Benzene → Methyl 3-bromo-5-methanesulfonylbenzoate

HRID 1454196Notes

Reaction equation

HRID 1454196 reaction equation
C1C=CC=CC=1.[CH3:7][S:8]([O-:10])=[O:9].[Na+].[Br:12][C:13]1[CH:14]=[C:15]([CH:19]=[C:20](I)[CH:21]=1)[C:16]([O-:18])=[O:17].[CH3:23]NCCNC>C(OCC)(=O)C.CS(C)=O>[Br:12][C:13]1[CH:14]=[C:15]([CH:19]=[C:20]([S:8]([CH3:7])(=[O:10])=[O:9])[CH:21]=1)[C:16]([O:18][CH3:23])=[O:17]

Participants

7

Reactant 4

HCID 241BenzeneHCID 8070N,N'-DimethylethylenediamineHCID 2733271Sodium methanesulfinateHCID 69315153-Bromo-5-iodobenzoate

Product 1

HCID 22101072Methyl 3-bromo-5-methanesulfonylbenzoateYield 440.9%

Reagents, catalysts & solvents 2

HCID 679Dimethyl SulfoxideSolventHCID 8857Ethyl AcetateSolvent

Procedure

To a sealable tube equipped with a stir bar were added (CuOTf)2.PhH (164 mg, 0.29 mmol), sodium methanesulfinate (847.8 mg, 7.06 mmol) and 3-bromo-5-iodobenzoate (2.0 g, 5.88 mmol). The tube was then covered with a rubber septa and a nitrogen atmosphere was established. N,N′-dimethylethylenediamine (54.6 mg, 0.07 mL, 0.588 mmol) and anhydrous DMSO (5.88 mL) were added via syringe and the septa was replaced by a Teflon-coated screw cap and the reaction vessel was placed in a 110° C. oil bath. After stirred for 20 h, the reaction mixture was allowed to cool to room temperature, diluted with ethyl acetate (60 mL) and filtered through a pad of silica gel. The filtrate was washed with H2O (100 mL) twice, brine (100 mL), dried over sodium sulfate, filtered and concentrated under vacuum. The crude mixture was purified by reverse phase prep HPLC to give the title compound (760 mg): 1H NMR (CD3OD, 500 MHz) δ ppm 3.21 (3H, s), 3.99 (3H, s), 8.36 (1H, m), 8.46 (1H, m), 8.50 (1H, m). HPLC retention time: 1.578 min (method A). MS (ESI) (M+H)+ 292.00.

Workup

  1. customTo a sealable tube equipped with a stir bar
  2. customcap
  3. customwas placed in a 110° C.
  4. filtrationfiltered through a pad of silica gel
  5. washThe filtrate was washed with H2O (100 mL) twice
  6. dry with materialbrine (100 mL), dried over sodium sulfate
  7. filtrationfiltered
  8. concentrationconcentrated under vacuum
  9. customThe crude mixture was purified by reverse phase prep HPLC

Sources & evidence

ORD record
ord-eb3386255b76454dae29ef46a60e773e
Source dataset
uspto-grants-2009_01
Patent number
US07476764B2

Reaction notes

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