1,1'-Carbonyldiimidazole → (S)-(+)-5,5-Dimethyl-4-phenyl-2-oxazolidinone

HRID 523885Notes

Reaction equation

HRID 523885 reaction equation
[NH2:1][C@@H:2]([C:7]1[CH:12]=[CH:11][CH:10]=[CH:9][CH:8]=1)[C:3]([CH3:6])([OH:5])[CH3:4].[C:13](N1C=CN=C1)(N1C=CN=C1)=[O:14]>ClCCl>[CH3:4][C:3]1([CH3:6])[O:5][C:13](=[O:14])[NH:1][C@H:2]1[C:7]1[CH:12]=[CH:11][CH:10]=[CH:9][CH:8]=1

Participants

4

Reactant 2

HCID 682631,1'-CarbonyldiimidazoleHCID 46941324(S)-1-amino-2-methyl-1-phenylpropan-2-ol

Product 1

HCID 2733820(S)-(+)-5,5-Dimethyl-4-phenyl-2-oxazolidinone

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Conditions

Temperature
25 °C

Procedure

A solution of C2 (38.8 g, 235 mmol) in dichloromethane (1000 mL) was treated with carbonyldiimidazole (45.6 g, 281 mmol) and heated at reflux for 2 hours. The reaction mixture was cooled to 25° C., quenched with 1 N hydrochloric acid (560 mL), and extracted with dichloromethane (3×). The combined organic extracts were dried over sodium sulfate and concentrated, and the resultant residue was purified by trituration with 4:1 hexanes:ethyl acetate, followed by chromatography on silica gel (gradient: 9:1 hexanes:ethyl acetate to 1:1 hexanes:ethyl acetate) to provide C3 as a white solid. Yield: 24.7 g, 55%. MS (APCI) m/z 192.2 (M+1). 1H NMR (400 MHz, CDCl3) δ 0.91 (3H, s), 1.58 (3H, s), 4.62 (1H, s), 5.53-5.60 (1H, br s), 7.20-7.39 (5H, m).

Workup

  1. temperatureheated
  2. temperatureat reflux for 2 hours
  3. customquenched with 1 N hydrochloric acid (560 mL)
  4. extractionextracted with dichloromethane (3×)
  5. dry with materialThe combined organic extracts were dried over sodium sulfate
  6. concentrationconcentrated
  7. customthe resultant residue was purified by trituration with 4:1 hexanes

Sources & evidence

ORD record
ord-31f0f5c110c046e2a6cd54d4c8bb2dd9
Source dataset
uspto-grants-2016_05
Patent number
US09340493B2

Reaction notes

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