Cesium carbonate → 1,3-Bis(1,1-dimethylethyl) 2-(3-cyanophenyl)imidodicarbonate

HRID 459726ノート

反応式

HRID 459726 の反応式
BrC[C:3]1[CH:4]=[C:5]([CH:8]=[CH:9][CH:10]=1)[C:6]#[N:7].[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]([C:16]([O:15][C:12]([CH3:14])([CH3:13])[CH3:11])=[O:17])[C:3]1[CH:4]=[C:5]([CH:8]=[CH:9][CH:10]=1)[C:6]#[N:7])=[O:20])([CH3:25])([CH3:24])[CH3:23]

参加物

6

反応物 3

HCID 10796Cesium carbonateHCID 97249Benzonitrile, 3-(bromomethyl)-HCID 279800Di-tert-butyl Iminodicarboxylate

生成物 1

HCID 219309841,3-Bis(1,1-dimethylethyl) 2-(3-cyanophenyl)imidodicarbonate収率 91%

試薬・触媒・溶媒 2

HCID 66321Lithium iodide触媒HCID 8028Tetrahydrofuran溶媒

反応条件

温度
70 °C

実験手順

3-(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 22 h and the reaction was worked up as described in Preparative Example 89, Step B above. The residue was chromatographed on a silica gel column (60×5 cm) using 5% ethyl acetate in hexane as the eluant to give 3-(di-tert-butoxycarbonylamino)benzonitrile (7.39 g, 87%): FABMS: m/z 333.2 (MH+); HRFABMS: m/z 333.1815 (MH+); Calcd. for C18H25N2O4: m/z 333.1814; δH (CDCl3) 1.52 (18H, s, —COOC(CH3)3), 4.84 (2H, s, CH2), 7.48 (1H, m, Ar—H), 7.60 (2H, m, Ar—H) and 7.65 ppm (1H, m, Ar—H); δC (CDCl3) CH3: 28.1, 28.1, 28.1, 28.1, 28.1, 28.1; CH2: 48.4; CH: 129.2, 131.0, 131.0, 131.9; C: 83.2, 83.2, 112.5, 118.8, 140.1, 152.5, 152.5.

後処理

  1. customThe residue was chromatographed on a silica gel column (60×5 cm)

出典と根拠

ORDレコード
ord-9e668e4741ad44dc9456fba309af4df7
出典データセット
uspto-grants-2007_03
特許番号
US07196078B2

反応ノート

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