Diethyl (ethoxymethylene)malonate → HCID 12535800, compound

HRID 437430Notes

Reaction equation

HRID 437430 reaction equation
[O-]CC.[Na+].[Na].FS(O)(=O)=O.[CH2:11]([O:13][C:14]1[CH:22]=[CH:21][CH:20]=[CH:19][C:15]=1[C:16]([NH2:18])=[NH:17])[CH3:12].C([O:25][CH:26]=[C:27]([C:33](OCC)=O)[C:28]([O:30][CH2:31][CH3:32])=[O:29])C>C(O)C.C(O)(=O)C.O>[O:25]=[C:26]1[NH:18][C:16]([C:15]2[CH:19]=[CH:20][CH:21]=[CH:22][C:14]=2[O:13][CH2:11][CH3:12])=[N:17][CH:33]=[C:27]1[C:28]([O:30][CH2:31][CH3:32])=[O:29]

Participants

8

Reactant 4

HCID 6871Diethyl (ethoxymethylene)malonateHCID 2723922Sodium ethoxideHCID 5360545SodiumHCID 20360294HCID 20360294, compound

Product 1

HCID 12535800HCID 12535800, compoundYield 97.3%

Reagents, catalysts & solvents 3

HCID 176Acetic AcidSolventHCID 702EthanolSolvent3×HCID 962WaterSolvent

Procedure

To a solution of sodium ethoxide at 18° prepared from sodium (41 g., 1.78 g-atoms) in ethanol (1 l.), was added a solution of 2-ethoxybenzamidine fluorosulfonate (206.5 g., 0.78 mole) in ethanol (500 ml.). The resulting solution was cooled to 13° and then treated with a solution of diethyl ethoxymethylenemalonate (180 ml., 0.89 mole) in ethanol (400 ml.). The mixture was heated under reflux for 2.25 hours. The mixture was cooled to 10° and then poured into cold water (5 l.) with good stirring. Ice was added as necessary to keep the temperature of the mixture below 20°. The mixture was acidified to pH 5 with glacial acetic acid. The solid material was collected by filtration, washed with water, and dried to give the title compound (218.7 g., 97%). Recrystallization from acetonitrile gave product with m.p. 144°-147°.

Workup

  1. temperatureThe resulting solution was cooled to 13°
  2. temperatureThe mixture was heated
  3. temperatureunder reflux for 2.25 hours
  4. temperatureThe mixture was cooled to 10°
  5. additionIce was added as necessary
  6. customthe temperature of the mixture below 20°
  7. filtrationThe solid material was collected by filtration
  8. washwashed with water
  9. customdried

Sources & evidence

ORD record
ord-d08125b620bf41898b1dc176516b8c2d
Source dataset
uspto-grants-1977_06
Patent number
US04031093

Reaction notes

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