Dinitropyrazole derivatives, their preparation, and energetic compositions comprising them
View Patent ↗The present invention provides: dinitropyrazole derivatives of formula (I) in which: R═NO 2 , NH 2 , NF 2 , NHOH, OH or NHNH 2 and R′═H when R═NH 2 , NF 2 , NHOH, OH or NHNH 2 or R′═H, NH 2 or a linear or branched C 1 -C 4 alkyl group, optionally substituted by at least one hydroxy and/or one fluoro group, when R═NO 2 ; other than 4-amino-3,5-dinitropyrazole; and also the salts of said derivatives of formula (I) in which R′═H; the preparation of said derivatives and of their salts; and energetic compositions comprising at least one of said derivatives and/or at least one salt of such a derivative.
1. A compound of formula (Ia):
in which: R═NO 2 , NF 2 , NHOH, OH or NHNH 2 ;
or a salt of said compound.
2. A compound of formula (Ic):
in which R′═NH 2 or a linear or branched C 1 -C 4 alkyl group, optionally substituted by at least one hydroxy and/or fluoro group.
3. A compound as claimed in claim 1 , selected from:
3,4,5-trinitropyrazole,
4-hydroxy-3,5-dinitropyrazole,
4-hydroxylamino-3,5-dinitropyrazole.
4. A salt of a compound of formula (Ia) as claimed in claim 1 , whose cation is selected from alkali metal, alkaline earth metal, ammonium, substituted ammonium, hydrazinium, guanidinium, aminoguanidinium, diaminoguanidinium, and iminium cations.
5. A process for preparing a compound of formula (Ia) or of a salt of a compound of formula (Ia) as claimed in claim 1 , characterized in that it comprises:
A) for preparing 4-difluoroamino-3,5-dinitropyrazole:
fluorinating 4-amino-3,5-dinitropyrazole;
B) for preparing other compounds of formula (Ia):
oxidizing 4-amino-3,5-dinitropyrazole or nitrating 3,5-dinitropyrazole to obtain 3,4,5-trinitropyrazole;
carrying out a substitution on said 3,4,5-trinitropyrazole, to give 3,5-dinitropyrazoles substituted in position 4 by the radical R═NH—NH 2 , OH or NHOH; and
C) for obtaining a salt, reacting the compound of formula (Ia) obtained above with a base.
6. The process as claimed in claim 5 , characterized in that the nitration of 3,5-dinitropyrazole is carried out in a sulfonitric or phosphonitric medium, containing from 0 to 100% by mass of sulfuric, phosphoric or nitric anhydride, at a temperature between 50° C. and the boiling temperature of said medium.
7. An energetic composition characterized in that it comprises at least one compound of formula (Ia) and/or at least one salt of such a compound, as claimed in of claim 1 .
8. The energetic composition as claimed in claim 7 , characterized in that it contains at least 20% by mass of said at least one compound of formula (Ia) and/or of said at least one salt of such a compound.
9. The energetic composition as claimed in claim 7 , characterized in that it contains from 90% to 100% by mass of said at least one compound of formula (Ia) and/or of said at least one salt of such a compound.
10. An energetic composition characterized in that it comprises at least one compound of formula (Ic) as claimed in of claim 2 .
11. The energetic composition as claimed in claim 10 , characterized in that it consists in a melt-cast explosive comprising at least one compound of formula (Ic).
12. The energetic composition as claimed in claim 11 , characterized in that it comprises at least one other energetic molecule, advantageously at a level of between 10% and 80% by mass.
13. A compound as claimed in claim 2 selected from
N-methyl-3,4,5-trinitropyrazole, and
N-amino-3,4,5-trinitropyrazole.
14. A process for preparing a compound of formula (Ic) as claimed in claim 2 , characterized in that it comprises:
obtaining 3,4,5-trinitropyrazole by oxidation of 4-amino-3,5-dinitropyrazole, nitration of 3,5-dinitropyrazole, oxidation of 5-amino-3,4-dinitropyrazole or diazotization of said 5-amino-3,4-dinitropyrazole;
obtaining its anion;
carrying out a nucleophilic substitution on said anion.
15. The process as claimed in claim 14 , characterized in that the nitration of 3,5-dinitropyrazole is carried out in a sulfonitric or phosphonitric medium, containing from 0 to 100% by mass of sulfuric, phosphoric or nitric anhydride, at a temperature between 50° C. and the boiling temperature of said medium.
16. The energetic composition as claimed in claim 7 , characterized in that it contains not more than 80% by mass of said at least one compound of formula (Ia) and/or of said at least one salt of such a compound, in a binder.
17. The energetic composition as claimed in claim 10 , characterized in that it contains at least 20% by mass of said at least one compound of formula (Ic).
18. The energetic composition as claimed in claim 10 , characterized in that it contains from 90% to 100% by mass of said at least one compound of formula (Ic).
19. The energetic composition as claimed in claim 10 , characterized in that it contains not more than 80% by mass of said at least one compound of formula (Ic).
20. A compound of formula (Ia):
in which: R═NO 2 , NHOH, OH or NHNH 2 ;
or a salt of said compound.
21. A compound of formula (Ia):
in which: R═NO 2 , or a salt of said compound.