Dimethyl Sulfide → HCID 59370752, compound

HRID 1873981Notes

Reaction equation

HRID 1873981 reaction equation
Cl[CH2:2][C:3]([C:5]1[CH:10]=[CH:9][C:8]([F:11])=[C:7]([N+:12]([O-:14])=[O:13])[CH:6]=1)=[O:4].S(C)C.[Cl-].[NH4+].C(OCC)(=O)C>C1COCC1>[F:11][C:8]1[CH:9]=[CH:10][C:5]([C@@H:3]2[CH2:2][O:4]2)=[CH:6][C:7]=1[N+:12]([O-:14])=[O:13]

Participants

6

Reactant 4

HCID 1068Dimethyl SulfideHCID 8857Ethyl AcetateHCID 25517Ammonium ChlorideHCID 230367702-Chloro-1-(4-fluoro-3-nitrophenyl)ethan-1-one

Product 1

HCID 59370752HCID 59370752, compoundYield 93.2%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Conditions

Temperature
0 °C

Procedure

Under nitrogen atmosphere, 2-chloro-1-(4-fluoro-3-nitrophenyl)ethanone (5.4667 g) which can be prepared according to the method described in Reference example 64, etc. was dissolved in dehydrated THF (100 mL), added with 1 mol/L-(R)—CBS-toluene solution (7.5 mL; manufactured by Sigma-Aldrich Co.), followed by cooling to 0° C. To the resulting solution, BH32.SMe2 (10 mL; manufactured by Sigma-Aldrich Co.) was added dropwise over 10 minutes and the mixture was stirred at 0° C. for 2 hours. An aqueous solution of ammonium chloride was added to the reaction solution and extraction was carried out twice with ethyl acetate. The organic layer was washed once with brine, dried over magnesium sulfate, and then the solvent was evaporated under reduced pressure. The resulting residue was added with 2-propanol (100 mL) and an aqueous solution of 1 mol/L-sodium hydroxide (25 mL; manufactured by Kanto Chemical Co., Inc.), and the mixture was stirred at 0° C. for 10 minutes. The reaction solution was poured to water and extracted twice with ethyl acetate. The organic layer was washed once with brine, dried over anhydrous sodium sulfate, and then concentrated under reduced pressure. The resulting residue was purified by column chromatography (“COLUMN-8”; n-hexane:ethyl acetate=88:12→67:33) to obtain the title compound (4.2885 g, optical purity; 92% ee).

Workup

  1. washThe organic layer was washed once with brine
  2. dry with materialdried over magnesium sulfate
  3. customthe solvent was evaporated under reduced pressure
  4. additionThe resulting residue was added with 2-propanol (100 mL)
  5. stirringan aqueous solution of 1 mol/L-sodium hydroxide (25 mL; manufactured by Kanto Chemical Co., Inc.), and the mixture was stirred at 0° C. for 10 minutes
  6. additionThe reaction solution was poured to water
  7. extractionextracted twice with ethyl acetate
  8. washThe organic layer was washed once with brine
  9. dry with materialdried over anhydrous sodium sulfate
  10. concentrationconcentrated under reduced pressure
  11. customThe resulting residue was purified by column chromatography (“COLUMN-8”; n-hexane:ethyl acetate=88:12→67:33)

Sources & evidence

ORD record
ord-5a06b79536a647f8a1d8b38ca6c747eb
Source dataset
uspto-grants-2012_11
Patent number
US08304443B2

Reaction notes

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