The allocation method is derived hexaazatetracyclo containing acyl group (options), the method of obtaining tetrazoles(arylmethyl)hexaazatetracyclo and method for producing tetraallylsilane

 

(57) Abstract:

Describes the allocation method derived hexaazatetracyclo containing acyl group, which comprises (I) obtaining a composition containing: (a) a mixed solvent comprising at least one first solvent selected from the group consisting of water and carboxylic acids, and at least one second solvent selected from the group consisting of containing amide or ester group of organic solvents; (b) derived hexaazatetracyclo containing acyl group of the following formula (1): WAnH(6-n)(1), where n is an integer equal to 4 or 6, each And independently represents an acyl group having from 1 to 10 carbon atoms, N represents a hydrogen atom and W represents a hexavalent balance hexaazatetracyclo the following formula (2); and at least part allstargame derived hexaazatetracyclo (b) dissolved in a mixed solvent (a); (II) removing from the composite system, at least part of the first solvent to precipitate crystals allstargame derived hexaazatetracyclo (b); and (III) Witwe predecessor explosive additives with high performance properties (in particular, hexanitrohexaazaisowurtzitane), can be easily obtained with high purity, high yield and at low cost. 4 C. and 32 C.p. f-crystals, 4 PL.

The present invention relates to a method of deriving hexaazatetracyclo containing acyl group, which is used as a precursor derived hexanitrohexaazaisowurtzitane used to improve the performance of conventional explosives. More specifically, the present invention relates to a method of deriving hexaazatetracyclo containing acyl group, which comprises the following stages: production of composite systems containing mixed solvent comprising a first solvent and a second solvent having respectively high and low dissolving ability in relation to the target compound, and the mixed solvent contains dissolved therein the target connection; (a) removing from the composite system of the first solvent having high dissolving ability, to precipitate crystals of the target compound or (a') the introduction of the above-mentioned composite system in the process of phase separation for p is ritala, not containing the target compounds or containing only a small amount of dissolved therein the target compounds, with subsequent removal of the first solvent from the first phase of the solvent, resulting in the precipitation of crystals of the target compound.

The claimed method is industrially advantageous because it can be used to obtain derived hexaazatetracyclo containing acyl group, with high yield and at low cost.

Prior art

Known standard way of deriving hexaazatetracyclo containing acyl group, in which hexacis(arylmethyl) hexaazatetracyclo subjected recovery dearylation in the presence Alliluyeva agent, getting derived hexaazatetracyclo, which has an acyl group and at least one group or atom selected from the group consisting of arylmethylidene groups, alkyl groups and hydrogen atoms, for example, tetrazoles(arylmethyl) hexaazatetracyclo, pentachlorodibenzofuran, sexuallytransmitted, tetracyclinecatdosagebuywith or tetraaryl the CSOs, known derivatives hexaazatetracyclo, which have the structure hexaazatetracyclo acetyl, formyl group and/or amino group (NH group). Examples of such derivatives hexaazatetracyclo include tetraacetylethylenediamine, tetraacetylethylenediamine and tetraacetylethylenediamine (see International publication N WO 97/20785).

These sources of information as the allocation method derived hexaazatetracyclo containing acyl group, use the way in which to obtain the target compound in the form of solids from the reaction mixture to remove the reaction solvent, or the way in which to obtain the target compound in the form of solids from the reaction mixture to remove the reaction solvent and then the solid is washed with an organic solvent.

However, when using such cues derived hexaazatetracyclo containing acyl group, there is the problem of achieving a sufficiently high degree of purification, and so dedicated allstargame derived hexaazatetracyclo must be cleaned by recrystallization that the Oia.

The invention

In this situation, the inventors have carried out numerous and intensive research aimed at creating a new way of getting allstargame hexaazatetracyclo high purity with high yield at low cost. In these studies, they focused on the fact that different types of solvents differ significantly on its ability to dissolve allstargame derived hexaazatetracyclo, which is the target compound. As a result of these studies it was found that the desired compound of high purity with high yield and at low cost can be obtained by using a method that includes: obtaining a composite system containing a mixed solvent consisting of first and second solvents having respectively high and low dissolving ability in relation to the target compound, and the mixed solvent contains dissolved therein a target compound; and (a) removal of the composite system of the first solvent having high dissolving ability, in order to obtain a crystalline precipitate of the target compound or (a'): videodeluxe dissolved the target connection, and the second solvent phase, not containing the target compound or containing only a small amount of dissolved the target compounds, with subsequent removal of the first solvent from the first solvent phase, resulting in the precipitation of crystals of the target compound.

Accordingly, the present invention is the provision of a method of obtaining from a solution allstargame derived hexaazatetracyclo high purity with high yield and at low production costs. All the objectives, features and advantages of the present invention will become obvious to specialists in this field from the subsequent detailed description and the claims.

Detailed description of the invention

In accordance with one aspect of the present invention, a method for obtaining acidsolitaire derived hexaazatetracyclo, including:

(I) obtaining a composition system containing:

(a) a mixed solvent comprising at least one first solvent selected from the group consisting of water and carboxylic acids, and at least one second solvent selected from the group consisting of PR is isovorticity, represented by the following formula (1):

WAnH(6-n)(1)

where n is an integer equal to 4 or 6, each A independently represents an acyl group containing from 1 to 10 carbon atoms, H represents a hydrogen atom and W represents a hexavalent balance hexaazatetracyclo, represented by the following formula

< / BR>
moreover, at least part allstargame derived hexaazatetracyclo (b) dissolved in a mixed solvent (a);

(II) removing from the composite system, at least part of the first solvent to precipitate crystals derived hexaazatetracyclo containing acyl group (b); and

(III) isolation of the precipitated crystals of the composite system.

In accordance with another aspect of the present invention proposes a method of obtaining allstargame derived hexaazatetracyclo, including:

(A) obtaining a composition system containing:

(a') a mixed solvent consisting of water and at least one organic solvent which can be separated from water, and

(b') derived hexaazatetracyclo containing acyl group, predstavlennyy A independently represents an acyl group, having from 1 to 10 carbon atoms, H represents a hydrogen atom, and W represents a hexavalent balance hexaazatetracyclo, represented by the following formula (13):

< / BR>
where composite system includes the organic phase and the aqueous phase having dissolved therein at least part of the derived hexaazatetracyclo containing acyl group (b');

(B) separating the aqueous phase from the composite system; and

(C) evaporating water from the aqueous phase to obtain a derived hexaazatetracyclo in its purest form.

To facilitate understanding of the present invention the following are the essential features and variants of the present invention.

1. The method of deriving hexaazatetracyclo containing acyl group, including:

(I) obtaining a composition system containing:

(a) a mixed solvent comprising at least one first solvent selected from the group consisting of water and carboxylic acids, and at least one second solvent selected from the group consisting of organic solvents, containing amide or ester group, and

(b) derived eXasis is/BR> where n is an integer equal to 4 or 6, each A independently represents an acyl group having from 1 to 10 carbon atoms, H represents a hydrogen atom, and W represents a hexavalent balance hexaazatetracyclo, represented by the following formula (2):

< / BR>
moreover, at least part of the derived hexaazatetracyclo containing acyl group (b) dissolved in a mixed solvent (a);

(II) removing from the composite system, at least part of the first solvent to precipitate crystals derived hexaazatetracyclo containing acyl group (b); and

(III) isolation of the precipitated crystals of the composite system.

2. The method in accordance with section 1, which contains the acyl group derived hexaazatetracyclo (b) represented by the formula (1) is the product obtained by synthesis using a reaction solvent consisting of first and second solvent.

3. The method in accordance with section 2, where the composite system obtained in stage (1), a mixed solvent consisting of first and second solvents, receive at least one dissolve the reaction is above the boiling point of the first solvent, and removing at least part of the first solvent from the composite system is performed by distillation.

5. The method in accordance with section 3, where the second solvent has a boiling point which is above the boiling point of the first solvent, and removing at least part of the first solvent from the composite system is performed by distillation.

6. The method in accordance with section 5, where allstargame derived hexaazatetracyclo (b) is tetraallylsilane, which is represented by the following formula (3):

WA4H2(3)

where each of A, H and W is as defined above for formula (1), and which is obtained by synthesis using at least two reaction solvents,

where at least two of the reaction solvent are the same as at least one first solvent and at least one second solvent,

where in the composite system obtained in stage (1) at least one first solvent and at least one second solvent receive at least two reaction solvents, and

where at least one first solvent selected from Groupama of organic solvents, having a boiling point higher than the boiling point of water, when the first solvent is water, or having a boiling point which is above the boiling point of acetic acid, when the first solvent is acetic acid or a mixture of water and acetic acid.

7. The method in accordance with section 5, where allstargame derived hexaazatetracyclo (b) is tetraallylsilane which is represented by the following formula (3):

WA4H2, (3)

where each of A, H and W is as defined above for formula (1) and which is obtained by synthesis using at least two reaction solvents,

where at least two of the reaction solvent are the same as at least one first solvent and at least one second solvent,

where in the composite system obtained in stage (1) at least one first solvent and at least one second solvent receive at least two reaction solvents, and

where the first solvent is water, and at least one second solvent selected from the group consisting of organic solvents, containing amide gruson in accordance with section 6, where the synthesis tetraallylsilane represented by the formula (3), includes the introduction of tetrazoles(arylmethyl)hexaazatetracyclo, represented by the following formula (4):

WA4B2, (4)

where is each independently represents arylmethyl group having from 7 to 21 carbon atoms, and each of W and A are defined above for the formula (1), in response diarylethylene in the presence of at least two reaction solvents.

9. The method in accordance with section 7, where the synthesis tetraallylsilane represented by the formula (3), includes the introduction of tetrazoles(arylmethyl)hexaazatetracyclo, represented by the following formula (4):

WA4B2, (4)

where is each independently represents arylmethyl group having from 7 to 21 carbon atoms, and each of W and A are defined above for the formula (1) in the reaction diarylethylene in the presence of at least two reaction solvents.

10. The method in accordance with section 5, where allstargame derived hexaazatetracyclo (b) is tetraallylsilane, which is represented by the following formula (3):

WA4H2,

where each of A, H and W are defined in the

where at least two of the reaction solvent are the same as at least one first solvent and at least one second solvent,

where in the composite system obtained in stage (I) at least one first solvent and at least one second solvent receive at least two reaction solvents, and

where the first solvent is water and at least one second solvent selected from the group consisting of containing amide group of an organic solvent having compatibility with water and having a boiling point higher than the boiling point of water,

where the synthesis tetraallylsilane represented by the formula (3), involves the following stages:

(i) introduction hexacis(arylmethyl)hexaazatetracyclo in response restorative diarylethylene in the presence Alliluyeva agent to obtain a reaction mixture (i) containing tetrazoles(arylmethyl)hexaazatetracyclo, represented by the following formula (4):

WA4B2, (4)

where is each independently represents arylmethyl group having from 7 to 21 carbon atoms, and each of W and A are defined above for the formula (1),

and sod the mixture, and

(iii) subsequent diarylethylene the resulting reaction mixture to obtain the reaction mixture (iii) containing tetrachlorodibenzofuran formulas (3) and Arellano as a by-product.

11. The method in accordance with section 10, obtained in stage (i) by-product, which is a carboxylic acid, is removed from the reaction mixture (i) obtained in stage (i), azeotropic distillation together with Arellano, including kilmacanogue by-product obtained in stage (i).

12. The method in accordance with section 10, obtained in stage (i) by-product, which is a carboxylic acid, is removed by azeotropic distillation together with Arellano, including kilmacanogue by-product obtained in stage (i) and stage (iii) of the composite system during removal of the first solvent by distillation in stage (II) or from portions of the composite system, which remains after separation of precipitated crystals of the composite system at stage (III).

13. The method in accordance with section 10, where the second solvent is at least one containing amide group with an organic solvent selected from the A.

14. The method in accordance with section 11, where the second solvent is at least one containing amide group with an organic solvent selected from the group consisting of N,N-dimethylacetamide, N,N-dimethylformamide, 1,3-dimethyl-2-imidazolidone and N-methyl-2-pyrrolidone.

15. The method in accordance with section 12, where the second solvent is at least one containing amide group with an organic solvent selected from the group consisting of N,N-dimethylacetamide, N,N-dimethylformamide, 1,3-dimethyl-2-imidazolidone and N-methyl-2-pyrrolidone.

16. The method in accordance with section 11, the side where the carboxylic acid is acetic acid and Arellano is toluene.

17. The method in accordance with section 12, where the side-carboxylic acid is acetic acid and Arellano is toluene.

18. The method in accordance with section 14, the side where the carboxylic acid is acetic acid and Arellano is toluene.

19. The method in accordance with section 15, where side-carboxylic acid is acetic acid and Arellano is toluene.

20. The method in accordance with section 4, where allstargame phormula (8):

WA6(8)

where each of W and A are defined above for the formula (1) and where at least one first solvent selected from the group consisting of water and acetic acid, and at least one second solvent selected from the group consisting of containing the ether group of organic solvents having a boiling point higher than the boiling point of water, when the first solvent is water, or having a boiling point which is above the boiling point of acetic acid, when the first solvent is acetic acid or a mixture of water and acetic acid.

21. The method in accordance with section 5, where allstargame derived hexaazatetracyclo (b) is tetracyclineresistant, which is represented by the following formula:

WA4F2r(9)

where each Frrepresents a formyl group, and each of W and A are defined above for the formula (1), and which is obtained by synthesis using at least two reaction solvents,

where at least two of the reaction solvent are the same as at least one first solvent and at least one second solvent,

where in the composite system, poruchaut, at least two of the reaction solvent, and

where the first solvent is formic acid, and at least one second solvent selected from the group consisting of containing the ether group of organic solvents having a boiling point which is above the boiling point of formic acid.

22. The method in accordance with section 21, where the synthesis tetracyclineresistant represented by the formula (9), includes the introduction of tetrazoles(arylmethyl)hexaazatetracyclo, represented by the following formula (4):

WA4B2(4)

where is each independently represents arylmethyl group having from 7 to 21 carbon atoms, and each of W and A is as defined above for formula (1), in response diarylethylene in the presence of the reaction solvent.

23. The method in accordance with section 21 or 22, where the synthesis tetracyclineresistant represented by the formula (9), involves the following stages:

(iii) introduction hexacis(arylmethyl)hexaazatetracyclo in response restorative diarylethylene in the presence Alliluyeva agent to obtain the reaction mixture containing tetrazoles(arylmethyl)Gecko is arylmethyl group, having from 7 to 21 carbon atoms, and each of W and A is as defined above for formula (1),

(iv) adding to the reaction mixture of formic acid and

(v) subsequent diarylethylene the resulting reaction mixture.

24. The method in accordance with section 21, where the second solvent is at least one containing ester group with an organic solvent selected from the group consisting of etilenpropilendienovogo ether, ethylene glycol-di-n-butyl ether, dietilaminoetilovogo ether and dietilaminoetilovogo ether.

25. The method in accordance with section 22, where the second solvent is at least one containing ester group with an organic solvent selected from the group consisting of etilenpropilendienovogo ether, ethylene glycol-di-n-butyl ether, dietilaminoetilovogo ether and dietilaminoetilovogo ether.

26. The method in accordance with section 23, where the second solvent is at least one containing ester group with an organic solvent selected from the group consisting of etilenpropilendienovogo ether, ethylene glycol-di-n-butyl ether, diethylamido derived hexaazatetracyclo, including:

(A) obtaining a composition system containing:

(a') a mixed solvent consisting of water and at least one organic solvent which can be separated from water, and

(b') derived hexaazatetracyclo containing acyl group represented by the following formula (12):

WAnH(6-n)(12)

where n is an integer equal to 4 or 6, each A independently represents an acyl group having from 1 to 10 carbon atoms, H represents a hydrogen atom and W represents a hexavalent balance hexaazatetracyclo, represented by the following formula (13):

< / BR>
where composite system includes the organic phase and the aqueous phase containing dissolved therein at least part of the derived hexaazatetracyclo containing acyl group (b');

(B) separating the aqueous phase from the composite system, and

(C) evaporating water from the aqueous phase to obtain a derived hexaazatetracyclo (b') in pure form.

28. The method in accordance with section 27, where n in the formula (12) is equal to 4.

29. The method in accordance with section 27, where n in the formula (12) is equal to 6 and where two of the group A in the formula (12) yavlyaetsya.

As mentioned above, the method in accordance with one aspect (first aspect) of the present invention includes the above stage (I)-(III), and the method in accordance with another aspect (second aspect) of the present invention includes the above stage (A)-(C).

1. The method according to the first aspect:

At stage (I) of this method is proposed composite system containing:

(a) a mixed solvent consisting of at least one first solvent selected from the group consisting of water and carboxylic acids, and at least one second solvent selected from the group consisting of organic solvents, excluding carboxylic acid, and

(b) derived hexaazatetracyclo containing acyl group represented by the following formula (1):

WAnH(6-n) (1)

where n is an integer equal to 4 or 6, each A independently represents an acyl group having from 1 to 10 carbon atoms, H represents a hydrogen atom and W represents a hexavalent balance hexaazatetracyclo, represented by the following formula (2):

< / BR>
in this case, at least the part containing acyl group derived gexas the pout aspect of the composite system for the deposition of crystals allstargame derived hexaazatetracyclo (b) remove, at least a portion of the first solvent.

At stage (III) of the method in accordance with the first aspect of the composite system give us the precipitated crystals.

The method of the first aspect of the present invention has the advantage consisting in the fact that allstargame derived hexaazatetracyclo represented by the formula (1), almost insoluble in the usual organic solvents, but can be easily dissolved in proton high-polar solvent, such as water and carboxylic acids, which distinguishes derivatives hexaazatetracyclo formula (1) from other derivative hexaazatetracyclo and decomposition products of his skeleton when these other derivatives hexaazatetracyclo and decomposition products of the skeleton contained in the composite system in the form of impurities. Using this property derived hexaazatetracyclo formula (1) in the method according to the first aspect, allstargame derived hexaazatetracyclo formula (1) dissolved in a mixed solvent comprising a first solvent and a second solvent, for education, as a result, the composite system, where the first solvent (i.e. water or carboxylic acid) has spatial (i.e., organic solvent excluding carboxylic acid) almost has no ability to dissolve containing acyl group derived hexaazatetracyclo formula (1), but has the ability to dissolve the above-mentioned impurities, and then for the deposition of crystals containing acyl group derived hexaazatetracyclo at least a portion of the first solvent is removed from the composite system and separate from it precipitated crystals. Thus there can be obtained high-purity derived hexaazatetracyclo formula (1).

Examples containing acyl group derived hexaazatetracyclo formula (1) include compounds which have structures represented by the following formulas (1-1) to(1-3):

< / BR>
< / BR>
< / BR>
where each A1independently represents an acyl group having from 1 to 10 carbon atoms, each A2independently represents an acyl group having from 1 to 10 carbon atoms, and H represents a hydrogen atom, where A1and A2differ from each other. In relation to the acyl group of A in formula (1) has no specific limitation as long as it is acyl group, Emppu, propionyloxy group, butyryloxy group, isobutyryloxy group, valerino group, hexanoyl group and 2-phenylacetylene group. Of them, preferred are acyl groups having from 1 to 3 carbon atoms, such as formyl group, acetyl group and propylaniline group, and particularly preferred are formyl group and acetyl group.

The above-mentioned first solvent is at least one solvent selected from the group consisting of water and carboxylic acids. In respect of carboxylic acids there are no particular limitations as long as they are liquid at atmospheric pressure and at a temperature of 40oC or higher. Examples of carboxylic acids include carboxylic acid with a straight chain, for example formic acid, acetic acid, propionic acid, butyric acid and somaclonal acid. In respect of carboxylic acids should be noted that, when intending to remove by distillation the first solvent, preferred are carboxylic acids with a low molecular weight, for example formic acid, acetic acid and propionic acid, due to the fact that each e is scoi molecular weight especially preferred are formic acid and acetic acid.

In relation to the above second solvent there is no specific limitation as long as he is an organic solvent other than the carboxylic acid. However, it is preferable to use as the second solvent is an organic solvent, which contains the acyl group derived hexaazatetracyclo has a solubility of 1% by weight or less, more preferably 0.5% by weight or less.

In respect of derivative hexaazatetracyclo (b) of formula (1) contained in the above-mentioned composite system, which is subjected to the deposition of crystals on the stage (II), it should be noted that it is preferable to apply the product obtained by the method of synthesis using at least one reaction solvent. In this case, more preferably, the aforementioned at least one reaction solvent used in the method of synthesis was the same as at least one solvent selected from the group consisting of the first solvent and the second solvent. The reason for this is that as the reaction solvent used in the method of synthesis), using essentially mixed R is CLASS="ptx2">

Regarding the above-mentioned composite system, it should be noted that there is no need to derived hexaazatetracyclo (b) of formula (1) was completely dissolved in a mixed solvent (a), and derived hexaazatetracyclo (b) may be present in the composite system in the form of a suspension, where the part derived hexaazatetracyclo (b) is not dissolved in a mixed solvent (a). However, it is preferable that the composite system does not contain solid particles.

On the above-mentioned phase deposition of crystals (stage (II)) of the method of the present invention requires the deposition of crystals derived hexaazatetracyclo of the composite system has been removed, at least a portion of the first solvent at least one solvent selected from the group consisting of water and carboxylic acids). In the method of implementation deposition of crystals there are no particular limitations. However, as typical examples of such a method can be mentioned the following four methods.

A. (Distillation method for the deposition of crystals)

Distillation method for the deposition of crystals can be applied, when the second R is th system is subjected to distillation to remove, consequently, at least part of the first solvent, to precipitate crystals derived hexaazatetracyclo (b).

Century (Method of separation and membrane filtration)

Method of separation and membrane filtration includes confirmation of the composite filtration using a membrane filter for the selective removal of the first solvent and the precipitation of crystals derived hexaazatetracyclo (b).

C. (Adsorption method).

The adsorption method is a method in which the removal of the first solvent is performed with the use of the adsorber which is capable of selective adsorption of the first solvent, to precipitate, as a result, crystals derived hexaazatetracyclo (b).

D) (a Method using a chemical reaction).

Method using a chemical reaction involves the transformation of the first solvent into other compounds through chemical reactions for the deposition, as a result, crystals derived hexaazatetracyclo (b).

In any one of the aforementioned methods, almost all of the impurities dissolved in the second solvent to the resulting wasp is Mesa.

Of the above four methods is preferred distillation method for the deposition of crystals, due to the fact that this is the most suitable method to obtain containing acyl group derived hexaazatetracyclo particularly in high-purity form.

Below is a detailed explanation of the distillation method, deposition of crystals (method A).

In the present invention when carrying out the deposition of crystals on the stage (11) distillation method for the deposition of crystals, there are no particular restrictions on the combination of the first solvent and the second solvent until until the second solvent has a boiling point which is above the boiling point of the first solvent.

The first examples of solvents include water (boiling point: 100oC), formic acid (boiling point: 100oto 101oC), acetic acid (boiling point: 118oC), propionic acid (boiling point: 141oC). Examples of the second solvent include containing amide group of organic solvents such as N, N-dimethylformamide (boiling point: 153oC), N,N-dimethylacetamide (boiling point: 165oto 166oC), 1,3-is readie ester group of organic solvents, for example etilenglikolevye ether (boiling point: 121oC), ethylene glycol-di-n-butyl ether (boiling point: 203oC), diethylethylenediamine ether (boiling point: 162oC), dietilenglikoluretan ether (boiling point: 188oC) and dietilenglikoluretan ether (boiling point: 256oC).

In this regard, it should be noted that when the first solvent using an organic solvent having a boiling point, which is the same as the boiling point of propionic acid or higher, then as the second solvent can be used a solvent having a boiling point below the boiling point of propionic acid, for example etilenglikolevye ether.

The above-mentioned second solvents are polar solvents having, in particular, high compatibility with the above-mentioned first solvent and can therefore be used to obtain a homogeneous mixture of the first solvent and the second solvent. However, in the present invention it is not necessary that a mixed solvent (a) was homogeneous mixture of first solvent and second solvent, and a mixed solvent (a) may byi (a) is a two-phase mixture, can be applied distillation method of deposition until then, until you are above the ratio between the boiling point of the first solvent and the boiling point of the second solvent. The weight ratio of the first solvent to the second solvent in the mixed solvent (a) is usually from 0.01 to 10, preferably from 0.02 to 5, more preferably from 0.05 to 2.

With regard to pressure by distillation, can be applied to either atmospheric pressure or reduced pressure. In terms of the temperature of distillation, there is no special limitation as long until the first solvent may be distilled under pressure, used for distillation. However, to complete the distillation in a short period of time, the distillation is preferably carried out under reduced pressure and at a temperature equal to the boiling point of the first solvent or above the boiling point of the first solvent, which is measured under the applied reduced pressure. The distillation is preferably carried out under reduced pressure and at a temperature equal to the boiling point of the first solvent or above the boiling point of the solvent and which is equal to or below the point CIPA measured under applied reduced pressure. When the distillation is carried out under such pressure and at such temperature, it becomes possible separation of the first solvent from the composite system in the course of a single distillation, so that each of the first solvent and the second solvent can be easily recycled. When the distillation is performed under reduced pressure, the pressure is chosen in the range from 0.0000001 mm Hg to 760 mm Hg. In this case, the lower the pressure, the less the time required for distillation and the lower the temperature required for the implementation of distillation, and therefore, it becomes possible to suppress the occurrence of thermal decomposition containing acyl group derived hexaazatetracyclo (b) of formula (1). The distillation is preferably carried out under reduced pressure of 200 mm Hg or less.

When the present invention is used distillation method for the deposition of crystals and when the first solvent is removed by distillation, can be distilled part of the second solvent until, while in the original composite system will remain remote about 10% by weight or more presence of the second solvent. In addition, it is not the t from the type of the first solvent and the type of the second solvent, it is very difficult to completely remove from the composite system of the first solvent in the implementation of distillation on a commercial scale. Therefore, in the distillation method, deposition of crystals distillation can be performed up until the quantity of the first solvent remaining in the resulting distillation residue becomes equal to 0.2 or less based on the weight ratio of the first solvent remaining in the composite system, the second solvent. To obtain the desired compound in high yield, it is preferable to carry out the distillation until then, until the quantity of the first solvent remaining in the composite system becomes equal to 0.02 or less per weight ratio of the first solvent to the second solvent. When the method of the first aspect of the present invention is used distillation method for the deposition of crystals is particularly preferable that the connection is subjected to the deposition of crystals was tetraallylsilane, represented by the following formula (3), which is a compound of formula (1) in which n is 4:

WA4H2(3)

where each of A, H and W is as defined in Obedinenie is high hydrophilic, and it has low solubility in almost all organic solvents, excluding carboxylic acids.

The first examples of solvents that can be used in the composite system for the deposition of crystals tetraallylsilane include water, acetic acid and propanolol acid. Of them, preferred are water and acetic acid, with the preferred solvent is water. Regarding the second solvent, here there are no particular restrictions as long as he is an organic solvent not including carboxylic acids. However, it is preferable to use organic solvents in which tetrachlorodibenzofuran represented by the above formula (3) has a solubility of 0.5% by weight or less. Preferred examples of the second solvent include a solvent,

containing amide group, and a solvent containing an ester group. Of those, more preferred is a solvent containing an amide group, because it can be advantageously used to obtain containing acyl group hexaazatetracyclo particularly in high-purity form. In particular, b is repectfully is N,N-dimethylacetamide.

As for tetraallylsilane formula (3), subjected to the deposition of crystals, there are no particular restrictions on the method of its synthesis. However, it is preferable to apply tetrachlorodibenzofuran synthesized by exposure of tetrazoles(arylmethyl)hexaazatetracyclo, represented by the following formula (4):

WA4B2(4)

dearylation, which is schematically shown in the following reaction (5):

< / BR>
where each B independently represents arylmethyl group having from 7 to 21 carbon atoms, and each of W, A, and H is the same as defined above for formula (1).

As for the reaction represented by the reaction scheme (5), any reaction method can be used up until it can be used to carry out the reaction diarylethylene. Examples of the reaction method include a method of rehabilitation diarylethylene, the method of oxidative dearylation with the use of an oxidant such as peroxide, oxide of ruthenium or (NH4)[Ce(IV)(NO3)6] ; the reaction method, in which after carbamasepine using chloroformiate implemented the equipment is a method of rehabilitation diarylethylene.

In respect of the reaction solvent used in the reaction of diarylethylene represented by the reaction scheme (5), there are no particular limitations as long as the solvent is capable of dissolving tetrazoles(arylmethyl)hexaazatetracyclo formulas (4) and does not adversely affect the reaction. Examples of reaction solvents include solvents containing amide group, for example, N,N-dimethyl-ndimethylacetamide, N, N-dimethylformamide, 1,3-dimethyl-2-imidazolidone and N-methyl-2-pyrrolidone; and carboxylic acids such as acetic acid and propionic acid. These solvents have a relatively high ability to dissolve tetrazoles(arylmethyl)hexaazatetracyclo, so when these solvents are used as the first component of the reaction solvent, as a second component of the reaction solvent may be used any other solvents, while the first and second components of the reaction solvent together comprise the system of the reaction solvent.

The following solvents which can be advantageously used as the second component of the reaction solvent, when used as the first components is CLASS="ptx2">

When the first component of the reaction solvent used solvent containing an amide group, as the second component of the reaction solvent used water or a carboxylic acid, e.g. acetic acid, propionic acid or similar acids which are capable of dissolving tetraallylsilane formula (3). The reason for this is not only in the fact that when the second component of the reaction solvent used water or carboxylic acid, the reaction can be carried out in a homogeneous reaction system, but also that water or carboxylic acid containing amide group solvent may respectively serve as first and second solvent in the composite system, exposed distillation deposition of crystals by removing the first solvent to the resulting reaction mixture containing tetrachlorodibenzofuran formula (3), can be used as such when the distillation deposition of crystals without the need for removal of the reaction solvent. The type of carboxylic acid used as the second component of the reaction solvent, do not limit the special obreve second component of the reaction the preferred solvent is water, because it has a lower boiling point than the carboxylic acid.

Carboxylic acid capable of dissolving both tetrazoles(arylmethyl)hexaazatetracyclo and tetraallylsilane. Therefore, when the first component of the reaction solvent used carboxylic acid, as a second component of the reaction solvent used without limitation any organic solvent, and the reaction proceeds in a homogeneous system. Carboxylic acid used as the first component of the reaction solvent in the composite system, exposed distillation deposition of crystals, also functions as the first solvent. Therefore, when an organic solvent which has a boiling point above the boiling point of the carboxylic acid used as the first component of the reaction solvent, and which, therefore, can serve as the second solvent in the composite system, exposed distillation deposition of crystals, used as the second component of the reaction solvent, the reaction mixture containing tetrachlorodibenzofuran formula (3) may Estallo. Adding a second component of the reaction solvent may be carried out after completion of the synthesis reaction tetraallylsilane formulas (3) and to exposure resulting from the synthesis of distillation of the reaction mixture to the deposition of crystals.

When the first component of the reaction solvent used carboxylic acid, there are no special restrictions with regard to the second component of the reaction solvent. However, preferred are organic solvents in which tetrachlorodibenzofuran formula (3) has a solubility of 0.5% by weight or less, and which have a boiling point above the boiling point of the carboxylic acid. Examples of such preferred solvents include solvents containing ester group, for example etilenglikolevye ether, ethylene glycol-di-n-butyl ether, diethylethylenediamine ether, dietilenglikoluretan ether, dietilenglikoluretan ether and similar substances, and solvents containing amide group, such as N, N-dimethylacetamide, N,N-dimethylformamide, 1,3-dimethyl-2-imidazolidone, N-methyl-2-pyrrolidone and the like substances. The above solvents can be ispolzovaniem in the reaction scheme (5), is usually in the range from 0.001 to 1, preferably 0.005 to 0.5, more preferably from 0.01 to 0.4 in the calculation of its weight with respect to the reaction solvent.

As reducing agent, it is not necessarily used for the reaction of diarylethylene, can be called the hydrogen gas, hydrazine, or similar substances, while preferred is hydrogen gas. The reducing agent is usually used in an amount of from 1 to 10000, preferably from 1 to 1000, more preferably from 2 to 50 per molar ratio of reducing agent to arylmethyl groups tetrazoles(arylmethyl)hexaazatetracyclo. When the reductant used hydrogen gas, the reaction pressure is typically in the range from 0.01 to 100, preferably from 0.1 to 30, more preferably from 0.1 to 20 FCT/cm2in the calculation of the partial pressure of hydrogen. In addition to the hydrogen gas in the reaction system can be inert gases such as nitrogen, argon and helium.

In respect of not necessarily used catalyst recovery, there is no special limitation as long as he is able to accelerate diarylethylene tetrazoles(arylmethyl)hexaazatetracyclo. What is the group of platinum, or containing derivative. Preferred examples of catalysts of the reducing agent include compounds Pd /for example Pd(OAc)2, PdCl2Pd(NO3)2, PdO, Pd(OH)2Pd3Pb1and Pd3Te1/ Pd alloys and metallic Pd; and connections EN (for example Ru Cl3), Ru alloys and metallic Ru. More preferred are compounds of Pd (e.g., Pd(OAc)2, PdCl2and similar substances), Pd alloys and metallic Pd. Such catalysts recovery can be used as such. Alternative these catalysts recovery can be applied in a form that can be transferred to various types of media, such as activated carbon, silica, alumina, silica-alumina, zeolite, activated clay, Zirconia and titanium dioxide. To improve the catalytic activity preferably, the catalyst was subjected to reduction processing before use in the above reaction rehabilitation diarylethylene. As for the reducing agent in the implementation of this recovery processing, preferred are a hydrogen gas or hydrazine. When done inactivate acid centers, present on the surface of the carrier, through sililirovanie, acylation or similar methods, or in such a way as to adsorb alkaline substance (e.g., NaOH) on the surface of the carrier, or in such a way as to carry out the activation of the media to increase as a consequence of acid centers on the surface of the media.

When using a heterogeneous catalyst recovery, it can be used either in the form of a fixed layer, or in the form of a fluidized bed.

The reaction temperature reconstruction diarylethylene is usually in the range from the temperature of the coagulation solvent to 200oC, preferably from 30 to 180oC, more preferably from 40 to 165oC.

Regarding the method of obtaining tetraallylsilane formula (3) is subjected to distillation to deposition of crystals in the method of the present invention, it should be noted that the preferred is the use of two-stage reaction method includes a first stage in which hexacis(arylmethyl)hexaazatetracyclo subjected recovery dearylation in the presence Alliluyeva agent to obtain tetrazoles(Ari who tetrazoles(arylmethyl)hexaazatetracyclo are dearylation to get tetraallylsilane (which shows the reaction scheme (5)).

< / BR>
where B represents arylmethyl group having from 7 to 21 carbon atoms, and each of W and A is as defined above for formula (1).

In respect of the reaction solvent used in the rehabilitation diarylethylene (presented above (6)), which is carried out in the presence of Alliluyeva agent, there are no particular limitations as long as the solvent is capable of dissolving WB6and not adversely affect the reaction. Examples of solvents include solvents containing amide group, for example, N,N-dimethylacetamide, N, N-dimethylformamide, 1,3-dimethyl-2-imidazolidone and N-methyl-2-pyrrolidone, and solvents containing ester group, for example etilenglikolevye ether, ethylene glycol-di-n-butyl ether, diethylethylenediamine ether, dietilenglikoluretan ether and dietilenglikoluretan ether. Among these solvents, preferred are N,N-dimethylacetamide and N,N-dimethylformamide. The above solvents can be used individually or in combination.

The above-mentioned solvents which are suitable for the reaction represented by the scheme (6), operating the deposition of crystals, as the second solvent. Therefore, when tetrazoles(arylmethyl)hexaazatetracyclo get through reactions presented in the above reaction scheme (6) using the above-mentioned solvent (second solvent), there is no need to allocate the resulting tetrazoles(arylmethyl)hexaazatetracyclo from the reaction mixture obtained by the reaction represented by the reaction scheme (6). Subsequent operations can easily be implemented by a method in which the solvent is used as the first solvent in the composite schema subjected to distillation deposition of crystals add to the reaction mixture obtained by the reaction represented by the reaction scheme (6), and the resulting mixture containing tetrazoles(arylmethyl)hexaazatetracyclo and the first and second solvents are dearylation or as dearylation and acylation to obtain a reaction mixture (composite system) containing the desired tetrachlorodibenzofuran formula (3), and the composition system is subjected to distillation to deposition of crystals posredstvennoj connection and then the precipitated crystals are separated from the composite system.

The number WB6used in the reaction represented by the reaction scheme (6), is typically in the range from 0.001 to 1, preferably 0.005 to 0.5, more preferably from 0.01 to 0.4 per weight ratio WB6to the reaction solvent.

As the reductant used in the rehabilitation diarylethylene and acylation /which presents the above reaction scheme (6)/, and which is carried out in the presence of Alliluyeva agent, can be called the hydrogen gas or formic acid. Preferred is hydrogen gas.

The amount of reducing agent is typically in the range from 0.1 to 10000, preferably from 0.67 to 1000, more preferably from 2 to 50 per molar ratio of reducing agent to arylmethyl groups contained in WB6. When the reductant used hydrogen gas, the pressure of the reaction is usually in the range from 0.1 to 100, preferably from 0.1 to 30, more preferably from 0.1 to 15 FCT/cm2in the calculation of the partial pressure of hydrogen. In addition to the hydrogen gas in the reaction system can be inert gases such as nitrogen, argon and helium.

Regarding the cat is his agent in the process according to the above reaction scheme (6), there is no specific limitation as long as it can accelerate the reaction rehabilitation diarylethylene WB6. Can be used catalyst recovery and terms of recovery, which is mentioned in connection with diarylethylenes above tetrazoles(arylmethyl)hexaazatetracyclo.

Relatively Alliluyeva agent used in the process according to reaction scheme (6), presents for rehabilitation diarylethylene, accompanied by acylation, there are no particular limitations as long as he is capable of acylation of the secondary amino groups with the formation of N-acyl communication. Examples alleluya agents include anhydrides of carboxylic acids, for example acetic anhydride, propionic anhydride, formic anhydride, lactic anhydride and anhydride mixture of acetic acid and formic acid; esters of carboxylic acids and N-hydroxysuccinimide, for example N-acetoxystyrene, N-propionylcarnitine and N-(2-phenylacetate)succinimide; and illimitably, such as acetylimidazole and propylimidazol. Among these alleluya agents are preferred anhydrides of carboxylic acids, for example acetic Titanium is acetic anhydride.

The number Alliluyeva agent varies depending on the reactivity of Alliluyeva agent, type of reaction and reaction conditions. Allerease agent is usually used in an amount of from 0.67 to 100, preferably from 0.67 to 10, more preferably from 0.67 to 3 per molar ratio Alliluyeva agent to arylmethyl groups WB6.

The reaction temperature reconstruction diarylethylene in the presence Alliluyeva agent in the process according to reaction scheme (6), above, is typically in the range from the temperature of coagulation of the reaction solvent to 200oC, preferably from 30 to 180oC, more preferably from 40 to 165oC. To suppress the decomposition of the skeleton WB6that probably happens when WB6is a solvent for a long period of reaction time, preferably, the process according to reaction scheme (6) is carried out at a relatively low temperature, namely at a temperature of from 40 to 80oC. However, the reaction can also be carried out at relatively high temperature, namely at a temperature of from 100 to 200oC, as at a temperature of from 100 to 200oC and at high concentrations WB6but, in addition, received WA4B2may remain dissolved in the reaction solvent and, therefore, can be easily separated from the solid catalyst.

When the recovery diarylethylene (which is carried out in the presence of Alliluyeva agent), apply an organic solvent containing an amide group, there is an advantage consisting in the fact that the decomposition of the skeleton WB6can be suppressed even in the case when the reaction is carried out at a temperature of from 20 to 165oC. the effect of organic solvent containing an amide group, which represents the suppression of decomposition of the skeleton WB6affects the weak basicity of the solvent. The reason for this effect is the following. During the restoration diarylethylene, which is carried out in the presence of Alliluyeva agent, due to acylation of the secondary amine allermuir agent formed acidic protons that cause the decomposition of the skeleton WB6. However, when used as the reaction solvent weakly basic organic solvent containing an amide group, acid protons are neutralized, resulting in sour is but even in that case, when the reaction is carried out at high temperatures.

As follows from the above, the application of the reductive diarylethylene (which is carried out in the presence of Alliluyeva agent) in accordance with reaction scheme (6), as the reaction solvent of an organic solvent containing an amide group, is particularly preferred, due to the fact that the suppression of the decomposition of the skeleton WB6increases the yield of the reaction.

The same effect is achieved when using solvent containing an amide group (which has a weak basicity), can also be obtained by using solvents containing ester group, for example etilenpropilendienovogo ether, ethylene glycol-di-n-butyl ether, dietilaminoetilovogo ether, dietilaminoetilovogo ether and dietilaminoetilovogo ether.

With respect to the method for remediation of diarylethylene (which is carried out in the presence of Alliluyeva agent) in the process in accordance with the reaction scheme (6), it should be noted that the method can be applied, in which WB6, allerease agent, the reaction rastvorjaemoj temperature. Preferred is a reaction method in which the reaction vessel is first placed catalyst recovery and reducing agent, and is maintained at a predetermined temperature and then the reaction vessel together with allermuir agent add a solution obtained by dissolving WB6in the reaction solvent. Preferred is the reaction method in which the reaction vessel first add the catalyst recovery and reducing agent and is maintained at a predetermined temperature, and then the reaction vessel is added a solution obtained by dissolving WB6and Alliluyeva agent in the reaction solvent.

When the desired compound contained in the composite system, exposed distillation deposition of crystals is tetrachlorodibenzofuran formula (3), particularly preferably, the reaction solvent used for rehabilitation diarylethylene (which is carried out in the presence of Alliluyeva agent) in the process carried out in accordance with the reaction scheme (6), represented "a solvent containing an amide group. The reason for this is as follows. Dissolve the Tang. Therefore, when as a reaction solvent in the recovery diarylethylene (which is carried out in the presence of Alliluyeva agent) in the process in accordance with the reaction scheme (6) apply solvent containing an amide group, received tetrazoles(arylmethyl)hexaazatetracyclo may remain dissolved in the reaction mixture. After completion of the reaction in accordance with reaction scheme (6) to the reaction mixture, water is added (which will serve during the distillation the deposition of crystals in the first solvent, and the resulting reaction mixture is subjected to dearylation in accordance with the reaction scheme (5) to obtain, as a consequence, the reaction mixture containing the desired tetrachlorodibenzofuran, that is dissolved in water. Thus, the reaction in accordance with reaction schemes (6) and (5) can be implemented consistently by providing dissolve all compounds hexaazatetracyclo (namely hexacis(arylmethyl)hexaazatetracyclo, tetrazoles(arylmethyl)hexaazatetracyclo and tetraallylsilane) in the reaction solvent. In addition, since the reaction mixture, extracting the reaction mixture can be used as such as a composite system, subjected to distillation precipitation of crystals.

When the reaction diarylethylene in accordance with the reaction schemes (6) and (5) perform consistently (i.e., when consistently carried out obtaining tetrazoles(arylmethyl)hexaazatetracyclo and then getting out of it tetraallylsilane to obtain a composite system, which can be sequentially subjected to distillation deposition of crystals), it is preferable that allerease agent used in the rehabilitation diarylethylene in accordance with the reaction scheme (6), represents a carboxylic acid anhydride, preferably acetic anhydride. In the reaction of acylation (using carboxylic acid anhydride) according to reaction scheme (6) as a by-product is obtained carboxylic acid which has a boiling point above the boiling point of water. When used, the reaction solvent intend to recycle and reuse, you must delete obtained as a by-product carboxylic acid. To delete the received side-carboxylic acid, it is preferable to employ a method in which poluchenii xylene.

With regards to the above Arellano used for the above-mentioned azeotropic distillation, it is preferred to use:

Arellano obtained as a side product during the recovery of diarylethylene in accordance with the reaction scheme (6); or

the mixture Arellano obtained as a side product during the recovery of diarylethylene in accordance with the reaction scheme (6), and Arellano obtained as a byproduct in diarylethylene in accordance with the reaction scheme (5). In addition, it is preferable to add to the reaction system obtained in accordance with reaction scheme (6), and/or to the reaction mixture obtained by the reaction in accordance with reaction scheme (6), an additional amount Arellano. As for the time of carrying out the azeotropic distillation and the way of its implementation, there is no certain restrictions. However, preferably, the azeotropic distillation was carried out by a method in which obtained as a by-product carboxylic acid, and obtained as a by-product allmetal and/or to whom the execution of rehabilitation diarylethylene in accordance with the reaction scheme (6); (y) of the composite system during removal of the first solvent by distillation in stage (II); or (z) from a portion of the composite system, which remains after separation of precipitated crystals of the composite system at stage (III). For example, more specifically, in the case where the above-mentioned reaction mixture, which was mentioned above in (x), is subjected to azeotropic distillation, and when the first solvent intend to apply water, is preferably used as compounds (b) tetrachlorodibenzofuran obtained by the method including the implementation of restorative diarylethylene in accordance with the reaction scheme (6) in the presence of Alliluyeva agent using as solvent an organic solvent containing an amide group; implementation of diarylethylene in accordance with the reaction scheme (5) using as a solvent an organic solvent containing an amide group; and carrying out the azeotropic distillation, which is carried out after completion of the reaction in accordance with reaction scheme (5) and to add to the reaction system of water, in order to prevent the hydrolysis of organic rastvoritelei with the reaction scheme (6) carboxylic acid. In addition, in cases where the composite system, which is mentioned in (y), and when part of a composite system, which is mentioned in (z), is subjected to azeotropic distillation, azeotropic distillation can advantageously respectively to carry out by applying Arellano obtained as a by-product during the reaction in accordance with reaction scheme (6), and by applying Arellano obtained as a by-product during the reaction in accordance with reaction schemes (6) and (5). As another example, the preferred mode of the present invention, in which the conduct azeotropic distillation, can be called a method, in which the first solvent used water and in which: (1) distillation precipitation of crystals is carried out under reduced pressure of 200 mm Hg or less (i.e., distillation method for the deposition of crystals), so that the distillation can be performed at low temperature to suppress, as a consequence, the occurrence of hydrolysis of an organic solvent containing an amide group, and (2) conduct azeotropic distillation (i.e., the azeotropic distillation is carried out after removal by distillation of water). What casaer CLASS="ptx2">

As another preferred example tetraallylsilane formula (3) can be called tetrachlorodibenzofuran, which is obtained by the synthesis method using at least one reaction solvent, which is the same as at least one solvent selected from the group consisting of the first solvent and the second solvent, where the method of synthesis to obtain tetraallylsilane includes exposure hexacis(arylmethyl)hexaazatetracyclo recovery dearylation represented by the following reaction scheme (7), in the presence of Alliluyeva agent to obtain, as a consequence, the reaction mixture containing tetrachlorodibenzofuran and at least one reaction solvent;

< / BR>
where each B independently represents arylmethyl group having from 7 to 21 carbon atoms, and each of W, A, and H is the same as defined for formula (1).

The reaction in accordance with reaction scheme (7) can be accomplished by appropriate modification of the conditions that are mentioned in connection with the reaction in accordance with reaction scheme (6). As in the case of reactions in soo is om reaction in accordance with reaction scheme (7) is preferably used as the reaction solvent of the above-mentioned organic solvent, containing amide group.

In addition, when the method of the present invention, which use the distillation precipitation of crystals, intend to use the compound obtained by the reaction in accordance with reaction scheme (7), it is preferable that the reaction in accordance with reaction scheme (7) is carried out using at least two reaction solvents, which are the same as the first solvent and the second solvent, to obtain, as a consequence, the reaction mixture containing tetrachlorodibenzofuran, the first solvent and the second solvent, because this reaction mixture can be used as such as a composite mixture, subjected to distillation precipitation of crystals. When the reaction mixture obtained after the reaction in accordance with reaction scheme (7), contains the first solvent, this reaction mixture can be used as such, as the above-mentioned composite system, which is subjected to distillation to precipitation of crystals. On the other hand, when as a reaction solvent for the reaction in accordance with reaction scheme (7) is not primeniajutsia in accordance with the reaction scheme (7) or to the reaction mixture, obtained by the reaction in accordance with reaction scheme (7), it is preferable to add a solvent which is the same as the first solvent, to obtain, as a consequence, the mixture, which can be used as a composite system, exposed distillation precipitation of crystals.

In relation to the quantity of solvent (which is the same as the first solvent) contained in the reaction mixture obtained by the reaction in accordance with reaction scheme (7), which can be used as a composite system, exposed distillation deposition of crystals, there are no particular limitations as long until the reaction mixture contains a solvent (which is the same as the first solvent in a quantity sufficient to dissolve the obtained tetraallylsilane. Therefore, the amount of solvent (which is the same as the first solvent) varies depending on the number of connections WA6used as source material and output tetraallylsilane. As for the weight ratio of the solvent (which is takimoto reaction mixture, used as a composite mixture subjected to distillation deposition of crystals, it is usually the weight ratio is in the range from 0.1 to 10, preferably from 0.2 to 5, more preferably from 0.5 to 2.

Additional preferred examples tetraallylsilane (b) of formula (1) include those in which n in the formula (1) is equal to 6. Specific examples of these tetraallylsilane (b) include hexachlorodibenzofuran, respectively represented by the following formula (8) and tetracyclineresistant, represented by the following formula (9):

WA6(8)

and

WA4F2r(9)

where each Errepresents a formyl group, and each of W and A is as defined above for formula (1).

For example, hexaazatetracyclo (compound of formula (8)) and tetraacetylethylenediamine (compound of formula (9)) is highly soluble in the above-mentioned first solvent (i.e. water and/or carboxylic acids). Therefore, these compounds can be advantageously used in the method of the present invention, in which the distillation precipitation of crystals.

the TBE compounds (b) in the composite system used above hexaazatetracyclo or tetraacetylethylenediamine, preferably, the first solvent used water, formic acid or acetic acid and so as the second solvent used above organic solvent containing an ester group in which hexaazatetracyclo and tetraacetylethylenediamine laboratorii. In addition, when the method of the present invention, in which conduct the distillation precipitation of crystals, as compounds (b) in the composite system used tetraacetylethylenediamine, more preferably, the first solvent used formic acid, because formic acid is used as formuliruiutsia agent upon receipt tetraacetylethylenediamine, can be used as the first solvent.

When the method of the present invention, the desired connection is hexachlorodibenzofuran, as compounds (b) composite systems is preferable to apply hexachlorodibenzofuran, which is obtained by the exposure tetrazoles(arylmethyl)hexaazatetracyclo dearylation and acylation, which Knymi group, having from 7 to 21 carbon atoms, and each of W and A is as defined above for formula (1). When carrying out the process in accordance with the reaction scheme (10) above, it is preferable to use reaction method, in which tetrazoles(arylmethyl)hexaazatetracyclo formula (4) is subjected to dearylation for synthesis tetraallylsilane, and then received tetrachlorodibenzofuran subjected to acetylation.

This reaction is the preferred method, because if it is applied is suppressed by the formation of side compounds containing alkyl group, for example tetracyclinesolutionbuywithou. When the desired compound in the process carried out in accordance with the reaction scheme (10), above, is tetracyclineresistant, examples of the reaction method include a method in which tetrazoles(arylmethyl)hexaazatetracyclo formula (4) is subjected to dearylation for synthesis tetraallylsilane, and then received tetrachlorodibenzofuran are formirovanie for synthesis tetracyclineresistant and the method in which tetrazoles(Ari added to the reaction system of formic acid for the implementation of diarylethylene and synthesis tetracyclineresistant.

In the process according to the above reaction scheme (10) is preferable that each of the acyl groups is desirable compounds represented an acetyl group. Regarding the reaction conditions for diarylethylene in accordance with the reaction scheme (10) it should be noted that there may be applied such conditions as mentioned above for diarylethylene carried out in accordance with the reaction scheme (5).

As for Alliluyeva agent used in the process according to the reaction scheme (10), there can be applied alleluya agents that have been mentioned for the process to be carried out in accordance with the reaction scheme (6).

Preferred examples alleluya agents suitable for use in the synthesis hexachlorodibenzofuran include acylhomoserine, such as acetylchloride, acetylmuramic and similar compounds.

Examples formuliruya agents suitable for use in the synthesis tetracyclineresistant include formic acid; anhydrides of carboxylic acids, for example formic anhydride and anhydride mixture of acetic acid and formic acid; and complex Mouravi formic acid, because formic acid functions as a reducing agent. When formic acid is used as solvent in the synthesis tetracyclineresistant, it is advantageously performs the following functions (a)-(C):

(a) the function of a solvent which has a high ability to dissolve tetrazoles(arylmethyl)hexaazatetracyclo or tetracyclineresistant;

(b) the function of the reducing agent in the recovery diarylethylene; and

(c) the function formuliruiutsia agent.

Preferably, the second component of the reaction solvent used for the synthesis of tetracyclineresistant represented an organic solvent capable of functioning as the second solvent by distillation precipitation of crystals. Regarding the second solvent, there can be mentioned organic solvent, in which tetracyclineresistant has a solubility of 1% or less and which has a boiling point above the boiling point of the applied first solvent. Examples of such organic solvents include solvents containing ester group, for example, etilendiaminova ether and di-etilenglikolevye ether.

In the method of the present invention is particularly preferable that tetracyclineresistant subjected to distillation deposition of crystals was obtained in accordance with the following reaction scheme (11):

< / BR>
where Frrepresents a formyl group, each B independently represents arylmethyl group having from 7 to 21 carbon atoms, and each of W and A is as defined above for formula (1).

As shown above in reaction scheme (11) in the first stage of the process in accordance with this scheme (11) hexacis(arylmethyl)hexaazatetracyclo subjected recovery dearylation in the presence Alliluyeva agent for synthesis, as a consequence, tetrazoles(arylmethyl)hexaazatetracyclo, and in the second stage of the process tetrazoles(arylmethyl)hexaazatetracyclo are dearylation and formirovanie or simultaneously or in order to synthesize, as a consequence, tetracyclineresistant through tetraallylsilane. In the process according to the above reaction scheme (11) is preferable that each of the acyl group is th, used in the rehabilitation diarylethylene hexacis(arylmethyl)hexaazatetracyclo (which is carried out in the presence of Alliluyeva agent) on the first stage of the process in accordance with the reaction scheme (11), can be applied such reaction conditions that are referred for rehabilitation diarylethylene (which is carried out in the presence of Alliluyeva agent) in the process in accordance with the reaction scheme (6). Among the reaction solvents mentioned in connection with the process according to reaction scheme (6), in the first stage of the process in accordance with the reaction scheme (11) is preferable organic solvent containing an amide or ester group, which has a boiling point above the boiling point of formic acid and which is used in the composite system, exposed distillation deposition of crystals, as the second solvent.

As for the reaction conditions used in the synthesis tetracyclineresistant of tetrazoles(arylmethyl)hexaazatetracyclo in the second stage of the process in accordance with the reaction scheme (11), can be applied such reaction conditions that will process in accordance with the reaction scheme (10), above.

As mentioned above, the distillation method for the deposition of crystals can be advantageously applied in the first aspect of the method of the present invention. However, as mentioned above, can also be applied to other methods of deposition of crystals, namely: the separation membrane filtration, adsorption method and a method using a chemical reaction. These other methods are explained in more detail below.

Below explained in detail the method of separation and membrane filtration (method B).

In the method of separation of membrane filtration, which is a method of removing the first solvent from the composite system for the deposition of crystals of the desired compound, apply a separation membrane having a selective transmission capacity in respect of the first solvent. When removing the first solvent is carried out using the method of membrane separation is most preferred that the first solvent was water. Type separation membrane used for separation of water from the composite system can be selected according to various factors, for example with regard to the form of the reactor and other fantasytennis to separate ethanol from water. Specific examples of such separation membranes include Polyoxymethylene membrane; the membrane of a copolymer of acrylic acid and Acrylonitrile; ionized hits new membrane; organic membrane, for example, a composite membrane having an active layer of a maleic acid - crosslinked PVA, and a membrane made of a polymer alloy (see the descriptions of pending patent applications in Japan, is available for public review NN 59-109204 and 60-129104); and inorganic membrane, for example A-zeolite membrane, described in: "Kagakukougaku Sinpojyumu Siriizu (Chemical Engineering Symposium Series)", 41, 102-105 (1994). From the point of view of commercial use of the method of the present invention, in which use the method of separation of membrane filtration, it is preferable to use a membrane having a long life, high resistance against chemical substances contained in the reaction system and the reaction mixture, and high mechanical strength. An example of such a preferred membrane is an inorganic membrane, as it usually has a high critical temperatures and high chemical resistance. The above A-zeolite membrane can be obtained in accordance with the method, opisanego substrate, having approximately the diameter of pores of 1 mm, immersed in a solution containing sodium silicate, sodium hydroxide, aluminate sodium and aluminum hydroxide in the weight ratios of H2O/Na2O=60, Na2O/SiO2= 1 and SiO2/Al2O3=2, and then subjected to hydrothermal reaction at a temperature of from 80 to 100oC for a time ranging from 3 to 12 hours. Properties of the membrane can be adjusted by repeating the dipping and hydrothermal reactions.

The morphology of the separation membrane is not especially limited, and a separation membrane having a desired morphology can be obtained by using a substrate having a desired morphology. The morphology of the separation membrane can be selected in accordance with the design of the applied reactor. Usually used, for example, the membrane sheet type, module, obtained by using the membrane sheet type, a tubular membrane module obtained by the use of the tubular membrane.

As for the temperature to effect the removal of water that is used as the first solvent, to increase the permeability of the barrier membrane is best high temperature, and to increase the accuracy from the in the range from room temperature to 200oC. When the reactor include the separation membrane, the temperature for membrane separation is chosen within the reaction temperature, which is typically in the range from 40 to 165oC, preferably from 40 to 100oC.

The separation of water from the composite system is theoretically possible as long as the membrane is the pressure difference and the pressure when the separation is typically in the range from 0.5 to 20 kg/cm2. In addition, the water effectively removed from the composite system by pumping on the output side of the separation membrane when viewed in the direction of water flow.

Below are explained in detail adsorption method (method C).

Adsorption method, which is a method of removal of the composite system of the first solvent to precipitate crystals of the desired compound, includes the adsorption of the first solvent to the adsorbent.

For this method it should be noted the following points (a) and (b):

(a) When the first solvent is water, the adsorbent can be mentioned, for example, molecular sieve (pore of which are used for the adsorption of water molecules); and salts, for example, chlorine water).

(b) When the first solvent is a carboxylic acid, as the adsorbent can be mentioned, for example, anion exchange resins and similar substances which are capable of adsorption of carboxylic anion.

Below explained in detail the method of using a chemical reaction (method D).

Chemical method, which is a method of removal of the composite system of the first solvent to precipitate crystals of the desired compound, includes the transformation of the first solvent in another substance by chemical reaction. For this method it should be noted the following points (a) and (b):

(a) When the first solvent is water, the water interacts with matter, which is energetically interacts with water, for example with potassium, sodium, lithium aluminum hydride, sodium borohydride or calcium borohydride, therefore, is the transformation of substances in the hydroxide of the metal.

(b) When the first solvent is a carboxylic acid, carboxylic acid interacts with the main connection, for example, an amine or metal hydride with the formation of the salt and then subjected to salt or dehydration reaction with the alcohol to form complex the aqueous product through the above-mentioned reactions, dehydration, it should be noted that it may be removed by any of the aforementioned methods of removal, i.e., a distillation, B-separation membrane filter, C-adsorption and D-chemical reaction.

In relation to the selection method of precipitated crystals of the composite system at stage (III) there are no specific limitations.

2. The method in accordance with the second aspect:

At stage (A) of the method of the second aspect of the present invention provides a composition system containing:

(a') a mixed solvent consisting of water and at least an organic solvent, which can be separated from water, and

(b') derived hexaazatetracyclo containing acyl group represented by the following formula (12):

WAnH(6-n), (12)

where n is an integer equal to 4 or 6, each A independently represents an acyl group having from 1 to 10 carbon atoms, H represents a hydrogen atom and W represents a hexavalent balance hexaazatetracyclo, represented by the following formula:

< / BR>
where composite system includes the organic phase and the aqueous phase having dissolved therein at least a portion of the sod is known of the present invention the aqueous phase is separated from the composite system.

At the stage (C) of the method of the second aspect of the present invention the water is evaporated from the aqueous phase, thus receive a derived hexaazatetracyclo (b') in pure form.

As follows from the above, the method in accordance with the second aspect of the present invention is essentially the same as the aforementioned method of the first aspect of the present invention, except that necessarily apply mixed solvent (a') consisting of water and at least one organic solvent which can be separated from water, and the fact that the desired compound (containing acyl group derived hexaazatetracyclo (b')) is obtained by evaporation of the water from a separate water phase.

In the method of the second aspect of the present invention containing acyl group derived hexaazatetracyclo (b') of the formula (12) is the same as containing acyl group derived hexaazatetracyclo (b) of formula (1) used in the method of the first aspect, and hexavalent balance hexaazatetracyclo formula (13) is the same as hexavalent balance hexaazatetracyclo formula (2) mentioned in the method of the first aspect.

That cases the military restrictions as long while the above-mentioned organic solvent can be separated from the water.

As for the organic solvent used in a mixed solvent (a'), which can be separated from water, it is preferable to use such an organic solvent, which contains the acyl group derived hexaazatetracyclo (b') of the formula (12) has a solubility of 0.5% by weight or less. Examples of organic solvents used in multicomponent solvent (a') include ester solvents such as ethyl acetate and butyl acetate; solvents, representing a simple ether, such as diethyl ether and diisopropyl ether; halogenated solvents such as chloroform and dichloromethane; aromatic solvents such as benzene, toluene and xylene.

As for specific examples containing acyl group derived hexaazatetracyclo (b'), it can be called such compounds, which were mentioned above as specific examples of compounds (b) of formula (1). In addition, as for the method of synthesis of compounds (b'), synthesis conditions, substances used for the synthesis, amount of substance, and such facts, there can be PR is wearing a method of separating the aqueous phase from the composite system and a method of evaporating water from the aqueous phase are not available to certain restrictions.

The following is an explanation of the structures of the above compounds WB6THAT WA4B2THAT WA4H2and WA4F2r.

Arylmethylidene group represented by B in each of the reaction schemes(5), (6), (7), (10) and (11), means an aryl group (Ar)-substituted methyl group, which usually has from 7 to 21 carbon atoms. As a specific example arylmethyl groups B may be referred to a group having a structure represented by the following formula (14):

-CH2Ar (14)

where Ar represents an aryl group having from 6 to 20 carbon atoms.

As mentioned above, the number of carbon atoms in the Ar in the formula (14) above, is typically in the range from 6 to 20, preferably from 6 to 10, most preferably it is equal to 6. Examples include A phenyl group; alkylphenyl group, for example taillow group (O-, m - and p-isomers), ethylphenyl group (O-, m - and p - isomers), and kalilou group; alkoxyphenyl group, for example metoksifenilny group (O-, m - and p-isomers), ethoxyphenyl group (O-, m - and p-isomers), and butoxyphenyl group (O-, m - and p-isomers); and unsubstituted and substituted raftiline group. Of them, preferred are a phenyl group is

In relation to the connection represented by the formula WA4B2in the reaction schemes(5), (6), (10) and (11) above, we can assume a variety of stereoisomeric configurations that differ by the provisions of the acyl groups and arylmethyl groups. The compound represented by the formula WA4B2used in the present invention, can be any of the stereoisomers, represented by the following formulas (15-1) to (15-6):

< / BR>
< / BR>
< / BR>
where each of A and W is as defined above for the above formula (12), and B is as defined above, and their optical isomers.

Of these compounds the most preferred is a compound of the formula (15-1), as it can provide the most hydrophilic structure, when each of the two arylmethyl groups (each represented by B) substituted by a hydrogen atom.

In respect of derivative hexaazatetracyclo represented by the formula WA4H2accordingly, in the formula above, and the schemes (3), (5) and (7), we can assume a variety of stereoisomeric configurations that differ by the provisions of the acyl groups and hydrogen atoms. Derived hexaazatetracyclo represented WAis reisopera. More specifically, these stereoisomers are derived hexaazatetracyclo represented by the formula (15-1) to (15-6), where each of arylmethyl groups substituted by a hydrogen atom. Of these the most preferred is derived hexaazatetracyclo represented by the above formula (15-1), where each of arylmethyl groups substituted by a hydrogen atom, because it has a very high hydrophilicity.

In addition, in relation to tetraacetylethylenediamine above formula (9), (where A is an acetyl group), which is a desirable connection for distillation precipitation of crystals, we can assume a variety of stereoisomeric configurations, which differ in the positions of acetyl and formyl groups. Tetraacetylethylenediamine obtained by the method of synthesis used in the present invention, can be any of the stereoisomers. More specifically, these stereoisomers are derived hexaazatetracyclo represented by the formula (15-1) to (15-6), where each of arylmethyl groups substituted formyl group, and each of the acyl group is the acetyl group. Of them the most (15-1), where each of arylmethyl groups substituted formyl group and each of the acyl group is an acetyl group, because it has a very high hydrophilicity.

The reaction represented by the above reaction schemes (6), (7) and (11) described below.

Each of the above reactions involves the following stages: 1) exposure WB6restorative dearylation in the presence Alliluyeva agent to convert the contained N-arylmethylidene group in the N-H group; and 2) subsequent exposure resulting from connection to the acylation for the conversion of the N-H group in the N-acyl group. In addition, because the recovery of the N-acyl group which may occur depending on the reaction conditions (as a side reaction), may be formed of an N-alkyl group, while as a by-product can be derived hexaazatetracyclo containing N-alkyl group. Based on the reaction products were expected path of the reaction in accordance with reaction schemes (6), (7) and (11), and the ways shown in the diagram of the reaction scheme (16) (see the end of the description), where B is arylmethyl gruppovoj carbon; and each of W, A, and H is the same as defined above for the above formula (1).

Any of the compounds shown in the reaction scheme (16), can be contained in the compound of formula (1) and in the products obtained by reaction in accordance with reaction schemes(5), (6), (7), (10) and (11) above.

The method of the present invention, intended for deriving hexaazatetracyclo containing acyl group is commercially advantageous, because containing acyl group derived hexaazatetracyclo can be easily obtained in high purity form with high yield and at low cost by removing from the composite system of the first solvent (water or carboxylic acids) or by removing the first solvent by evaporation from a phase of the first solvent (which was separated from the phase of the second solvent), which is dissolved at least part of the derived hexaazatetracyclo containing acyl group. The path of the reactions included in the method of the present invention, are summarized in the following diagram.

The best way of carrying out the invention

The present invention is described below in more sublattice is th present invention.

In the examples were produced in different dimensions in accordance with the methods listed in the chart at the end of the description.

(1) Quantitative analysis tetraazacyclotetradecane and hexaazatetracyclo high-performance liquid chromatography (HPLC):

The measurements were carried out under the following conditions by means of the following equipment:

i) Equipment

Apparatus for HPLC:LC - 10A (manufactured and sold by Shimadzu Corporation, Japan) (Shimadzu Corporation, Japan) Column: TSK - GEL AMIDE-80 4,h mm (manufactured and sold by TOSOH, Japan) (TOCOX, Japan)

ii) Conditions:

Detection: UV (210 nm)

The column temperature: 40oC

Mobile phase: tetrahydrofuran/H2O (90/10) (about/on)

Flow rate: 1 ml/min

The number of sample injection: 10 l

Samples subjected to HPLC analysis, was obtained through the following ways:

(i) a method of obtaining a sample from the reaction mixture obtained recovery diarylethylenes WB6in the presence of Alliluyeva agent:

0.5 ml of the reaction mixture (slurry containing the catalyst) was subjected to evaporation under reduced pressure to remove the liquid component of the reaction mixture and obtain estate and obtain a filtrate. The filtrate was used as a sample for HPLC.

(ii) a method of obtaining a sample from the reaction mixture obtained recovery diarylethylenes WA4B4:

The reaction mixture was subjected to filtration to remove the catalyst and obtain, as a consequence, the filtrate. 0.5 ml of the filtrate was subjected to evaporation under reduced pressure to remove, as a result, the liquid component and obtain the remainder. To the residue was added 9.5 mm of water, vigorously mixed and subjected to filtration to remove insoluble substances, and obtain, as a consequence, the filtrate. The filtrate was used as a sample for HPLC.

(2) Quantitative analysis tetraacetylethylenediamine HPLC:

The measurements were carried out under the following conditions by means of the following equipment:

i) Equipment

Apparatus for HPLC:LC-10A (manufactured and sold by Shimadzu Corporation, Japan) (Shimadzu Corporation, Japan)

Column: L-Column ODS 4,h mm (manufactured and sold (Chemical Inspection & Testing Institute, Japan) (Chemical Inspection and Testing Institute, Japan)

ii) Conditions

Detection: UV (210 nm)

The column temperature: 40oC

Mobile phase: acetonitrile/H2O (5/95) (about./about.)

Scili in the following way.

The reaction mixture containing tetraacetylethylenediamine, was subjected to filtration to remove the catalyst and obtain a filtrate. 0.5 ml of the filtrate was subjected to evaporation under reduced pressure to remove the liquid component and obtain the remainder. To the residue was added to 9.5 ml of water, vigorously mixed and subjected to filtration to remove undissolved substances and obtain a filtrate. The filtrate was used as a sample for HPLC.

(3) Quantitative analysis of other derivative hexaazatetracyclo gas chromatography (GC):

The measurements were carried out under the following conditions by means of these instruments.

i) Equipment

Apparatus for gas chromatography: GC-14B (manufactured and sold by Shimadzu Corporation, Japan) (Shimadzu Corporation, Japan)

Column: Metal capillary

Column, Ultraslow (NT), 0.25 mm (inner diameter) x 15m, the thickness of the film deposited on the inner wall of the capillary column: 0.15 mm

ii) Conditions

Detection: FID

Inlet temperature: 340oC

Column: supported 200oC for 1 minute and at a temperature of 340oC

within 4 minutes: the rate of increase of temperature up to 340o

The number of sample injection: 5 l

As an external standard was used of triclosan.

Samples subjected to GC analysis, obtained by the following method.

To 0.5 ml of reaction mixture containing hexaazatetracyclo, to obtain the solution was added to 23.5 ml of chloroform. To 4 ml of the solution was added 0.5 ml of a solution obtained by dissolving 0.1 g of tricosane in 100 ml of chloroform, and the resulting mixture was used as a sample for GC.

Comparative example /solubility of various types of derivative hexaazatetracyclo containing acyl group, in different types of solvents/

Investigated the solubility of various types of derivative hexaazatetracyclo containing acyl group, in different types of solvents. The results are shown in table 1.

Abbreviations are given in table 1 represent the respective compounds described below:

WA4H2: tetraazacyclotetradecane

WA6: hexaazatetracyclo

WA4F2r: tetraacetylethylenediamine

WA4B2: tetraacetylethylenediamine

WA4E2: tetraacetylethylenediamine

NMP: N-methyl-2-pyrrolidone

EDE: etilenglikolevye ether

EDB: etilenglikoli-n-butyl ether

DEDM: diethylethylenediamine ether

DEDE: dietilenglikoluretan ether

DEDB: dietilenglikoluretan ether

Example 1. /Distillation precipitation of crystals of various types of derivative hexaazatetracyclo containing acyl group, from different types of mixed solvent comprising a first solvent and a second solvent/

To obtain a composite system each of the different types of derivatives hexaazatetracyclo containing acyl group, separately dissolved in a mixed solvent consisting of first and second solvent. Then from the composite system for the deposition of crystals derived hexaazatetracyclo drove the first solvent. Corresponding amount (g) applied to the first and second solvents and distillation results in the deposition of crystals shown in table 2. In example 1, the distillation for the deposition of crystals was carried out to such an extent that the content of the first solvent was equal to 1% by weight or less based on the total weight of the first and second solvents.

WA4H2: tetraazacyclotetradecane

WA6: hexaazatetracyclo

WA4F2r: tetraacetylethylenediamine

DMAc: N,N-dimethylacetamide

DMF: N,N-dimethylformamide

EDE: etilenglikolevye ether

EDB: ethylene glycol di-n-butyl ether

DEDM: diethylethylenediamine ether

DEDE: dietilenglikoluretan ether.

Example 2. /Distillation precipitation of crystals WA4H2obtained by reactions according to the reaction scheme:

WB6---> WA4B2---> WA4H2/ /first solvent: water; a second solvent: N,N-dimethylacetamide (DMAc)/

B 100 ml autoclave was loaded 2.1 g hexabenzylhexaazaisowurtzitane and 3.15 g of 10% Pd-C as catalyst), 1.84 g of acetic anhydride and 30 ml of DMAc and the autoclave was closed. The autoclave was purged with nitrogen. Then, the autoclave was filed by the hydrogen gas to the internal pressure in the autoclave was equal to 1.1 FCT/cm2.

For the implementation of the reaction began to stir the contents of the autoclave with a speed of 700 rpm or more, and the internal temperature of the autoclave was increased to 60oC. During the reaction to maintain 3 hours from the beginning of the reaction, analysis of the reaction system GC showed the output tetraacetylethylenediamine reached about 60% per hexabenzylhexaazaisowurtzitane. Then the reaction was completed and the reaction mixture was removed from the autoclave, filtered, the catalyst contained in the reaction mixture, and the obtained solution.

In the autoclave was loaded obtained a solution of 3.15 g of 10% Pd-C as catalyst) and water (30 ml) and the autoclave was closed. The autoclave was purged with nitrogen. Then, the autoclave was filed by the hydrogen gas to the internal pressure in the autoclave became 3,3 FCT/cm2.

For the implementation of the reaction began to stir the contents of the autoclave with a speed of 700 rpm or more, and the internal temperature of the autoclave was increased to 130oC. During the reaction to maintain the internal pressure in the autoclave 3,3 FCT/cm2in the autoclave was continuously applied hydrogen gas. After 1 hour from the start of the reaction, analysis of the reaction system HPLC showed that the output tetraazacyclotetradecane reached about 60% per hexabenzylhexaazaisowurtzitane (yield of this reaction was varied in the range from 58 to 68%). Then the reaction was completed and the reaction mixture was removed from the autoclave, filtered, the catalyst, the content is from the obtained solutions were mixed together and the obtained mixed solution.

Removal of the solvent mixed solution was subjected to distillation (70oC, 1 mm Hg) using a rotary evaporator equipped with a constant temperature bath, a vacuum pump and a vacuum regulator, resulting received 17.0 g of a viscous suspension (contents tetraazacyclotetradecane: 56,8% by weight).

In a mixed solvent consisting of 15 ml of DMAc and 150 ml of water to obtain solution was dissolved 5.0 g of suspension. The solution was loaded into a 300 ml flask having the shape of an eggplant, and subjected to distillation (70oC, 50 mm Hg) using a rotary evaporator equipped with a constant temperature bath, a vacuum pump and a vacuum regulator, when this was removed about 150 ml of water. After distillation flask shaped eggplant, disconnected from the rotary evaporator and the resulting distillation residue in the flask-shaped eggplant has cooled to room temperature and kept for 6 hours at room temperature, due to what happened the precipitation of the solid particles.

Precipitated solids were collected by filtration under suction and then washed with 10 ml DMAc, because it got wet solid. The wet solid was dried posna in the form of a white solid / yield during the precipitation of crystals: 80%; purity: 98% (HPLC certain).

Example 3. /Highlighting WA4H2high yield by distillation precipitation of crystals WA4H2obtained by the reaction in accordance with reaction scheme:

WB6---> WA4B2---> WA4H2/

B 100 ml autoclave was loaded 0.84 g of 10% Pd-C as catalyst) and the autoclave was purged with hydrogen gas to the internal pressure in the autoclave was equal to 1.1 FCT/cm2. Then the contents of the autoclave were mixed at 50 rpm at 60oC for 2 hours. In the autoclave via syringe quickly loaded a solution obtained by dissolving 2.1 g hexabenzylhexaazaisowurtzitane and 1,82 g of acetic anhydride in 30 ml of DMAc, the mixing speed is immediately increased to 700 rpm, and over 1 hour at a temperature of 60oC carried out the reaction. During the reaction to maintain the internal pressure in the autoclave is 1,1 FCT/cm2in the autoclave was continuously applied hydrogen gas. Through the above-mentioned reaction received tetraacetylethylenediamine (containing tetraazacyclotetradecane). Further, this reaction will be referred to "the first reaction stanage pressure in the autoclave is 9 FCT/cm2in the autoclave filed hydrogen gas, the reaction temperature was increased to 90oC and continued stirring at 700 rpm for 1 hour to effect dibenzylamine. After a specified period of time the reaction was completed, the reaction mixture is pulled out of the autoclave and to obtain the solution was filtered contained in the reaction mixture a catalyst. Analysis of this solution HPLC showed that the solution contained 0,80 g tetraazacyclotetradecane and output it reached 80%. In further response dibenzylamine be attributed to the reaction of the second stage".

The solution was loaded into a flask having the shape of an eggplant, and subjected to distillation (50oC, 10 mm Hg) using a rotary evaporator equipped with a constant temperature bath, a vacuum pump and a vacuum regulator, and as a result have removed 32 ml of low-boiling fractions (for example, water and toluene) having a boiling point below the boiling point of DMAc. After distillation flask shaped eggplant, disconnected from the rotary evaporator and the resulting distillation residue in the flask-shaped eggplant has cooled to room temperature, resulting in the deposited solids.

Osajdenie solid. The wet solid was dried by a vacuum dryer (70oC 1 mm Hg or less), got 0,775 g tetraazacyclotetradecane in the form of a white solid /yield during the precipitation of crystals: 97%; purity: 98% (determined HPLC)/.

Example 4. /Distillation precipitation of crystals WA4/H2obtained by reactions according to the reaction scheme: WB6---> WA4B2---> WA4H2/ / first solvent: acetic acid; the second solvent: dietilenglikoluretan ether/

Repeated essentially the same method described in example 3, except that as the reaction solvent for the reaction of the first stage instead of DMAc was used dietilenglikoluretan ether, the reaction time for the first stage of the reaction changed from 1 hour to 10 hours, and as the first solvent, which is added to the reaction system in the time between the first stage reaction and the second reaction stage, instead of water was used acetic acid. As a result, the output tetraazacyclotetradecane was 72% (based on hexabenzylhexaazaisowurtzitane /output during the precipitation of crystals: 96%, purity: 97% (HPLC certain).

4B2---> WA4H2/ first solvent: acetic acid; the second solvent: diethylethylenediamine ether/

B 100 ml autoclave was loaded 1.22 g tetraacetylethylenediamine, 0.84 g of 10% Pd-C as catalyst), which is a restored hydrazine, and a mixed solvent consisting of 30 ml of acetic acid and 30 ml dietilaminoetilovogo ether as the reaction solvent), and the autoclave was closed. The autoclave was purged with nitrogen. Then, the autoclave was filed by the hydrogen gas to the internal pressure of the autoclave was set to 9 FCT/cm2.

To perform the reaction for 1 hour stirring the contents in the autoclave were carried out with a speed of 700 revolutions per minute and the temperature of the autoclave was increased to 90oC.

Analysis of the reaction system HPLC showed that the output tetraazacyclotetradecane was 95% (based on tetraacetylethylenediamine.

Then the reaction was completed, the reaction mixture is pulled out of the autoclave, and to obtain the solution in the form of filtrate contained in the reaction mixture, the catalyst was filtered. The solution was subjected to distillation deposition of crystals essentially wurtzite /output during the precipitation of crystals: 95%, purity: 99% (HPLC certain).

Example 6. Distillation precipitation of crystals WA4H2obtained by the reaction in accordance with reaction scheme:

WA4B2---> WA4H2/ first solvent: acetic acid; the second solvent: ethylene glycol di-n-butyl ether (added after reaction) /

Repeated essentially the same reaction described in example 5, except that the reaction solvent was used only 30 ml of acetic acid. After completion of the reaction the reaction mixture is pulled out of the autoclave contained in the reaction mixture, the catalyst was filtered, whereupon the solution obtained in the form of filtrate.

To the solution was added 30 ml of ethylene glycol di-n-butyl ether and mixed to obtain a homogeneous solution. The homogeneous solution was subjected to distillation deposition of crystals in essentially the same manner as that described in example 3, thus obtained crystals tetraazacyclotetradecane. As a result, the output tetraazacyclotetradecane was 87% (based on tetraacetylethylenediamine /output during the precipitation of crystals: 94%; purity: 99% (the definition is according to the reaction scheme: WA4B2---> WA4H2/ /first solvent: acetic acid + water; the second solvent: dietilenglikoluretan ether /

Repeated essentially the same reaction and distillation precipitation of crystals, which are described in example 5, except that the reaction solvent used mixed solvent consisting of 20 ml of acetic acid and 10 ml of water. As a result, the output tetraazacyclotetradecane was 81% (based on tetraacetylethylenediamine/ output during the precipitation of crystals: 96%, purity: 97% (defined HPLC)/.

Example 8. /Distillation precipitation of crystals WA4H2obtained by the reaction in accordance with reaction scheme:

WB6---> WA4B2---> WA4H2/ /first solvent: acetic acid; the second solvent: dietilenglikoluretan ether + diethylethylenediamine ether/

Repeated essentially the same method described in example 3, except that as the reaction solvent for the first stage of the reaction was used a mixed solvent consisting of 15 ml dietilaminoetilovogo ether and 15 ml of diethylene glycol Dimitrova is, the which is added to the reaction system in the time between the first stage reaction and the second reaction stage, instead of water was used acetic acid. As a result, the output tetraazacyclotetradecane was 69% (based on hexabenzylhexaazaisowurtzitane/ output during the precipitation of crystals: 95%, purity 98% (HPLC certain)/.

Example 9. /Distillation precipitation of crystals WA4H2obtained by the reaction in accordance with reaction scheme:

WB6---> WA4H2/ /first solvent: water (added after the reaction); the second solvent: DMAc/

Repeated essentially the same step of the reaction, which is described in example 3, except that the amount of 10% Pd-C as catalyst) was changed to 3,15 g and the reaction time was changed to 3 hours, resulting in the received reaction mixture containing tetraazacyclotetradecane.

Analysis of the reaction mixture HPLC showed that the output tetraazacyclotetradecane reached 60% per hexabenzylhexaazaisowurtzitane.

To the reaction mixture were added 30 ml of water and mixed for 30 minutes at 40oC to dissolve the precipitated tetraazacyclotetradecane. Then containing adversly distillation deposition of crystals in essentially the same way, which is described in example 3, receiving crystals tetraazacyclotetradecane / output during the precipitation of crystals: 98%, purity: 99% (HPLC certain) /.

Example 10. / Distillation precipitation of crystals WA6obtained by the reaction in accordance with reaction scheme:

WA4B2---> WA4H2---> WA6/ /first solvent: dietilenglikoluretan ether/

Repeated essentially the same reaction described in example 5, except that the reaction solvent used dietilenglikoluretan ether. The reaction mixture was removed from the autoclave, filtered, contained in the reaction mixture, the catalyst, resulting in the received solution in the form of filtrate. To the solution was added 2 g of acetylchloride and mixed at room temperature for 1 hour to perform the reaction. Through this reaction has azetilirovanie N-H group tetraazacyclotetradecane to get hexaazatetracyclo approximately stoichiometric quantity per tetraacetylethylenediamine. The resulting reaction mixture was subjected to distillation deposition of crystals in the su is asatourian with the release of 90% per tetraacetylethylenediamine / output during the precipitation of crystals: 85%, purity: 97% (defined HPLC)/.

Example 11. /Distillation precipitation of crystals WA6obtained by the reaction in accordance with reaction scheme:

WB6---> WA4B2---> WA4H2---> WA6/ /first solvent: acetic acid; the second solvent: diethylethylenediamine ether /

Repeated essentially the same method described in example 3, except that as the reaction solvent for the reaction of the first stage was used diethylethylenediamine ether, the reaction time was changed to 10 hours, and as the first solvent, which is added to the reaction system in the time between the first stage reaction and the second reaction stage, used acetic acid. The reaction mixture was removed from the autoclave, filtered, contained in the reaction mixture, the catalyst thus obtained solution in the form of filtrate. To the solution was added 2 g of acetylchloride and mixed for 1 hour at 40oC. the resulting reaction mixture was subjected to distillation deposition of crystals in essentially the same manner as that described in example 3, as a consequence, the obtained crystals hexaazatetracyclo HPLC)/.

Example 12. / Distillation precipitation of crystals WA4F2robtained by the reaction in accordance with reaction scheme:

WB6---> WA4B2---> WA4F2r/ /first solvent: formic acid; the second solvent: dietilenglikoluretan ether)

Repeated essentially the same method described in example 3, except that as the reaction solvent for the reaction of the first stage instead of DMAc was used dietilenglikoluretan ether; the reaction time for the reaction of the first stage was changed from 1 hour to 10 hours, and as the first solvent, which is added to the reaction system in the time between the first stage reaction and the second reaction stage, instead of water was used formic acid; the second stage reaction was carried out in nitrogen atmosphere instead of an atmosphere of hydrogen gas and the reaction time for the reaction of the second stage was changed from 1 hour to 5 hours. Formic acid added to the reaction system in the time between the first stage reaction and the second reaction stage, had the following four functions:

(1) the function formuliruiutsia agent (for formirovaniya N-H groups in tetraazacyclotetradecane urticina);

(2) the function of the solvent for dissolving tetraacetylethylenediamine;

(3) the function of the reducing agent (with this feature, formic acid eliminated the need for carrying out the second stage reaction in the atmosphere of hydrogen gas); and

(4) the function of the first solvent which is evaporated during the distillation precipitation of crystals.

The reaction mixture obtained by the reaction of the second stage, pulled out from the autoclave, filtered, the catalyst contained in the reaction mixture, resulting in the received solution in the form of filtrate. The solution was subjected to distillation deposition of crystals in essentially the same way as described in example 3, as a consequence received tetraacetylethylenediamine with the release of 68% per hexabenzylhexaazaisowurtzitane / output during the precipitation of crystals: 97%; purity: 98% (HPLC certain).

Example 13. /Distillation precipitation of crystals WA4/F2robtained by the reaction in accordance with reaction scheme:

WA4B2---> WA4F2r/ (first solvent: formic acid; the second solvent: etilenglikolevye ether /

Repeated essentially the same with litovali 30 ml of formic acid and 30 ml etilenpropilendienovogo ether; the reaction is carried out in an atmosphere of nitrogen instead of hydrogen gas; the reaction time was changed from 1 hour to 3 hours; and the reaction temperature was changed from 90oC 80oC. as a result received tetraacetylethylenediamine with the release of 95% (based on tetraacetylethylenediamine / output during the precipitation of crystals: 98%; purity: 98% (HPLC certain) /.

Example 14. / Synthesis WA4H2in which by-product carboxylic acid was removed by azeotropic distillation / /WB6---> WA4B2---> (azeotropic distillation) ---> WA4H2/ (first solvent: water; a second solvent: DMAc)

The first stage reaction was carried out in essentially the same manner as that described in example 3, as a consequence, the obtained reaction mixture containing tetraacetylethylenediamine. The reaction mixture was removed from the autoclave and then to remove the catalyst was subjected to filtration. To an educated filtrate to obtain the mixture was added 60 ml of toluene. With the use of distillation column, the bottom of which is connected to an evaporation apparatus, and the resulting mixture was subjected to distillation for removal of acetic acid with toluene through azeotrope. Then, the DMAc solution was subjected to distillation for removal of the toluene. The resulting solution DMAc has a concentration of acetic acid is 2% or less.

In a 100 ml autoclave was loaded above the DMAc solution, 0.84 g of 10% Pd-C as catalyst), which prior application was reduced by hydrazine, and 30 ml of water and the autoclave was closed. The autoclave was purged with nitrogen. Then, the autoclave was filed by the hydrogen gas to the internal pressure in the autoclave was set to 9 FCT/cm2. Then began a stirring solution of DMAc in the autoclave with stirring speed of 700 rpm, and the reaction temperature in the autoclave was increased to 90oC. After the temperature in the autoclave was set to 90oC, the reaction was continued for 1 hour. After completion of the reaction the reaction mixture is pulled out of the autoclave and to remove the catalyst was subjected to filtration. The obtained filtrate was subjected to distillation deposition of crystals in essentially the same manner as that described in example 3, as a consequence, the obtained mixture containing tetraazacyclotetradecane / yield: 76%; purity: 98% (defined

HPLC); exit when the deposition of crystals: 98% /.

Because in this way their, you can easily implement recycling DMAc by exposure of the mixture of repeated distillation (as acetic acid causes the decomposition of the skeleton hexabenzylhexaazaisowurtzitane, used as starting material, the solvent containing a large amount of acetic acid, cannot be used as solvent for the reaction of the first stage).

Example 15. /Synthesis WA4H2in which side-carboxylic acid was removed by azeotropic distillation /

The reaction path: WB6----> WA4B2---> WA4H2---> (azeotropic distillation) /

(first solvent: water; a second solvent: DMAc)

To obtain the reaction mixture of the first reaction stage and the second stage was carried out in essentially the same manner as that described in example 3. The reaction mixture was removed from the autoclave and then to remove the catalyst threw the filter. The resulting mixture was subjected to distillation deposition of crystals in essentially the same manner as that described in example 3, as a consequence, the obtained mixture containing tetraazacyclotetradecane /yield: 79%, purity: 97% (HPLC certain); exit when the deposition of crystals: 94% /.

Examples 16 to 20. / Experiments illustrating the advantage achieved through the use in the reaction in accordance with reaction scheme: WB6---> WAnB(6-n)organic solvent containing an amide group (n is an integer equal to 4 or 5) /

To assess the effects of acidity and basicity of the reaction solvent to the reaction in accordance with reaction scheme: WB6---> WAnB(6-n)carried out experiments using, respectively as the reaction solvent of acetic acid (AcOH: acid solvent), telebasel (EB: neutral solvent), N,N-dimethylacetamide (DMAc: weakly basic solvent), 1,3-dimethyl-2-imidazolidone (DMI: weakly basic solvent) and N,N-dimethylaniline (DMA: basic solvent). Each of the experiments were carried out as follows.

In a 300 ml pressure pipes (made of stainless steel SUS) downloaded amount of 0.118 g (0,167 mmole) hexabenzylhexaazaisowurtzitane, 0,106 the high pressure purged with nitrogen. Then the trumpet gave the hydrogen gas to the internal pressure of the pipe was equal to 2 FCT/cm2. The tube was placed in a vibrator having a temperature of 60oC, and realized the shaking speed from 90 to 100 shaking per minute for 4 hours to conduct reaction. After completion of the reaction the reaction mixture is pulled from the tube and subjected to GC analysis. The results are shown in table 3.

All quantities in table 3 are given in mmol.

B represents a benzyl group;

A represents an acetyl group; and

E represents an ethyl group.

*1: Connection obtained from the benzyl groups by reaction dibenzylamine. Formed quantity of toluene shows degree of reaction.

*2: Connection generated by acetylation of benzylamine where benzylamine is a product of decomposition of the skeleton WB6by acid in the food. Educated quantity of this compound shows degree of decomposition of the skeleton.

*3: the Total number of compounds having a skeleton hexaazatetracyclo, which is detected by gas chromatography. General>

As follows from table 3, when the reaction is performed with the use of a weakly basic solvent containing an amide group, such as DMAc or DMI, the emergence of decomposition of the skeleton is suppressed and the output of the compounds having the skeleton hexaazatetracyclo is high compared with the case where the reaction is carried out using an acidic solvent such as AcOH, or neutral solvent, such as EB. In addition, when the reaction is performed with the use of the primary solvent, such as MA, the decomposition of the skeleton essentially does not occur; however, the reactivity is too low, resulting in only WA2B4that is an intermediate compound formed in the early stages of the reaction in accordance with reaction scheme: WB6---> WAnB(6-n).

Examples 21 to 24.

In these examples was carried out experiments to show that even if the reaction WB6---> WAnB(6-n)carried out at high temperature, used in this reaction weakly basic organic solvent containing an amide group, provides suppression of decomposition of the skeleton. The experiments were carried out as follows.

300 ml Isovorticity, 0,106 g 10% Pd-C as catalyst), 0,510 g (5.00 mmol) of acetic anhydride and 10 ml of DMAc. The tube was purged with nitrogen. Then the trumpet gave the hydrogen gas to the internal pressure of the pipe was equal to 2 FCT/cm2. The tube was placed in a vibrator and implemented a shaking speed of 100 to 110 shaking at the minute for 4 hours at different constant temperature.

After completion of the reaction the reaction mixture is pulled from the tube and subjected to GC analysis. The results are shown in table 4.

Table 4:

B represents a benzyl group;

A represents an acetyl group; and

E represents an ethyl group.

*1: Connection obtained from the benzyl groups by reaction dibenzylamine. Formed quantity of toluene shows degree of reaction.

*2: the Total number of compounds having a skeleton hexaazatetracyclo, which is detected by gas chromatography. The total number contains the number of derivatives hexaazatetracyclo, which are shown in table 4.

As follows from table 4, used as the reaction solvent base, organic the Oia is carried out at high temperature (up to 165oC), decomposition of the skeleton almost never happens.

As a comparative experiment was repeated essentially the same method described in example 7, except that the reaction solvent used in the EB. As a result, the output of the compounds having the skeleton hexaazatetracyclo amounted to only 60% or less (0,100 mmole or less).

Example 25.

This example was carried out by the experience in order to show that if the reaction in accordance with reaction scheme: WB6---> WAnB(6-n)apply the reaction solvent containing AcOH in an amount of about 5% by weight or less based on the weight of the reaction solvent AcOH contained in the reaction solvent in such a small amount that does not adversely influence the reaction.

The first stage reaction was carried out in essentially the same manner as that described in example 3, except that the DMAc (reaction solvent) was added 1.5 ml of acetic acid and the reaction time was changed to 2 hours.

As a result, the outputs tetraacetylethylenediamine and tetraazacyclotetradecane were respectively 52% and 21% per examinsight, if the first reaction stage is performed with the use WB6in such great numbers as about 14% by weight based on the weight of the reaction solvent, the reaction of the first stage still occurs.

The first stage reaction was carried out in essentially the same way as described in example 3, except that the number hexabenzylhexaazaisowurtzitane and 10% Pd-C was changed accordingly 4.2 g and 2.1 g and the reaction time was changed to 40 minutes.

As a result, the outputs tetraacetylethylenediamine and tetraazacyclotetradecane were, respectively, 53% and 19% per hexabenzylhexaazaisowurtzitane.

Example 27.

To 5.0 g of a viscous suspension containing 56,8% by weight tetraazacyclotetradecane obtained in the same manner as that described in example 2, was added 150 ml of water and 100 ml of chloroform, and then to dissolve the suspension was carried out by stirring. The resulting solution was passed for the formation of the chloroform layer and water layer. Then extracted the aqueous layer and was subjected to distillation under reduced pressure to remove the liquid component, and as a result received of 2.26 g tetraazacyclotetradecane dry R> The method of the present invention is commercially advantageous, because it can be applied for deriving hexaazatetracyclo containing acyl group, in high-purity form, with high yield and at low cost, while derived hexaazatetracyclo is suitable as precursor derived hexanitrocobaltate, which can be used to improve performance of conventional explosives.

1. The allocation method is derived hexaazatetracyclo containing acyl group, characterized in that it comprises: (I) obtaining a composition containing: (a) a mixed solvent comprising at least one first solvent selected from the group consisting of water and carboxylic acids, and at least one second solvent selected from the group consisting of containing amide or ester group of organic solvents, (b) derived hexaazatetracyclo containing acyl group of the following formula 1:

WAnH(6-n),

where n is an integer equal to 4 or 6;

each And independently represents an acyl group, the ima is fair balance hexaazatetracyclo the following formula 2:

< / BR>
moreover, at least part allstargame derived hexaazatetracyclo (b) dissolved in a mixed solvent (a); (II) removing from the composite system, at least part of the first solvent to precipitate crystals allstargame derived hexaazatetracyclo (b); and (III) isolation of the precipitated crystals of the composite system.

2. The method according to p. 1, characterized in that allstargame derived hexaazatetracyclo (b) formula 1 is the product obtained by synthesis using a reaction solvent consisting of first and second solvents.

3. The method according to p. 2, characterized in that the composite system obtained at the first stage, a mixed solvent consisting of first and second solvents, receive at least one reaction solvent.

4. The method according to p. 1, wherein the second solvent has a boiling point above the boiling point of the first solvent and removing at least part of the first solvent from the composite system is performed by distillation.

5. The method according to p. 3, wherein the second solvent has a boiling point above the boiling point of the first is by distillation.

6. The method according to p. 5, characterized in that allstargame derived hexaazatetracyclo (b) is tetrachlorodibenzofuran the following formula 3:

WA4H2,

where each of a, H and W are defined above for formula 1,

and which is obtained by synthesis using at least two reaction solvents, representing at least one first solvent and at least one second solvent, where the composite system obtained at the first stage, at least one first solvent and at least one second solvent receive at least two reaction solvent, and where the at least one first solvent selected from the group consisting of water and acetic acid, and at least one second solvent selected from the group consisting of organic solvents having a boiling point above the boiling point of water, when the first solvent is water, or having a boiling point above the boiling point of acetic acid, when the first solvent is acetic acid or a mixture of water and acetic acid.

7. The method according to p. 5, characterized in that allstargame derived hexassistant the>where each of a, H and W are defined above for formula 1,

and which is obtained by synthesis using at least two reaction solvents, representing at least one first solvent and at least one second solvent, where the composite system obtained at the first stage, at least one first solvent and at least one second solvent receive at least two reaction solvent, and where the first solvent is water and at least one second solvent selected from the group consisting of organic solvents, containing amide group, having compatibility with water and having a boiling point above the boiling point of water.

8. The method according to p. 6, characterized in that the synthesis tetraallylsilane formula 3 includes the introduction of tetrazoles(arylmethyl)hexaazatetracyclo the following formula 4:

WA4IN2,

where is each independently represents arylmethyl group having from 7 to 21 carbon atoms;

each W and a are defined above for formula 1,

in response diarylethylene in the presence of at least two reaction solvents.

9. The method according to p. 7, ITIL)hexaazatetracyclo the following formula 4:

WA4IN2,

where is each independently represents arylmethyl group having from 7 to 21 carbon atoms;

each of W and a are defined above for formula 1,

in response diarylethylene in the presence of at least two reaction solvents.

10. The method according to p. 5, characterized in that allstargame derived hexaazatetracyclo (b) is tetrachlorodibenzofuran the following formula 3:

WA4H2,

where each of a, H and W are defined above for formula 1,

and which is obtained by synthesis using at least two reaction solvents, representing at least one first solvent and at least one second solvent, where the composite system obtained in stage (I) at least one first solvent and at least one second solvent receive at least two reaction solvent, and where the first solvent is water and at least one second solvent selected from the group consisting of containing amide group of organic solvents, having compatibility with water and having a boiling point which is above the boiling point of votel)hexaazatetracyclo in response restorative diarylethylene in the presence Alliluyeva agent with obtaining a reaction mixture (i), containing tetrazoles(arylmethyl)hexaazatetracyclo the following formula 4:

WA4IN2,

where is each independently represents arylmethyl group having from 7 to 21 carbon atoms;

each of W and a are defined above for formula 1,

and containing carboxylic acid and allmetal as by-products, (ii) adding water to the reaction mixture and (iii) the subsequent introduction of the reaction mixture in the reaction diarylethylene with obtaining the reaction mixture (iii) containing tetrachlorodibenzofuran formula 3 and allmetal as a by-product.

11. The method according to p. 10, characterized in that the side-carboxylic acid, obtained in stage (i), remove from the reaction mixture (i) obtained in stage (i), method of azeotropic distillation together with Arellano representing kilmacanogue by-product obtained in stage (i).

12. The method according to p. 10, characterized in that the side-carboxylic acid, obtained in stage (i), delete a method of azeotropic distillation together with Arellano representing kilmacanogue by-product obtained in stage (i) and stage (iii) of the composite system during removal of Pervov the Oia precipitated crystals of the composite system at stage (III).

13. The method according to p. 10, wherein the second solvent represents at least one organic solvent containing an amide group, selected from N, N-dimethylacetamide, N, N-dimethylformamide, 1,3-dimethyl-2-imidazolidone and N-methyl-2-pyrrolidone.

14. The method according to p. 11, wherein the second solvent represents at least one organic solvent containing an amide group, selected from N, N-dimethylacetamide, N, N-dimethylformamide, 1,3-dimethyl-2-imidazolidone and N-methyl-2-pyrrolidone.

15. The method according to p. 12, wherein the second solvent represents at least one organic solvent containing an amide group, selected from N, N-dimethylacetamide, N, N-dimethylformamide, 1,3-dimethyl-2-imidazolidone and N-methyl-2-pyrrolidone.

16. The method according to p. 11, characterized in that the side-carboxylic acid is acetic acid and Arellano is toluene.

17. The method according to p. 12, characterized in that the side-carboxylic acid is acetic acid and Arellano is toluene.

18. The method according to p. 14, characterized in that the side-carboxylic acid is acetic acid and Arellano Sosna acid and Arellano is toluene.

20. The method according to p. 4, characterized in that allstargame derived hexaazatetracyclo (b) is sexuallytransmitted the following formula 8:

WA6,

where each of W and a are defined above for formula 1,

and where at least one first solvent selected from the group consisting of water and acetic acid, and at least one second solvent selected from the group consisting of containing the ether group of organic solvents having a boiling point above the boiling point of water, when the first solvent is water, or having a boiling point above the boiling point of acetic acid, when the first solvent is acetic acid or a mixture of water and acetic acid.

21. The method according to p. 5, characterized in that allstargame derived hexaazatetracyclo (b) is tetracyclineresistant the following formula 9:

WA4F2r,

where each Frrepresents a formyl group;

each of W and a are defined above for formula 1,

and which is obtained by synthesis using at least two of the reaction solvent represents at least one of the first p is), at least one first solvent and at least one second solvent receive at least two reaction solvent, and where the first solvent is formic acid and at least one second solvent selected from the group consisting of containing the ether group of organic solvents having a boiling point above the boiling point of formic acid.

22. The method according to p. 21, characterized in that the synthesis tetracyclineresistant formula 9 includes the introduction of tetrazoles(arylmethyl)hexaazatetracyclo the following formula 4:

WA4B2,

where is each independently represents arylmethyl group having from 7 to 21 carbon atoms;

each of W and a are defined above for formula 1,

in response diarylethylene in the presence of the reaction solvent.

23. The method according to p. 21 or 22, characterized in that the synthesis tetracyclineresistant formula 9 includes the following stages: (iii) introduction hexacis(arylmethyl)hexaazatetracyclo in response restorative diarylethylene in the presence Alliluyeva agent to obtain the reaction mixture containing tetrazoles(arylmethyl) is arylmethyl group, having from 7 to 21 carbon atoms;

each of W and a are defined above for formula 1,

(iv) adding to the reaction mixture of formic acid and (v) subsequent diarylethylene obtained reaction mixture.

24. The method according to p. 21, wherein the second solvent represents at least one organic solvent containing an ester group selected from etilenpropilendienovogo ether, ethylene glycol-di-n-butyl ether, dietilaminoetilovogo ether and dietilaminoetilovogo ether.

25. The method according to p. 22, wherein the second solvent represents at least one organic solvent containing an ester group selected from etilenpropilendienovogo ether, ethylene glycol-di-n-butyl ether, dietilaminoetilovogo ether and dietilaminoetilovogo ether.

26. The method according to p. 23, wherein the second solvent represents at least one organic solvent containing an ester group selected from etilenpropilendienovogo ether, ethylene glycol-di-n-butyl ether, dietilaminoetilovogo ether and dietilaminoetilovogo ether.

27. Osposoblyaet introduction hexacis(arylmethyl)hexaazatetracyclo in response restorative diarylethylene in the presence Alliluyeva agent and an organic solvent, containing amide group.

28. The method according to p. 27, where an organic solvent containing an amide group, a represents at least one compound selected from the group consisting of N,N-dimethylacetamide, N,N-dimethylformamide, 1,3-dimethyl-2-imidazolidone and N-methyl-2-pyrrolidone.

29. The method of obtaining allstargame derived hexaazatetracyclo, including: (A) obtaining a composition containing: (a') a mixed solvent consisting of water and at least one organic solvent which can be separated from water, and (b') derived hexaazatetracyclo containing acyl group of the following formula 12:

WAnH(6-n),

where n is an integer equal to 4 or 6;

each And independently represents an acyl group having from 1 to 10 carbon atoms;

H represents a hydrogen atom;

W represents a hexavalent balance hexaazatetracyclo the following formula 13:

< / BR>
moreover, the compositional scheme includes the organic phase and the aqueous phase containing dissolved therein at least part allstargame derived hexaazatetracyclo (b'); (C) separating the aqueous phase from the AC (b') in pure form.

30. The method according to p. 29, wherein n in the formula 12 is equal to 4.

31. The method according to p. 29, wherein n in the formula 12 is equal to 6 and where two groups As in formula 12 are formyl groups, and the remaining four groups are acyl groups, excluding the formyl group.

32. The method of obtaining tetrazoles(arylmethyl)hexaazatetracyclo the following formula 4:

WA4B2,

where each And independently represents an acyl group having from 1 to 10 carbon atoms;

Represents arylmethyl group having from 7 to 21 carbon atoms;

W represents the balance hexaazatetracyclo the following formula 2

< / BR>
includes introduction hexacis(arylmethyl)hexaazatetracyclo in response restorative diarylethylene in the presence Alliluyeva agent and an organic solvent containing an amide group, obtaining tetrazoles(arylmethyl)hexaazatetracyclo in the form of its mixture containing the amide group with an organic solvent.

33. The method according to p. 32, characterized in that the organic solvent containing an amide group, a represents at least one compound selected from the group comp

34. The method of obtaining tetraallylsilane the following formula 3:

WA4H2,

where each And independently represents an acyl group having from 1 to 10 carbon atoms;

H represents a hydrogen atom;

W represents the balance hexaazatetracyclo the following formula 2:

< / BR>
includes introduction tetrazoles(arylmethyl)hexaazatetracyclo the following formula 4:

WA4B2,

where each And independently represents an acyl group having from 1 to 10 carbon atoms;

In is arylmethyl group having from 7 to 21 carbon atoms;

W represents the balance hexaazatetracyclo the following formula 2:

< / BR>
in response restorative diarylethylene in the presence Alliluyeva agent and solvent, and the specified solvent includes a mixture of water and an organic solvent containing an amide group.

35. The method according to p. 34, characterized in that tetrazoles(arylmethyl)hexaazatetracyclo produced by restoration diarylethylene hexanes(arylmethyl)hexaazatetracyclo the following formula:

WB6,

where each of W and b defined above for ptx2">

36. The method according to p. 34 or 35, characterized in that the organic solvent is at least one compound selected from the group consisting of N, N-dimethylacetamide, N, N-dimethylformamide, 1,3-dimethyl-2-imidazolidone and N-methyl-2-pyrrolidone.

Priority points:

14.10.96 on PP.32-36;

17.04.97 on PP.1-10, 13, 27, 28, 29, 30.

 

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FIELD: organic chemistry, chemical technology.

SUBSTANCE: invention relates to a method for synthesis of 1,8-dimethyl-3,6-diazadihomoadmantane-9,10-dione. Compounds of class 3,6-diazadihomoadamantane-9,10-dione possess an antiviral effect comparable with antiviral effect of aminoadamantane, elicit strychnine-like activity and show bactericidal, fungicide and algicidic properties also. Proposed method for preparing 1,8-dimethyl-3,6-diazadihomoadamantane-9,10-dione involves interaction of 1,8-dimethyl-3,6,10,13-tetraazatetracyclo[8,4,1,18,1302,7]hexadeca-2,6-diene with water in the presence of hydrochloric acid and sodium nitrite at room temperature. The parent 1,8-dimethyl-3,6,10,13-tetraazatetracyclo[8,4,1,18,1302,7]hexadeca-2,6-diene is prepared in the condensation reaction of tetramethylenediethylenetetramine and 3,4-hexanedione in the presence of acetic acid in isopropyl alcohol medium at room temperature. Then the reaction mixture is neutralized with potash aqueous solution, water is evaporated under vacuum and solid residue is extracted with heptane. After recrystallization from heptane 1,8-dimethyl-3,5-diazadihomoadamantane-9,10-dione is prepared. The yield of the compound is 78%. Invention provides the development of available method of synthesis of 1,8-dimethyl-3,6-diazadihomoadamantane-9,10-dione.

EFFECT: improved method of synthesis.

1 ex

FIELD: organic chemistry, chemical technology.

SUBSTANCE: invention relates to a method for synthesis of novel addition agents used as regulators of viscoelastic properties of associated multicomponent petroleum systems that can be used in petroleum and petroleum chemical industry. Method involves interaction of monochloroacetic acid with alcoholic component in the presence of acidic catalysts, for example, with H+-form of cation-exchange resin KU-2-8, in boiling organic solvent medium and azeotropic removing formed water and the following treatment of the synthesized reaction substance with amines. As a alcoholic component methods involves using 1,2,3-tris-[(hydroxypoly(alkyleneoxy)]propanes of the general formula: wherein a + c + e (the total degree of oxypropylation) = 48-78, b + d + f (the total degree of oxyethylation) = 0-20, and 1,3,5,7-tetraazaadamantane of the formula: is used as amines in the molar ratio of reagents - propane hydroxyl derivative : monochloroacetic acid : tetraazaadamantane = 1.0:(3.0-3.2):(0.75-3.2), respectively. As a rule, as organic solvents in interaction of propane hydroxyl derivative with monochloroacetic acid method involves using aromatic hydrocarbon solvents, for example, toluene, xylene, nefras A-120/200. Usually, treatment of the reaction product of monochloroacetic acid with propane hydroxyl derivative with 1,3,5,7-tetraazaadamantane is carried out in polar solvents medium at temperature 40-85°C. As a rule, mixtures of water with low-molecular alcohols, for example, ethanol, isopropanol are used as polar solvents in the volume ratio water : alcohol = 1.0:(15-25).

EFFECT: improved method of synthesis.

5 cl, 1 tbl, 6 ex

FIELD: organic chemistry, chemical technology.

SUBSTANCE: invention describes {[1-(ammonio)-3,5,7-triazaadamantyl]methylcarbonyloxypoly-(alkyleneoxy)}-propane chlorides of the general formula: wherein at X+ = Y+ means ; R1 means aliphatic unsaturated hydrocarbon C17-radical; a + c + e = 49; b + d + f = 9; at X+ = Y+ means ; R1 means aliphatic unsaturated hydrocarbon C17-radical; a + c + e = 55; b + d + f = 10; at X+ = Y+ means ; a + c + e = 49; b + d + f = 9; at X+ = Y+ means ; a + c + e = 55; b + d + f = 10; at X+ = Y+ means ; R1 means aliphatic unsaturated hydrocarbon C17-radical; a + c + e = 49; b + d + f = 0; at X+ = Y+ means ; R1 means aliphatic unsaturated hydrocarbon C17-radical; a + c + e = 55; b + d + f = 0; at X+ = Y+ means -RNH2+-; R means aliphatic hydrocarbon (C10-C16)-radical; a + c + e = 49; b + d + f = 9; at X+ = Y+ means -RNH2+-; R means aliphatic hydrocarbon (C10-C16)-radical; a + c + e = 55; b + d + f = 10. Also, invention describes a method for synthesis of abovementioned compounds that possess antibactericidal and fungicide activity and can be used for control of bacterial and fungal damages in medicine, veterinary science and agriculture.

EFFECT: improved method of synthesis, valuable properties of compounds.

7 cl, 2 tbl, 8 ex

FIELD: organic chemistry, chemical technology.

SUBSTANCE: invention relates to a method for synthesis of 8-nitro-1,3,6-triazahomoadamantane. Method involves using nitromethane and derivative of tetraazaadamantane that react in the presence of acetic acid as a catalyst in n-butyl or isopropyl alcohol at weak boiling and wherein 1,3,6,8-tetraazatricyclo[4.3.1.13,8]undecane is used as a derivative of tetraazaadamantane. Reaction is carried out at weak boiling for 20-30 min and synthesized product is extracted with hot heptane and re-crystallized from isopropyl alcohol or acetone. Invention provides enhancing yield and simplifying process in synthesis of the end product.

EFFECT: improved method of synthesis.

2 ex

FIELD: chemistry.

SUBSTANCE: invention relates to method for obtaining a new compound, i.e. 9-phenyl-3,6-diazatricyclo[4.3.1.13,8]undecan with formula . Compounds of class of 3,6-diazahomoadamantan have anti-virus action comparable to that of aminoadamantan, demonstrate strychnine-like activity, have bactericidal, fungicidal and analgicidal properties. According to the present method, 1-(phenyltio)-3,6-diazatricycio[4.3.1.13,8]undecan-9-on(1) is subjected to interaction with phenyllithium in absolute ether to obtain 9-phenyl-1-(phenyltio)-3,6-diazatricyclo[4.3.1.13,8]undecan-9-ol (2) which is de-sulfated with Rene nickel when boiling in isopropyl alcohol. Yield comprises 76%.

EFFECT: obtaining a compound that has anti-virus action comparable to that of aminoadamantan, demonstrates strychnine-like activity, and has bactericidal, fungicidal and analgicidal properties.

1 cl, 2 ex

FIELD: chemistry, biochemistry.

SUBSTANCE: invention relates to field of biotechnology, namely to bacteriochlorophyll derivatives and can be used for medical and diagnostic purposes. Anion-containing water-soluble tetracyclic and pentacyclic bacteriochlorophyll (Bchl) derivatives contain one, two or three negatively charged groups and/or acid groups, which transform into negatively charged groups at physiological pH. Obtained derivatives are used for photodynamic therapy and for tumor diagnostics, as well as for killing cells or infectious agents.

EFFECT: increasing selectivity of binding with target in photodynamic therapy and diagnostics.

25 cl, 34 dwg, 5 tbl, 57 ex

FIELD: chemistry.

SUBSTANCE: invention relates to organic chemistry, more specifically to novel individual azatricycloeicosanic class compounds. Described are methyl 11-aryl-12-aroyl-9-hydroxy-4,6-dimethyl-3,5,10-trioxo-4,6,8,11-tetraazatricyclo[7.2.1.02,7]dodec-2(7)-ene-1-carboxylates of formula , where Ar1=Ar2=Ph (a), Ar1=C6H4Br-4, Ar2=C6H4Me-4 (b). Also described is a method for synthesis of methyl 11-aryl-12-aroyl-9-hydroxy-4,6-dimethyl-3,5,10-trioxo-4,6,8,11-tetraazatricyclo[7.2.1.02,7]dodec-2(7)-ene-1-carboxylates.

EFFECT: novel compounds are obtained, which can be used as precursors for synthesis of novel heterocyclic systems and in pharmacology.

4 cl, 2 ex

FIELD: chemistry.

SUBSTANCE: invention describes a novel compound CLARANT, which is a crystalline hydrate of 1,6,3,8-dimethano-1,3,6,8-tetraazacyclodecane-sodium carbonate with structural formula: , which can be used in sanitation, veterinary and medicine for disinfecting buildings, equipment, inventory, instruments, devices, dishes, cosmetics, animals, feedstuff, soil and other sanitation objects from pathogenic viruses, bacteria, protozoa and fungi; the compound can also be used as an antiseptic agent.

EFFECT: obtaining a new non-toxic agent with bactericidal and virucidal activity.

1 cl, 3 tbl

FIELD: medicine, pharmaceutics.

SUBSTANCE: there are described new N-cyclic sulphonamido-compounds and their pharmaceutically acceptable salts of formula : of formula 1a of formula 1b of formula 1c where the ring A means phenyl, thienyl which can be substituted by halogen, or pyridinyl; a value of the ring B is presented in the patent claim, and also a pharmaceutical composition containing them, and a method of treating Alzheimer's disease.

EFFECT: compounds are gamma-secretase inhibitors and can be used for treating Alzheimer's disease.

16 cl, 98 ex

FIELD: medicine, pharmaceutics.

SUBSTANCE: declared invention refers to a continuous disinfectant showing antimycotic, antibacterial, antiviral action and applicable in the following fields of national economy: medicine, veterinary science and veterinary sanitary, and also manufacture of cosmetic and hygienic preparations, as an additional agent for manufacture of vaccines; chemical industry, including water, waste, closed-loop recirculation system disinfection, vent and room disinfection, manufacture of building materials, varnishes and paints with special properties, manufacture of cleaners and household chemical goods; food industry, including manufacture and processing of meat of farm animals, fish and poultry, milk manufacture and processing, conservation of animal raw materials and half-finished products; agriculture, including plant growing and seed growing, procuring, tanning, down and fur, fur farming, rabbit breeding, poultry farming, animal industry and horse breeding. A method for preparing it is described.

EFFECT: agent shows high efficacy and stability, cause no irritant action on skin if contacted; it is non-toxic.

2 cl, 1 tbl

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