2-Thiopheneacetyl chloride → HCID 18341340, compound

HRID 566827Notes

Reaction equation

HRID 566827 reaction equation
[CH2:1]([C@H:8]1[CH2:12][O:11][C:10](=[O:13])[NH:9]1)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.C([Li])CCC.[S:19]1[CH:23]=[CH:22][CH:21]=[C:20]1[CH2:24][C:25](Cl)=[O:26]>C1COCC1>[CH2:1]([C@H:8]1[CH2:12][O:11][C:10](=[O:13])[N:9]1[C:25](=[O:26])[CH2:24][C:20]1[S:19][CH:23]=[CH:22][CH:21]=1)[C:2]1[CH:3]=[CH:4][CH:5]=[CH:6][CH:7]=1

Participants

5

Reactant 3

HCID 1623622-Thiopheneacetyl chlorideHCID 736225(S)-4-Benzyl-2-oxazolidinoneHCID 178418339Butyllithium

Product 1

HCID 18341340HCID 18341340, compoundYield 53%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Conditions

Temperature
-78 °C

Procedure

To a solution of (S)-(−)-4-benzyl-2-oxazolidinone (350 mg, 2.00 mmol) in dry THF (10 mL) at −30° C. was added dropwise n-butyllithium (2.59 M in hexanes, 0.8 mL). The mixture was cooled to −78° C. and treated with 2-thiopheneacetyl chloride (0.25 mL, 2 mmol). After stirring at −78° C. for 45 minutes, the mixture was allowed to warm to ambient temperature and stir for 1 hour. The mixture was diluted with hexanes (10 mL), quenched with 1M pH7 phosphate buffer, and stirred for 45 minutes. The layers of the resultant biphasic mixture were separated and the aqueousueous phase extracted with EtOAc. The combined organic layers were washed with 0.5N aqueous HCl two times, saturated aqueous NaHCO3 two times, and brine, dried over Na2SO4, and concentrated to provide a crude residue which was purified via flash column chromatography with 20% EtOAc/hex as eluant to yield 319 mg (53%) of 4(S)-benzyl-3-(2-thien-2-yl-acetyl)-2-oxazolidinone as a tan solid, mp 56-9° C. 1H NMR: δ 7.34-7.26 (m, 5H), 7.17-7.14 (m, 2H), 7.02-6.98 (m, 1H), 4.72-4.67 (m, 1H), 4.57, 4.48 (AB quartet, 2H, J=16.8 Hz), 4.26-4.17 (m, 2H), 3.29 (dd, 1H, J=3.2, 13.4 Hz), 2.78 (dd, 1H, J=9.5, 13.4 Hz). Anal. Calculated for C16H15NO3S: C, 63.77; H, 5.02; N, 4.65; S, 10.64. Found: C, 63.87; H, 5.04; N, 4.71; S, 10.74.

Workup

  1. temperatureto warm to ambient temperature
  2. stirringstir for 1 hour
  3. customquenched with 1M pH7 phosphate buffer
  4. stirringstirred for 45 minutes
  5. customThe layers of the resultant biphasic mixture were separated
  6. extractionthe aqueousueous phase extracted with EtOAc
  7. washThe combined organic layers were washed with 0.5N aqueous HCl two times, saturated aqueous NaHCO3 two times, and brine
  8. dry with materialdried over Na2SO4
  9. concentrationconcentrated
  10. customto provide a crude residue which
  11. customwas purified via flash column chromatography with 20% EtOAc/hex as eluant

Sources & evidence

ORD record
ord-bda409b310234095b32ba82a8b88f4cc
Source dataset
uspto-grants-2001_01
Patent number
US06174915B1

Reaction notes

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