Ethyl Acetoacetate → Ethyl diazoacetoacetate

HRID 1930109Notes

Reaction equation

HRID 1930109 reaction equation
S([N:11]=[N+:12]=[N-])(C1C=CC(C)=CC=1)(=O)=O.[C:14]([O:20][CH2:21][CH3:22])(=[O:19])[CH2:15][C:16]([CH3:18])=[O:17]>C(Cl)Cl>[N+:11](=[C:15]([C:16](=[O:17])[CH3:18])[C:14]([O:20][CH2:21][CH3:22])=[O:19])=[N-:12]

Participants

4

Reactant 2

HCID 8868Ethyl AcetoacetateHCID 13661p-Toluenesulfonyl azide

Product 1

HCID 538206Ethyl diazoacetoacetateYield 92%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent2×

Procedure

Polymer-bound tosylazide (11 g, 15.4 mmol) (typical loading 1.4 mmol/g, prepared according to Merz et al J. Org. Chem. 2001, 66, 2509-2511) was swollen in dry DCM (40 mL). Ethyl acetoacetate (1.0 g, 7.7 mmol, CAS 141-97-9) and TEA (3.2 mL, 23.1 mmol) were dissolved in DCM (10 mL) and added to the polymer containing solution. The resulting mixture was then shaken at RT under nitrogen until the reaction was judged completed by TLC, typically 6 h. The supernatant was filtered off, then the resin was washed with DCM (3×30 mL) to rinse out residual product. The reaction mixture was then evaporated to dryness to afford the title compound (1.1 g, 92%) as yellow oil.

Workup

  1. additionadded to the polymer
  2. additioncontaining solution
  3. customwas judged completed by TLC, typically 6 h
  4. filtrationThe supernatant was filtered off
  5. washthe resin was washed with DCM (3×30 mL)
  6. washto rinse out residual product
  7. customThe reaction mixture was then evaporated to dryness

Sources & evidence

ORD record
ord-b33ff7aec85342ddb259ddd79acbe407
Source dataset
uspto-grants-2012_05
Patent number
US08188092B2

Reaction notes

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