Energetic, Low‐Melting Salts of Simple Heterocycles

Abstract

Public reporting burden for this collection of information is estimated to average 1 fiour per response, including ttie time for reviewing instructions, searctiing existing data sources gathering and maintaining the data needed, and completing and reviewing this collection of information. Send comments regarding this burden estimate or any other aspect of this collection of information including suggestions for reducing this burden to Department of Defense, Washington Headquarters Sen/ices, Directorate for Infomiation Operations and Reports (0704-0188), 1215 Jefferson Davis Highway, Suite 1204, Arlington, VA 22202-4302. Respondents should be aware that notwithstanding any other provision of law, no person shall be subject to any penalty for failing to comply with a collection of infomiation if it does not display a currently valid 0MB control number. PLEASE DO NOT RETURN YOUR FORM TO THE ABOVE ADDRESS. REPORT DATE (DD-MM-YYYY) AFRL-PR-ED-TP-2003-007 SPONSORING / MONITORING AGENCY NAME(S) AND ADDRESS(ES)Air Force Research Laboratory (AFMC) AFRL/PRS 5 Pollux Drive Edwards AFB CA 93524-7048 SPONSOR/MONITOR'S ACRONYM(S) SPONSOR/MONITOR'S NUMBER(S) AFRL-PR-ED-TP-2003-007 DISTRIBUTION / AVAILABILITY STATEMENTApproved for public release; distribution unlimited. SUPPLEMENTARY NOTES ABSTRACT U8 SUMMARYThe synthesis of three new families of heterocycHc based salts was undertaken and accomplished. Three triazole systems, 1-H-l, 2, 4-triazole 4-amino-l, 2, 4-triazole, and 1-H-l, 2, 3-triazole were used as proton bases with nitric (HNO3), perchloric (HCIO4), and dinitramidic ("HN(N02)2") acid systems. In all cases, stable salts were recovered and folly characterized by vibrational spectra (IR, Raman), multinuclear nmr spectroscopy, material balance, density measures, elemental analyses, as well as DSC, TGA and initial safety testing (impact). Many of these salts have melting points well below 100°C, yet high decomposition onsets, defining them as new, highly energetic members of the well known class of materials identified as ionic liquids. INTRODUCTIONThe Air Force continues a quest for new energetic materials as part of its basic and apphed research program. The general requirements for the molecules include, (1) High density and energy; (2) Thermal/Storage stability; (3) Low handling hazards (e.g., low sensitivity to impact, fiiction, electrostatic discharge, and low toxicity); and (4) Simple production routes (i.e., three or less synthesis steps) for low cost. In our laboratory, we have been pursuing the synthesis of new energetic salts. Energetic materials that are saU-based often possess advantages over nonionic molecules. First, salts tend to have very low vapor pressure, which essentially eliminates the risk of exposure of personnel to new materials via a major exposure route (inhalation). Second, ionic compounds often have higher density than atomically similar, nonionic molecules.

A green chemical route for the synthesis of Mn3O4 nanoparticles

“…ILs are organic salts with low melting temperature (< 100°C), composed of ions, and exhibiting high thermal stability. These liquids have interesting chemical and physical properties including large electrochemical window, high chemical and thermal stability, non-volatility, controlled miscibility, non-flammability, negligible vapor pressure, and good electrical stability for separations [19,20] and electrochemistry [21]. Ionic liquids can act as solvents for reactants and as morphology templates for the products at the same time, which enables the synthesis of inorganic materials with improved properties [22].…”

Synthesis, Characterization, and Structural Investigations of 1‐Amino‐3‐substituted‐1,2,3‐triazolium Salts, and a New Route to 1‐Substituted‐1,2,3‐triazoles.

“…Unlike the weak acidic behavior noted for the 1-alkyl-4-amino-1,2,4-triazolium based salts [25], 1 M aqueous solutions of 1-amino-3-alkyl-1,2,3-triazolium halides (3a-e) were essentially pH neutral at 7. Vibrational spectra of all the triazolium salts revealed evidence of N-alkylation of the heterocyclic ring with well defined sharp peaks in the area of 3200-3100 cm -1 (NH 2 stretching modes), and in the area of 3100-2900 cm -1 typical of both heterocyclic C-H and alkyl C-H stretching modes [34,35] The presence of broad, intense band in the area 3300-2600 cm -1 is a strong evidence of complex hydrogen bonding interactions, involving N-H and C-H protons as well as NH 2 …X -, and are not unusual and have been observed in several other salt systems [24,25] Distribution A: Approved for public release; distribution unlimited. [17,18,25].…”

Structure and Dynamics of the 1-Hydroxyethyl-4-amino-1,2,4-triazolium Nitrate High-Energy Ionic Liquid System

“…A recent report by Drake and co-workers 22 on low-melting, potentially energetic salts lists their desired characteristics, as well as potential benefits, that might be derived from using them in energetic materials applications. The same authors have discussed the 1-R-4-amino-1,2,4-triazolium family of salts 23 that are of interest owing to their high nitrogen content.…”