Benzaldehyde → HCID 14291989, compound

HRID 1682340Notes

Reaction equation

HRID 1682340 reaction equation
[C:1]1([S:7]([CH:10]([F:12])[F:11])(=[O:9])=[O:8])[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1.[OH-].[Na+].[CH:15](=[O:22])[C:16]1[CH:21]=[CH:20][CH:19]=[CH:18][CH:17]=1>CCCCCCCC[N+](CCCCCCCC)(CCCCCCCC)C.[Cl-].ClCCl>[F:11][C:10]([F:12])([S:7]([C:1]1[CH:2]=[CH:3][CH:4]=[CH:5][CH:6]=1)(=[O:9])=[O:8])[CH:15]([C:16]1[CH:21]=[CH:20][CH:19]=[CH:18][CH:17]=1)[OH:22]

Participants

6

Reactant 3

HCID 240BenzaldehydeHCID 14798Sodium HydroxideHCID 11816356((Difluoromethyl)sulfonyl)benzene

Product 1

HCID 14291989HCID 14291989, compoundYield 90.3%

Reagents, catalysts & solvents 2

HCID 21218Trioctylmethylammonium chlorideCatalystHCID 6344DichloromethaneSolvent2×

Procedure

A mixture of 100 mg (0.52 mmol) of difluoromethyl phenyl sulfone, 1.0 mL of dichloromethane, 1.0 mL of 50% aqueous sodium hydroxide and 20 mg (0.050 mmol) of Aliquat 336 was stirred vigorously for 10 minutes and treated with a solution of 0.16 mL (1.6 mmol) of benzaldehyde in 0.5 mL of dichloromethane. Vigorous stirring was continued for four hours and the resulting mixture was poured into 20 mL of 1N HCL. Extraction of the aqueous mixture with three 10 mL portions of dichloromethane followed by combination, drying (MgSO4), and concentration in vacuo of the organic layers gave a residue which was purified by preparative TLC (two 2 mm silica gel plates eluted with dichloromethane), affording 140 mg (90% yield) of 2,2-difluoro-1-phenyl-2-phenylsulfonylethanol as a solid. Crystallization from toluene provided an analytical sample: mp 77°-79° C.; IR (neat) 3503, 3064, 2922, 1447, 1335, 1312, 1197, 1154, 1113, 1089, 996, 738, 715, 698, 685, 585, 558, cm-1 : 1H NMR (CDCl3) δ 3.54 (broad s, 1H), 5.54 (dd, 1H JHF =21, 3 Hz), 7.20-8.10 (m, 10H); 19F NMR (CDCl3, relative to CFCl3) -106.4 ppm (dd, 1F, JFF =238 Hz, JHF =3Hz), -121.6 ppm (dd, 1F, JFF =238 Hz, JHF =21 Hz); mass spectrum (70 eV) m/e (relative intensity) 298 (8, M+), 156(18), 109(31), 107(100), 79(30), 78(18), 77(56), 51(20). Anal. Calcd. for C14H12F2O3S:C, 56.37; H, 4.06. Found: C, 56.58; H, 4.08.

Workup

  1. stirringVigorous stirring
  2. waitwas continued for four hours
  3. additionthe resulting mixture was poured into 20 mL of 1N HCL
  4. extractionExtraction of the aqueous mixture with three 10 mL portions of dichloromethane
  5. customdrying
  6. concentration(MgSO4), and concentration in vacuo of the organic layers
  7. customgave a residue which
  8. customwas purified by preparative TLC (two 2 mm silica gel plates eluted with dichloromethane)

Sources & evidence

ORD record
ord-33e5a939d8f04d25b55549318a479e8c
Source dataset
uspto-grants-1992_12
Patent number
US05175302

Reaction notes

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