Sulfuryl chloride → 2-Chloro-1-[4'-[(difluoromethyl)thio][1,1'-biphenyl]-4-yl]ethanone

HRID 1108150Notes

Reaction equation

HRID 1108150 reaction equation
[F:1][CH:2]([F:22])[S:3][C:4]1[CH:9]=[CH:8][C:7]([C:10]2[CH:15]=[CH:14][C:13]([C:16]3([CH3:21])OCC[O:17]3)=[CH:12][CH:11]=2)=[CH:6][CH:5]=1.S(Cl)([Cl:26])(=O)=O>ClCCCl>[Cl:26][CH2:21][C:16]([C:13]1[CH:14]=[CH:15][C:10]([C:7]2[CH:8]=[CH:9][C:4]([S:3][CH:2]([F:22])[F:1])=[CH:5][CH:6]=2)=[CH:11][CH:12]=1)=[O:17]

Participants

4

Reactant 2

HCID 24648Sulfuryl chlorideHCID 187864322-[4'-[(Difluoromethyl)thio][1,1'-biphenyl]-4-yl]-2-methyl-1,3-dioxolane

Product 1

HCID 187864052-Chloro-1-[4'-[(difluoromethyl)thio][1,1'-biphenyl]-4-yl]ethanoneYield 71.6%

Reagents, catalysts & solvents 1

HCID 111,2-DichloroethaneSolvent

Procedure

A solution of 8.0 g (25 mmol) of 2-[4'-[(difluoromethyl)thio][1,1'-biphenyl]-4-yl]-2-methyl-1,3-dioxolane and 30 mL of anhydrous 1,2-dichloroethane was cooled to 5° C. and sulfuryl chloride (2.3 mL, 3.8 g, 28 mmol) was added via syringe. The solution was allowed to warm to ambient temperature and concentrated to dryness. Acetone (40 mL), 5 mL of water, and 2 mL of 37% HCl were added, and the mixture was heated at 55° C. for 18 h. The mixture was diluted with 20 mL of water with cooling and seeding to precipitate the product. After filtration, washing with cold 50% aqueous MeOH and drying, the crude solid (7.2 g, 92%) was slurried in 80 mL of hot isopropanol (i-PrOH) allowed to cool with good stirring for 30 min, and filtered to afford 5.6 g of 2-chloro-1-[4'-[(difluoro-methyl)thio][1,1'-biphenyl]-4-yl]ethanone, m.p. 102-104° C. A second crop of 0.9 g was obtained by partial concentration of the filtrate. An analytical standard was prepared by chromatography and/or recrystallization from CH2Cl2 /MeOH, m.p. 104 to 105° C. 1H-NMR(CDCl3): δ4.75 (s, 2H), 6.88 (t, 1H), 7.65 (ABq, 4H) 7.7 (d, A of ABq, 2H), 8.05 (d, B of ABq, 2H).

Workup

  1. concentrationconcentrated to dryness
  2. additionAcetone (40 mL), 5 mL of water, and 2 mL of 37% HCl were added
  3. temperaturethe mixture was heated at 55° C. for 18 h
  4. additionThe mixture was diluted with 20 mL of water
  5. temperaturewith cooling
  6. customto precipitate the product
  7. filtrationAfter filtration
  8. washwashing with cold 50% aqueous MeOH
  9. customdrying
  10. temperatureto cool
  11. filtrationfiltered

Sources & evidence

ORD record
ord-c7a7669a7ec241fb922efbff79d9966a
Source dataset
uspto-grants-2000_05
Patent number
US06063932

Reaction notes

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