Dimethyl Sulfide → Methyl 5-chloro-2-formylbenzoate

HRID 1476816Notes

Reaction equation

HRID 1476816 reaction equation
[Cl:1][C:2]1[CH:3]=[CH:4][C:5]([CH:12]=C)=[C:6]([CH:11]=1)[C:7]([O:9][CH3:10])=[O:8].[O:14]=[O+][O-].CSC>C(Cl)Cl>[Cl:1][C:2]1[CH:3]=[CH:4][C:5]([CH:12]=[O:14])=[C:6]([CH:11]=1)[C:7]([O:9][CH3:10])=[O:8]

Participants

5

Reactant 3

HCID 1068Dimethyl SulfideHCID 24823OzoneHCID 15110998Methyl 5-chloro-2-ethenylbenzoate

Product 1

HCID 58437623Methyl 5-chloro-2-formylbenzoateYield 60%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

Into a solution of methyl 5-chloro-2-vinylbenzoate (16.3 g, 82.89 mmol) in dry DCM (250 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 (10.3 g, 165.79 mmol) was added dropwise. The resulting mixture was warmed to RT, stirred for 2 hours, and concentrated. The crude product was purified by silica gel column chromatography eluting with petroleum ether and ethyl acetate (PE/EtOAc=40:1) to give the title compound as a white solid (10 g, 60%). 1H NMR (400 MHz, CDCl3) δ ppm 10.52 (s, 1H), 7.89 (d, J=2.0 Hz, 1H), 7.84 (d, J=8.0 Hz, 1H), 7.55 (dd, J=8.0 Hz and 2.0 Hz, 1H), 3.93 (s, 3H).

Workup

  1. customNext, nitrogen gas was bubbled into the solution until it
  2. concentrationconcentrated
  3. customThe crude product was purified by silica gel column chromatography
  4. washeluting with petroleum ether and ethyl acetate (PE/EtOAc=40:1)

Sources & evidence

ORD record
ord-65361dd4548b4634b08734c86794d7f3
Source dataset
uspto-grants-2016_08
Patent number
US09402841B2

Reaction notes

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