Skip to main content
Log in

Hexamethylenetetramine as an Efficient and Reusable Organocatalyst in Henry Reaction Under Mild and Aqueous Solution

  • Research Paper
  • Published:
Iranian Journal of Science and Technology, Transactions A: Science Aims and scope Submit manuscript

Abstract

Henry reaction is a base-catalyzed reaction which can produce β-nitroalcohol or nitroethylene derivatives from the condensation of aryl aldehydes and nitromethane under different conditions. In the present article, we introduce hexamethylenetetramine as a basic organocatalyst for Henry reaction, which can produce β-nitroalcohol derivatives from the condensation of aryl aldehydes and nitromethane under different conditions. By application of this organic base, β-nitroalcohol compounds were produced as the only product in good to excellent yields. In addition, reusability of hexamethylenetetramine in this reaction makes our method green.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Scheme 1

Similar content being viewed by others

References

  • Ballini R, Bosica G, Livi D, Palmieri A, Maggi R, Sartori G (2003) Use of heterogeneous catalyst KG-60-NEt2 in Michael and Henry reactions involving nitroalkanes. Tetrahedron Lett 44:2271–2273

    Article  Google Scholar 

  • Boruwa J, Barua NC (2006) Stereoselective total synthesis of (+)-boronolide. Tetrahedron 62:1193–1196

    Article  Google Scholar 

  • Caldarelli M, Habermann J, Ley SV (1999) Clean five step synthesis of an array of 1,2,3,4-tetra-subsitutated pyrroles using polymer supported reagents. J Org Chem Perkin Trans 1:107–110

    Article  Google Scholar 

  • Cao C, Lu Z, Cai Z et al (2012) Cheap Cu(I)/hexamethylenetetramine (HMTA) catalytic system for C–N coupling reactions. Synth Commun 42:279–284

    Article  Google Scholar 

  • Cwik A, Fuchs A, Hell Z, Clacens JM (2005) Nitroaldol-reaction of aldehydes in the presence of non-activated Mg: Al 2:1 hydrotalcite; a possible new mechanism for the formation of 2-aryl-1,3-dinitropropanes. Tetrahedron 61:4015–4021

    Article  Google Scholar 

  • Dalko PI, Moisan L (2004) In the golden age of organocatalysis. Angew Chem Int Ed 43:5138–5175

    Article  Google Scholar 

  • Fatehi M, Saleh TM, Fatehi-Hassanabad Z, Farrokhfal K, Jafarzadeh M, Davodi S (2005) A pharmacological study on Berberis vulgaris fruit extract. J Ethnopharmacol 102:46–52

    Article  Google Scholar 

  • Gan C, Chen X, Lai G, Wang Z (2006) Rapid microwave-assisted Henry reaction in solvent-free processes. Synlett 387–390

  • Han J, Xu Y, Su Y, She X, Pan X (2008) Guanidine-catalyzed Henry reaction and Knoevenagel condensation. Catal Commun 9:2077–2079

    Article  Google Scholar 

  • Hara T, Kanai S, Mori K, Mizugaki T, Ebitani K, Jitsukawa K, Kaneda K (2006) Highly efficient C–C bond-forming reactions in aqueous media catalyzed by monomeric vanadate species in an apatite framework. J Org Chem 71:7455–7462

    Article  Google Scholar 

  • Henry LCR (1895) Highly enantioselective Henry (nitroaldol) reaction of aldehydes and α-ketoesters catalyzed by N, N′-dioxide-copper(I) complexes. Hebd Seances Acad Sci 120:1265–1268

    Google Scholar 

  • Hirata N, Hayashi M (2007) Nitroaldol reaction catalyzed by tris(2,4,6-trimethoxyphenyl) phosphine (TTMPP). Synth Commun 37:1653–1657

    Article  Google Scholar 

  • Kaur N, Kishore D (2013) An insight into hexamethylenetetramine: a versatile reagent in organic synthesis. J Iran Chem Soc 10:1193–1228

    Article  Google Scholar 

  • Khosravi K, Kazemi S (2012) Synthesis of 2-arylbenzimidazoles and 2-arylbenzothiazoles in both room temperature and microwave condition catalyzed by hexamethylenetetramine–bromine complex. Chin Chem Lett 23:61–64

    Article  Google Scholar 

  • Li Y, Feng JP, Wang WH, Chen J, Cao XP (2007) Total synthesis and correct absolute configuration of malyngamide U. J Org Chem 72:2344–2350

    Article  Google Scholar 

  • Luzzio FA (2001) The Henry reaction: recent examples. Tetrahedron 57:915–1138

    Article  Google Scholar 

  • Majhi A, Kadam ST, Kim SS (2009) TMEDA catalyzed Henry (nitroaldol) reaction under metal and solvent-free conditions. Bull Korean Chem Soc 30:1767–1770

    Article  Google Scholar 

  • McNulty J, Dyck V, Larichev A, Capretta A, Robertson J (2004) Phosphonium salt catalyzed Henry nitroaldol reactions. Lett Org Chem 1:137–139

    Article  Google Scholar 

  • Palacios F, De los Santos JM, Aparicio D (2005) Use of polymer-supported amines in the catalytic nitroaldol reaction of nitroalkanes with aldehydes. Arkivok ix:405–414

    Google Scholar 

  • Phukan M, Borah KJ, Borah R (2008) Imidazole catalyzed Henry reactions in aqueous medium. Synth Commun 38:3068–3073

    Article  Google Scholar 

  • Rosini G (1991) The Henry (nitroaldol) reaction. In: Trost BM, Fleming I (eds) Comprehensive organic synthesis. Pergamon, New York, pp 321–340

    Chapter  Google Scholar 

  • Sato KI, Akai S, Shoji H, Sugita N, Yoshida S, Nagai Y, Suzuki K, Nakamura Y, Kajihara Y, Funabashi M, Yoshimura J (2008) Stereoselective and efficient total synthesis of optically active tetrodotoxin from d-glucose. J Org Chem 73:1234–1242

    Article  Google Scholar 

  • Shinde PS, Shinde SS, Dake SA, Sonekar VS, Sonekar VS, Deshmukh SU, Thorat VV, Andurkar NM, Pawar RP (2010) CsF/[bmim][BF4]: an efficient and reusable system for Henry. Arab J Chem. doi:10.1016/j.arabjc.2010.12.028.reaction

  • Simoni D, Rondanin R, Morini M, Baruchello R, Invidiata FP (2000) 1,5,7-Triazabicyclo[4.4.0]dec-1-ene (TBD), 7-methyl-TBD (MTBD) and the polymer-supported TBD (P-TBD): three efficient catalysts for the nitroaldol (Henry) reaction and for the addition of dialkyl phosphites to unsaturated systems. Tetrahedron Lett 41:1607–1610

    Article  Google Scholar 

  • Vovard-Le Bray C, Jiang F, Wu XF, Sortais JB, Darcel C (2010) Cyclen-catalyzed Henry reaction under neutral conditions. Tetrahedron Lett 51:4555–4557

    Article  Google Scholar 

  • Wang X, Fang F, Zhao C, Tian SK (2008) Dual-reagent organocatalysis with a phosphine and electron-deficient alkene: application to the Henry reaction. Tetrahedron Lett 49:6442–6448

    Article  Google Scholar 

  • Weeden JA, Chisholm JD (2006) Phosphine-catalyzed nitroaldol reactions. Tetrahedron Lett 47:9313–9578

    Article  Google Scholar 

  • Yadav JS, Reddy BVS, Basak AK, Visali B, Narsaiah AV, Nagaiah K (2004) Phosphane-catalyzed knoevenagel condensation: a facile synthesis of α-cyanoacrylates and α-cyanoacrylonitrile. Eur J Org Chem 3:546–551

    Article  Google Scholar 

  • Youn SW, Kim YH (2000) Facile synthesis of 2-nitroalkanols mediated with LiAlH4 as catalyst. Synlett 880–882

  • Zhou GP, Hui YH, Wan NN, Liu QJ, Xie ZF, Wang JD (2012) Mn(OAc)2/Schiff base as a new efficient catalyst system for the Henry reaction of nitroalkanes with aldehydes. Chin Chem Lett 23:690–694

    Article  Google Scholar 

Download references

Acknowledgments

We are grateful to the Research Council of Shiraz University for the partial support of this work.

Author information

Authors and Affiliations

Authors

Corresponding author

Correspondence to A. R. Sardarian.

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Fathi, S., Sardarian, A.R. Hexamethylenetetramine as an Efficient and Reusable Organocatalyst in Henry Reaction Under Mild and Aqueous Solution. Iran. J. Sci. Technol. Trans. Sci. 40, 103–107 (2016). https://doi.org/10.1007/s40995-016-0002-2

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s40995-016-0002-2

Keywords

Navigation