Iodine → Methyl 3-oxovalerate

HRID 1471330Notes

Reaction equation

HRID 1471330 reaction equation
[O:1]=[C:2]([CH2:8]OCC#C)[CH2:3][C:4]([O:6][CH3:7])=[O:5].[C:13]1(C2C=CC(C=O)=CC=2)C=CC=CC=1.CC1(C)CC(=O)CC(=O)C1.C([O-])(=O)C.[NH4+].II>C(O)C>[O:1]=[C:2]([CH2:8][CH3:13])[CH2:3][C:4]([O:6][CH3:7])=[O:5]

Participants

7

Reactant 5

HCID 807IodineHCID 31358DimedoneHCID 76689(1,1'-Biphenyl)-4-carboxaldehydeHCID 517165Ammonium AcetateHCID 59373098HCID 59373098, compound

Product 1

HCID 121699Methyl 3-oxovalerateYield 113.2%

Reagents, catalysts & solvents 1

HCID 702EthanolCatalyst

Procedure

A mixture of methyl 3-oxo-4-(prop-2-ynyloxy)butyrate (2) (220 mg, 1.29 mmol), 4-phenylbenzaldehyde (247 mg, 1.29 mmol), dimedone (183 mg, 1.29 mmol), ammonium acetate (103 mg, 1.29 mmol), I2 (98 mg, 0.39 mmol), and ethanol (15 drops) is stirred under argon for 17 h, quenched with 5% Na2S2O3 (30 mL), and extracted with ethyl acetate (50 mL and 30 mL). The extract is washed (5% Na2S2O3, H2O, and brine), and dried. After solvent removal at reduced pressure, the residue is crystallized (ethanol) to give 190 mg (32%) of 3 (BI-3036) as a cream solid, mp 204-205° C. IR 3370, 2949, 1691, 1638, 1469, 1216 cm−1; NMR (CDCl3) δ 0.99 (s, 3H, CH3), 1.12 (s, 3H, CH3), 2.19-2.48 (m, 4H, COCH2, CH2), 2.56 (t, J=2.4 Hz, 1H, CH≡CCH2), 3.67 (s, 3H, OCH3), 4.34 (d, J=2.4 Hz, 2H, CH≡CCH2), 4.86-4.98 (m, 2H, CH2O), 5.14 (s, 1H, CH), 7.15 (bs, 1H, NH), 7.30-7.60 ppm (m, 9H, 4-BiphenylH).

Workup

  1. customquenched with 5% Na2S2O3 (30 mL)
  2. extractionextracted with ethyl acetate (50 mL and 30 mL)
  3. washThe extract is washed (5% Na2S2O3, H2O, and brine)
  4. customdried
  5. customAfter solvent removal at reduced pressure
  6. customthe residue is crystallized (ethanol)

Sources & evidence

ORD record
ord-2e514c265deb4b92815ad5c825217be7
Source dataset
uspto-grants-2015_04
Patent number
US09012217B2

Reaction notes

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