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    Reduction Research Paper

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    Udai Pratapsingh
    This document describes a method for preparing sulphur-containing aromatic amines by reducing sulphur-containing aromatic nitro compounds with hydrazine hydrate over an iron oxide hydroxide catalyst. The reduction reactions proceeded rapidly within 20-50 minutes and achieved yields of 97-99%. Compared to traditional reduction methods, this method is more environmentally friendly as it produces only nitrogen gas and water as byproducts. The iron oxide hydroxide catalyst was found to effectively catalyze the reduction reactions.

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    Reduction Research Paper

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    Udai Pratapsingh
    91 views3 pages
    This document describes a method for preparing sulphur-containing aromatic amines by reducing sulphur-containing aromatic nitro compounds with hydrazine hydrate over an iron oxide hydroxide catalyst. The reduction reactions proceeded rapidly within 20-50 minutes and achieved yields of 97-99%. Compared to traditional reduction methods, this method is more environmentally friendly as it produces only nitrogen gas and water as byproducts. The iron oxide hydroxide catalyst was found to effectively catalyze the reduction reactions.

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    This document describes a method for preparing sulphur-containing aromatic amines by reducing sulphur-containing aromatic nitro compounds with hydrazine hydrate over an iron oxide hydroxide catalyst. The reduction reactions proceeded rapidly within 20-50 minutes and achieved yields of 97-99%. Compared to traditional reduction methods, this method is more environmentally friendly as it produces only nitrogen gas and water as byproducts. The iron oxide hydroxide catalyst was found to effectively catalyze the reduction reactions.

    Copyright:

    Attribution Non-Commercial (BY-NC)
    Download as PDF, TXT or read online from Scribd
    Download as pdf or txt
    91 views3 pages

    Reduction Research Paper

    Uploaded by

    Udai Pratapsingh
    This document describes a method for preparing sulphur-containing aromatic amines by reducing sulphur-containing aromatic nitro compounds with hydrazine hydrate over an iron oxide hydroxide catalyst. The reduction reactions proceeded rapidly within 20-50 minutes and achieved yields of 97-99%. Compared to traditional reduction methods, this method is more environmentally friendly as it produces only nitrogen gas and water as byproducts. The iron oxide hydroxide catalyst was found to effectively catalyze the reduction reactions.

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    Attribution Non-Commercial (BY-NC)
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    of 3

    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: [email protected]
    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.

    References

    1. T. J. Walter, Ethyl Corp., 1980, US 4186147.


    2. R. J. Gyurik, V. J. Theodorides, Smithkline Corp., 1975, US 3915986.
    3. T. Papenfuhs, Hoechst Ag., 1986, US 4613704.
    4. A. Junino, A. Genet, G. Lang, L’ Oreal, 1992, US 5084067.
    5. A. Junino, A. Lagrange, A. Genet, L’ Oreal, 1995, US 5451236.
    6. T. Papenfuhs, Hoechst Ag., 1992, US 5101069.
    7. H. Ohi, Ihara Chemical Ind. Co., 1993, US 5248822.
    8. K. Nomura, J. Mol. Catal. A: Chemical, 1998, 130, 1.
    9. M. B. Zhang, D. Ryckman, G. H. Chen, et al., Synthesis, 2003, (1), 112.
    10. S. Gowda, D. C. Gowda, Indian J. Chem., 2003, 42B, 180.
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    13. D. L. Clive, A. G. Angoh, B. M. Sharon, J. Org. Chem., 1987, 52(7), 1339.
    14. J. Hine, S. Hahn, D. E. Miles, et al., J. Org. Chem., 1985, 50(25), 5092.
    15. B. H. Han, D. H. Shin, S. Y. Cho, Tetrahedron Lett., 1985, 26(50), 6233.
    16. T. Miyata, Y. Ishino, T. Hirashima, Synthesis, 1978, 834.
    17. M. Lauwiner, P. Rys, J. Wissmann, Appl. Catal. A-Gen., 1998, 172, 141.

    Received 13 February, 2006

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