Dimethyl Carbonate → Methyl 3-(4-cyanophenyl)-3-oxopropanoate

HRID 1732045Notes

Reaction equation

HRID 1732045 reaction equation
[C:1](=[O:6])([O:4][CH3:5])OC.[H-].[Na+].[C:9]([C:11]1[CH:16]=[CH:15][C:14]([C:17](=[O:19])[CH3:18])=[CH:13][CH:12]=1)#[N:10]>O1CCOCC1>[C:9]([C:11]1[CH:16]=[CH:15][C:14]([C:17]([CH2:18][C:1]([O:4][CH3:5])=[O:6])=[O:19])=[CH:13][CH:12]=1)#[N:10]

Participants

5

Reactant 3

HCID 12021Dimethyl CarbonateHCID 24758Sodium hydrideHCID 740444'-Cyanoacetophenone

Product 1

HCID 2757970Methyl 3-(4-cyanophenyl)-3-oxopropanoate

Reagents, catalysts & solvents 1

HCID 312751,4-DioxaneSolvent2×

Procedure

Dimethyl carbonate (126 g, 1.4 moles) was added dropwise to a slurry of NaH (50% in mineral oil, 13.44 g, 0.28 mole) slurried in 280 ml of dry dioxane. The reaction mixture was warmed to 80°-85° and p-cyanoacetophenone (40.7 g, 0.28 mole) in 140 ml dioxane added dropwise (at about 3/4 addition, mechanical loss due to foaming occurred; such losses are avoided by slower addition, e.g., over 1 hour). After addition was complete, heating at 80° was continued for 2 hours and crude product recovered by hot filtration. The cake was distributed between dilute CH3CO2H and ether. The ether layer was separated; washed in sequence with H2O, saturated NaHCO3, H2O and brine; dried; and stripped to yield title product: 39 g, (68.6%); m.p. 93°-98°; tlc (4:1 toluene:ethyl acetate) Rf 0.58. Recrystallization of 0.5 g from 2-propanol gave 0.403 g; m.p. 96°-99°.

Workup

  1. temperatureThe reaction mixture was warmed to 80°-85°
  2. addition(at about 3/4 addition, mechanical loss due to foaming occurred; such losses are avoided by slower addition, e.g., over 1 hour)
  3. additionAfter addition
  4. temperatureheating at 80°
  5. filtrationcrude product recovered by hot filtration
  6. customThe ether layer was separated
  7. washwashed in sequence with H2O, saturated NaHCO3, H2O and brine
  8. customdried

Sources & evidence

ORD record
ord-177a386fc5734738bb267969e170790a
Source dataset
uspto-grants-1986_11
Patent number
US04624958

Reaction notes

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