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

HRID 2042025노트

반응식

HRID 2042025 반응식
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]

참가 물질

6

반응물 3

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

생성물 1

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

시약·촉매·용매 2

HCID 66321Lithium iodide촉매HCID 8028Tetrahydrofuran용매

반응 조건

온도
70 °C

실험 절차

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.

후처리

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

출처 및 근거

ORD 기록
ord-cf24c600bf424f9f8087b98cb66c1eb4
출처 데이터셋
uspto-grants-2013_11
특허 번호
US08586576B2

반응 노트

불러오는 중…