Dimethyl Sulfide → Methyl 2-fluoro-6-formylbenzoate

HRID 1476809Notes

Reaction equation

HRID 1476809 reaction equation
[F:1][C:2]1[CH:11]=[CH:10][CH:9]=[C:8]([CH:12]=C)[C:3]=1[C:4]([O:6][CH3:7])=[O:5].[O:14]=[O+][O-].CSC>ClCCl>[F:1][C:2]1[CH:11]=[CH:10][CH:9]=[C:8]([CH:12]=[O:14])[C:3]=1[C:4]([O:6][CH3:7])=[O:5]

Participants

5

Reactant 3

HCID 1068Dimethyl SulfideHCID 24823OzoneHCID 90387241Methyl 2-fluoro-6-vinylbenzoate

Product 1

HCID 87166864Methyl 2-fluoro-6-formylbenzoateYield 67%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

Into a solution of methyl 2-fluoro-6-vinylbenzoate (31 g, 0.172 mol) in dry dichloromethane (300 mL) was bubbled O3 at −78° C. over a 30 minute period. Next, nitrogen gas was bubbled into the solution until it turned colorless. Dimethylsulfane (84.13 g, 1.36 mol) was added dropwise to the solution, which was subsequently warmed to RT and stirred for 2 hours. The mixture was then washed with water (30 mL) and extracted with DCM (3×300 mL). The combined organic layers were dried over Na2SO4 and concentrated. The crude product was purified by column chromatography eluting with a gradient of EtOAc (10-100%) and PE to give the title compound (21 g, 67%). 1H NMR (400 MHz, CDCl3) δ ppm 10.01 (s, 1H), 7.65-7.63 (d, J=7.6 Hz, 1H), 7.56-7.53 (dd, J1=5.2 Hz, J2=8.0 Hz, 1H), 7.35-7.30 (t, J=8.4 Hz, 1H), 3.94 (s, 3H).

Workup

  1. customNext, nitrogen gas was bubbled into the solution until it
  2. washThe mixture was then washed with water (30 mL)
  3. extractionextracted with DCM (3×300 mL)
  4. dry with materialThe combined organic layers were dried over Na2SO4
  5. concentrationconcentrated
  6. customThe crude product was purified by column chromatography
  7. washeluting with a gradient of EtOAc (10-100%) and PE

Sources & evidence

ORD record
ord-766c4db37b984116a7c7ede596bc53b6
Source dataset
uspto-grants-2016_08
Patent number
US09402841B2

Reaction notes

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