Methyl acetoacetate → HCID 23319388, compound

HRID 1981536Notes

Reaction equation

HRID 1981536 reaction equation
[CH2:1]([O:8][CH2:9][C:10]1[CH:17]=[CH:16][C:15]([Cl:18])=[CH:14][C:11]=1[CH:12]=O)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.[C:19]([O:25][CH3:26])(=[O:24])[CH2:20][C:21]([CH3:23])=O.[NH2:27]/[C:28](/[CH3:34])=[CH:29]\[C:30]([O:32][CH3:33])=[O:31]>CC(O)C>[CH3:23][CH:21]1[C:20]([C:19]([O:25][CH3:26])=[O:24])=[C:12]([C:11]2[CH:14]=[C:15]([Cl:18])[CH:16]=[CH:17][C:10]=2[CH2:9][O:8][CH2:1][C:2]2[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=2)[C:29]([C:30]([O:32][CH3:33])=[O:31])=[C:28]([CH3:34])[NH:27]1

Participants

5

Reactant 3

HCID 7757Methyl acetoacetateHCID 643918Methyl 3-aminocrotonateHCID 14059830HCID 14059830, compound

Product 1

HCID 23319388HCID 23319388, compound

Reagents, catalysts & solvents 1

HCID 3776IsopropanolSolvent

Procedure

To a 250 ml round bottomed flask was added the compound (2c) (5.70 g, 22.90 mmol), methyl acetoacetate (2.66 g, 22.90 mmol), methyl 3-aminocrotonate (2.64 g, 22.90 mmol) and 2-propanol (30 ml). The flask was equipped with a stirring bar, reflux condenser and argon inlet and the mixture was heated at reflux for 20 hours with stirring. The reaction mixture was cooled to room temperature and the solvent was removed in vacuo. The crude product was chromatographed on 300 g of silica gel using 1:3 ethyl acetate-hexanes as eluant. The yellow oil obtained from the chromatography was triturated with ethyl ether and the resulting crystals of pure compound (2d) were collected on a first and dried. mp 156-158° C. 'H NMR (CDCl3) δ2.26 (s, 6H), 3.50 (s, 6H), 4.69 (s, 2H), 4.95 (s 2H), 5.00 (s, 1H), 5.95 (br s, 1H), 7.00-7.60 (m, 8H).

Workup

  1. customThe flask was equipped with a stirring bar
  2. temperaturereflux condenser and argon inlet
  3. temperaturethe mixture was heated
  4. temperatureat reflux for 20 hours
  5. customthe solvent was removed in vacuo
  6. customThe crude product was chromatographed on 300 g of silica gel using 1:3 ethyl acetate-hexanes as eluant
  7. customThe yellow oil obtained from the chromatography
  8. customwas triturated with ethyl ether
  9. customthe resulting crystals of pure compound (2d) were collected on a first and
  10. customdried

Sources & evidence

ORD record
ord-8ffc4011251b4cfb9b26bdcf7d5c7ebd
Source dataset
uspto-grants-1986_06
Patent number
US04593033

Reaction notes

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