Selective reduction of aromatic nitro compounds containing o- and n-benzyl groups with hydrazine and raney nickel

Yuste, Francisco; Saldaña, M. C.; Walls, F.

doi:10.1016/s0040-4039(00)86770-2

Cited by 67 publications

(22 citation statements)

References 5 publications

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“…The reduction of nitro compounds is of paramount importance for the preparation of amino derivatives in the organic synthesis. The synthesis and biological evaluation of aromatic amines are also active and most important areas of research and their chemistry by derivative formation is widely studied [2,3]. Likewise, the conversion of carbonyl compound to alcohol or alkane is important in pharmaceutical industries as the transformation changes the hydrophilicity of the compound.…”

Section: Introductionmentioning

confidence: 99%

Feasibility of Room Temperature Reduction of Aromatic Carbonyl and Nitro Compounds by Zn/dil. HCl-Et2O System: An Experimental and DFT Study

Rajamathe¹,

Selvaraj²

2017

Asian J. Chem.

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This experimental study is about the feasibility of the room temperature reduction of the ether soluble aromatic carbonyl/nitro compounds by atomic hydrogen. The atomic hydrogen is produced by the novel Zn/dil. HCl-Et2O reducing system (wherein dil. HCl is slowly added to the ethereal solution of Zn and substrate).This study resulted in single or mixture of anticipated reduced products in different yields. The DFT study with B3LYP/6.311g ++ (d,p) basis set revealed that the stability of the first formed free radical (energy factor) and the homo nuclear nature of the carbonyl and nitro group (charge factor) decide the yield. It is also found that the presence of-M group at oor p-position to the carbonyl/nitro group results in the favourable modification of above-mentioned factors. The above-mentioned factors also explain the preferential reduction of nitro group when it is present along with carbonyl group. The free radical mechanism was confirmed by the formation of pinacol coupled product in one instance. In one of the reduction reactions, an unreported compound viz. the dimer of o-amino benzaldehyde was obtained in good yield.

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Section: Introductionmentioning

confidence: 99%

Feasibility of Room Temperature Reduction of Aromatic Carbonyl and Nitro Compounds by Zn/dil. HCl-Et2O System: An Experimental and DFT Study

Rajamathe¹,

Selvaraj²

2017

Asian J. Chem.

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“…Reduction is one of the frequently used reaction in organic synthesis and a vast variety of reducing agents have been introduced for this achievement [1,2]. The synthesis and biological evaluation of aromatic amines by derivative formation [3,4] constitutes the most important study in chemistry.…”

Section: Introductionmentioning

confidence: 99%

Solvent Free Facile Room Temperature Reduction of Aromatic Carbonyl and Nitro Compounds by Zn/Conc. HCl System-An Experimental and DFT Study

Rajamathe¹,

Bhuvaneswari²

2018

Asian J. Chem.

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This experimental and DFT studies involve a novel technique for the reduction of aromatic carbonyl/nitro compounds to the corresponding alcohols/amines, in high yield under laboratory conditions. The reducing species is the nascent hydrogen generated by the Zn/HCl system. The novelty of this work is that the comparison of yield with and without solvent. The yield is increased by many folds in the solvent free method compared to the solvent method reported earlier. The technique followed is to make a 'slurry' of the substrate with zinc dust (zinc slurry) and to add (in small portion of the dry slurry) to the optimized amount of conc. HCl, over a period of 3 to 4 h at room temperature. In this technique the substrate, adsorbed on zinc dust being very proximal to the site of generation nascent hydrogen, the reduction is very effective and the yield is high. The novelty is that zinc dust acts as catalyst (adsorbent role) and reactant (hydrogen generation role). The DFT study with B3LYP/6.311g ++ (d,p) basis set revealed that the stability of first formed free radical (energy factor) and the homo nuclear nature of carbonyl and nitro group (charge factor) decide the yield. The electrostatic potential calculated by DFT studies correlates well with Mullikan charges in deciding the charge factor. The free radical mechanism was confirmed by the formation of pinacol coupled product in one instance.

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“…Raney nickel catalyzed transfer hydrogenations utilizing 2-propanol have been reported for the reduction of olefins [10], aldehydes [11], ketones [10,12,13], phenols [10], aromatic alcohols [14], nitriles [15], aromatic nitro compounds [16][17][18], and certain aromatic hydrocarbons [10,19]. Other commonly used hydrogen donors for Raney nickel are ethanol, cyclohexanol [20], formic acid [21], hydrazine [22], etc. To our knowledge, studies on borohydride together with Raney nickel in CTH are scarce.…”

Section: Introductionmentioning

confidence: 99%

Catalytic transfer hydrogenation of 7-ketolithocholic acid to ursodeoxycholic acid with Raney nickel

Tian

Zhao

Cao

2013

Journal of Industrial and Engineering Chemistry

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Selective reduction of aromatic nitro compounds containing o- and n-benzyl groups with hydrazine and raney nickel

Cited by 67 publications

References 5 publications

Feasibility of Room Temperature Reduction of Aromatic Carbonyl and Nitro Compounds by Zn/dil. HCl-Et2O System: An Experimental and DFT Study

Feasibility of Room Temperature Reduction of Aromatic Carbonyl and Nitro Compounds by Zn/dil. HCl-Et2O System: An Experimental and DFT Study

Solvent Free Facile Room Temperature Reduction of Aromatic Carbonyl and Nitro Compounds by Zn/Conc. HCl System-An Experimental and DFT Study

Catalytic transfer hydrogenation of 7-ketolithocholic acid to ursodeoxycholic acid with Raney nickel

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