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Organic Reaction in Water

Organic Reaction in Water

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Published by: dalexthg01 on Jul 23, 2012
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Organic reaction in water. Part 5.
1
Novel synthesis of anilinesby zinc metal-mediated chemoselective reduction of nitroarenes
Takehito Tsukinoki* and Hirohisa Tsuzuki
Tohwa Institute for Science, Tohwa University, 1-1-1 Chikushigaoka Minami-ku, Fukuoka815-8510, Japan. E-mail: takehito@tohwa-u.ac.jp
Received 12th October 2000 First published as an Advance Article on the web 22nd January 2001
Nitroarenes can be reduced in high yields to the corresponding anilines using zinc metal and NH
4
Cl in waterwithout any organic solvent at 80 °C with a simple procedure at low cost. The procedure is powerful enough toreduce sterically hindered 2,6-dimethylnitrobenzene and is chemoselective for nitro groups; ester, amide andhalide substituents on aromatic rings are unaffected.
Introduction
Reduction of nitroarenes leading to aromatic amines is animportant key step in the industrial syntheses of dyes, medicinalsupplies and agricultural chemicals. Furthermore, the primaryaromatic amines are readily converted into diazonium salts,which can be substituted for many other functional groups.Therefore, a variety of methods for the reduction of nitro groupshave been developed.
2
The methods employed generally arecatalytic hydrogenation
3
such as with Raney Ni, Pd/C and PtO
2
,or dissolving metal reduction, for example, with Fe/HCl
4
andSn/HCl.
5
In addition, recently, chemoselective reduction of nitro groups using metallic reducing reagents such as Sm,
6
In
7
and B
10
H
148
was reported. However, these reactions require anexpensive and/or a moisture-sensitive reagent and an organicsolvent, and for catalytic hydrogenation, it is necessary topressurize the reactor with hydrogen gas. In these methods,there is little consideration given to the environment, cost,safety, or simplicity of operation. On the other hand, recently, inview of human health and environmental concerns, muchattention is being paid to ‘Green Chemistry’, which is achemical methodology to decrease or eliminate the use orgeneration of hazardous substances in the design, preparationand application of chemical production.
9
In this area of investigation, there is growing interest in synthetic organicreactions in environmentally friendly water.
10
We have demon-strated a facile reductive coupling of aromatic imines by zincmetal and NH
4
Cl in water.
1
In continuation of our progressiveinvestigation into the application of this methodology, we arestrongly interested in the development of the chemoselectivereduction of nitro groups using a cheap reagent with easyoperation in water without any organic solvent, a methodologywhich would have some advantages in terms of cost, safety,simple operation, human health and environmental concerns ascompared with use of an organic solvent. Here, we wish toreport that in water without any organic solvent, aromaticamines can be obtained in high yields by an operationally easychemoselective reduction of aromatic nitro compounds facili-tated by cheap zinc metal.
Results and discussion
In preliminary work, we investigated the influence of additivesand solvent on reduction of nitrobenzene
1
using zinc metal(Scheme 1 and Table 1). Some zinc and ammonium salts, exceptfor ammonium nitrate, were effective for the reduction of nitrobenzene using zinc metal in water to give aniline
2
in highyield without any other coupling products such as azo- andhydrazo-benzenes (runs 1–9).
11
Furthermore, when using
a
-amino acids as an additive, the reduction of 
1
proceeds readilyat a neutral pH (runs 10 and 11). We found that an additive was
Scheme 1Table 1
Reduction of nitrobenzene under various conditions
a
RunAdditiveSolventReactiontime/hIsolatedyield(%)1NH
4
ClMeOH1792NH
4
ClEtOH6803NH
4
ClWater0.5844NH
4
NO
3
WaterNo reaction5(NH
4
)
2
SO
4
Water1876MeCO
2
NH
4
Water0.5897HCOONH
4
Water0.5818ZnCl
2
Water0.5819ZnSO
4
Water18210
L
-AlanineWater0.58711
L
-GlutamineWater0.578
a
1
: 2 mmol, Zn: 14.5 mmol, additive: 4 mmol, solvent: 15 ml.
Green Context
The reduction of aromatic nitro compounds to anilines is avery important synthetic transformation since the nitrogroup is often used to activate the aromatic nucleus tonucleophilic substitution but the amino group is often usedfor further derivitisation towards valuable products such aspharmaceuticals. There are many methods for carrying outthis reaction and these are generally hazardous to theenvironment due to the use of organic solvents and cansuffer from the need for expensive and sensitive metallicreagents. Here both of these problems are dealt with byusing water as the solvent and the relatively benign andinexpensive reagents zinc with ammonium chloride. Theprocedure is versatile, quick and enables easy separation of the products from the inorganic reagents.
 JHC 
This journal is © The Royal Society of Chemistry 2001
DOI: 10.1039/b008219h
Green Chemistry
, 2001,
3
, 37–38
37
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