Synthesis and Characterization of 5-Amino-1-nitriminotetrazole and Its Salts

Liu, Long; He, Chunlin; Li, Chunshan; Li, Zengxi

doi:10.1007/s10870-012-0319-4

Cited by 14 publications

(13 citation statements)

References 28 publications

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“…12 Additionally, Li et al found that a mixture of fuming nitric acid and concentrated sulfuric acid (98%) could be a suitable nitration agent to obtain 5-amino-1-nitrimino-4H-tetrazole. 13 In recent years, Christe successfully synthesized and characterized several novel polynitrogen cations, such as the V-shaped N 5 + cation, 14 the N 3 NOF + cation both as a Z-and E-isomers, 15 and the N 7 O + cation. 16 All the catenated nitrogen cations were obtained by the substitution reaction of [N-F] + with HN 3 to replace the F atom by an azido …”

Section: Scheme 2 Extending the Nitrogen Chain By N-aminationmentioning

confidence: 99%

Recent Advanced Strategies for Extending the Nitrogen Chain in the Synthesis of High Nitrogen Compounds

Yang

Cheng

Tang

2013

Synlett

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The synthesis and handling of compounds containing long catenated nitrogen chains are challenging for researchers in this field. These challenges arise from their high endothermic, thermodynamic instability, and a serious lack of nitrogen-nitrogen bond-forming reactions. This paper addresses techniques of azocoupling reaction between the diazonium salt of N-NH 2 and amine derivative to form the longest nitrogen chain (N 11 ). This type of nitrogen-nitrogen bond formation opens a new strategy for the construction of novel compounds containing odd or even numbers of catenated nitrogen atoms (≥9) especially for polynitrogen compounds.Key words: azo coupling, energetic materials, catenated nitrogenatom chain, formation of nitrogen-nitrogen bond, tetrazole Compounds containing long catenated nitrogen-atom chains and polynitrogen compounds are attracting and challenging in research areas such as propellants, explosives, and pyrotechnics. This attraction is due to their high heat of formation and environmentally bening decomposition products of nitrogen gas.However, there are also two challenges in synthesizing and handling high nitrogen compounds containing directly linked N-N single or double bonds for chemists in this fascinating field. One arises from their high endothermic and thermodynamic unstability. The triple bond in molecular nitrogen (N 2 ) with 942 kJ/mol bond energy is characterized as the strongest bond in nature. The sum of the bond energies of the N-N single and double bonds possesses much less than that of triple bonds. As a result, energetic compounds containing catenated N-N single and double bonds could be easily triggered to produce diatomic nitrogen gas accompanied by a very large energy release. 2 Therefore, the larger the string of the catenated nitrogen-nitrogen bond, the more unstable the compound is. The other challenge results from a serious lack of nitrogen-nitrogen bond-forming reactions in comparison with carbon analogues. With the development of synthetic organic chemistry, chemists have a wealth of methods to construct C-C and C-N bonds. In comparison, methods for the synthesis of nitrogen-nitrogen bonds are extremely limited.

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Section: Scheme 2 Extending the Nitrogen Chain By N-aminationmentioning

confidence: 99%

Recent Advanced Strategies for Extending the Nitrogen Chain in the Synthesis of High Nitrogen Compounds

Yang

Cheng

Tang

2013

Synlett

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“…[1] Thec ombination of both aspects yields very powerful energetics.T he known nitramino tetrazoles without alkyl chains [2] are limited to the examples shown in Scheme 1. [3,4] Thes ynthesis of 1,s hown in Scheme 2, starts with commercially available dimethylcarbonate,w hich is treated with hydrazine hydrate to give the methyl carbazate (2). Thes ynthesis of this compound has been al ong-term goal in energetic materials research because of its outstanding predicted performance.T o date,many attempts of direct nitration have failed.…”

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confidence: 99%

“…Thes ynthesis of this compound has been al ong-term goal in energetic materials research because of its outstanding predicted performance.T o date,many attempts of direct nitration have failed. [3,4] Thes ynthesis of 1,s hown in Scheme 2, starts with commercially available dimethylcarbonate,w hich is treated with hydrazine hydrate to give the methyl carbazate (2). Species 2 is reacted with cyanogen azide to yield Nmethoxycarbonyl protected 1,5-diaminotetrazole (3), which is then nitrated in acetonitrile with N 2 O 5 .T he nitramide 4 is decomposed in solution with aqueous KOHt og ive 5 as aw hite precipitate from which 1 can be isolated by acidification and extraction into organic solvents.…”

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confidence: 99%

1,5‐Di(nitramino)tetrazole: High Sensitivity and Superior Explosive Performance

2015

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Highly energetic 1,5-di(nitramino)tetrazole and its salts were synthesized. The neutral compound is very sensitive and one of the most powerful non-nuclear explosives to date. Selected nitrogen-rich and metal salts were prepared. The potassium salt can be used as a sensitizer in place of tetracene. The obtained compounds were characterized by low-temperature X-ray diffraction, IR and Raman spectroscopy, multinuclear NMR spectroscopy, elemental analysis, and DSC. Calculated energetic performances using the EXPLO5 code based on calculated (CBS-4M) heats of formation and X-ray densities support the high energetic performances of the 1,5-dinitraminotetrazolates as energetic materials. The sensitivities towards impact, friction, and electrostatic discharge were also explored.

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“…They play roles as ligands to form energetic complexes [7][8][9][10][11][12][13][14][15] or as anions to construct energetic salts together with guanidine, amine, etc. [16][17][18][19][20][21][22]. 1,5-Diaminotetrazole (DAT) is one of the highest nitrogen content (84.0 wt%) compounds and is shown in figure 1.…”

Section: Introductionmentioning

confidence: 99%

Synthesis, structure, and thermal decomposition of two copper coordination compounds [Cu(DAT)₂(PA)₂] and [Cu(DAT)₂(HTNR)₂] with nitrogen rich 1,5-diaminotetrazole (DAT)

Feng

et al. 2014

Journal of Coordination Chemistry

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2015)Synthesis, structure, and thermal decomposition of two copper coordination compounds [Cu(DAT) 2 (PA) 2 ] and [Cu(DAT) 2 (HTNR) 2 ] with nitrogen rich 1,5-diaminotetrazole (Two similar complexes combined with 1,5-diaminotetrazole (DAT) and copper trinitrophenol were characterized by elemental analysis, FT-IR spectroscopy and single crystal X-ray diffraction and the sensitivity were studied.Both [Cu(DAT) 2 (PA) 2 ] (1) and [Cu(DAT) 2 (HTNR) 2 ] (2) were prepared from 1,5-diaminotetrazole (DAT) and copper trinitrophenol, 1 for picrate (PA) and 2 for styphnate acid (2,4,6-trinitro resorcinol, TNR), and were characterized by elemental analysis, FT-IR spectroscopy, and single crystal X-ray diffraction. The space group of these compounds is P2 1 /c (monoclinic). The lattice parameters are similar [a = 11.405(3) Å, b = 14.867(3) Å, c = 8.099(2) Å for 1 and a = 12.262(3) Å, b = 14.900(3) Å, c = 7.243(2) Å for 2], except the β = 106.257(3)°in 1 and β = 92.989(4)°in 2. Both have extended structures due to hydrogen bonds, but there are some differences because of the ligands induced effect. Differential scanning calorimetry analysis shows that two exothermic processes take place in both complexes, the first peak temperatures are 488.2 K for 1 and 519.2 K Downloaded by [University of Western Ontario] at 04:29 06 February 2015 for 2. The kinetic parameters of the first exothermic process were studied by using Kissinger's method and Ozawa's method, in which the enthalpy of formation (−7346 and −5706 kJ M −1 ), critical temperature of thermal explosion (475.0 and 515.8 K), entropy of activation (ΔS ≠ ), enthalpy of activation (ΔH ≠ ), and free energy of activation (ΔG ≠ ) were calculated and obtained as −117.25 J K −1 M −1 , 140.64 kJ M −1 , 196.44 kJ M −1 and −219.1 J K −1 M −1 , 383.56 kJ M −1 , 495.34 kJ M −1 for 1 and 2, respectively. The sensitivity test results showed that both compounds were sensitive to impact (<5 J) and flame (>20 cm) rather than friction.

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Synthesis and Characterization of 5-Amino-1-nitriminotetrazole and Its Salts

Cited by 14 publications

References 28 publications

Recent Advanced Strategies for Extending the Nitrogen Chain in the Synthesis of High Nitrogen Compounds

Recent Advanced Strategies for Extending the Nitrogen Chain in the Synthesis of High Nitrogen Compounds

1,5‐Di(nitramino)tetrazole: High Sensitivity and Superior Explosive Performance

Synthesis, structure, and thermal decomposition of two copper coordination compounds [Cu(DAT)₂(PA)₂] and [Cu(DAT)₂(HTNR)₂] with nitrogen rich 1,5-diaminotetrazole (DAT)

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Synthesis and Characterization of 5-Amino-1-nitriminotetrazole and Its Salts

Cited by 14 publications

References 28 publications

Recent Advanced Strategies for Extending the Nitrogen Chain in the Synthesis of High Nitrogen Compounds

Recent Advanced Strategies for Extending the Nitrogen Chain in the Synthesis of High Nitrogen Compounds

1,5‐Di(nitramino)tetrazole: High Sensitivity and Superior Explosive Performance

Synthesis, structure, and thermal decomposition of two copper coordination compounds [Cu(DAT)2(PA)2] and [Cu(DAT)2(HTNR)2] with nitrogen rich 1,5-diaminotetrazole (DAT)

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Synthesis, structure, and thermal decomposition of two copper coordination compounds [Cu(DAT)₂(PA)₂] and [Cu(DAT)₂(HTNR)₂] with nitrogen rich 1,5-diaminotetrazole (DAT)