碳酸氢铯 → N,N-DI-BOC-4-AMINOMETHYL BENZONITRILE

HRID 459727笔记

反应方程式

HRID 459727 反应方程式
Br[CH2:2][C:3]1[CH:10]=[CH:9][C:6]([C:7]#[N:8])=[CH:5][CH:4]=1.[CH3:11][C:12]([O:15][C:16]([NH:18][C:19]([O:21][C:22]([CH3:25])([CH3:24])[CH3:23])=[O:20])=[O:17])([CH3:14])[CH3:13].C(=O)([O-])[O-].[Cs+].[Cs+]>C1COCC1.[I-].[Li+]>[C:22]([O:21][C:19]([N:18]([CH2:2][C:3]1[CH:10]=[CH:9][C:6]([C:7]#[N:8])=[CH:5][CH:4]=1)[C:16]([O:15][C:12]([CH3:14])([CH3:13])[CH3:11])=[O:17])=[O:20])([CH3:25])([CH3:24])[CH3:23]

参与物

6

反应物 3

HCID 10796碳酸氢铯HCID 869964-氰基溴苄HCID 279800双(叔丁氧羰基)胺

产物 1

HCID 3683768N,N-DI-BOC-4-AMINOMETHYL BENZONITRILE收率 83.4%

试剂、催化剂与溶剂 2

HCID 66321碘化锂(无水)催化剂HCID 8028四氢呋喃溶剂

反应条件

温度
70 °C

实验过程

4-(Bromomethyl)benzonitrile (5 g, 25.5 mmoles) and di-tert-butyliminodicarboxylate (5.54 g, 25.5 mmoles) were dissolved in anhydrous THF (50 mL) and cesium carbonate (16.62 g, 25.5 mmoles) and lithium iodide (170.5 mg, 1.275 mmoles) were added. The mixture was stirred at 70° C. for 23 h and the reaction was worked up as described in Preparative Example 244, Step B above. The residue was chromatographed on a silica gel column (50×5 cm) using 5% ethyl acetate in hexane as the eluant to give 4-(di-tert-butoxycarbonylaminomethyl)benzonitrile (7.07 g, 83%): FABMS: m/z 333.2 (MH+); HRFABMS: m/z 333.1816 (MH+). Calcd. for C18H25N2O4: m/z 333.1814; δH (CDCl3) 1.45 (18H, s, —COOC(CH3)3), 4.81 (2H, s, CH2), 7.37 (2H, d, Ar—H) and 7.62 ppm (2H, d, Ar—H); δC (CDCl3) CH3: 28.1, 28.1, 28.1, 28.1, 28.1, 28.1; CH2: 49.2; CH: 127.8, 127.8, 132.3, 132.3; C: 83.2, 83.2, 111.1, 118.9, 144.1, 152.4, 152.4.

后处理

  1. customThe residue was chromatographed on a silica gel column (50×5 cm)

来源与证据

ORD记录
ord-78704b2cc0164e6fa4749cabcab749dc
来源数据集
uspto-grants-2007_03
专利号
US07196078B2

反应笔记

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