Spiro[3<i>H</i>-diazirine-3,2′-tricyclo[3.3.1.1]decane]

Spiro[3H-diazirine-3,2(1tricyclo[3.3.1.1]decane] [41736-95-2] C10H14N2 (MW 162.23) InChI = 1S/C10H14N2/c1-6-2-8-4-7(1)5-9(3-6)10(8)11-12-10/h6-9H,1-5H2 InChIKey = PNVXTJMLAFYDOJ-UHFFFAOYSA-N (carbene precursor, electrophilic nitrogen source) Alternate Names: 2-adamantane-2,3′-[3H]-diazirine; diazirine adamantylidene; spiro[1,2-diazirine-3,2′-adamantane]; adamantane-2-spiro-3′-diazirine; adamantanone diazirine; adamantane diazirine; aziadamantane. Physical Data: mp 132–134 °C. Solubility: Soluble in most organic solvents. Form Supplied in: white solid. Analysis of Reagent Purity: 1H NMR (300 MHz, CDCl3) δ 2.10–2.04 (m, 6H), 1.82–1.75 (m, 6H), 0.65 (s, 2H). Preparative Methods: not commercially available. Aziadamantane was first synthesized in 1973.1 It is obtained in two steps from adamantanone.2 Adamantanone is first stirred with ammonia in methanol (25% w/v) for 45 min at −10 °C. Hydroxylamine-O-sulfonic acid (1.5 equiv) in 10 mL of methanol is then added dropwise. The mixture is stirred for 18 h at 4 °C and the solvent is removed by evaporation. The solid residue is extracted with CH2Cl2. The organic phase is then extracted with a 2N aq. H2SO4 solution. The aqueous phase is made alkaline with a 2N aq. NaOH solution and extracted with CH2Cl2. The organic phase is dried over K2CO3, filtered, and evaporated under reduced pressure to give the crude diaziridine (82%). It is used in the next step without further purification. A solution of CrO3 (1.5 equiv) in 2N aq. H2SO4 is added dropwise over 20 min to a vigorously stirred diaziridine suspension in acetone cooled at 0 °C. The resulting solution is then stirred at room temperature for 40 min. The mixture is poured onto ice and the precipitated product is extracted with pentane. The organic phase is washed sequentially with H2O, 5% aq. Na2CO3, and H2O, and then dried over Na2SO4. The solvent is evaporated and the crude is purified on a short silica column (pentane elution, 90% yield). Alternatively, an aqueous sodium hypochlorite solution can be used for the oxidation of the diaziridine to diazirine (99% yield), without the need for further purification.3 Handling, Storage, and Precautions: while no explosion of the title compound has been reported, it is advised to handle this product with caution, due to reported explosion of other diazirines.4, 5

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