Sodium hydride → Methyl 3-chloro-5-(methylsulfonyl)benzoate

HRID 878299Notes

Reaction equation

HRID 878299 reaction equation
N1CCC[C@H]1C(O)=O.[H-].[Na+].[Cl:11][C:12]1[CH:13]=[C:14]([CH:19]=[C:20](I)[CH:21]=1)[C:15]([O:17][CH3:18])=[O:16].[CH3:23][S:24]([O-:26])=[O:25].[Na+].C([O-])(O)=O.[Na+]>CS(C)=O.[Cu]I.CCOC(C)=O>[Cl:11][C:12]1[CH:13]=[C:14]([CH:19]=[C:20]([S:24]([CH3:23])(=[O:26])=[O:25])[CH:21]=1)[C:15]([O:17][CH3:18])=[O:16]

Participants

9

Reactant 5

HCID 24758Sodium hydrideHCID 145742L-ProlineHCID 516892Sodium BicarbonateHCID 2733271Sodium methanesulfinateHCID 24721134Methyl 3-chloro-5-iodobenzoate

Product 1

HCID 18952494Methyl 3-chloro-5-(methylsulfonyl)benzoate

Reagents, catalysts & solvents 3

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 679Dimethyl SulfoxideSolventHCID 8857Ethyl AcetateSolvent

Conditions

Temperature
120 °C

Procedure

To a solution of L-proline (77.7 mg, 675 μmol) in DMSO (4 mL) was added sodium hydride (27.0 mg, 675 μmol, 60% dispersion in mineral oil) and the mixture was stirred at room temperature for 30 minutes before copper(I)iodide (128 mg, 675 μmol), methyl 3-chloro-5-iodobenzoate (0.25 g, 843 μmol) and sodium methanesulfinate (689 mg, 6.75 mmol) were added. The reaction mixture was heated to 120° C. in a sealed tube to give a turbid blue solution. After 2 hours the reaction mixture was allowed to cool down and was poured on saturated aqueous NaHCO3 solution and EtOAc and filtered. The filtrate layers were separated and the aqueous layer was extracted twice with EtOAc. The organic layers were washed once with brine, dried over MgSO4, filtered and evaporated. Light brown solid (0.135 g; 64%). MS (EI): m/z=248 [M].

Workup

  1. additionwere added
  2. customto give a turbid blue solution
  3. temperatureto cool down
  4. filtrationfiltered
  5. customThe filtrate layers were separated
  6. extractionthe aqueous layer was extracted twice with EtOAc
  7. washThe organic layers were washed once with brine
  8. dry with materialdried over MgSO4
  9. filtrationfiltered
  10. customevaporated

Sources & evidence

ORD record
ord-c87a3e579f3b4936b0f60b9d2586a583
Source dataset
uspto-grants-2015_03
Patent number
US08987307B2

Reaction notes

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