Trifluoromethanesulfonic anhydride → HCID 68474444, compound

HRID 387688Notes

Reaction equation

HRID 387688 reaction equation
C[O:2][C:3](=O)[N:4]([CH2:12][CH2:13][C:14]1[CH:19]=[CH:18][C:17]([F:20])=[CH:16][C:15]=1[Br:21])[CH:5]([CH2:9][CH2:10][CH3:11])[CH2:6][CH2:7][CH3:8].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:21][C:15]1[CH:16]=[C:17]([F:20])[CH:18]=[C:19]2[C:14]=1[CH2:13][CH2:12][N:4]([CH:5]([CH2:9][CH2:10][CH3:11])[CH2:6][CH2:7][CH3:8])[C:3]2=[O:2]

Participants

6

Reactant 3

HCID 67749Trifluoromethanesulfonic anhydrideHCID 516892Sodium BicarbonateHCID 68473066HCID 68473066, compound

Product 1

HCID 68474444HCID 68474444, compoundYield 96.6%

Reagents, catalysts & solvents 2

HCID 142844-(Dimethylamino)pyridineCatalystHCID 6344DichloromethaneSolvent3×

Conditions

Temperature
0 °C

Procedure

540 mg of methyl[2-(2-bromo-4-fluorophenyl)ethyl](1-propylbutyl)carbamate are dissolved under an inert atmosphere in 40 cm3 of dichloromethane at a temperature close to 20° C. 529 mg of 4-dimethylaminopyridine are added to the reaction mixture. The latter is cooled to a temperature in the vicinity of 0° C. 1.91 cm3 of trifluoromethanesulfonic anhydride in solution in 15 cm3 of anhydrous dichloromethane are poured into the reaction mixture over 30 min. The suspension is kept stirring for 15 h at a temperature close to 20° C. 20 cm3 of a saturated aqueous solution of sodium hydrogen carbonate are added to the reaction medium. This stirring is continued for 30 min, then 20 cm3 of dichloromethane are added to the mixture. The organic phase is decanted then washed successively with 100 cm3 of a 0.1M aqueous solution of hydrochloric acid and 20 cm3 of a saturated aqueous solution of sodium hydrogen carbonate. Next, the organic phase is dried then concentrated using a rotary evaporator under reduced pressure (5 kPa). The residual brown oil is then taken up in ethyl acetate and purified by filtration through silica (silica 60—particle size 15-40 μm). The organic phase is concentrated under reduced pressure (5 kPa). 477 mg of 5-bromo-7-fluoro-2-(1-propylbutyl)-3,4-dihydroisoquinoline-1(2H)-one are obtained in the form of a dark orange oil.

Workup

  1. customclose to 20° C
  2. customclose to 20° C
  3. waitThis stirring is continued for 30 min
  4. customThe organic phase is decanted
  5. washthen washed successively with 100 cm3 of a 0.1M aqueous solution of hydrochloric acid and 20 cm3 of a saturated aqueous solution of sodium hydrogen carbonate
  6. customNext, the organic phase is dried
  7. concentrationthen concentrated
  8. customa rotary evaporator under reduced pressure (5 kPa)
  9. filtrationpurified by filtration through silica (silica 60—particle size 15-40 μm)
  10. concentrationThe organic phase is concentrated under reduced pressure (5 kPa)

Sources & evidence

ORD record
ord-79d56f27e5b94274adc2d39b83f404a7
Source dataset
uspto-grants-2013_02
Patent number
US08372864B2

Reaction notes

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