Trifluoromethanesulfonic anhydride → 5-bromo-2-(2-hydroxyethyl)-3,4-dihydroisoquinolin-1(2H)-one

HRID 387643Notes

Reaction equation

HRID 387643 reaction equation
C[O:2][C:3](=O)[N:4]([CH2:10][CH2:11][C:12]1[CH:17]=[CH:16][CH:15]=[CH:14][C:13]=1[Br:18])[CH2:5][CH2:6][O:7]CC.FC(F)(F)S(OS(C(F)(F)F)(=O)=O)(=O)=O.C(=O)([O-])O.[Na+]>ClCCl.CN(C)C1C=CN=CC=1>[Br:18][C:13]1[CH:14]=[CH:15][CH:16]=[C:17]2[C:12]=1[CH2:11][CH2:10][N:4]([CH2:5][CH2:6][OH:7])[C:3]2=[O:2]

Participants

6

Reactant 3

HCID 67749Trifluoromethanesulfonic anhydrideHCID 516892Sodium BicarbonateHCID 68470585Methyl[2-(2-bromophenyl)ethyl](2-ethoxyethyl)carbamate

Product 1

HCID 684736355-bromo-2-(2-hydroxyethyl)-3,4-dihydroisoquinolin-1(2H)-oneYield 65.2%

Reagents, catalysts & solvents 2

HCID 142844-(Dimethylamino)pyridineCatalystHCID 6344DichloromethaneSolvent2×

Conditions

Temperature
0 °C

Procedure

1.5 g of methyl[2-(2-bromophenyl)ethyl](2-ethoxyethyl)carbamate are dissolved under an inert atmosphere in 140 cm3 of dichloromethane at a temperature close to 20° C. 1.6 g of 4-dimethylaminopyridine are added to the reaction mixture, which is cooled to a temperature in the vicinity of 0° C. 3.7 cm3 of trifluoromethanesulfonic anhydride in solution in 15 cm3 of dichloromethane are poured in to the reaction mixture over 30 min. The suspension is kept stirring for 1 h at 0° C., then for 48 h at a temperature close to 20° C. 100 cm3 of a saturated aqueous solution of sodium hydrogen carbonate are added to the reaction medium. Stirring is continued for 1 h at a temperature close to 20° C. After decanting, the organic phase is washed with 100 cm3 of a 20% aqueous solution of acetic acid then with 150 cm3 of a saturated aqueous solution of sodium hydrogen carbonate, dried over magnesium sulfate, filtered and concentrated using a rotary evaporator under reduced pressure (5 kPa). The crude product obtained is purified by filtration through a bed of silica of 20 g. The latter is washed with 100 cm3 of ethyl acetate. The filtrate is concentrated using a rotary evaporator under reduced pressure (5 kPa). 0.8 g of 5-bromo-2-(2-hydroxyethyl)-3,4-dihydroisoquinolin-1(2H)-one is obtained in the form of a beige oil.

Workup

  1. customclose to 20° C
  2. customfor 48 h at a temperature close to 20° C
  3. stirringStirring
  4. waitis continued for 1 h at a temperature
  5. customclose to 20° C
  6. customAfter decanting
  7. washthe organic phase is washed with 100 cm3 of a 20% aqueous solution of acetic acid
  8. dry with materialwith 150 cm3 of a saturated aqueous solution of sodium hydrogen carbonate, dried over magnesium sulfate
  9. filtrationfiltered
  10. concentrationconcentrated
  11. customa rotary evaporator under reduced pressure (5 kPa)
  12. customThe crude product obtained
  13. filtrationis purified by filtration through a bed of silica of 20 g
  14. washThe latter is washed with 100 cm3 of ethyl acetate
  15. concentrationThe filtrate is concentrated
  16. customa rotary evaporator under reduced pressure (5 kPa)

Sources & evidence

ORD record
ord-eb3c968a98844ba3843447bb0bc983cd
Source dataset
uspto-grants-2013_02
Patent number
US08372864B2

Reaction notes

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