Boron trifluoride etherate → 2-[2-Azido-2-(3-bromo-phenyl)-propoxy]-3,3,3-trifluoro-2-methyl-propionic acid methyl ester

HRID 221717노트

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HRID 221717 반응식
[CH3:1][O:2][C:3](=[O:22])[C:4]([O:10][CH2:11][C:12]([C:15]1[CH:20]=[CH:19][CH:18]=[C:17]([Br:21])[CH:16]=1)(O)[CH3:13])([CH3:9])[C:5]([F:8])([F:7])[F:6].C[Si]([N:27]=[N+:28]=[N-:29])(C)C.B(F)(F)F.CCOCC>C1(C)C=CC=CC=1>[CH3:1][O:2][C:3](=[O:22])[C:4]([O:10][CH2:11][C:12]([N:27]=[N+:28]=[N-:29])([C:15]1[CH:20]=[CH:19][CH:18]=[C:17]([Br:21])[CH:16]=1)[CH3:13])([CH3:9])[C:5]([F:8])([F:7])[F:6]

참가 물질

5

반응물 3

HCID 8000Boron trifluoride etherateHCID 78378AzidotrimethylsilaneHCID 666655182-[2-(3-Bromo-phenyl)-2-hydroxy-propoxy]-3,3,3-trifluoro-2-methyl-propionic acid methyl ester

생성물 1

HCID 866502592-[2-Azido-2-(3-bromo-phenyl)-propoxy]-3,3,3-trifluoro-2-methyl-propionic acid methyl ester

시약·촉매·용매 1

HCID 1140Toluene용매

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온도
40 °C

실험 절차

To a solution of 2-[2-(3-bromo-phenyl)-2-hydroxy-propoxy]-3,3,3-trifluoro-2-methyl-propionic acid methyl ester (5.1 g, 11.92 mmol) in toluene (50 ml) was added trimethylsilyl azide (3.95 ml, 29.8 mmol) and at 0° C. BF3-Et2O (4.53 ml, 35.8 mmol). The reaction mixture was stirred for 2 days at 25° C. and for another day at 40° C. The reaction was carefully quenched by slow addition of the reaction mixture to a cold aqueous NH4OH solution. The product was extracted with EtOAc and the combined organic layers were washed with brine, dried over MgSO4, filtered and evaporated. The crude product was purified by flash-chromatography on silica gel (toluene to toluene/EtOAc 10:1) to provide a diastereomeric mixture of the title compound as a light yellow oil: TLC (toluene/EtOAc 10:1): Rf=0.69; HPLC RtH5=1.560 min; 1H NMR (360 MHz, CDCl3): δ 7.65 (s, 1H), 7.48 (d, 1H), 7.41 (d, 1H), 7.27 (t, 1H), 3.87 and 3.85 (s, 3H), 3.76 (m, 2H), 1.78 and 1.75 (s, 3H), 1.65 and 1.61 (s, 3H); ESIMS: 427, 429 [(M+NH4)+].

후처리

  1. customat 0° C
  2. customThe reaction was carefully quenched by slow addition of the reaction mixture to a cold aqueous NH4OH solution
  3. extractionThe product was extracted with EtOAc
  4. washthe combined organic layers were washed with brine
  5. dry with materialdried over MgSO4
  6. filtrationfiltered
  7. customevaporated
  8. customThe crude product was purified by flash-chromatography on silica gel (toluene to toluene/EtOAc 10:1)
  9. customto provide

출처 및 근거

ORD 기록
ord-9593e326cbe240a9a4a3db1f827e84c8
출처 데이터셋
uspto-grants-2012_06
특허 번호
US08207164B2

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