The synthesis of azo compounds from nitro compounds using lead and triethylammonium formate

Aromatic nitro compounds were reduced to the corresponding symmetrically substituted azo compounds using lead as catalyst and triethylammonium formate as hydrogen donor. Various azo compounds containing additional reducible substituents including halogens, nitrile, acid, phenol, ester, methoxy functions, etc, have been synthesized in a single step by the use of this reagent. The conversion is reasonably fast, clean, high yielding and occurs at room temperature in methanol.     

The reduction of aromatic nitro compounds by oxiranes

Aromatic nitro compounds are reduced to the corresponding amines by epoxides at elevated temperatures (>170 °C).Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1491–1494, August, 1994.The authors are grateful to Prof. Yu. N. Belokon' for his participation in the discussion of the results of the work.This work was financially supported by the Russian Foundation for Basic Research (code No. 93-03-18044).     

Energetic nitrogen-rich salts and ionic liquids

Energetic salts offer many advantages over conventional energetic molecular compounds. The use of nitrogen containing anions and cations contributes to high heats of formations and high densities. Their low carbon and hydrogen content gives rise to a good oxygen balance. The decomposition of these compounds is predominantly through the generation of dinitrogen which makes them very promising candidates for highly energetic materials for industrial or military applications.     

Oxidative dimerization of aromatic amines using tBuOI: entry to unsymmetric aromatic azo compounds

It's all the hype: An oxidative dimerization reaction of aromatic amines utilizing tert-butyl hypoiodite (tBuOI) under mild reaction conditions leads to aromatic azo compounds. The method allows access to unsymmetric aromatic azo compounds, which are difficult to prepare by conventional synthetic methods, in a selective manner.     

Carbonylation of nitro and azo compounds in the presence of iron carbonyl catalysts

The reactions of nitro and azo compounds with carbon monoxide were studied in the presence of iron carbonyl catalysts. It was shown that these catalytic systems differ substantially from Pd- and Rh-containing catalysts. In the case of the iron catalysts, the products of coupling of molecules are formed as intermediates and azo compounds are the final reaction products. The reactions involving the palladium and rhodium catalysts proceed without the intermediate formation of the coupling products and lead to isocyanates or carbamates. When combined using PdCl₂ and Fe(CO)₅/Al₂O₃, the catalysts inhibit each other, especially in the presence of pyridine.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 10, pp. 2460–2463, October, 1996.     

Mukaiyama aldol reaction using ketene silyl acetals with carbonyl compounds in ionic liquids

Mukaiyama aldol reactions using ketene silyl acetals with various aldehydes proceed smoothly in ionic liquids to afford the corresponding aldol products in moderate yields.     

Low-melting, low-viscous, hydrophobic ionic liquids: aliphatic quaternary ammonium salts with perfluoroalkyltrifluoroborates

A novel class of low-melting, hydrophobic ionic liquids based on relatively small aliphatic quaternary ammonium cations ([R(1)R(2)R(3)NR](+), wherein R(1), R(2), R(3) = CH(3) or C(2)H(5), R = n-C(3)H(7), n-C(4)H(9), CH(2)CH(2)OCH(3)) and perfluoroalkyltrifluoroborate anions ([R(F)BF(3)](-), R(F) = CF(3), C(2)F(5), n-C(3)F(7), n-C(4)F(9)) have been prepared and characterized. The important physicochemical and electrochemical properties of these salts, including melting point, glass transition, viscosity, density, ionic conductivity, thermal and electrochemical stability, have been determined and comparatively studied with those based on the corresponding [BF(4)](-) and [(CF(3)SO(2))(2)N](-) salts. The influence of the structure variation in the quaternary ammonium cation and perfluoroalkyltrifluoroborate ([R(F)BF(3)](-)) anion on the above physicochemical properties is discussed. Most of these salts are liquids at 25 degrees C and exhibit low viscosities (58-210 cP at 25 degrees C) and moderate conductivities (1.1-3.8 mS cm(-1)). The electrochemical windows of these salts are much larger than those of the corresponding 1,3-dialkyimidazolium salts. Additionally, a number of [R(F)BF(3)](-) salts exhibit plastic crystal behavior.     

Synthesis of azo compounds by nanosized iron-promoted reductive coupling of aromatic nitro compounds

Treatment of a variety of aromatic nitro compounds with the active-iron based reducing system composed of FeCl₂·4H₂O, an excess of lithium powder and a catalytic amount of 4,4′-di-tert-butylbiphenyl (DTBB, 5 mol %) in THF at room temperature, led to the formation of the corresponding symmetrically substituted azo compounds in good yield, resulting from a reductive coupling process. Some other functionalities including carbonyl, halogen, amino and hydroxyl groups, demonstrated to be compatible with the reaction conditions, giving none reduced or coupled by-products. In all cases, the azo compounds formed have not experienced over-reduction to the corresponding hydrazo or amino derivatives even upon prolonged heating or using an excess of the reducing system.     

Electrocatalytic reduction of CO2 in neat and water-containing imidazolium-based ionic liquids

Energetically efficient electrochemical reduction of CO₂ would offer the possibility of storing electricity from renewables in the form of fuels and other valuable chemicals. It may also help mitigate the increase of atmospheric CO₂ associated with global warming. However, the process suffers from a low energy efficiency because of the large overpotentials required. In aqueous electrolytes, the competing hydrogen evolution reaction also decreases the faradaic efficiency (which contributes to the low energy efficiency of the process). Recent claims of high faradaic efficiency and low overpotentials for the reduction of CO₂ in room-temperature ionic liquids (RTILs) and RTIL–water mixtures have spurred considerable research. Here, we offer a critical review of those claims and of recent work aimed at understanding the details of this important reaction in these nonconventional electrolytes.     

Eutectic-based ionic liquids with metal-containing anions and cations

Eutectic mixtures of zinc chloride and donor molecules such as urea and acetamide are described and it is proposed that these constitute a new class of ionic liquids. FAB-MS analysis shows that the liquids are made up of metal-containing anions and cations in which the donor is coordinated to the cation. Data on the viscosity, conductivity, density, phase behaviour and surface tension are presented and these are shown to be significantly different to other related ionic liquids that incorporate quaternary ammonium salts. The conductivity and viscosity are comparable with other ionic liquids and the data fit well to the Hole theory model recently proposed.     

活性炭负载氢氧化氧铋催化水合肼还原芳香族硝基化合物

采用浸渍法制备了BiO(OH)/C催化剂。催化剂的XRD谱表明,当催化剂中BiO(OH)的质量分数小于10%时,BiO(OH)在活性炭中高度分散。反应温度为75 ℃时,催化剂重复使用7次仍保持较高活性。在5 mL乙醇中以0.05 g 10%（质量分数）BiO(OH)/C,1 mmol芳香族硝基化合物和2 mmol水合肼于75 ℃反应一定的时间,所得芳胺的收率为88%～99%。     

Synthesis of novel spiro imidazolium salts as chiral ionic liquids

A library of 13 novel chiral spiro imidazolium salts has been synthesized. The effects of N-substituents and counteranions on the melting point of spiro bis(imidazolium) salts are studied in efforts toward the development of room temperature chiral ionic liquids.     

High‐throughput microscale extraction using ionic liquids and derivatives: A review

Ionic liquids and derivatives—mainly polymeric ionic liquids and magnetic ionic liquids—have been extensively used in microscale extraction over the past few years. Current trends in analytical sample preparation gear toward linking microextraction approaches with high‐throughput sample processing to comply with green analytical chemistry requirements. A variety of high sample throughput strategies that are coupled to both ionic‐liquid‐based solid‐phase microextraction and ionic liquid‐based liquid‐phase microextraction are herein reported. The review is focused on microscale extraction methods that use (i) custom‐made and dedicated extraction devices, (ii) parallel extraction, (iii) magnetic‐based separation, and (iv) miniaturized systems employing semi‐automatic or fully automatic flow injection methods, related micro/millifluidic devices, and robotic equipment.     

Fabrication of ZnO nanorods in ionic liquids and their photoluminescent properties

A novel and simple approach is reported to fabricate uniform single-crystal ZnO nanorods in ionic liq-uids. The as-obtained ZnO nanorods have been characterized by XRD,TEM,HRTEM,SAED,XPS,EDXA,PL and UV-vis absorption spectra. The rod diameters of the nanostructures can be controlled by tuning the amount of sodium hydroxide in the synthesis. Photoluminescence results show that the nanos-tructural ZnO exhibits better optical properties than bulk ZnO does and interestingly,the smaller the rod diameters are,the better optical property 1D nanostructural ZnO exhibits. The possible growth mechanism of ZnO nanorods is also investigated.     

A metal-catalyst-free oxidative coupling of anilines to aromatic azo compounds in water using bleach

A simple route toward the synthesis of symmetrical and unsymmetrical aromatic azo compounds through oxidative coupling of anilines using widely available NaOCl is presented. This metal catalyst-free protocol is performed in water and affords the desired products in high yields.     

Recent developments of task-specific ionic liquids in organic synthesis

Abstract

Task-specific ionic liquids (TSILs) have received increased attention over the past few years as it is possible to form any specific ionic liquid (IL) composition depending upon user's need of the desired physical, chemical, and biological properties. These fascinating materials have shown promising results in various areas such as organic synthesis, catalysis, and specially recent emerging trend of use as functionalized ILs for chiral and nanoparticle synthesis. Present review gives an update of recent developments in the field of TSILs with emphasis on their applications in organic synthesis.     

Convenient synthesis of various ionic liquids from onium hydroxides and ammonium salts

Hydroxide ionic liquids, such as 1-alkyl-3-methylimidazolium hydroxides, undergo smooth anion metathesis with ammonium salts to produce a variety of ionic liquids in excellent yields. It is a practical supplement of traditional neutralization method due to the broader range of starting materials containing desired anions.     

Synthesis of methyl orange using ionic liquids

Two ionic liquids were synthesized, each system consisting of the 1-hexyl-3-methylimidazolium ion ([hmim]⁺) as the cation and either hexafluorophosphate ([PF₆]⁻), or perchlorate ([ClO₄]⁻) as the anions. This study involves the synthesis of methyl orange (4-[[(4-dimethylamino)phenyl]-azo] benzene sulfonic acid sodium salt) using the ionic liquids as replacement solvents for the reaction. The advantage of using ionic liquids as substitutes for organic solvents includes: recyclable/reclaimable solvents, stabilization of intermediates and higher product yields. The 1-hexyl-3-methylimidazolium derivatives can be used for syntheses conducted at low temperatures and are less toxic than typical organic solvents.     

Sodium dithionite in the regioselective reduction of the ortho-positioned nitro group in 1-R-2,4-dinitrobenzenes

1-R-2,4-Dinitrobenzenes are regioselectively reduced with sodium dithionite at near-neutral pH into the product having amino group ortho to the substituent R. Although the yields of products varied from moderate to good, the procedure does not involve the use of transition metals.