Malononitrile → 2-[Hydroxy(4-nitrophenyl)methylene]malononitrile

HRID 227614Notes

Reaction equation

HRID 227614 reaction equation
[N+:1]([C:4]1[CH:12]=[CH:11][C:7]([C:8](Cl)=[O:9])=[CH:6][CH:5]=1)([O-:3])=[O:2].[C:13](#[N:17])[CH2:14][C:15]#[N:16].[OH-].[Na+]>ClCCl>[OH:9][C:8]([C:7]1[CH:11]=[CH:12][C:4]([N+:1]([O-:3])=[O:2])=[CH:5][CH:6]=1)=[C:14]([C:13]#[N:17])[C:15]#[N:16]

Participants

5

Reactant 3

HCID 8010MalononitrileHCID 85024-Nitrobenzoyl chlorideHCID 14798Sodium Hydroxide

Product 1

HCID 858427932-[Hydroxy(4-nitrophenyl)methylene]malononitrileYield 82.2%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Conditions

Temperature
0 °C

Procedure

A 0° C. solution of 4-nitrobenzoyl chloride (24.12 g, 130 mmol) and malononitrile (8.60 g, 130 mmol) in dichloromethane (200 mL) was treated with PhCH2N(CH2CH3)3Cl (3.0 g), treated dropwise with 10N NaOH (30 mL), stirred at 0° C. for 1 hour, and filtered. The filter cake was washed with dichloromethane and diethyl ether, dissolved in 5% HCl, and extracted with ethyl acetate. The extract was dried (MgSO4), filtered, and concentrated. The concentrate was recrystallized from ethyl acetate/hexanes to provide 23 g of the desired product. MS(ESI(−)) m/e 214 (M−H)−.

Workup

  1. filtrationfiltered
  2. washThe filter cake was washed with dichloromethane and diethyl ether
  3. dissolutiondissolved in 5% HCl
  4. extractionextracted with ethyl acetate
  5. dry with materialThe extract was dried (MgSO4)
  6. filtrationfiltered
  7. concentrationconcentrated
  8. customThe concentrate was recrystallized from ethyl acetate/hexanes

Sources & evidence

ORD record
ord-ce0f7655daa54c23ad8751c48a478aee
Source dataset
uspto-grants-2009_07
Patent number
US07560552B2

Reaction notes

Loading…