O-(2,4-Dinitrophenyl)hydroxylamine

Introduction

O-(2,4-Dinitrophenyl)hydroxylamine (1) is an orange solid (mp = 112 °C)[1] and fairly stable when exposed to air. It is commercially available and can be readily synthesized by Charette’s method on a large scale:[1] Nucleophilic aromatic substitution of 2,4-dinitrochlorobenzene by N-hydroxyphthalimide followed by hydrazinolysis gives 1 in 94% yield over two steps (Scheme [1]).

Scheme 1

As an electrophilic amination reagent, 1 is used to donate a free NH₂ group to a variety of C-, N-, and O-nucleophiles to give products of significant importance in both synthetic and medicinal chemistry. The byproduct is 2,4-dinitrophenol (Scheme [2]). Amination with 1 features the advantages of mild reaction conditions, simple and safe operations, and wide substrate scope.

Scheme 2

• References

• 1 Legault C, Charette AB. J. Org. Chem. 2003; 68: 7119
• 2a Sheradsky T, Salemnick G, Nir Z. Tetrahedron 1972; 28: 3833
• 2b Radhakrishna AS, Loudon GM, Miller MJ. J. Org. Chem. 1979; 44: 4836
• 3a Chatzopoulou E, Davies PW. Chem. Comm. 2013; 49: 8617
• 3b Xiao Q, Ling L, Ye F, Tan R, Tian L, Zhang Y, Li Y, Wang J. J. Org. Chem. 2013; 78: 3879
• 3c Zhao J, Wu C, Li P, Ai W, Chen H, Wang C, Larock RC, Shi F. J. Org. Chem. 2011; 76: 6837
• 3d Mousseau JJ, Bull JA, Ladd CL, Fortier A, Roman DS, Charette AB. J. Org. Chem. 2011; 76: 8243
• 3e Mousseau JJ, Bull JA, Charette AB. Angew. Chem. Int. Ed. 2010; 49: 1115
• 3f Larivee A, Mousseau JJ, Charette AB. J. Am. Chem. Soc. 2008; 130: 52
• 4a Guernon H, Legault CY. Organometallics 2013; 32: 1988
• 4b Katritzky AR, Jishkaiani D, Sakhuja R, Hall CD, Steel PJ. J. Org. Chem. 2011; 76: 4082
• 5a Tran TP, Ellsworth EL, Watson BM, Sanchez JP, Showalter HD. H, Ruin JR, Stier MA, Yip J, Nguyen DQ, Bird P, Singh R. J. Heterocyclic Chem. 2005; 42: 669
• 5b Tran TP, Ellsworth EL, Watson BM, Sanchez JP, Watson BM, Showalter HD. H, Domagala JM, Shapiro MA, Joannides ET, Gracheck SJ, Nguyen DQ, Bird P, Yip J, Sharadendu A, Ha C, Ramezani S, Wu X, Singh R. Bioorg. Med. Chem. 2007; 17: 1312
• 5c Chen Z, Kim S.-H, Barbosa SA, Huynh R, Tortolani DR, Leavitt KJ, Wei DD, Manne V, Ricca CS, Gullo-Brown J, Poss MA, Vaccaro W, Salvati ME. Bioorg. Med. Chem. Lett. 2006; 16: 628
• 5d Hitotsuyanagi Y, Lee J.-E, Kato S, Kim I.-H, Kohashi H, Fukaya H, Takeya K. Bioorg. Med. Chem. Lett. 2011; 19: 2458
• 6 Castellino AJ, Rapoport H. J. Org. Chem. 1984; 49: 1348
• 7 Zhu C, Li G, Ess DH, Falck JR, Kürti L. J. Am. Chem. Soc. 2012; 134: 18253
• 8 Wang J.-J, Lao J.-H, Li X.-M, Lu R.-J, Miao H, Yan M. Synth. Comm. 2012; 42: 1577
• 9 Jat JL, Paudyal MP, Gao H, Xu Q.-L, Yousufuddin M, Devarajan D, Ess DH, Kürti L, Falck JR. Science 2014; 343: 61