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

HRID 221717

Reaktionsgleichung

Reaktionsgleichung von HRID 221717
[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]

Komponenten

5

Edukt 3

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

Produkt 1

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

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 1140TolueneLösungsmittel

Reaktionsbedingungen

Temperatur
40 °C

Versuchsvorschrift

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)+].

Aufarbeitung

  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

Quellen und Nachweise

ORD-Eintrag
ord-9593e326cbe240a9a4a3db1f827e84c8
Quelldatensatz
uspto-grants-2012_06
Patentnummer
US08207164B2

Verknüpfte Notizen

Wird geladen…