Derived hexaazatetracyclo containing acyl group, method thereof, and intermediates and methods for their production

 

(57) Abstract:

Proposed containing acyl group derived hexaazatetracyclo represented by formula I: WAtQ(6-t),

where t denotes an integer from 4 to 6; A is independently denotes an acyl group with 1 to 10 carbon atoms, each Q independently represents a hydrogen atom or alkyl group with 1 to 10 carbon atoms; W represents hexavalent balance hexaazatetracyclo represented by formula II. Also described is a method of obtaining the above containing acyl group derived hexaazatetracyclo formula III: WA6where W and A as above, consists in the fact that the compound of formula IV: WAnH(6-n)where W and A as above, n is 4 or 5, is subjected to the interaction with allermuir agent. In the invention stated numerous ways to obtain various derivatives hexaazatetracyclo. Containing acyl group derived hexaazatetracyclo can be used as a precursor derived printrequestattributeset, which can be used not only as a matter for explosive compounds, but also as additives for rocket fuel and Trieste feedstock to obtain a highly polar polymer and as a polyfunctional crosslinking agent and filler for polymers. 19 C. and 34 C.p. f-crystals, 1 PL.

The invention relates to the production of hexaazatetracyclo containing acyl group, and how to obtain it.

Containing acyl group derived hexaazatetracyclo of the present invention contains N-A group (where A denotes an acyl group), and optionally N-H group in a high concentration, and this is derived each of the N-A-groups and N-H group may be converted into N-NO2group in various ways nitration.

Thus, containing acyl group derived hexaazatetracyclo this invention is useful as a precursor derived printrequestattributeset, which can be used not only as raw materials for explosives, but also as additives to rocket fuels and explosives. In particular, the derived printrequestattributeset can be successfully used as additives to improve various properties such as mechanical properties, velocity of detonation, detonation pressure, burning rate, the rate exponent pressure sensitivity and resistance to heat) rocket fuel and explosives. Wabaseemoong printrequestattributeset, is a promising material to create the next generation of explosives with high performance. As mentioned above, containing acyl group derived hexaazatetracyclo this invention is useful as a precursor of such securities derivative printrequestattributeset.

Besides containing acyl group derived hexaazatetracyclo according to this invention can be successfully used, due to the reactivity of each of the N-A group (where A stands for an acyl group and N-H groups contained therein, to obtain a highly polar polymer containing high concentrations of acyl groups in its main and/or side chain. This highly polar polymer is useful not only as a high hydrophilic polymer, but also as vysokoelastichny polymer.

Besides containing acyl group derived hexaazatetracyclo according to this invention can be successfully used as a polyfunctional crosslinking agent, due to the reactivity of the derivative.

Moreover, containing acyl group derived hexaazatetracyclo according to this invention may also be the Prior art

In addition to the above HNW, well-known compounds that have the same hexaazatetracyclo (denoted hereinafter "W") skeleton, as containing acyl group hexaazatetracyclo derived in this invention include the following:

1) hexacis(arylmethyl)hexaazatetracyclo (denoted for simplicity "HBW");

2) tetraacetylethylenediamine (denoted for simplicity TADBW") and

3) hexaazatetracyclo with carbamino group (denoted for simplicity "HCW") (see non-examination application laid Japan N 6-321962).

It is known that HBW can be obtained by condensation reaction of various arylmethylidene with glyoxal [see J. Org. Chem., Vol. 55, 1459-1466(1990)].

It was reported that TADBW useful as agents to obtain explosives [see The Military Critical Technologies List, Office of the Under Secretary of Defense for Aquisition, 12-22, October (1992)]. However, this message is no way of turning TADBW in explosive or chemical structure of such explosives obtained from TADBW, no way of getting the TADBW.

Properties HNW, which, as mentioned above, can be expected to serve as a promising raw material for explosives with high etc, but nowhere in the literature there is no information on obtaining HNW.

Previously, with the aim of developing a method of deriving printrequestattributeset, such as HNW, these applicants tried to netravati HBW and TADBW under different conditions of nitration. However, it was impossible to obtain a sufficient number of derived printrequestattributeset. In addition, HBW and TADBW contain benzyl group, so when HBW or TADBW subjected to nitration, as a by-product inevitably formed by reduction of compounds with high affinity to various nitro compounds. As a result, it is difficult to separate the target derived printrequestattributeset from the reduction side of the connection.

It is also hard to get HCW with high yields. The grounds for this conclusion is that while obtaining HCW is formed chloride-hydrogen acid (strong acid) and the resulting chloride-hydrogen acid seems decomposes HBW that serves as the starting material.

Thus, none of the W-selectarray compounds HBW, TADBW and HCW is not suitable as its predecessor, which could be successfully used for the tion.

Brief description of the invention

In such a situation to develop suitable commercial method of deriving printrequestattributeset the present applicants have made extensive and intensive studies with the aim of finding not only predecessor, which could be easily converted into a derivative printrequestattributeset, but also the way to obtain this predecessor.

The result was unexpectedly found that, as a predecessor derived printrequestattributeset useful derived hexaazatetracyclo having a polar group, consisting only of N-acyl group and optionally N-H group. The present applicants have found industrial expedient way of obtaining the above derived hexaazatetracyclo with high yield. In addition, it is found that the derived hexaazatetracyclo containing N-acyl group, N-alkyl group and optionally N-H group can be used as polyfunctional cross linking agent. This invention is based on these new results.

The purpose of this invention consists in obtaining lysosome receiving this product.

In addition, the purpose of this invention is to obtain a new functional substances containing high concentrations of strongly polar functional group, such as N-acyl group and N-H group.

Detailed description of the invention

One aspect of this invention is to obtain a derived hexaazatetracyclo containing acyl group represented by the following formula I:

WAtQ(6-t),

where t denotes an integer from 4 to 6, each Deputy A independently denotes an acyl group containing from 1 to 10 carbon atoms, each Q independently represents a hydrogen atom or alkyl group with 1 to 10 carbon atoms, and W denotes hexavalent balance hexaazatetracyclo, represented by the following formula II:

< / BR>
Another aspect of the present invention is to develop a method of obtaining the above derived hexaazatetracyclo containing acyl group.

Below are explanations relating containing acyl group derived hexaazatetracyclo represented by the following formula I-a as a specific example of the compounds of the above formula I

WAtH(6-t)
< / BR>
As for the acyl group in A derived hexaazatetracyclo according to this invention, there are no special restrictions except that it contains from 1 to 10 carbon atoms. The acyl group may be substituted by the Deputy, which remains stable in the reaction conditions in the reaction rehabilitation diarylethylene performed by the method according to this invention as described below. Examples of acyl groups include acetyl group, propionyl group, butyryloxy group, isobutyryloxy group, valerino group, hexanoyl group and 2-phenylacetylene group. Which one is preferable acyl group with 2-5 carbon atoms, such as acetyl group, proposalsa group, Butyrina group and valerina group. More desirable acyl group with 2-3 carbon atoms, such as acetyl group and propylaniline group. Acyl group denoted by Atin formula I, above, may be the same or different.

For containing acyl group derived hexaazatetracyclo according to this invention, not only is achene t, but different N-acyl groups and N-H groups.

For example, as a specific example of the compounds represented by formula I-a: WAtH(6-t)where t is equal to 4, i.e., compounds of formula WA4H2may be mentioned a compound represented by the following formula I-a', although the compound represented by the formula WA4H2can be any of the structural isomers of the compounds of the following formula I-a'

< / BR>
In containing acyl group derived hexaazatetracyclo WAtH(6-t)this invention t denotes an integer from 4 to 6, preferably 4 or 6.

Another preferred example containing acyl group derived hexaazatetracyclo this invention is a compound represented by formula I-a, where t is equal to 6, i.e., derived Hexachlorobutadiene the following formula III:

WA6< / BR>
where A denotes an acyl group with 1-10 carbon atoms, and W denotes hexavalent balance hexaazatetracyclo.

Sexuallytransmitted formula III, above, has the advantage, since the connection structure is simple and the connection can easily butterine connection can be easily purified by sublimation, so from the reaction mixture can be easily obtained highly refined WA6(A: acetyl group).

Another preferred example containing acyl group derived hexaazatetracyclo this invention is a compound represented by formula I-a, where t is equal to 4. This connection has the advantage, as contained in the N-H groups have high reactivity, which makes possible the selective interaction of the N-H groups. For example, by selective nitration of N-H groups can be easily obtained with high yield derived denitrogenization.

As mentioned above, containing acyl group derived hexaazatetracyclo according to this invention contains N-A group (where A denotes an acyl group), and optionally N-H group in high concentrations, where each of the N-A - N-H group may be converted into N-NO2group in various ways nitration.

The following examples describe how to obtain containing acyl group derived hexaazatetracyclo formula I-a.

Sexuallytransmitted WA6, which is the preferred sample containing acelerado acyl group derived hexaazatetracyclo WAnH(6-n)(where n is 4 or 5) allermuir agent, as shown in the following reaction scheme 1:

< / BR>
where n denotes an integer from 4 to 5, A represents an acyl group with 1-10 carbon atoms, H represents a hydrogen atom and W represents hexavalent balance hexaazatetracyclo.

WAnH(6-n)(where n is 4 or 5) used in the above reaction scheme 1, is not described in any literature that defines the prior art, and was originally synthesized by the present applicant. To explain the method of obtaining WAnH(6-n)initially, an explanation of the method of obtaining WA6.

In relation Alliluyeva agent used in the reaction scheme 1, there is no particular limitation except that it must be capable of acylation of the secondary amino group contained in WAnH(6-n)(where n is 4 or 5). Examples alleluya agents include acylhomoserine, as well as acetylchloride, acetylmuramic and propionitrile; esters of carboxylic acids and N-hydroxysuccinimide, such as N-acetoxystyrene, N-propionylcarnitine and N-(2-phenylacetate)succinimide; carboxylic anhydrides colorview acid; and illimitably, such as acetylimidazole and propylimidazol. Among the above-mentioned alleluya agents preferred acylhomoserine (such as acetylchloride, propionitrile and the like).

In respect of the reaction solvent used in the reaction scheme 1, there is no particular limitation except that the solvent must be capable of dissolving WAnH(6-n)(where n is 4 or 5) and the solvent should not adversely affect the reaction. Examples of such solvents include carboxylic acids such as acetic acid, propionic acid and lactic acid; aprotic polar solvents such as dimethylsulfoxide and dimethylacetamide; and anhydrides of carboxylic acids, such as acetic anhydride and propionic anhydride. Of them preferred anhydrides of carboxylic acids (such as acetic anhydride, propionic anhydride and the like). The above solvents may be used individually or in combination.

The reaction temperature for reaction scheme 1 usually corresponds to the interval from -10 to 300oC, preferably from 0 to 150oC.

WA6received by reactionally solvent from the reaction mixture after completion of the reaction (see, for example, example 1). Also, cleaning WA6can be done the conventional way. Examples of purification methods include a method in which a dedicated WA6sublimate at 270oC under reduced pressure of 10 mm RT.article (see, e.g., example 1); a method in which a dedicated WA6recrystallized from toluene (see, e.g., example 2), and the way in which the selected WA6recrystallized from chloroform.

WA6according to this invention can also be obtained recovery diarylethylenes derived hexaazatetracyclo containing acyl group and arylmethyl group represented by the formula WAnB(6-n)and then acylation of the resulting product allermuir agent, as shown in the following reaction scheme 2:

< / BR>
where n denotes an integer from 4 to 5; A represents an acyl group with 1-10 carbon atoms; B represents arylmethyl group represented by formula XIII below; H denotes a hydrogen atom and W represents hexavalent balance hexaazatetracyclo.

For WAnB(6-n)as source materials in the above reaction scheme 2, there is a special ograniczenia WAnB(6-n)obtained from hexacis(arylmethyl)hexaazatetracyclo (WB6) method, described below, or manufactured.

In the above reaction scheme 2 recovery diarylethylene (stage a) can be performed in any conventional manner conducive to the reaction of restorative diarylethylene WAnB(6-n). Usually the recovery diarylethylene (stage a) is carried out by contact WAnB(6-n)with regenerating catalyst in the presence of a reducing agent.

As the reducing agent, normally using gaseous hydrogen, hydrazine, formic acid or the like, and preferably using gaseous hydrogen. As a reducing catalyst typically use a catalyst containing a metal belonging to the platinum family, or derivatives containing these metals. Preferred examples of regenerating catalysts include compounds of Pd [such as Pd(OAc)2, PdCl2Pd(NO3)2, PdO, Pd(OH)2Pd3Pb1and Pd3Te1] Pd-Pd alloys and metal; and connections EN (such as RuCl3), EN-spline] , alloys of Pd and Pd metal. These regenerating catalysts can be used as such. Or else, these regenerating catalysts can be used in printed on various types of media form, on such media as activated carbon, silica, alumina, silica - alumina, zeolite, and activated clay. The catalyst prior to use in the above reaction rehabilitation diarylethylene may be subjected to recovery processing. In the case of the catalyst supported on a carrier, the acidity of the surface of the carrier can be controlled by inactivation of acid sites present on the surface of the carrier, similarobama, acylation or the like, or treatment media so that the alkaline substance (e.g., NaOH) was adsorbirovannoi on the surface of the carrier. The amount of the reducing catalyst vary depending on restoring the activity of the catalyst. Typically, however, the catalyst used is from 0.0001 to 10, preferably from 0.001 to 1 weight ratio of the metal catalyst to WAnB(6-n).

In respect of the reaction solvent used restriction, except that the solvent must be capable of dissolving WAnB(6-n)and the solvent should not have undesirable effects no reaction. Examples of solvents include carboxylic acids such as acetic acid, propionic acid and lactic acid; amide compounds such as dimethylacetamide and amino compounds, such as N,N-dimethylaniline. The above solvents may be used individually or in combination. From the point of view of achieving a high response speed, it is preferable to use a carboxylic acid (such as acetic acid, propionic acid or the like) as solvent.

The amount of solvent varies depending on its dissolving ability and reaction temperature. The solvent is used usually in an amount of from 1 to 500, preferably from 5 to 100, the values of the ratio of the weight of the solvent and WAnB(6-n).

The reaction pressure for the restoration diarylethylene (stage a) according to the method described in reaction scheme 2, is usually taken in the range from 0.1 to 1000 kgf/cm2preferably from 1 to 100 kgf/cm2. When the reducing agent is m2, more preferably from 1 to 100 kgf/cm2the values of partial pressure of hydrogen. In addition to gaseous hydrogen in the reaction system may contain an inert gas, such as nitrogen, argon or helium.

The reaction temperature for rehabilitation diarylethylene (stage a) according to the method described in reaction scheme 2, is typically in the range of from -20 to 300oC, preferably from 0 to 200oC.

The reaction time for recovery diarylethylene (stage a) according to the method described in reaction scheme 2, varies depending on the type of catalyst, solvent and the like. The reaction time is usually in the range from 0.1 to 500 hours, preferably from 1 to 200 hours.

Reaction rehabilitation diarylethylene (stage a) according to the method described in reaction scheme 2, synthesize WAnH(6-n)(where n is 4 or 5). Then the synthesized WAnH(6-n)acelerou (stage b) according to the method described in reaction scheme 2.

As for Alliluyeva agent, solvent, and reaction conditions such as reaction temperature and the like) used in the acylation (stage b is to reaction scheme 1 above.

Isolation and purification of the obtained WA6can be made in the manner specified above, for the reaction described in reaction scheme 1.

WA6one of the examples containing acyl group derived hexaazatetracyclo according to this invention, can also be obtained recovery diarylethylenes WB6in the presence of Alliluyeva agent in order to obtain a first reaction product, and then reducing diarylethylenes first reaction product in the absence of Alliluyeva agent to obtain the second reaction product and then acylation of the second reaction product, as shown in the following reaction scheme 3:

< / BR>
where n denotes an integer from 4 to 5; A represents an acyl group with 1-10 carbon atoms; B represents arylmethyl group, and W represents hexavalent balance hexaazatetracyclo.

Restorative diarylethylene in the presence Alliluyeva agent on a stage according to the method described in reaction scheme 3 above, usually performed by contacting WB6with regenerating catalyst in the presence of Alliluyeva agent and a reducing agent. Relatively VOSTOCHNOGO the reaction rehabilitation diarylethylene WB6and not inactivate allerease agent in the reaction system. As a restorative agent typically use hydrogen gas, formic acid or the like connection and it is preferable to use hydrogen gas. As a reducing catalyst can be used those compounds that are referred for rehabilitation diarylethylene (stage a) according to the method described in reaction scheme 2 above.

The amount of catalyst varies depending on restoring the activity of the catalyst. Regenerating the catalyst is used usually in amounts of from 0.0001 to 20, preferably from 0.001 to 10 values of the ratio of the weight of the metal catalyst to WB6.

In relation atsiliruyuscikh agent used in the recovery diarylethylene in the presence Alliluyeva means a stage according to the method described in reaction scheme 3, there are no particular limitations, except that it must be capable of acylation of the secondary amino group, formed by reduction diarylethylene WB6. Examples alleluya agents include esters of carboxylic acids N-hydroxide carboxylic acid, such as acetic anhydride, propionic anhydride, the anhydride of lactic acid and anhydride mixture of acetic and formic acids; and illimitably, such as acetylimidazole and propylimidazol. Among these alleluya agents preferred esters of carboxylic acids N-hydroxysuccinimide (such as N-acetoxystyrene, N-propionylcarnitine and the like), because they have a greater selectivity for WAnB(6-n)(where n is 4 or 5). These alleluya agents can be used individually or in combination. Especially preferred as Alliluyeva agent mixture of ester carboxylic acid N-hydroxysuccinimide (such as N-acetoxystyrene, N-propionylcarnitine or the like) and the carboxylic acid anhydride (such as acetic anhydride, propionic anhydride or the like), because not only the speed of response and restoration diarylethylene on stage a according to the method described in reaction scheme 3 becomes high, but also increases the selectivity for WAnB(6-n)(where n is 4 or 5).

The number Alliluyeva agent varies depending on the reactivity of illinoisaddrianne from 1 to 50, the values of the molar ratio Alliluyeva agent to arylmethyl groups WB6. As Alliluyeva agent, a mixture of ester carboxylic acid N-hydroxysuccinimide anhydride and carboxylic acid, the amount of carboxylic acid anhydride is usually in the range from 0.01 to 100, preferably from 0.1 to 10, the values of the molar ratio of carboxylic acid anhydride to the complex ether carboxylic acid N-hydroxysuccinimide.

In respect of the reaction solvent used in the recovery diarylethylene in the presence Alliluyeva agent at the stage and according to the method described in reaction scheme 3, there are no special restrictions with the exception that the solvent must be capable of dissolving WB6and the solvent must not exert undesirable influence on the reaction. Examples of the solvents include aromatic compounds such as benzene, toluene, ethylbenzene, xylene, cumene, zymol, diisopropylbenzene and phenethyl ether; cyclic, linear or branched ethers, such as tetrahydrofuran, dioxane, tetrahydropyran, diethyl ether, DIPROPYLENE ether and diisopropyl ether; and aliphatic JV is to be used individually or in combination. Among the above solvents, the preferred aromatic compounds (such as benzene, toluene, ethylbenzene, xylene and the like), because the speed of response and restoration diarylethylene WB6in these solvents increases.

The amount of solvent varies depending on the solvent capacity of the solvent and the reaction temperature. Typically, the solvent is used in an amount of from 0.1 to 100, preferably from 1 to 100, the values of the weight ratio of solvent to WB6.

The reaction pressure for the restoration diarylethylene (in the presence of Alliluyeva agent) on stage and according to the method described in reaction scheme 3, use is usually in the range from 0.1 to 1,000 kgf/cm2preferably from 1 to 300 kgf/cm2. When the recovery agent using gaseous hydrogen, in some cases, the reaction rate increases with increasing reaction pressure. The reaction pressure used is preferably in the range from 0.1 to 500 kgf/cm2, more preferably from 1 to 200 kgf/cm2in the values of partial pressure of hydrogen. In addition to gaseous hydrogen in the reaction system Monna temperature to restorative diarylethylene (in the presence of Alliluyeva agent) in the stage and on the way, the described reaction scheme 3, is typically in the range of from -20 to 300oC, preferably from 0 to 200oC.

According to the method described in reaction scheme 3, reaction of restorative diarylethylene (stage a) break off (upload) when WAnB(6-n)is formed in a substantial (significant) number. In particular, the course of the reaction of diarylethylene monitored by gas chromatography or liquid chromatography, and the reaction being removed when WAnB(6-n)formed in predetermined quantities.

The reaction time varies depending on the type of catalyst, Alliluyeva agent, solvent and the like. The reaction time is usually 0.1 to 500 hours, preferably 1-200 hours.

WAnB(6-n)(where n is 4 or 5) are synthesized by restorative diarylethylene (in the presence of Alliluyeva agent) in stage a by the method described in reaction scheme 2. Then the synthesized WAnB(6-n)put recovery diarylethylene (in the absence of Alliluyeva agent) in stage b according to the method described in reaction scheme 3.

As for the catalyst, a reducing agent, restwood in the recovery dearylation (in the absence of Alliluyeva agent) at stage b by the way the described reaction scheme 3, then you can use the same connection and the settings that you specify for the reaction of restorative diarylethylene (in the presence of Alliluyeva agent) on a stage according to the method described in reaction scheme 3.

Or, can be used catalyst, reducing agent, solvent and reaction conditions described for the recovery of diarylethylene in stage a by the method described in reaction scheme 2 above.

From the reaction mixture obtained recovery diarylethylenes (in the presence of Alliluyeva agent) on a stage according to the method described in reaction scheme 3, remove allerease agent and formed after removal Alliluyeva agent mixture is subjected to regenerative diarylethylene (in the absence of Alliluyeva agent) on stage b according to the method described in reaction scheme 3. In this case, it is preferable not to remove regenerating the catalyst and the solvent used in the recovery diarylethylene in stage a, and leave them in the reaction mixture obtained in the recovery diarylethylene in stage a and to use in situ (in place) in follow(in the absence of Alliluyeva agent) at stage b by the way the described reaction scheme 3, synthesize WAnH(6-n)(where n is 4 or 5), which is then acelerou on stage c according to the method described in reaction scheme 3.

As for Alliluyeva agent, solvent, and reaction conditions (reaction temperature and the like) used in the acylation stage c according to the method described in reaction scheme 3, can be used the same compounds and the parameters specified for the reaction of acylation by reaction scheme 1 above.

Received during the restoration diarylethylene the reaction mixture (in the absence of Alliluyeva agent) on stage b according to the method described in reaction scheme 3, above, may be subjected to in situ (in place) to acylation using Alliluyeva agent at the stage c according to the method described in reaction scheme 3. Or else, the reaction mixture obtained recovery diarylethylenes at the stage b, may be subjected to acylation at the stage c after removal from the reaction mixture of catalyst recovery and/or solvent.

Isolation and purification of the obtained WA6can be done in the manner specified for the reaction in the reaction is(6-n)in the presence of Alliluyeva agent, as shown in the following reaction scheme 4:

< / BR>
where n denotes an integer from 4 to 5, A represents an acyl group with 1-10 carbon atoms, B denotes arylmethyl group, and W represents a hexavalent balance hexaazatetracyclo.

As for the reducing agent, catalyst recovery, Alliluyeva agent, solvent, reaction conditions (e.g. reaction temperature, reaction pressure and the like), can be used the same compounds and the parameters that are specified for the reaction according to reaction scheme 9, below.

WA6can also be obtained recovery diarylethylenes WB6in the presence of Alliluyeva agent, as shown in the following reaction scheme 5:

< / BR>
where B denotes arylmethyl group, A denotes an acyl group with 1-10 carbon atoms, and W denotes hexavalent balance hexaazatetracyclo.

As for the reducing agent, catalyst recovery, Alliluyeva agent, solvent, reaction conditions and the like used in the reaction according to reaction scheme 5, above, they may be the same as onogo WA6can be conducted in the manner specified for the reaction according to reaction scheme 1 above.

As another example, derived hexaazatetracyclo containing acyl group, according to this invention may be mentioned a compound represented by the formula WAnH(6-n)(where n is 4 or 5) that receive recovery diarylethylenes WAnB(6-n)(where n is 4 or 5) in the absence of Alliluyeva agent, as shown in the following reaction scheme 6:

< / BR>
where n denotes an integer from 4 to 5, A represents an acyl group with 1-10 carbon atoms, B denotes arylmethyl group, and W represents hexavalent balance hexaazatetracyclo.

As for the reducing agent, catalyst recovery, solvent, reaction conditions and the like used in the reaction according to reaction scheme 6, above, there can be used the same as specified for stage a according to the method described in reaction scheme 2 above.

WAnH(6-n)obtained by the reaction in reaction scheme 6, can be allocated accepted way. For example, the selection can be made by the process comprising: adaleen filtering and obtaining thus the filtrate and distillation of the solvent from the resulting filtrate (see for example, example 5).

Containing acyl group derived hexaazatetracyclo WAnH(6-n)(where n is 4 or 5) according to this invention can also be obtained by

a) rehabilitation of diarylethylene WB6and then,

b) rehabilitation diarylethylene of the obtained product in the absence of Alliluyeva agent, as shown in the following reaction scheme 7:

< / BR>
where n denotes an integer from 4 to 5, A represents an acyl group with 1-10 carbon atoms, B denotes arylmethyl group, H represents a hydrogen atom and W represents hexavalent balance hexaazatetracyclo.

As for the reducing agent, catalyst recovery, Alliluyeva agent, the reaction conditions and the like used in the recovery diarylethylene (in the presence of Alliluyeva agent) in stage a by the method described above reaction scheme 7, it can be used the same as mentioned for stage a according to the method described in reaction scheme 3.

Through restorative diarylethylene (in the presence of Alliluyeva agent) on a stage in the manner described reaction the t recovery diarylethylene (in the absence of Alliluyeva agent) at stage b by the way the described reaction scheme 7.

As for the reducing agent, catalyst recovery, solvent, reaction conditions and the like used in the recovery diarylethylene (in the absence of Alliluyeva agent) on stage b according to the method described in reaction scheme 7, there can be used those mentioned for stage b according to the method described in reaction scheme 3 above.

The allocation received WAnH(6-n)can be done in the manner specified for the reaction described in reaction scheme 6, above.

WAnB(6-n), which is the starting material of the synthesis containing acyl group derived hexaazatetracyclo WAnH(6-n)according to this invention, can be obtained recovery diarylethylenes WB6in the presence of Alliluyeva agent, as shown in the following reaction scheme 8:

< / BR>
where n denotes an integer from 4 to 5, A represents an acyl group with 1-10 carbon atoms, B denotes arylmethyl group, and W represents hexavalent balance hexaazatetracyclo.

As for the reducing agent, catalyst recovery, Alliluyeva, that can be used are the same as specified for stage and according to the method described in reaction scheme 3 above.

WAnB(n-6)obtained by the reaction of scheme 8, can be selected by a common way. For example, the selection can be carried out by a method comprising: filtering the reaction mixture obtained in the recovery diarylethylene, using filter paper with the aim of separating the sludge and catalyst handling precipitate on filter paper chloroform order of dissolution in the sediment; the distillation of the solvent and chloroform from the filtrate to obtain a solid residue; dissolving the solid residue in chloroform to obtain a solution; adding to the resulting solution an aqueous solution of ammonia; the mixture is divided into the aqueous phase and the chloroform phase; separating the chloroform phase and the Stripping of the solvent from the chloroform phase (see e.g., example 19).

In the above reaction rehabilitation diarylethylene in the presence Alliluyeva agent flows adverse reaction in which N-acyl group, formed in the main reaction, is recovered on to the N-alkyl groups.

Thus, as indicated visualstate the following formula XII:

WAnQ(6-n)< / BR>
where n denotes an integer from 4 to 5, each Deputy A independently denotes an acyl group with 1-10 carbon atoms, each Q independently represents a hydrogen atom or alkyl group with 1-10 carbon atoms, provided that all Q are not simultaneously hydrogen atoms, and W denotes hexavalent balance hexaazatetracyclo, represented by the following formula II:

< / BR>
As mentioned above, containing N-alkyl group derived hexaazatetracyclo can be successfully used as a polyfunctional crosslinking agent.

Examples containing N-alkyl group of hexaazatetracyclo include diethylethylenediamine (WA4R2) obtained in examples 6-12, etilendiamintetraatsetata (WA5R1) obtained in examples 13 and 14, and monoesterification (WA4RH), shown in scheme [formula (12)], is given at the end of the description.

Containing N-alkyl group derived hexaazatetracyclo can be obtained recovery diarylethylenes WAnB(6-n)in the presence of Alliluyeva agent, as shown in the following reaction scheme 9:

The reaction rehabilitation diarylethylene in reaction scheme 9 above, mainly effective under the same conditions as specified for the reaction of restorative diarylethylene on stage and according to the method described in reaction scheme 2 above, with the exception that the reaction of scheme 9 is carried out in the presence of Alliluyeva agent.

In the reaction of restorative diarylethylene (in the presence of Alliluyeva agent) according to reaction scheme 9 mentioned for stage and according to the method described above reaction scheme 3, alleluya agents can be used in much the same way as described for this stage.

As for the solvent, catalyst recovery, Alliluyeva agent, the reaction conditions (e.g. reaction temperature and the reaction pressure and the like used in the reaction according to scheme 9, they may be the same as described for stage and according to the method described in reaction scheme 3 above.

WAnQ(6-n)can also be obtained recovery diarylethylenes WB6in the presence of Alliluyeva agent, as shown in the following reaction scheme 10:

< / BR>
where n denotes an integer from 4 to 5, A represents an acyl group with 1-10 carbon atoms, B denotes arylmethyl group, each Q independently represents a hydrogen atom or alkyl group with 1-10 carbon atoms, provided that all Q cannot simultaneously be hydrogen atoms, and W denotes hexavalent balance hexaazatetracyclo.

As for the solvent, catalyst recovery, Alliluyeva agent, the reaction conditions and the like used in the reaction according to scheme 10, there can be used those indicated for stage and according to the method described in reaction scheme 3 above.

The allocation received WAnQ(6-n)can be made in the manner specified for the reaction according to scheme 9 above.

IN WB6and WAnB(6-n)(where n is 4 or is the Republican derived hexaazatetracyclo according to this invention, arylmethylidene group, labeled B, is a methyl group, substituted aryl group, and usually contains 7-21 carbon atoms. Typical structure arylmethylidene group B depicts the following structural formula XIII:

-CH2Ar

where Ar denotes an aromatic group with 6-20 carbon atoms.

The number of carbon atoms in the Ar of the formula XIII above, is typically in the range of from 6 to 20, preferably from 6 to 10, most preferably is 6. Examples of Ar include phenyl group; alkylphenyl groups, such as tailgroup (o-, m-, and p-isomers), ethylenimine group (o-, m - and p-isomers) and cellgroup; alkoxyphenyl groups, such as metoksifenilny group (o-, m - and p-isomers), ethoxyphenyl group (o-, m - and p-isomers) and butoxyaniline group (o-, m - and p-isomers); and unsubstituted and substituted aftercrop. Of them, preferred phenyl group and alkoxyphenyl group. In each WB6and WAnB(6-n)(where n is 4 or 5) arylmethyl groups may be the same or different.

Containing acyl group derived hexaazatetracyclo according to this invention, denoted by the formula I: WAtQ(6-t)(where t is an integer Chi is the first feature of the methods of obtaining containing acyl group derived hexaazatetracyclo according to this invention, represented by reaction scheme 1, is that the reaction of restorative diarylethylene WB6carried out in the presence of Alliluyeva agent.

This interaction is described by the following reaction scheme 11:

< / BR>
where p denotes an integer from 1 to 5, t represents an integer from 4 to 6, B represents arylmethyl group, A denotes an acyl group with 1-10 carbon atoms, each Q independently represents a hydrogen atom or alkyl group with 1-10 carbon atoms, and W denotes hexavalent balance hexaazatetracyclo.

The molar ratio WApB(6-p)it WAtQ(6-t)in the reaction mixture obtained in the reaction according to scheme 11 above is usually from 0.001 to 1,000, preferably from 0.01 to 100.

As for the solvent, catalyst recovery, Alliluyeva agent, the reaction conditions and the like used in the reaction according to scheme 11, then you can use them the same as described above for reaction scheme 8.

During receipt containing acyl group derived hexaazatetracyclo according to this invention, represented by formula I-a, by restorative diarylethylene WB rehabilitation eliminowanie arylmethylidene group B, and b) formation of N-acyl groups with the acylation of the N-H group.

The above reaction scheme 11 indicates that WB6formed not only WApB(6-p)(where p denotes an integer from 1 to 5), but also WAnH(6-n)by further interaction WApB(6-p).

In reaction scheme 11, the reaction of restorative diarylethylene break off after getting the reaction mixture [containing WApB(6-p)and WAtQ(6-t))] of a given composition. In particular, the reaction of diarylethylene control using gas chromatography or liquid chromatography, and the reaction process after obtaining a reaction mixture having a given composition.

Below, the first is an explanation of the intended path of reaction scheme 11, and then explains about the usefulness and application of reaction scheme 11.

The assumed course of the reaction according to scheme 11 is described in detail in the scheme of [formula (12)], is given at the end of the description. Since N-alkyl group can be obtained by recovering (as a side reaction of the N-acyl group, whose recovery may occur depending on react is isano in the scheme of [formula (12)]. In the scheme of [formula (12)], A denotes an acyl group with 1-10 carbon atoms, B denotes arylmethyl group, R denotes an alkyl group with 1-10 carbon atoms, H represents a hydrogen atom and W represents hexavalent balance hexaazatetracyclo.

When the reaction according to scheme 11 is performed by way of periodic loading, the ratio of the obtained reaction products vary depending on the reaction time. When the reaction according to scheme 11 continuously way, the ratio of the resulting reaction products change depending on the time of contact. In addition, the ratio of the resulting reaction products may also vary depending on the types of catalyst and solvent, the reaction temperature and the like. So in reaction scheme 11, the ratio of the reaction products can be changed in the specified proportions by appropriate selection of reaction conditions.

The practical application of the reaction scheme 11 are described in detail below.

When trying to get containing acyl group derived hexaazatetracyclo according to this invention from WB6first restorative diarylethylenes and then acylation received WHnB(6-n)the specified product cannot be obtained with a high yield due to the decay of the W skeleton. It is assumed that the reason for this is that formed by restorative diarylethylene WB6in the absence of Alliluyeva agent containing a secondary amino group derived hexaazatetracyclo (such as WH5, WH2B4and WH3B3) structurally unstable. In contrast, the use of the method according to this invention, based on the reaction scheme 11, in which the recovery detailirohke WB6carried out in the presence of Alliluyeva agent containing acyl group derived hexaazatetracyclo can be synthesized without the destruction of the W skeleton. It is assumed that the reason for this is that in reaction scheme 11 unstable, containing a secondary amino group derived hexaazatetracyclo (such as WHB5and WH2B4) (which are obtained in the initial stage of the reaction) immediately allroots and thus stabilized in the reaction system, so that the decay of the W skeleton is suppressed, thus enabling the further course of diarylethylene and acylation.

As described the TES formula I-a can be synthesized at the initial stage, through rehabilitation diarylethylene WB6in the presence of Alliluyeva agent. However, when you try to perform the reaction in a single phase at the same time formed a number of reaction products and largely adverse reactions occur. The objective of the invention is to develop ways to solve these problems and get WAtH(6-t)(where t denotes an integer from 4 to 6), mainly in industrial scale, with high selectivity and high yield. As a result, found that when carrying out the above reaction schemes 8, 6 and 1 in the order listed, can be achieved very good results.

The following is a more detailed explanation of each of the reactions in schemes 8, 6 and 1.

I. Reaction scheme 8.

To obtain WAnB(6-n)high yield in the above reaction scheme 8 can be used in different ways. Examples of such methods include:

1) the method by which the types and amounts of reaction of the reactants are chosen so that the reaction rehabilitation diarylethylene can be interrupted before completion;

2) the method by which the course of the reaction rehabilitation diarylethylene control using gas chromatography or the Ute solvent, which is a good solvent for WB6but a poor solvent for WAnB(6-n)(for example, an aromatic compound such as benzene or toluene), in order to cause the deposition WAnB(6-n)obtained recovery diarylethylenes WB6from the reaction mixture.

The above methods 1), 2) and 3) fashion 3) the most profitable in industrial relations from the point of view of ease of operation.

In reaction scheme 8 to suppress side reactions with the aim of improving the selectivity in respect of the WAnB(6-n)it is advantageous to use as Alliluyeva agent is an ester of carboxylic acid N-hydroxysuccinimide, such as N-acetoxystyrene, or a mixture of ester carboxylic acid N-hydroxysuccinimide anhydride and carboxylic acid. When using this Alliluyeva agent can be improved not only the selectivity for WAnB(6-n)but also the output WAnB(6-n). The reason that selectivity for WAnB(6-n)improved by the use of ester carboxylic acid and N-hydroxysuccinimide as Alliluyeva agent is not yet installed. However, predpolagaete is hydroxysuccinimide and other allerease agents, such as the anhydride of carboxylic acid, is explained not only by differences in reactivity, but also the specificity of the substrate, due to steric constraints (including specific three-dimensional structure and volume) Alliluyeva agent.

The above fact, which is that the use of ester carboxylic acid N-hydroxysuccinimide as Alliluyeva agent significantly increases the selectivity for WAnB(6-n), was first established by the present applicants. This discovery is very important in the synthesis WAnB(6-n)on an industrial scale.

II. The reaction according to scheme 6.

When the recovery diarylethylene WAnB(6-n)obtained in the reaction according to scheme 8, is carried out in the presence of Alliluyeva agent for the purpose of synthesis WA6easily run side reactions such as the formation of N-alkyl in the recovery of N-acyl, so that it becomes difficult to synthesize WA6with high selectivity.

In contrast, when the recovery diarylethylene WAnB(6-n)carried out in the absence of Alliluyeva agent, as shown in reactivating diarylethylene proceeds with high selectivity. This phenomenon established by these applicants. From the reaction mixture obtained by the reaction of restorative diarylethylene scheme 6, by a simple selection operation can be obtained with high purity WAnH(6-n)high yield. Therefore, this reaction scheme 6 is very useful in the synthesis WAnH(6-n).

As mentioned above, if the reaction rehabilitation diarylethylene WB6in the absence of Alliluyeva agent obtained WHnB(6-n)(where n denotes an integer from 1 to 6) unstable in the reaction system, so that it is difficult to get a WHnB(6-n)high yield. In contrast, as mentioned above, WAnH(6-n)(where n denotes an integer from 4 to 5) is stable in the reaction system, so that WAnH(6-n)can be synthesized with high yield.

The reason WHnB(6-n)(where n denotes an integer from 1 to 6) and WAnH(6-n)(where n denotes an integer from 4 to 5) are different from other properties, it is still not clear. However, it is assumed that the difference in properties between arylmethylidene group B and acyl group causes A difference in stability between omanyte the difference in properties between WHnB(6-n)(where n denotes an integer from 1 to 6) and WAnH(6-n)(where n denotes an integer from 4 to 5) was first found by the present applicants. In addition, the connection hexaazatetracyclo represented by the formula WAnH(6-n)(where n denotes an integer from 4 to 5), nowhere in the literature are not described, and for the first time synthesized according to the method of the present applicants.

III. The reaction according to scheme 1.

As mentioned above in the section "prior art", WAnH(6-n)(where n denotes an integer from 4 to 5) as such can be successfully used as various functional compounds, such as the original connection for the derived printrequestattributeset and raw materials for highly polar polymer. If desired, WAnH(6-n)(where n denotes an integer from 4 to 5) can be easily transformed into WA6the reaction according to scheme 1.

WA6not described anywhere in the literature and was first synthesized by the present applicants. WA6you can also successfully be used as various functional compounds, as in the case of WAnH(6-n)(where n denotes an integer from 4 to 5).

Containing acyl group derived Huck is aloe number from 4 to 6) can be used as a starting compound in the reaction nitration with the aim of deriving printrequestattributeset.

The following explanation provides an example of how the reaction of nitration WAtH(6-t)(where t denotes an integer from 4 to 6) according to this invention with the aim of turning it N-H group and N-A-group N-NO2group.

N-H group group WAnH(6-n)(where n denotes an integer from 4 to 5) according to this invention can be converted into N-NO2group in various ways nitration. For example, WAnH(6-n)(where n denotes an integer from 4 to 5) can be easily transformed into WAn(NO2)(6-n)(where n denotes an integer from 4 to 5) in one stage. However, from the point of view of increasing the output of a given WAn(NO2)(6-n)preferably the conversion of N-H groups in N-NO2-group method includes two stages, as shown below in reaction scheme 13.

Schematically, as shown in reaction scheme 13 below, the N-H group WAnH(6-n)nitrosonium to N-NO group, and N-NO-group nitrous to N-NO2group, thereby WAn(NO2)(6-n).

< / BR>
where n denotes an integer from 4 to 5, A represents an acyl group with 1-10 carbon atoms, H represents a hydrogen atom, (NO) denotes nitrosopropane, (NO2) oboznachayuschego agent, used by the method of scheme 13, may be any nitrotyrosine agent, provided that he is able to nitrotyrosine WAnH(6-n)to WAn(NO)(6-n). Usually as nitrogenous agents use a mixture of sodium nitrite and acid; N2O4; nitrosylchloride and the like.

The reaction temperature of nitrosation is usually in the range from -50oC to 200oC, preferably from -30oC to 100oC, more preferably from -20oC to 50oC.

As the oxidizing agent used in the nitration reaction according to the method of scheme 13, can be used any oxidizing agent capable of oxidizing nitrosopropane to obtain the nitro-group. Typically, examples of oxidizing agents include nitric acid and hydrogen peroxide. Of them preferred nitric acid. These oxidizing agents may be used individually or in combination.

The temperature of the oxidation reaction is usually in the range from -50oC to 200oC, preferably from -30oC to 130oC, more preferably from -20oC to 60oC.

Also N-A-group WAtH(6-t)(where t denotes an integer from 4 to 6) according to this invention may b the TRC nitrogen, as is evident from example 21 (below). For example, WA6can be turned into a derived printrequestattributeset, such as WA4(NO2)2various methods of nitration, for example using a mixture of nitric acid and nitrogen pentoxide as nitrouse agent.

Next, as shown in reaction scheme 14 below various derivatives hexaazatetracyclo represented by the formula WAnE(6-n)you can netravati to get hexanitrohexaazaisowurtzitane [W(NO2)6].

< / BR>
where n denotes an integer from 4 to 6, A denotes an acyl group with 1-10 carbon atoms, E represents nitrosourea or nitrogroup and W denotes hexavalent balance hexaazatetracyclo.

As nitrouse agent used in the conversion of N-A-group WAnE(6-n)N-NO2group may be any nitrouse agent capable of converting N-A-group N-NO2-group. For example, can be used in a variety nitrouse agents containing nitric acid. Illustrative examples nitrous agents include nitrous agents containing strong proton acid, such as nitric acid/sulfuric-acid nitro temperature for the reaction according to scheme 14 is typically in the range from -50oC to 120oC, preferably from -20oC to 60oC.

The reaction time for the reaction according to scheme 14 is usually 0.1 to 500 hours, preferably 1-200 hours.

As described above, the N-H group and N-A-band W-skeleton are functional groups that can easily be converted into nitro. Therefore, using WAtH(6-t)(where t denotes an integer from 4 to 6) as an intermediate product, you can get various derivative printrequestattributeset with high output.

As can be seen from the above, this invention provides a method of obtaining hexanitrohexaazaisowurtzitane, represented by the following formula IX:

W(NO2)6< / BR>
where NO2denotes the nitrogroup and W denotes hexavalent balance genasauria, represented by the following formula II:

< / BR>
which includes nitration nitrous agent at least one compound selected from the group consisting of compounds respectively represented by the following formula:

formula III

WA6< / BR>
where each A is independently denotes an acyl group with 1-10 carbon atoms, and W is as defined above,

formula IV W - such as defined above,

formula VII

WAn(NO)(6-n)< / BR>
where NO denotes nitrosopropane and each of n, A and W, as defined above, and

formula VIII

WAn(NO2)(6-n)< / BR>
where each of n, A, NO2and W is such as defined above.

Derived printrequestattributeset obtained from containing acyl group derived hexaazatetracyclo according to this invention, can be successfully used as additives to modify the properties of rocket fuel and explosives, such as mechanical properties, velocity of detonation, detonation pressure, burning rate, rate pressure sensitivity, heat resistance and the like, as well as substances with high performance for explosives.

The advantages derived printrequestattributeset obtained from containing acyl group derived hexaazatetracyclo according to this invention.

For example, WA4(NO2)2has the following primary properties:

1) WA4(NO2)2has the same molecular structure as the structure of vzryvchatomu, as HNW an intimate (hereinafter denoted for simplicity "HMX"), and RDX (hereinafter denoted for simplicity, "RDX"), and has excellent thermal stability in comparison with HNW, HMX and RDX. [Even when WA4(NO2)2used as additives to rocket fuel or explosive compounds, there is no danger that it will significantly reduce the heat resistance of rocket fuel and explosives].

2) In contrast to the above nitrobenzoate (i.e., HNW, HMX and RDX) WA4(NO2)2contains in its skeleton, not only N-nitrogroup, but also N-A-group, which has a high affinity for binding substance, such as polyurethane.

Adding WA4(NO2)2with the above-mentioned advantages in the properties for rocket fuel or explosive compounds containing nitrobenzoate (such as HNW, HMX, RDX, or the like) and a binder, such as polyurethane, it is possible to improve adhesion between the solid component (i.e. nitrobenzenediazonium) and a binder.

WA4(NO2)2can easily be turned into HNW by nitration, so it is useful as sys for explosives with high performance and nudemassage rocket fuel.

Interaction tetrachloroazobenzene WA4H2this invention derived from dicarboxylic acids, such as galoyanized dicarboxylic acid or complex fluids dicarboxylic acid, it is possible to obtain a highly polar polymer having a skeleton hexaazatetracyclo in the main chain.

In the synthesis containing acyl group derived hexaazatetracyclo WAnH(6-n)(where n denotes an integer from 4 to 6) according to this invention using Alliluyeva agent having a specific functional group can be obtained capable of crosslinked policyregistration.

WAnH(6-n)(where n denotes an integer from 4 to 6) according to this invention, by itself, can be used as additives, such as polymer modifier.

Schema transformations, showing the preferred embodiment of the methods of preparation, are included in this invention are given to the end of the description.

As can be seen from the schema transformations containing acyl group derived hexaazatetracyclo WAtQ(6-t)(where W denotes hexavalent balance hexaazatetracyclo, each Q independently is t to be obtained from hexacis(arylmethyl)hexaazatetracyclo WB6(where W is accepted above designations and B represents C7-C21-arylmethyl group), directly or through containing acyl group and arylmethyl group derived hexaazatetracyclo WAnB(6-n)(where W and B are such as defined above and n is 4 or 5) or WApB(6-p)(where W and B are such as defined above and p is from 1 to 5). Containing acyl group derived hexaazatetracyclo WAtQ(6-t)(where W, A, Q and t are such as defined above) can easily be turned into hexanitrohexaazaisowurtzitane W(NO2)6(where W is the same as defined above) with high output directly, or through containing nitrosourea derived hexaazatetracyclo WAn(NO)(6-n)(where W and A are as defined above and n is 4 or 5) and/or containing a nitro-group is derived hexaazatetracyclo WAn(NO2)(6-n)(where W and A are such as defined above and n is 4 or 5).

Below the invention is described in more detail in the examples and the comparison examples, which should not be considered as limiting the scope of the present invention and attached items.

Various measurements were carried out in the following ways:

(1) H-NMR:

iovlen and implemented JEOL LTD, Japan).

(3)13C1H COSY NMR:13-1H correlation shift:

used JNM-GX-400. In this way measure the interaction between13C and1H. In this way, when you identify the peak related to either13C, or1H, we can determine the chemical shift or1H, chemically associated with13C, or13C having chemically associated1H.

(4) EI (electron impact) mass spectrometry: use HP 5790B (manufactured and implemented by Hewlett-Packard Company, USA).

(5) GC (gas chromatography-mass spectrometry:

1) use a HP5890A (manufactured and implemented by Hewlett-Packard Company, USA).

2) column: metal capillary column, 0.25 mm (inner diameter) x 15 mm, Ultra ALLOY (HT) (column for use in elevated temperatures), the thickness of the film coating on the inner wall of the capillary: 1,15 mm.

3) temperature: column; use high temperature from 100oC to 340oC at a rate of temperature increase of 20oC/min, and keep the temperature at 340oC for 20 min,

output: 340oC,

GM/MS connection: 340oC,

4) carrier gas: helium (flow rate entering PR, sportsouth JEOL HX-110 (manufactured and implemented JEOL LTD., Japan). Sample a few mg are dissolved in approximately 10 μl of methanol to obtain a solution. A few µl of the resulting solution is applied to the emitter and provide measurements.

(7) Infrared absorption spectrometry.

The measurements are carried out by way KBr-pellets using FT/IR-5M (manufactured and implemented by Japan Spectroscopic Co., Ltd., Japan).

(8) Differential scanning calorimeter (DSC). Use DSC-220 (manufactured and implemented Seiko Instruments Inc., Japan).

(9) Liquid chromatography high performance.

The measurements are carried out under the following conditions using the following equipment:

1) Hardware: 610 ISOCRATIC System (manufactured and implemented Waters Assoc. Co., USA):

600 controller,

600E pump,

486 - adjustable absorption detector.

2) Column: / -Bondasphere (manufactured and implemented Waters Assoc. Co. (USA)):

particle diameter 5 μm,

the fill material C18,

pore size 100 ,

column size 3.9 mm x 15 cm

3) Liquid mobile phase: acetonitrile/water 60/40.

4) Volumetric flow rate: 0.5 ml/min

5) column Temperature: 40oC.

To bring the example 1. Synthesis WA6the acetylation WA4H2.

1.0 g (2,98 mmol) tetraazacyclotetradecane dissolved in 100 ml of acetic anhydride. To the resulting solution was added 5 g (of 63.7 mmol) acetylchloride and the resulting mixture is stirred for 1 hour for reaction. Then the solvent is distilled off under reduced pressure from the resulting reaction mixture to obtain a residue. The resulting residue is dissolved in ethyl acetate. To the resulting solution was added hexane to obtain a precipitate, representing the white mass hexaazatrinaphthylene (1,16 g; yield: 93%).

Received sexualitysexuality placed in sublimator and then the device is immersed in an oil bath at 270oC. it was determined that sexualitysexuality sublimates under reduced pressure (10 mm RT.cent.).

Below are the results of the analysis hexaazatetracyclo.

The results of the PMR [solvent: CDCl3; standard: tetramethylsilane was (hereinafter labelled as conventional, "TMS"); temperature measurement: 60oC; units: (M. D.)]:

is 2.05 (s, 6H, COCH3), and 2.14 (s, 6H, COCH3), is 2.41 (s, 6H, COCH3), 6.42 per (s, 2H, CH), 6.48 in (s, 2H, CH) and 6,94 (d, 2H, CH).

TMR UB>; standard: TMS: units (M. D. )]:

20,74 (CH3), 21,55 (CH3), 61,09 (CH), 66,55 (CH), 72,17 (CH), 167,60 (C= O), 168,31 (C=O) and 169,79 (C=O).

Method13C-NMR identified the carbon atom of the methyl group and the carbon atom of the carbonyl group, both groups belong to the acetyl group, and the carbon atoms of the W skeleton.

Method13C1H COSY, can be identified13C associated with1H, identified above TMR.

The results of EI-mass spectrometry (m denotes the molecular weight of the parent molecule):

420 (5%, m/z) 377 [5%, (m minus molecular weight COCH3)/z], 335 (10%), 295 (15%), 208 (12%), 165 (10%), 123 (12%) and 43 (100%, COCH3).

Method EI-mass spectrometry identify the source ion peak (420) hexaazatrinaphthylene, ion peak (377), attributed to the residual molecule, the structure of which is presumably formed by the removal of acetyl groups from the original molecule, and ion peak (43), relating to the acetyl group.

The results of infrared absorption spectrometry KBr-way show the absorbance around 1660 cm-1where the absorption attributed to the variations in the stretching of the carbonyl group (C=O), a member of the acetyl group.

Example 2. Sin,11 mmol) Pd(OAc)2as a catalyst recovery and 150 ml of acetic acid contribute together with the mixing element 300 ml microbomb. The bomb blow nitrogen gas. Then the bomb injected hydrogen gas so that the internal pressure in the bomb was 5 kgf/cm2- G, and then the contents of the bomb is stirred for 15 hours to perform the reaction. The resulting reaction mixture was removed from the bomb and filtered to remove the catalyst. Then, the resulting filtrate is distilled under reduced pressure for removal of the solvent, thus obtaining a solid residue. The resulting solid residue was washed with 100 ml of ethyl acetate. The obtained white solid residue is dissolved in 200 ml of acetic anhydride. To the resulting solution was added 5 g (of 63.7 mmol) acetylchloride and the resulting mixture is stirred for 1 hour. Then the solvent is distilled off under reduced pressure from the reaction mixture. The resulting residue is recrystallized from toluene, getting 2,09 g hexaazatrinaphthylene in the form of a white mass (yield, 70%).

Example 3. Synthesis WA6from WA4B2in which the reaction mixture obtained recovery diarylethylenes put in place acetylation without at illegalization carried out basically in the same way, as in example 2, thus obtaining the reaction mixture containing the catalyst and recovery of the solvent. To the reaction mixture are added 5 g (of 63.7 mmol) acetylchloride (acetylide agent) and the resulting reaction mixture is stirred for 3 hours for reaction. The resulting reaction mixture is filtered, thereby removing catalyst. The resulting filtrate is distilled under reduced pressure for removal of the solvent. The resulting solid residue is recrystallized from toluene, thus obtaining 1.92 g hexaazatrinaphthylene in the form of a white mass (yield: 64%).

Example 4. Synthesis WA6from WB6.

1.89 g (2,66 mmol) hexabenzylhexaazaisowurtzitane, 1.70 g (1,60 mg-atom) Pd-C (Pd content: 10%) as catalyst recovery, 5.0 g (of 31.8 mmol) N-acetoxystyrene (acetylide agent), 160 ml of ethylbenzene or 3.24 g (of 31.8 mmol) of acetic anhydride (acetylide agent) contribute, together with the mixing element 300 ml microbomb. The bomb blow gaseous hydrogen. Then hydrogen gas is fed to the bomb so that the internal pressure in the bomb was 10 kgf/cm2- G, and then the bomb is immersed in an oil bath at 60oC. Then the contents of the bomb peroratory. Then the reaction mixture containing WAnB(6-n)(where n is 4 or 5), in the form of sediment removed from the bomb and filtered to separate by filtering sediment and catalyst recovery. The precipitate extracted catalyst recovery and 50 ml of acetic acid as solvent make 300 ml of microbomb. In the bomb serves hydrogen gas so that the internal pressure in the bomb was 5 kgf/cm2- G, and the contents of the bomb is stirred for 20 hours for reaction. After completion of the reaction to the resulting reaction mixture is added 5 g (of 63.7 mmol) acetylchloride and the mixture is stirred for 1 hour. The resulting mixture is distilled under reduced pressure for removal of the solvent, thus obtaining a solid residue. To the resulting solid residue is added 200 ml of chloroform, so that the solid residue containing mainly WA6was dissolved in chloroform. The resulting solution is filtered to remove catalyst. The resulting filtrate is distilled under reduced pressure, driving thus the solvent. The resulting residue is recrystallized from toluene, receiving 0.50 g hexaazatrinaphthylene (yield: 45%) as a white mass.

Example 5. Synthesis WAn
B(6-n)(where n is 4 or 5). After completion of the reaction, the reaction mixture containing the precipitate are then removed from the bomb and filtered using filter paper to filter sediment and catalyst recovery. The precipitate on filter paper treated on site 200 ml of chloroform to dissolve the sediment in it. The filtrate (containing chloroform, used for processing) is distilled with the purpose of removal of the solvent (benzene and chloroform). The obtained solid residue is dissolved in 200 ml of chloroform to obtain a solution. To the solution was added aqueous 28% solution of ammonia and the resulting mixture vigorously stirred for 30 minutes so that the reaction mixture was distributed between water phase and the chloroform phase, where N is acetoxystyrene decomposes and goes into the aqueous phase. The chloroform phase is separated and distilled, fending off the solvent (chloroform). The resulting white solid residue was dissolved in 50 ml of acetic acid. To the resulting solution was added 0.6 g (2,66 mmol) of Pd(OAc)2as a catalyst for recovery. The solution containing the catalyst recovery, make 100 ml - microbomb. The bomb is filled g who're asked for 20 hours of reaction (by this time, the output hexaazatrinaphthylene is 0.3% according to gas chromatography). To the reaction mixture are added 5 g (of 63.7 mmol) acetylchloride and the resulting mixture is stirred for 1 hour. After which the solvent (acetic acid) is distilled off from the mixture, obtaining a solid residue. To the resulting solid residue is added 200 ml of chloroform. The resulting solution is filtered to remove catalyst. The remaining filtrate is distilled, fending off the solvent and thus obtaining a solid residue. The obtained solid residue is recrystallized from toluene, getting 0.39 g hexaazatrinaphthylene (yield: 35%).

This means that the connection hexaazatetracyclo containing a secondary amino group, such as tetraacetylethylenediamine and pentaerythritol, was formed to add acetylchloride and that such compounds containing a secondary amino group, turned into sexualitysexuality adding acetylchloride.

Example 6. Synthesis WA4Et2(where Et denotes the ethyl group) from WA4B2.

0.50 g (0.97 mmol) tetraacetylethylenediamine, 0.21 g (0.19 mg-atom) Pd-C (Pd content: 10%) as catalyst recovery, 2.37 g (23,3 mmol) acetic anhydride (acetylide agent) and 50 ml of gorodom. Then hydrogen gas is introduced into the bomb so that the internal pressure of the bomb was 50 kgf/cm2- G. Then the contents of the bomb is stirred for 15 hours for reaction. After completion of the reaction the reaction mixture is removed from the bomb and filtered by filtering out the catalyst recovery. The resulting filtrate is distilled away so the solvent (acetic acid). The resulting solid residue periostat from a mixture of chloroform and hexane to clean, thus obtaining diethylethylenediamine. The reaction conditions and the output is given in the table.

The results diethylethylenediamine below.

The results of EI-mass spectrometry:

392 (1%, m/z), 278 (1%), 236 (10%), 193 (25%), 138 (30%), 109 (45%), 97 (20%), 81 (81%), 69 (60%), 56 (20%), 43 (100%, COCH3), 29 (20%, CH2CH3), 28 (52%) and 15 (20%, CH3).

Method EI-mass spectrometry identify the source ion peak (392) tetraacetylethylenediamine, ion peak (43) acetyl group, and the ion peak (29) ethyl group.

The results of the PMR-spectrometry [solvent: CDCl3; standard: TMS; unit: (M. D.)]:

1,25 (so-6H, CH3ethyl group), and 2.14 (s, 12H, COCH3

Examples 7-12. Synthesis WA6and WA4R2and WA4B2restorative diarylethylenes in the presence Alliluyeva agent and study the changes in the qualitative relations obtained WA6to the resulting WA4R2depending on the reaction conditions.

In examples 7-12 interaction is carried out in basically the same way as in example 6, except that vary the type and number of Alliluyeva agent, type of solvent, type and amount of catalyst, hydrogen pressure and reaction time. The reaction conditions and the yields of products of the reaction are shown in the table.

As shown in the table, to get hexaazatrinaphthylene and diethylethylenediamine can be used in a variety of catalysts.

Example 13. The synthesis of various derivatives hexaazatetracyclo containing acetyl group, such as WA4B2and WA5B, recovery diarylethylenes WB6in the presence of Alliluyeva agent.

Restorative dibenzylamine hexabenzylhexaazaisowurtzitane in the presence acetylides agent is carried out in the OS which is 50 kgf/cm2the reaction temperature is room temperature and the reaction time is 200 hours.

After completion of the reaction the analysis of the reaction products in the reaction mixture is conducted by a method GC-mass spectrometry. As a result, found that the reaction mixture contains the following connections: tetraacetylethylenediamine, pentaerythritoltetranitrate, sexualitysexuality, etilendiamintetraatsetata, diethylethylenediamine. The output of each of the above compounds is determined by gas chromatography. As a result, the output of each of the compounds was: tetraacetylethylenediamine - 70%; pentaerythritoltetranitrate - 6,2%; hexaazatrinaphthylene - 0,9%; etilendiamintetraatsetata - 1.3% and diethylethylenediamine - 1,1%.

The results of EI-mass spectrometry for these compounds are as follows.

The results of EI-mass spectrometry pentaerythritoltetranitrate:

468 (2%, m/z), 425 (3%, [m minus molecular weight COCH3]/z), 255 (12%), 91 (66%, CH2Ph) and 43 (100%, COCH3).

The results of EI-mass spectrometry ethylphenylacetylene is), 29 (15%, CH2CH3) and 15 (8%, CH3).

The results of EI-mass spectrometry diethylethylenediamine:

392 (1%, m/z), 278 (1%), 236 (10%), 193 (25%), 138 (30%), 109 (45%), 97 (20%), 81 (81%), 69 (60%), 56 (20%), 43 (100%, COCH3), 29 (20%, CH2CH3), 28 (52%) and 15 (20%, CH3).

The results of EI-mass spectrometry hexaazatrinaphthylene:

420 (5%, m/z) 377 (5%, [m minus molecular weight COCH3]/z), 335 (10%), 295 (15%), 208 (12%), 165 (10%), 123 (12%) and 43 (100%, COCH3).

Example 14. Restorative diarylethylene WB6in the presence of Alliluyeva agent using only the anhydride of carboxylic acid as Alliluyeva agent without the use of ester carboxylic acid N-hydroxysuccinimide as Alliluyeva agent.

Restorative dibenzylamine carried out mainly by the method according to example 13, except that only use 32,4 g of acetic anhydride as Alliluyeva agent without the use of N-acetoxystyrene. During the reaction a sample is taken of the reaction mixture. The composition of the sample analyzed by FD-mass spectrometry. As a result, found that the sample contains as intermediates of diacetylethylenediamine is in connection with at least one acetyl group, split when restoring, etilditsiklogeksilbenzolov (M+550), utilitieselectricity (M+502) and Diethyldithiophosphoric (M+486).

Upon completion of the reaction, the output of each of the reaction products formed in the reaction mixture is measured by gas chromatography. In the result, the output of each of the reaction products is as follows:

treaclytrebu.exactpages.com: 13%;

etilditsiklogeksilbenzolov: 3,1%;

tetraacetylethylenediamine: 7,5%;

ethyltrimethoxysilane: 32%;

diethyldiethylenetriamine: 30%;

pentaerythritoltetranitrate: 1,6%;

ateliereenarchitecten: 1,1%;

diethylthiadicarbocyanine: 6,2%;

hexaazatrinaphthylene: 0,5%;

etilendiamintetraatsetata: 1.2% and

diethylethylenediamine: 1,1%.

The above results show that without the use of ester carboxylic acid and N-hydroxysuccinimide as Alliluyeva agent when recovered shall diarylethylene WB6in the presence of Alliluyeva agent using only N-acetoxystyrene as Alliluyeva agent.

Restorative dibenzylamine carried out basically according to the method of example 13, except that as Alliluyeva agent using 7.5 g N-acetoxystyrene without the use of acetic anhydride. During the reaction are selected samples of the reaction mixture. The composition of the sample analyzed FD-mass spectrometry. As a result, found that the sample contains intermediate compounds, pentamethylcyclopentadiene ([M+H]+619), acetylethylenediamine (M+660), diacetylethylenediamine (M+612) and createtimerqueuetimer (M+564). After completion of the reaction, the yield of each reaction product was measured by gas chromatography. The output of each of the reaction products following: diacetylethylenediamine: 74%;

treaclytrebu.exactpages.com: 15%;

tetraacetylethylenediamine: 3%.

the above results show that when using only an ester of carboxylic acid and N-hydroxysuccinimide as Alliluyeva agent in Vosstanie group WAnB6-n(in which n denotes an integer from 1 to 4) to the alkyl group in the course of successive diarylethylene WB6to WAnB6-n(where n denotes an integer from 1 to 5). However, the results also show that the reaction rate of the above reaction is lower than the rate of the reaction conducted using as Alliluyeva agent mixture of ester of carboxylic acid and N-hydroxysuccinimide anhydride and carboxylic acids.

Example 16. Synthesis WA4H2from WA4B2.

to 3.67 g (7,11 mmol) tetraacetylethylenediamine, 1,60 g (7,11 mmol) of Pd(OAc)2as a catalyst recovery and 150 ml of acetic acid as solvent contribute together with the mixing element 300 ml microbomb and the bomb blow nitrogen gas. Then the bomb is filled with gaseous hydrogen so that the pressure inside the bomb was 5 kgf/cm2- G, and then the contents of the bomb is stirred for 15 hours for reaction. Retrieved from microbomb the reaction mixture is filtered to filter the catalyst. The resulting filtrate is distilled for removal of the solvent under reduced pressure. The resulting solid residue : 71%).

The results obtained tetraazacyclotetradecane the following.

The results of the PMR-spectrometry [solvent: D2O; standard: TMS; unit: (M. D.)]:

to 1.98 (s, 6H, COCH3), from 2.00 (s, 6H, COCH3), from 5.29 (m, 2H, CH), 5,50 (m, 2H, CH) and 6.35 (m, 2H, CH).

PMR can be identified methine group of the W skeleton and 4 acetyl group.

The results of IR-spectrometry are two peaks of absorption in the region 3300-3400 cm-1, each of which refers to the stretching vibrations of the secondary amino group (N-H) and, in addition, the absorption around 1660 cm-1attributed to the stretching vibrations of the carbonyl group (C=O) acetyl group. The above results show that W-skeleton contains as Vice-acetyl group and N-H groups.

Example 17. Synthesis WA4H2from WA4B2conducted using a catalyst other than the catalyst used in example 16, the reaction temperature different from the temperature used in example 16.

1.20 g (2,33 mmol) tetraacetylethylenediamine, 0,496 g (0,466 mol) Pd-C (Pd/content 10%) as a reaction catalyst and 60 ml of acetic acid (solvent) vocab hydrogen gas, so that the internal pressure of the bomb was 3 kgf/cm2- G, and then microbomb immersed in an oil bath at 40oC. Then the contents of microbomb stirred for 5 hours using a stirring for reaction. The reaction mixture is removed from microbomb and filtered by filtering out the catalyst. The resulting filtrate is distilled under reduced pressure, fending off the solvent. The resulting solid precipitate was washed with 100 ml of ethyl acetate, thus obtaining 0,57 g tetraazacyclotetradecane as a white mass.

The above results show that even when the reaction is carried out using a catalyst different from the one used in example 16 at a temperature different from the temperature used in example 16, the same as in example 16, get WA4H2.

Example 18. Proof of education WAnH(6-n)during restoration diarylethylene WB6in the presence of Alliluyeva agent.

Restorative dibenzylamine hexabenzylhexaazaisowurtzitane in the presence acetylurea agents carried out basically according to the method of example 4, except that the reaction time is 200 hours. Upon completion of the reaction reaccession is only 0.8%. On the other hand, tetraazacyclotetradecane (WA4H2) identified liquid chromatography high performance. To the above reaction mixture add acetylchloride and then the resulting mixture is stirred for 1 hour for reaction. The reaction mixture is analyzed by gas chromatography. The results of the analysis show that the output hexaazatrinaphthylene is 5%. It also confirms that WA4H(6-n)such as tetraacetylethylenediamine and pentaerythritol, was present in the reaction system to add acetylchloride.

Example 19. Synthesis WA4B2through restorative diarylethylene WB6in the presence of Alliluyeva agent.

1.89 g (2,66 mmol) hexabenzylhexaazaisowurtzitane, 1.70 g (1.6 mg-atom) Pd-C (Pd content: 10%) as catalyst recovery, 5.0 g (of 31.8 mmol) N-acetoxystyrene (acetylide agent), 160 ml of benzene (solvent) or 3.24 g (of 31.8 mmol) of acetic anhydride (acetylide agent) contribute, together with the mixing element 300 ml microbomb. The bomb blow gaseous hydrogen. Then, hydrogen gas enter wasow, using the mixer to the reaction. The resulting reaction mixture was removed from the bomb and filtered using filter paper to filter out the sludge and catalyst recovery. The precipitate on filter paper treated on site 200 ml of chloroform, precipitate dissolving in it. The filtrate (containing used for the treatment of chloroform) is distilled for removal of the solvent. The resulting solid residue is dissolved in 200 ml of chloroform, obtaining the solution. To the solution was added 200 ml of aqueous 28% ammonia solution and the resulting mixture vigorously stirred for 30 minutes so that the reaction mixture be divided into two phases: water and chloroformate phase, with N-acetoxystyrene decomposes and goes into the aqueous phase. The chloroform phase is separated and distilled with the purpose of removal of the solvent, thus obtaining 1.29 g of a white solid residue. The obtained white solid residue is recrystallized from ethyl benzene, getting 1,03 g tetraacetylethylenediamine (yield: 75%). The following results of the analysis by FD-mass spectrometry, PMR,13C-NMR and13C1H COSY, we can conclude that white mass obtained by recrystallization, is the SS-spectrum: 517 ([M+H]+).

PMR-spectrum [solvent: CDCl3; standard: TMS; unit: (M. D.)]:

of 1.94 (s, 6H, COCH3), of 2.15 (s, 6H, COCH3), 4,06 (d, 2H, CH2), the 4.29 (d, 2H, CH2), 5,09 (d, 2H, CH), 5,70 (d, 2H, CH), 6.42 per (s, 2H, CH) and 7.3-7.5 (m, 10H, P).

By TMR identified 6 marinovich groups of the W skeleton, 4 acetyl group and 2 of benzyl group.

13C-NMR [solvent: CDCl3; standard: TMS; unit: (M. D.)]:

20,737 (CH3), 22,111 (CH3), 56,428 (CH2), 69,679 (CH), 70,592 (CH), 128,056 (Ph), 128,673 (Ph), 128,928 (Ph), 136,742 (Ph) and 168,263 (CO).

Using13C-NMR identify methine group of the W skeleton, acetyl group, phenyl group and methyl group, benzyl group.

By1H13C COSY can be identified13C associated with1H.

Example 20. Synthesis WA4(NO2)2nitrotyrosine WA4H2to obtain WA4(NO)2and oxidation WA4(NO)2.

0,336 g (1 mmol) tetraazacyclotetradecane and 10 ml of 50% acetic acid as solvent to make 100 ml reaction flask. The resulting mixture is cooled and maintained at 0oC. While stirring the mixture at 0oC to the mixture gradually added dropwise 2 ml of the live at the 30oC and then stirred for 4 hours for reaction of nitrosation. To the resulting reaction mixture is added 50 ml of chloroform. The resulting mixture was vigorously stirred and then left to stand, the mixture was separated into an organic phase and inorganic phase. The organic phase is separated and the solvent is distilled off under reduced pressure from the organic phase, receiving 0,373 g dinitrosopentamethylenetetramine (yield: 95%).

30 ml of 100% nitric acid (oxidizing agent) to make 100 ml reaction flask. Then the reaction flask add 0,9262 g (2,35 mmol) of the above-mentioned dinitrosopentamethylenetetramine. The resulting mixture was stirred at room temperature for 5 hours for reaction nitration. Then the resulting mixture is distilled under reduced pressure for distillation of nitric acid, thus obtaining 0,955 g dinitrotetraaminecobalt (yield: 95%).

The results are obtained dinitrosopentamethylenetetramine the following.

The results of the PMR [solvent: CDCl3; standard: TMS; unit: (M. D.)]:

is 2.05 (s, 6H, COCH3), 2,17 (s, 6H, COCH3), 5,46 (m, 2H, CH), 6,62 (m, 2H, CH) and 7,30 (s, 2H, CH).

With the aid of ogladanie in the area of 1,670 cm-1where the absorption corresponds to a carbonyl group (C=O) acetyl group, and absorption in the region of 1,500 cm-1, 1,380 cm-1and 1,350 cm-1where each absorption refers to nitrosopropane.

The results of IR suggest that the uptake of describing the N-H group identified in the IR spectrum tetraazacyclotetradecane, completely disappears.

Further analyses dinitrotetraaminecobalt below.

The results of the PMR [solvent: DMCO-d6standard: TMS: unit: (M. D.)] :

of 2.10 (s, 12H, COCH3), to 6.75 (m, 2H, CH) and 7.35 (this peak is a singlet peak (maximum) during 7,35 M. D. and shoulder moved into the region of low magnetic field peaks singlet peak, 4H, CH).

The results of IR give the region the absorption 1,680 cm-1where absorption refers to the oscillation of the stretching of the carbonyl group (C=O) acetyl group, as well as acquisitions in the area of 1,570 cm-1and 1,300 cm-1where each of acquisitions refers to the variations in tension of the nitro group. This shows that the nitro-group and acetyl group are substituents of the W skeleton dinitrotetraaminecobalt.

FD-mass spectrometry identifiziert by differential scanning calorimetry (DSC) (rate of temperature rise: 10oC/min) using DSC 22OC, manufactured and implemented by Seiko Instruments Inc., Japan. As a result, found that the maximum temperature is about 314oC, which is higher than the maximum temperature (about 250oC) for HNW. This means that dinitrotetraaminecobalt is nitramino connection with excellent temperature stability.

Example 21. Synthesis WA(NO2)2nitration WA6.

5 ml of acetic anhydride bring in 100 ml reaction flask and cooled to 0oC and kept at this temperature. When mixing acetic anhydride at 0oC in the reaction flask is gradually added dropwise to 100% nitric acid (nitrouse agent). To the resulting mixture is added 0.5 g of nitrogen pentoxide. Then to the resulting mixture is added 0.1 g (0,238 mmol) hexaazatrinaphthylene. Then to the resulting mixture is added 0.5 g of nitrogen pentoxide. This operation by adding 0.5 g of nitrogen pentoxide repeat 4 times with an interval of 1 hour. The resulting mixture was quenched with water with ice. Liquid components of the mixture is distilled under reduced pressure and the resulting solid residue is analyzed liquid chromatography high performance is N.

Example 22. Synthesis of W(NO2)6nitration WA4(NO2)2.

200 ml reaction flask is immersed in a bath at 0oC. In the flask make 25 ml of sulfuric acid and then with 25 ml of 100% nitric acid added gradually dropwise to the reaction flask to obtain a mixed acid (nitrouse agent). To the obtained mixed acid is added 0.2 g (0,457 mmol) dinitrotetraaminecobalt and the resulting reaction mixture was stirred at 0oC 8 hours. The mixture is then stirred at room temperature for 67 hours for reaction. After completion of the reaction to the resulting reaction mixture is added 200 ml of chloroform for the extraction of organic substances of the reaction mixture in the chloroform phase (the extraction was repeated twice). The chloroform phase is distilled under reduced pressure, fending off the solvent. The obtained solid residue was washed with 10% aqueous solution of NaHCO3receiving 0.06 g hexanitrohexaazaisowurtzitane (yield: 30%). The results of the analysis hexanitrohexaazaisowurtzitane the following.

The results of IR spectroscopy method KBr give the following acquisitions in the field 1605 cm-1related to the unbalanced oscillation stretching nitro; absorption on the tensile nitro; acquisitions in the area of 945 cm-1and in the area of 880 cm-1, each of which belongs to deformation oscillation nitro; and absorption in the region 3030 cm-1related to the variations in stretching retinovoy group on W-skeleton.

These thermal characteristics thermal characteristics hexanitrohexaazaisowurtzitane shown in COMBUSTION AND FLAME 87:145-151 (1991). The above results IR spectrometry show that the absorption around 1680 cm-1relating to a carbonyl group (C=O) acetyl group denitrocyclisation (which is the starting compound) is completely absent.

The above results show that the acetyl group dinitrotetraaminecobalt are replaced by nitro groups, forming hexanitrohexaazaisowurtzitane.

The results are obtained hexanitrohexaazaisowurtzitane (HNW) liquid chromatography high performance in the conditions described in International Symposium on Energetic Materials Technology PROCEEDINGS, SEPTEMBER 24-27 (1995) (which lists the various characteristics of HNW) indicate that you have received HNW has the same retention time, and HNW for the specified publication.

The results of EI-mass - ion) minus a molecular weight of NO2], 316, 213 and 46 (NO2), where ion peaks correspond to the ion peaks HNW listed as above in International Symposium on Energetic Materials Technology PROCEEDINGS, SEPTEMBER 24-27, 76-81 (1995).

Example of comparison 1. The acylation reaction after rehabilitation diarylethylene WB6in the absence of Alliluyeva agent.

3.0 g (4,24 mmol) hexabenzylhexaazaisowurtzitane, 0,476 g (2,12 mmol) Pb(OAc)2, 75 ml of tetrahydrofuran (THF) and 75 ml of ethanol contribute together with the mixing element 300 ml microbomb. The bomb blow gaseous hydrogen. Then the bomb run, the hydrogen gas so that the internal pressure of the bomb was 10 kgf/cm2- G. Then the contents of the bomb was stirred at room temperature 300 hours for reaction. After completion of the reaction the amount of toluene formed by diarylethylenes WB6, measured by gas chromatography. As a result, found that almost 100% of the benzyl groups tsapelas. Then the reaction mixture was removed from the bomb and catalyst recovery is removed from the reaction mixture. The solvent is then distilled off under reduced pressure from the mixture. To the obtained residue was added 100 ml of acetic anhydride as acetylides agent, then to Vaticana, having the acyl group is not formed.

From the above results, it was established that when the recovery diarylethylene WB6carried out in the absence of Alliluyeva agent, there is a decomposition W-patterns.

Example 2 comparison. The acylation reaction, post-rehabilitation diarylethylene WB6in the absence of Alliluyeva agent.

Restorative diarylethylene hexabenzylhexaazaisowurtzitane in the absence Alliluyeva agent is conducted mainly by the method of example 19, except that allerease agent is not used. After completion of the reaction, to the reaction mixture add the same quantity of the same Alliluyeva agent that in example 19. The mixture is stirred under nitrogen atmosphere for 5 hours for reaction. The resulting reaction mixture is treated in the same manner as in example 19. However, the presence of tetraacetylethylenediamine in the reaction mixture not found.

Industrial applicability

According to this invention can be obtained containing acyl group derived hexaazatetracyclo. Containing acyl group derived hexazinone is used not only as raw materials for explosives, but also as additives to rocket fuel and explosives. Containing acyl group derived hexaazatetracyclo this invention is also useful as a raw material to obtain a highly polar polymer, such as a polyfunctional crosslinking agent and as a filler for polymers.

1. Derived hexaazatetracyclo containing acyl group of the General formula I

WAtQ(6-t),

where W means hexavalent balance hexaazatetracyclo formula II

< / BR>
each And independently means1-10alalou group;

Q is independently means a hydrogen atom or a C1-10alkyl group;

t is an integer from 4 to 6.

2. Derived hexaazatetracyclo under item 1, where t in the formula I is 6.

3. Derived hexaazatetracyclo under item 1, where t in the formula I is 4.

4. The method of obtaining Hexachlorobutadiene, represented by the following formula III

WA6,

where W and a are specified in paragraph 1 values

characterized in that the derived hexaazatetracyclo General formula IV

WAnH(6-n),

where W and A have the above meanings;

n means an integer of 4 or 5,

p/P> 6. The method of obtaining Hexachlorobutadiene General formula III

WA6,

where A and W have the above values,

characterized in that the derived hexaazatetracyclo General formula

WAnB(6-n),

where W, A and n have the above values,

each independently means arylmethyl group, is subjected to regenerative dearylation in the absence Alliluyeva agent and derived hexaazatetracyclo General formula IV, where W, A and n have the above meanings, is subjected to the interaction with allermuir agent.

7. The method according to p. 6, where n in each of formulas IV and V equal to 4.

8. The method of obtaining Hexachlorobutadiene General formula III, where A and W have the above values, wherein hexacis (arylmethyl) hexaazatetracyclo General formula XI

WB6< / BR>
where In means arylmethyl group, and W are defined above,

put recovery dearylation in the presence Alliluyeva agent, completion of specified remedial diarylethylene exercise, when formed containing acyl group and arylmethyl group derived gexazianoferrit, put recovery dearylation in the absence Alliluyeva agent derivatization hexaazatetracyclo General formula IV

WAnH(6-n),

where each of W, A and n are defined above,

which is subjected to interaction with allermuir agent.

9. The method according to p. 8, where n in each of formulas IV and V equal to 4.

10. The method according to p. 8 or 9, where the specified allerease agent used in the first stage, is a complex ether carboxylic acid N-hydroxysuccinimide and specified allermuir agent used at the final stage, is allalone.

11. The method according to p. 8 or 9, where the specified allermuir agent used in the first stage, is a mixture of carboxylic acid anhydride and a complex ester of carboxylic acid N-hydroxysuccinimide, and the specified allermuir agent used at the final stage, is allalone.

12. The method according to p. 8 or 9, where the specified allermuir agent used in the first stage, is the anhydride of carboxylic acid and the specified allermuir agent used at the final stage, is allalone.

13. The method of deriving hexaazatetracyclo total f is the function group derived hexaazatetracyclo General formula V, where each of W, B, A and n are defined above, is subjected to regenerative dearylation in the absence Alliluyeva agent.

14. The method according to p. 13, where n in each of formulas IV and V equal to 4.

15. The method of deriving hexaazatetracyclo General formula IV, where W, A and n have the above values, wherein hexacis (arylmethyl) hexaazatetracyclo General formula XI, where W and B are defined above, is subjected to regenerative dearylation in the presence Alliluyeva agent, completion of specified remedial diarylethylene exercise, when formed containing acyl group and arylmethyl group derived hexaazatetracyclo General formula V, where each of W, A, B, and n are defined above, is formed in substantial amount, which, in turn, is subjected to regenerative dearylation in the absence Alliluyeva agent.

16. The method according to p. 15, where n in each of formulas IV and V equal to 4.

17. The method according to p. 15 or 16, where the specified allerease agent used in the first stage, is a complex ether carboxylic acid N-hydroxysuccinimide.

18. The method according to p. 15 or 16, where the specified allermuir agent used is of oxysuccinimide.

19. The method according to p. 15 or 16, where the specified allermuir agent used in the first stage, is the anhydride of carboxylic acid.

20. The method of obtaining containing acyl group and arylmethyl group derived hexaazatetracyclo General formula V, where W, A, B and n have the above values, wherein hexacis (arylmethyl) hexaazatetracyclo General formula XI, where B and W are defined above, is subjected to regenerative dearylation in the presence Alliluyeva agent, completion of specified remedial diarylethylene exercise, when formed containing acyl and arylmethyl group derived hexaazatetracyclo General formula V is formed in significant amounts that allocate.

21. The method according to p. 20, where n in the formula V is equal to 4.

22. The method according to p. 20 or 21, where the specified allermuir agent used in the first stage, is an ester of carboxylic acid N-hydroxysuccinimide.

23. The method according to p. 20 or 21, where the specified allermuir agent used in the first stage, is a mixture of carboxylic acid anhydride and a complex ester of carboxylic acid N-hydroxysuccinimide.

24. The method according to p. Ty.

25. The method of deriving hexaazatetracyclo General formula I or mixtures thereof containing acyl group and arylmethyl group derived hexaazatetracyclo General formula VI

WApB(6-p),

where W, A, Q, B, and t are defined above;

p means an integer from 1 to 5,

characterized in that hexacis (arylmethyl) hexaazatetracyclo General formula XI, where each of B and W are defined above, is subjected to regenerative dearylation in the presence Alliluyeva agent for a period of time sufficient for the formation containing acyl and arylmethyl group derived hexaazatetracyclo General formula VI in a significant number of which is further subjected to recovery dearylation in the presence Alliluyeva agent, and this additional recovery diarylethylene hold up until containing acyl and arylmethyl group derived hexaazatetracyclo formula VI will not turn into a derived hexaazatetracyclo represented by formula I, or a specified additional recovery diarylethylene stop, when not all containing acyl group and arylmethylidene General formula I.

26. The method according to p. 25, where the specified allermuir agent at all stages is an ester of carboxylic acid N-hydroxysuccinimide.

27. The method according to p. 25, where the specified allermuir agent used at all stages, is a mixture of carboxylic acid anhydride and a complex ester of carboxylic acid N-hydroxysuccinimide.

28. The method according to p. 25, where the specified allermuir agent used at all stages, is the anhydride of carboxylic acid.

29. Contains nitrosopropane derived hexaazatetracyclo General formula VII

WAn(NO)6-n,

where W, A and n have the above values.

30. Containing nitrogroup derived hexaazatetracyclo General formula VIII

WAn(NO2)(6-n),

where W, A and n have the above values.

31. The method of obtaining hexanitrohexaazaisowurtzitane General formula IX

W(NO2)6,

where W has the above value,

characterized in that it is subjected to nitration nitrous agent, at least one of the compounds selected from the group consisting of compounds of General formula III, where W and A have the abovementioned meanings, compounds of General formula IV, where W, A and n ODA is e each n, A and W are defined above.

32. The method according to p. 31, where the specified nitrouse agent includes a mixture of a source of nitrate and strong proton acid.

33. The method according to p. 32, where indicated strong proton acid is at least one acid selected from the group consisting of sulfuric acid and triperoxonane acid.

34. The method of obtaining hexanitrohexaazaisowurtzitane General formula IX, where W has the above values, wherein hexacis (arylmethyl) hexaazatetracyclo derivative of General formula XI

WB6,

where W and B are defined above,

put recovery dearylation in the presence Alliluyeva agent with obtaining containing acyl group and arylmethyl group derived hexaazatetracyclo General formula V, where each of B, W and n are defined above, which is optionally subjected to recovery dearylation in the absence Alliluyeva agent to obtain a derived hexaazatetracyclo General formula IV, where each of W, A and n are defined above, which in turn is subjected to nitration nitrous agent.

35. The method according to p. 34, where the specified nitrouse agent includes a mixture of a source of nitria at least one acid, selected from the group consisting of sulfuric acid and triperoxonane acid.

37. The method of obtaining hexanitrohexaazaisowurtzitane General formula IX, where W has the above value, characterized in that the derived hexaazatetracyclo General formula IV, where W, A and n have the above meanings, is subjected to the interaction with nitrotyrosine agent to obtain nitrobacteria derived hexaazatetracyclo General formula VII, where each of n, A and W are defined above, followed by nitration of the obtained compound nitrous agent with derivatization hexaazatetracyclo containing nitrogroup of General formula VIII, where each of n, A and W are defined above, which is optionally subjected to nitration nitrous agent.

38. The method according to p. 37, where the specified nitrotyrosine agent used in the first stage, is a mixture of sodium nitrite and acid.

39. The method according to p. 37, where the specified nitrous agent used in the second stage, is nitric acid.

40. The method according to p. 37, where the specified nitrous agent used in the second stage, is hydrogen peroxide or a mixture of hydrogen peroxide and nitric acid.

41. The method according to p. 37, Cotonou acid.

42. The method according to p. 41, where indicated strong proton acid is at least one acid selected from the group consisting of sulfuric acid and triperoxonane acid.

43. The method of obtaining containing nitrosourea derived hexaazatetracyclo General formula VII, where W, A and n have the above values, characterized in that the derived hexaazatetracyclo General formula IV, where each of n, A and W are defined above, is subjected to nitrotyrosine nitrotyrosine agent.

44. The method according to p. 43, where the specified nitrotyrosine agent is a mixture of sodium nitrite and acid.

45. The method of obtaining containing nitrogroup derived hexaazatetracyclo General formula VIII, where W, A and n have the above values, characterized in that it contains nitrosopropane derived hexaazatetracyclo General formula VII, where each of n, A and W are defined above, is subjected to the interaction with nitrous agent.

46. The method according to p. 45, where the specified nitrous agent is nitric acid.

47. The method according to p. 45, where the specified nitrous agent is hydrogen peroxide or a mixture of hydrogen peroxide and nitric acid.

48. The method of obtaining contain nia, characterized in that the derived hexaazatetracyclo General formula IV, where each of W, A and n are defined above, is subjected to the interaction with nitrous agent.

49. The method according to p. 48, where the specified nitrous agent is nitric acid or a mixture of nitric acid and N2O5.

50. The method of obtaining containing nitrogroup derived hexaazatetracyclo General formula VIII, where W, A and n have the above values, wherein sexuallytransmitted General formula III, where each of A and W are defined above, is subjected to the interaction with nitrous agent.

51. The method according to p. 50, where specified nitrouse agent is nitric acid or a mixture of nitric acid and N2O5.

52. The method of deriving hexaazatetracyclo General formula XII,

WAnQ(6-n),

where W, A, Q and n have the above values, provided that all Q cannot simultaneously be hydrogen atoms, characterized in that hexacis (arylmethyl)hexaazatetracyclo General formula XI, where W and B are defined above, is subjected to regenerative dearylation in the presence Alliluyeva agent for a period of time sufficient for the formation of the derived hexaazatetracyclo General formula XII, where W, A, Q and n have the above values, provided that all Q cannot simultaneously be hydrogen atoms, characterized in that the containing acyl group and arylmethyl group derived hexaazatetracyclo General formula V, where each of W, A , B, and n are defined above, is subjected to regenerative dearylation in the presence Alliluyeva agent.

 

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The invention relates to the field of analytical chemistry and technology and can be used in medical diagnostics, clinical medicine, biotechnology, food industry, veterinary medicine, environmental studies

The invention relates to a new derivative of formula 1, which can be used as an intermediate product in the synthesis of novel di-tert-butylsilane phthalocyanines and their complexes used as dyes, organic semiconductor materials, and so on

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The invention relates to organic chemistry, in particular to an improved process for the preparation of porphyrins, in particular to a method for producing chlorin e6(18-carboxy-20-(carboxymethyl)-8-ethynyl-13-ethyl-2,3-dihyd - ro-3,7,12,17 - tetramethyl-n, n

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FIELD: organic chemistry.

SUBSTANCE: invention relates to new derivatives of metalloporphyrazine of the general formula (I): wherein M means Cu, Co. These compounds can be used as dyes, catalysts in different processes and materials of sensitive members of gas sensor.

EFFECT: valuable properties of compounds.

2 cl, 6 sch, 1 dwg, 5 ex

FIELD: biochemistry.

SUBSTANCE: invention relates to method for production of synthetic chlorophyll (Chl) or bacteriochlorophyll (Bchl) derivatives of general formula I , wherein X is O;. Claimed method includes interaction under anaerobic conditions of Chl, Bchl derivatives containing COOCH3-group in C-132-position and COOR3-group in C-172-position in presence of tetraethyl orthotitanate. Further compounds of formula I wherein R1 and R2 are different radicals are obtained in aproton solvent such as peroxide-free tetrahydrofurane and dimethyl formamide, and compounds of formula I wherein R1 and R2 are the same ones are produced by using R1OH as a solvent. Derivatives of present invention are useful as stabilizers, linkage/spacer for binding another acceptable molecules to Chl/Bchl macrocycle.

EFFECT: simplified method for production of various chlorophyll or bacteriochlorophyll derivatives.

13 cl, 3 ex, 2 tbl, 8 dwg

FIELD: microbiology.

SUBSTANCE: invention relates to method for production of porphyrinopeptides satisfying the formula I , wherein R1 and R2 independently from one another represent amino acids or peptides comprising 2-15 of amino acid residues, wherein α-carboxylic groups of amino acids or peptides may be modified by C1-C8-alkyl ester and side functional groups of amino acids or peptides may be protected; in particular R1 is ArgOMe; R2 is -OH (III); R1 is LeuHisOMe; R2 is -OH (IV); R1 is LeuLeuValPheOMe; R2 is -OH (V); porphyrin carboxylic group may be modified by methyl or other C1-C9-ester or pharmaceutically acceptable salt; Y- represents Cl-; Me represents Zn, Cu, Fe, Mn. Claimed method includes activation of porphyrin carboxylic group with N-oxy-5-norbornene-2,3-dicarboxyimede in molar ratio of 1:1 in presence of N,N'-dicyclohexylcarbodiinide; or with diphenylphosphorylazide (DPPA) in equimolar ratio of porphyrin/DPPA in presence of base. Then porphyrin with activated carboxylic group is brought into reaction with amino component (amino acid or peptide) in form of mineral acid salt, which is neutralized with base. Also disclosed are methods for application of compounds (I) as nucleotic agents.

EFFECT: new nucleotic agents.

4 cl, 7 ex, 1 tbl

FIELD: chemistry of metalloorganic compounds.

SUBSTANCE: invention relates to new derivatives of metalloporphyrazines of the general formula (I):

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EFFECT: valuable properties of complexes.

4 fig, 1 dwg, 5 ex

FIELD: organic chemistry, medicine, oncology.

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EFFECT: valuable medicinal properties of agent.

6 cl, 1 dwg

FIELD: organic chemistry, chemical technology.

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that is characterized by melting point value Tm 207°C. This compound can be used as the parent substance in synthesis of metal complexes tetra(-di-6,7-carboxy)-anthraquinonoporphyrazine used as dyes and catalysts. Also, invention describes methods for synthesis and using compound of the formula (I).

EFFECT: value properties of compound and complexes.

4 dwg, 6 ex

FIELD: organic chemistry.

SUBSTANCE: invention relates to 2,3-dicarboxy-5,6,8-trimethylanthraquinone of the formula (I):

. This compound can be used in synthesis of metal complexes of tetra-(tri-5,6,8-carboxy)-anthraquinonoporphyrazine used as dyes and catalysts. Compound of the formula (I) is characterized by melting point value (Tm) 207°C. Also, invention describes methods for synthesis and using compound of the formula (I).

EFFECT: valuable properties of compound.

4 cl, 6 ex

FIELD: organic chemistry of complex compounds.

SUBSTANCE: invention relates to new derivatives of metalloporphyrazines, namely: to metal complexes of tetra-(tri-5,6,8-methyl)-anthraquinonoporphyrazine of the general formula:

. These compounds can be used as parent substances for synthesis, respectively, copper and cobalt complexes of tetra-(tri-5,6,8-carboxy)-anthraquinonoporphyrazine used as dyes, catalysts in different processes, materials in sensitive members of gas transducers.

EFFECT: valuable properties of complexes.

2 cl, 7 dwg, 8 ex

FIELD: organic chemistry of complex compounds.

SUBSTANCE: invention relates to new derivatives of metalloporphyrazines, namely to metal complexes of tetra-(tri-5,6,8-carboxy) -anthraquinonoporphyrazine of the general formula:

. These compounds can be sued as dyes, catalysts in different processes and materials for sensitive members of gas transducers.

EFFECT: valuable properties of compounds.

2 cl, 5 dwg, 6 ex

FIELD: chemistry of metalloorganic compounds, chemical industry.

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that can be used as a catalyst in oxidation reactions of sulfur-containing compounds, in particular, cysteine and thioureas, and diethylamine also being both in acid and neutral media.

EFFECT: valuable properties of compound.

2 cl, 2 dwg, 4 ex

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