Diethyl Malonate → Diethyl 2-(benzyloxyhexyl)malonate

HRID 492656Notes

Reaction equation

HRID 492656 reaction equation
[Na].[C:2]([O:10][CH2:11][CH3:12])(=[O:9])[CH2:3][C:4]([O:6][CH2:7][CH3:8])=[O:5].[CH2:13]([O:20][CH2:21][CH2:22][CH2:23][CH2:24][CH2:25][CH2:26]Cl)[C:14]1[CH:19]=[CH:18][CH:17]=[CH:16][CH:15]=1>C(O)C>[CH2:13]([O:20][CH2:21][CH2:22][CH2:23][CH2:24][CH2:25][CH2:26][CH:3]([C:4]([O:6][CH2:7][CH3:8])=[O:5])[C:2]([O:10][CH2:11][CH3:12])=[O:9])[C:14]1[CH:19]=[CH:18][CH:17]=[CH:16][CH:15]=1

Participants

5

Reactant 3

HCID 7761Diethyl MalonateHCID 5360545SodiumHCID 15890138HCID 15890138, compound

Product 1

HCID 10383239Diethyl 2-(benzyloxyhexyl)malonateYield 68.2%

Reagents, catalysts & solvents 1

HCID 702EthanolSolvent

Procedure

To sodium metal (1.32 g, 0.0573 mol) dissolved in dry ethanol (150 ml) under argon at room temperature was added diethyl malonate (14.13 g, 0.088 mol) over a period of 10 minutes and the solution left for 2 hours. B1 (10.0 g 0.044 mol) was then added dropwise over 2 hours and this solution heated at reflux overnight. Excess salts were quenched by the addition of 50 ml of water and the total solvent volume reduced to 50-100 ml. Diethyl ether (100 ml) and water (50 ml) were added and the aqueous layer extracted 3 times with diethyl ether. The organic fractions were combined, dried (K2CO3), and the solvent removed to yield the crude product as a yellow oil. Distillation of the oil (0.5 mBar, 220° C.) gave the title compound (10.52 g, 68%) as a colourless viscous oil. δH (CDCl3) 1.32 (6H, t, Me), 1.43 (6H, br s, (CH2)3CH2CH), 1.69 (2H, p, CH2CH2O), 1.99 (2H, q, CH2CH), 3.39 (1H, t, CH), 3.53 (2H, t, CH2OCH2Ph), 4.25, 4.28 (4H, 2×q, OCH2Me), 4.57 (2H, s, CH2Ph), 7.3-7.4 (5H, m, Ph). δC (CDCl3) 13.9 (2 C, Me), 25.7 (1 C, CH2(CH2)2CH), 27.1 (1 C, CH2(CH2)2O), 28.5 (1 C, CH2CH2CH), 28.9 (1 C, CH2CH2O), 29.5 (1 C, CH2CH), 51.8 (CHCO2Et), 61.0 (2C, OCH2Me), 70.1, 72.7 (2C, CH2OCH2), 127.3 (1C, CH(CH)2C), 127.4 (2C, CGC), 128.1 (2C, CHCHC), 138.5 (1C, CCH2O) 169.3 (2C, CO2).

Workup

  1. temperaturethis solution heated
  2. temperatureat reflux overnight
  3. customExcess salts were quenched by the addition of 50 ml of water
  4. additionDiethyl ether (100 ml) and water (50 ml) were added
  5. extractionthe aqueous layer extracted 3 times with diethyl ether
  6. dry with materialdried (K2CO3)
  7. customthe solvent removed
  8. customto yield the crude product as a yellow oil
  9. distillationDistillation of the oil (0.5 mBar, 220° C.)

Sources & evidence

ORD record
ord-1b17d947805948688cbaa2a41f8a0f65
Source dataset
uspto-grants-2009_05
Patent number
US07531676B2

Reaction notes

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