Diethyl Malonate → Diethyl 4-bromophenylmalonate

HRID 515456Notes

Reaction equation

HRID 515456 reaction equation
[H-].[Na+].CN(C)P(N(C)C)(N(C)C)=O.[C:14]([O:22][CH2:23][CH3:24])(=[O:21])[CH2:15][C:16]([O:18][CH2:19][CH3:20])=[O:17].[Br:25][C:26]1[CH:31]=[CH:30][C:29](I)=[CH:28][CH:27]=1>O1CCOCC1.[Cu]Br>[Br:25][C:26]1[CH:31]=[CH:30][C:29]([CH:15]([C:16]([O:18][CH2:19][CH3:20])=[O:17])[C:14]([O:22][CH2:23][CH3:24])=[O:21])=[CH:28][CH:27]=1

Participants

7

Reactant 4

HCID 7761Diethyl MalonateHCID 115221-Bromo-4-iodobenzeneHCID 12679HexamethylphosphoramideHCID 24758Sodium hydride

Product 1

HCID 10519382Diethyl 4-bromophenylmalonateYield 45.4%

Reagents, catalysts & solvents 2

HCID 24593copper(I) bromideCatalystHCID 312751,4-DioxaneSolvent

Procedure

To a solution of 60 wt %-sodium hydride (2.47 g, 61.7 mmol) in 1,4-dioxane (103 ml) and hexamethylphosphoramide (7.70 ml) was added diethyl malonate (9.88 g, 61.7 mmol) at room temperature under nitrogen atmosphere. The resulting mixture was stirred at room temperature for one hour and copper(I) bromide (10.6 g, 74.0 mmol) and 1-bromo-4-iodobenzene (19.2 g, 67.9 mmol) was added. The mixture was refluxed for 5 hours and cooled to room temperature. The solid materials were filtered off through a pad of Celite. After concentration, the residue was partitioned between water and ethyl acetate. The organic layer was dried over sodium sulfate, and concentrated in vacuo. The residue was purified by silica gel column chromatography (eluant: hexane/ethyl acetate=24/1) to afford diethyl 2-(4-bromophenyl)malonate as colorless oil (8.82 g, 41%).

Workup

  1. temperatureThe mixture was refluxed for 5 hours
  2. temperaturecooled to room temperature
  3. filtrationThe solid materials were filtered off through a pad of Celite
  4. concentrationAfter concentration
  5. customthe residue was partitioned between water and ethyl acetate
  6. dry with materialThe organic layer was dried over sodium sulfate
  7. concentrationconcentrated in vacuo
  8. customThe residue was purified by silica gel column chromatography (eluant: hexane/ethyl acetate=24/1)

Sources & evidence

ORD record
ord-ea8a864bb5d742bd9faa8a6b6cef0f9e
Source dataset
uspto-grants-2015_08
Patent number
US09108957B2

Reaction notes

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