Ethyl diazoacetate → HCID 12425355, compound

HRID 601498Notes

Reaction equation

HRID 601498 reaction equation
[Sn](Cl)Cl.[N+](=[CH:6][C:7]([O:9][CH2:10][CH3:11])=[O:8])=[N-].[O:12]=[CH:13][CH2:14][CH2:15][O:16][C:17](=[O:19])[CH3:18]>C(Cl)Cl>[CH2:10]([O:9][C:7](=[O:8])[CH2:6][C:13](=[O:12])[CH2:14][CH2:15][O:16][C:17](=[O:19])[CH3:18])[CH3:11]

Participants

5

Reactant 3

HCID 12192Ethyl diazoacetateHCID 24479Stannous ChlorideHCID 877003-Oxopropyl acetate

Product 1

HCID 12425355HCID 12425355, compoundYield 31.2%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

Charge a round-bottom flask with tin(II) chloride (16.6 g, 0.088 mol), purge with nitrogen, and add dichloroethane (300 mL) by cannula. Add ethyl diazoacetate (92 mL, 0.88 mol) by cannula and stir 10 min. Add a solution of acetic acid 3-oxo-propyl ester (0.44 mol) in CH2Cl2 (600 mL) slowly by cannula over 1 h, then stir the reaction in a 50° C. oil bath for 3 h. Concentrate under vacuum, add saturated aqueous NaHCO3 and remove the organic phase. Extract the aqueous portion with EtOAc (2×). Wash the combined organic portions with brine, dry over MgSO4, filter through Celite®, and concentrate under vacuum. Purify by flash chromatography on silica gel, eluting with a gradient of EtOAc/hexane 8%-25% to give the title compound (27.8 g, 31%), exact mass 202.08, mass spectrum (ES) 225.1 (M+Na). 1H NMR (CDCl3): δ 4.34 (t, J=6.1 Hz, 2H), 4.20 (q, J=7.1 Hz, 2H), 3.46 (s, 2H), 2.89 (t, J=6.1 Hz, 2H), 2.03 (s, 3H), 1.28 (t, J=7.1 Hz, 3H).

Workup

  1. custompurge with nitrogen
  2. additionadd dichloroethane (300 mL) by cannula
  3. customthe reaction in a 50° C. oil bath for 3 h
  4. concentrationConcentrate under vacuum
  5. additionadd saturated aqueous NaHCO3
  6. customremove the organic phase
  7. extractionExtract the aqueous portion with EtOAc (2×)
  8. washWash the combined organic portions with brine
  9. dry with materialdry over MgSO4
  10. filtrationfilter through Celite®
  11. concentrationconcentrate under vacuum
  12. customPurify by flash chromatography on silica gel
  13. washeluting with a gradient of EtOAc/hexane 8%-25%

Sources & evidence

ORD record
ord-70aac20204094b1cab8e841ca2346fa0
Source dataset
uspto-grants-2011_03
Patent number
US07902356B2

Reaction notes

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