Formamide → Ethyl formate

HRID 1457274Notes

Reaction equation

HRID 1457274 reaction equation
[CH2:1]1[CH2:6][O:5][CH:4]=[CH:3][CH2:2]1.C(C(N)=O)C(N)=[O:9].C(N)=O.[O-:17][CH2:18][CH3:19].[Na+:20]>CO.C[O-].[Na+].C(O)C>[CH:6]([O:5][CH2:4][CH3:3])=[O:9].[O-:17][CH2:18][CH3:19].[Na+:20].[CH2:1]1[CH2:6][O:5][CH:4]=[CH:3][CH2:2]1

Participants

10

Reactant 4

HCID 713Formamide2×HCID 7911Malonamide2×HCID 80803,4-dihydro-2H-pyranHCID 2723922Sodium ethoxide

Product 3

HCID 8025Ethyl formateHCID 80803,4-dihydro-2H-pyranHCID 2723922Sodium ethoxide

Reagents, catalysts & solvents 3

HCID 702EthanolSolventHCID 887MethanolSolventHCID 10942334Sodium MethoxideSolvent

Procedure

The DHP yield was improved by approximately 30% to a maximum of 81% by A. Sommer, DE-OS 1 200 308 by reacting malonodiamide with formamide in alcoholic solution with more than 2 moles, advantageously with 3.0 to 3.9 moles, of alkali metal alkoxide. As opposed to Brown, this worker employed formamide in the examples in amounts of just over 2 moles per mole of malonodiamide. The alkali metal alkoxides used were sodium ethoxide in methanol and sodium methoxide in ethanol. In the latter case, the methanol was distilled off from the reaction mixture, thus dispensing with filtration of the salts which had precipitated. Ethyl formate instead of formamide yielded, together with sodium ethoxide, DHP in a yield of only 61.5%.

Workup

  1. distillationIn the latter case, the methanol was distilled off from the reaction mixture
  2. filtrationthus dispensing with filtration of the salts which
  3. customhad precipitated

Sources & evidence

ORD record
ord-392f83eff5da4871b4868b05c3caaadf
Source dataset
uspto-grants-1998_12
Patent number
US05847139

Reaction notes

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