Dichloromethane → HCID 11515492, compound

HRID 1904519Notes

Reaction equation

HRID 1904519 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.[Cl:13][C:14]1[CH:21]=[CH:20][C:17]([CH:18]=[O:19])=[CH:16][CH:15]=1.ClCCl.[OH-].[Na+]>CCCCCCCC[N+](CCCCCCCC)(CCCCCCCC)C.[Cl-].Cl>[Cl:13][C:14]1[CH:21]=[CH:20][C:17]([CH:18]([OH:19])[C:10]([F:12])([F:11])[S:7]([C:1]2[CH:2]=[CH:3][CH:4]=[CH:5][CH:6]=2)(=[O:9])=[O:8])=[CH:16][CH:15]=1

Participants

7

Reactant 4

HCID 6344DichloromethaneHCID 77264-ChlorobenzaldehydeHCID 14798Sodium HydroxideHCID 11816356((Difluoromethyl)sulfonyl)benzene

Product 1

HCID 11515492HCID 11515492, compoundYield 88.4%

Reagents, catalysts & solvents 2

HCID 21218Trioctylmethylammonium chlorideCatalystHCID 313Hydrochloric AcidSolvent

Procedure

A reaction mixture generated from 100 mg (0.52 mmol) of difluoromethyl phenyl sulfone, 225 mg (1.6 mmol) of 4-chlorobenzaldehyde, 1.5 mL of dichloromethane, 1 mL of 50% aqueous sodium hydroxide and 20 mg (0.050 mmol) of Aliquat 336 was poured into 20 mL of IN HCl. Extraction of the aqueous mixture with three 10 mL portions of ethyl acetate 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 10% ethyl acetate in toluene), affording 153 mg (88% yield) of 1-(4-chlorophenyl)-2,2-difluoro-2-phenylsulfonylethanol as a solid. Crystallization from toluene provided an analytical sample: mp; 100°-102° C; IR (KBr) 3530, 3060, 2921, 1491, 1446, 1332, 1157, 1120, 1113, 1090, 1016, 1005, 784, 723, 683, 589, 538 cm-1 ; 1H NMR (CDCl3) 6 3.62 (broad s, IH), 5.56 (dd, IH, J =20, 3 Hz), 7.26-8.13 (m, 9H); 19F NMR (CDCl3, relative to CFCl3) -104.8 ppm (dd, IF, JFF =238 Hz, JHF =3 Hz), -119.2 ppm (dd, lF, JFF =238 Hz, JHF =20 Hz); mass spectrum (70 eV) m/e (relative intensity) 332 (9, M+), 143(44), 141(100), 77(33). Anal. Calcd. for C14H11ClF2O3S: C, 50.53; H, 3.33. Found: C, 50.49; H, 3.41.

Workup

  1. extractionExtraction of the aqueous mixture with three 10 mL portions of ethyl acetate
  2. customdrying
  3. concentration(MgSO4), and concentration in vacuo of the organic layers
  4. customgave a residue which
  5. customwas purified by preparative TLC (two 2 mm silica gel plates eluted with 10% ethyl acetate in toluene)

Sources & evidence

ORD record
ord-5400b22377224c07a0d7f98b7e21aee2
Source dataset
uspto-grants-1989_06
Patent number
US04837327

Reaction notes

Loading…