Thiophenol → HCID 21253503, compound

HRID 377383Notes

Reaction equation

HRID 377383 reaction equation
C(O[CH:5]1[CH:9]2[O:10][C:11](=[O:13])[CH2:12][CH:8]2[CH:7]([CH2:14][O:15][C:16](=[O:23])[C:17]2[CH:22]=[CH:21][CH:20]=[CH:19][CH:18]=2)[O:6]1)(=O)C.[C:24]1([SH:30])[CH:29]=[CH:28][CH:27]=[CH:26][CH:25]=1.B(F)(F)F.CCOCC.C([O-])(O)=O.[Na+]>C(Cl)(Cl)Cl.CCCCCC.CCOCC.CCOC(C)=O.ClCCl.C1(C)C=CC=CC=1>[C:16]([O:15][CH2:14][CH:7]1[CH:8]2[CH:9]([O:10][C:11](=[O:13])[CH2:12]2)[CH:5]([S:30][C:24]2[CH:29]=[CH:28][CH:27]=[CH:26][CH:25]=2)[O:6]1)(=[O:23])[C:17]1[CH:18]=[CH:19][CH:20]=[CH:21][CH:22]=1

Participants

11

Reactant 4

HCID 7969ThiophenolHCID 8000Boron trifluoride etherateHCID 516892Sodium BicarbonateHCID 19603973HCID 19603973, compound

Product 1

HCID 21253503HCID 21253503, compoundYield 72.6%

Reagents, catalysts & solvents 6

HCID 1140TolueneSolventHCID 3283Diethyl EtherSolventHCID 6212ChloroformSolventHCID 6344DichloromethaneSolventHCID 8058HexaneSolventHCID 8857Ethyl AcetateSolvent

Conditions

Temperature
-78 °C

Procedure

To a suspension of 7 (35.7 g, 0.11 mol) and thiophenol (14.8 mL, 0.13 mol) in 220 mL of a 4:1 mixture of anhydrous toluene and dichloromethane at room temperature, boron trifluoride etherate (6.9 mL, 0.05 mol) was added dropwise. The resulting mixture was stirred at the same temperature for 6.5 h and then carefully poured into a biphasic mixture of 1000 mL of EtOAc and 100 mL of a saturated aqueous solution of NaHCO3 (sat. NaHCO3). The layers were separated and the organic layer was washed with 2×100 mL of saturated NaHCO3, 100 mL of water and 100 mL of brine. The organic layer was dried over anhydrous MgSO4, filtered and concentrated to afford a yellow liquid. This material was dissolved in 50 mL of CHCl3, and to it was added 200 mL of ether and 50 mL of hexane. The resulting solution was briefly cooled to -78° C. to induce crystallization. White powdery solid formed which was filtered off and washed with cold ether to afford 29.6 g of 8 (72% yield) as a mixture of two diastereomers: Rf 0.70 and 0.53 (minor and major isomers, respectively, 60% EtOAc/hexane); 1H-NMR (CDCl3) δ (for major isomer only) 8.01 (m, 2H), 7.42-7.70 (m, 5H), 7.27 (m, 3H), 5.89 (d, 1H, J=5.2 Hz), 5.29 (dd, 1H, J=7.7, 5.2 Hz), 4.55 (m, 2H), 4.48 (m, 1H), 2.60-3.12 (m, 3H).

Workup

  1. customThe layers were separated
  2. washthe organic layer was washed with 2×100 mL of saturated NaHCO3, 100 mL of water and 100 mL of brine
  3. dry with materialThe organic layer was dried over anhydrous MgSO4
  4. filtrationfiltered
  5. concentrationconcentrated
  6. customto afford a yellow liquid
  7. customcrystallization
  8. customWhite powdery solid formed which
  9. filtrationwas filtered off
  10. washwashed with cold ether

Sources & evidence

ORD record
ord-d3a01e651f2a4de6a8492fe1a4404b68
Source dataset
uspto-grants-2000_02
Patent number
US06025392

Reaction notes

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