Methane → Dimethyl isocyanatomalonate

HRID 247215Notes

Reaction equation

HRID 247215 reaction equation
[O:1]=[C:2](Cl)OC(Cl)(Cl)Cl.Cl.[NH2:10][CH:11]([C:16]([O:18][CH3:19])=[O:17])[C:12]([O:14][CH3:15])=[O:13].C>O1CCOCC1>[N:10]([CH:11]([C:16]([O:18][CH3:19])=[O:17])[C:12]([O:14][CH3:15])=[O:13])=[C:2]=[O:1]

Participants

5

Reactant 3

HCID 297MethaneHCID 10426DiphosgeneHCID 2734846Dimethyl 2-aminomalonate hydrochloride

Product 1

HCID 14876291Dimethyl isocyanatomalonateYield 80%

Reagents, catalysts & solvents 1

HCID 312751,4-DioxaneSolvent

Procedure

9.7 mL diphosgene is added dropwise over 50 minutes to a mixture of 12.85 g dimethyl aminomalonate hydrochloride and 0.1 g activated charcoal in 25 mL dioxane under N2. The reaction mixture is warmed to 75°-80° C. during this time. The reaction mixture is then heated and stirred at reflux for 21/2 hours. The reaction mixture is then cooled, filtered, and concentrated to dryness by rotary evaporator, keeping exposure to moisture to a minimum. The crude product is purified by fractional distillation (bp 80°-85° C., <1 mm Hg) to give pure dimethyl isocyanatomalonate in >80% yield.

Workup

  1. temperatureThe reaction mixture is warmed to 75°-80° C. during this time
  2. temperatureThe reaction mixture is then heated
  3. temperatureat reflux for 21/2 hours
  4. temperatureThe reaction mixture is then cooled
  5. filtrationfiltered
  6. concentrationconcentrated to dryness by rotary evaporator
  7. distillationThe crude product is purified by fractional distillation (bp 80°-85° C., <1 mm Hg)

Sources & evidence

ORD record
ord-d9249776a4714b3286c31313aac0452f
Source dataset
uspto-grants-1987_11
Patent number
US04705864

Reaction notes

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