Methyl 3-bromobenzoate → HCID 86594754, compound

HRID 250955Notes

Reaction equation

HRID 250955 reaction equation
C([Sn](CCCC)(CCCC)[C:6]1[C:7]([CH:12]=[O:13])=[N:8][CH:9]=[CH:10][CH:11]=1)CCC.Br[C:23]1[CH:24]=[C:25]([CH:30]=[CH:31][CH:32]=1)[C:26]([O:28][CH3:29])=[O:27]>CN(C=O)C.C([O-])(O)=O.[Na+].CCOC(C)=O.Cl[Pd](Cl)([P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1)[P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1>[CH3:29][O:28][C:26](=[O:27])[C:25]1[CH:30]=[CH:31][CH:32]=[C:23]([C:6]2[C:7]([CH:12]=[O:13])=[N:8][CH:9]=[CH:10][CH:11]=2)[CH:24]=1

Participants

7

Reactant 2

HCID 12070Methyl 3-bromobenzoateHCID 59095930HCID 59095930, compound

Product 1

HCID 86594754HCID 86594754, compoundYield 17.6%

Reagents, catalysts & solvents 4

HCID 178418476HCID 178418476, compoundCatalystHCID 6228DimethylformamideSolventHCID 8857Ethyl AcetateSolventHCID 516892Sodium BicarbonateSolvent

Conditions

Temperature
110 °C

Procedure

A stirred solution of 3-Tributylstannanyl-pyridine-2-carbaldehyde (256 mg, 0.65 mmol) and methyl 3-bromobenzoate (128 mg, 0.59 mmol) in DMF (2.1 mL) was degassed with Ar for 5 minutes, after which PdCl2(PPh3)2 (25 mg, 0.036 mmol) and CuO (34 mg, 0.43 mmol) was added and the mixture heated to 110° C. overnight. The reaction was cooled to room temperature, and diluted with saturated aqueous NaHCO3 (15 mL) and EtOAc (40 mL). The organic phase was separated, washed with brine (3×15 mL), dried (MgSO4), filtered, and concentrated under reduced pressure. Purification by flash chromatography on silica gel (Hexanes/EtOAc, 60:40) gave 3-(2-Formyl-pyridin-3-yl)-benzoic acid methyl ester (25 mg, 17%) as a white solid. 1H NMR (CDCl3) δ 3.92 (s, 3H), 7.47-7.56 (m, 2H), 7.58 (d, 1H, J=4.9 Hz), 8.03 (s, 1H), 8.07-8.20 (m, 1H), 8.86 (dd, 1H, J=4.9, 1.8 Hz), 10.08 (s, 1H).

Workup

  1. temperatureThe reaction was cooled to room temperature
  2. customThe organic phase was separated
  3. washwashed with brine (3×15 mL)
  4. dry with materialdried (MgSO4)
  5. filtrationfiltered
  6. concentrationconcentrated under reduced pressure
  7. customPurification by flash chromatography on silica gel (Hexanes/EtOAc, 60:40)

Sources & evidence

ORD record
ord-f46f6a8aaa1146758adaf79668efe6bb
Source dataset
uspto-grants-2011_01
Patent number
US07863293B2

Reaction notes

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