Acetic Acid → HCID 10858478, compound

HRID 1108164Notes

Reaction equation

HRID 1108164 reaction equation
[F:1][CH:2]([F:16])[S:3][C:4]1[CH:9]=[CH:8][C:7]([C:10]2[CH:15]=[CH:14][CH:13]=[CH:12][CH:11]=2)=[CH:6][CH:5]=1.C(O)(=[O:19])C.OO.[OH2:23]>[O-][W]([O-])(=O)=O.[Na+].[Na+]>[F:16][CH:2]([F:1])[S:3]([C:4]1[CH:5]=[CH:6][C:7]([C:10]2[CH:15]=[CH:14][CH:13]=[CH:12][CH:11]=2)=[CH:8][CH:9]=1)(=[O:19])=[O:23]

Participants

6

Reactant 4

HCID 176Acetic AcidHCID 784Hydrogen PeroxideHCID 962Water2×HCID 187864074-[(Difluoromethyl)sulfanyl]-1,1'-biphenyl

Product 1

HCID 10858478HCID 10858478, compound

Reagents, catalysts & solvents 1

HCID 26052Sodium tungstateCatalyst

Conditions

Temperature
60 °C

Procedure

To a 1-L three-necked flask equipped with an overhead stirrer, thermometer, and vented addition funnel was charged 71.8 g (0.304 mol) of 4-[(difluoromethyl)thio]-1,1'-biphenyl, 280 mL of glacial acetic acid, and 3.0 g of sodium tungstate predissolved in 10 mL of water. The mixture was heated to 60° C., heating was removed, and 90 mL (0.87 mol, 2.9 equiv) of 30% hydrogen peroxide was added dropwise, maintaining the temperature at 60-70° C. After the addition was complete, the mixture was heated at 80° C. for 2 h to finish the conversion. The solution was cooled to 25° C. and 140 mL of water was added gradually to complete precipitation of the product. The product was filtered, washed with three 50-mL portions of water, suction-dried, then washed with 150 mL of isopropanol, suction-dried, and oven-dried at 50° C./150 mm to afford 78 g (96%) of ca. 98%-pure 4-[(difluoromethyl)sulfonyl]-1,1'-biphenyl, m.p. 81-83° C. An analytical sample prepared by recrystallization from isopropanol/water had m.p. 83-85° C. IR(KBr): 1593, 1334, 1159, 1113, 1080, 754, 607 cm-1. 1H-NMR(CDCl3): δ6.22 (t, 1H, J=60 Hz), 7.5 (m, 3H), 7.62 (dd, 2H, 7.82 (d, 2H), 8.05 (d, 2H). 13C-NMR (CDCl3): δ114.7 (t, JCF =286 Hz), 127.4, 128.1, 129.1, 129.2, 130.1, 131.1, 138.6, 148.8 ppm. 19F-NMR (CDCl3): δ-120.5 (d, JHF =53.4 Hz).

Workup

  1. customTo a 1-L three-necked flask equipped with an overhead stirrer
  2. additionaddition funnel
  3. temperatureheating
  4. customwas removed
  5. temperaturemaintaining the temperature at 60-70° C
  6. additionAfter the addition
  7. temperaturethe mixture was heated at 80° C. for 2 h
  8. temperatureThe solution was cooled to 25° C.
  9. filtrationThe product was filtered
  10. washwashed with three 50-mL portions of water
  11. customsuction-dried
  12. washwashed with 150 mL of isopropanol
  13. customsuction-dried
  14. customoven-dried at 50° C./150 mm

Sources & evidence

ORD record
ord-3049ae0f31084f92a626ef32be30fd12
Source dataset
uspto-grants-2000_05
Patent number
US06063932

Reaction notes

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