl, trifluoroacetyl and the like are used. In addition, (6-
The x) acyl groups may be the same or different. Further, the (6-y) acyl groups of the formula (4) may be the same or different.

The arylmethyl group in the present invention is a substituent represented by the general formula (5) --CH ₂ Ar (5) (Ar represents an aromatic group having 6 to 10 carbon atoms), Any group may be used as long as methylene is bonded to the group. Examples of such Ar include phenyl; tolyl (o
-, M-, p- each substitution product), ethylphenyl (o-, m
-, P- each substituent), xylyl (2,3-, 2,4-,
2,5-, 2,6-, 3,4-, 3,5-each substitution product),
Trimethylphenyl (2,3,4-, 2,4,5-,
2,5,6-, 2,3,5-, 2,4,6-, 3,4
5-various alkyl phenyl groups, etc .; methoxyphenyl (o-, m-, p-each substituted), ethoxyphenyl (o-, m-, p-each substituted), butoxyphenyl ( various alkoxyphenyl groups such as o-, m-, p-substitutes); fluorophenyl (o-, m-,
various halogenated phenyl groups such as p-respective substituents; naphthyl groups and various substituted naphthyl groups, and the like, preferably various alkylphenyl groups; various alkoxyphenyl groups are used. The six arylmethyl groups may be the same or different.

The alkyl group referred to in the present invention has 1 to 10 carbon atoms.
Any of the above alkyl groups can be used, and it may have a functional group stable under the reductive dearylmethyl conditions employed in the present invention. Usually, methyl, ethyl, propyl, 2-phenylethyl, butyl,
Isobutyl, pentyl, hexyl, 2,2,2-trifluoroethyl, 2,2,3,3,3-pentafluoropropyl, 2,2,3,3,4,4,4-heptafluorobutyl, etc. are used. And preferably a lower alkyl group having 1 to 4 carbon atoms, such as methyl, ethyl, propyl or butyl. The (6-y) alkyl groups of formula (4) may be the same or different.

The hexakis (arylmethyl) hexaazaisourtitanium used in the present invention is represented by the general formula (1). WB ₆ (1) [In the formula, B represents an arylmethyl group, and W represents the hexaazaisosoul titanium residue. The hexaazaisourtitanium derivative having an acyl group represented by the formula (3) of the present invention [WB _X A _(6-X) ] is arylmethyl depending on the number of x even if they are the same x. A plurality of isomers can be taken depending on the difference in the substituting position of the group or acyl group, but the present invention may have any of these structures. When x = 5, that is, pentakis (arylmethyl) hexaazaisosoultitanium [WB ₅ A], the following formulas (6-1) and (6-2)

[0010]

[Chemical 4]

The isomers having a stereo structure and the enantiomeric structures thereof can be adopted. In the case of x = 4, that is, diacetyltetrakis (arylmethyl) hexaazaisosoultitanium [WB ₄ A ₂ ], the following formulas (6-3) to (6)
-8)

[0012]

Embedded image

The isomers having the three-dimensional structure and the enantiomeric structures thereof can be adopted. Further, in the case of x = 3, that is, triacetyltris (arylmethyl) hexaazaisourtitanium [WB ₃ A ₃ ], the following formulas (6-9) to (6-
14)

[0014]

[Chemical 6]

The isomers having the stereo structure and the enantiomeric structures thereof can be taken. In the case of x = 2, that is, tetraacetylbis (arylmethyl) hexaazaisosoultitanium [WB ₂ A ₄ ], the following formulas (6-15) to (6)
-20)

[0016]

[Chemical 7]

The isomers having the stereo structure and the enantiomeric structures thereof can be adopted. In addition, x = 1, that is, pentaacetylarylmethylhexaazaisole titanium [W
BA ₅ ], the following equations (6-21) and (6-2
2)

[0018]

Embedded image

The isomers having the stereo structure and the enantiomeric structures thereof can be adopted. In the hexaazaisosoul titanium derivative [WB _x A _(6-x) ] having an acyl group of the present invention, x is 1 to 5, preferably 2 to 5, and more preferably 3 to 5. The hexaazaisourtitanium derivative [WA _y R _(6-y) ] having an acyl group of the present invention may have the same acyl group, alkyl group, or
A plurality of isomers can be taken depending on the difference in the substitution position of the hydrogen raw paper, but the present invention may have any of these structures. In the case of y = 3, that is, in the case of triacetylhexaazaisosoul titanium derivative [WA ₃ R ₃ ],
-1) to (7-6)

[0020]

[Chemical 9]

The isomers having the stereo structure and the enantiomeric structures thereof can be adopted. Further, in the case of y = 4, that is, in the case of tetraacetylhexaazaisosoul titanium derivative [WA ₄ R ₂ ], the following formulas (7-7) to (7-12)

[0022]

[Chemical 10]

The isomers having the stereo structure and the enantiomeric structures thereof can be adopted. Further, when y = 5, that is, in the case of the tetraacetylhexaazaisourtitanium derivative [WA ₅ R], the following formulas (7-13) to (7-14) are used.

[0024]

[Chemical 11]

The isomers exhibiting the three-dimensional structure and their enantiomeric structures are possible. In the above-mentioned hexaazaisosoul titanium derivative [WA _y R _(6-y) ] having an acyl group, y
Is 3 to 6, preferably 4 to 6. Of the present invention,
An acyl group-containing hexaazaisosoul titanium derivative represented by the general formulas (3) and (4) [WB _x A _(6-x) ]
And [WA _y R _(6-y) ] are reductive dearyl of hexakis (arylmethyl) hexaazaisosoultitanium [WB ₆ ] in the presence of an acylating agent as represented by the following reaction formula (10). Obtained by methylation and acylation.

[0026]

[Chemical 12]

(In the formula, x is an integer of 1 to 5, y is an integer of 3 to 6, A is the acyl group, B is the arylmethyl group,
W represents the hexaazaisosoul titanium residue of the general formula (2). ) By reductively dearylmethylating in the presence of an acylating agent, hexakis (arylmethyl) hexaazaisourtitanium [WB ₆ ] has 1) elimination of arylmethyl group and formation of N-acyl group by acylation. , And 2) It is considered that the formation of the N-alkyl group by the reduction of the produced N-acyl group proceeds sequentially, and the reaction formula (10) represents the reaction scheme. Hexakis (arylmethyl)
The detailed reaction pathway estimated from the substance confirmed to be produced in the reaction of reductive dearylmethylation of hexaazaisourtitanium [WB ₆ ] in the presence of an acylating agent is shown by the following formula (1)
It is shown in 1).

[0028]

[Chemical 13]

(In the formula, A is the acyl group, and B is the ant.
Methyl group, R¹Is an alkyl group, H is a hydrogen atom,
W represents the above-mentioned hexaazaisosoul titanium residue. ) That is, hexakis (arylmethyl) hexaazai
Soul Titanium [WB₆] By reductive dearylmethylation of
Pentakis (arylmethyl) hexaazai
Soul Titanium [WB_FiveH] is an immediate remedy under reaction conditions.
Acyl pentakis (arylmethyl) hexa
Zysoul Titanium [WB_FiveA]. Similarly, reductive
Formation of NH group by dearylmethyl and addition of NH group
As silylation continues, acyl tetrakis
(Arylmethyl) hexaazaisole titanium [WB_Four
AH] via diacyl tetrakis (arylmethyi)
Le) Hexaazai Soul Titanium [WB_FourA₂] Is
Lutris (arylmethyl) hexaazaisole titanium
[WB₃A₂H] via triacyltris (aryl)
Methyl) Hexaazai Soul Titanium [WB₃A₃] Is
Lyacyl bis (arylmethyl) hexaazai soulchi
Tan [WB₂A₃H] via tetraacyl bis (Ari
Methyl) hexaaza soul titanium [WB₂A_Four]
Are generated respectively. Tetraacyl bis (arylme
Chill) Hexaazai Soul Titanium [WB₂A_Four] Is more
Reacts with tetraacyl arylmethyl hexaazaiso
Ur Titanium [WBA_FourH]
Reel Methyl Hexaazai Soul Titanium [WBA_Five] Or
Tetraacyl hexaaza soul titanium [WA_FourH₂],
Is generated. Pentaacyl arylmethyl hexaazai
Soul Titanium [WBA_Five] Dearylmethyl or te
Trasyl Hexaazai Soul Titanium [WA_FourH₂]
Pentaacylhexaazaisole produced by silation
Titanium [WA_FiveH] is acylated
Luhexa Azai Soul Titanium [WA₆] Will generate. It
When the reaction proceeds further, hexaacyl hexaazaiso
Ur Titanium [WA ₆] By the reduction of the acyl group
Alkyl pentaacyl hexaaza soul Soul titanium
[WA_FiveR¹], Dialkyl tetraacyl hexaazaiso
Ur Titanium [WA_FourR¹ ₂], Trialkyl triacyl
Kisaazai Soul Titanium [WA₃R¹ ₃] Produces
it is conceivable that.

An acyl group such as WA ₅ R ¹ is reduced to give W
A route in which BA ₄ R ^{1 is formed} , which is then reductively dearylmethylated to WA ₄ R ¹ H, which is acylated to form BA ₄ R ¹ , is also conceivable. In addition, a route in which WA ₅ R ¹ is produced by reducing the acyl group of WA ₅ H to WA ₄ R ¹ H and then acylating it is also conceivable. In the reaction of reductive dearylmethylation of hexakis (arylmethyl) hexaazaisourtitanium [WB ₆ ] represented by the reaction formula (10) in the presence of an acylating agent, when the reaction is carried out in batch reaction, Accordingly, the composition ratio of the obtained product changes depending on the contact time when the reaction is carried out by a flow reaction. Further, the composition ratio may vary depending on the type of catalyst or solvent used, reaction temperature, reaction time, and the like. Therefore, by appropriately setting the reaction conditions, the production ratio of these products can be arbitrarily changed.

In the reaction represented by the reaction formula (10),
Is WB₆Reductive dearyl methylation in the presence of an acylating agent
One of the features is that Ie acylation
WB without co-agent₆Reductive dearyl methyl of
If done, WB₆The skeleton is disassembled, the purpose
The product cannot be obtained in high yield. This is WB₆Reed
WB obtained by dearylmethylation in the absence of a deoxidizing agent
_FiveH, WB_FourH₂, WB ₃H₃Secondary amines such as
It is presumed to be unstable. Therefore, WB₆I
Without reductive dearylmethyl to dearylmethyl product
And then acylation
In the general synthetic method based on
It is very difficult to synthesize azusayl titanium
It On the other hand, in the method represented by the reaction formula (10) of the present invention,
According to the method, a hex having an acyl group without skeleton decomposition
Saazai Soul Titanium Derivative [WB_nA_(6-n)]
Can be This is the WB produced in the early stage of the reaction_FiveH
Unstable secondary amines having arylmethyl groups such as
In order to stabilize the reaction system immediately by acylation, the skeleton
Solution is suppressed, and dearylmethyl and acylation proceed
It is thought to be possible.

Further, the reaction conditions represented by the reaction formula (10)
In, WA_FourH₂, WA_FiveSecondary amine structure such as H
The derivative having is also obtained as a stable product. this is,
WB ₆With the progress of dearylmethyl and acylation of
Hexaazaisol titanium having a secondary amine structure
It is speculated that the stability of the skeleton is improved. Formula of the invention
Reductive dearylme in the reaction represented by (10)
The chill reaction is usually carried out by contacting with a catalyst in the presence of a reducing agent.
Is performed by As such reducing agents and catalysts
For WB₆For promoting the dearylmethyl reaction of
So any combination can be used
It Usually, as the reducing agent, hydrogen, hydrazine, formic acid,
Formic acid amide or the like is used, and preferably hydrogen is used.
Be done. In addition, as a catalyst, the transition of Group 8 of the periodic table is usually used.
Metal transfer or a derivative thereof is used, and preferably,
Pd (OAc)₂, PdCl₂, Pd (NO₃)₂, Pd
O, Pd (OH)₂, Pd₃Pb₁Pd derivatives such as
And Pd metal; RuCl₃Ru derivatives such as, and Ru
A metal or the like is used, and more preferably Pd (OA
c)₂, PdCl₂Pd derivative and Pd metal such as
used. You can use these catalysts as they are,
Also, activated carbon, silica, alumina, silica-alumina,
Used by loading on various carriers such as zeolite and activated clay
You can also. Even if the catalyst is subjected to reduction treatment before being subjected to the reaction
Good. In the case of solid catalysts, treatments such as silylation and acylation
It is also possible to inactivate surface acid points by performing
Wear. The amount of catalyst also depends on the reducing activity of the catalyst.
WB of the catalytic metal used₆To weight ratio
Is usually expressed as 0.0001 to 20, preferably,
Used in 0.001-1.

Further, the inverse of the formula (10) of the present invention
The reductive dearylmethyl reaction in the reaction requires a catalyst
It is also possible to use a reducing agent that does not. Such a reduction
Examples of agents include NaBH_Four, LiAlH_FourSuch as gold
Group hydrides may be mentioned. It is represented by the formula (10) of the present invention.
As the acylating agent used in the reaction
Any one that can be acylated can be used.
Usually, N-acetoxysuccinimide, N-propionyl
Oxysuccinimide, N- (2-phenylacetoxy
A) N-hydroxysuccinimide such as succinimide
Ester; acetic anhydride, propionic anhydride, butyric anhydride, none
Water trifluoroacetic acid, pentafluoropropion anhydride
Acid, heptafluorobutyric anhydride, acetic acid-formic acid mixed acid anhydride
Carboxylic acid anhydrides such as; acetylimidazole, propyi
Onyl imidazole, trifluoroacetyl imidazole
And acyl imidazoles such as le. these
Among the acylating agents, N-acetoxysuccinimide, N
-N-hydroxy compounds such as propionyloxysuccinimide
When using succinic acid imide ester, WA_FiveR ¹,
WA_FourR¹ ₂Such as having an alkyl group as a substituent.
Kisaazai Soul Titanium production rate is suppressed, WB₂
A_FourAnd WA₆And the selectivity is improved. Therefore, WA
₆N-hydroxysuccinimide ester
Tell is preferably used. Furthermore, these acylations
The agents can be used alone or in combination of two or more. Especially,
N-acetoxysuccinimide, N-propionyloxy
N-hydroxysuccinimide such as succinimide
Stells and carboxylic acids such as acetic anhydride and propionic anhydride
The use of a mixture of anhydrides, WA₆, WA
_FourR¹ ₂, WA_FourH₂] Hexaaza having an acyl group
Isoul titanium derivative [WA_yR _(6-y)And WB₂A_Fourof
This is a preferable method because the production rate is improved.

Although the amount of the acylating agent varies depending on its reactivity, it is usually 0.1 to 100, preferably 1 to 100, expressed as a molar ratio of WB _{6 to} the arylmethyl group.
Used at 50. When N-hydroxysuccinimide ester and carboxylic anhydride are mixed and used as an acylating agent, the amount of the carboxylic acid anhydride is usually expressed as a molar ratio to N-hydroxysuccinimide ester, and is usually 0. It is used at 0.01 to 100, preferably 0.1 to 10.

The solvent used in the reaction represented by the formula (10) of the present invention may be any solvent which dissolves WB ₆ and does not adversely affect the reaction. For example, aromatic compounds such as benzene, toluene, ethylbenzene, xylene, cumene, cymene, diisopropylbenzene, phenylethyl ether, acetophenone and phenyl acetate; aliphatic esters such as ethyl acetate and methyl acetate; tetrahydrofuran, dioxane, tetrahydropyran, Cyclic or linear or branched ethers such as diethyl ether, dipropyl ether and diisopropyl ether; aliphatic alcohols such as methanol, ethanol, propanol, isopropyl alcohol and t-butyl alcohol; aliphatic ketones such as acetone and methyl ethyl ketone Is mentioned. These solvents may be used alone or in combination of two or more. If an aromatic compound such as benzene, toluene, ethylbenzene or xylene is used among the above solvents, W
This is a preferred method because the reaction rate of dearylmethylation of B ₆ is improved.

Aromatic compounds such as benzene, toluene, ethylbenzene and xylene can be used as reaction products such as WB ₂ A ₄ having an acyl group-containing hexaazaisosoul titanium derivative [WB _x A _(6-x). ], The hexaazaisourtitanium derivative having an acyl group produced by appropriately setting the amount of the solvent [WB _x
A _(6-x) ] can also be precipitated as a solid. This is effective for suppressing the further progress of the reaction, and the hexaazaissoultitanium derivative [WB _x A _(6-x) ] having an acyl group, which is a target product, is obtained as a liquid component by filtration or the like. It is a preferable method because it can be easily separated.

The amount of the solvent may vary depending on the solubility of the solvent used and the reaction temperature, but it is usually 0.1 to 100, preferably 0.1 to 100, expressed as a weight ratio with respect to the hexakis (arylmethyl) hexaazaisourtitanium used. Is 1
Used at 100. The reaction pressure is usually 0 to 1000.
kgf / cm ² -G, and when hydrogen is used as the reducing agent, the higher the pressure, the higher the reaction rate. Therefore, it is expressed by the partial pressure of hydrogen, preferably 0.1 to 500 kg.
f / cm ² -G, more preferably 0.5 to 200 k
gf / cm ² -G. In addition to hydrogen, an inert gas such as nitrogen, argon or helium may be present.

The reaction temperature is generally -20 to 300 ° C, preferably 0 to 200 ° C. The reaction time may vary depending on the conditions such as the catalyst used, the acylating agent, the solvent, etc., but is usually 0.1 to 500 hours, preferably,
It takes 1 to 200 hours. Polynitrohexaazaisourtitanium can be obtained by using the acyl-containing hexaazaisowurtzol titanium derivative [WB _x A _(6-x) ] of the present invention as a starting material and combining it with a nitration reaction. Further, when an acylating agent having a specific functional group is used as an acylating agent when synthesizing the hexaazaisowurthititanium derivative having an acyl group of the present invention [WB _x A _{( 6-x)} ], crosslinkability is improved. Polyacylhexaazaisosoul titanium of is obtained.

[0039]

【Example】

[0040]

Example 1 1.89 g (2.66 mmol) of hexabenzyl hexaazaisosoul titanium, 10% Pd-C
1.70 g (1.70 mg atom), N-acetoxysuccinimide 5.0 g (31.8 mmol), ethylbenzene 160 ml, acetic anhydride 3.24 g (31.8 mmo)
1) and the rotor were placed in a micro-bomb having an internal capacity of 300 ml, and the inside of the bomb was replaced with hydrogen. Then, 50 kgf / cm ² -G of hydrogen was introduced into the cylinder and stirred with a stirrer for 20 hours. The reaction solution was taken out from the bomb, the catalyst was filtered, and the solid on the filter paper was washed with chloroform 200
washed with ml. Filtrate (reaction solution and chloroform washing solution)
Was distilled off, the remaining solid was dissolved in 200 ml of chloroform, and 200 ml of 28% ammonia water was added from above.
Stir vigorously for 30 minutes. By this operation, N-acetoxysuccinimide is removed from the organic layer. The chloroform layer was taken out and the solvent was distilled off to obtain 1.29 g of a white solid. This was recrystallized from ethylbenzene to obtain 1.03 g of white solid (yield 75%). Analysis of this thing F
D-mass spectrum, ¹ H and ¹³ C-NMR, ¹³ C- ¹
Structural analysis was carried out using HCOSY, and it was confirmed to be tetraacetyldibenzylhexaazaisourtitanium. The analysis results of tetraacetyldibenzylhexaazaisourtitanium are shown below. FD-Mass spectrum 517 ([M + H] ^< +>). ¹ H-NMR spectrum (solvent CDCl ₃ , TMS standard)
δ (ppm) 1.94 (s, 6H, COCH ₃ ), 2.15 (s, 6)
_{H, COCH 3), 4.06 (} d, 2H, CH 2), 4.
29 (d, 2H, CH ₂ ), 5.09 (d, 2H, C
H), 5.70 (d, 2H, CH), 6.42 (s, 2)
H, CH), 7.3-7.5 (m, 10H, Ph). ¹³ C-NMR (solvent CDCl ₃ , TMS standard) δ (p
_{pm) 20.737 (CH 3),} 22.111 (CH 3), 5
_{6.428 (CH 2), 69.679 (} CH), 70.
592 (CH), 128.056 (Ph), 128.6
73 (Ph), 128.928 (Ph), 136.74
2 (Ph), 168.263 (CO). By ¹ H- ¹³ C COZY, it was identified by ¹³ C bound of ¹ H.

[0041]

Example 2 Example 1 except that the reaction time was 200 hours.
The reaction was carried out in the same manner as described above. The reaction product was analyzed by GC-mass spectrum, and the products were tetraacetyldibenzylhexaazaisourtitanium, pentaacetylbenzylhexaazaissoultitanium, hexaacetylhexaazaissoultitanium, and ethylpentaacetylhexaazaisoletitanium. It was confirmed that titanium and diethyl tetraacetylhexaazaisol titanium were produced. The yields were calculated based on the gas chromatographic detection sensitivities of the isolated tetraacetyldibenzylhexaazaisourtitanium and diethyltetraacetylhexaazaisourtitanium. 70%, pentaacetyl benzyl hexaaza soul Soul titanium 6.2%, hexaacetyl hexa aza soul Soul titanium 0.9%, ethyl penta acetyl hexa aza soul soul titanium 1.3%, diethyl tetra acetyl hexa aza aza It was found that soul titanium was produced in a yield of 1.1%. EI-of these products
The mass spectrum is shown below.

EI-mass spectrum of pentaacetylbenzyl hexaazaisosoul titanium 468 (2%, m / z), 425 (3%, [m-COC
H ₃ ] / Z), 255 (12%), 91 (66%, CH
_{2 Ph), 43 (100%} , COCH 3). Ethyl pentaacetyl hexaaza soul Soul titanium EI
-Mass spectrum 406 (1%, m / z), 363 (1%, [m-COC
H ₃ ] / Z), 278 (2%), 236 (5%), 19
3 (10%), 109 (12%), 43 (100%, C
OCH ₃ ), 29 (15%, CH ₂ CH ₃ ), 15 (8
%, CH _3).

EI-mass spectrum of diethyl tetraacetyl hexaazaisosoul titanium 392 (1%, m / z), 278 (1%, [m-COC
H ₃ ] / z), 236 (10%), 193 (25%),
138 (30%), 109 (45%), 97 (20
%), 81 (81%), 69 (60%), 56 (20
%), 43 (100%, COCH ₃ ), 29 (20%,
CH ₂ CH ₃ ), 28 (52%), 15 (20%, CH
₃ ). Hexaacetylhexaazaisosoul EI-mass spectrum of titanium 420 (5%, m / z), 377 (5%, [m-COC
H ₃ ] / z), 335 (10%), 295 (15%),
208 (12%), 165 (10%), 123 (12
%), 43 (100%, COCH ₃ ).

[0044]

Example 3 Without using N-acetoxysuccinimide,
The reaction was performed in the same manner as in Example 2 except that 32.4 g of acetic anhydride was used. During the reaction, the reaction solution was sampled and the components were analyzed by FD-mass spectrum. As a result, diacetyltetrabenzylhexaazaisourtitanium (M ⁺ 612) and triacetyltribenzylhexaazaissoultitanium (M ⁺ 564) were identified. It was found that it was produced as an intermediate. In addition, as products obtained by reducing the acetyl group, ethyldiacetyltribenzylhexaazaisourtitanium (M ⁺ 550), ethyltriacetyldibenzylhexaazaisourtitanium (M ⁺ 50)
2), the formation of diethyldiacetyldibenzylhexaazaisourtitanium (M ⁺ 488) was confirmed. The GC yield of the product after the completion of the reaction is as follows: triacetyltribenzylhexaazaisowurtzitane 13%, ethyldiacetyltribenzylhexaazaisourtitanium 3.1%, tetraacetyldibenzylhexaazaisourtitanium 7.5%. %,
Ethyltriacetyldibenzylhexaazaisoultitanium 32%, Diethyldiacetyldibenzylhexaazaisoultitanium 30%, Pentaacetylbenzylhexaazaisoultitanium 1.6%, Ethyltetraacetylbenzylhexaazaisoultitanium 1.1 %, Diethyltriacetylbenzylhexaazaisol titanium 6.2%,
Hexaacetylhexaazaisole titanium 0.5%, ethyl pentaacetylhexaazaisole titanium 1.2
%, And diethyltetraacetylhexaazaisourtitanium was 1.1%.

[0045]

Example 4 A reaction was carried out in the same manner as in Example 2 except that 7.5 g of N-acetoxysuccinimide was used without using acetic anhydride. During the reaction, the reaction solution was sampled and the components were analyzed by FD-mass spectrum. As a result, pentabenzylhexaazaisourtitanium ([M
+ H] ⁺ 619), acetylpentabenzylhexazaissoultitanium (M ⁺ 660), diacetyltetrabenzylhexaazaissoultitanium (M ⁺ 612), triacetyltribenzylhexazaissoultitanium (M ⁺ 5)
It was found that 64) was produced as an intermediate. The GC yield of the product after completion of the reaction was 74% for diacetyltetrabenzylhexaazaisourtitanium, 15% for triacetyltribenzylhexaazaisoultitanium, and 3% for tetraacetyldibenzylhexaazaisoultitanium.

[0046]

Examples 5 to 7 The reaction was carried out in the same manner as in Example 4 except that the reaction time was 300 hours and the type and amount of the acylating agent, the hydrogen pressure and the catalyst amount were changed. The reaction conditions and product yields are shown in Table 1. From Table 1, the yield of tetraacetyldibenzylhexaazaisourtitanium is 1) increase hydrogen pressure, 2) increase catalyst amount, 3)
It can be seen that the improvement can be obtained by mixing N-acetoxysuccinimide and acetic anhydride.

[0047]

[Table 1]

[0048]

Comparative Example 1 The reaction was carried out in the same manner as in Example 4 except that N-acetoxysuccinimide as an acylating agent was not used. After completion of the reaction, the reaction solution was taken out from the cylinder and 5.0 g of N-acetoxysuccinimide (3
1.8 mmol), acetic anhydride 3.24 g (31.8 mm)
ol) was added and the mixture was stirred for 3 hours. Then, the reaction solution was taken out and analyzed by gas chromatography. Hexaazaisourtitanium having an acyl group was not produced at all, and production of diacetylpiperazine (0.14 g) was confirmed. It is considered that this was generated by the decomposition of the hexaazaisourtitanium skeleton, and this result indicates that about 30% of the hexaazaisourtitanium was decomposed.

[0049]

INDUSTRIAL APPLICABILITY According to the present invention, a precursor of a high-density nitro compound, which is a raw material for explosives, a monomer of a high-molecular material such as polyamide, and hexaazaisourtitanium having an acyl group which is useful as a high-density crosslinking agent The derivative is obtained.

Claims (4)

[Claims] 1. Hexakis (arylmethyl) hexaazaisosoultitanium represented by the general formula (1) is reductively dearylmethylated in the presence of an acylating agent and is represented by the general formula (1). A process for producing an acyl-substituted hexahexaisosoul titanium. WB ₆ (1) [In the formula, B represents an arylmethyl group, and W represents a hexavalent hexaazaisosoul titanium residue represented by the following formula (2). ] [Chemical 1] 2. A method for producing a hexaazaisosoul titanium derivative represented by the general formulas (3) and (4) by the method according to claim 1. WB _X A _(6-X) (3) WA _y R _(6-y) (4) [wherein, x and y are integers of 1 to 5, A is an acyl group having 1 to 10 carbon atoms, and B is aryl. The methyl group and W represent a hexavalent hexaazaisosoul titanium residue represented by the following formula (2). ] [Chemical 2] 3. The method for producing a hexaazaisourtitanium derivative according to claim 2, wherein the acylating agent is N-hydroxysuccinimide ester. 4. The method for producing a hexaazaisourtitanium derivative according to claim 2, wherein the acylating agent is a mixture of N-hydroxysuccinimide ester and carboxylic acid anhydride.