Ethanol → Diethyl-2-(1-pyrenylmethyl)-2-acetamidomalonate

HRID 1070366Notes

Reaction equation

HRID 1070366 reaction equation
[C:1]([NH:4][CH:5]([C:11]([O:13][CH2:14][CH3:15])=[O:12])[C:6]([O:8][CH2:9][CH3:10])=[O:7])(=[O:3])[CH3:2].[H-].[Na+].C(O)C.Br[CH2:22][C:23]1[C:36]2[C:37]3=[C:38]4[C:33](=[CH:34][CH:35]=2)[CH:32]=[CH:31][CH:30]=[C:29]4[CH:28]=[CH:27][C:26]3=[CH:25][CH:24]=1>C1COCC1>[CH2:9]([O:8][C:6](=[O:7])[C:5]([CH2:22][C:23]1[C:36]2[C:37]3=[C:38]4[C:33](=[CH:34][CH:35]=2)[CH:32]=[CH:31][CH:30]=[C:29]4[CH:28]=[CH:27][C:26]3=[CH:25][CH:24]=1)([NH:4][C:1](=[O:3])[CH3:2])[C:11]([O:13][CH2:14][CH3:15])=[O:12])[CH3:10]

Participants

6

Reactant 4

HCID 702EthanolHCID 14041Acetamidomalonic acid diethyl esterHCID 24758Sodium hydrideHCID 12740433-(Bromomethyl)pyrene

Product 1

HCID 22395542Diethyl-2-(1-pyrenylmethyl)-2-acetamidomalonateYield 83.1%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

A 9.78 g (45.04 mmol) sample of diethyl acetamidomalonate, and 1.08 g sodium hydride (45.04 mmol) were suspended in 100 mL of anhydrous THF, under nitrogen, and at 0°C. After stirring for 5 min., 2.5 mL of anhydrous ethanol were added slowly, and the solution returned to room temperature. A solution of 1-(bromomethyl)pyrene (12.03 g, 40.9 mmol, dissolved in 100 mL dry THF) was slowly added to the reaction mixture, and the solution brought to reflux for 18 h. The bulk of the THF was removed under reduced pressure, and the remaining yellow slurry was dissolved in 400 mL 1:1 CH2Cl2:H2O. The organic fraction was washed 3× with 100 mL H2O, and dried over anhydrous Na2SO4. Solvent was removed under reduced pressure to produce Diethyl-2-(1-pyrenylmethyl)-2-acetamidomalonate (14.70 g, 83.1%) as a light yellow powder. TLC (SiO2, 1:1 Hexane:EtOAc) Rƒ=0.57. Mp=135-140° C. 1H NMR (CDCl3), δ1.37 (t, 6H), 1.95 (s, 3H), 3.76 (s, 2H), 4.30 (q, 6H), 6.42 (s, NH), 8.00-825 (m, 9H from pyrene).

Workup

  1. customat 0°C
  2. customreturned to room temperature
  3. temperatureto reflux for 18 h
  4. customThe bulk of the THF was removed under reduced pressure
  5. dissolutionthe remaining yellow slurry was dissolved in 400 mL 1:1 CH2Cl2
  6. washThe organic fraction was washed 3× with 100 mL H2O
  7. dry with materialdried over anhydrous Na2SO4
  8. customSolvent was removed under reduced pressure

Sources & evidence

ORD record
ord-473c372186044f259f42cd8a49ea3297
Source dataset
uspto-grants-2005_06
Patent number
US06902720B2

Reaction notes

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