Oxalyl chloride → HCID 70085843, compound

HRID 1379607Notes

Reaction equation

HRID 1379607 reaction equation
[CH2:1]([C:4]1[CH:9]=[CH:8][C:7]([CH2:10][CH2:11][CH2:12][C:13]([OH:15])=O)=[CH:6][CH:5]=1)[CH2:2][CH3:3].C(Cl)(=O)C(Cl)=O.[C:22]1([CH2:28][C@H:29]2[CH2:33][O:32][C:31](=[O:34])[NH:30]2)[CH:27]=[CH:26][CH:25]=[CH:24][CH:23]=1.C([Li])CCC>ClCCl.C1COCC1>[CH2:1]([C:4]1[CH:5]=[CH:6][C:7]([CH2:10][CH2:11][CH2:12][C:13]([N:30]2[C@@H:29]([CH2:28][C:22]3[CH:27]=[CH:26][CH:25]=[CH:24][CH:23]=3)[CH2:33][O:32][C:31]2=[O:34])=[O:15])=[CH:8][CH:9]=1)[CH2:2][CH3:3]

Participants

7

Reactant 4

HCID 65578Oxalyl chlorideHCID 736225(S)-4-Benzyl-2-oxazolidinoneHCID 10845958Benzenebutanoic acid, 4-propyl-HCID 178418339Butyllithium

Product 1

HCID 70085843HCID 70085843, compoundYield 60.8%

Reagents, catalysts & solvents 2

HCID 6344DichloromethaneSolventHCID 8028TetrahydrofuranSolvent2×

Procedure

4-(4-(1-n-Propyl)phenyl)butanoic acid (19.3 g) was disolved in dichloromethane and 25 mL of oxalyl chloride was added. After gas evolution ceased (~3 h) the mixture was concentrated in vacuo. To a solution of 4(S)-phenylmethyl-2-oxazolidinone (16.6 g, 93.6 mmol) in 250 mL of dry THF at -78° C. was added butyl lithium (64.4 mL, 1.6M, 102.99 mmol). After 5 min, a solution of the acid chloride in THF was added via cannula. After 15 min, the reaction was partitioned between ethyl acetate and 2N hydrchloric acid and the layers separated. The organics were washed twice with 2N hydrochloric acid and three times with dilute sodium bicarbonate then dried over sodium sulfate, filtered, and concentrated in vacuo. The product was purified by flash filtration through silica-gel eluting with 10% ethyl acetate in hexane to give a pale-yellow oil which crystallized upon dissolution in 5% ethyl acetate in hexane. The mixture was concentrated and recrystallized from hexane to afford the title compound as colorless needles (20.8 g): 400 MHz 1H NMR (CDCl3) δ 7.4-7.0 (m, 9H), 4.63 (m, 1H), 4.14 (m, 2H), 3.20 (dd, 1H, J=3.30, 13.27 Hz), 2.97 (m, 2H), 2.73 (dd, 1H, J=9.72, 13.42 Hz), 2.67 (t, 2H, J=7.68 Hz), 2.53 (t, 2H, J=7.61 Hz), 2.00 (m, 2H), 1.61 (m, 2H), 0.92 (t, 3H, J=7.33 Hz).

Workup

  1. custom(~3 h)
  2. concentrationwas concentrated in vacuo
  3. waitAfter 15 min
  4. customthe reaction was partitioned between ethyl acetate and 2N hydrchloric acid
  5. customthe layers separated
  6. washThe organics were washed twice with 2N hydrochloric acid and three times with dilute sodium bicarbonate
  7. dry with materialthen dried over sodium sulfate
  8. filtrationfiltered
  9. concentrationconcentrated in vacuo
  10. filtrationThe product was purified by flash filtration through silica-gel
  11. washeluting with 10% ethyl acetate in hexane
  12. customto give a pale-yellow oil which
  13. customcrystallized upon dissolution in 5% ethyl acetate in hexane
  14. concentrationThe mixture was concentrated
  15. customrecrystallized from hexane

Sources & evidence

ORD record
ord-ebbb5ce5b0f845fa8de066a6ddd1f81f
Source dataset
uspto-grants-1997_09
Patent number
US05672583

Reaction notes

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