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, CO2 ) 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.

Prospective Symbiosis of Green Chemistry and Energetic Materials

Dinitrodialkoxybenzene derivatives are important precursors for Schiff base macrocycles and a variety of other molecules. During our investigations, we have found that the dinitration reaction of 1,2-dialkoxybenzenes proceeds with unusual regioselectivity, giving exclusively the desired 1,2-dialkoxy-4,5-dinitrobenzene product, but we have been unable to find a good explanation for this result. The dinitration of 1,4-dialkoxybenzene derivatives also exhibits surprising regioselectivity that has hitherto been left unexplained. Herein, we report a detailed DFT analysis of the regioselective dinitration of both 1,2- and 1,4-dimethoxybenzene. These results show that the reaction mechanism likely involves a single electron transfer (SET) process. In the case of the former isomer, the regioselectivity is mainly determined by the symmetry of the HOMO of the aromatic moiety that defines the structure of the SHOMO of the aromatic radical cation formed by the SET process. In the case of the latter isomer, the select...

Regioselectivity in the Nitration of Dialkoxybenzenes

Aromatic nitration has tremendous importance in organic chemistry as nitroaromatic compounds serve as versatile building blocks. This study represents the electrochemical aromatic nitration with NBu4 NO2 , which serves a dual role as supporting electrolyte and as a safe, readily available, and easy-to-handle nitro source. Stoichiometric amounts of 1,1,1-3,3,3-hexafluoroisopropan-2-ol (HFIP) in MeCN significantly increase the yield by solvent control. The reaction mechanism is based on electrochemical oxidation of nitrite to NO2 , which initiates the nitration reaction in a divided electrolysis cell with inexpensive graphite electrodes. Overall, the reaction is demonstrated for 20 examples with yields of up to 88 %. Scalability is demonstrated by a 13-fold scale-up.

Electrochemical Nitration with Nitrite

Novel acylamino-directed relay disubstitutions realize the sequential difunctionalizations of anilides (1) under mild and metal-free conditions for the first time. This [bis(trifluoroacetoxy)iodo]benzene (PIFA) and BF3·Et2O promoted straightforward reaction produces a series of p-acetoxyl- or p-alkoxyl- o-nitro- N-arylamides (2), which are key scaffolds of various drugs, functional materials, and bioactive molecules. The flexibility with respect to the functional groups in these products affords this novel protocol excellent versatility for synthetic applications.

Acylamino-Directed Specific Sequential Difunctionalizations of Anilides via Metal-Free Relay Reactions for p-Oxygen and o-Nitrogen Incorporation.

The synthesis and catalytic activity of pyridine-fused triazolylidene as a novel abnormal N-heterocyclic carbene (aNHC) ligand is described. The evaluation of physical properties using X-ray crystallographic analysis and infrared spectroscopy revealed that these triazolylidenes have a high electron-donating ability toward the metal center. The application of this triazolylidene to the palladium-catalyzed cross-coupling of chloroarenes and nitroarenes with arylboronic acids showcased its ability to activate C-Cl and C-NO2 bonds.

Synthesis and Properties of Pyridine-Fused Triazolylidene-Palladium: Catalyst for Cross-Coupling Using Chloroarenes and Nitroarenes.

Aromatic molecules have a strong affinity for silver(I) and dissolve to a limited extent in Ag0.51K0.42Na0.07NO3, a low-melting eutectic mixture of silver, potassium, and sodium nitrates. Aromatic nitration in this inorganic ionic liquid leads to products which arise from nonelectrophilic substitution pathways.

Aromatic nitration in liquid Ag0.51K0.42Na0.07NO3.

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Aromatic nitration in liquid Ag0.51K0.42Na0.07NO3.