Strategies toward the design of energetic ionic liquids: nitro- and nitrile-substituted N,N′-dialkylimidazolium salts

Katritzky, Alan R.; Yang, Hongfang; Zhang, Dazhi; Kirichenko, Kostyantyn; Śmiglak, Marcin; Holbrey, John D.; Reichert, W. Matthew; Rogers, Robin D.

doi:10.1039/b509260d

Cited by 60 publications

(51 citation statements)

References 51 publications

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“…But oxygen-rich cations remain elusive because once nitrated, the ability of neutral Lewis bases to form cationic species is greatly reduced. Nitroimidazoles can be quaternized, but dinitroimidazole cannot [23]. Similarly, 1,4-alkylated 3-nitro-1,2,4-triazoles have been reported, but they are hydrolytically unstable [24].…”

Section: Introductionmentioning

confidence: 95%

New Takes on Nitrate Ester Chemistry: Salts with Oxygen‐Rich Ammonium Cations

Drake

Bolden

Dailey

et al. 2012

Propellants Explo Pyrotec

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Recent efforts have established the possibility of pharmaceutical applications for several nitrate ester salts, and their Abstract: Nitrate (anion) salts with nitroxy-functionalized ammonium cations were synthesized. Several revealed surprising thermal and hydrolytic stability. Various physical properties were measured, and Gibbs free energy (DG r (298)) differences between the salts and postulated products of their thermal decomposition were computed. The computed differences indicate that salts with cations that have more than one nitroxy group are endothermic at 298 K. Nevertheless, the stability observed for some salts with this property indicates that kinetic barriers are sufficient to prevent facile decomposition at this temperature. This is in contrast to the case observed for nitrate salts of nitroxy-functionalized ammonium cations with acidic protons.

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Section: Introductionmentioning

confidence: 95%

New Takes on Nitrate Ester Chemistry: Salts with Oxygen‐Rich Ammonium Cations

Drake

Bolden

Dailey

et al. 2012

Propellants Explo Pyrotec

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“…As such, the negative G r (298) values found for the notional imidazolium nitrates whose cations have a single (primary) nitroxy group suggest they will be stable, while the positive G r (298) values for the nitrate salts of the three notional imidazolium cations with two NO x groups suggest they will be unstable. Corroborating the latter predictions, Katritzky et al (2006) report that they were unable to N-alkylate or protonate dinitro-substituted imidazoles.…”

Section: Salts Having a Cation With A Heterocyclic Ringmentioning

confidence: 78%

Property Predictions for Nitrate Salts with Nitroxy-Functionalized Cations

McQuaid¹,

Drake²

2011

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“…Of importance,i st hat when an azole is further substituted by electron-withdrawing groups (which need not be halides), they furthers tabilize the anion through inductive and mesomeric effects, improving both stabilitya nd utility synergistically. [18] We, alongside the researchers whose publications we have surveyedi nt his article, suggest that the use of an azolatebased anioni sa ni mportant but routinelyi gnored membero f the IL chemist's toolbox. In its inherent delocalized charge, it is capable of formingI Ls by the above-mentioned strategies withoutt he requirement for hazardousc omponents,s uch as halide atoms, while also introducing an ew suite of architectural flexibility through functionalization of the azolate ring.…”

Section: Why Useanazole As An Anion?mentioning

confidence: 93%

“…This same delocalization by resonance can be exploited for anions by deprotonating the pyrrole‐like nitrogen atom to make an anionic azolate. Of importance, is that when an azole is further substituted by electron‐withdrawing groups (which need not be halides), they further stabilize the anion through inductive and mesomeric effects, improving both stability and utility synergistically …”

Section: Introductionmentioning

confidence: 99%

Azolate Anions in Ionic Liquids: Promising and Under‐Utilized Components of the Ionic Liquid Toolbox

Easton

Choudhary

Rogers

2018

Chemistry A European J

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Owing to their ease of synthesis, diffuse positive charge, and chemical stability, 1-alkyl-3-methylimidazolium cations (i.e., [C mim] ) are one of the most routinely utilized and historically important components in ionic liquid (IL) chemistry. However, while this is a routinely encountered member of the IL family as cations, relatively few workers have explored the versatile chemistry of azoles to allow their use as an anionic component in ILs, as azolates. Azolate anions possess many of the desired properties for IL formation, including a diffuse ionic charge, tailorable asymmetry, and synthetic flexibility, with the added advantages of not relying on halogen atoms for electron-withdrawing effects, as is commonly encountered with IL anions such as hexafluorophosphate. This review explores the 122 azolate-containing ILs known in the literature (prepared from only 39 disparate azolate anions), with a view to highlighting not only their demonstrated utility as an IL component, but the ways in which the larger scientific community may utilize their advantageous properties for new tailored materials.

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Strategies toward the design of energetic ionic liquids: nitro- and nitrile-substituted N,N′-dialkylimidazolium salts

Cited by 60 publications

References 51 publications

New Takes on Nitrate Ester Chemistry: Salts with Oxygen‐Rich Ammonium Cations

New Takes on Nitrate Ester Chemistry: Salts with Oxygen‐Rich Ammonium Cations

Property Predictions for Nitrate Salts with Nitroxy-Functionalized Cations

Azolate Anions in Ionic Liquids: Promising and Under‐Utilized Components of the Ionic Liquid Toolbox

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