反应详情

To a solution of (1-cyano-spiro[2.5]oct-1-ylmethyl)-carbamic acid tert-butyl ester (10.0 g, 37.8 mmol) in ethanol (150 mL) was added 50% aqueous hydroxylamine (12 mL, 189 mmol). The solution was heated to reflux for 14 hours, cooled to room temperature and the solvent removed under reduced vacuum. The residue was partitioned between water (200 mL) and ether (300 mL). An emulsion formed in the ether layer, which was separable. The aqueous layer was extracted with ether (2×300 mL). The combined organic layers were filtered to remove emulsified material. The organic layer was washed with brine (200 mL), dried over sodium sulfate, filtered and evaporated to give 6.1 g (54%) of [1-(N-hydroxycarbamimidoyl)-spiro[2.5]oct-1-ylmethyl]-carbamic acid tert-butyl ester as a white solid: 1H NMR (300 MHz, CDCl3) δ 0.52 (d, J=4.8 Hz, 1H), 0.90 (d, J=4.8 Hz, 1H), 1.4 (m, 1H), 1.43 (s, 9H), 1.3-1.7 (m, 9H), 3.11 (s, 1H), 3.23 (dd, J=5.2, 13.9 Hz, 1H), 3.47 (dd, J=5.2, 13.9 Hz, 1H), 4.68 (s, 2H), 5.12 (s, 1H); MS (APCI) m/z 298 [M+H]+.

1. temperatureThe solution was heated
2. temperatureto reflux for 14 hours
3. customthe solvent removed under reduced vacuum
4. customThe residue was partitioned between water (200 mL) and ether (300 mL)
5. customAn emulsion formed in the ether layer, which
6. extractionThe aqueous layer was extracted with ether (2×300 mL)
7. filtrationThe combined organic layers were filtered
8. customto remove
9. washThe organic layer was washed with brine (200 mL)
10. dry with materialdried over sodium sulfate
11. filtrationfiltered
12. customevaporated