Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D413/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
  • C07D413/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings
  • C07D413/04—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings directly linked by a ring-member-to-ring-member bond
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D413/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
  • C07D413/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing three or more hetero rings

Definitions

• the subject of the present invention is: new heterocyclic molecules: novel compounds, derived from furazane, resulting from a coupling between a furazane and an azole;
• Furazanes are a family of nitrogenous heterocycles with high formation enthalpies due to high aromatic ring energy. Their energy potential and their high thermal stability make them interesting and promising molecules in the field of energetic materials.
• DAF diaminofurazane furazanes
• the performances announced in this document are once again weak (speed of detonation: 8090 km / s).
• Said novel furazanes constitute the first object of the present invention. They correspond to formula (I) below:
• Het is an azolyl radical selected from nitroazolyl and tetrazolyl radicals; and are different from 3-nitro-4- (4-nitro-1,2,3-triazol-1-yl) furazane (see above).
• Het is an azolyl radical, that is to say “derivative" of a nitrogenous heterocycle with 5 members, at least one nitrogen is bonded to a hydrogen atom.
• Het is an azolyl radical chosen from nitroazolyl radicals (azolyl radicals substituted by at least one nitro group) and tetrazolyl radical (unsubstituted tetrazolyl radicals).
• Het generally contains a single heterocycle (5-membered) or two heterocycles (5-membered) linked by a C-C bond.
• Het is chosen from:
• pyrazolyl and bipyrazolyl ((b) pyrazolyl) radicals, substituted by at least one nitro group; the triazolyl and bitriazolyl ((b)) triazolyl radicals, substituted by at least one nitro group (said radicals and particularly the triazolyl radicals are very advantageously substituted with a single nitro group); and the tetrazolyl and biterazolyl ((b) tetrazolyl) radicals, substituted by at least one nitro group.
• Het may especially be chosen from nitrotriazolyl radicals (in particular nitro-1,2,3-triazolyl and nitro-1,2,4-triazolyl); dinitrotriazolyl; dinitropyrazolyl (3,4-dinitropyrazolyl and 3,5-dinitropyrazolyl); tetrazolyl; 5-nitrotetrazolyl; poly (nitropyrolyl) (more particularly bi (nitropyrolyl)); biterazolyl; bi (nitrotriazolyl) and bi (dinitropyrazolyl).
• nitrotriazolyl radicals in particular nitro-1,2,3-triazolyl and nitro-1,2,4-triazolyl
• dinitrotriazolyl dinitropyrazolyl (3,4-dinitropyrazolyl and 3,5-dinitropyrazolyl
• tetrazolyl 5-nitrotetrazolyl
• poly (nitropyrolyl) more particularly bi (nitropyrolyl)
• biterazolyl bi
• Het is advantageously chosen from the radicals: 3-nitro-1,2,4-triazol-1-yl, 4-nitro-1,2,3-triazol-2-yl,
• the present invention relates to the preparation of said novel compounds of formula (I).
• said new compounds can be obtained by coupling a nitrofurazane of formula (IIa) in which R is as defined above with reference to formula (I), and an azole of formula (Hb)
• the reaction is carried out in the presence of an organic or inorganic base, in a polar organic solvent, preferably anhydrous.
• the solvent used may in particular be selected from acetone, tetrahydrofuran, dimethylformamide, dimethylsulfoxide, acetonitrile, nitromethane, sulfolane and mixtures thereof.
• Said reaction may be carried out at a temperature between room temperature and the reflux temperature of the solvent used.
• the coupling is carried out in acetonitrile at room temperature.
• a nitrofurazane of formula (IIa) which plays the role of electrophile, chosen from: a) dinitrofurazane, b) dinitrofurazanyl ether, c) dinitroazofurazane, d) the dinitroazoxyfurazane; and e) dinitrohydrazofurazane.
• electrophile chosen from: a) dinitrofurazane, b) dinitrofurazanyl ether, c) dinitroazofurazane, d) the dinitroazoxyfurazane; and e) dinitrohydrazofurazane.
• Azoles (of formula (Hb)) capable of acting as nucleophiles are numerous. They may in particular consist of the azoles corresponding to the azole radicals specified above. Said azoles are known Persian compounds.
• the coupling method specified above is suitable for the preparation of all compounds of the invention. It is exemplified in Examples 1, 2, 6 and 7 below. Some of the compounds of the invention can, however, be obtained under more favorable conditions by other methods. It is proposed to specify hereinafter such other methods, more selective.
• Het is a tetrazolyl radical as specified above, it is recommended to implement: the addition of an orthoformate to the amino function of an amino furazane of formula (IUa) (by successive reaction with, for example, methyl orthoformate and sodium azide).
• Channel A in the reaction scheme presented below, is schematised as the chemical reaction mentioned above.
• R is as defined above;
• Het triazolyl radical
• the two routes use the same intermediate (the diazonium salt of the starting aminofurazane).
• the linkage with the furazane nucleus can be carried out either by the central nitrogen (2) (route B) or by the nitrogen (1) of the 4-nitro ring -1,2,3-triazolyl (lane C).
• Example 3 The implementation of track B above is illustrated in Example 3 below.
• route C it can obviously be limited to the cycloaddition of azidofurazane with morpholino-nitroethene, if said azidofurazane is available.
• Said azidofurazane may indeed consist of a known compound (when R represents a nitro, nitroazofurazanyl or nitroazooxylfurazanyl radical). This condensation step is illustrated in Example 5 below.
• Said method comprises the implementation of the reactions
• Het is as defined above (in general), by reducing, under mild conditions, the corresponding compound (even Het) of formula (I) in which:
• the present invention therefore relates to energy compositions comprising (an effective amount of) at least one compound selected from those of formula (I) (those of the invention, as described above and 3- nitro-4- (4-nitro-1,2,3-triazol-1-yl) furazane).
• Said energy compositions may especially consist of explosive compositions or propellant compositions. These two types of energetic compositions (with conventional energetic molecules) are familiar to those skilled in the art.
• the energy compositions of the invention of the first type - explosive compositions contain or do not contain a binder (inert or energetic). They generally consist of at least 20% by weight (advantageously at least 50% by weight) of at least one compound chosen from those of the invention of formula (I) and 3-nitro-4- (4- nitro-1,2,3-triazol-1-yl) furazane, very generally consisting of at least 20% by weight (advantageously at least 50% by weight) of such a compound chosen from those of the formula (I) and 3-nitro-4- (4-nitro-1,2,3-triazol-1-yl) furazane.
• They generally contain at most 80% by weight (advantageously between 50 and 80% by weight) of at least one compound chosen from those of the invention of formula (I) and 3-nitro-4- (4-nitro- 1,2,3-triazol-1-yl) furazane, very generally at most 80% by weight (advantageously between 50 and 80% by weight) of a compound chosen from those of the invention of formula (I) and the 3-nitro-4- (4-nitro-l, 2,3-triazol-l-yl) furazan.
• the product obtained is the same as that obtained in Example 1 (see the first column of Table 1 below).
• Example 3 Between 0-5 ° C., 2.05 g of aminonitrofurazane (15 mmol) is added to a concentrated solution of sulfuric acid (12 ml) and phosphoric acid (12 ml). Sodium nitrite (1.10 g, 15.8 mmol) is added in small portions. 1.64 g of nitroacetaldoxime are added in one go to the reaction medium. The mixture is stirred for 1 hour and then the medium is poured into 40 g of ice. It is allowed to settle for a few hours, then the intermediate is filtered, rinsed with water and then dried over P 2 O 5 . 0.46 g of dry product previously obtained is placed in 15 ml of distilled water.
• 3-Hydroxy-4- (4-nitro-1,2,3-triazol-2-yl) furazane is prepared from the amino-hydroxyfurazane by adopting the same procedure described in Example 3 above. .
• a dry tricolor under argon place 5 ml of anhydrous acetonitrile and then 264.7 mg (1.34 mmol) of 3-hydroxy-4- (4-nitro-1,2,3-triazol-2-yl) furazane followed by 39 mg ( 1.62 mmol) of sodium hydride.
• the medium is heated to 40 ° C. and then dinitrofurazanylether (323 mg) is added rapidly thereto. The medium is stirred at reflux for 6 hours. 20 ml of chloroform are then added.
• the precipitated salts are filtered.
• the medium is concentrated under vacuum and the product is purified on silica gel. 170 mg of pure product are thus isolated (yield 56%).
• Example 6 In a dry three-necked argon, 20 ml of anhydrous acetonitrile are placed, then 600 mg of dinitrofurazane (3.75 mmol) followed by 592 mg (3.75 mmol) of 3,4-dinitropyrazole are added. 10 ml of a solution of pyridine (296 mg, 3.75 mmol) diluted in acetonitrile are added dropwise to the reaction medium at 20 ° C. The medium is stirred at room temperature for 5 hours. 20 ml of water are then added. The product is extracted with chloroform, dried over magnesium sulphate, filtered and then evaporated. The product is purified on silica gel. 300 mg of pure product are thus isolated (30% yield).
• HMX octogen
• Sensitivity to impact The test performed corresponds to that described in standard NF T 70-500, itself similar to UN test 3a) ii) from the "Recommendations on the Transport of Dangerous Goods - manual”. Tests and Criteria, Fourth Revised Edition, ST / SG / AC.10 / ll / Rev.4, ISBN 92-1-239083-8ISSN 1014-7179 ".
• the energy resulting in 50% (method of treatment of Bruceton results) of positive results of an explosive substance subjected to shocks of a sheep is determined.
• the material to be tested is confined in a steel device consisting of two rollers and a guide ring.
• the energy can be varied from 1 to 50 J. Given the small amount of material available for some of the products tested, it was not realized for these products. , that a reduced number of reproducibility tests, compared to the recommendations of standard NF T 70-500.
• Sensitivity to friction The test carried out corresponds to that described in standard NF T 70-503, itself similar to UN test 3b) i). By a minimum series of 30 tests, the force resulting in 50% positive results of an explosive substance subjected to friction is determined using the Bruceton method.
• the material to be tested is placed on a porcelain plate of defined roughness, animated by a single back and forth motion, of 10 mm of amplitude at the speed of 7 cm / s empty, compared to a porcelain pencil. resting on the material.
• the force applied to the porcelain pencil which is pressed on the material may vary from 7.8 to 353 N. Given the small quantity of material available for some of the products tested, it has not been realized for these products, a reduced number of reproducibility tests, compared to the recommendations of standard NF T 70-503.
• Sensitivity to ignition by electric spark is a test developed by the Applicant with no equivalent NF or UN.
• the material to be tested placed in a cup of diameter 10 mm and height 1.5 mm, is placed between two electrodes and is subjected to an electric spark of variable energy from 5 to 726 ml. pyrotechnic or not and we determine the threshold of energy no longer ensuring the initiation of the material. This value is confirmed by 20 successive tests. Given the small amount of material available for some of the products tested, only a small number of reproducibility tests were carried out for the products.
• the thermal stability has, for its part, been determined as follows.
• Thermal stability is analyzed by the Differential Thermal Analysis (DTA) method.
• DTA Differential Thermal analysis
• the compounds of the invention display relatively low sensitivities to the different tests.
• the sensitivity of the ether (compound of Example 4) is of the same level as that of the mono-furazanes (compounds of Examples 1, 2, 3, 6 and 7).
• the sensitivity of the azoxy derivative (compound of Example 5) appears to be greater than that of the other furazanes.
• the energy level of the products of the invention was determined by calculating their density and their enthalpy of formation.
• the ratio used for propellant performance prediction is 85/15 (load / binder).

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