Methyl acetoacetate → HCID 117664500, compound

HRID 2199499Notes

Reaction equation

HRID 2199499 reaction equation
[Na].[C:2]([O:8][CH3:9])(=[O:7])[CH2:3][C:4]([CH3:6])=[O:5].[C:10](OC)(=[O:14])/[CH:11]=[CH:12]/[CH3:13].COC1C=C(OC)C=C(/C=C/CC)C=1C(OC)=O>CO>[O:14]=[C:10]1[CH:3]([C:2]([O:8][CH3:9])=[O:7])[CH:4]([OH:5])[CH2:6][C:12]([CH3:13])=[CH:11]1

Participants

6

Reactant 4

HCID 7757Methyl acetoacetateHCID 638132Methyl CrotonateHCID 5360545SodiumHCID 117664188HCID 117664188, compound

Product 1

HCID 117664500HCID 117664500, compoundYield 70%

Reagents, catalysts & solvents 1

HCID 887MethanolSolvent

Procedure

Dissolve sodium metal (3.1 g, 0.134 mol) in dry methanol (200 ml), add in methyl acetoacetate (12.0 g, 0.103 mol) and methyl crotonate (12.4 g, 0.124 mol at room temperature), after finishing the addition, reflux to react for 6h to complete the reaction, then distill out most of the methanol, pour the residue into ice water (200 ml), extract with ethyl acetate (3×50 ml), adjust pH of the aqueous layer to less than 2 with dilute 15% hydrochloric acid, extract again with ethyl acetate (3×50 ml). Pool the organic layer, and wash with saturated brine, dry the solution over anhydrous MgSO4. Filter and evaporate the solution to dryness, redissolve the residue, recrystallize the solution to obtain a white solid as the target product (13.2 g, 70%) with petroleum ether/ethyl acetate and recrystallized. 1H NMR (400 MHz, DMSO-d6): 0.94 (d, J=6.0 Hz, 3H), 2.32 (m, 3H), 3.09 (d, J=9.2 Hz, 1H), 3.63 (s, 3H), 5.21 (s, 1H), 11.37 (s, 1H).

Workup

  1. additionthe addition
  2. temperaturereflux
  3. customthe reaction
  4. distillationdistill out most of the methanol
  5. additionpour the residue into ice water (200 ml)
  6. extractionextract with ethyl acetate (3×50 ml)
  7. additionwith dilute 15% hydrochloric acid
  8. extractionextract again with ethyl acetate (3×50 ml)
  9. washPool the organic layer, and wash with saturated brine
  10. dry with materialdry the solution over anhydrous MgSO4
  11. filtrationFilter
  12. customevaporate the solution to dryness
  13. dissolutionredissolve the residue
  14. customrecrystallize the solution

Sources & evidence

ORD record
ord-87de7564261242bf85584e41f55d52aa
Source dataset
uspto-grants-2016_06
Patent number
US09359298B2

Reaction notes

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