Methanol → HCID 53769835, compound

HRID 2416692Notes

Reaction equation

HRID 2416692 reaction equation
C[O:2][C:3]1[CH:19]=[CH:18][C:6]2[CH2:7][C@@H:8]([CH2:13][C:14]([O:16][CH3:17])=[O:15])[C:9](=[O:12])[NH:10][CH2:11][C:5]=2[CH:4]=1.B(Br)(Br)Br.CO>C(Cl)(Cl)Cl.O.CO>[OH:2][C:3]1[CH:19]=[CH:18][C:6]2[CH2:7][C@@H:8]([CH2:13][C:14]([O:16][CH3:17])=[O:15])[C:9](=[O:12])[NH:10][CH2:11][C:5]=2[CH:4]=1

Participants

6

Reactant 3

HCID 887Methanol2×HCID 25134Boron tribromideHCID 54208816HCID 54208816, compound

Product 1

HCID 53769835HCID 53769835, compoundYield 68.3%

Reagents, catalysts & solvents 2

HCID 6212ChloroformSolvent2×HCID 22242641Methanol--water (1/1)Solvent

Conditions

Temperature
-8 °C

Procedure

A solution of methyl (S)-(−)-8-methoxy-3-oxo-2,3,4,5-tetrahydro-1H-2-benzazepine-4-acetate (15.0 g, 0.057 mole) in CHCl3 (160 mL) was added dropwise over 30 min to a solution of boron tribromide (20.53 mL, 0.217 mole) in CHCl3 (160 mL) at −8° C. under argon, maintaining the temperature between −5° C. and 0° C. The reaction mixture was stirred at ca. −8° C. for 30 min and then MeOH (200 mL) was added, dropwise initially, maintaining the temperature at ca. 0° C. The reaction mixture was concentrated to give a viscous oil which was reconcentrated from MeOH (100 mL). The oil was dissolved in H2O/MeOH and a small amount of dark solid was removed by filtration. The filtrate was neutralized (to pH 7) with 50% sodium hydroxide, depositing a white solid. The suspension pH was adjusted to 4.5 by the addition of a small amount of acetic acid and the solid was collected and dried in vacuum to give afford the title compound (9.7 g, 68%). The product was assayed for chiral purity by HPLC: Chiralpak AS® column (4.6×50 mm), 100% EtOH mobile phase, 0.5 mL/min flow rate, uv detection at 215 nm; tR=7.5 min (S-enantiomer, 99%); tR=4.4 min (R-enantiomer, 1%).

Workup

  1. temperaturemaintaining the temperature between −5° C. and 0° C
  2. temperaturedropwise initially, maintaining the temperature at ca. 0° C
  3. concentrationThe reaction mixture was concentrated
  4. customto give a viscous oil which
  5. customa small amount of dark solid was removed by filtration
  6. additionThe suspension pH was adjusted to 4.5 by the addition of a small amount of acetic acid
  7. customthe solid was collected
  8. customdried in vacuum
  9. customto give

Sources & evidence

ORD record
ord-88416fd997124b908c99d7b7d51abed2
Source dataset
uspto-grants-2004_11
Patent number
US06825188B2

Reaction notes

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