Diethyl Malonate → HCID 68209743, compound

HRID 2405014Notes

Reaction equation

HRID 2405014 reaction equation
C([O-])(C)(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:37])[N:21]([C:25]2[CH:30]=[CH:29][C:28]([N+:31]([O-:33])=[O:32])=[CH:27][C:26]=2[CH2:34][O:35][CH3:36])[CH:22]=[CH:23][CH:24]=1>O1CCOCC1.C(OCC)(=O)C.Cl>[CH2:16]([O:15][C:7](=[O:14])[CH:8]([C:19]1[C:20](=[O:37])[N:21]([C:25]2[CH:30]=[CH:29][C:28]([N+:31]([O-:33])=[O:32])=[CH:27][C:26]=2[CH2:34][O:35][CH3:36])[CH:22]=[CH:23][CH:24]=1)[C:9]([O:11][CH2:12][CH3:13])=[O:10])[CH3:17]

Participants

7

Reactant 3

HCID 7761Diethyl MalonateHCID 23665647Potassium tert-butoxideHCID 594101973-Bromo-1-[2-(methoxymethyl)-4-nitrophenyl]pyridin-2(1H)-one

Product 1

HCID 68209743HCID 68209743, compound

Reagents, catalysts & solvents 3

HCID 313Hydrochloric AcidSolventHCID 8857Ethyl AcetateSolventHCID 312751,4-DioxaneSolvent

Procedure

Under argon, a suspension of 49.3 g (513 mmol) of potassium tert-butanolate was introduced as initial charge at RT in 360 ml of dioxane, and 82.2 g (513 mmol) of diethyl malonate were added such that the temperature remained below 30° C. The reaction mixture was stirred for 1 h at RT, 3.4 g (11.0 mmol) of bis(2-pyridinecarboxylato)copper(II) complex and 49.7 g (147 mmol) of 3-bromo-1-[2-(methoxymethyl)-4-nitrophenyl]pyridin-2(1H)-one were added and the mixture was stirred for 4.5 h at 95° C. A further 2.0 g (6.5 mmol) of bis(2-pyridinecarboxylato)copper(II) complex were added and the reaction mixture was stirred overnight at 95° C. After cooling to RT, the mixture was diluted with 0.9 l of ethyl acetate, 1.8 l of 3N hydrochloric acid were added and the mixture was stirred for 15 min at RT. The aqueous phase was extracted with 0.9 l of ethyl acetate and the combined organic phases were washed with saturated aqueous sodium chloride solution. After drying over sodium sulphate, filtration and removal of the solvent on a rotary evaporator, the residue was dried in vacuo. This gave 115 g of crude product, which was reacted further without purification.

Workup

  1. additionwas introduced
  2. customremained below 30° C
  3. stirringthe mixture was stirred for 4.5 h at 95° C
  4. additionA further 2.0 g (6.5 mmol) of bis(2-pyridinecarboxylato)copper(II) complex were added
  5. stirringthe reaction mixture was stirred overnight at 95° C
  6. temperatureAfter cooling to RT
  7. additionwere added
  8. stirringthe mixture was stirred for 15 min at RT
  9. extractionThe aqueous phase was extracted with 0.9 l of ethyl acetate
  10. washthe combined organic phases were washed with saturated aqueous sodium chloride solution
  11. dry with materialAfter drying over sodium sulphate, filtration and removal of the solvent on a rotary evaporator
  12. customthe residue was dried in vacuo
  13. customThis gave 115 g of crude product, which was reacted further without purification

Sources & evidence

ORD record
ord-53c70bda6f694939b4576b98d7ec4658
Source dataset
uspto-grants-2014_08
Patent number
US08802860B2

Reaction notes

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