S-2-Pyridinyl 4-bromo-2-chlorobenzenecarbothioate → 1-(4-Bromo-2-chlorophenyl)ethan-1-one

HRID 1453020Notes

Reaction equation

HRID 1453020 reaction equation
N1C=CC=CC=1S[C:8](=[O:17])[C:9]1[CH:14]=[CH:13][C:12]([Br:15])=[CH:11][C:10]=1[Cl:16].[CH3:18][Mg]Br.C1(C)C=CC=CC=1.C1COCC1>C1COCC1>[Br:15][C:12]1[CH:13]=[CH:14][C:9]([C:8](=[O:17])[CH3:18])=[C:10]([Cl:16])[CH:11]=1

Participants

5

Reactant 3

HCID 21062254S-2-Pyridinyl 4-bromo-2-chlorobenzenecarbothioateHCID 22635083Tetrahydrofuran tolueneHCID 178418573HCID 178418573, compound

Product 1

HCID 155609501-(4-Bromo-2-chlorophenyl)ethan-1-oneYield 80%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Conditions

Temperature
-78 °C

Procedure

4-Bromo-2-chloro-thiobenzoic acid S-pyridin-2-yl ester (1.86 g, 5.66 mmol) from Step 1 above was dissolved in dry THF (30 mL) and cooled to −78° C. A solution of methyl magnesium bromide in 75:25 toluene/THF (1.4 M, 4.45 mL, 6.23 mmol) was added dropwise. After stirring 35 min, the cooling bath was removed. The reaction mixture was quenched with saturated 1N HCl and extracted with EtOAc (30 mL). The organic phase was washed with brine (50 mL), dried over Na2SO4 and evaporated. The residue was purified by flash column chromatography (10% EtOAc in hexanes) to give the product (1.05 g, 80%) as a colorless oil. 1H NMR (CDCl3) δ 2.64 (s, 3H), 7.46-7.48 (m, 2H), 7.61 (s, 1H).

Workup

  1. customthe cooling bath was removed
  2. customThe reaction mixture was quenched with saturated 1N HCl
  3. extractionextracted with EtOAc (30 mL)
  4. washThe organic phase was washed with brine (50 mL)
  5. dry with materialdried over Na2SO4
  6. customevaporated
  7. customThe residue was purified by flash column chromatography (10% EtOAc in hexanes)

Sources & evidence

ORD record
ord-e5e3f9e8a0ed4f3d842396cfc4f94665
Source dataset
uspto-grants-2009_01
Patent number
US07473790B2

Reaction notes

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