• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    The invention relates to a new polymorphic form, called the beta form, of hexanitrohexa-azaisowurtzitan, as well as to a process for the preparation of this form. According to this method, a solution of hexanitrohexaazaisowurtzitan is prepared in some polymorphic form in tetrahydrofuran, after which a halogenated solvent is added to the solution, which causes precipitation of the beta form of hexanitrohexaazaisowurtzitan. Hexanitrohexaazaisowurtzitan, especially when the dense, polymorphic beta form, is used as an explosive or oxidizing charge in pyrotechnic compositions. A: P3336lSE00.besk.d0C
    公开号:SE534560C2
    申请号:SE9701784
    申请日:1997-05-14
    公开日:2011-10-04
    发明作者:Guy Cagnon；Guy Jacob；Helene Mace
    申请人:Snpe Materiaux Energetiques；
    IPC主号:
    专利说明:

    534 550 2 2 hexaazaisowurtzitan, by reaction at 60 ° C for 6 hours of hexabenzylhexaazaisowurtzitan with acetane hydride in the presence of hydrogen and with Pd / C as catalyst. The yield is 25%.
    The author also states that he has investigated different working conditions for nitration of tetraacetyldibenzylhexaazaisowurtzitan with the aim of obtaining hexanitrohexaazaisowurtzitan, but this compound has never been obtained.
    Despite this prejudice, working conditions have been demonstrated which make it possible to obtain in an excellent exchange of hexanitrohexaazaisowurtzitan starting from tetraacetyldibenzylhexaazaisowurtzitan. The hexanitrohexaazaisowurtzitane thus obtained is in the polymorphic form alpha, with reference to the previously mentioned publications of FOLTZ. Its density is 1.97 g / cm 2.
    It is now the case that according to the same publications by FOLTZ, other polymorphic forms, especially the beta form, have a higher density, and for this reason appear to be of greater interest, especially for use in pyrotechnic compositions.
    Although certain properties and performance of the beta form of hexanitrohexaazaisowurtzitan are known to those skilled in the art, the information contained in the prior art, even supplemented by the general knowledge of the skilled artisan, does not allow it to produce and isolate it.
    The person skilled in the art e fi therefore seeks a process which makes it possible to obtain this polymorphic beta form. The present invention enables this problem to be solved.
    It mainly concerns the polymorphic beta form of hexanitrohexaazaisowurtzitan, the preparation of which has not been known to those skilled in the art, nor has it been indicated by the state of the art.
    It also relates to a process for the preparation of this polymorphic beta form, the density of which is 1.99 g / cm This elevated density makes this polymorphic beta form particularly interesting as an explosive or oxidizing charge in pyrotechnic compositions.
    According to the invention, the process for preparing the polymorphic beta form consists in first preparing a solution of hexanitrohexaazaisowurtzitan in some polymorphic form, for example the alpha form, in tetrahydrofuran (THF), after which a halogenated solvent is added to the solution, which results in precipitation of hexanitrozithrox in polymorphic beta form, which can be recovered, for example by filtration.
    Hexanitrohexaazaisowurtzitan is insoluble in halogenated solvents. In the present description, however, the term "halogenated solvents" is used in a conventional manner in the sense that the person skilled in the art clearly understands which compounds are in question, namely organic compounds which are liquid under normal temperature and pressure conditions. aliphatic or aromatic, containing at least one halogen atom, in which a number of organic compounds are soluble.
    Preferably, the halogenated solvent is a chlorinated aliphatic solvent, such as methylene chloride, chloroform or 1,2-dichloroethane.
    Chlorophone is especially preferred.
    According to the invention, unexpectedly, only THF can be used to dissolve hexanitrohexa azaisowurtzitan in any polymorphic form for recrystallization. Otherwise, for example when using ketones, such as acetone, or alcohols, such as methanol or ethanol, the polymorphic laeta form is not obtained.
    The volume ratios of halogenated solvent to THF can be any, but it is preferred to use a volume ratio of halogenated solvent / TI-IF which is between 1 and 3, for example when close to 2.
    Furthermore, and also unexpectedly, it has been found that a product of higher purity is obtained, i.e. especially free from other polymorphs of hexanitrohexaazaisowurtzitan, when the process according to the invention is carried out at a temperature between 0 and 40 ° C, for example when between 5 and 35 ° C and is preferably between 10 and 30 ° C, and is preferably preferred at room temperature, for example between 15 and 25 ° C.
    According to the invention, after precipitation of hexanitrohexaazaisowurtzitan in polymorphic beta form, this can be isolated by conventional methods, for example by filtration of the medium.
    After isolation, the product can be washed, for example with the same halogenated solvent as that used for the filtration, and then dried, suitably at reduced pressure and a temperature below 40 ° C, for example between 15 and 35 ° C, which can be removed. make the ambient temperature.
    The following non-limiting examples illustrate the invention and the advantages it provides.
    Example 1: Preparation of tetraacetyldibenzylhexaazaisowurtzitan In a 250 ml double-jacketed reactor, equipped with a magnetic stirrer, water cooler and inlet tube equipped with a sinter plate for hydrogen introduction, charge at room temperature (15-30) 67 ml of dimethylformamide (DMF), 17 ml ml of acetane hydride, 0.23 g (1.46 mmol) of bromobenzene, 20.8 g (29.4 mmol) of hexabenzylhexaazaisowurtzitan and 1.15 g of palladium hydroxide on carbon (moisture content 50%, palladium content in the dry matter: 5%). After purging the apparatus with an inert gas, and simultaneously with the introduction of hydrogen into the medium and while maintaining its pressure in the reactor between 1.13 x 105 Pa and 1.25 x 105 Pa is set the reaction medium from room temperature to 55 ° C for 3 hours, after which this temperature is maintained for 2 hours.
    The introduction of hydrogen is stopped, after which 58 ml of acetane hydride are added to the medium, which is then adjusted to a temperature between 80 and 90 ° C.
    This medium is filtered to separate the catalyst, after which the filtrate is concentrated at 60 DEG-70 DEG C. under reduced pressure at 2.5 x 103 Pa, s x 103 Pa (about 20 DEG-40 DEG C. Hg).
    After returning to room temperature, the residue is taken up in 100 ml of acetone. The resulting tetraacetyldibenzylheigaazaisowurtzitane, which has precipitated, is filtered off and washed with 50 ml of acetone. After drying for 24 hours at 30 ° C under reduced pressure at 5 x 103 Pa (about 40 mm Hg), 12.1 g (yield 80%) of tetraacetyldibenzylhexaazaisowurtzitan are obtained, which is identified by conformity with reference spectra by mass spectrometry, infrared and proton. -NMR at 200 MHz.
    Example 2: Preparation of hexanitrohexaazaisowurtzitan in polymorphic alphaform In a 1 liter double-jacketed reactor equipped with a mechanical stirrer and temperature sensor, 313 g (3.37 mol) of liquid N2O4 are charged at 0 ° C.
    Between 0 ° C and 5 ° C, 133 g (0.25 mol) of tetraacetyldibenzylhexaazaisowurtzitan, prepared according to Example 1, are added.
    The temperature of the reaction medium is allowed to rise to 15-16 ° C (re-desolation of N2O4) after which it is left stirring and refluxing N2O4 for 20 hours.
    After cooling the medium to 0 ° C, 667 ml of a sulphonitration mixture with a volume fi ratio of 20/80 are added between 0 and 8 ° C, which corresponds to the addition of 12.8 moles of nitric acid.
    Thereafter, the medium is progressively heated to remove excess N 2 O 4 by distillation, after which, when the temperature of the medium reaches 73 -75 ° C, the mixture is left under stirring for 4 hours.
    After cooling to 40 ° C, the mixture is poured onto 2 liters of an ice-water mixture. A solid product precipitates, which is recovered by filtration and washed in a room with hot water (40 ° C) to the neutral pH of the wash water.
    After drying, 104 g of solid white hexanitrohexaazaisowurtzitan (yield 97%) are obtained, which is identified by proton NMR at 200 MHz in dimethylsulfoxide (DMSO), by carbon NMR under the same conditions, by IR, by elemental analysis and by X-ray crystallographic studies. 10 15 20 25 30 534 560 S Its melting temperature is close to> 170 ° C and its purity can be estimated to be higher than 95%.
    Its density is 1.97 g / cm 3 according to crystallographic data obtained by X-ray.
    X-ray crystallographic examination of a single crystal shows that this compound crystallizes with about 25 mole percent water and that it exhibits an orthorhombic crystal structure of the space group Pbca with the following lattice parameters: a = 9,546Å, b = 13232Å, c = 23,634Å, and Z = 8.
    Furthermore, the Fourie-transformed IR spectrum of a 1% dispersion in KBr between 700 and 1200 cm 2 shows the characteristic peaks of the polymorphic alpha form, with reference to the previously mentioned publication of FOLTZ, Table 1, p. 66. The characteristic peaks of the forms epsilon, beta and yarn are not observed. The resulting hexanitrohexaazaisowurtzitane is thus present in the polymorphic alphaphone.
    Examples 3 and 4: Preparation of hexanitrohexaazaisowtirtzitane in polymorphic beta form.
    Example 3 A solution of 1 g of hexanitrohexaazaisowurtzitan, prepared according to Example 2, in 3 ml of THF at room temperature close to 20 ° C, is added at the same temperature 6 ml of chloroform.
    A solid, white product precipitates and is recovered by filtration.
    After washing with chloroform in a chamber and subsequent drying at 30 ° C under reduced pressure of about 2.5 103 Pa (about 20 mm Hg), 0.58 g (yield 58%) of hexanitrohexa-azaisowurtzitan are collected, which is identified as in Example 2.
    Its density at 20 ° C is 1.99 g / cma according to X-ray crystalline data.
    X-ray crystallographic examination shows that the product has an orthorhombic crystal structure of the space group Pb21a, whose lattice parameters obtained by indexing the pulse spectrum are: a = 9,679Å, b = 11,655Å, c = 1,2998Å and Z = 4.
    Furthermore, the Fourietrally-formed IR spectrum of a 1% dispersion in KBr between 700 and 1200 cm -1 shows the peaks characteristic of the polymorphic beta-phoneme, with reference to the previously mentioned publication of FOLTZ, Table 1, page 66. .
    The characteristic peaks of the forms alpha, gamma and epsilon are not observed.
    The resulting hexanitrahexaazaisowortzitane, the purity of which can be estimated to exceed 97%, is thus present in the polymorphic beta form. 534 550 Example 4 In a 15 liter enamelled reactor equipped with an anchor stirrer, Example 3 is repeated, but with 1 kg of hexanitrohexaazaisowurtzitan, prepared according to Example 2, 3 liters of THF and 6 liters of chlorophone.
    569 g (yield 56.9%) of hexanitrohexaazaisowimzitan of polymorphic beta form are obtained, which is identified and analyzed as in Example 3.
    权利要求:
    Claims (8)
    [1] 1. Beta polymorph form of hexanitrohexaazaiso-wurtzitane.
    [2] 2. Process of synthesis of the beta polymorph form of hexanitrohexaazaisowurtzitane, characterized in that a solution of hexanitrohexaazaisowurtzitane of anypolymorph form in tetrahydrofuran is produced and in thata halogenated solvent is then added to the solution. according to Claim 2,
    [3] 3. Process of synthesis characterized in that the halogenated solvent is achlorinated aliphatic solvent.
    [4] 4. Process of synthesis according to Claim 3,characterized in that the chlorinated aliphatic solventis chloroform.
    [5] 5. Process of synthesis according to Claim 2,characterized in that the volume ratio of halogenatedsolvent/tetrahydrofuran is between 1 and 3.
    [6] 6. Process of; synthesis according to Claim 2,characterized in that it is carried out at a temperatureof between 10°C and 30°C.
    [7] 7. Process of synthesis according to Claim 2,characterized in that hexanitrohexaazaisowurtzitane ofbeta polymorph form is recovered by filtering the mixtureand then washing and drying the product. Claim 7, characterized in that the drying is performed at reduced
    [8] 8. Process of synthesis according to pressure and at a temperature of between 15°C and 35°C. CONFIDETEAL~ [FÉNFIPD ENTIP
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    同族专利:
    公开号 | 公开日
    DE19719831A1|2004-11-18|
    FR2830864B1|2006-11-10|
    DE19719831B4|2013-10-31|
    SE9701784A1|2011-05-17|
    FR2830864A1|2003-04-18|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    JPH06321962A|1993-05-14|1994-11-22|Asahi Chem Ind Co Ltd|Hexakis hexaazaisowurtzitane|
    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    FR9605959A|FR2830864B1|1996-05-14|1996-05-14|BETA POLYMERIC FORM OF ISOWURTZITANE DERIVATIVE AND PROCESS FOR SYNTHESIS|
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