# US 8,273,784 B2 · Dinitropyrazole derivatives, their preparation, and energetic compositions comprising them > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 8,273,784 B2 - Document ID: US8273784B2 - Status: Granted - Kind: B2 - Application number: 12/314,726 - Filed: 2008-12-16 - Published: 2009-07-23 - Granted: 2012-09-25 - Earliest claimed: 2008-06-06 - Assignees: Herakles; Eurenco - Inventors: Gregoire Herve - Web page: https://patentgrep.com/patent/US8273784B2 ## CPC - C07D 231/16: Halogen atoms or nitro radicals - A61P 3/00: Drugs for disorders of the metabolism (of the blood or the extracellular fluid A61P7/00) - C06B 25/34: the compound being a nitrated acyclic, alicyclic or heterocyclic amine - C07D 231/38: Nitrogen atoms (nitro radicals C07D231/16) - C07D 231/46: Oxygen atom in position 3 or 5 and nitrogen atom in position 4 - C07D: HETEROCYCLIC COMPOUNDS (macromolecular compounds C08) - A61P: SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS - C06B: EXPLOSIVES OR THERMIC COMPOSITIONS (blasting F42D); MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES (compounds in general C01, C07 or C08; {demolition agents based on cementitious or like materials C04B41/0009}) ## Abstract The present invention provides: dinitropyrazole derivatives of formula (I) in which: R═NO2, NH2, NF2, NHOH, OH or NHNH2 and R′═H when R═NH2, NF2, NHOH, OH or NHNH2 or R′═H, NH2 or a linear or branched C1-C4 alkyl group, optionally substituted by at least one hydroxy and/or one fluoro group, when R═NO2; 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. ## Claims ### Claim 1 A compound of formula (Ia): in which: R═NO2, NF2, NHOH, OH or NHNH2; or a salt of said compound. ### Claim 2 A compound of formula (Ic): in which R′═NH2 or a linear or branched C1-C4 alkyl group, optionally substituted by at least one hydroxy and/or fluoro group. ### Claim 3 (depends on 1) A compound as claimed in claim 1, selected from: 3,4,5-trinitropyrazole, 4-hydroxy-3,5-dinitropyrazole, 4-hydroxylamino-3,5-dinitropyrazole. ### Claim 4 (depends on 1) 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. ### Claim 5 (depends on 1) 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—NH2, OH or NHOH; and C) for obtaining a salt, reacting the compound of formula (Ia) obtained above with a base. ### Claim 6 (depends on 5) 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. ### Claim 7 (depends on 1) 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. ### Claim 8 (depends on 7) 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. ### Claim 9 (depends on 7) 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. ### Claim 10 (depends on 2) An energetic composition characterized in that it comprises at least one compound of formula (Ic) as claimed in of claim 2. ### Claim 11 (depends on 10) 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). ### Claim 12 (depends on 11) 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. ### Claim 13 (depends on 2) A compound as claimed in claim 2 selected from N-methyl-3,4,5-trinitropyrazole, and N-amino-3,4,5-trinitropyrazole. ### Claim 14 (depends on 2) 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. ### Claim 15 (depends on 14) 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. ### Claim 16 (depends on 7) 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. ### Claim 17 (depends on 10) 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). ### Claim 18 (depends on 10) 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). ### Claim 19 (depends on 10) 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). ### Claim 20 A compound of formula (Ia): in which: R═NO2, NHOH, OH or NHNH2; or a salt of said compound. ### Claim 21 A compound of formula (Ia): in which: R═NO2, or a salt of said compound.