Dichloromethane → 1-[(2-Bromoethyl)thio]-3,5-difluorobenzene

HRID 2186406Notes

Reaction equation

HRID 2186406 reaction equation
[OH-].[Na+].[F:3][C:4]1[CH:5]=[C:6]([SH:11])[CH:7]=[C:8]([F:10])[CH:9]=1.ClCCl.[Br:15][CH2:16][CH2:17]Br>O.CCCCCCCC[N+](CCCCCCCC)(CCCCCCCC)C.[Cl-]>[Br:15][CH2:16][CH2:17][S:11][C:6]1[CH:5]=[C:4]([F:3])[CH:9]=[C:8]([F:10])[CH:7]=1

Participants

7

Reactant 4

HCID 6344DichloromethaneHCID 78391,2-DibromoethaneHCID 14798Sodium HydroxideHCID 27583613,5-Difluorothiophenol

Product 1

HCID 224542321-[(2-Bromoethyl)thio]-3,5-difluorobenzene

Reagents, catalysts & solvents 2

HCID 21218Trioctylmethylammonium chlorideCatalystHCID 962WaterSolvent

Procedure

A solution of 2.59 g of sodium hydroxide pellets in 27 cm3 of distilled water and then 0.27 cm3 of aliquat 336 (tricaprylylmethylammonium chloride) were added, with stirring and under an inert atmosphere, to a mixture, maintained at a temperature in the region of 23° C., of 7.5 g of 3,5-difluorothiophenol in 9.01 cm3 of 1,2-dibromoethane. After stirring for 15 minutes at a temperature in the region of 20° C., 50 cm3 of dichloromethane were added to the mixture and then, after a few minutes, the organic phase was separated by settling, washed with 25 cm3 of water and 25 cm3 of a saturated 10% sodium chloride solution, dried over magnesium sulfate, filtered, and evaporated under reduced pressure (5 kPa) at a temperature in the region of 40° C. The evaporation residue was purified by chromatography under a nitrogen pressure of 50 kPa on a column of silica gel (particle size 40-63 μm; diameter 5 cm; height 30 cm), elution was carried out with cyclohexane, and first a fraction of 500 cm3 was collected, followed by 50-cm3 fractions. Fractions 9 to 26 were combined and then concentrated under reduced pressure (5 kPa) at a temperature in the region of 40° C. 5.9 g of 1-[(2-bromoethyl)thio]-3,5-difluorobenzene were obtained in the form of a colorless liquid. Infrared spectrum (CCl4): 3094, 1607, 1587, 1429, 1192, 1122, 988, 876, 841, and 667 cm−1.

Workup

  1. additionwere added to the mixture
  2. waitafter a few minutes
  3. customthe organic phase was separated
  4. washwashed with 25 cm3 of water and 25 cm3 of a saturated 10% sodium chloride solution
  5. dry with materialdried over magnesium sulfate
  6. filtrationfiltered
  7. customevaporated under reduced pressure (5 kPa) at a temperature in the region of 40° C
  8. customThe evaporation residue was purified by chromatography under a nitrogen pressure of 50 kPa
  9. washon a column of silica gel (particle size 40-63 μm; diameter 5 cm; height 30 cm), elution
  10. customfirst a fraction of 500 cm3 was collected
  11. concentrationconcentrated under reduced pressure (5 kPa) at a temperature in the region of 40° C

Sources & evidence

ORD record
ord-b9e66967544d44bc9245fa3e9e9ae669
Source dataset
uspto-grants-2002_06
Patent number
US06403610B1

Reaction notes

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