Dimethyl malonate → Dimethyl (alpha-amino-3-nitrobenzylidene)malonate

HRID 2106808Notes

Reaction equation

HRID 2106808 reaction equation
[C:1]([O:8][CH3:9])(=[O:7])[CH2:2][C:3]([O:5][CH3:6])=[O:4].[N+:10]([C:13]1[CH:14]=[C:15]([CH:18]=[CH:19][CH:20]=1)[C:16]#[N:17])([O-:12])=[O:11]>ClCCCl>[NH2:17][C:16](=[C:2]([C:1]([O:8][CH3:9])=[O:7])[C:3]([O:5][CH3:6])=[O:4])[C:15]1[CH:18]=[CH:19][CH:20]=[C:13]([N+:10]([O-:12])=[O:11])[CH:14]=1

Participants

4

Reactant 2

HCID 7943Dimethyl malonateHCID 120793-Nitrobenzonitrile

Product 1

HCID 9970879Dimethyl (alpha-amino-3-nitrobenzylidene)malonateYield 65.8%

Reagents, catalysts & solvents 1

HCID 111,2-DichloroethaneSolvent

Procedure

To a mixture of dimethyl malonate (100 g) and 3-nitrobenzonitrile (112 g) in 1,2-dichloroethane (500 ml) was added stannic chloride (177 g) at once with a syringe and refluxed for 1 hour with stirring. The white precipitates were collected by filtration, dissolved in a mixture of acetone (2 l) and water (2 l) and adjusted to pH 9.0 with 20% aqueous sodium hydroxide. The resulting white solid was filtered off, and the filtrate was extracted with methylene chloride (2 l). The extract was washed with saturated aqueous sodium chloride, dried over magnesium sulfate and evaporated in vacuo. The resulting precipitates were recrystallized from a mixture of diethyl ether and methylene chloride to give dimethyl (α-amino-3-nitrobenzylidene)malonate (139.5 g).

Workup

  1. temperaturerefluxed for 1 hour
  2. customThe white precipitates
  3. filtrationwere collected by filtration
  4. dissolutiondissolved in a mixture of acetone (2 l) and water (2 l)
  5. filtrationThe resulting white solid was filtered off
  6. extractionthe filtrate was extracted with methylene chloride (2 l)
  7. washThe extract was washed with saturated aqueous sodium chloride
  8. dry with materialdried over magnesium sulfate
  9. customevaporated in vacuo
  10. customThe resulting precipitates
  11. customwere recrystallized from a mixture of diethyl ether and methylene chloride

Sources & evidence

ORD record
ord-a80eb2e979f4472c8d5f646ce4e1cbb6
Source dataset
uspto-grants-1990_06
Patent number
US04931453

Reaction notes

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