Chloroform → Ethyl 3-(phenylsulfanyl)propanoate

HRID 1110980Notes

Reaction equation

HRID 1110980 reaction equation
[C:1]1([SH:7])[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1.[C:8]([O:12][CH2:13][CH3:14])(=[O:11])[CH:9]=[CH2:10].C(Cl)(Cl)Cl>C(N(CC)CC)C>[C:1]1([S:7][CH2:10][CH2:9][C:8]([O:12][CH2:13][CH3:14])=[O:11])[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1

Participants

5

Reactant 3

HCID 6212ChloroformHCID 7969ThiophenolHCID 8821Ethyl Acrylate

Product 1

HCID 320403Ethyl 3-(phenylsulfanyl)propanoateYield 92.1%

Reagents, catalysts & solvents 1

HCID 8471TriethylamineSolvent

Procedure

To a solution of 12.12 g (0.11 mol) of thiophenol, 10.01 g (0.10 mol) ethyl acrylate, 20 mL of HCCl3 at 0° C. in a 100-mL, round-bottom flask, 0.50 mL of triethylamine was added under N2. The ice bath was removed after the addition of triethylamine and the solution was allowed to stir at room temperature for 3 hours. The resulting solution was idluted with 150 mL of ether and washed with 10% NaOH, H2O, and saturated NaCl solution. The mixture was dried (Na2SO4, overnight) and the solvents were removed. Vacuum distillation gave 19.36 g (92.1%) of ethyl 3-(phenylthio)propionate as a clear, colorless liquid: bp 112°-115° C./0.2 mm [literature reports 117° C./2.5 mm; see K. Iwai, H. Kosugi, A. Miyazaki, and Huda, Synthetic Communications, 6, 357 (1976)]; IR (neat) 1740 cm-1 (C=O); 1H NMR (DCCl3) δ1.14 [t, 3H, CO2CH2CH3 ], 2.54 [t, 2H, CH2CO2CH2CH3 ], 3.10 [t, 2H, ArSCH2 ], 4.06 [q, 2H, CO2CH2CH3 ], 7.13-7.32 [m, 5H, ArH]; 13C NMR (DCCl3) ppm 13.6 [CO2CH2CH3 ], 28.3 [ArSCH2 ], 33.8 [CH2CO2CH2CH3 ], 60.0 [CO2CH2CH3 ], 125.8, 128.4, 129.3, 134.8, 170.9 [C=O]. Both hydrogen and carbon-13 NMR spectra shifts were measured from tetramethylsilane (TMS) standard on a Varian XL-300 spectrometer confirming the correct hydrogen distribution and carbon atom assignments. ##STR11##

Workup

  1. customThe ice bath was removed
  2. additionafter the addition of triethylamine
  3. washwashed with 10% NaOH, H2O, and saturated NaCl solution
  4. dry with materialThe mixture was dried (Na2SO4, overnight)
  5. customthe solvents were removed
  6. distillationVacuum distillation

Sources & evidence

ORD record
ord-556b108cd3df4c9586af5b3a376027b6
Source dataset
uspto-grants-1990_12
Patent number
US04977276

Reaction notes

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