Dimethyl malonate → HCID 12942701, compound

HRID 848724Notes

Reaction equation

HRID 848724 reaction equation
[H-].[Na+].[CH2:3]([Si:13]([CH3:19])([CH3:18])[CH2:14][CH2:15][CH2:16]I)[CH2:4][CH2:5][CH2:6][CH2:7][CH2:8][CH2:9][CH2:10][CH2:11][CH3:12].[C:20]([O:27][CH3:28])(=[O:26])[CH2:21][C:22]([O:24][CH3:25])=[O:23].[H][H]>CN(C)C=O.O.C(O)(=O)C>[CH3:25][O:24][C:22](=[O:23])[CH:21]([C:20]([O:27][CH3:28])=[O:26])[CH2:16][CH2:15][CH2:14][Si:13]([CH3:19])([CH3:18])[CH2:3][CH2:4][CH2:5][CH2:6][CH2:7][CH2:8][CH2:9][CH2:10][CH2:11][CH3:12]

Participants

8

Reactant 4

HCID 7943Dimethyl malonateHCID 24758Sodium hydrideHCID 12942700HCID 12942700, compoundHCID 178418361HCID 178418361, compound

Product 1

HCID 12942701HCID 12942701, compound

Reagents, catalysts & solvents 3

HCID 176Acetic AcidSolventHCID 962WaterSolventHCID 6228DimethylformamideSolvent

Procedure

To a reaction vessel system filled with nitrogen, 964 mg (24.5 mmole) of 61.1% sodium hydride in mineral oil is added, which is washed free of the oil by employing 3 portions of petroleum ether/hexane (1:1). The thus-washed sodium hydride is then suspended in 20 ml of fresh hexane and added in several portions to 8.1 g (22.0 mmoles) of n-decyl-dimethyl-(3-iodopropyl)-silane plus 3.6 g (27.3 mmole) of dimethyl malonate in 25 ml of dry dimethylformamide plus 25 ml of dry petroleum ether, with stirring and cooling at such a rate that hydrogen gas evolution is controlled, and the temperature is at 0° to 10° (new solids form). The reaction mixture is then stirred in a bath at 55° for 2 hrs. and then at 65° for 1 hr. After cooling to room temperature, 2 ml of acetic acid (85%) is added, followed by an excess of water and petroleum ether. The organic layer is separated, washed thrice with water, dried and then concentrated to obtain the crude title product of this step as an oily residue, which is distilled through a Vigreux column to obtain refined title product of this step at 135°-139° at 0.105 mm Hg.

Workup

  1. additionis added
  2. washwhich is washed free of the oil
  3. customis at 0° to 10°
  4. stirringThe reaction mixture is then stirred in a bath at 55° for 2 hrs
  5. customThe organic layer is separated
  6. washwashed thrice with water
  7. customdried
  8. concentrationconcentrated
  9. customto obtain the crude title product of this step as an oily residue, which
  10. distillationis distilled through a Vigreux column

Sources & evidence

ORD record
ord-27a2f0e71a934b9280daeaa0f57d2459
Source dataset
uspto-grants-1981_10
Patent number
US04297349

Reaction notes

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