Pyridine → Trifluoromethanesulfonic acid 3-bromo-quinolin-6-yl ester

HRID 1890926Notes

Reaction equation

HRID 1890926 reaction equation
[N:1]1[C:10]2[C:5](=[CH:6][C:7]([O:11][S:12]([C:15]([F:18])([F:17])[F:16])(=[O:14])=[O:13])=[CH:8][CH:9]=2)[CH:4]=[CH:3][CH:2]=1.N1C=CC=CC=1.[Br:25]Br>C(Cl)(Cl)(Cl)Cl>[Br:25][C:3]1[CH:2]=[N:1][C:10]2[C:5]([CH:4]=1)=[CH:6][C:7]([O:11][S:12]([C:15]([F:18])([F:16])[F:17])(=[O:13])=[O:14])=[CH:8][CH:9]=2

Participants

5

Reactant 3

HCID 1049PyridineHCID 24408BromineHCID 152903586-Quinolinyl trifluoromethanesulfonate

Product 1

HCID 57911035Trifluoromethanesulfonic acid 3-bromo-quinolin-6-yl esterYield 26.1%

Reagents, catalysts & solvents 1

HCID 5943Carbon TetrachlorideSolvent

Procedure

To a mixture of trifluoromethanesulfonic acid quinolin-6-yl ester (3.88 g, 14 mmol) and pyridine (2.26 mL, 28 mmol) in CCl4 (50 mL) was added bromine (0.86 mL, 16.8 mmol) dropwise. The mixture was heated to reflux for 2 hrs and cooled to room temperature. The liquid in the flask was decanted and washed with NaHCO3 and water. The dark solid on the bottom of the flask was treated with NaHCO3 and dichloromethane. The combined organic layers were washed with water again and dried before being evaporated to dryness. The crude product was purified by flash column chromatography eluting with petroleum ether/ethyl acetate (10/1˜1/1) to give 1.3 g of trifluoromethanesulfonic acid 3-bromo-quinolin-6-yl ester: 1H NMR (300 MHz, CDCl3) δ: 7.62 (m, 1H), 7.68 (d, 1H), 8.20 (d, 1H), 8.36 (m, 1H), 8.98 (d, 1H); MS (m/z) 356 [M+H]+.

Workup

  1. temperatureThe mixture was heated
  2. temperatureto reflux for 2 hrs
  3. customThe liquid in the flask was decanted
  4. washwashed with NaHCO3 and water
  5. additionThe dark solid on the bottom of the flask was treated with NaHCO3 and dichloromethane
  6. washThe combined organic layers were washed with water again
  7. customdried
  8. custombefore being evaporated to dryness
  9. customThe crude product was purified by flash column chromatography
  10. washeluting with petroleum ether/ethyl acetate (10/1˜1/1)

Sources & evidence

ORD record
ord-09c656a4ff984e74a261e348bd17b0a7
Source dataset
uspto-grants-2013_08
Patent number
US08507489B2

Reaction notes

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