Ethanethiol → HCID 66891866, compound

HRID 250182Notes

Reaction equation

HRID 250182 reaction equation
[H-].[Na+].C(S)C.[CH2:6]([C:8]([C:19]1[CH:24]=[CH:23][C:22]([CH2:25][CH2:26][CH:27]([OH:32])[C:28]([CH3:31])([CH3:30])[CH3:29])=[C:21]([CH3:33])[CH:20]=1)([C:11]1[CH:16]=[CH:15][C:14]([O:17]C)=[CH:13][CH:12]=1)[CH2:9][CH3:10])[CH3:7]>CN(C=O)C>[CH2:6]([C:8]([C:11]1[CH:12]=[CH:13][C:14]([OH:17])=[CH:15][CH:16]=1)([C:19]1[CH:24]=[CH:23][C:22]([CH2:25][CH2:26][CH:27]([OH:32])[C:28]([CH3:30])([CH3:31])[CH3:29])=[C:21]([CH3:33])[CH:20]=1)[CH2:9][CH3:10])[CH3:7]

Participants

5

Reactant 3

HCID 6343EthanethiolHCID 24758Sodium hydrideHCID 66890846HCID 66890846, compound

Product 1

HCID 66891866HCID 66891866, compoundYield 37.6%

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent2×

Conditions

Temperature
0 °C

Procedure

A stirred suspension of NaH (60% dispersion in mineral oil, 80 mg, 2.0 mmol) in anhyd DMF (0.5 mL) was chilled to 0° C. and charged dropwise with ethanethiol (74 μL, 1.0 mmol). The reaction mixture was removed from the ice-bath and stirred at ambient temperature. After 10 min, additional DMF (0.5 mL) was added to facilitate stirring. To the resulting mixture was added dropwise a solution of 1-{4-[1-ethyl-1-(4-methoxyphenyl)-propyl]-2-methylphenyl}-4,4-dimethylpentan-3-ol (0.10 g, 0.26 mmol) in anhyd DMF (0.7 mL). The reaction mixture was transferred to an oil bath and heated at reflux. After 3 h the mixture was cooled, quenched with satd NH4Cl (50 mL), extracted with Et2O (2×50 mL). The combined extracts were washed with H2O (2×50 mL) and brine, then dried (Na2SO4), concentrated under reduced pressure and chromatographed (silica, EtOAC/Hex, 0:100 to 25:75) to give the title compound (36 mg, 37% non-optimized) as a tacky white solid: 1H-NMR (CD2Cl2) δ 7.00-7.06 (3H, m), 6.90-6.94 (2H, m), 6.71 (2H, d), 4.95 (1H, br s), 3.24 (1H, dd, J=1.8, 10.6), 2.85 (1H, ddd, J=5.1, 10.6, 13.9), 2.54 (1H, ddd, J=6.1, 10.4, 13.9), 2.24 (3H, s), 2.05 (4H, q, J=7.3), 1.72-1.84 (1H, m), 1.42-1.54 (1H, m), 0.88 (9H, s), 0.59 (6H, t, J=7.3).

Workup

  1. customThe reaction mixture was removed from the ice-bath
  2. additionadditional DMF (0.5 mL) was added
  3. stirringto facilitate stirring
  4. customThe reaction mixture was transferred to an oil bath
  5. temperatureheated
  6. temperatureat reflux
  7. temperatureAfter 3 h the mixture was cooled
  8. customquenched with satd NH4Cl (50 mL)
  9. extractionextracted with Et2O (2×50 mL)
  10. washThe combined extracts were washed with H2O (2×50 mL) and brine
  11. dry with materialdried (Na2SO4)
  12. concentrationconcentrated under reduced pressure
  13. customchromatographed (silica, EtOAC/Hex, 0:100 to 25:75)

Sources & evidence

ORD record
ord-6fa446c754f845dbb3272799c773f84a
Source dataset
uspto-grants-2011_01
Patent number
US07863298B2

Reaction notes

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