Methanesulfonic Acid → Methyl 6-bromoquinoline-2-carboxylate

HRID 2423386Notes

Reaction equation

HRID 2423386 reaction equation
[Br:1][C:2]1[CH:3]=[C:4]2[C:9](=[CH:10][CH:11]=1)[N:8]=[C:7]([C:12]([OH:14])=[O:13])[CH:6]=[CH:5]2.[CH3:15]S(O)(=O)=O.C(=O)(O)[O-].[Na+]>CO.O>[Br:1][C:2]1[CH:3]=[C:4]2[C:9](=[CH:10][CH:11]=1)[N:8]=[C:7]([C:12]([O:14][CH3:15])=[O:13])[CH:6]=[CH:5]2

Participants

6

Reactant 3

HCID 6395Methanesulfonic AcidHCID 516892Sodium BicarbonateHCID 123862086-Bromoquinoline-2-carboxylic acid

Product 1

HCID 23568554Methyl 6-bromoquinoline-2-carboxylateYield 325%

Reagents, catalysts & solvents 2

HCID 887MethanolSolventHCID 962WaterSolvent

Conditions

Temperature
20 °C

Procedure

A mixture of 6-bromo-2-quinolinecarboxylic acid (331 g, from multiple batches, 1.31 mol) and methanesulfonic acid (22 mL, 33 g, 0.34 mol) in methanol (2 L) was refluxed for 6 hr. The mixture was treated with a solution of sodium bicarbonate (29 g, 0.34 mol) in water (350 mL) and the resulting suspension was slowly cooled to 20° C. and stirred overnight. The suspension was filtered and the cake was washed with water (1 L). The solid was dried in a vacuum oven at 50° C. for 3 days to yield methyl 6-bromo-2-quinolinecarboxylate (294 g, 85%). 1H NMR (400 MHz, DMSO-d6) δ 8.52 (d, J=9 Hz, 1H), 8.40 (d, J=2 Hz, 1H), 8.14 (d, J=9 Hz, 1H), 8.08 (d, J=9 Hz, 1H), 7.97 (m, 1H), 3.93 (s, 3H). ES-LCMS m/z 267 (M+H)+.

Workup

  1. temperaturewas refluxed for 6 hr
  2. filtrationThe suspension was filtered
  3. washthe cake was washed with water (1 L)
  4. customThe solid was dried in a vacuum oven at 50° C. for 3 days

Sources & evidence

ORD record
ord-76f73e2b92744f3193487e6e85cb1e01
Source dataset
uspto-grants-2011_06
Patent number
US07960552B2

Reaction notes

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