The method of acylation hexacis(phenylmethyl)hexaazatetracyclo

 

(57) Abstract:

Describes how acylation hexacis(phenylmethyl)hexaazatetracyclo formula (1): WB6(1) where In is phenylmethyl and W represents the residue of hexavalent hexaazatetracyclo represented by the formula (2)

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restorative diphenylmethylsilane, comprising contacting hexacis(phenylmethyl)hexaazatetracyclo heterogeneous catalyst recovery in the presence of Alliluyeva agent and reducing agent in a solvent for the specified hexacis(phenylmethyl)hexaazatetracyclo, characterized in that the contacting between WB6and heterogeneous catalyst recovery is permitted only with the obligatory presence of both reagents: Alliluyeva agent and a reducing agent to obtain a mixture containing at least one derivative tetraallylsilane formula (3) WA4BnH(2-n)where W, as defined above, N represents a hydrogen atom, a represents a1-WITH10acyl group, n is 0-2. The technical result - obtaining the desired products with consistently high yield and effective suppression of decomposition hexaazatetracyclo skeleton. 4L)hexaazatetracyclo. More specifically, the present invention relates to a method of acylation hexacis(phenylmethyl) hexaazatetracyclo (hereinafter, often refers simply to "WB6") restorative diphenylmethylsilane in the presence Alliluyeva reagent comprising contacting (a) WB6and (b) heterogeneous catalyst recovery in the presence of (C) Alliluyeva agent and (d) reducing agent (e) solvent suitable for WB6spending so the reaction rehabilitation diphenylmethylsilane/acylation WB6(a), and in the absence of one of the reagents is Alliluyeva reagent (s) and reductant (d) interaction between WB6(a) and heterogeneous catalyst recovery (b) does not occur. In the method according to the present invention, upon receipt derivatives tetraallylsilane (which are suitable as precursors hexanitrohexaazaisowurtzitane used to improve performance characteristics of conventional explosives) by acylation WB6can effectively suppress the decomposition hexanitrohexaazaisowurtzitane skeleton, which probably occurs at the initial stage of the reaction allisonia WB6as an initial matter what but the method according to the present invention is industrially useful. Additionally, the method according to the present invention is also useful because in comparison with conventional methods can effectively suppress the decrease of the catalytic activity of the catalyst recovery taking place during the reaction.

As a conventional method of obtaining tetrazoles(phenylmethyl)hexaazatetracyclo (hereinafter, often refers simply to "WA4B2") there is a method in which hexacis(phenylmethyl)hexaazatetracyclo (i.e. WB6subject to the recovery diphenylmethylsilane in the presence Alliluyeva reagent to obtain thus WA4B2(see "Tetrahedron", vol. 51, 16, 4711-4722 (1995), application for international patent publication WO 96/23792 and WO 97/20785 and U.S. patent 5693794).

In addition, there is a method in which WA4B2subject restorative diphenylmethylsilane to get so tetraallylsilane (hereinafter, often refers simply to "WA4H2") (see the above-mentioned WO 96/23792).

In each of these patent and non-patent documents the receipt WA4B2is sposobnosti and the like) are loaded into the reactor at a relatively low temperature (so E. from 5 to 25o(C) to obtain a mixture, and then is introduced into the reactor, the hydrogen gas as a reducing agent, at the same time maintaining the temperature of the mixture at the above-mentioned relatively low temperature, followed by stirring, spending thus reaction (exothermic reaction), and the temperature of the reaction system is increased to the desired level (i.e., from the 40oup to 70oC) due to the heat generated in the reaction. In this way WB6subject restorative diphenylmethylsilane in the presence Alliluyeva reagent in order to carry out the acylation WB6gently, thus preventing decomposition WB6. In this way, because the original substance and other reagents are loaded into the reactor at a relatively low temperature, decomposition WB6under the influence of temperature can be suppressed. However, even this method is not possible with a satisfactory result to suppress the decomposition WB6. Moreover, this method is accompanied by the occurrence of unwanted side reactions such as adverse reaction recovery, in which the acyl group associated with hexaethylguanidinium the skeleton, resulting in acylation WB6

In the above method of the prior art the reaction begins at a relatively low temperature (i.e., from 5 to 25oC). However, it is possible to start the reaction so that the reaction was started after the temperature of the mixture of the source materials and reagents increases to a predetermined level (i.e., from 40 to 70oC). As an example of such a method in which the reaction begins after raising the temperature of the mixture of starting compound/other reagents to a predetermined level, can be mentioned a method in which the temperature of the mixture of the source materials (i.e. WB6) and other reagents (including allerease reagent, solvent, catalyst and the like) is increased to a predetermined level without adding to the mixture of hydrogen gas as a reducing agent, and then added to the mixture of gaseous hydrogen for the reaction. However, this method has several disadvantages, because there is a noticeable decomposition WB6, i.e., problems associated with the above-mentioned method of the prior art, it is impossible to solve.

In addition, the disadvantage of the above known method is that the catalytic activity of Goethe th reaction, probably reduced. Usually it is desirable that the deactivated catalyst is subjected to regeneration with a view to its recycling. However, for the regeneration of the deactivated catalyst should be repeated activation, which is costly and expensive. Therefore, from the industrial point of view, the recycling of the catalyst impractical. In addition, the above problem of the decrease of catalytic activity has another disadvantage in case of difficulty carrying out industrial-continuous way. Therefore, it is desirable to prevent the reduction in the activity of a heterogeneous catalyst recovery during the reaction.

As mentioned above, a known method consists in reducing diphenylmethylsilane WB6in the presence of Alliluyeva reagent, it is impossible to derive tetraallylsilane with consistently high yield and to prevent decomposition hexaazatetracyclo skeleton. In addition, the lack of commonly accepted method is the reduction of catalytic activity of the catalyst during the reaction. Therefore, there are difficulties in carrying out reactions of industrial-NEPA, aimed at solving the above problems associated with the methods of the prior art. The result was unexpectedly found that the method of obtaining a reaction mixture containing at least one derivative tetraallylsilane, which consists in contacting (a) hexacis(phenylmethyl)hexaazatetracyclo (WB6and (b) heterogeneous catalyst recovery in the presence of (C) Alliluyeva reagent and (d) reducing agent (e) solvent suitable for WB6(a) is the reaction of restorative diphenylmethylsilane/acylation WB6(a) eliminating the contact between WB6(a) and heterogeneous catalyst recovery (b) in the absence of one alleluya reagent (s) and reductant (d), it becomes possible to prevent not only the decomposition hexaazatetracyclo skeleton (which probably occurs at the initial stages of the reaction acylation WB6), but also decrease the activity of the catalyst recovery during the reaction, obtaining the desired derivative tetraallylsilane with consistently high output. The present invention is based on the above-mentioned opening.

The main objective of the infusion> that can be used to obtain stable derivatives tetraallylsilane high yield, at the same time preventing the decomposition hexaazatetracyclo skeleton WB6(which probably occurs at the initial stages of the reaction acylation WB6and at the same time preventing the decrease in catalyst activity recovery during the reaction.

The above and other objectives, features and advantages of the present invention will become apparent from the subsequent detailed description and the accompanying drawings and the appended claims.

Brief description of drawings

Figure 1 is a micrograph (h) taken with a scanning electron microscope (SEM) raw hexabenzylhexaazaisowurtzitane obtained in comparative example 3, in which the spent washing;

Figure 2 is a photomicrograph taken with a SEM (h), crystals hexabenzylhexaazaisowurtzitane obtained in comparative example 4, in which raw hexabenzylhexaazaisowurtzitane obtained in comparative example 3, recrystallized;

Figure 3 is a photomicrograph taken with a SEM (h), to illegalisation, obtained in comparative example 3, and recrystallized

Figure 4 is a photomicrograph taken with a SEM (h), crystals hexabenzylhexaazaisowurtzitane obtained in comparative example 9, after washing.

A detailed description of the invention

In accordance with the present invention results from the method of acylation hexacis(phenylmethyl)hexaazatetracyclo recovery diphenylmethylsilane in the presence Alliluyeva reagent hexacis(phenylmethyl)hexaazatetracyclo, represented by the following formula (1):

WB6,

where is each independently represents phenylmethylene group, and W represents the residue of hexavalent hexassistant, represented by the following formula (2):

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which comprises contacting (a) hexacis(phenylmethyl)hexaazatetracyclo and (b) heterogeneous catalyst recovery in the presence of (C) Alliluyeva reagent and (d) reducing agent (e) solvent suitable for hexacis(phenylmethyl)hexaazatetracyclo (a), in which the reaction occurs rehabilitation diphenylmethylsilane/acylation hexacis(phenylmethyl)hexaazatetracyclo (a) obtaining the reaction SMEs alleluya reagent (s) and reductant (d) interaction between hexacis(phenylmethyl)hexaazatetracyclo (a) and heterogeneous catalyst recovery (b) is missing.

For easier understanding of the present invention the main features and the various preferred embodiments of the present invention are listed below:

1. The method of acylation hexacis(phenylmethyl)hexaazatetracyclo recovery diphenylmethylsilane in the presence Alliluyeva reagent hexacis(phenylmethyl)hexaazatetracyclo, represented by the following formula (1):

WB6,

where is each independently represents phenylmethylene group, and W represents the residue of hexavalent hexaazatetracyclo, represented by the following formula (2):

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which comprises contacting (a) hexacis(phenylmethyl)hexaazatetracyclo and (b) heterogeneous catalyst recovery in the presence of (C) Alliluyeva reagent and (d) reducing agent (e) solvent suitable for hexacis(phenylmethyl)hexaazatetracyclo (a), resulting in the reaction of restorative diphenylmethylsilane/acylation hexacis(phenylmethyl)hexaazatetracyclo (a) obtaining a reaction mixture containing at least one derivative tetraallylsilane, and in the absence of one alleluya reagent (s) and reductant (d) vzaimodeistvuet.

2. The method under item 1 above, in which the reaction rehabilitation diphenylmethylsilane/acylation hexacis(phenylmethyl)hexaazatetracyclo (a) is conducted at a temperature of from 40 to 160oC.

3. The method according to p. p. 1 or 2 above, in which the solvent (e) is a solvent containing an amide group.

4. The method according to one of the PP 1-3 above, in which hexacis(phenylmethyl)hexaazatetracyclo (a) and the solvent (e) is a solution of (a) to (e) and the heterogeneous catalyst recovery (b) and the reducing agent (d) is a mixture of (b) and (d), and where the solution (a) to (e) is in contact with the mixture (b) and (d) in the presence of Alliluyeva reagent (s).

5. The method according to one of paragraphs.1-3 above, in which hexacis(phenylmethyl)hexaazatetracyclo (a) and the solvent (e) is a solution of (a) to (e) and the heterogeneous catalyst recovery (b), allerease reagent (s) and reducing agent (d) is a mixture of (b), (C) and (d), and the mixture (b), (C) and (d) is prepared by mixing heterogeneous catalyst recovery (b) and reductant (d) and then adding Alliluyeva reagent (s) to this solution, and where the solution (a) to (e) is in contact with the mixture (b), (C) and (d).

6. The method according to one of the PP 1-5 above, in which the th following formula (3):

WA4BnH(2-n),

where n is an integer from 0 to 2, each And independently represents C1-C10acyl group, N represents a hydrogen atom and each of V and W is defined above.

A characteristic feature of the method of the present invention is that the recovery diphenylmethylsilane WB6is carried out in the presence of Alliluyeva reagent in contact WB6and heterogeneous catalyst recovery in the conditions under which the interaction between WB6and heterogeneous catalyst recovery occurs only in the presence of as Alliluyeva reagent and a reducing agent. As a result, the decomposition WB6that probably occurs during the reaction of acylation WB6, can effectively be suppressed.

It is known that, when WB6subject restorative diphenylmethylsilane in the absence Alliluyeva reagent formed derivatives hexaazatetracyclo containing a secondary amino group (such as WB5H, WB4H2and WB3H3), which have an unstable structure, and they readily undergo decomposition them hexaazatetracyclo skeleton. On the other hand, also Izv the reagent, the above-mentioned unstable derivatives hexaazatetracyclo containing a secondary amino group, allroots immediately after their formation to the formation of stable acylated derivatives hexaazatetracyclo so that the decomposition hexaazatetracyclo skeleton can be prevented (see application for international patent publication WO 96/23792). However, quite unexpectedly, that if the reaction rehabilitation diphenylmethylsilane WB6in the presence of Alliluyeva reagent at the same time to avoid interaction between WB6and heterogeneous catalyst recovery in the absence of one of the reagents is Alliluyeva reagent and a reducing agent, it is possible to effectively suppress the decomposition WB6compared with conventional methods.

In addition, the method according to the present invention can effectively suppress the decrease of catalytic activity during the reaction as compared with conventional methods. Due to this advantage of the method according to the present invention is that the heterogeneous catalyst recovery used in the reaction, can be recycled without conducting time-consuming processing for regeneration of the catalyst. This from what I catalyst to remove solvent and other components, adhering to the catalyst. (Usually the regeneration of deactivated heterogeneous catalyst for recovery is carried out using an industrial unsuitable operation, which is not only time consuming but also costly. For example, in the case of deactivation of the catalyst on the carrier regeneration is carried out, for example, cumbersome and expensive method, in which the catalyst is subjected to oxidation, and then the treated catalyst is dissolved in a solvent, followed by immobilization of the catalyst on the carrier). In addition, due to the aforementioned effect of suppressing the decrease of catalytic activity the method according to the present invention can be used best for the industry continuous method.

Below the present invention will be described in more detail.

The method of synthesis WB6represented by the formula (1), with no restrictions. However, it is preferable that WB6used in the present invention, was synthesized by cyclization of arylmethylidene and glyoxal with the allocation of water in the presence of an acid catalyst. As for purity WB6it is preferable that WB6was a product of high purity, purity pornositeleri diarylethylene/acylation.

In the method according to the present invention WB6(a) of formula (1) is typically used in amounts of from 0.0001 to 0.4, preferably from 0.001 to 0.3, more preferably from 0.01 to 0.15, expressed in the weight ratio WB6(a) to the solvent (e).

Preferably, during downloading WB6in the reactor, WB6was dissolved in the solvent (e). However, WB6may not completely dissolve in the solvent and placed in a solvent in the form of a suspension, in which only a portion WB6soluble in the solvent. It is preferable to use a solution in which WB6completely dissolves in the solvent.

Regarding the reaction solvent (e) used in the method according to the present invention, there are no particular restrictions provided that the solvent does not affect adversely on the reaction. In particular, an organic solvent containing an amide group, is preferable for increasing the reaction rate and yield derivatives tetraallylsilane. Examples of organic solvents containing amide group include N,N-dimethylacetamide, N,N-dimethylformamide, 1,3-dimethyl-2-imidazolidone, N-methyl-2-pyrrolidone and the fact podobnie solvents can be used individually or in combination.

In the method according to the present invention as a reducing agent (d) is commonly used gaseous hydrogen.

The reducing agent (d) is usually used in an amount of from 0.67 to 10000, preferably from 0.67 to 1000, more preferably from 2 to 50 in the molar ratio of reducing agent to arylmethyl groups WB6. When as a reducing agent (d) used hydrogen gas, the pressure of the reaction is usually in the range from 0.001 to 10 kgf/cm2, preferably from 0.01 to 30 kgf/cm2, more preferably from 0.01 to 10 kgf/cm2most preferably from 2 to 5 kgf/cm2, expressed as the partial pressure of hydrogen. When as a reducing agent (d) used hydrogen gas, the reaction can satisfactorily proceed, even if the pressure of the reaction (the partial pressure of hydrogen) is equal to 10 kgf/cm2or less. However, when using the reaction equipment with such a device, where the diffusion rate of hydrogen in the reactor and the rate of dissolution of hydrogen in the reaction solution becomes low (for example, when using an autoclave), you can use a high hydrogen pressure (up to about 50 kgf/cm2) to support asnau hydrogen in the reaction mixture can be inert gases such as nitrogen, argon and helium.

In respect of heterogeneous catalyst recovery (b) used in the method according to the present invention, there are no particular limitations provided that it is able to speed up the recovery diphenylmethylsilane WB6and remains in a heterogeneous state in the solvent (e). As a heterogeneous catalyst recovery (b) usually is used a catalyst containing a metal belonging to the platinum group or its containing derivative. Preferred examples of heterogeneous catalysts recovery include compounds Pd (such as Pd(OAc)2, PdCl2Pd(NO3)2, PdO, Pd(OH)2Pd3Pb and Pd3Te), alloys of Pd and Pd metal, and connections EN (such as RuCl3), alloys of Ru and metallic Ru. Of these compounds Pd (such as Pd(OAc)2and PdCl2), alloys of Pd and Pd metal are more preferable. It is possible that among the above catalysts, some catalysts become homogeneous during the reaction depending on the type of solvent. In respect of such catalyst preferably, before use, the catalyst gave this kind, in which he could not dissolve the al. Examples of carriers include activated carbon, silica, alumina, silicates, zeolite, activated clay, zirconium dioxide and titanium dioxide. Among these media, activated carbon is particularly useful because of its low reactivity in relation to the carboxylic acid derived Alliluyeva agent in the reaction system, and it also has a relatively low reactivity against other chemicals. In addition, to improve catalytic activity preferably, the catalyst was subjected to recover before use in the reaction of restorative diphenylmethylsilane. As the reductant for the implementation of its restoration preferred hydrogen gas, hydrazine or formaldehyde. When you want to use the catalyst on the carrier, the surface of the carrier can be processed so that inactivated acid sites on the surface of the media, were treated with similarobama, acylation and the like, or in such a way as to activate the acid sites present on the surface of the carrier, activating (such as Perella adsorption of substances with basic properties (for example, NaOH). Each of the treatments for modification of the acid sites on the surface of the carrier can be performed either before or after deposition of the catalyst on the carrier.

Preferably, the heterogeneous catalyst recovery (b) was used in the form of a suspension obtained by dispersing the catalyst in a liquid such as dispersion medium. Dispersion medium to prepare a suspension of the catalyst (b) has no special limitation, but it is preferable to use the same solvent as the solvent (e).

Allerease reagent (s) used in the method according to the present invention has no particular restrictions, provided that it is capable of allievate secondary amino groups with the formation of N-acyl. In General use allerease reagent such as anhydrides of carboxylic acids such as acetic anhydride, propionic anhydride, formic anhydride, the anhydride of lactic acid and anhydride mixture of acetic acid and formic acid. These anhydrides of carboxylic acids can be used individually or in combination. In the alternative case, the above anhydrides of carboxylic acids can be used in combination with carboxylic esters of N-N-propionylcarnitine and N-(2-phenylacetate)succinimide; examples of ellimination include acetylimidazole and propylimidazol. Among these alleluya reagents preferable to use only one anhydrides of carboxylic acids, and most preferred carboxylic acid anhydride is acetic anhydride. In addition, when used allerease reagent is a liquid (such as acetic anhydride, propionic anhydride, the anhydride mixture of acetic acid/formic acid), such allerease reagent can also be used as solvent.

Allerease reagent (C) is usually used in an amount of from 0.67 to 50, preferably from 0.67 to 5, more preferably from 0.67 to 2, expressed as the molar ratio Alliluyeva reagent to arylmethyl groups WB6(a).

The reaction temperature during the restoration diphenylmethylsilane/acylation WB6in the method according to the present invention will typically range from 40 to 160oC, preferably from 40 to 100oS, more preferably from 40 to 80oS, even more preferably from 50 to 80oC and most preferably from 50 to 70oC. When this reaction is carried out at a relatively low temperature, namely from the 40oTo lower the effect of temperature can be suppressed. Therefore, it is preferable to carry out the recovery diphenylmethylsilane/acylation at a relatively low temperature (40oWith up to lower than 80oC). When the reaction is carried out at relatively high temperatures, namely from 80 to 160oWith, despite the fact that the chemical decomposition WB6during diphenylmethylsilane/acylation WB6suppressed by the method according to the present invention, the decomposition WB6under the action of temperature occurs, and therefore, it becomes necessary to increase the rate of conversion WB6. In this case, it is favorable to increase the solubility WB6at high temperature, and thereby the reaction at relatively high concentrations WB6; however, from the viewpoint of suppressing the decomposition WB6under the action of temperature, it is preferable to avoid carrying out the reaction at a high temperature from 80 to 160oC. the Pressure of the reaction rehabilitation diarylethylene/acylation in the method according to the present invention will typically range from 0.001 to 100 kgf/cm2, preferably from 0.01 to 30 kgf/cm2, more preferably from 0.01 to 10 kgf/cm2most of predpochtitelnye in relation to the reaction time recovery diphenylmethylsilane/acylation in the method according to the present invention achieve the desired derivatives tetraallylsilane. In General, however, satisfactory is the reaction time is 10 hours or less.

The increase in the rate of transformation WB6in the reaction of restorative diphenylmethylsilane/acylation can be achieved by increasing the amount of reducing agent and/or catalyst or increasing the reaction temperature. In the method according to the present invention most preferably, the reaction rate was controlled by increasing or decreasing the number of catalyst. The amount of catalyst varies significantly depending on its catalytic activity, but is usually from 0.0001 to 1.0, preferably from 0.01 to 0.8, more preferably from 0.1 to 0.4, expressed as the weight ratio of the catalyst to be used WB6.

If you prefer, you can use the promoter of acid type as a promoter of the reaction. Examples of promoters acid type include organic acids such as carboxylic acids and phenols, and bromine(Br)-containing promoters of acid type. Among these promoters are organic acids have a low ability to cause decomposition WB6but have low promotor action against reaction restorative defenily tornam action against reaction rehabilitation diphenylmethylsilane/acylation and a relatively low ability to cause decomposition WB6. Therefore, bromine(Br)-containing promoter acid is preferable organic acid. Examples of the bromine(Br)-containing promoters acid type include NVG and a substance which forms NVG, undergoing hydrogenation reactions. Specifically, "a substance that forms NVG, undergoing hydrogenation reactions" is a substance that has such a property that when it is loaded into the reactor, it is aprotic form, and which forms NVG being gidrirovanny under the action of a heterogeneous catalyst for recovery in the atmosphere of the reducing agent (hydrogen atmosphere). Examples of substances that form NVG, undergoing hydrogenation reactions include phenylpropyl, benzylbromide, acetylmuramic and bromine (Br2). Since VG-containing promoter acid type has the ability to cause decomposition WB6then from the viewpoint of suppressing the decomposition WB6that is the subject of the present invention, it is preferable not to use bromine(Br)-containing promoter acid type.

To suppress decomposition WB6it is important to turn WB6(which is unstable when exposed to heat and acid) in the acylated soedinenii two nitrogen atom in the structure WB6etilirovany, the resulting acylated derivative hexaazatetracyclo has a very high stability to heat and acid compared with the stability WB6. To increase both the speed of response and restoration diphenylmethylsilane WB6and speed acylation WB6it is preferable that the reaction was carried out at relatively high temperatures. To accelerate the reaction Alliluyeva reagent used in the method according to the present invention, it is preferable to select a reaction temperature equal to 40oC or higher. However, because the decomposition WB6increases at temperatures higher than 160oSince, it is preferable that the reaction temperature was chosen in the range from 40 to 160oC. In the method according to the present invention, it is preferable to adjust the reaction conditions so that the reaction temperature was in the range of from 40 to 160oWhen WB6contact with a heterogeneous catalyst recovery, or to a reaction temperature in the range from 40 to 160oWith was achieved immediately after WB6contact with a heterogeneous catalyst recovery.

When to turn WBbe used as the solvent of the reaction solvent, containing amide group. An organic solvent containing an amide group, preferred because it is weakly basic and, therefore, can neutralize the acidic proton, formed by acylation as a by-product. That is, an organic solvent containing an amide group, can support the reaction system near the neutral point, thus suppressing the decomposition WB6under the action of the acid proton, even at high temperatures. In addition, the basicity of the solvent containing an amide group, contributes to the acylation WB6. The reason for this is as follows. The secondary amine formed in the reaction of restorative diphenylmethylsilane WB6is unstable so that the secondary amine, and probably undergoes decomposition hexaazatetracyclo skeleton, if only the skeleton immediately protected by acylation of the secondary amine. Because the solvent containing an amide group (which is alkaline), contributes to the acylation of the secondary amine, the decomposition WB6you can suppress solvent containing an amide group.

The reaction rate recovery devenny catalyst recovery is already in a reduced state before the reaction. Therefore, it is most preferable to use a heterogeneous catalyst recovery, which had been subjected to pre-treatment with a view to its recovery. As a way to recover a heterogeneous catalyst reductant is used, the way in which the heterogeneous catalyst recovery in contact with the reducing agent. In respect of reducing agent used in the method of recovery, there are no particular limitations provided that it has a restorative activity. Examples of reducing agents include hydrogen gas, formic acid, hydrazine, alcohol, aldehyde, and the like. Among these reducing agents is preferred gaseous hydrogen. The reason for this lies not only in the fact that hydrogen gas has a high regenerative ability, but also in the fact that after recovering gaseous hydrogen is no need to wash the recovered catalyst, and the recovered catalyst, as such, can be used in the method according to the present invention.

As examples of methods for contacting hexacis(phenylmethyl)hexaazatetracyclo (a) and heterogeneous catalyst for restoring the AI requirements, defined in the present invention (i.e., requirements about the lack of contact between WB6(a) and heterogeneous catalyst recovery (b) in the absence of one alleluya reagent (s) and reductant (d) ), may be mentioned the following methods (a) to (H):

(A) the way in which hexacis(phenylmethyl)hexaazatetracyclo (a) and the solvent (e) are in the form of a solution (a) to (e) and the heterogeneous catalyst recovery (b) and the reducing agent (d) are in the form of a mixture (b) and (d) solution (a) to (e) is in contact with the mixture (b) and (d) in the presence of Alliluyeva reagent (s);

(B) the way in which hexacis(phenylmethyl)hexaazatetracyclo (a) and the solvent (e) are in the form of a solution (a) to (e) and the heterogeneous catalyst recovery (b), allerease reagent (s) and reducing agent (d) are in the form of a mixture (b), (C) and (d), formula (b), (C) and (d) is prepared by mixing heterogeneous catalyst recovery (b) and reductant (d) and then adding Alliluyeva reagent (s), moreover, the solution (a) to (e) is in contact with the mixture (b), (C) and (d);

(C) the way in which hexacis(phenylmethyl)hexaazatetracyclo (a), the heterogeneous catalyst recovery (b), allerease reagent (s), reducing agent (d) and the solvent (e) contact the maker (s) are in the form of a mixture (C), (d) and (e) and hexacis(phenylmethyl)hexaazatetracyclo (a) and heterogeneous catalyst recovery (b) separately introducing into the mixture (C), (d) and (e) so that (a) and (b) in contact with each other in the presence of a mixture of (C), (d) and (e);

(E) the manner in which the heterogeneous catalyst recovery (b), allerease reagent (s), reducing agent (d) and the solvent (e) are in the form of a mixture (b), (C), (d) and (e) and hexacis(phenylmethyl)hexaazatetracyclo (a) is in contact with the mixture (b), (C), (d) and (e);

(F) the way in which hexacis(phenylmethyl)hexaazatetracyclo (a), allerease reagent (s), reducing agent (d) and the solvent (e) are in the form of a mixture (a), (C), (d) and (e) and the heterogeneous catalyst recovery (b) is in contact with the mixture (a), (C), (d) and (e);

(G) the manner in which the heterogeneous catalyst recovery (b), the reducing agent (d) and the solvent (e) are in the form of a mixture (b), (d) and (e) and hexacis(phenylmethyl)hexaazatetracyclo (a) and allerease reagent (s) are in the form of a mixture (a) and (C), where the mixture (b), (d) and (e) contact with the mixture (a) and (C), and

(N) the way in which hexacis(phenylmethyl)hexaazatetracyclo (a), the reducing agent (d) and the solvent (e) are in the form of a mixture (a), (d) and (e) and the heterogeneous catalyst recovery (b) and allerease what their methods (A), (C) and (G) are preferred.

In any of the above methods (a) to (H) above interaction is usually performed in the reactor. For example, in method (A) mixture (b) and (d) receive a download of the reducing agent (d) (described below) in a reactor containing a heterogeneous catalyst recovery (b), loaded it, and then a solution obtained by dissolving hexacis(phenylmethyl)hexaazatetracyclo (a) and Alliluyeva reagent (s) in the solvent (e) is added to viseporodicnog mixture (b) and (d).

Preferably for each of the above methods (a) to (H), so that the temperature of the mixture (a), (b), (C), (d) and (e) were in the range from 40 to 160oC and under pressure of from 0.001 to 100 kgf/cm2(the partial pressure of hydrogen) was carried out after preparation of the mixture (a), (b), (C), (a) and (e), or were executed as early as possible (for example, approximately 10 min after preparation of the above mixture.

The reaction mixture obtained by the method according to the present invention, includes at least one derived tetraallylsilane, heterogeneous catalyst recovery (b), the reducing agent (d) and the solvent (e). The reaction mixture may contain nebulosity, contained in the reaction mixture obtained by the method according to the present invention, generally represented by the following formula (3):

WA4BnH(2-n),

where n is an integer from 0 to 2, each And independently represents C1-C10acyl group, N represents a hydrogen atom and each of V and W defined above. Examples of derivatives tetraallylsilane represented by the formula (3) include tetrazoles(phenylmethyl)hexaazatetracyclo (WA4IN2), tetrachlorodibenzofuran (WA4BH) and tetrachlorodibenzofuran (WA4H2). WA4IN2turns into WA4H2through WA4BH in the further course of the reaction rehabilitation diphenylmethylsilane.

Of these three derivatives tetraallylsilane WA4H2especially suitable as predecessor hexanitrohexaazaisowurtzitane. In relation to the way nitration WA4H2you can refer to, for example, WO 96/23792.

Also WA4B2you can turn in hexanitrohexaazaisowurtzitane nitration by the conventional method (see, for example, WO 97/20785).

Regarding relations with the education you what to achieve, appropriately adjusting the reaction rate and reaction time. The reaction rate can be adjusted by changing the quantity of reducing agent, the reaction temperature and the activity and amount of the used catalyst. Most effectively regulate the speed can change the activity and amount of catalyst.

The reaction rate has a particularly great influence on the recovery diphenylmethylsilane WA4B2. When the reaction is carried out in conditions when it is low, the ratio of education WA4B2becomes high. At the same time, when the reaction is carried out under conditions where the reaction rate is high, then the rate of formation WA4H2becomes high. In addition, when longer reaction time, the ratio of education WA4H2increased.

For example, when the reaction is carried out under conditions under which a through 1 h after start of the reaction the total mass WB6WAB5THAT WA2B4and WA3B3in the reaction system becomes equal to 10% or less of the total mass of all derivatives hexaazatetracyclo in the reaction system (such conditions can be achieved by using as heterogeneous catalysis is A4BH and WA4H2obtained after 1 h after start of the reaction, respectively about 60%, about 15% and about 10%. In addition, when the reaction is carried out for 4 h in the above conditions, the outputs WA4B2THAT WA4BH and WA4H2become equal respectively to about 10%, about 5% and about 70%.

When it is desirable to obtain only WA4H2as at least one derived tetraallylsilane represented by the formula (3), the reaction is carried out with a high reaction rate over a long period of time. In particular, for example, when the reaction is carried out for 5 to 6 h in the conditions under which the total mass WB6WAB5THAT WA2B4and WA3B3becomes equal to 10% or less of the total mass of all derivatives hexaazatetracyclo in the reaction system within 1 h after start of the reaction (such conditions can be achieved by using as a heterogeneous catalyst recovery (b), 10% Pd-C in an amount of about 20 wt.% or more from WB6), you can only get WA4H2as at least one tetraallylsilane represented by the formula (3).

With Drogo tetraallylsilane, represented by formula (3), the reaction is carried out with a low reaction rate, for example, by using a catalyst having a low catalytic activity. In particular, for example, when the reaction is carried out in the conditions under which it occurs within 6 hours or more to obtain the total mass WB6WAB5THAT WA4B4and WA3B3equal to 10% or less of the total mass of all derivatives hexaazatetracyclo in the reaction system (such conditions can be achieved by using a catalyst having a very low catalytic activity), when the recovery diphenylmethylsilane received WA4B2almost does not occur and, therefore, WA4B2you can get as at least one derived tetraallylsilane represented by the formula (3).

The resulting WA4H2you can select from the reaction mixture as follows. After completion of the reaction to the resulting reaction mixture are added water (which is a good solvent for WA4H2for dissolution WA4H2in the water, and then the heterogeneous catalyst recovery (b) is separated from the reaction mixture, obtaining a liquid mixture. Then the >high purity (in the following this method refers to the method of deposition of crystals in the refinery").

Therefore, in the method according to the present invention, preferably, the heterogeneous catalyst recovery (b) was separated from the reaction mixture (containing WA4H2) obtained in the reaction, to obtain a liquid mixture, containing no catalyst, but containing the solvent (e), WA4H2and water, and then the obtained liquid mixture is subjected to distillation to remove water, precipitating crystals (the deposition of crystals in distilled) tetraallylsilane (WA4H2).

The most characteristic feature of the method of deposition of crystals when the distillation is that the crystals WA4H2high purity can be precipitated with a high yield of just deleting from the reaction mixture of components (such as water and allmetal) using distillation, having a boiling point lower than that of the solvent (such as a solvent containing an amide group).

WA4H2that precipitates as crystals, almost insoluble in the usual organic solvents, but it can be easily dissolved in proton a highly polar solvent such as outlets decomposition hexaazatetracyclo skeleton, where these other derivatives hexaazatetracyclo and decomposition products of the skeleton are contained in the solvent as an impurity. Using this property WA4H2water is used as a suitable solvent in which the substance dissolves) for the desired WA4H2is removed by distillation from a mixed solvent consisting of water and organic solvent, to precipitate crystals of the desired WA4H2, and the precipitated crystals are separated from the mixed solvent by dissolving the above-mentioned impurities in a conventional organic solvent (for example, a solvent containing an amide group). Thus, it is possible to obtain WA4H2high purity.

In relation to the liquid mixture used in the above method of deposition of crystals by distillation, does not require complete dissolution WA4H2in the liquid mixture, and WA4H2may be present partly in dissolved form (i.e., in the form of a suspension). However, it is preferable that in the above method of deposition of crystals when the distillation was used a liquid mixture containing no solid particles.

With regard to the pressure at which effect the Stripping of prigodin the hydrated solvent corresponds to the "first solvent", described in the examples below), you can use either the atmospheric pressure or a reduced pressure. In relation to the temperature at which carry out the distillation, there are no particular restrictions provided that suitable solvent can to drive away when the pressure specified for the distillation. For carrying out the distillation in a short period of time, it is preferable to carry out the distillation under reduced pressure specified for distillation, and the temperature, which is equal to or higher than the boiling point suitable solvent, installed at the specified reduced pressure. In addition, it is preferable to carry out the distillation under reduced pressure specified for distillation, and the temperature, which is equal to or above the boiling point suitable solvent and which is equal to or below the boiling point of the poor solvent (which corresponds to the "second solvent", as described in the examples below), where each point is suitable and unsatisfactory solvent is determined at the specified reduced pressure. When the distillation is carried out at this pressure and temperature, it becomes possible to separate suitable solvent from the poor solvent in this way Oh from 0.0000001 to 760 mm RT. Art. the lower the pressure, the less time required for distillation and requires a lower temperature for distillation, so that it becomes possible winning to reduce or suppress the manifestation of decay WA4H2under the action of temperature and hydrolysis of the solvent (s) (for example, a solvent containing an amide group). Therefore, it is preferable to carry out the distillation under reduced pressure of 200 mm RT. Art. or below.

In the method according to the present invention, when used in the deposition of crystals in the refinery, some amount of poor solvent may also otohata when a suitable solvent is removed by distillation under the condition that about 10 wt.% or more unsatisfactory solvent present in the initial liquid mixture remains unremoved. In addition, the complete removal of suitable solvent from a liquid mixture is not necessary. In fact, depending on the type suitable solvent and the type of the poor solvent is very difficult to completely separate suitable solvent from the poor solvent in the distillation in an industrial scale. Therefore, in the method of deposition of crystals peregusna the distillation residue, becomes equal to 0.2 or less, expressed as the weight ratio suitable solvent remaining in a poor solvent to the poor solvent. To obtain the desired compounds in high yields it is preferable to carry out the distillation until the amount of suitable solvent remaining in a poor solvent, becomes equal to 0.02 or less, expressed as the weight ratio suitable solvent to poor solvent.

The allocation method WA4H2filtration after precipitation of crystals by distillation briefly explained below.

The suspension containing WA4H2as the main solid component and a solvent (e) (for example, a solvent containing an amide group) as the primary liquid component, which is obtained by carrying out the method of deposition of crystals in distilled, and subjected to filtration using substances and devices that are suitable for the filtration of the suspension.

Typical examples of ways of filtering include a method in which filtration is carried out using filter paper, membrane filter or metalloceramic precipitated crystals WA4H2. You can use filters with different pore size, in combination with multi-stage filtration system.

The allocation of the resulting WA4IN2from the reaction mixture can be, for example, as follows. When the solvent of the reaction (e) is used, the solvent containing the amide group formed WA4IN2is dissolved in the solvent of the reaction (e). Therefore, the obtained WA4IN2you can select the way in which the heterogeneous catalyst is filtered off from the reaction mixture, receiving the filtrate, and then the resulting filtrate is subjected to distillation to remove the solvent (e), to obtain such images WA4IN2in solid form. In addition, when WA4B2is present in the reaction mixture in such a high concentration that WA4IN2spontaneously precipitates, WA4IN2you can select the way in which a good solvent for WA4IN2add to the reaction mixture to dissolve the precipitated there WA4IN2and heterogeneous catalyst recovery is filtered off from the reaction mixture with subsequent removal of restoredeletedfiles for WA4IN2include solvents containing an amide group such as N,N-dimethylacetamide, N,N-dimethylformamide, 1,3-dimethyl-2-imidazolidone and N-methyl-2-pyrrolidone; carboxylic acids such as formic acid, acetic acid and propionic acid; amines such as triethylamine and ethyldimethylamine; halogenated solvents such as chloroform, dichloromethane, carbon tetrachloride and phenylboronic.

In the method according to the present invention tetrachlorodibenzofuran (WA4H2), which is derived from one of tetraallylsilane formulas (3) and which is particularly useful as a precursor hexanitrohexaazaisowurtzitane, may be obtained by the above reaction rehabilitation diphenylmethylsilane/acylation to obtain at least one derived tetraallylsilane formula (3) in the above reaction conditions (temperature and pressure) until 100% of the derivatives hexaazatetracyclo formed in the reaction system is not turned in WA4H2.

However, to increase the rate of formation WA4H2preferably, the reaction temperature was increased when the total mass WB4
H2it becomes possible with the method in which the reaction rehabilitation diphenylmethylsilane WB6formula (1) is carried out at a relatively average temperature (for example, from 40 to lower than 80o(C) to obtain thus the reaction mixture containing derivatives tetraallylsilane formula (3), and then the reaction temperature increases (for example, up to 80-160oC) to conduct thus restorative diphenylmethylsilane derivatives tetraallylsilane. In the following, for convenience, the above reaction rehabilitation diphenylmethylsilane/acylation carried out at a relatively average temperature, often referred to as "the first stage reaction and the subsequent reaction of restorative diphenylmethylsilane conducted at a higher temperature reactions, often referred to as "reaction in the second phase. ne or more time points before and during the second reaction stage (preferably before the reaction of the second stage).

That is, in the method according to the present invention it is preferable that the reaction mixture (containing at least one derivative tetraallylsilane) obtained in the reaction of the first stage was the reaction system for rehabilitation diphenylmethylsilane, and the reaction system for rehabilitation diphenylmethylsilane was heated to and maintained at a temperature of from 80 to 160oWith, at the same time maintaining the amount of reducing agent in the reaction system recovery diphenylmethylsilane, at the level of the stoichiometric amount or higher, preferably significantly higher than the stoichiometric quantity, to restore at least one derived tetraallylsilane, where the reaction system at one or more time points add water before and during the second stage reaction, thus obtaining a reaction mixture containing tetrachlorodibenzofuran, represented by the following formula (4):

WA4H2,

where each of a, H and W are defined above.

Examples of typical methods for implementation of the above preferred method in the method according to nasociliary method simply refers to a "method of reaction of the first stage/second stage), include the following methods (1) to (5):

(1) a method in which after the reaction of the first stage in situ carry out the reaction of the second stage, using the same reactor, which was used in the first reaction stage;

(2) a method in which after the first reaction stage, the reaction mixture obtained in the reaction of the first stage is transferred into another reactor than that used in the first reaction stage and the second stage reaction is conducted in the other reactor (in method (2), the heterogeneous catalyst recovery contained in the reaction mixture obtained in the reaction of the first stage, it is possible to separate and isolate from the reaction mixture by filtration, and the like, and to the resulting mixture, you can add fresh heterogeneous catalyst recovery);

(3) a method in which the reaction of the first stage or the second stage reaction is conducted continuously;

(4) the way in which each reaction of the first stage and the second stage reaction is conducted continuously, where the reaction mixture obtained in the first reaction stage is saved before the second reaction stage, and maintain the reaction mixture was subjected to reaction of the second stage and

(5) the way in which each reaction of the first stage and the second stage reaction is conducted n is discontinuously transferred to another reactor, than that used in the first reaction stage.

As described in detail below, the method (1) has the advantage that even when part of the product WA4H2formed in the first reaction stage, is deposited on a heterogeneous catalyst recovery products WA4H2deposited on the catalyst, will be contained in the reaction mixture obtained in the reaction of the second stage, thus preventing the loss WA4H2. In the second reaction stage to the reaction system, water is added, and therefore, the composition of the reaction system, the reaction of the first stage is different from that of the reaction system the reaction of the second stage. Therefore, in method (1) for the reaction of the first stage when using the reactor, which was already involved in the reaction of the second stage, it is necessary to clean the reactor inside before setting it to the first reaction stage. On the other hand, in method (2) reaction of the first stage and the second stage reaction is conducted using different reactors. Therefore, the method (2) is advantageous in that by using two different reactors, which are, respectively, were involved only in the reaction of the first stage and only in reakcija the first stage and the second stage reaction is carried out or is carried out continuously) each of these methods (continuous media) is more advantageous in that, even when the first reaction stage and/or the second reaction stage is carried out or are carried out using the reactor(s) having a small capacity, it is possible to achieve a satisfactory rate of education. However, each of these methods has the disadvantage that the yield of the desired product tends to decrease. Methods (1) and (2), each of which is batchwise (not continuous), not have the above advantage, resulting in the formulation of continuous processes, however, these batch methods is advantageous in that the desired product can be obtained with high yield in comparison with how it takes place in the case of continuous methods.

Below is the explanation regarding the above-mentioned preferred method (method of reaction of the first stage/second stage) in the method according to the present invention, using as examples the method (1) (in which, after reaction of the first stage in situ is the reaction of the second stage using the same reactor, which was used in the reaction of the first stage) and the ways in which at least one of the first reaction stage and the second stage reaction is carried out continuously.

One recognized what is the reaction of the second stage, using the same reactor, which was used in the reaction of the first stage) is that the heterogeneous catalyst recovery used in the first reaction stage, it is also used as a heterogeneous catalyst recovery in the second reaction stage. This method is very advantageous in comparison with the method in which the catalyst contained in the reaction mixture of the first stage, is filtered to obtain a filtrate, and then to the obtained filtrate add fresh heterogeneous catalyst recovery for the reaction of the second stage. That is, in this way, when the solvent containing an amide group is used as the solvent (e), due to the low solubility WA4H2in a solvent containing an amide group, some food WA4H2formed in the reaction system in the reaction of the first stage, is deposited on a heterogeneous catalyst recovery depending on the reaction conditions. Even in this case, in method (1), in which the heterogeneous catalyst recovery used in the first reaction stage, is also used as a heterogeneous catalyst recovery in the reaction valachennai in the second reaction stage, preventing loss WA4H2.

In addition, another feature of the method (1) method of reaction of the first stage/second stage is that during the period of time between the end of the first reaction stage and the beginning of the second reaction stage and/or during the reaction of the second stage, the amount of reducing agent in the reaction system is maintained at a level sufficient to restore derivatives tetraallylsilane contained in the reaction mixture obtained in the reaction of the first stage (for example, the reducing agent may be in the reaction system in an amount which is 80% or more of the saturation concentration of reducing agent in the reaction system used in the reaction conditions (temperature and pressure)). The method of reaction of the first stage/second stage can advantageously be used to achieve a high rate of formation of the desired WA4H2. However, when the period of time between the end of the first reaction stage and the beginning of the second reaction stage and/or during the reaction of the second stage, the amount of reducing agent in the reaction system becomes insufficient to restore derivative tetraallylsilane to have a reduction in the activity of the catalyst. Therefore, for reliable high speed needed WA4H2it is important to maintain the amount of reducing agent in the reaction system at a level which is sufficient for recovery of derivatives tetraallylsilane. As described in detail below, in the reaction of the second stage for easy selection formed WA4H2from the reaction system to the reaction system (reaction mixture) add water. However, adding water to the reaction system leads to lower amounts of reducing agents (such as hydrogen gas) dissolved in the reaction system. Therefore, if there is a danger that the addition of water will result in reducing the quantity of reducing agent dissolved in the reaction system, to a level that is lower than the stoichiometric amount for the reaction of the second stage (reaction rehabilitation diphenylmethylsilane derivatives tetraallylsilane), it is necessary to increase the addition of the reducing agent in the reaction system (for example, increasing the pressure of hydrogen used as a reducing agent, to a level that is higher than that of the first reaction stage) for podderjanie.

Another feature of the method (1) method of reaction of the first stage/second stage is that after the first reaction stage to the reaction system, water is added in one or more time points before or during the reaction of the second stage (preferably before the reaction of the second stage). The reason for adding water to the reaction system is as follows. WA4H2has the property that it is almost insoluble in a solvent containing an amide group, and other common organic solvents; however, it is soluble in water. In the present invention, using the above property WA4H2that water is used for dissolving it WA4H2for the Department thus WA4H2from catalyst. Concerning the time of adding water to the reaction system, there are no particular restrictions provided that the addition is carried out after the reaction of the first stage and before separating the heterogeneous catalyst recovery from the reaction mixture containing WA4H2, which is described below. However, to prevent the strong adsorption WA4H2on a heterogeneous catalyst recovery is preferable to add water to the reaction with klonoa mixture, usually is in the range from 0.01 to 100, preferably from 0.1 to 10, more preferably from 0.2 to 5, expressed as the weight ratio of water to solvent (for example, a solvent containing an amide group) used in the reaction of the first stage.

Examples of the reducing agents used in the reaction of the second stage include gaseous hydrogen and hydrazine. Of these, the hydrogen gas is preferred.

When as a reductant in the reaction of the second stage using gaseous hydrogen, the pressure (pressure of the reaction) is usually in the range from 0.01 to 200 kgf/cm2preferably from 0.1 to 100 kgf/cm2, more preferably from 1 to 50 kgf/cm2, more preferably from 8 to 12 kgf/cm2expressed in the form of a partial pressure of hydrogen gas. In the present invention, the hydrogen gas can be used in combination with an inert gas such as gaseous nitrogen, gaseous argon and gaseous helium. When the reaction of the second stage uses a different reducing agent than hydrogen gas (such as hydrazine), the amount of reducing agent (other than hydrogen) is usually in the range from 1 to 10000, prefer2and WA4NR that are in the reaction system.

The reaction temperature in the second reaction stage is usually in the range from 40 to 200oC, preferably from 60 to 160oS, more preferably from 80 to 160oS, more preferably from 80 to 130oC.

After completion of the reaction of the second stage WA4H2high purity can be obtained as follows. First heterogeneous catalyst recovery (b) is separated from the reaction mixture of the second stage to obtain thus the liquid mixture. Then, the resulting liquid mixture is exposed above the deposition of crystals in the distillation to precipitate thus WA4H2high purity.

Therefore, in the method according to the present invention, preferably, the heterogeneous catalyst recovery (b) was separated from the reaction mixture (containing WA4H2) obtained in the reaction of the second stage in the method of the reaction of the first stage/second stage, to obtain thereby a liquid mixture not containing the catalyst (which contains the solvent (e), WA4H2and water), and then the obtained liquid mixture is subjected to distillation to remove water, thus precipitating the ri distillation of the precipitated crystals WA4H2can be separated by filtration in the same manner as mentioned above.

In the method according to the present invention is most preferable to recycle the solvent of the reaction (e) and water used in the reaction of the second stage.

After separation of the heterogeneous catalyst recovery (b) filtering and removing water from the reaction mixture by distillation of the reaction solvent (e) can be separated and identified, subjecting the liquid mixture is distilled. Below, the separation and isolation of the reaction solvent (e) are explained, taking as an example the case when a solvent containing an amide group (which is preferably used in the present invention), is used as the solvent (e).

The liquid mixture obtained after separation of the heterogeneous catalyst recovery (b) filtration and removal of water by distillation, includes not only the solvent containing an amide group, but also the carboxylic acid formed as a by-product derived Alliluyeva reagent. Since the carboxylic acid formed as a by-product, causing decomposition WB6when you want to recycle the solvent A byproduct. The amount of carboxylic acid formed as a by-product in recycled solvent should preferably be in the range from 0.000001 to 0.1, more preferably from 0.000001 to 0.05, most preferably from 0.000001 to 0.02, expressed as the weight ratio of carboxylic acid to the solvent.

Some solvents containing amide group, form a high-boiling azeotropic mixture with a carboxylic acid formed as a by-product. In the case of such solvents is very difficult to remove the carboxylic acid from the solvent. However, such solvents are carboxylic acid can be removed in such a way that a different solvent, capable of forming a low-boiling azeotropic mixture with a carboxylic acid, is added to the solvent, and the resulting azeotropic mixture is distilled. There are various solvents that can form a low-boiling azeotropic mixture with a carboxylic acid, and any of these solvents can be used in the present invention. However, it is preferable to use allmetal such as toluene or xylene, which is a typical example of solvents capable of forming nicotianamine as a by-product, during the restoration diarylethylene in the first reaction stage and/or the second reaction stage. Time of carrying out the azeotropic distillation and the method of carrying out the azeotropic distillation has no special restrictions. For example, it is preferable that the azeotropic distillation was carried out with the way, where is formed as a by-product carboxylic acid and ailean was removed by azeotropic distillation of: (x) the reaction mixture obtained recovery diarylethylenes/acylation (first reaction stage); or (y) the reaction mixture while removing water by distillation after the reaction of the second stage and z) of the reaction mixture, the part which remains after separation of the reaction mixture, the precipitated crystals WA4H2.

In addition, when using a solvent containing an amide group, which forms a high-boiling mixture with a carboxylic acid, the removal of the carboxylic acid formed as a by-product, can also be the way in which the carboxylic acid is reacted with a compound having basic properties, for linking thus the carboxylic acid formed as a by-product, with a basic compound, and then the light is Oh acid include: fashion, which forms a salt of carboxylic acid in the neutralization between the main connection and carboxylic acid and () the way in which the carboxylic acid is bound by adsorption on the adsorbent such as aminoalkenes amine type, which is able to adsorb on her anions of carboxylic acids.

In the way that () there are no special restrictions in respect of the principal compounds used for the formation of salts of carboxylic acid, in the reaction of neutralization; however, it is preferable to use the primary connection of the metal. In respect of the principal compounds of the metal used in method (), it is preferable to apply the basic compound of the metal containing alkali metal or alkaline earth metal such as sodium, potassium, lithium, magnesium or calcium. Preferred examples of the basic metal compounds include hydroxides of alkali metal or alkaline earth metal such as NaOH, KOH, LiOH, Mg(OH)2and CA(Oh)2; and the oxide of the alkali metal or alkaline earth metal such as MgO and Cao. Among these basic compounds of the metal are particularly preferred basic compounds of magnesium (such as SB(OH)2and Mao), since these compounds form the polyurethane foam. In respect to the manner of removal of the solvent containing an amide group, after the formation of salts of carboxylic acids, the preferred distillation. When a solvent containing a salt of carboxylic acid, is subjected to distillation, because salt of carboxylic acid, which is the main component of the residue remaining in the distillation apparatus, has a high affinity for the solvent containing an amide group (magnify salt of carboxylic acid has a particularly high affinity to the solvent containing an amide group), the residue can be disposed of as a slurry with a low viscosity. Similar properties of salts of carboxylic acids are very useful because not happen adhesion solids to the inner wall of the distilling apparatus, which changes the coefficient of heat transfer between a heat source and a solvent, which Argonauts, thus leading to the creation of unstable conditions in the refinery.

In the following, explanation is given regarding the reaction conditions for binding of carboxylic acid in the neutralization with a base connection.

In relation to the number of primary connection primary connection can be used in such a ve more than the above number. Alternate adding the basic substance can be the way in which the basic substance is added dropwise to the solvent, at the same time determining the pH value of the mixture, and the addition is stopped when the pH value of the mixture becomes equal to 6.5 or higher. In this case, especially, it is preferable to stop the reaction neutralization at pH value of 7 or higher (i.e., at an alkaline pH in order to increase the ratio of neutralized carboxylic acid.

In terms of the temperature of the neutralization neutralization can be carried out at from 20 to 160oC.

After removal from the liquid mixture of the carboxylic acid formed as a by-product, method () or (), the resulting mixture is subjected to distillation, thus obtaining a solvent containing an amide group, which can be recycled. The resulting solvent-containing amide group includes not only formed as a by-product carboxylic acid, but also allmetal formed as a side product during diarylethylene, and water used in the reaction of the second stage. In relation containing amide group of the solvent, the extraction is more preferably from 0.0001 to 0.05, most preferably from 0.0001 to 0.03, and the content of arimethea the solvent was in the range of from 0.0000001 to 0.1, more preferably from 0.0000001 to 0.05, most preferably from 0.0000001 to 0.01, expressed as the weight ratio to the solvent containing an amide group.

The water used in the reaction of the second stage, is removed from the reaction mixture during the precipitation of crystals during the distillation. Water removed from the reaction mixture during the precipitation of crystals during the distillation, has a low purity, but such water with low purity can be put in the recycling, as such, the system of the second reaction stage, without negative influence on the course of the reaction. However, it is preferable to treat this water with low purity of the way in which water with a low purity (including distilled water and formed as a by-product allmetal) is divided into two phases, and then water (aqueous phase) is separated.

Method (2) method of reaction of the first stage/second stage is the way in which, after reaction of the first stage of the reaction mixture obtained in the reaction of the first stage is transferred into another reactor than that used in the reaction of the first stud is to be placed, contained in the reaction mixture obtained in the reaction of the first stage, it is possible to separate and isolate from the reaction mixture by filtration, and the like, and to the resulting mixture, you can add fresh heterogeneous catalyst recovery.

In method (2) is preferable to prevent the manifestation of such a phenomenon that the reducing agent (such as hydrogen) disappears from the first stage of the reaction mixture after the reaction of the first stage so that the derivative tetraallylsilane formula (3) in contact with a heterogeneous catalyst recovery in the absence of reductant. For this purpose, preferably continuously add the reducing agent in the reaction mixture until the start of the second reaction stage. When the heterogeneous catalyst recovery contained in the reaction mixture of the first stage is separated and recovered from the reaction mixture and add fresh heterogeneous catalyst recovery to the reaction mixture, it is difficult to continue adding reducing agent to the reaction mixture. In this case, preferably after starts adding a reducing agent to the reaction mixture, adding to the reaction mixture of fresh catalyst to start the reaction.

The number svishti from the catalytic activity of the used catalyst; however, the amount of fresh catalyst is normally in the range from 0.0001 to 0.5, preferably from 0.001 to 0.3, more preferably from 0.01 to 0.2, expressed as the weight ratio of the solvent.

After the reaction of the second stage it is possible to carry out the deposition of crystals in the distillation in the same manner as described above for the method (1), to obtain thus crystals WA4H2high purity.

Hereinafter, WA4H2can be obtained by filtration after precipitation of crystals in distilled mainly thus, as described above for the method (1).

In addition, it is most preferable to recycle the solvent of the reaction (e) and water used in the reaction of the second stage, mainly thus, as described above for the method (1).

Method (3) method of reaction of the first stage/second stage (i.e., the way in which the reaction of the first stage or the second stage reaction is conducted continuously) is a method in which the reaction rehabilitation diarylethylene/acylation WB6is carried out continuously using a reactor with complete mixing.

It first provides an explanation for the case when the reaction of the first stage Prov is me finding the reaction mixture in the reactor was in the range of 10 PM

In addition, it is preferable that a continuous reaction using a reactor with a complete stirring was carried out at high speed so that the total mass WB6WAB5THAT WA4B2and WA3B3that are in the reaction system becomes equal to 10% by weight or less of the total mass derived hexaazatetracyclo present in the reaction system.

The reaction rate can be adjusted by adjusting the amount of reducing agent, the reaction temperature and activity, and the amount of used catalyst. It is especially effective to regulate the reaction rate by changing the amount of catalyst used. The desired amount of the catalyst is influenced by the activity of the catalyst. However, typically, these high response speed can be achieved when using the catalyst in amounts of from 0.01 to 0.4, preferably from 0.02 to 0.2, expressed as the weight ratio of the solvent.

The reaction rate is also influenced very considerably the weight ratio of catalyst (b) to WB6(a). For example, in the case where the catalyst (b) is first loaded into the reactor and then the reaction was carried out under continuous zagruzki within 0.00001 to 0.5, preferably from 0,00005 to 0.1, more preferably from 0.0001 to 0.01, expressed as the ratio of the speed of loading WB6(a) (K1(g/min)) to the amount of catalyst (Q (g)) in the reactor.

When the first reaction stage is carried out continuously, it is preferable that the amount of carboxylic acid formed as a by-product (derived Alliluyeva reagent), present in the reaction system, was equal to 0.1 or less, expressed as the weight ratio to the solvent in the reaction system. To reduce the number of carboxylic acid formed as a by-product present in the reaction system, to less than 0.1, expressed as the weight ratio to the solvent in the reaction system, WB6applied in such a quantity that the concentration WB6in the reaction system is from 0.0001 to 0.2, preferably from 0.001 to 0.15, more preferably from 0.01 to 0.1, expressed as the weight ratio WB6the solvent in the reaction system.

In method (3), in which the reaction is carried out with the introduction of heterogeneous catalyst recovery is and solubility WA4BnH(2-n)(n is 1 or 2) in the solvent of the reaction is influenced by the type of solvent used in the reaction and the reaction temperature; however, to obtain a reaction mixture, where WA4BnH(2-n)(n equals 1 or 2) is dissolved in the reaction solvent (s), preferably the reaction is carried out in such conditions that the weight ratio WA4BnH(2-n)(n equals 1 or 2) in the reaction mixture to the reaction solvent (e) is from 0.001 to 0.2, more preferably from 0.01 to 0.1, most preferably from 0.02 to 0.07.

WA4BnH(2-n)(n equals 1 or 2) is relatively stable when the connection is in a solvent containing an amide group, and the solution is supersaturated. Therefore, even when a large number of WA4BnH(2-n)(n equals 1 or 2) in a solvent containing an amide group, a deposition substance is not easy, and the connection remains in a dissolved state in a solvent over a relatively long period of time. Therefore, with little time spent in the reactor it is possible to continuously remove the reaction mixture, which WA

In addition, in the reaction of the first stage also produces a small amount WA4H2as a result of subsequent remedial diphenylmethylsilane WA4BnH(2-n)(n equals 1 or 2). As in the case of WA4BnH(2-n)(n equals 1 or 2), WA4H2also relatively stable in solvent containing an amide group in a state of supersaturation. Therefore, using a short residence time in the reactor, it is possible to remove the reaction mixture, which WA4H2present in the state of saturation, without deposition of compounds on a heterogeneous catalyst recovery in the reactor.

Alternative when carrying out continuous reactions heterogeneous catalyst recovery (b) can flow through the reactor instead be present in the reactor. In particular, for example, the continuous reaction can be conducted by a method in which a solution obtained by dissolving WB6(a) in an organic solvent containing an amide group, (e)), allerease reagent (s), the heterogeneous catalyst recovery (b) (which may be in the form of a suspension obtained by dispersing katalysatoren in the present invention, and the reaction mixture containing the heterogeneous catalyst recovery is removed from the reactor in the form of a suspension. In this way even when WA4H2having low solubility in an organic solvent containing an amide group, (e), is formed in large quantities in the first reaction stage, the reaction mixture (containing as a catalyst, and WA4H2) obtained in the reaction of the first stage is subjected to the second reaction stage, where in the reaction mixture, water is added as a good solvent for WA4H2followed by the separation of the catalyst from the reaction mixture.

In respect of the reactor for the reaction of the first stage in a continuous mode, it is preferable to use a multi-stage reactor commonly used in this field to carry out a continuous reaction. There are no particular restrictions on the number of stages provided that the number of stages is equal to 2 or more. However, the larger the number of stages, so it is more profitable.

In addition, in the present invention the reaction of the first stage can be performed periodically by repeating the sequence: the first stage reaction in the reactor within a predetermined period of time is essential; and introduction into the reactor of a fluid from a source substance in an amount corresponding to the above predetermined number. When the reaction is carried out in such a way that the number of the reaction mixture removed at the same time, preferably in the range of 1/1000 of the total reaction mixture in the reactor.

During periodic loading in the reactor WB6the amount of catalyst (Q'1(g)) in the reactor, the number WB6(p1(g)), loaded into the reactor simultaneously, the interval (t1(min) between downloads WB6in the reactor are selected so that the value (p1/t1)/Q'1is normally in the range from 0.00001 to 0.5, preferably from 0,00005 to 0.1, more preferably from 0.0001 to 0.01.

In method (3) reaction of the first stage can be continuously done in essentially the same manner as described above for the reaction of the first stage of the method (1), except for the special conditions mentioned above.

Then given an explanation for the case when the reaction of the second stage is carried out continuously.

When the second stage reaction is carried out continuously, preferably, WA4BnH(2-n)was dissolved in Bolshevo in the reaction solvent and the reaction temperature; however, to obtain a reaction mixture, where WA4BnH(2-n)(n equals 1 or 2) is dissolved in the reaction solvent (s), preferably the reaction is carried out in such conditions that the weight ratio WA4BnH(2-n)in the reaction mixture to the reaction solvent (s) was equal to from 0.001 to 0.1, preferably 0.005 to 0.07, more preferably from being 0.007 to 0.05.

WA4BnH(2-n)is relatively stable in the solvent when the supersaturation of the solution. Therefore, even when a large number of WA4BnH(2-n)(n equals 1 or 2) in a solvent containing an amide group, a deposition substance is not easy, and the connection remains in a dissolved state in a solvent over a relatively long period of time. Therefore, using a small amount of time spent in the reactor it is possible to continuously remove the reaction mixture, which WA4BnH(2-n)(n equals 1 or 2) is in a state of saturation.

In respect of reductant and catalyst recovery, which can be used for the reaction of the second stage in the continuous mode the stage.

In the reaction of the second stage catalyst used in the reaction of the first stage, can be used as such; however, if desirable, the reaction of the second stage can be performed by adding fresh catalyst to the reaction system of the second stage. The desired amount of catalyst in the reaction system varies depending on the catalytic activity of the catalyst. However, the fresh catalyst added to the reaction system in an amount such that the weight ratio of the catalyst in the reaction system, the solvent was equal from 0.0001 to 0.5, preferably from 0.001 to 0.3, more preferably from 0.01 to 0.2.

In respect of the reactor for the reaction of the second stage in the continuous mode, it is preferable to use a multi-stage reactor commonly used in this field to carry out a continuous reaction. There are no particular restrictions on the number of stages provided that the number of stages is equal to 2 or more. However, the larger the number of stages, so it is more profitable.

In addition, in the present invention the reaction of the second stage can be carried out in a periodic process by repeating the sequence: reaction of the second stage during pre-determine the Noi in the second reaction stage; and introduction into the reactor of the first stage of the reaction mixture in an amount corresponding to the above predetermined number. When the reaction is carried out in such a way that the number of the reaction mixture removed at the same time, preferably in the range of 1/1000 of the total number of the reaction mixture in the reactor.

After the reaction of the second stage it is possible to carry out the deposition of crystals in the refinery in essentially the same manner as described above for the method (1), to obtain thus crystals WA4H2high purity.

Hereinafter, WA4H2can be obtained by filtration after precipitation of crystals during the distillation in essentially the same manner as described above for the method (1).

In addition, it is most preferable to recycle the solvent of the reaction (e) and water used in the reaction of the second stage in essentially the same manner as described above for the method (1).

(4) the method of reaction of the first stage/second stage (i.e., the way in which each reaction of the first stage and the second stage reaction is conducted continuously, where the reaction mixture obtained in the first reaction stage is saved before the second reaction stage, and save reactio the action of the second stage is carried out continuously, as described above for the method (3), where the reaction mixture obtained in the first reaction stage is saved before the second reaction stage, and maintain the reaction mixture was subjected to reaction of the second stage. This way you can effectively get the desired WA4H2.

After the reaction of the second stage it is possible to carry out the deposition of crystals in the distillation in the same manner as described above for the method (1), to obtain thus crystals WA4H2high purity.

Hereinafter, WA4H2can be obtained by filtration after precipitation of crystals during the distillation in essentially the same manner as described above for the method (1).

In addition, it is most preferable to recycle the solvent of the reaction (e) and water used in the reaction of the second stage in essentially the same manner as described above for the method (1).

Method (5) of the reaction of the first stage/second stage (i.e., the way in which each reaction of the first stage and the second stage reaction is conducted continuously, in which the reaction mixture is continuously removed from the reactor used for the reaction of the first stage, continuously transferred to another reactor), is the way in which each reaction is blend, continuously removed from the reactor used for the reaction of the first stage, continuously transferred to another reactor. This way you can effectively get the desired WA4H2even compared with the method (4).

After the reaction of the second stage it is possible to carry out the deposition of crystals in distilled similar to that described above for the method (1) to obtain such crystals WA4H2high purity.

Hereinafter, WA4H2can be obtained by filtration after precipitation of crystals during the distillation is similar to method (1).

In addition, it is most preferable to recycle and reuse the solvent of the reaction (e) and water used in the reaction of the second stage is similar to method (1).

In the method according to the present invention, it is preferable to use WB6having a purity of 95% or more. Using WB6such high purity is advantageous not only because you can improve the speed of response and restoration diphenylmethylsilane/acylation hexacis(arylmethyl)hexaazatetracyclo (i.e. WB6), but also because the desired derivative tetraallylsilane can be obtained with high whoem water. The reaction is carried out in a solvent in the presence of a catalyst, and the resulting WB6falls in the form of crystals obtained from the reaction mixture. Purity WB6has a great influence on the reaction rate recovery diphenylmethylsilane/acylation. Therefore, a stable way of obtaining WB6high purity is a very important method for obtaining derivatives tetraallylsilane on an industrial scale. Below is the explanation regarding the method of obtaining WB6high purity, in particular the method of synthesis and crystallization WB6.

Crystals WB6high purity can be obtained by using phenylethylamine and glyoxal (i.e., the original substance) in such quantities that the molar ratio of phenylethylamine to glyoxal is equal to 3 or more. The molar ratio of phenylethylamine to glyoxal is preferably in the range from 3 to 100, more preferably from 4 to 10.

Reaction conditions for the synthesis WB6below.

In regard to the solvent used for the synthesis WB6you can use a solvent having a high polarity. Examples of highly polar solvents include riccitello to use, at least one solvent selected from the group consisting of alcohols, NITRILES and water. In particular, it is preferable to use at least one solvent selected from the group consisting of NITRILES such as acetonitrile, propionitrile and butyronitrile; amides such as N, N-dimethylacetamide, N,N-dimethylformamide and N-methyl-2-pyrrolidone; amines such as benzylamine; alcohols such as methanol, ethanol, propanol and butanol; and water. More preferred is a mixed solvent of acetonitrile and water. In addition, the use of a solvent having a low ability to dissolve WB6is advantageous in that the yield of precipitated crystals synthesized WB6becomes high.

Examples of catalysts used for the synthesis WB6include brandstedt acid, ammonium salts, salts of alkylamines followed, polymeric solid acid substances and their salts.

Examples brandsteder acids include carboxylic acids such as formic acid, acetic acid, propionic acid and benzoic acid; and inorganic acids such as sulfuric acid and nitric acid. Among them, preferred are formic acid, acetic Ki is ropionate ammonium; salt of alkylamine such as benzylamine hydrochloride, benzylamine sulfate, ethylamine hydrochloride, Propylamine hydrochloride, triethylamine hydrochloride, benzylamine propionate, benzylamine acetate, benzylamine format, aniline acetate, aniline format, ethylamine acetate, Propylamine acetate butylamine acetate, diethylamine acetate and triethylamine acetate and salt arylamine.

As a polymeric solid acid substances and their salts can be used, the cation-exchanger acidic or neutral salt type and aminoalkenes neutral salt type. It is preferable to use slightly acidic ion exchanger type and weakly basic ion exchanger neutral salt type.

The concentration of catalyst is in the range from 0.001 to 10, preferably from 0.1 to 5, expressed as the molar ratio of the catalyst to glyoxal. When a catalyst is used, the ion exchanger, the concentration of catalyst is in the range from 0.1 to 1000, preferably from 0.1 to 20, expressed as the weight ratio of the catalyst to glyoxal.

There are no particular restrictions on the temperature in the synthesis WB6provided that the temperature is in the range of points forC.

In respect of glyoxal used for the synthesis WB6you can use either an aqueous solution of glyoxal, or 100% of glyoxal. In the case of an aqueous solution of glyoxal using an aqueous solution of glyoxal, having a concentration of 10 wt. percent or more by weight of the total aqueous solution. The concentration of glyoxal in the solution of glyoxal is preferably in the range from 10 to 90 wt.%, more preferably from 20 to 60 wt.%. In addition, when glyoxal is used in aqueous solution, the purity of glyoxal with respect to its parts, excluding water, is typically in the range of 80% or higher, preferably 90% or higher, and more preferably from 95% and above.

The concentration of glyoxal in the reaction solution for the synthesis WB6is in the range from 0.001 to 0.5, preferably 0.005 to 0.4, more preferably 0.005 to 0.2, expressed as the weight ratio of glyoxal to the solution.

Synthesis WB6includes the following stages (I) to (III):

(I) adding glyoxal to a solution obtained by mixing phenylethylamine, catalyst and solvent, where the molar ratio of phenylethylamine to glyoxal appropriately selected so as to be equal to 3 or more, BR> (II) separating the crystals WB6that fell from the reaction mixture, and

(III) washing the crystals WB6solvent containing an organic solvent.

Adding glyoxal in the above method (I) can be carried out in a period of from 5 minutes to 10 o'clock

In relation to the allocation method of the crystals WB6in the above stage (II) it is possible to use a common way of separating the solid phase from the liquid phase. Examples of such methods include filtration under vacuum and filtered under pressure using a membrane filter and centrifugation.

In relation to the solvent for washing the crystals WB6in the above stage (III) there are no particular restrictions provided that the solubility WB6in the solvent is 10 g/l or less, and the solvent does not react with WB6. In particular, it is possible to use the same solvent that was used for the synthesis and crystallization WB6. Solubility WB6in such a solvent in some cases higher than 10 g/l at room temperature. However, in this case, the solubility WB6such solvent can be decreased to 10 g/l or less by carrying out washing at a temperature of primernie at room temperature, include NITRILES such as acetonitrile, propionitrile and butyronitrile; alcohols such as methanol, ethanol, propanol, butanol, pentanol, hexanol, heptanol and octanol. Furthermore, it is preferable to use a mixed solvent of the above nitrile and/or alcohol and water as a solvent for washing the crystals WB6due to the excellent leaching effect of such a mixed solvent, and a low solubility WB6in this mixed solvent. When the solvent for washing the crystals WB6use a mixed solvent, the water content in the mixed solvent can usually be 30 wt. % or less, preferably from 5 to 20 wt.% from the total mass of the mixed solvent. It is most preferable to use as the solvent for washing the crystals WB6a mixed solvent consisting of acetonitrile and water, where the water content in the mixed solvent is from 5 to 20 wt.%, from the total mass of the mixed solvent.

The above method using excessive phenylethylamine (i.e., the molar ratio of phenylethylamine to glyoxal is 3 or more) makes possible alzueta another way, the purity of the final WB6is low. In other words, when to get WB6use the method that is basically identical to the above except that the molar ratio of phenylethylamine to glyoxal is less than 3, get WB6unsatisfactory low purity. However, impurities contained in WB6low purity, can be removed by proper cleaning using an organic solvent, to obtain WB6having high purity.

One of the common methods of cleaning WB6described in Journal of Organic Chemistry, vol. 55, 1459-1466 (1990). According to this method, raw WB6(hexabenzylhexaazaisowurtzitane) suspended in cold acetonitrile and then filtered to collect WB6followed by washing. Next, the washed WB6will recrystallized from acetonitrile. However, in the above document, there is no description concerning the concentration WB6with respect to the solvent and the crystallization temperature. That is, in the above document conditions to remove impurities contained in WB6low purity not specified.

The authors of the present invention conducted a recrystallization WB6several times is lsua 1 l of acetonitrile, to obtain crystals WB6and this recrystallization was repeated several times. Determined the purity of the obtained crystals, and it was confirmed that the purity WB6obtained by the method in accordance with the above document, ranges from 85 to 100%.

In addition, each batch of crystals WB6obtained in the above manner, individually subjected to reaction diphenylmethylsilane in the presence Alliluyeva reagent (using a palladium catalyst) to obtain the derivatives hexaazatetracyclo containing acyl group. In the result, it was found that the reaction time required for diphenylmethylsilane, largely varies depending on the batch of crystals WB6and if necessary a long time to diphenylmethylsilane outputs the desired derivatives hexaazatetracyclo containing acyl group, a very low due to the decomposition hexaazatetracyclo WB6.

In this situation, the authors of the present invention have conducted extensive and intensive studies with the aim of developing an improved method for recrystallization WB6where could reliably produces in order to achieve the following way (in the following, often related to the "way recrystallization to achieve high purity"). The way recrystallization to achieve high purity is a way recrystallization WB6that includes:

dissolving crude WB6in an organic solvent to obtain a solution, and

the deposition of crystals WB6high purity, where the type and amount of organic solvent is selected so that the by-products contained in the raw WB6, were completely dissolved in an organic solvent at a temperature deposition of crystals WB6high purity, and by-products are high-performance liquid chromatography.

The deposition of crystals WB6it is possible to carry out conventional recrystallization. As an example, recrystallization can be mentioned a method based on the difference in solubility WB6depending on the difference of temperature of the solvent used for recrystallization, which includes:

the mixture of raw WB6with an appropriate solvent;

heating the resulting mixture to a temperature equal to or below the boiling point of the solvent to dissolve WB6to dissolve the s crystals WB6high purity.

As an example of another way recrystallization can be mentioned a method based on the difference in solubility WB6in a suitable solvent for WB6and solubility WB6in a poor solvent for WB6that includes:

dissolving crude WB6in a suitable solvent for WB6at the corresponding temperature and

adding portions poor solvent for WB6to the resulting solution WB6in a suitable solvent for WB6for the deposition of such crystals WB6high purity.

When dissolving WB6system for recrystallization is heated, preferably, to avoid reduction of the output of the desired compound as a result of decomposition WB6under the action of temperature, to heat up to 130oOr less.

The deposition of crystals WB6high purity of the system for recrystallization containing WB6usually ends in a period of from one hour to several days, and the system for recrystallization containing WB6you can mix or let it stand. When the deposition of crystals of p is to be placed WB6high purity in the form of relatively large needle-shaped crystals. On the other hand, when the deposition of crystals under stirring system for recrystallization is formed WB6high purity in the form of relatively small crystals. The reproducibility of the yield and purity of the crystals WB6high purity can be improved by maintaining the temperature of the system for recrystallization containing WB6when the appropriate temperature during the deposition of crystals.

In the above method recrystallization to achieve high purity is used, the solvent system comprising at least one type of organic solvent, where the solvent is the dilution factor from 0.1 to 20, where the dilution factor is R represented by the following formula (5):

P=H/I,

where N represents the solubility WB6(g/l) in an organic solvent, and I represents the solubility of solids (g/l) (determined by HPLC) in an organic solvent.

Below is a brief description of solubility WB6and solubility of impurities detected liquid chromatography.

Solubility WB6calculated on the basis of the results of the analysis AImost impurities, mentioned above were calculated based on the results of liquid chromatography amounts of impurities dissolved in the solution, assuming that the amount of impurities detected liquid chromatography, is a whole balance obtained by subtracting the number WB6the number of raw WB6.

Examples of organic solvents used in the method of recrystallization to obtain a product of high purity, include aromatic hydrocarbons such as toluene and benzene, ethers such as tetrahydrofuran, diethyl ether, DIPROPYLENE ether and disutility ether; NITRILES such as acetonitrile, propionitrile and butyronitrile; amides such as N,N-dimethylacetamide, N, N-dimethylformamide, 1,3-dimethyl-2-imidazolidone, N-methyl-2-pyrrolidone and N,N-diethyldodecanamide; alcohols such as methanol, ethanol, propanol, butanol, pentanol, hexanol, heptanol and octanol; esters such as ethylformate, ethyl acetate, methyl acetate, propyl, butyl acetate, methylpropionate, ethylpropane, propylphosphonate and butylphosphonate; halogenated hydrocarbons such as dichloromethane, chloroform and 1,2-dichloroethane. These solvents can be used individually or in combination.

Preferably, the organic solvent used in the method of recrystallization to achieve high purity, had a temperature in the range from 5 to 60oWith in which it dissolves impurities to 0.90 g/l, expressed as the solubility of the impurities in the raw WB6. When using such an organic solvent, it is possible to reduce the amount of solvent. In addition, to increase the output by recrystallization to achieve high purity, it is preferable to use a solvent which has a high dissolving power against impurities and a low dissolving power against WB6. In particular, it is preferable that R8. Therefore, more preferably, the solvent had a temperature in the range from 5 to 60oWith in which it dissolves impurities 0,90 g/l and more (in relation to impurities in the raw WB6), and dissolution for WB6less of 3.42 g/L.

In the method of recrystallization to achieve high purity of the number of used solvent is not particularly limited, provided that the amount of solvent sufficient to dissolve all impurities in raw WB6when the temperature of recrystallization. For example, in the case of recrystallization to achieve high purity with respect to 100 g of raw WB6contains 10% impurities by weight, when used, the solvent dissolves the impurities of 1 g/l at room temperature, the solvent is used in an amount of 10 liters or more. The amount of solvent used in the method of recrystallization to achieve high purity, typically range from 10 to 10000, preferably from 20 to 200, expressed as the weight ratio of solvent to raw WB6.

Below is the explanation for the structures of the above compounds WB6THAT WA4B2and WA4H2.

The group has the structure ol the acyl group (A) in formulas (3) and (4) preferably, to the acyl group has from 1 to 10 carbon atoms. Examples of acyl groups include formyl group, acetyl group, propionyl group, butyryloxy group, isobutyryloxy group, valerino group, hexanoyl group and 2-phenylacetylene group. Of these acyl groups are preferred acyl groups having from 1 to 3 carbon atoms, such as formyl group, acetyl group and propylaniline group. More preferred is an acetyl group.

In respect of derivative hexaazatetracyclo represented by the formula WA4B2you can prevent many stereoisomeric configurations that differ in the position of the acyl groups and arylmethyl groups. Derived hexaazatetracyclo represented WA4B2, which is obtained by the method according to the present invention, may represent one of the stereoisomers. This may be the isomer having stereostructure, represented by the following formulas (7-1) to (7-6), or their optical isomers.

< / BR>
< / BR>
< / BR>
where a is the above-mentioned acyl group and is above phenylmethylene group. Of these compounds the most preferred is stereoisomeric configurations, which differ by the position of the acyl groups and hydrogen atoms. Derived hexaazatetracyclo represented WA4H2, which is obtained by the method according to the present invention, may be one of the stereoisomers. In particular, these stereoisomers are derived hexaazatetracyclo represented by the formulas (7-1) to (7-6) above, where each of arylmethyl groups substituted by a hydrogen atom. Of these the most preferred is derived hexaazatetracyclo represented by the formula (7-1) above.

The reaction rehabilitation diphenylmethylsilane/acylation in the method of the present invention is described below.

This reaction consists of two stages: 1) the recovery diphenylmethylsilane WB6in the presence of Alliluyeva reagent for the conversion of N-arylmethylidene groups contained therein, in NH-group; and 2) the subsequent acylation of the resulting product for the conversion of the NH-group in the N-acyl group. In addition, since the N-alkyl group may be formed when restoring (as a side reaction of the N-acyl group, the restoration of which can occur depending on the reaction conditions, as a by-product formed is Lena on the basis of the reaction products and are shown below in scheme (8):

< / BR>
where And independently represents an acyl group having from 1 to 10 carbon atoms, In is phenylmethylene group, R independently represents an alkyl group having from 1 to 10 carbon atoms, N represents a hydrogen atom and W represents a hexavalent hexaazatetracyclo represented by the formula (2).

Therefore, one of the compounds represented by the scheme (8) can be contained in the reaction mixture obtained by the method according to the present invention.

The method according to the present invention is industrially advantageous, because derivatives tetraazacyclotetradecane can be stably obtained with a high yield. In addition, the method according to the present invention can effectively suppress the decrease of the catalytic activity of the catalyst recovery during the reaction.

A preferred method of carrying out the invention

The present invention is illustrated in more detail with reference to examples in accordance with the prior art, examples in accordance with the invention and comparative examples, which should not be construed as limiting the scope of the present invention.

(1) Abbreviations used in the following Premantura for analysis.

WB6: hexabenzylhexaazaisowurtzitane

WA4B2: tetraacetylethylenediamine

WA4BH: tetraacetylethylenediamine

WA4H2: tetraazacyclotetradecane

WA3B3: createtestcasemenubar

WA2B4: diacetylethylenediamine

DMAc: N,N-dimethylacetamide (organic solvent)

AU2A: acetic anhydride (as Alliluyeva reagent)

Pd-C: palladium on coal (as a heterogeneous catalyst recovery)

HPLC: liquid chromatography high pressure liquid chromatography)

GC: gas chromatography

(2) Purity WB6used in each of the following examples and comparative examples, 100%, unless otherwise indicated.

(3) In the examples and comparative examples, the quantitative analyses of various derivatives hexaazatetracyclo conducted by the following methods.

(i) Quantitative analysis WA4H2performed HPLC under the following conditions using the following equipment.

<Conditions of HPLC analysis>

Apparatus for HPLC: system is R: CLASS-LC10

Column: TSK-GEL AMIDE-80 (manufactured and delivered TOSOH, Japan)

Size: 4,6 mm cm

The column temperature: 40oWITH

Mobile phase: tetrahydrofuran/N2On (90/10) (volume/volume)

The rate of elution solvent: 1 ml/min

Detection: UV (220 nm)

The amount of injected sample: 5 ál

<Preparation of samples>

Samples for HPLC were prepared as follows, unless otherwise indicated.

To 0.5 ml of reaction mixture (containing heterogeneous catalyst recovery) obtained by diarylethylenes in the presence or in the absence of Alliluyeva reagent, or the filtrate (containing the catalyst) obtained after filtration of the reaction mixture, added 30,8 ml of water and then the resulting mixture was subjected to sonication for 5 min using an ultrasonic cleaner, and then subjected to filtration to obtain thus filtrate. The obtained filtrate was used as a sample for HPLC analysis.

(ii) Quantitative analyses WA2B4THAT WA3B3THAT WA4B2and WA4BH GC was performed under the following conditions using the following equipment.

<Conditions of GC analysis>

Apparatus for GC: gas chromatograph type GC-14B (about the Deno and delivered Frontier Lab, Japan)

Inner diameter: 0.25 mm

Length: 15 m

The thickness of the film covering the inner wall of the capillary column: 0,15 µm

Detection: flame ionization detector (FID)

Temperature:

Column: from 200 to 340o(The rate of temperature rise: 15oC/min) --> 340o(10 min)

Injector: 340oWITH

Detector: 340oWITH

Carrier gas: N2(the velocity of the gas: 100 ml/min and the internal column pressure: 100 kPa)

The amount of injected sample: 5 µl.

<Preparation of samples>

To 0.5 ml of reaction mixture (containing heterogeneous catalyst for recovery) obtained by diarylethylenes in the presence or in the absence of Alliluyeva agent, or the filtrate (containing the catalyst) obtained after filtration of the reaction mixture, added to 23.5 ml of chloroform and then the resulting mixture was subjected to sonication for 5 min using an ultrasonic cleaner, and then was filtered to obtain a filtrate. To 4 ml of the resulting filtrate was added 0.5 ml of a solution tricosane in chloroform (as internal standard) (which is obtained by dissolving 0.4 g tricosane in 100 ml of chloroform) to obtain the solution. Obtained races is ASH in the following conditions, using the apparatus described below.

<Conditions of HPLC analysis>

Apparatus for HPLC: system CLASS LC-10 (manufactured and supplied by Shimadzu Corporation, Japan)

Pump: LC10AD

Detector: SPD-10A

Controller: CLASS-LC10

Column: TSK-GEL AMIDE-80 (manufactured and delivered TOSON, Japan) 2

Size: 4,6 mm cm

The column temperature: 40oWITH

Mobile phase: tetrahydrofuran/N2On (90/10) (volume/volume)

The rate of elution solvent: 1 ml/min

Detection: UV (254 nm)

The amount of injected sample: 5 ál

<Preparation of samples>

Samples for HPLC were prepared as follows, unless otherwise indicated.

Sample containing WB6was dissolved in tetrahydrofuran to obtain a solution having a concentration WB6about 0.01 wt.% The resulting solution was used as a sample for HPLC analysis.

(4) a Study using scanning electron microscope (SEM) was performed under the following conditions.

Equipment: scanning electron microscope for x-ray microanalysis type X-650 (manufactured and supplied by Hitachi, Ltd., Japan).

Accelerating voltage: 20 kV

<Preparation of samples for research with SAM>

Product WB6pomeo 300 , with the help of the apparatus for spraying (apparatus for ion coating; manufactured and delivered Eiko Engineering Co., Ltd., Japan), thereby obtaining a sample for research using SAM.

Example 1

(The way in which the heterogeneous catalyst recovery and the reducing agent is loaded into the reactor and heated to a predetermined reaction temperature, then it loads the solution obtained by dissolving AT6and Alliluyeva reagent in the solvent).

In the autoclave with a capacity of 100 ml was loaded 0.84 g of 10% Pd-C (as a heterogeneous catalyst recovery) and then the autoclave was purged with gaseous hydrogen, setting the internal pressure in the autoclave, equal to 1.1 kgf/cm2. Then the contents of the autoclave was stirred at the stirring speed of 50 rpm at 60oWith over 2 hours a Solution obtained by dissolving 2.1 g WB6(hexabenzylhexaazaisowurtzitane) and 1,82 g of acetic anhydride (as Alliluyeva reagent) in 30 ml of DMAc (N,N-dimethylacetamide as solvent) and quickly loaded into the autoclave using a syringe. Then the stirring speed was increased to 700 rpm, at the same time maintaining the temperature at 60oC and a pressure of 1.1 kgf/cm2blend relate respectively to the first reaction stage and the first stage of the reaction mixture".

Analysis of the obtained reaction mixture of the first stage of GC showed that the outputs WA4B2(tetraacetylethylenediamine) and WA4BH (tetraacetylethylenediamine) were, respectively, 39% and 21% (i.e., in General, 60%) from WB6and analysis of the obtained reaction mixture of the first phase HPLC showed that the output WA4H2(tetraazacyclotetradecane) amounted to 22% from WB6.

After completion of the reaction the first stage in the autoclave containing the reaction mixture of the first stage in situ, downloaded 30 ml of water, simultaneously introducing (in autoclave) gaseous hydrogen. The internal hydrogen pressure was raised to 9 kgf/cm2and the reaction temperature raised to 90oFor carrying out the reaction for 1 hour, thus obtaining the reaction mixture. Further, this reaction and the resulting reaction mixture are, respectively, to the second reaction stage and the second stage of the reaction mixture".

Analysis of the obtained reaction mixture of the second phase HPLC showed that the output WA4H2amounted to 82% from WB6.

Example 2

(The way in which the heterogeneous catalyst recovery and the reducing agent is loaded into the reactor and heated to the solvent).

of 8.4 g of 10% Pd-C was loaded into the autoclave with a capacity of 1 l, autoclave purged with gaseous hydrogen, setting the internal pressure of the hydrogen in the autoclave, equal to 1.1 kgf/cm2. Then the contents of the autoclave were heated at 60oC for 1 hour In an autoclave using a syringe loaded of 18.2 g of acetic anhydride and a solution of 21 g WB6in 300 ml of DMAc (pre-heated to 55oC) mixing the contents of the autoclave with a speed of 1500 rpm and at the same time maintaining the temperature at 60oC and a pressure of 1.1 kgf/cm2the first stage reaction was carried out for 1 h, getting the reaction mixture of the first stage.

Analysis of the obtained reaction mixture of the first stage of GC showed that the outputs WA4B2and WA4BH were, respectively, 35% and 26% (i.e., 61%) per WB6analysis of the reaction mixture of the first phase HPLC showed that the output WA4H2was 29% (based on WB6.

Upon completion of the first stage reaction in the autoclave containing the reaction mixture of the first stage in situ, downloaded 300 ml of water, simultaneously introducing into the autoclave, hydrogen gas. The internal hydrogen pressure in the autoclave was set to 10 kgf/cm2and the reaction temperature raised to 90oWith the C obtained reaction mixture of the second phase HPLC showed the output WA4H2was 90% (based on WB6.

Example 3

(The manner in which the catalyst contained in the first stage of the reaction mixture, is filtered off with receiving the filtrate, and the reaction of the second stage is conducted using fresh catalyst and the resulting filtrate).

The first stage reaction was conducted in substantially similar to example 1. Then immediately the reaction mixture of the first stage were removed from the autoclave, filtered, the catalyst contained in the reaction mixture of the first stage, receiving the filtrate. Using the obtained filtrate, the second stage reaction was conducted as follows.

0.84 g of 10% Pd-C was loaded into the autoclave with a capacity of 100 ml, then the autoclave was purged with gaseous hydrogen, setting the internal pressure in the autoclave, equal to 1.5 kgf/cm2. Then the contents of the autoclave were heated at 90oC for 1H. In the autoclave downloaded the above filtrate and 30 ml of water. Then, the inner pressure of hydrogen in the autoclave was raised to 10 kgf/cm2began stirring the contents of the autoclave with stirring speed of 700 rpm and the temperature of the contents of the autoclave was raised to 90oC for 8 min for the reaction of the second stage during the second phase HPLC showed the output WA4H2was 80%, based on WB6.

Example 4

(The manner in which the catalyst contained in the reaction mixture of the first stage filter, receiving the filtrate, and the reaction of the second stage is conducted using fresh catalyst and the resulting filtrate).

The first stage reaction was conducted in substantially similar to example 2. Then immediately from the autoclave, the reaction mixture is first phase was removed and filtered, the catalyst contained in the reaction mixture the reaction of the first stage of obtaining a filtrate. Using the obtained filtrate, have carried out a reaction of the second stage as follows.

of 8.4 g of 10% Pd-C was loaded into the autoclave with a capacity of 1 l and then the autoclave was purged with gaseous hydrogen so that the internal pressure in the autoclave became equal to 1.5 kgf/cm2. Then the contents of the autoclave were heated at 90oC for 1 hour In an autoclave downloaded the above filtrate and 300 ml of water. Then, the inner pressure of hydrogen in the autoclave was raised to 10 kgf/cm2, mixing the contents in the autoclave began with a stirring speed of 1500 rpm and the temperature of the contents of the autoclave was raised to 90oC for 8 min for the reaction of the second article is ionic mixture of the second phase HPLC showed the output WA4H2was 90% (based on WB6.

Comparative example 1

This comparative example shows that when interacting WB6with heterogeneous catalyst recovery in the absence of at least one of Alliluyeva reagent and a reducing agent, the yield of the desired product are greatly reduced.

2.1 g WB6and 3.15 g of 10% Pd-C, 1.84 g of acetic anhydride and 30 ml of DMAc was loaded into the autoclave with a capacity of 100 ml, and the autoclave was purged with gaseous nitrogen at room temperature. Then, the autoclave was introduced hydrogen gas so that the internal pressure in the autoclave was equal to 1.1 kgf/cm2. The reaction of the first stage began raising the temperature of the contents of the autoclave to 60oWith over 12 min, while stirring the contents of the autoclave with a speed of 700 rpm During the reaction in the autoclave was continuously introduced hydrogen gas, maintaining the internal pressure in the autoclave of 1.1 kgf/cm2and the first stage reaction was carried out for 3 hours, getting the reaction mixture of the first stage. Analysis of the obtained reaction mixture of the first stage of GC and HPLC showed that the conversion of WA3B3full and outputs WA4B2THAT WA4BH and WA4H2from the stage the reaction mixture of the first stage were removed from the autoclave and the catalyst was filtered, contained in the reaction mixture, to obtain the filtrate. Using the obtained filtrate, have carried out a reaction of the second stage as follows. In the autoclave with a capacity of 100 ml was loaded obtained filtrate and 3.15 g of 10% Pd-C and 30 ml of water. The autoclave was purged with gaseous nitrogen. Then, the autoclave was introduced hydrogen gas so that the internal pressure in the autoclave was equal to 3.3 kgf/cm2. The reaction of the second stage began raising the temperature of the contents of the autoclave to 130oWith over 20 min with stirring the contents of the autoclave with stirring speed of 700 rpm the second stage Reaction was carried out for 1 h at 130o(With continuous introduction into the autoclave, hydrogen gas so that the internal pressure in the autoclave was maintained at a 3.3 kgf/cm2). Analysis of the reaction mixture of the second phase HPLC showed that the output WA4H2amounted to 60% (based on WB6.

Comparative example 2

This comparative example shows that in case of interaction WB6and heterogeneous catalyst recovery in the absence of at least one of Alliluyeva reagent and a reducing agent, the yield of the desired product are greatly reduced.

2.1 g WB6and 3.15 g of 10% Pd-C, 1.84 g of the criminal code of the room temperature. Then, the autoclave was introduced hydrogen gas so that the internal pressure in the autoclave was equal to 1.1 kgf/cm2while stirring , the autoclave at 50 rpm, and the temperature of the contents of the autoclave was raised to 60oWith over 12 minutes Then immediately the mixing speed was increased to 700 rpm, starting the reaction. During the reaction in the autoclave was continuously introduced hydrogen gas so that the internal pressure in the autoclave was maintained at 1.1 kg/cm2and the reaction was conducted for 3 hours, getting the reaction mixture. Analysis of the obtained reaction mixture of GC and HPLC showed that respectively output WA3IN325% per WB6and the output WA4B2was 28% (based on WB6.

Example 5

(The way in which allerease reagent and a reducing agent is loaded into the reactor and then it loads the solution WB6and the suspension of catalyst).

0.84 g of 10% Pd-C was subjected to a recovery in 10 ml of DMAc for 2 h under hydrogen pressure of 3 kgf/cm2, a temperature of 60oWith and the stirring speed of 700 rpm, receiving a suspension of the catalyst.

1,82 g of acetic anhydride was loaded into the autoclave with a capacity of 100 ml and was stirred techeniya 60oC. In the autoclave was successively loaded with a syringe solution WB6in DMAc (obtained by dissolving 2.1 g WB6in 20 ml of DMAc and the aforementioned suspension of the catalyst. Then immediately the mixing speed was increased to 700 rpm, keeping the temperature at 60oC and a pressure of 1.1 kgf/cm2and the reaction was conducted for 1 h, resulting in the obtained reaction mixture. Analysis of the obtained reaction mixture GC showed that the outputs WA4B2and WA4BH were respectively 55% and 8% (i.e., in General, 63%) per WB6and analysis of the obtained reaction mixture HPLC showed that the output WA4H218% per WB6.

Example 6

(The manner in which the catalyst used in the reaction of the first stage, is used in the reaction of the second stage and the sequence of reactions of the first stage and the second stage is repeated using the same catalyst without replacement with fresh catalyst).

of 9.8 g of 10% Pd-C (as a heterogeneous catalyst recovery) was dispersible in 200 ml of DMAc (N,N-dimethylacetamide as solvent) to obtain thus the suspension of catalyst and the resulting suspension was loaded into the autoclave with a capacity of 2 l*) that the internal pressure in the autoclave became equal to 2 kgf/cm2. The contents of the autoclave were stirred with a stirring speed of 300 rpm for 1 h, maintaining the internal pressure at 2 kg/cm2and the temperature at 60oWith, for the recovery of catalyst contained in the slurry of the catalyst.

49 g WB6(hexabenzylhexaazaisowurtzitane) was dissolved in 500 ml of DMAc at 60oWith for a solution. To the resulting solution was added 42,4 g of acetic anhydride (as Alliluyeva agent) and the resulting liquid mixture was quickly loaded into the autoclave containing a suspension of the catalyst. (When the liquid mixture was loaded into the autoclave, the temperature is temporarily lowered, but after about 4 min again raised to 60oC). Then immediately the mixing speed was increased to 1000 rpm and at the same time maintaining the temperature at 60oC and a pressure of 2 kgf/cm2and carried out the first stage reaction for 1 h, getting the reaction mixture of the first stage. Analysis of the reaction mixture of the first stage of GC showed that the outputs WA4B2(tetraacetylethylenediamine) and WA4BH (tetraacetylethylenediamine) were respectively 64% and 11% (i.e., in General, 75% of hexaazatetracyclo) amounted to 10% from WB6.

After the reaction the first stage, the hydrogen pressure in the autoclave with a capacity of 2 l, which was the reaction mixture of the first stage, increased to 9 kgf/cm2and the reaction temperature increased from 60oWith up to 90oC for 30 min to start the reaction of the second stage. The introduction of water in the autoclave is started simultaneously with the beginning of the rise of temperature, and for 1 h with a pump in the autoclave were introduced 700 ml of water. The second stage reaction was continued for another 40 min after introduction of water to obtain thus the second stage of the reaction mixture. Analysis of the obtained reaction mixture of the second phase HPLC showed that the output WA4H2amounted to 84% from WB6.

The catalyst was removed from the reaction mixture of the second stage as follows. All operations were performed under an atmosphere of hydrogen gas, unless otherwise indicated. The reaction mixture of the second stage was moved to the filtering apparatus under pressure and the catalyst contained in the second stage of the reaction mixture was filtered under pressure, receiving the filtrate. The catalyst remaining in the filtering apparatus under pressure, washed with 500 ml of water, the water was separated from the catalyst by filtration under pressure. Then the catalyst ptelnet operations of the first reaction stage, operations of the second reaction stage and allocation of catalyst was repeated 10 times above. Each of the reaction mixtures in the second stage, obtained by carrying out successive operations separately analyzed HPLC for determining the output WA4H2from WB6. The results showed that the output values WA4H21 through 10 stages of operations equaled 84% (1st), 82% (2nd), 85% (3rd), 80% (4th), 79% (5th), 81% (6th), 84% (7th), 83% (8th), 84% (9th) and 80% (10th).

As stated above, the output WA4H2does not change, even when the same catalyst is used repeatedly without replacement by fresh catalyst.

Example 7

(The way in which the reaction is repeated using the same catalyst).

The reaction was carried out similarly to the reaction of the first stage of example 1, obtaining the reaction mixture. The catalyst contained in the resulting reaction mixture was allocated mainly analogously to example 6, except that every quantity of water and DMAc were 50 ml.

The sequence of the above operations response and the allocation of the catalyst was repeated 5 times by the above method. Each of the reaction mixtures obtained in th number WA4B2and WA4BH per WB6and separately were analyzed by HPLC to determine the output WA4H2per WB6. The results are presented in table.1.

As is evident from the above, the output derived tetraazacyclotetradecane has not changed, even when the reaction re-used the same catalyst.

Example 8

(The way in which the reaction is continuously carried out using the same catalyst (continuous reaction in which the reaction mixture is filtered in a reactor, and the resulting filtrate containing the reaction products is periodically removed from the reactor, at the same time in the reactor is periodically downloaded to the solution of the original substances) ).

As the reactor used autoclave with a capacity of 200 ml, provided with a sintered filter (pore diameter: 2 μm) and a tube for removing liquid obtained from the reaction mixture by filtration through a sintered filter. Using this type of autoclave, it is possible to filter the reaction mixture which is obtained in the reaction catalyzed by a heterogeneous catalyst recovery, then autoclave) and remove the resulting filtrate (i.e., the catalyst can Attila the same catalyst).

Using the above autoclave with a capacity of 200 ml, was performed in the continuous reaction, where a portion of the reaction mixture obtained in the reaction, is subjected to filtering in the reactor, and the resulting filtrate containing the reaction products are periodically removed from the reactor, at the same time periodically in the reactor is loaded the solution of the original substances.

14,7 g WB6dissolved in 210 ml of DMAc at approximately the 60oC and the resulting solution was then allowed to cool to room temperature, and added 12,74 g of acetic anhydride, getting solution of the original substances.

The reaction was carried out similarly to the reaction of the first stage of example 1, except that the number WB6, acetic anhydride, solvent and catalyst were respectively four times more than the amount used in example 1, and that the hydrogen pressure was 4 kg/cm2and the mixing speed was equal to 1500 Rev/min After 1 h from the beginning of the reaction of the resulting reaction mixture was removed from the autoclave through a sintered filter, receiving 40 g of the filtrate, at the same time maintaining the hydrogen pressure at 4 kg/cm2and reaction speed 1500 Rev/min Then the autoclave was loaded with 40 g of the solution of the original in the s hydrogen, the speed of stirring and the temperature of the reaction mixture so that the reaction can continue.

40 minutes after loading the autoclave solution of the original substance repeated sequence of reaction, filtration of the reaction mixture, removal of the filtrate from the vessel and the loading solution starting materials in the autoclave at the same time continuing the reaction. This sequence of operations is repeated 11 times similarly described above, at the same time continuing the reaction in the autoclave. Each of the filtrates obtained when carrying out the successive stages of operations, separately were analyzed by GC to determine the total output quantity WA4IN2and WA4BH per WB6, and was also analyzed by HPLC to determine the output WA4H2per WB6. The results are presented in table.2.

As is evident from the above, the output derived tetraazacyclotetradecane has not changed, even when the reaction re-used the same catalyst.

Example 9

(The way in which the reaction is continuously carried out using the same catalyst (continuous reaction, where a portion of the reaction mixture obtained in the reaction, is subjected filtrowanie it continuously loads the solution of the original substances) ).

Using the same autoclave with a capacity of 200 ml, which was used in example 8, were continuous reaction, where a portion of the reaction mixture obtained in the reaction, was filtered in the reactor, and the resulting filtrate containing the reaction products are continuously removed from the reactor, at the same time in the reactor is continuously loaded the solution of the original substances.

The reaction was conducted in substantially similar reaction the first stage of example 1, except that the number WB6, acetic anhydride, solvent and catalyst were respectively four times larger than in example 1, and that the hydrogen pressure was 4 kg/cm2and the mixing speed was equal to 1500 Rev/min After 1 h after start of the reaction of the resulting reaction mixture was continuously removed from the autoclave through a sintered filter so that the filtrate is continuously removed through the tube with a speed of 0.33 g/min, at the same time maintaining the hydrogen pressure at 4 kg/cm2the stirring speed of 1500 rpm and the temperature of the reaction mixture and at the same time loading the solution of the original substances in the autoclave with the speed of 0.33 g/min This continuous reaction was carried out for 20 h, and a part of the filtrate is removed from the autoclave, was selected by the Oia output total WA4B2and WA4BH per WB6, and was also analyzed by HPLC to determine the output WA4H2in calculating the total number WA4B2and WA4BH. The results are presented in table.3.

As is evident from the above, the output of tetraazacyclotetradecane has not changed, even when the reaction was carried out continuously.

Example 10

(The way in which the reaction of the second stage is repeated using the same catalyst).

All filtrates (each of which represents the reaction mixture is filtered catalyst) obtained in example 8 were brought together and allowed to stand at room temperature for obtaining in this way a suspension containing precipitated in the sludge WA4B2THAT WA4BH and WA4H2and things like that. Using the resulting slurry, spent the reaction of the second stage as follows.

0.84 g of 10% Pd-C was loaded into the autoclave with a capacity of 100 ml, and then the autoclave was introduced hydrogen gas so that the internal pressure in the autoclave was equal to 1.1 kgf/cm2. The contents of the autoclave were stirred for 1 h with stirring speed of 50 rpm, at the same time maintaining the pressure ol the tro was loaded into the autoclave using a syringe. Then immediately the pressure and stirring speed was raised to 10 kgf/cm2and 700 rpm for carrying out the second stage reaction for 1 h at a temperature of 90oWith under a pressure of 10 kgf/cm2, thus obtaining a reaction mixture of the second stage. Then immediately the reaction mixture of the second stage filter, receiving the filtrate and the catalyst.

The sequence of operations of the second reaction stage and the filtering operation was repeated 5 times in this way. Each of the filters obtained when carrying out the sequence of operations separately analyzed GC to determine the conversion of the total number WA4B2and WA4BH and also were analyzed by HPLC to determine the output WA4H2in calculating the total number WA4B2and WA4BH. The results are presented in table.4.

As is evident from the above, the output of tetraazacyclotetradecane has not changed, even when the reaction re-used the same catalyst.

Example 11

(The way in which the second reaction stage is carried out continuously using the same catalyst).

The filtrate, which was obtained in example 9, the reaction is containing a series of loose sediments WA4B2THAT WA4BH, WA4H2and things like that. 400 g of the resulting suspension and 140 g of water were mixed together, getting solution of the original substances. Analysis of the solution of the original substances GC showed that the total number WA4B2and WA4BH, contained in the solution of the original substance, amounted to 13.9 g, and analysis of the solution of the original substances HPLC showed that the number WA4H2contained in the solution of the original mixture, 1.7,

6,72 g 10% Pd-C was loaded into the autoclave with a capacity of 200 ml, used in example 8, and then the autoclave was introduced hydrogen gas so that the internal pressure in the autoclave was equal to 1.1 kgf/cm2. The contents of the autoclave were stirred for 1 h at 50 rpm, at the same time maintaining the pressure at 1.1 kg/cm2and the temperature at 90oC. 120 g of the solution of the original substances quickly loaded into the autoclave using a syringe. Then immediately the mixing speed and the pressure raised to 1400 rpm and 10 kgf/cm2for the reaction of the second stage within 30 minutes After 30 min from the beginning of the reaction part of the reaction mixture was continuously removed from the autoclave through a sintered filter so that the filtrate is continuously removed across the masiania 1400 rpm and the temperature of the reaction mixture at 90oWith and at the same time loading the solution of the original substances in the autoclave with a speed of 0.3 ml/min This continuous reaction was carried out for 20 h, and a part of the filtrate is removed from the autoclave, were selected for analyses of GC and HPLC every 2 hours Every selected filtrates separately were analyzed by GC to determine the conversion of the total number WA4B2and WA4BH and also were analyzed by HPLC to determine the output WA4H2in calculating the total number WA4B2and WA4BH. The results are presented in table.5.

As is evident from the above, the output of tetraazacyclotetradecane has not changed, even when the reaction was carried out continuously.

Comparative example 3

This comparative example 3 shows that when the reaction mixture of the first stage is subjected to the reaction of the second stage without introduction into the reactor of the hydrogen gas, the reaction rate of the second stage becomes much lower.

The first stage reaction was carried out similarly to example 6, getting the reaction mixture of the first stage. Analysis of the obtained reaction mixture of the first stage of GC showed that the outputs WA4B2and WA4BH were respectively 65% and 7% (i.e., generally 4
H2amounted to 10% (based on WB6.

After the first stage reaction in the autoclave was introduced nitrogen gas so that the inside pressure became equal to 9 kgf/cm2. The temperature of the contents of the autoclave was raised to 60oWith up to 90oC for 30 minutes Introduction of water in the autoclave began immediately with the beginning of the increasing temperature and for 1 h in an autoclave were introduced 700 ml of water using a pump. Then, the autoclave was introduced hydrogen gas so that the inside pressure became equal to 9 kgf/cm2and the second stage reaction was carried out for 2 h to obtain thus the second stage of the reaction mixture.

Analysis of the obtained reaction mixture of the second stage of GC showed that the outputs WA4B2and WA4BH were respectively 42% and 3% (i.e., in total, 45%) per WB6and analysis of the obtained reaction mixture of the first phase HPLC showed that the output WA4H2amounted to 30% (based on WB6.

As follows from the above, when the introduction of gaseous hydrogen in the autoclave is interrupted, at the same time when changing the reaction conditions between the end of the first reaction stage and the beginning of the second reaction stage, the reaction rate in the reactor of the second stage was sometimesthe flow when loading WB6)/Q (catalyst) is equal to 0.5 or more, the yield of the desired product becomes significantly lower.

The reaction was carried out analogously to example 9, except that each download speed of solution of the initial substances and the removal rate of the filtrate (the reaction mixture is filtered catalyst) was equal to 30 ml/min. the Reaction was carried out continuously for 2 hours portion of the filtrate is removed from the autoclave, were selected for analyses of GC and HPLC after 30, 60 and 120 min from the start of the reaction. Analyses of the leachate removed from the autoclave showed that as the output WA4B2and the output WA4BH amounted to 10% or less per WB6all filtrates obtained after 30 min from the beginning of the reaction.

Example 12

(The way in which the reaction is carried out in the presence of a carboxylic acid, where the content of carboxylic acid in the solvent used for the reaction is equal to about 10 wt.%).

This example shows that even when the reaction system contains carboxylic acid (derived Alliluyeva reagent used in the reaction) at a concentration of about 10 wt.% in the calculation of the mass of solvent used in the reaction is not affected adversely by the way, except, that added 3.0 g of acetic acid to the solution obtained by dissolving WB6and acetic anhydride in DMAc, immediately before the solution was loaded into the autoclave. Analysis of the obtained reaction mixture GC showed that the outputs WA4B2and WA4BH were, respectively, 53% and 9% (i.e., in General, 62%) per WB6and analysis of the obtained reaction mixture HPLC showed that the output WA4H2was 17% (based on WB6.

Comparative example 5

This comparative example shows that when the solvent for the reaction contains acetic acid in a concentration of more than 10 wt.% in the calculation of the mass of solvent input the desired product substantially lower.

The reaction was carried out basically as in example 12, except that used 6.0 g (instead of 3.0 g) of acetic acid. Analysis of the obtained reaction mixture GC showed that out of the total number WA4B2and WA4BH was 40% or less per WB6and analysis of the obtained reaction mixture of the first phase HPLC showed that the output WA4H2was 5% or less per WB6.

Example 13

(The way in which WB6used in high concentrations).

6(as starting substances in concentrations as high as 14 wt.% in the calculation of the solvent.

The reaction was conducted in substantially similar reaction the first stage of example 1, except that used was 4.2 g (instead of 2.1 g) WB6the internal temperature in the autoclave before loading solution WB6and acetic anhydride DMAc in the autoclave was equal to 55oWith (instead of the 60oC) used 2.1 g of 10% Pd-C (instead of 0.84 g), getting the reaction mixture. Analysis of the obtained reaction mixture GC showed that the outputs WA4B2and WA4BH were, respectively, 39% and 19% (i.e., in General, 58%) per WB6and analysis of the obtained reaction mixture of the first phase HPLC showed that the output WA4H2amounted to 20% (based on WB6.

The standard example 1 (prior art)

(The solubility of derivatives hexaazatetracyclo different types containing acyl group, in different solvents).

Investigated the solubility of derivatives hexaazatetracyclo different types containing acyl group, in different solvents. The results are presented in table.6.

The standard example 2 (prior art)

(Deposition of cristalli second solvent to obtain a solution. Then first the solvent was distilled from the solution to precipitate crystals WA4H2. Appropriate used amount (g) of the first and second solvents and the results of the deposition of crystals in the refinery are presented in table 7. In the standard example 2 distillation to precipitate crystals was performed to such an extent that the quantity of the first solvent was equal to 1 wt.% or less based on the total weight of the first and second solvents.

Example 14

(The way in which the reaction mixture of the second stage (which received batchwise when conducting the reaction in situ with the reaction mixture of the first stage) is subjected to the method of deposition of crystals by distillation).

The reaction mixture of the second stage, obtained in example 2 was subjected to the deposition of crystals by distillation as follows.

300 ml of the second stage of the reaction mixture obtained in example 2 was filtered to remove the catalyst, in the reaction mixture, receiving the filtrate. The obtained filtrate was loaded in baklazhanovyuyu flask with a capacity of 500 ml and was subjected to distillation (50oC, 10 mm RT. Art.) using a rotary evaporator equipped with a bath with a constant temperature, a vacuum pump is to be placed, which is lower than the DMAc. After the distillation flask was disconnected from the rotary evaporator, and the obtained after the distillation residue in the flask is allowed to cool to room temperature and to stand at room temperature for 12 hours to precipitate solids.

Precipitated particles were collected by filtration under vacuum and then washed about 10 ml of DMAc, getting wet solid. The wet solid was dried using a vacuum dryer (70oWith, 1 mm RT. Art. or less) to give 4.4 g WA4H2in the form of a white solid (yield deposition of crystals: 98%; purity: 98% (determined by HPLC)).

Example 15

(The way in which the reaction mixture of the second stage (which is obtained in a continuous mode by continuously carrying out the reaction of the first stage) is subjected to the method of deposition of crystals by distillation).

The filtrate (the reaction mixture is filtered catalyst) obtained in example 11 was subjected to the method of deposition of crystals by distillation as follows.

The filtrate (the reaction mixture is filtered catalyst) were analyzed by HPLC. In the result, it was found that the content WA4H2the filtrate was 1,90 g/100 ml Hipolito rotary evaporator, to remove approximately 28 ml of low-boiling fractions (such as toluene and water) having a boiling point lower than that of DMAc. After distillation flask was disconnected from the rotary evaporator, and the obtained after the distillation residue in the flask is allowed to cool to room temperature and to stand for 12 h at room temperature to precipitate thus the solid particles.

Precipitated solids were collected by filtration under vacuum and then washed about 5 ml of DMAc, getting wet solid. The wet solid is dried using a vacuum dryer (70oWith, 1 mm RT. Art. or less) to give 1.84 g WA4B2in the form of a white solid (yield deposition of crystals: 97%; purity: 99% (determined by HPLC) ).

Example 16

(The manner in which the solvent for crystallization is recycled (method of neutralization of NaOH) ).

In example 14, when besieged WA4H2collected by filtration under vacuum after deposition of crystals WA4B2distillation also got the filtrate containing DMAc. Analysis of the filtrate GC showed that the content of acetic acid in the filtrate was 2.30 g with respect to 100 ml of the filtrate.

To 100 ml vycherknul acid, contained in the filtrate. Then the mixture was distilled, receiving 95 ml of distillate consisting mainly of DMAc. The content of acetic acid in the distillate obtained was less than 0.5 wt.%.

The above quantitative analyses on the content of acetic acid in the above filtrate and the distillate GC was performed under the following conditions using the following equipment.

<Conditions of GC analysis>

Apparatus for GC: gas chromatograph type GC-10 (manufactured and delivered Schimadzu Corporation, Japan)

Column: capillary column DB-1 (manufactured and supplied by J &W Scientific Co., Ltd., USA)

Inner diameter: 0.25 mm

Length: 30 m

The thickness of the film covering the inner wall of the capillary column: 0.25 μm

Detection: flame ionization detector (FID)

Temperature: 60o(3 min)

Column: rises to 300o(The rate of temperature rise: 10oC/min) --> 300o(5 minutes)

Injector: 300oWITH

Detector: 300oWITH

Carrier gas: N2(the velocity of the gas: 100 ml/min and the internal column pressure: 100 kPa)

The amount of injected sample: 5 ál (obtained filtrate or distillate per se).

Example 17

(The way in which the/P> In example 14, when the precipitated crystals were collected by filtration under vacuum, after deposition of crystals WA4H2distillation also got the filtrate containing DMAc. Analysis of the filtrate GC showed that the content of acetic acid in the filtrate was $ 2,30 g with respect to 100 ml of the filtrate.

To 100 ml of the above filtrate was added Mg(OH)2so that the pH value of the filtrate was equal 8,00, obtaining a suspension containing Mg(OAc)2. (About 2.4 g of Mg(OH)2it is necessary to bring the pH of the filtrate to 8.00.) The resulting suspension is distilled using a distillation apparatus at a temperature of 100oC and a pressure of 50 Torr, receiving 95 ml of distillate, which mainly consisted of DMAc. The content of acetic acid in the distillate obtained was 0.5 wt.% or less. Quantitative analysis of acetic acid GC was performed in the same conditions as described in example 16. The survey insides still after distillation it found only a pale brown liquid and not found adhering to the inner wall of the distilling apparatus of the substance.

The standard example 3 (prior art)

(Raw WB6conventional JV the funnel, downloaded the 1.1 l of acetonitrile, 100 ml of distilled water, to 117.9 g (1.1 mmol) of benzylamine and 4.6 ml (0.11 mol) of formic acid, and the resulting mixture was cooled to 10oWith in the bath with a constant temperature. Then to the mixture was gradually added 72.5 g of 40% aqueous glyoxal (containing 0.5 mol of glyoxal) via the dropping funnel over 1 h, at the same time stirring and maintaining the temperature of the mixture at 10oC. After addition of a solution of glyoxal obtained mixture was heated to 25oWith stirring and then further stirred for 18 h to conduct thus reaction. The result of the resulting yellow reaction mixture dropped a white solid. The reaction mixture containing the white solid was filtered under vacuum, collecting the solid, and then collected solid was washed with mixed solvent (cooled to 0o(C) containing 275 ml of acetonitrile and 25 ml of distilled water. The washed solid was dried over night at room temperature under reduced pressure to obtain 92,34 g wet WB6(hexabenzylhexaazaisowurtzitane). Analysis of the obtained crude WB6HPLC showed that the purity of the raw WB6was equal to the CSOs microscope (SEM) to obtain micrographs (h), and the micrograph shown in Fig.1.

The standard example 4 (prior art)

(Purification of crude WB6conventional recrystallization).

The following describes a common way recrystallization purification WB6that uses a small amount of solvent for crystallization.

16,58 g wet WB6(purity: 90,2%) obtained in the standard example 3, and 1 ml of acetonitrile was loaded in chemical beaker 2 sheets Obtained in the beaker, the mixture was heated to 90oWith in the bath with a constant temperature with stirring for complete dissolution WB6in acetonitrile. After dilution WB6in acetonitrile, the temperature of the resulting solution WB6lowered to 20oC, and the solution was stirred for 4 h, at the same time maintaining the temperature of the solution at 20oFor recrystallization WB6. Recrystallized WB6collected by filtration under vacuum and dried to obtain 14,52 g of white crystals WB6.

The analysis of the obtained crystals WB6HPLC showed that the purity of the crystals WB6was the equal of 92.7%.

Crystals WB6obtained above, issledovano can be seen from Fig.2, the purity of the crystals WB6received conventional purification method was satisfactorily low.

The standard example 5 (prior art)

(Solubility WB6in organic solvents of various types).

Using raw WB6obtained in the standard example 3 was determined solubility WB6(H) in different organic solvents and the solubility of the impurities (I) (contained in the raw WB6in various organic solvents was determined as follows.

10 ml of an organic solvent and raw WB6obtained in the standard example 3 was loaded into a chemical beaker, and the resulting mixture was stirred at a predetermined temperature for 1 h, upon receiving the suspension. (Raw WB6used in such a quantity that the proportion WB6remained dispersed in an organic solvent even after stirring for 1 h at a predetermined temperature). The resulting suspension was filtered, receiving the filtrate. Part of the filtrate was taken for HPLC analysis. Samples for HPLC were prepared by diluting the selected filtrate mixed solvent comprising tetrahydrofuran and water (90/10 vol/vol), h the scheme. The chromatogram was observed one peak corresponding WB6and another peak corresponding to impurity. Retention time WB6was equal to 2.4 min, and the retention time of impurity was 2.2 minutes Contents WB6in the filtrate was determined based on the TLC results. A certain amount WB6the filtrate was taken as an index of solubility WB6in an organic solvent at a predetermined temperature.

The solubility of the impurities was determined as follows. To the filtrate obtained above, was added a predetermined amount of raw WB6(containing impurities), obtained in the standard example 3. Then the mixture was filtered as described above and the resulting filtrate was analyzed by HPLC as described above. Add WB6to the filtrate, filtration and HPLC analysis was repeated until the ratio of the intensity of the peak corresponding to impurity, relative to the peak, which corresponds WB6on the chromatogram is no longer increased, even when the filtrate was added raw WB6. The content of impurities in the filtrate was determined from the chromatogram showing the peak corresponding to impurity, where the ratio of the peak intensity, Alceste impurities in the filtrate was taken as the solubility of the impurities in the organic solvent at a predetermined temperature.

Using the solubility WB6(H) and the solubility of the impurities (I), determined by HPLC, was calculated the ratio of solubilities (R) by the following formula:

P=H/I,

where N represents the solubility WB6(g/l) in an organic solvent, and I represents the solubility of solids (g/l) (detected by HPLC analysis) in an organic solvent. The results are presented in table.8.

The standard example 6

(Purification of crude WB6the advanced method of recrystallization).

An improved method of recrystallization, used for cleaning WB6that uses a large amount of solvent for crystallization, is described below.

of 3.9 g of crude WB6(purity: 90,2%) obtained in the standard example 3, and 1 ml of acetonitrile was loaded in chemical beaker 2 L. the mixture was heated in a beaker to 90oWith in the bath with a constant temperature under stirring until complete dissolution WB6in acetonitrile. After dilution WB6in acetonitrile, the temperature of the resulting solution WB6reduced to 20oAnd the solution was stirred for 4 h, at the same time maintaining the temperature of the solution when the mind and dried, receiving 2.5 g of white crystals WB6.

The analysis of the obtained crystals WB6HPLC showed that the purity of the crystals WB6100%.

The standard example 7

(Purification of crude WB6the advanced method of recrystallization).

50 g raw WB6(purity: 90,2%) obtained in the standard example 3, and 1 l of ethyl acetate were loaded into a chemical beaker 2 sheets Obtained in the beaker and the mixture was heated to 60oWith in the bath with a constant temperature under stirring until complete dissolution WB6in ethyl acetate. After dilution WB6in ethyl acetate, the temperature of the resulting solution WB6reduced to 15oAnd the solution was stirred for 4 h, at the same time maintaining the temperature of the solution at 15oFor recrystallization WB6. Precrystallization WB6was collected by filtration under vacuum and dried, obtaining and 22.6 g of white crystals WB6.

The analysis of the obtained crystals WB6HPLC showed that the purity of the crystals WB6100%.

The standard example 8

(Purification of crude WB6the advanced method of recrystallization).

25 g of raw WB6(purity: La, downloaded in chemical beaker 2 sheets Obtained in the beaker and the mixture was heated to 60oWith in the bath with a constant temperature under stirring until complete dissolution WB6in the mixed solvent. After dilution WB6in a mixed solvent the temperature of the resulting solution WB6reduced to 15oAnd the solution was stirred for 4 h, at the same time maintaining the temperature of the solution at 15oFor recrystallization WB6. Precrystallization WB6was collected by filtration under vacuum and dried, obtaining 18.0 g of white crystals WB6.

The analysis of the obtained crystals WB6HPLC showed that the purity of the crystals WB6100%.

Crystals WB6obtained above, was investigated using SEM to obtain micrographs (h), and the resulting micrograph shown in Fig.3. As is clear from Fig.3, each of the crystals WB6had a clear needle-like shape, and purity of the crystals WB6was very high.

The standard example 9

(Obtaining high-purity WB6the advanced method).

In a removable flask with a capacity of 1 l equipped with a stirrer, thermometer, refrigerator and cap the ml) of acetic acid and the mixture in the flask was cooled to 20oWith in the bath with a constant temperature. Then to the mixture was gradually added 36,28 g of 40% aqueous glyoxal (containing 0.25 mol of glyoxal) via the dropping funnel over 30 min with stirring and maintaining the temperature of the mixture at 20oC. After addition of a solution of glyoxal obtained mixture was heated to room temperature with stirring and then kept stirring for 18 h for the reaction. The result of the resulting yellow reaction mixture dropped a white solid. The reaction mixture containing a white solid, was filtered in vacuum, collecting the white solid, and then assembled white substance was washed as follows. Assembled wet white solid was dispersively in a mixed solvent consisting of 170 ml of acetonitrile and 30 ml of distilled water, followed by stirring for 30 minutes, obtaining a suspension. The resulting suspension was filtered under vacuum, collecting the white needle crystals. The obtained crystals were dried overnight at room temperature under reduced pressure, thus obtaining 40,68 g of white needle-shaped crystals WB6. The analysis of the obtained crystals WB6HPLC showed that the purity to what I use SAM to get microphotographs (h), and the micrograph shown in Fig.4. As is clear from Fig.4, each of the crystals WB6received advanced method, had a clear needle-like shape and purity of the crystals WB6was very high.

The standard example 10

(Obtaining high-purity WB6the advanced method).

Getting WB6spent basically the same as the standard example 9 by the way, except that used 235,8 g (2.2 mol) of benzylamine (instead of to 117.9 g (1.1 mol) and the temperature of the contents in the removable flask was equal to 0oWith (instead of the 20oC) receiving with 32.5 g of white needle-shaped crystals WB6. The analysis of the obtained crystals HPLC showed that the purity of the crystals WB6100%.

The standard example 11

(Obtaining high-purity WB6the advanced method).

Getting WB6conducted in much the same way as in the standard example 9, except that he used to 85.7 g (0.8 mol) of benzylamine (instead of to 117.9 g (1.1 mol) and the temperature of the contents in the removable flask was 30oWith (instead of the 20oC) receiving of 38.2 g of white needle-shaped crystals WB6. The analysis of the obtained crystals HPLC showed coho WB6the advanced method).

Getting WB6conducted in much the same way as in the standard example 10, except that used 4.8 ml (0,075 mol) of acetic acid (instead of 3.2 ml (by 0.055 mol) and the mixture was gradually added 40% aqueous solution of glyoxal using a dropping funnel over 6 hours (instead of 30 min) at 35oWith (instead of the 20oC) receiving of 38.7 g of white needle-shaped crystals WB6. The analysis of the obtained crystals HPLC showed that the purity of the crystals WB6100%.

The standard example 13

(Obtaining high-purity WB6the advanced method).

In a removable flask with a capacity of 2 l, equipped with a stirrer, thermometer, refrigerator and addition funnel, was loaded 1100 ml of acetonitrile, 100 ml of distilled water, 235,8 g (2.2 mol) of benzylamine and 12.8 ml (0.22 mol) of acetic acid and the mixture in the flask was cooled to 0oWith in the bath with a constant temperature. Then to the mixture was gradually added to 72.6 g of 40% aqueous glyoxal (containing 0.5 mol of glyoxal) via the dropping funnel over 2 h with stirring and maintaining the temperature of the mixture at 0oC. After addition of a solution of glyoxal obtained mixture was heated on the effect of the resulting yellow reaction mixture precipitated white solid. The reaction mixture containing a white solid, filtered under vacuum, collecting the white solid, and then collected white solid was dispersively in a mixed solvent comprising 260 ml of acetonitrile and 40 ml of distilled water, followed by stirring for 30 minutes, obtaining a suspension. The resulting suspension was filtered under vacuum for collection of white needle-shaped crystals. The obtained white needle crystals were dried overnight at room temperature under reduced pressure, thus obtaining a 71,6 g of white needle-shaped crystals WB6. The analysis of the obtained crystals WB6HPLC showed that the purity of the crystals WB6amounted to 99.3 percent.

Example 18

(The way in which WB6(purity: 95% or more) obtained improved method of recrystallization, was used as the starting material).

This example 18 shows that the desired product can be obtained with high yield when using WB6having a purity of 95% or more, which receive the advanced method of recrystallization.

0,41 g 10% Pd-C (as a heterogeneous catalyst recovery) were loaded into the autoclave with a capacity of 100 ml is Vittel) that the internal pressure in the autoclave became equal to 2 kgf/cm2. The contents in the autoclave were heated at 60oC for 1 h In the autoclave was loaded liquid mixture (supported at 60o(C) obtained by dissolving 2.1 g WB6(hexabenzylhexaazaisowurtzitane) (purity: 100%, obtained in the standard example 8) in 30 ml of DMAc as a solvent) and then adding to the resulting solution of 1.84 g of acetic anhydride (as Alliluyeva agent). Then immediately began to stir the contents of the autoclave with stirring speed of 700 rpm and at the same time maintaining the temperature at 60oC and a pressure of 2 kgf/cm2and the reaction was conducted for 1 h, getting the reaction mixture.

Analysis of the obtained reaction mixture GC showed that the outputs WA4B2(tetraacetylethylenediamine) and WA4BH (tetraacetylethylenediamine) were, respectively, 35% and 22% (i.e., overall, 57%) per WB6and analysis of the reaction mixture HPLC showed that the output WA4H2(tetraazacyclotetradecane) was 24% (based on WB6.

Example 19

(The way in which WB6(purity: 95% or more), the resulting usovershenstvovannykh can be obtained with a very high yield when using WB6having a purity of 95% or more, which is obtained by the method applied in the present invention.

The reaction was carried out analogously to example 18, except that used WB6(purity: 100%) obtained in the standard example 9, receiving the reaction mixture.

Analysis of the obtained reaction mixture GC showed that the outputs WA4B2and WA4BH were, respectively, 37% and 22% (i.e. a total of 59%) per WB6and analysis of the reaction mixture HPLC showed that the output WA4H2was 24% (based on WB6.

Comparative example 7

This comparative example shows that the yield of the desired products is markedly reduced when using WB6having a purity less than 95%, which was obtained and purified by known methods.

The reaction was carried out in much the same way as in example 18, except that used WB6(purity: 92.7% of), obtained in the standard example 4, and the reaction was conducted for 4 h instead of 1 h), receiving the reaction mixture.

Analysis of the obtained reaction mixture of GC and HPLC showed that out of the total number WA4B2THAT WA4BH and WA4H2amounted to 10% or less per WB6 This example shows that WA4B2can be obtained with high yield by controlling the reaction conditions (in particular, using a small amount of water containing the catalyst).

14,50 g 10% Pd-C catalyst containing water (water content: 51,67%, the content of the catalyst: 7.0 g) and 200 ml of DMAc was loaded into the autoclave with a capacity of 2 l and the autoclave was purged with gaseous nitrogen. Then, the autoclave was introduced hydrogen gas so that the internal pressure in the autoclave became equal to 2 kgf/cm2and the contents of the autoclave were stirred with a stirring speed of 1000 rpm at 60oC for 1 h stirring Speed and the internal pressure in the autoclave was reduced to 300 rpm and 1.1 kgf/cm2maintaining the temperature at 60oC. In an autoclave using a syringe quickly downloaded 60 g of acetic anhydride, and then the autoclave was loaded solution (temperature: 60o(C) obtained by dissolving 70 g WB6(hexabenzylhexaazaisowurtzitane) in 800 ml of DMAc with a syringe. Then immediately the mixing rate and the internal pressure was raised to 1000 rpm and 2 kgf/cm2maintaining the temperature at 60oC, and the reaction was conducted for 6 hours, getting the reaction mixture.

6.

Example 21

(The way in which WA4H2get with high selectivity).

0,42 g 10% Pd-C were loaded into the autoclave with a capacity of 100 ml, and the autoclave was purged with gaseous nitrogen. Then, the autoclave was introduced hydrogen gas so that the internal pressure in the autoclave was equal to 1.1 kgf/cm2and the contents of the autoclave were stirred with a stirring speed of 300 rpm at 60oC for 1 hour, a Solution obtained by dissolving 2.1 g WB6and 1,82 g of acetic anhydride in 30 ml of DMAc was quickly loaded into the autoclave. Then immediately the mixing rate and the internal pressure was raised to 2000 rpm and 2 kgf/cm2maintaining the temperature at 60oC, and the reaction was carried out for 5.5 hours, getting the reaction mixture.

Analysis of the obtained reaction mixture HPLC showed that the output WA4H2was 75% (based on WB6and neither WA4B2nor WA4BH were not detected in the analysis of the reaction mixture GC.

In this example, the sample for HPLC analysis were prepared as follows. The reaction mixture (containing the catalyst) and evaporated under reduced pressure (1 mm RT. Art. or less at 50oWith, removing the liquid substance contained in the Rea is their between solid particles and air (i.e., oxygen), thus obtaining a mixture. The resulting mixture was subjected to ultrasonic treatment for 10 minutes using an ultrasonic cleaner and filtered, removing the catalyst, to obtain the filtrate. The obtained filtrate was used as a sample for HPLC analysis.

The method according to the present invention when receiving derivatives tetraallylsilane (which are suitable as precursors hexanitrohexaazaisowurtzitane used to improve performance characteristics of conventional explosives) from WB6the acylation can very effectively suppress the decomposition hexaazatetracyclo skeleton, which probably occurs at the initial stages of the reaction acylation WB6as an initial matter, while the desired derivative tetraallylsilane can be stably obtained with a high yield. Therefore, the method according to the present invention is industrially applicable. Furthermore, the method of the present invention also allows you to effectively suppressed in comparison with known ways of reducing the catalytic activity of the heterogeneous catalyst recovery taking place during the reaction.

1. The way azimuthal and W represents the residue of hexavalent hexaazatetracyclo, represented by the following formula II

< / BR>
restorative diphenylmethylsilane, comprising contacting hexacis(phenylmethyl)hexaazatetracyclo heterogeneous catalyst recovery in the presence of Alliluyeva agent and reducing agent in a solvent for the specified hexacis(phenylmethyl)hexaazatetracyclo, characterized in that the contacting between WB6and heterogeneous catalyst recovery is permitted only with the obligatory presence of both reagents: Alliluyeva agent and a reducing agent to obtain a mixture containing at least one derivative tetraallylsilane formula (3)

WA4BnH(2-n),

where W, as defined above;

H represents a hydrogen atom;

A represents C1-C10acyl group;

n is 0-2.

2. The method according to p. 1, characterized in that the reaction rehabilitation diphenylmethylsilane/acylation specified hexacis(phenylmethyl)hexaazatetracyclo is carried out at 40 160oC.

3. The method according to p. 1 or 2, characterized in that the solvent is a solvent containing an amide group.

4. The method according to one of paragraphs. 1-3, Aut a solution hexacis(phenylmethyl)hexaazatetracyclo in the solvent, containing amide group, and the specified heterogeneous catalyst recovery, and the reducing agent is a mixture of the specified heterogeneous catalyst recovery and the specified reducing agent, and where the specified solution hexacis(phenylmethyl)hexaazatetracyclo in the specified solvent in contact with the specified mixture indicated a heterogeneous catalyst recovery and the specified reducing agent in the presence of the specified Alliluyeva reagent.

5. The method according to one of paragraphs. 1-3, characterized in that the specified hexacis(phenylmethyl)hexaazatetracyclo and the solvent are the solution hexacis(phenylmethyl)hexaazatetracyclo in the specified solvent, and the specified heterogeneous catalyst recovery specified allerease agent and the reducing agent is a mixture of heterogeneous catalyst recovery specified Alliluyeva agent and a reducing agent, and this mixture of heterogeneous catalyst recovery specified Alliluyeva agent and the reducing agent is prepared by mixing the specified heterogeneous catalyst recovery and the specified reducing agent followed by the addition pointed to by the maker of the contact with the specified mixture of heterogeneous catalyst recovery specified Alliluyeva agent and reductant.

Priority points and features:

14.10.1997 on PP. 1-5;

26.12.1997 and 13.02.1998 - clarification of signs.

 

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