Di‐ Tert ‐Butyl Hyponitrite

[14976-54-6] C8H18N2O2 (MW 174.24) InChI = 1S/C8H18N2O2/c1-7(2,3)11-9-10-12-8(4,5)6/h1-6H3 InChIKey = OAPFBXRHYINFDV-UHFFFAOYSA-N (E) [82554-97-0] C8H18N2O2 InChI = 1S/C8H18N2O2/c1-7(2,3)11-9-10-12-8(4,5)6/h1-6H3/b10-9+ InChIKey = OAPFBXRHYINFDV-MDZDMXLPSA-N (a convenient, low-temperature source of tert-butoxyl radicals1; induces serial cyclization of polyunsaturated hydroperoxides,2 rearrangement of allylic hydroperoxides,3 and reduction of alkyl halides or dialkyl sulfides with Et3SiH4; used in radical-trapping experiments5; and as initiator for dimerization6 and polymerization7) Alternative Names: DTBN; TBHN; DBH; BONNOB. Physical Data: white crystals mp 84.5 °C (dec)1d; volatile (0.1 mmHg at rt)1a; 1H NMR (CDCl3, 300 MHz) δ 1.40 (s, 18H)18; 13C NMR (CDCl3, 75.5 MHz) δ 81.4, 28.0.18 Solubility: insol H2O; sol common organic solvents (e.g. hexane, benzene, toluene, CCl4, and EtOH). Analysis of Reagent Purity: NMR (CDCl3, δ) 1H 1.33 (s); IR (cm−1) 2959, 1368, 1183, 9951a; for IR and Raman band assignments, see Ogle et al.8; UV (λmax, pentane) 223.4 nm (ϵ 7140 M−1 cm−1)1d; the trans structure has been established by X-ray analysis.8 Preparative Method: obtained in 80–90% yield by reaction of sodium hyponitrite with tert-BuBr in the presence of Iron(III) Chloride or Zinc Chloride.9 The preparation of sodium hyponitrite (from Na, benzophenone, and nitric oxide)10a must be performed with extreme care.10b Handling, Storage, and Precautions: although DTBN appears to be insensitive to scratching and is considered as safe,1a it can detonate when struck.1d Mixtures of DTBN with formamides undergo violent reaction or explosion when heated at 60–70 °C.6 Due to the potential risk of explosion, it is strongly recommended that all operations involving DTBN be carried out behind a safety shield using tongs, gloves, and a safety mask. Since DTBN is quite volatile, most of the unchanged material can be conveniently removed at the end of a reaction by flushing the mixture with N2 or Ar.5,11a Solid DTBN can be kept intact for several months at −10 °C or below.