Diethyl Malonate → Diethyl 2-(5-bromo-3-nitropyridin-2-yl)malonate

HRID 2077526Notes

Reaction equation

HRID 2077526 reaction equation
[H-].[Na+].[C:3]([O:11][CH2:12][CH3:13])(=[O:10])[CH2:4][C:5]([O:7][CH2:8][CH3:9])=[O:6].[Br:14][C:15]1[CH:16]=[C:17]([N+:22]([O-:24])=[O:23])[C:18](Cl)=[N:19][CH:20]=1>CN(C=O)C>[Br:14][C:15]1[CH:16]=[C:17]([N+:22]([O-:24])=[O:23])[C:18]([CH:4]([C:5]([O:7][CH2:8][CH3:9])=[O:6])[C:3]([O:11][CH2:12][CH3:13])=[O:10])=[N:19][CH:20]=1

Participants

5

Reactant 3

HCID 7761Diethyl MalonateHCID 24758Sodium hydrideHCID 70194125-Bromo-2-chloro-3-nitropyridine

Product 1

HCID 57516275Diethyl 2-(5-bromo-3-nitropyridin-2-yl)malonate

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent3×

Procedure

Sodium hydride (60% in mineral oil, 1.28 g, 0.032 mol) was suspended in DMF (25 ml) and diethyl malonate (4.0 ml, 26 mmol) was added via syringe slowly over 20 minutes, and more DMF (5 ml) was added as a rinse. The reaction stirred at room temperature for 20 minutes, and then 5-bromo-2-chloro-3-nitropyridine (3.2 g, 14 mmol) was added as a solution in DMF. The reaction was placed in a preheated oil bath (40° C.) and stirred under nitrogen for 1 hour. The reaction was cooled to room temperature, quenched with water (50 ml) and allowed to stand at room temperature overnight. The aqueous phase was extracted with Et2O (3×100 ml, 50 ml), then EtOAC (100 ml) and Et2O (50 ml, 2×100 ml). The organic extracts were combined, dried over magnesium sulfate, filtered, and concentrated, and taken to the next step. MS (ESI pos. ion) m/z: 361 (MH+, 79Br), 363 (MH+, 81Br). Calculated exact mass for C12H13BrN2O6: 360 (79Br), 362 (81Br).

Workup

  1. customThe reaction was placed in a preheated oil bath
  2. stirring(40° C.) and stirred under nitrogen for 1 hour
  3. temperatureThe reaction was cooled to room temperature
  4. customquenched with water (50 ml)
  5. waitto stand at room temperature overnight
  6. extractionThe aqueous phase was extracted with Et2O (3×100 ml, 50 ml)
  7. dry with materialdried over magnesium sulfate
  8. filtrationfiltered
  9. concentrationconcentrated

Sources & evidence

ORD record
ord-c4bd9cabbad644beb5c49f3bbc47ca1c
Source dataset
uspto-grants-2011_04
Patent number
US07928140B2

Reaction notes

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