Diethyl Malonate → Ethyl 2-ethoxycarbonyl9-oxa-12-thiatetradecanoate

HRID 1090945Notes

Reaction equation

HRID 1090945 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](Br)[CH2:14][CH2:15][CH2:16][CH2:17][CH2:18][O:19][CH2:20][CH2:21][S:22][CH2:23][CH3:24]>CCO>[CH2:11]([O:10][C:2]([CH:3]([CH2:13][CH2:14][CH2:15][CH2:16][CH2:17][CH2:18][O:19][CH2:20][CH2:21][S:22][CH2:23][CH3:24])[C:4]([O:6][CH2:7][CH3:8])=[O:5])=[O:9])[CH3:12]

Participants

5

Reactant 3

HCID 7761Diethyl MalonateHCID 5360545SodiumHCID 233724747-Oxa-10-thiadodecyl bromide

Product 1

HCID 23372470Ethyl 2-ethoxycarbonyl9-oxa-12-thiatetradecanoateYield 60%

Reagents, catalysts & solvents 1

HCID 702EthanolSolvent3×

Procedure

Sodium metal (0.31 g, 0.014 mol) was dissolved in absolute EtOH (20 mL). To this mixture was added diethyl malonate (2.2 g, 0.014 mol) in EtOH (5 mL) and the above 7-oxa-10-thiadodecyl bromide (3 g, 0.011 mol) in EtOH (5 mL) at room temperature. The reaction mixture was refluxed for 5 h. After evaporation of the solvent, the residue was dissolved in ethyl acetate (120 mL). The organic phase was washed with water (2×30 mL), brine (30 mL), and dried (Na2SO4). The crude product was purified by Kugelrohr distillation to give ethyl 2-ethoxycarbonyl9-oxa-12-thiatetradecanoate (2.3 g, 58%); bp 122° C.-128° C./0.04 torr; NMR: 1.27 (6H, t, J=7 Hz), 3.3-3.7 (5H, m), and 4.17 ppm (4H, q, J=7 Hz), 1.2-1.9 (10H, m), 2.59 (2H, q, J=7 Hz), 2.68 (2H, t, J=7 Hz), 3.1-3.7 (5H, m), and 4.17 ppm (4H, q, J=7 Hz).

Workup

  1. customat room temperature
  2. temperatureThe reaction mixture was refluxed for 5 h
  3. customAfter evaporation of the solvent
  4. dissolutionthe residue was dissolved in ethyl acetate (120 mL)
  5. washThe organic phase was washed with water (2×30 mL), brine (30 mL)
  6. dry with materialdried (Na2SO4)
  7. distillationThe crude product was purified by Kugelrohr distillation

Sources & evidence

ORD record
ord-814871e7e3f2467bab5fadfbd0c66d4a
Source dataset
uspto-grants-1992_01
Patent number
US05082967

Reaction notes

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