Boron tribromide → HCID 54302492, compound

HRID 2416691Notes

Reaction equation

HRID 2416691 reaction equation
B(Br)(Br)Br.C[O:6][C:7]1[CH:28]=[CH:27][C:10]2[CH2:11][CH:12]([CH2:22][C:23]([O:25][CH3:26])=[O:24])[C:13](=[O:21])[N:14]([CH2:16]C(F)(F)F)[CH2:15][C:9]=2[CH:8]=1>C(Cl)Cl>[OH:6][C:7]1[CH:28]=[CH:27][C:10]2[CH2:11][CH:12]([CH2:22][C:23]([O:25][CH3:26])=[O:24])[C:13](=[O:21])[N:14]([CH3:16])[CH2:15][C:9]=2[CH:8]=1

Participants

4

Reactant 2

HCID 25134Boron tribromideHCID 54106116HCID 54106116, compound

Product 1

HCID 54302492HCID 54302492, compoundYield 120.5%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent2×

Conditions

Temperature
-5 °C

Procedure

A solution of BBr3 in CH2Cl2 (1.0 M, 60 mL, 60 mmole) was added dropwise over 30 min to a solution of methyl (±)-8-methoxy-3-oxo-2-(2,2,2-trifluoroethyl)-2,3,4,5-tetrahydro-1H-2-benzazepine-4-acetate (5.16 g, 14.94 mmole) in anhydrous CH2Cl2 (60 mL) at −5 to −10° C. under argon. After an additional 1 hr at −5 to −10° C., the reaction was recooled thoroughly to −10° C. and quenched by careful dropwise addition of MeOH (60 mL). The reaction was stirred at −10 to 0° C. for 1 hr, then was concentrated on the rotavap. The residue was reconcentrated from MeOH (2×) then from EtOAc, then was filtered through a pad of silica gel (EtOAc eluent). Concentration of the filtrate left a yellow solid which was triturated with hot hexanes. The title compound (4.74 g, 96%) was obtained as an off-white solid: TLC (1:1 EtOAc/hexanes) Rf 0.40; 1H NMR (400, DMSO-d6) δ 9.28 (s, 1 H), 6.90 (d, J=8.3 Hz, 1 H), 6.62 (dd, J=8.3, 2.5 Hz, 1 H), 6.57 (d, J=2.5 Hz, 1 H), 5.27 (d, J=16.7 Hz, 1 H), 4.22-4.38 (m, 1 H), 4.07-4.22 (m, 1 H), 4.07 (d, J=16.7 Hz, 1 H), 3.72-3.83 (m, 1 H), 3.58 (s, 3 H), 2.94 (dd, J=17.0, 3.8 Hz, 1 H), 2.72 (dd, J=16.7, 9.1 Hz, 1 H), 2.65 (dd, J=17.0, 14 Hz, 1 H), 2.49 (dd, J=16.7, 5.0 Hz, 1 H, partially obscured by residual solvent signal); MS (ES) m/e 354 (M+Na)+.

Workup

  1. customwas recooled thoroughly to −10° C.
  2. customquenched by careful dropwise addition of MeOH (60 mL)
  3. concentrationwas concentrated on the rotavap
  4. filtrationfrom EtOAc, then was filtered through a pad of silica gel (EtOAc eluent)
  5. waitConcentration of the filtrate left a yellow solid which
  6. customwas triturated with hot hexanes

Sources & evidence

ORD record
ord-8a565c6277cf4c5bb6b070998d45aedb
Source dataset
uspto-grants-2004_11
Patent number
US06825188B2

Reaction notes

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