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.     

Catalytic hydrogenation of aromatic nitro compounds by non-noble metal complexes of chitosan

Silica-supported mono-metal (such as Ni, Cu) complexes and mixed metal (such as Cu/Zn, Cu/Cr) complexes of chitosan have been prepared. It is found that these non-noble metal complexes could be used as efficient catalysts for the hydrogenation of aromatic nitro compounds. The effects of type of metal, reaction temperature and pressure, solvent, nitrogen/metal molar ratio in the complex catalysts on the yields from nitrobenzene to aniline have been examined. It was also found that catalysts are active for the catalytic hydrogenation of other aromatic nitro compounds such as 2-nitroanisole, 2-nitroaniline, 2-nitrotoluene and 1-chloro-4-nitrobenzene.     

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).     

Catalytic asymmetric hydrogenation of aromatic ketones in room temperature ionic liquids

Polar bisphosphonic acid-derived Ru(BINAP)(DPEN)Cl₂ precatalysts were synthesized and immobilized in room temperature ionic liquids (RTILs) for asymmetric hydrogenation of aromatic ketones with ee values of up to 98.7%. The performance of the Ru catalysts is highly dependent on the nature of imidazolium ILs. For the imidazolium ILs without acidic protons, both ILs and Ru catalysts were recycled by simple extraction and reused. Such a simple immobilization approach also prevented the leaching of Ru (and Ru catalysts) into the chiral secondary alcohol products, and should prove desirable for the production of pharmaceutical intermediates that are free from metal contaminants.     

Highly chemoselective reduction of aromatic nitro compounds by copper nanoparticles/ammonium formate

A highly chemoselective reduction of aromatic nitro compounds to the corresponding amino derivatives has been achieved by a combination of copper nanoparticles and ammonium formate in ethylene glycol at 120 degrees C. The reductions are successfully carried out in presence of a wide variety of other reducible functional groups in the molecule, such as Cl, I, OCH2Ph, NHCH2Ph, COR, COOR, CN, etc. The reactions are very clean and high yielding.     

Selective hydrogenation of aromatic compounds using modified iridium nanoparticles

Till now, Ionic liquid‐stabilized metal nanoparticles were investigated as catalytic materials, mostly in the hydrogenation of simple substrates like olefins or arenes. The adjustable hydrogenation products of aromatic compounds, including quinoline and relevant compounds, aromatic nitro compounds, aromatic ketones as well as aromatic aldehydes, are always of special interest, since they provide more choices for additional derivatization. Iridium nanoparticles (Ir NPs) were synthesized by the H₂ reduction in imidazolium ionic liquid. TEM indicated that the Ir NPs is worm‐like shape with the diameter around 12.2 nm and IR confirmed the modification of phosphine‐functionalized ionic liquids (PFILs) to the Ir NPs. With the variation of the modifier, solvent and reaction temperature, substrate like quinoline and relevant compounds, aromatic nitro compounds, aromatic ketones as well as aromatic aldehydes could be hydrogenated by Ir NPs with interesting adjustable catalytic activity and chemoselectivity. Ir NPs modified by PFILs are simple and efficient catalysts in challenging chemoselective hydrogenation of quinoline and relevant compounds, aromatic nitro compounds, aromatic ketones as well as aromatic aldehydes. The activity and chemoselectivity of the Ir NPs could be obviously impacted or adjusted by altering the modifier, solvent and reaction temperature.     

Biphasic hydrogenation over PVP stabilized Rh nanoparticles in hydroxyl functionalized ionic liquids

Polyvinyl pyrrolidone stabilized rhodium nanoparticles are highly soluble in hydroxyl-functionalized ionic liquids, providing an effective and highly stable catalytic system. In hydrogenation reactions, excellent results were obtained, and transmission electron microscopy, solubility determinations, and leaching experiments were employed to quantify the advantages of this catalytic system.     

Palladium-catalysed transfer hydrogenation of aromatic nitro compounds — an unusual chain elongation

Aromatic nitro compounds are reduced via transfer hydrogenation in the presence of palladium on magnesium-lanthanum mixed oxide support in ethanol yielding the corresponding amines. With several acetophenone derivatives, the reduction was accompanied by chain elongation whilst the carbonyl group remained intact.     

Catalytic deoxygenation of organic compounds by carbon monoxide: III. The reaction under pressure of aromatic nitro compounds in the presence of o-phthalaldehyde

The reaction of o-phthalaldehyde with several aromatic nitro compounds in the presence of carbon monoxide and catalytic quantities of hexarhodium-hexadecacarbonyl eventuated in the formation of the corresponding N-substituted isoindolinone as the major product. A reaction mechanism has been suggested incorporating deoxygenation of the nitro compound by carbon monoxide to a nitrene intermediate and the subsequent interception of the latter by o-phthalaldehyde.     

The Raman spectra of some aromatic nitro compounds

The paper provides a re-appraisal of the analytical value of Raman spectroscopy in the investigation of aromatic nitro compounds. Correlations are found between the frequencies of the NO vibrations and the electron-donating and -withdrawing effects of substituents on the phenyl rings. Further, relations are discussed between the highest-frequency CH stretching mode and the electron density and number of nitro groups. The paper contains a large number of spectra of typical aromatic nitro compounds.     

Reduction of aromatic nitro compounds with NaBH4 catalysed by nickel complexes ofo-aminothiophenol Schiff base derivatives

Summary The nickel complexes of Schiff bases formed fromo-aminothiophenol and -dicarbonyl compounds, Ni(o-SC₆H₄N=CRCR=NC₆H₄S-o) (R=H, Me, Ph) (1a-c), catalyse the reduction of aromatic nitro compounds by NaBH₄. The reduced species [Ni(o-SC₆H₄N=CHCH=NC₆H₄S-o)]^– (2) and [Ni(o-SC₆H₄NHCH₂CH=NC₆H₄S-o)]^– (3) were identified as intermediates in the catalytic cycle.     

Kinetics of the liquid-phase catalytic hydrogenation of chlorine-containing aromatic nitro compounds in the presence of pyridine

We have analyzed experimental kinetic data for nitro compound consumption, for the formation of the corresponding amino product, and for the accumulation of intermediate products and by-products in the hydrogenation of chlorine-containing aromatic nitro compounds. The reaction has been carried out under static conditions over a platinum catalyst on a porous support in the presence of pyridine. The effect of the admixture on different hydrogenation steps of a chlorine-containing aromatic nitro compound has been quantitatively interpreted.     

Pd/C-catalyzed transfer hydrogenation of aromatic nitro compounds using methanol as a hydrogen source

We describe the selective transfer hydrogenation of aromatic nitro compounds to anilines using Pd/C as a heterogeneous catalyst with methanol as a green reductant. Nitroarenes bearing both electron-releasing and electron-deficient groups are amenable to this method and enable the synthesis of corresponding arylamines in moderate to good selectivities including the synthesis of butamben, a local anesthictic drug molecule. This new concise protocol is simple, ligand-free and does not require the supply of external molecular hydrogen.     

Transfer hydrogenation of olefins catalysed by nickel nanoparticles

Nickel nanoparticles have been found to effectively catalyse the hydrogen-transfer reduction of a variety of non-functionalised and functionalised olefins using 2-propanol as the hydrogen donor. The heterogeneous process has been shown to be highly chemoselective for certain substrates, with all the corresponding alkanes being obtained in high yields. A synthesis of the natural dihydrostilbene brittonin A is also reported based on the use of nickel nanoparticles.     

Effect of the structure of the aromatic system on the rate of dimerization of radical anions of aromatic nitro compounds

The radical anions formed in the first stage of electrolytic reduction of 9-nitroanthracene, 1-nitronaphthalene, and nitrobenzene enter into a secondorder reaction in which the value of the rate constant increases as the degree of localization of the unpaired electron on the reaction site increases.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 7, pp. 1492–1495, July, 1990.     

Chemoselective reduction of aromatic nitro and azo compounds in ionic liquids using zinc and ammonium salts

Nitroarenes were chemoselectively reduced to the corresponding amines using zinc and aqueous ammonium salts in ionic liquids as a safe and recyclable reaction medium. Our results specify the effect of ammonium salts in the process; the combination of Zn/NH₄Cl in [bmim][PF₆] or Zn/HCO₂NH₄ in [bmim][BF₄] were the suitable conditions for the reduction of nitroarenes. Azobenzenes were also smoothly reduced to hydrazobenzenes with Zn/HCO₂NH₄ (aq.) in recyclable [bmim][BF₄] without any over reduction to the corresponding anilines.     

Peripheral mechanism for hydrogenation of aromatic nitro compounds: Reaction of nitrobenzene with copper(II)-alizarin complex

Conclusions Nitrobenzene forms a molecular complex with copper bis(alizarinate) in which the nitro group is oriented in a direction opposite to the metal ion.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 4, pp. 921–923, April, 1981.