Tin atom → 4-Mercapto-2-propylphenoxy-acetic acid ethyl ester

HRID 1991150Notes

Reaction equation

HRID 1991150 reaction equation
[CH2:1]([O:3][C:4](=[O:20])[CH2:5][O:6][C:7]1[CH:12]=[CH:11][C:10]([S:13](Cl)(=O)=O)=[CH:9][C:8]=1[CH2:17][CH2:18][CH3:19])[CH3:2].[Sn].Cl.O1CCOCC1>C(O)C>[CH2:1]([O:3][C:4](=[O:20])[CH2:5][O:6][C:7]1[CH:12]=[CH:11][C:10]([SH:13])=[CH:9][C:8]=1[CH2:17][CH2:18][CH3:19])[CH3:2]

Participants

5

Reactant 3

HCID 5352426Tin atomHCID 204431481,4-Dioxane hydrochlorideHCID 207681244-Chlorosulfonyl-2-propylphenoxy-acetic acid ethyl ester

Product 1

HCID 207681114-Mercapto-2-propylphenoxy-acetic acid ethyl esterYield 79.3%

Reagents, catalysts & solvents 1

HCID 702EthanolSolvent

Procedure

Compound 4.3 (43.27 g, 134.9 mmol) was dissolved in ethanol (168.6 mL). To the solution was added tin (80.1 g, 674.5 mmol) and the reaction was stirred at room temperature for 15 min., then cooled to 0° C. To the reaction was added 4N HCl/dioxane solution (168.6 mL, 674.5 mmol) dropwise at 0° C. Then the reaction was refluxed for 3.5 h. After cooling to room temperature, the reaction mixture was concentrated in vacuo and filtered to remove insoluble materials and the filtrate was concentrated in vacuo to give the residue. The resulting residue was purified using silica gel column chromatography (hexane/EtOAc=10/1) to give 4.4 (27.2 g). 1H NMR (400 MHz) (CDCl3) δ 7.13 (1H, d, J=2.3 Hz); 7.09 (1H, dd, J=2.4, 8.4 Hz); 6.60 (1H, d, J=8.4 Hz); 4.59 (2H, s); 4.25 (2H, q, J=7.1 Hz); 3.32 (1H, s); 2.63-2.55 (2H, m); 1.68-1.57 (2H, m); 1.28 (3H, t, J=7.1 Hz); 0.95 (3H, t, J=7.4 Hz).

Workup

  1. temperaturecooled to 0° C
  2. temperatureThen the reaction was refluxed for 3.5 h
  3. temperatureAfter cooling to room temperature
  4. concentrationthe reaction mixture was concentrated in vacuo
  5. filtrationfiltered
  6. customto remove insoluble materials
  7. concentrationthe filtrate was concentrated in vacuo
  8. customto give the residue
  9. customThe resulting residue was purified

Sources & evidence

ORD record
ord-511bbde448894466b659a0799a660e27
Source dataset
uspto-grants-2010_01
Patent number
US07645779B2

Reaction notes

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