Reduction of nitroarenes followed by propanol group transfer from tris(3‐hydroxypropyl)‐ amine and cyclization leading to quinolines under heterogeneous Pd?C catalysis

Nitroarenes having electron‐donating or ‐withdrawing substituents are reduced to anilines and cyclized with tris(3‐hydroxypropyl)amine in the presence of a catalytic amount of Pd? C along with tin(II) chloride and isopropanol in dioxane‐H₂O medium to give the corresponding quinolines in good to excellent yields. Copyright © 2009 John Wiley & Sons, Ltd.     

Book Reviews

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HANDBOOK FOR ESTIMATING PHYSICOCHEMICAL PROPERTIES OF ORGANIC COMPOUNDS, by M. Reinhard and A. Drefal, 228 pages, J. Wiley, New York (1999). ISBN 0—471—172634. UK £ 210.00

THE CHEMISTRY OF POLLUTION, by G. Fellenberg, 192 pp. J. Wiley & Sons, Chichester, U.K. (1999). ISBN 0—471—980889. UK£ 24,95.

NATURAL ATTENUATION OF FUELS AND CHLORINATED SOLVENTS IN THE SUBSURFACE, by T.H. Wiedemeier, H.S. Rifai, C.J. Newell and J.T. Wilson, 617 pages, J. Wiley, New York (1999). ISBN 0—471—19749—1. UK £ 58.50

UNDERSTANDING OUR ENVIRONMENT, 3^rd, edition, edited by R.M. Harrison, 445 pages, The Royal Society of Chemistry, Cambridge (UK) (1999). ISBN 0—85404—584—8. UK£ 19.95

ENDOCRINE DISRUPTING CHEMICALS, Vol. 12 of Issues in Environmental Science and Technology, edited by R.E. Hester and R.H. Harrison, 152 pages, Royal Society of Chemistry, Cambridge (U.K.) (1999). ISBN 0—85404—255—5. UK£ 25,00

METHOD PERFORMANCE STUDIES FOR SPECIATION ANALYSIS. by P. Quevauviller, 271 pages, The Royal Society of Chemistry, Cambridge (U.K.) (1998). ISBN 0—85404—467—1. UK£ 59.50

GLOBAL AQUATIC AND ATMOSPHERIC ENVIRONMENT, by H.D. Kumar and D.P. Häder, 393 pages, Springer, Berlin (1999). ISBN 3—540—65369—4. USD 229.00

BIOACCUMULATION. New Aspects and Developments, edited by B. Beek, 284 pages, Springer, Heidelberg, 2000. ISBN 3—540—62575. USD 143.00

INTERLABORATORY STUDIES AND CERTIFIED REFERENCE MATERIALS FOR ENVIRONMENTAL ANALYSIS. The BCR approach, by Ph. Quevauviller and E.A. Maier, 558 pages, Elsevier Science, Amsterdam NL, (1999). ISBN 0—444—82389—1. USD 251.50 (Euro 224.62).     

Palladium nitrosoarene complexes in reductive carbonylation of nitroarenes

The reactions of carbon monoxide with the palladium nitrosoarene complexes Pd₂(-OCOR)₂(—CH₂C₆H₄NO)₂ (1, R = Me, CF₃, Bu^t, or Ph) and Pd₂(-OCOR)₂(PhNC₆H₄NO)₂ (2, R = Me, CF₃, Bu^t, or Ph) were studied. Complexes 1 contain the o-nitrosotoluene molecule metallated at the methyl group. In complexes 2, the phenyl-o-nitrosophenylamide ligand coordinated via two nitrogen atoms can be considered as a nitrosobenzene derivative bearing the NPh group in the ortho position of the Ph ring. It all cases, carbonylation of the complexes afforded the corresponding aryl isocyanates Ar—N=C=O or the products of their further transformations. The mechanism of reductive carbonylation of nitroarenes catalyzed by palladium compounds and the role of palladium nitrosoarene complexes as possible intermediates in this process are discussed.     

Chemoselective Hydrogenation of Nitroaromatics at the Nanoscale Iron(III)–OH–Platinum Interface

Catalytic hydrogenation of nitroaromatics is an environment‐benign strategy to produce industrially important aniline intermediates. Herein, we report that Fe(OH)_x deposition on Pt nanocrystals to give Fe(OH)_x/Pt, enables the selective hydrogenation of nitro groups into amino groups without hydrogenating other functional groups on the aromatic ring. The unique catalytic behavior is identified to be associated with the Fe^III‐OH‐Pt interfaces. While H₂ activation occurs on exposed Pt atoms to ensure the high activity, the high selectivity towards the production of substituted aniline originates from the Fe^III‐OH‐Pt interfaces. In situ IR, X‐ray photoelectron spectroscopy (XPS), and isotope effect studies reveal that the Fe³⁺/Fe²⁺ redox couple facilitates the hydrodeoxygenation of the ‐NO₂ group during hydrogenation catalysis. Benefitting from Fe^III‐OH‐Pt interfaces, the Fe(OH)_x/Pt catalysts exhibit high catalytic performance towards a broad range of substituted nitroarenes.     

Ultra‐low‐loading palladium nanoparticles stabilized on nanocrystalline Polyaniline (Pd@PANI): A efficient,green, and recyclable catalyst for the reduction of nitroarenes

Ultra‐low‐loading Pd@PANI nanocomposites (0.048 w.t% Pd) were synthesized via a method that combined interfacial polymerization and in situ composite with camphor sulfonic acid ((+)‐CSA) as a dopant. Transmission electron microscopy (TEM), X‐ray diffraction (XRD), Fourier transform infrared (FTIR) spectra, and X‐ray photoelectron spectroscopy (XPS) were performed to characterize the structures. It can be used as an efficient catalyst for the reduction of nitroarenes in aqueous solution by using a smaller amount of NaBH₄ (2.5 equiv.) at room temperature with high activity (TON = 3.4 × 10³), good stability (cycled eight times), as well as wide applicability (27 substrates). The catalyst also showed a marvelous activity in the gram‐level reaction (yield = 92%). UV–Visible spectrophotometry was used to investigate the reaction kinetics for the reduction of 4‐nitrophenol to 4‐aminophenol, and the results reconfirmed the excellent performance of the catalyst. The unique properties and superior performance of the prepared ultra‐low‐loading Pd@PANI nanocomposites lead it be an attractive alternative catalyst for conventional organic catalytic applications.     

A Reusable Co Catalyst for the Selective Hydrogenation of Functionalized Nitroarenes and the Direct Synthesis of Imines and Benzimidazoles from Nitroarenes and Aldehydes

The use of abundantly available transition metals in reactions that have been preferentially mediated by rare noble metals, for example, hydrogenations, is a desirable aim in catalysis and an attractive strategy for element conservation. The observation of novel selectivity patterns with such inexpensive metal catalysts is especially appealing. Herein, we report a novel, robust, and reusable cobalt catalyst that permits the selective hydrogenation of nitroarenes in the presence of highly hydrogenation‐sensitive functional groups, as well as the direct synthesis of imines from nitroarenes and aldehydes or ketones in the presence of such substituents. Furthermore, we introduce the first base‐metal‐mediated direct synthesis of benzimidazoles from nitroarenes and aldehydes. Functional groups that are easy to hydrogenate are again well tolerated.     

Preparation and Application of a Hydrochar-Based Palladium Nanocatalyst for the Reduction of Nitroarenes

In the present study, a novel heterogeneous catalyst was successfully fabricated through the decoration of palladium nanoparticles on the surface of designed Fe₃O₄-coffee waste composite (Pd-Fe₃O₄-CWH) for the catalytic reduction of nitroarenes. Various characterization techniques such as XRD, FE-SEM and EDS were used to establish its nano-sized chemical structure. It was determined that Pd-Fe₃O₄-CWH is a useful nanocatalyst, which can efficiently reduce various nitroarenes, including 4-nitrobenzoic acid (4-NBA), 4-nitroaniline (4-NA), 4-nitro-o-phenylenediamine (4-NPD), 2-nitroaniline (2-NA) and 3-nitroanisole (3-NAS), using NaBH₄ in aqueous media and ambient conditions. Catalytic reactions were monitored with the help of high-performance liquid chromatography. Additionally, Pd-Fe₃O₄-CWH was proved to be a reusable catalyst by maintaining its catalytic activity through six successive runs. Moreover, the nanocatalyst displayed a superior catalytic performance compared to other catalysts by providing a shorter reaction time to complete the reduction in nitroarenes.     

基于超分子晶体制备超细铂纳米颗粒用于催化加氢硝基苯

由于纳米催化剂的独特催化活性,因而开发稳定的超细纳米催化剂的制备方法引起了广大科研工作者们的关注.然而,复杂的合成过程和结构的不稳定性己经成为纳米催化剂研究和实际应用的瓶颈.本工作通过原位还原氯铂酸和十甲基五元瓜环(Me10CB[5])构筑的超分子晶体材料,成功制备了粒径尺寸约为3.0 nm的超细铂纳米粒子.Me10C...     

Electroreductive heterocyclization of ortho-piperidino substituted nitro(het)arenes

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