Dimethyl malonate → Dimethyl 4-nitro-1H-indene-2,2(3H)-dicarboxylate

HRID 249695Notes

Reaction equation

HRID 249695 reaction equation
[H-].[Na+].[Na].[C:4]([O:11][CH3:12])(=[O:10])[CH2:5][C:6]([O:8][CH3:9])=[O:7].Br[CH2:14][C:15]1[CH:20]=[CH:19][CH:18]=[C:17]([N+:21]([O-:23])=[O:22])[C:16]=1[CH2:24]Br>CCOCC.CO>[CH3:9][O:8][C:6]([C:5]1([C:4]([O:11][CH3:12])=[O:10])[CH2:24][C:16]2[C:15](=[CH:20][CH:19]=[CH:18][C:17]=2[N+:21]([O-:23])=[O:22])[CH2:14]1)=[O:7]

Participants

7

Reactant 4

HCID 7943Dimethyl malonateHCID 24758Sodium hydride2×HCID 5360545SodiumHCID 123177511,2-Bis(bromomethyl)-3-nitrobenzene

Product 1

HCID 57565181Dimethyl 4-nitro-1H-indene-2,2(3H)-dicarboxylateYield 70.2%

Reagents, catalysts & solvents 2

HCID 887MethanolSolventHCID 3283Diethyl EtherSolvent

Procedure

To a solution stirred under nitrogen at room temperature of 5.0 mL methanol in 15.0 mL ether was added 0.84 g 60% sodium hydride (0.021 mol) in small portions (sodium hydride was used because metallic sodium was not available). After the addition was complete, the nearly clear and colorless solution was stirred for 5 minutes. To it was then added 1.3 g dimethyl malonate, giving a slightly cloudy colorless solution. To this was rapidly added a suspension of 3.1 g 1,2-bis(bromomethyl)3-nitrobenzene, which immediate gave a precipitate suspended in a dark green solution. This was removed by filtation and the filtrate was concentrated. The residue was purified on silica (20%-100% CH2Cl2 in hexanes) to give 1.93 g off-white solid (67%).

Workup

  1. additionAfter the addition
  2. customgiving a slightly cloudy colorless solution
  3. additionTo this was rapidly added
  4. customimmediate gave a precipitate
  5. customThis was removed by filtation
  6. concentrationthe filtrate was concentrated
  7. customThe residue was purified on silica (20%-100% CH2Cl2 in hexanes)

Sources & evidence

ORD record
ord-3333ab496f664a3aab3644d8d1b651ee
Source dataset
uspto-grants-2011_01
Patent number
US07863276B2

Reaction notes

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