Acetic Acid → Diethyl [5-cyano-2-(2-propenyl)-pentyl]-malonate

HRID 1494145Notes

Reaction equation

HRID 1494145 reaction equation
[C:1]([O:9][CH2:10][CH3:11])(=[O:8])[CH2:2][C:3]([O:5][CH2:6][CH3:7])=[O:4].[H-].[Na+].CS(O[CH2:19][CH:20]([CH2:26][CH:27]=[CH2:28])[CH2:21][CH2:22][CH2:23][C:24]#[N:25])(=O)=O.C(O)(=O)C>O1CCCC1>[C:24]([CH2:23][CH2:22][CH2:21][CH:20]([CH2:26][CH:27]=[CH2:28])[CH2:19][CH:2]([C:3]([O:5][CH2:6][CH3:7])=[O:4])[C:1]([O:9][CH2:10][CH3:11])=[O:8])#[N:25]

Participants

6

Reactant 4

HCID 176Acetic AcidHCID 7761Diethyl MalonateHCID 24758Sodium hydrideHCID 149867056-Methylsulfonyloxy-5-(2-propenyl)-hexanenitrile

Product 1

HCID 14986706Diethyl [5-cyano-2-(2-propenyl)-pentyl]-malonate

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent3×

Procedure

A solution of 5410 g of diethyl malonate in 2000 ml of tetrahydrofuran is added to a mixture of 1351 g of 60% sodium hydride in mineral oil in 36 L of tetrahydrofuran over a period of 4 hours, keeping the temperature below 26°, and the mixture is stirred for 1/2 hour. A solution of 3705 g of 6-methanesulfonyloxy-5-(2-propenyl)-hexanenitrile in 200 ml tetrahydrofuran is added rapidly and the mixture is heated under reflux for 24 hours and allowed to cool overnight. The mixture is neutralized to pH 7 with glacial acetic acid (about 1 L) and evaporated to dryness. A solution of the residue in 30 L of ether is washed consecutively with water, saturated sodium bicarbonate solution, water and brine, and evaporated to dryness. The mineral oil is separated in a separatory funnel and the remaining product is washed three times with heptane, concentrated at 80°/0.01 mm Hg, and distilled at 150° to remove diethyl malonate and obtain crude diethyl [5-cyano-2-(2-propenyl)-pentyl]-malonate.

Workup

  1. customthe temperature below 26°
  2. temperaturethe mixture is heated
  3. temperatureunder reflux for 24 hours
  4. temperatureto cool overnight
  5. customevaporated to dryness
  6. washA solution of the residue in 30 L of ether is washed consecutively with water, saturated sodium bicarbonate solution, water and brine
  7. customevaporated to dryness
  8. customThe mineral oil is separated in a separatory funnel
  9. washthe remaining product is washed three times with heptane
  10. concentrationconcentrated at 80°/0.01 mm Hg
  11. distillationdistilled at 150°
  12. customto remove diethyl malonate

Sources & evidence

ORD record
ord-bfebfeca230448acbd5388bfbd5b3896
Source dataset
uspto-grants-1991_06
Patent number
US05025025

Reaction notes

Loading…