Nitration of carbonic, sulfuric and oxalic acid-derived amides in liquid carbon dioxide

Kuchurov, Ilya V.; Fomenkov, Igor V.; Zlotin, Sergei G.; Tartakovsky, Vladimir A.

doi:10.1016/j.mencom.2013.03.008

Cited by 10 publications

(7 citation statements)

References 16 publications

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“…[185] As imilarn itration of 1,3-dimethylglycoluril led to compound 13 with both nitro groups attached to the same urea fragment. [187] The products 16 and 17 are key precursors of primary N-nitramines (in particular, methylnitraminea nd ethylenedinitramine), which are produced on ac ommercial scale and are used for the synthesis of useful HEMs through condensation reactions. 1,4-Dinitroglycouril (DINGU)i sc onsidered an insensitive high explosive (VOD % 7580 ms À1 , d = 1.99 gcm À3 ), and an advantage of the high-energyc ompound HK-55 (d = 1.905 gcm À3 )i s its low shock sensitivity.…”

Section: Reviewsmentioning

confidence: 99%

“…[186] N-Alkylcarbamates 14 and N-alkylamides 15 a-c of carbonic, sulfuric,a nd oxalic acids were nitrated readily with N 2 O 5 in a liquid CO 2 medium to yield the corresponding N-nitro compounds 16 and 17 a-c in high yields (Scheme 40). [187] The products 16 and 17 are key precursors of primary N-nitramines (in particular, methylnitraminea nd ethylenedinitramine), which are produced on ac ommercial scale and are used for the synthesis of useful HEMs through condensation reactions. [188][189][190] The successful application of the N 2 O 5 /liquid CO 2 nitrating system made it possible to achieve high yields of energetic products and avoid the use of environmentally harmful nitrating agents( e.g.,m ixed acids HNO 3 /H 2 SO 4 [191] or NH 4 NO 3 / (CF 3 CO) 2 [192] )a nd toxic chlorinated solvents.…”

Section: N-nitrationreactionsmentioning

confidence: 99%

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Prospective Symbiosis of Green Chemistry and Energetic Materials

et al. 2017

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A global increase in environmental pollution demands the development of new "cleaner" chemical processes. Among urgent improvements, the replacement of traditional hydrocarbon-derived toxic organic solvents with neoteric solvents less harmful for the environment is one of the most vital issues. As a result of the favorable combination of their unique properties, ionic liquids (ILs), dense gases, and supercritical fluids (SCFs) have gained considerable attention as suitable green chemistry media for the preparation and modification of important chemical compounds and materials. In particular, they have a significant potential in a specific and very important area of research associated with the manufacture and processing of high-energy materials (HEMs). These large-scale manufacturing processes, in which hazardous chemicals and extreme conditions are used, produce a huge amount of hard-to-dispose-of waste. Furthermore, they are risky to staff, and any improvements that would reduce the fire and explosion risks of the corresponding processes are highly desirable. In this Review, useful applications of almost nonflammable ILs, dense gases, and SCFs (first of all, CO ) for nitration and other reactions used for manufacturing HEMs are considered. Recent advances in the field of energetic (oxygen-balanced and hypergolic) ILs are summarized. Significant attention is paid to the SCF-based micronization techniques, which improve the energetic performance of HEMs through an efficient control of the morphology and particle size distribution of the HEM fine particles, and to useful applications of SCFs in HEM processing that makes them less hazardous.

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Section: Reviewsmentioning

confidence: 99%

Section: N-nitrationreactionsmentioning

confidence: 99%

Prospective Symbiosis of Green Chemistry and Energetic Materials

et al. 2017

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“…[15] The fully nitrated compound was also synthesized by Zlotin and Tartakovsky, but employing N 2 O 5 and supercritical CO 2 . [16] In our work, the procedure of Stuart and Wright was adapted and modified to current techniques by using 100 % nitric acid to give the nitrate 8 (Scheme 3).…”

Section: Synthesis and Characterizationmentioning

confidence: 99%

“…The bond length of the nitrogen and the bridging oxygen on the other hand is 1.39 Å, which is in the range of the literature value of a NÀ O single bond (NÀ O 1.45 Å). [16] 6), C2À N1À C1À C1' À 177.5(4), C3À O2À N2À O4 À 7.3(4), N1À C1À C1'À N1' 180.0(5), O1À C1À C1'À O1' 180.0 (5).…”

Section: Single Crystal Structure Analysismentioning

confidence: 99%

Oxygen Enriched Oxamides and N‐Dinitrated Oxamides: Trinitroethyl Esters, Nitrocarbamates and Nitrates

et al. 2021

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Dedicated to Professor Konstantin Karaghiosoff on the Occasion of his 65 th BirthdayStarting from the readily available starting materials diethyl oxalate, glycine and β-alanine, some new N-nitrated oxamides were synthesized. Oxamides formed by condensation reactions were subsequently nitrated to form the corresponding dinitroxamides. These were further converted to the corresponding acid chlorides with the utilization of thionyl chloride. The final reaction of the β-alanine based dinitroxamide with trinitroethanol generated the energetic target ester in moderate yield and high purity. Additionally, starting from diethyl oxalate and ethanolamine gave access to a nitrocarbamate based on an oxamide. Furthermore, the previously reported compound bis (2-nitratoethyl) oxamide was synthesized now in a more facile fashion and fully characterized, especially in case of the energetic properties, sensitivities and crystal structure. The compounds were fully analysed by NMR spectroscopy, vibrational analysis and elemental analysis. The heat of formation was calculated with the Gaussian program package and in combination with the experimental density the energetic properties were estimated utilizing the Explo5 computer code.

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“…Recently, the significantly less harmful for the environment synthesis of N-nitramides (N-nitrourethanes) by the nitration of corresponding amides (urethanes) with nearly equimolar amount of dinitrogen pentoxide (DNP) in liquid or supercritical carbon dioxide medium has been developed. [14][15][16] Yet, an expensive high-pressure (up to 150 bar) equipment is needed in this case. Moreover, carbon dioxide is not suitable as the medium for subsequent basic hydrolysis or ammonolysis reactions because it readily generates metal carbonates or ammonium carbamate, respectively, with corresponding reagents.…”

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Safe and Convenient Synthesis of Primary N-Nitramines in the Freon Media

et al. 2016

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A convenient one-pot synthesis of primary aliphatic N-nitramines, which includes the nitration of available N,N′-dialkyloxalamides or N-alkylcarbamates with dinitrogen pentoxide in the 1,1,1,2-tetrafluoroethane media followed by ammonolysis of intermediate N-nitroamides in the same solvent has been developed. The method is environmentally safe, and affords target N-nitramines in up to 94% overall yield.

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Nitration of carbonic, sulfuric and oxalic acid-derived amides in liquid carbon dioxide

Cited by 10 publications

References 16 publications

Prospective Symbiosis of Green Chemistry and Energetic Materials

Prospective Symbiosis of Green Chemistry and Energetic Materials

Oxygen Enriched Oxamides and N‐Dinitrated Oxamides: Trinitroethyl Esters, Nitrocarbamates and Nitrates

Safe and Convenient Synthesis of Primary N-Nitramines in the Freon Media

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