Bromonitromethane: A Versatile Reagent in Organic Synthesis

Introduction

Bromonitromethane (BrCH₂NO₂) has received considerable attention as a one-carbon synthon for the synthesis of a variety of important organic intermediates. [¹] For examples, it was used in the synthesis of 2-nitrobenzofuran and 2-nitro-2,3-dihydrobenzofuran-3-ols, [²] nitrobenzo­thio-phenes, and nitrothiazoles, [³] polyfunctionalized nitrocyclopropanes. [4] It has also been utilized in the synthesis of 1-bromo-1-nitroalkan-2-ols [5] and aryl nitromethanes. In addition, it could be used as a bromine donor. [6]

Bromonitromethane is commercially available and can also be easily prepared according to the procedures reported by Fishwick et al. (Scheme  [¹] ). [³] A typical procedure is as following: freshly distilled nitromethane was stirred at 0 ˚C and bromine was dropped in 5 seconds. The resulted bromonitromethane could be used without further purification. [¹a]

Scheme 1

References

• 1a Rodríguez Dominguez JC. Thomae D. Seck P. Kirsch G. Synlett  2008,  286 
• 1b Thomae D. Rodríguez Dominguez JC. Kirsch G. Seck P. Tetrahedron  2008,  64:  3232 
• 2a Ohishi Y. Doi Y. Nakanishi T. Chem. Pharm. Bull.  1984,  32:  4260 
• 2b Tromelin A. Demerseman P. Royer R. Synthesis  1985,  1074 
• 3 Fishwick BR. Rowles DK. Stifling CJM. J. Chem. Soc., Perkin Trans. 1  1986,  1171 
• 4a Braish TF. Castaldi M. Chan S. Fox DE. Keltonic T. McGarry J. Hawkins JM. Norris T. Rose PR. Sieser JE. Sitter BJ. Watson HJr. Synlett  1996,  1100 
• 4b Ballini R. Fiorini D. Palmieri A. Synlett  2003,  1704 
• 5 Concellón JM. Rodríguez-Solla H. Concellón C. García-Granda S. Díaz MR. Org. Lett.  2006,  8:  5979 
• 6 Sherrill ML. J. Am. Chem. Soc.  1924,  46:  2753 
• 7 Gewald K. Hain U. Monatsh. Chem.  1992,  123:  455 
• 8 Shen Y. Yang B. Synth. Commun.  1993,  23:  1 
• 9 Concellón JM. Bernad PL. Rodríguez-Solla H. Concellón C. J. Org. Chem.  2007,  72:  5421 
• 10 Alcaide B. Almendros P. Luna A. Torres MR. Org. Biomol. Chem.  2008,  6:  1635 
• 11 Hansen HM. Longbottom DA. Ley SV. Chem. Commun.  2006,  4838 
• 12 Wascholowski V. Hansen HM. Longbottom DA. Ley SV. Synthesis  2008,  1269 
• 13 Lv J. Zhan J. Wang Y. Chem. Eur. J.  2009,  15:  972 
• 14 Dong L.-t. Lu R.-j. Du Q.-s. Zhang J.-m. Liu S.-p. Xuan Y.-n. Yan M. Tetrahedron  2009,  65:  4124 
• 15 Vesely J. Zhao GL. Bartoszewicz A. Córdova A. Tetrahedron Lett.  2008,  49:  4209 
• 16a (a) Zhang J.-m. Hu Z.-p. Zhao S.-q. Yan M. Tetrahedron  2009,  65:  802 
• 16b (b) Zhang J.-m. Hu Z.-p. Dong L.-t. Xuan Y.-n. Lou C.-l. Yan M. Tetrahedron: Asymmetry  2009,  20:  355