Diethyl isopropylmalonate → Diethyl 2-isopropyl-2-propylmalonate

HRID 866696

Reaction equation

HRID 866696 reaction equation
[CH2:1]([O:3][C:4](=[O:14])[CH:5]([CH:11]([CH3:13])[CH3:12])[C:6]([O:8][CH2:9][CH3:10])=[O:7])[CH3:2].CN(P(N(C)C)N(C)C)C.[H-].[Na+].[CH3:27][CH2:28][CH2:29]I>C1(C)C=CC=CC=1.CN(P(N(C)C)N(C)C)C.C1(C)C=CC=CC=1>[CH:11]([C:5]([CH2:27][CH2:28][CH3:29])([C:6]([O:8][CH2:9][CH3:10])=[O:7])[C:4]([O:3][CH2:1][CH3:2])=[O:14])([CH3:12])[CH3:13]

Participants

7

Reactant 4

HCID 12966Diethyl isopropylmalonateHCID 15355Hexamethylphosphorous triamideHCID 24758Sodium hydrideHCID 336431-Iodopropane

Product 1

HCID 599161Diethyl 2-isopropyl-2-propylmalonateYield 87%

Reagents, catalysts & solvents 2

HCID 1140TolueneSolventHCID 131710867HMPT tolueneSolvent

Procedure

A solution of diethylisopropylmalonate (10.1g) in 15 ml of a 25% solution of HMPT (hexamethylphosphorus triamide) in toluene was added dropwise over 15 minutes to a suspension of sodium hydride (70mM) in 25% HMPT/toluene (15ml) at 50°-70° C. N-propyl iodide (17.0g) was then added over 30 minutes at 70°-100° C and the mixture stirred at 120°-130° C for 11/2 hours. After cooling, methylated spirits (10ml) was added and the mixture poured onto a mixture of ice/hydrochloric acid. The product was extracted with ether, the ethereal extracts washed with sodium bicarbonate (X2), then water and dried over anhydrous magnesium sulphate. Removal of the solvent gave diethyl 2-isopropyl-2-propylmalonate as a yellow liquid b.p. 92°-94°/1 mm Hg. 87% yield.

Workup

  1. temperatureAfter cooling
  2. extractionThe product was extracted with ether
  3. washthe ethereal extracts washed with sodium bicarbonate (X2)
  4. dry with materialwater and dried over anhydrous magnesium sulphate
  5. customRemoval of the solvent

Sources & evidence

ORD record
ord-21d7cd48be5f4b0fbafaec30ff07e0b7
Source dataset
uspto-grants-1978_07
Patent number
US04100363

Linked notes

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