反応 #1743997

反応方程式

5-chlorovaleronitrile

sodium iodide

sodium hydride

O-benzyl-N-tert-butoxycarbonyl hydroxylamine

→

N-(tert-Butoxycarbonyl)-N-(4-cyanobutyl)-O-benzylhydroxylamine

溶媒

DMF

反応条件

後処理

1. 1
   温度the suspension heated at 80°-85° C. for 4 hours under argon
2. 2
   温度After cooling
3. 3
   その他the reaction was quenched with H2O (100 mi)
4. 4
   抽出extracted with ether (4×75 mL)
5. 5
   洗浄The combined organic layers were washed with 100 mL each of 1% aqueous Na2SO3, H2O and brine
6. 6
   濃縮concentrated
7. 7
   その他to give 4.39 g crude product

実験手順

N-(tert-Butoxycarbonyl)-N-(4-cyanobutyl)-O-benzylhydroxylamine (4) was synthesized by adding sodium iodide (84 mg, 0.56 mmol) and then sodium hydride (80% oil dispersion, 0.49 g, 16.3 mmol) to O-benzyl-N-tert-butoxycarbonyl hydroxylamine (2.68 g, 12.0 mmol) in dry DMF (40 ml). After stirring for 15 minutes, 5-chlorovaleronitrile (1.5 mL, 13.3 mmol) was added and the suspension heated at 80°-85° C. for 4 hours under argon. After cooling, the reaction was quenched with H2O (100 mi), then extracted with ether (4×75 mL). The combined organic layers were washed with 100 mL each of 1% aqueous Na2SO3, H2O and brine and then concentrated to give 4.39 g crude product. Column chromatography with 4.5% EtOAc/CHCl3 produced 3.17 g of O-benzyl-N-(tert-butoxycarbonyl)-N-(4-cyanobutyl)hydroxylamine (4) (87% yield): NMR δ 1.5-1.75 (s+m, 13 H), 2.3 (t, 2 H), 3.4 (t, 2 H), 4.77 (s, 2 H), 7.3 (s, 5 H). Anal. calcd. for C17H24N2O3 : C, 67.08; H, 7.95; N, 9.20. Found: C, 67.19; H, 7.99; N, 9.11.

出典