Ethyl 2-methylacetoacetate → HCID 86634870, compound

HRID 2354117Notes

Reaction equation

HRID 2354117 reaction equation
[H-].[Na+:2].[CH3:3][CH:4]([C:10]([CH3:12])=[O:11])[C:5]([O:7][CH2:8][CH3:9])=[O:6].[H][H].[CH2:15]1[CH2:22][O:21][S:18](=[O:20])(=[O:19])[CH2:17][CH2:16]1>CN(C=O)C>[CH2:8]([O:7][C:5]([C:4]([CH3:3])([C:10](=[O:11])[CH3:12])[CH2:22][CH2:15][CH2:16][CH2:17][S:18]([O-:21])(=[O:20])=[O:19])=[O:6])[CH3:9].[Na+:2]

Participants

6

Reactant 4

HCID 701Ethyl 2-methylacetoacetateHCID 154111,4-Butane sultoneHCID 24758Sodium hydrideHCID 178418361HCID 178418361, compound

Product 1

HCID 86634870HCID 86634870, compound

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent3×

Conditions

Temperature
0 °C

Procedure

Sodium hydride (60 wt %, 12 g≡0.3 mol NaH) was slurried in dry DMF (100 ml). The resulting suspension was cooled with stirring to 0° C. To this was added a solution of ethyl 2-methylacetoacetate (50 g, 0.346 mol) in DMF (25 ml), dropwise so as to maintain the temperature at <10° C. and control effervescence. Once addition was complete and hydrogen evolution ceased, the mixture was warmed in a warm water bath until a clear, pale yellow solution resulted. This was cooled again to 0° C. A solution of 1,4-butanesultone (45 g, 0.33 mol) in DMF (25 ml) was added over 15 mins, maintaining the temperature at <10° C. Once addition was complete, the mixture was heated at 50° C. for 16 hrs. The solvent was then evaporated under vacuum to dryness; the residue was partitioned between water and diethyl ether. The aqueous layer was retained; the organic layer was extracted with fresh water, then discarded. The combined aqueous extracts were washed with fresh ether, then evaporated under vacuum to give the product as a waxy solid.

Workup

  1. temperatureThe resulting suspension was cooled
  2. temperaturedropwise so as to maintain the temperature at <10° C.
  3. additionOnce addition
  4. temperaturethe mixture was warmed in a warm water bath until a clear, pale yellow solution
  5. customresulted
  6. temperatureThis was cooled again to 0° C
  7. temperaturemaintaining the temperature at <10° C
  8. additionOnce addition
  9. temperaturethe mixture was heated at 50° C. for 16 hrs
  10. customThe solvent was then evaporated under vacuum to dryness
  11. customthe residue was partitioned between water and diethyl ether
  12. extractionthe organic layer was extracted with fresh water
  13. washThe combined aqueous extracts were washed with fresh ether
  14. customevaporated under vacuum
  15. customto give the product as a waxy solid

Sources & evidence

ORD record
ord-e8536bdf3bcc42d288c4757e174b5266
Source dataset
uspto-grants-2010_07
Patent number
US07750163B2

Reaction notes

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