Methanesulfonic Acid → 7-Bromo-3,4-dihydroisoquinolin-1(2H)-one

HRID 1811037Notes

Reaction equation

HRID 1811037 reaction equation
[N-:1]=[N+]=[N-].[Na+].[Br:5][C:6]1[CH:14]=[C:13]2[C:9]([CH2:10][CH2:11][C:12]2=[O:15])=[CH:8][CH:7]=1.CS(O)(=O)=O>C(Cl)Cl>[Br:5][C:6]1[CH:14]=[C:13]2[C:9]([CH2:10][CH2:11][NH:1][C:12]2=[O:15])=[CH:8][CH:7]=1

Participants

5

Reactant 3

HCID 6395Methanesulfonic AcidHCID 33557Sodium AzideHCID 1397781-Indanone, 6-bromo-

Product 1

HCID 250673307-Bromo-3,4-dihydroisoquinolin-1(2H)-oneYield 61%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

Sodium azide (0.431 g, 6.63 mmol) was added slowly to a mixture of 6-bromo-2,3-dihydro-1H-inden-1-one (1 g, 4.74 mmol) and methanesulfonic acid (15 mL, 231 mmol) in DCM (30 mL) at 0° C. The mixture was stirred at rt for 15 hrs, then was carefully quenched with 1 M aqueous sodium hydroxide (50 mL). The aqueous layer was extracted with DCM (3×50 mL), and the combined organic layers were washed with water (20 mL) and brine (20 mL), dried and concentrated. The residue was purified by column chromatography (eluting with a gradient from 90:10 hexane-EtOAc to EtOAc) to give 7-bromo-3,4-dihydroisoquinolin-1(2H)-one as white solid (650 mg, 61%). 1H NMR (400 MHz, chloroform-d) δ 8.35 (1 H, br. s.), 7.08-7.17 (1 H, m), 6.98-7.06 (1 H, m), 6.95 (1 H, d, J=1.98 Hz), 2.93 (2 H, t, J=7.59 Hz), 2.49-2.68 (2 H, m). Mass spectrum m/z 226, 228 (M+H)+.

Workup

  1. customwas carefully quenched with 1 M aqueous sodium hydroxide (50 mL)
  2. extractionThe aqueous layer was extracted with DCM (3×50 mL)
  3. washthe combined organic layers were washed with water (20 mL) and brine (20 mL)
  4. customdried
  5. concentrationconcentrated
  6. customThe residue was purified by column chromatography (
  7. washeluting with a gradient from 90:10 hexane-EtOAc to EtOAc)

Sources & evidence

ORD record
ord-21f37c062d2047e5a3f618517212db3a
Source dataset
uspto-grants-2013_01
Patent number
US08362065B2

Reaction notes

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