Chinese Chemical Letters Vol. 17, No.

8, pp 1045-1047, 2006 1045

http://www.imm.ac.cn/journal/ccl.html

Preparation of Sulphur-containing Aromatic Amines by Reduction of

the Corresponding Aromatic Nitro Compounds with Hydrazine
Hydrate over Iron Oxide Hydroxide Catalyst

Qi Xun SHI, Rong Wen LU∗, Zhu Xia ZHANG, De Feng ZHAO
State Key Laboratory of Fine Chemicals, Dalian University of Technology, Dalian 116012

Abstract: Sulphur-containing aromatic nitro compounds were rapidly reduced to the

corresponding amines in high yields by employing hydrazine hydrate as a hydrogen donor in the
presence of iron oxide hydroxide catalyst. It was worth noting that the catalyst exhibited
extremely high activity. The reduction could be completed within 20-50 min and the yields were
up to 97-99 %.

Keywords: Iron oxide hydroxide catalyst, hydrazine hydrate, sulphur-containing aromatic nitro
compounds, reduction.

The sulphur-containing aromatic amines are an important class of compounds frequently

used as key intermediates in the synthesis of pharmaceutical products1,2, dyestuffs3-6 and
polymers7. The usual methods for preparing sulphur-containing aromatic amines are
stoichiometric reduction using iron powder or metal sulfides, such as alkali metal
sulfides and alkali metal hydrogen sulfides like NaHS8,9. However, some difficulties,
such as (1) seriously environmental pollution from residue, (2) waste water containing
sulphur moieties, still remain. On the other hand, with the increasing interest in human
health and environmental protection, more attention is being paid to “green chemistry”.
Therefore, an environmentally benign reduction of sulphur-containing aromatic nitro
compounds is thus an especially attractive subject from both scientific and practical
viewpoint.
In comparison to the conventional reduction processes with sulfide or Fe/HCl,
hydrazine reduction is an environmentally friendly method, its produces by-products
nitrogen gas and water are harmless (Scheme 1). Therefore, the hydrazine reduction of
nitro compounds was reported often in recent years10-12. The usual catalysts used in the
hydrazine reduction of aromatic nitro compounds are Zn10, Mg11, FeCl3.6H2O-activated
carbon13,14, graphite15 and iron(III) oxide16. Recently iron oxide hydroxide also has
been reported by Rys et al. as the catalyst for the reduction of aromatic nitro compound17.
However, further exploring the validity of their method for sulphur-containing aromatic
nitro compounds was not reported yet. In view of the particularity of sulphur atom

∗
E-mail: lurw@dlut.edu.cn
1046 Qi Xun SHI et al.

which may poison the metal and the urgency finding an environmentally friendly method
to prepare sulphur-containing aromatic amines, we believe the research on reduction of
sulphur-containing aromatic nitro compounds over iron oxide hydroxide catalyst is also
of significance. In continuation of our interest in the sieving and innovation of catalyst
applied to the reduction of sulphur-containing aryl nitro compounds, herein, we report a
highly effective and environmentally friendly method for preparing the sulphur-
containing aromatic amines through reduction of sulphur-containing aromatic nitro
compounds using hydrazine hydrate over iron oxide hydroxide catalyst.
Iron oxide hydroxide catalyst was prepared according to the literature17: 80 mL of 2
mol/L NaOH were added dropwise into an aqueous solution of 13.8 g FeCl3.6H2O
dissolved in 850 mL of distilled water under vigorous mechanical stirring. After the
addition, the pH of the mother liquor was 7-8. Then the suspension was heated to 60℃
and maintained at this temperature for 12 h. The solid formed was filtered, washed
with deionized water and dried at 50℃ for one day. Afterwards, the dried product was
milled to a fine powder (120 mesh) and characterized by X-ray diffraction.
General procedure for the preparation of sulphur-containing aromatic amines is as
follows: To a solution of sulphur-containing aromatic nitro compound (5 mmol) in
propan-2-ol (25 mL) was added iron oxide hydroxide catalyst (50 mg, 120 mesh). Then
hydrazine hydrate (7.5 mmol) was added dropwise and the reaction mixture was stirred
under reflux for several minutes. When the starting aromatic nitro compound had fully
reacted (monitored by TLC), the mixture was filtrated and the solid was washed with
acetone. Then the filtrate was evaporated in vacuo. The crude product was purified
by column chromatography on silica gel using n-hexane and ethyl acetate as eluent.
The results were summarized in Table 1.

Scheme 1

iron oxide hydroxide

R-C6H4NO2 + 3/2 N2H4H2O R-C6H4NH2 + 3/2N2 + 7/2H2O
propan-2-ol, reflux
(R=o-SC2H4OH, p-SC2H4OH, m-SCH3, p-SCH3, p-SCH2C6H5)

Table 1 Reduction of sulphur-containing aromatic nitro compounds using hydrazine hydrate over
iron oxide hydroxide catalysta

Entry Aromatic nitro compound Productb Time (min) Yieldc (%)

1 o-HOC2H4SC6H4NO2 o-HOC2H4SC6H4NH2 40 98
2 p-HOC2H4SC6H4NO2 p-HOC2H4SC6H4NH2 30 99
3 p-CH3SC6H4NO2 p-CH3SC6H4NH2 30 98
4 m-CH3SC6H4NO2 m-CH3SC6H4NH2 50 97
5 p-C6H5CH2SC6H4NO2 p-C6H5CH2SC6H4NH2 20 98
a: Reaction conditions: 5 mmol aromatic nitro compound, 7.5 mmol hydrazine hydrate, 50 mg
catalyst, 25 mL propan-2-ol, refluxed at 355 K.
b: 1H NMR spectra and MS of all the products were consistent with those of authentic samples.
c: Isolated yields were based on single experiment and the yields were not optimized.
 Preparation of Sulphur-containing Aromatic Amines 1047

From Table 1 we could see that the reduction was not affected by the presence of
sulfur atom and all the substrates were successfully reduced to the corresponding
aromatic amines within 20-50 min with hydrazine hydrate almost quantitatively. The
reaction conditions were mild.
A control experiment was performed using p-nitrophenylhydroethyl sulfide with
hydrazine hydrate, but without the use of iron oxide hydroxide. The reaction did not
produce any desired product. This clearly showed that iron oxide hydroxide catalyzed
the reaction.
In conclusion, the hydrazine hydrate reduction of sulphur-containing aromatic nitro
compounds over iron oxide hydroxide catalyst is entirely possible. The yields are
almost quantitative. Compared to the traditional methods (sulfide reduction and Fe/HCl
reduction), the present method is mild, exceedingly efficient, very rapid and especially
environmentally friendly.

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Received 13 February, 2006