Graphite catalyzed reduction of aromatic and aliphatic nitro compounds with hydrazine hydrate

Aromatic and aliphatic nitro compounds were readily reduced to amino compounds in excellant yields with graphite and hydrazine hydrate.     

Selective reduction of one, two, or three nitro groups in 1,3,5-trinitrobenzene with hydrazine hydrate

A method was developed for successive selective reduction of one, two, or three nitro groups in 1,3,5-trinitrobenzene with hydrazine hydrate in the presence of iron chloride and charcoal. This method provides an approach to the one-pot synthesis of 3,5-dinitroaniline, 1,3-diamino-5-nitrobenzene, or 1,3,5-triaminobenzene from 1,3,5-trinitrobenzene. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 5, pp. 904–905, May, 2006.     

Selective reduction of aromatic nitro compounds with stannous chloride in non acidic and non aqueous medium

Aromatic nitro compounds are readily reduced by SnCl₂, 2 H₂O in alcohol or ethyl acetate or by anhydrous SnCl₂ in alcohol where other reducible or acid sensitive groups such as aldehyde, ketone, ester, cyano, halogen and O-benzyl remain unaffected.     

One-step double reduction of aryl nitro and carbonyl groups using hydrazine

Single-step reduction of aryl nitro and carbonyl groups to the corresponding synthetically useful alkyl-anilines occurs with excellent yields by treatment with hydrazine and a base in a solvent-free reaction. The method has been applied to a broad range of compounds with different properties. Investigations into the mechanism of the reduction reveal that each group is reduced independently. A mechanism is proposed for this novel reduction of aromatic nitro groups.     

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).     

Rapid catalytic transfer reduction of aromatic nitro compounds to hydroxylamines

A general method has been developed for the rapid, metal-catalysed transfer reduction of nitro compounds to N-substituted hydroxylamines.     

Condensation reaction with methylketones and aromatic compounds containing electron-repelling groups

Aryl tellurium trichlorides and tribromides undergo condensation reactions with acetone, acetophenone, N-dimethylaniline and resorcinol, giving rise to aryl tellurium dihalides. Aryl tellurium triiodides are not reactive. The dihalides derived from N-dimethylaniline and resorcinol undergo ionic interchange reactions with halide ions. When treated with reducing agents the dihalides derived from N-dimethylaniline are reduced to the corresponding tellurides, while the other dihalides are cleaved to the diaryl-ditellurides.     

Reduction of aromatic nitro compounds with phosphine

The reduction of 1- and 2-nitronaphthalene and of some mono- and dinitro-biphenyls with phosphine was carried out under the conditions described by Buckler.¹ Reduction of 1-nitro-naphthalene did not yield any crystalline product while reduction of 2-nitronaphthalene yielded benzo[f]naphtho[2,1-c]cinnoline-N-oxide together with 2,2′-azoxynaphthalene. The mononitro-biphenyls and 4,4′-dinitrobiphenyl were readily reduced to azoxy compounds, while reduction of 2,2′-dinitrobiphenyl gave benzo[c]cinnoline-N,N′-dioxide.     

Microdetermination of aromatic nitro compounds

Conclusion A method was proposed for the microdetermination of nitro compounds, which is based on their reduction to amines by heating with potassium iodide and orthophosphoric acid.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 3, pp. 658–659, March, 1971.     

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%。     

Rapid,efficient and selective reduction of aromatic nitro compounds with hydrazine hydrate in the presence of the plain and supported platinum nanoparticles as catalysts

The current study aimed at application of the plain and supported platinum nanoparticles as a heterogenous catalyst for the reduction of aromatic nitro compounds. Monodispersed platinum nanoparticles were synthesized by reduction of H₂PtCl₆ by ethanol in the presence of polyvinyl pyrrolidone as a stabilizer, and then were immobilized on four types of zeolites. The obtained catalyst granules were characterized by X-ray diffractometry and transmission electron microscopy. The study then focused on elaboration of the catalytic activity of the nano catalysts under different operational conditions. It was found that reaction is adequately rapid at ambient temperature, and by utilizing a sufficient amount of catalyst, can be completed in nearly 30 min. Among the utilized zeolitic supports, zeolite 4A had the highest performance, but the mechanism of its synergetic effect on the activity of platinum nano catalyst was not found and requires more investigation.     

Catalytic transfer hydrogenation of aromatic nitro compounds in the presence of nickel thiolato-complexes

Summary Transfer hydrogenation of aromatic nitro compounds by hydrazine to the corresponding anilines is catalyzed by (Bu₄N)[Ni(tdt)₂] (tdt=toluene-3,4-dithiolate) and analogous Ni^III complexes in refluxing THF; hydroxylamine derivatives are formed as intermediates.     

Nucleophilic displacement of aromatic nitro groups

The relative nucleofugicity of the nitro group in many aromatic nucleophilic substitution reactions rivals, and in some cases surpasses, that of the fluorine atom. The use of the nitro function as a leaving group in such reactions facilitates the synthesis of novel substituted benzene derivatives and simplifies the synthesis of a wide variety of heterocycles.     

Low-temperature copper hydrosilicates: catalysts for reduction of aromatic nitro compounds with molecular hydrogen

Russian Chemical Bulletin - The catalytic reduction of aromatic nitro compounds with hydrogen was carried out for the first time over low-temperature copper hydrosilicates synthesized at...     

Selective reduction of aromatic nitro compounds affording aromatic amines under CO/H2O conditions catalyzed by phosphine-added rhodium and ruthenium carbonyl complexes

High catalytic activities for the selective reduction of aromatic nitro compounds to the corresponding amines under the mild reaction conditions of room temperature and 1 atm of CO were found to be exhibited by chelatephosphine (dppe, dppm, etc.; dppe: 1,2-bis(diphenylphosphino)ethane, dppm: bis(diphenylphosphino)methane)-added rhodium and ruthenium carbonyl complexes in a 5 N NAOH aqueous solution. The reduction proceeded not only with high catalytic activities, but also with remarkably high nitro group selectivities; for example, 1-nitroanthraquinone afforded 1-aminoanthraquinone without other unsaturated groups (such as CO) being reduced. PR₃-added Rh(CO)₂(acac) complexes (PR₃: PEtPh₂, PEt₂Ph, PEt₃, etc.; acac: acetylacetonato) in diglyme in a 5 N NaOH aqueous solution were also found to show significant catalytic activities for the reduction of aromatic nitro compounds under mild CO/H₂O conditions. Both electronic and steric factors of phosphine ligands are important in making this reaction proceed at such remarkable rates.