Malononitrile → 2-(Ethoxymethylene)propanedinitrile

HRID 358431Notes

Reaction equation

HRID 358431 reaction equation
C(O[CH:4]([O:8][CH2:9][CH3:10])OCC)C.[CH2:11]([C:14]#[N:15])[C:12]#[N:13]>C(OC(=O)C)(=O)C>[CH3:10][CH2:9][O:8][CH:4]=[C:11]([C:14]#[N:15])[C:12]#[N:13]

Participants

4

Reactant 2

HCID 8010MalononitrileHCID 31214Ethyl orthoformate

Product 1

HCID 671522-(Ethoxymethylene)propanedinitrileYield 98.7%

Reagents, catalysts & solvents 1

HCID 7918Acetic AnhydrideCatalyst

Procedure

A two-liter, four necked flask is charged with 1332 g (9 moles) of orthoformic acid triethyl ester, 198 g (3 moles) of malonic acid dinitrile and 4 g of acetic acid anhydride. With vigorous stirring, the solution is heated to ebullition. At about 110° C. sump temperature, alcohol begins to distil out through the top of the column. During the course of the reaction, approximately 8 g of acetic acid anhydride is fed in continuously, and the heating of the reaction mixture and the reflux flow are so regulated that the temperature at the top of the condenser is between 75° and 79° C. The condensed distillate is collected and consists substantially of ethanol, acetic acid ethyl ester, formic acid ethyl ester and a small amount of orthoformic acid triethyl ester. During the reaction the sump temperature rises slowly to 130 to 140 degrees C. After 2 to 3 hours the reaction has ended. The unreacted orthoformic acid triethyl ester is distilled out through the column and is fed back to the next batch. Then ethoxymethylene malonic acid dinitrile is separated from the remainder through a simple distillation bridge at 0.1 to 0.02 Torr. In this manner, 361 g of ethoxymethylene malonic acid dinitrile is obtained, with a melting point of 64° C. and a purity of better than 99%. This corresponds to a yield of 98.7% with respect to the malonic acid dinitrile charged.

Workup

  1. temperatureWith vigorous stirring, the solution is heated to ebullition
  2. customAt about 110° C.
  3. customto distil out through the top of the column
  4. customDuring the course of the reaction, approximately 8 g of acetic acid anhydride
  5. temperatureheating of the reaction mixture
  6. customis between 75° and 79° C
  7. distillationThe condensed distillate is collected
  8. customDuring the reaction the sump temperature
  9. customrises slowly to 130 to 140 degrees C
  10. distillationThe unreacted orthoformic acid triethyl ester is distilled out through the column
  11. customThen ethoxymethylene malonic acid dinitrile is separated from the remainder through a simple distillation bridge at 0.1 to 0.02 Torr

Sources & evidence

ORD record
ord-52c56992184146a3bc7c00e206ec6ef3
Source dataset
uspto-grants-1984_08
Patent number
US04468353

Reaction notes

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