Diethyl Malonate → HCID 68209677, compound

HRID 2405018Notes

Reaction equation

HRID 2405018 reaction equation
CC([O-])(C)C.[K+].[C:7]([O:15][CH2:16][CH3:17])(=[O:14])[CH2:8][C:9]([O:11][CH2:12][CH3:13])=[O:10].Br[C:19]1[C:20](=[O:36])[N:21]([C:25]2[C:30]([CH3:31])=[CH:29][C:28]([N+:32]([O-:34])=[O:33])=[CH:27][C:26]=2[CH3:35])[CH:22]=[CH:23][CH:24]=1>O1CCOCC1>[CH3:35][C:26]1[CH:27]=[C:28]([N+:32]([O-:34])=[O:33])[CH:29]=[C:30]([CH3:31])[C:25]=1[N:21]1[CH:22]=[CH:23][CH:24]=[C:19]([CH:8]([C:9]([O:11][CH2:12][CH3:13])=[O:10])[C:7]([O:15][CH2:16][CH3:17])=[O:14])[C:20]1=[O:36]

Participants

5

Reactant 3

HCID 7761Diethyl MalonateHCID 23665647Potassium tert-butoxideHCID 594102073-Bromo-1-(2,6-dimethyl-4-nitrophenyl)pyridin-2(1H)-one

Product 1

HCID 68209677HCID 68209677, compound

Reagents, catalysts & solvents 1

HCID 312751,4-DioxaneSolvent2×

Conditions

Temperature
57.5 °C

Procedure

Under argon, 42.5 g (379 mmol) of potassium tert-butylate were suspended in 530 ml of dioxane and heated to 55-60° C. At this temperature, a solution of 60.7 g (379 mmol) of diethyl malonate in 100 ml of dioxane was added over 20 min. When the addition was complete, the reaction mixture was stirred for 1 h at 60° C. 6.72 g (21.7 mmol) of bis(2-pyridinecarboxylato)copper(II) complex were then added, as were 35.0 g (108 mmol) of 3-bromo-1-(2,6-dimethyl-4-nitrophenyl)pyridin-2(1H)-one. The reaction mixture was heated at reflux for 8 h and then stirred overnight at RT. Filtering off the liquid from the solid with suction was carried out, followed by after-washing with dioxane, and the filtrate was evaporated to 250 g on a rotary evaporator. The crude solution was further reacted without purification.

Workup

  1. additionWhen the addition
  2. addition6.72 g (21.7 mmol) of bis(2-pyridinecarboxylato)copper(II) complex were then added
  3. temperatureThe reaction mixture was heated
  4. temperatureat reflux for 8 h
  5. stirringstirred overnight at RT
  6. filtrationFiltering off the liquid from the solid with suction
  7. washby after-washing with dioxane
  8. customthe filtrate was evaporated to 250 g on a rotary evaporator
  9. customThe crude solution was further reacted without purification

Sources & evidence

ORD record
ord-623a7b46ccc041719618e16778acf52a
Source dataset
uspto-grants-2014_08
Patent number
US08802860B2

Reaction notes

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