2,4-Dichlorobenzylidenemalononitrile → HCID 67214669, compound

HRID 2420788Notes

Reaction equation

HRID 2420788 reaction equation
[NH2:1][C:2]1[N:6]=[CH:5][NH:4][N:3]=1.[Cl:7][C:8]1[CH:19]=[C:18]([Cl:20])[CH:17]=[CH:16][C:9]=1[CH:10]=[C:11]([C:14]#[N:15])[C:12]#[N:13]>N1C=CC=CC=1>[NH2:15][C:14]1[N:3]2[N:4]=[CH:5][N:6]=[C:2]2[N:1]=[C:10]([C:9]2[CH:16]=[CH:17][C:18]([Cl:20])=[CH:19][C:8]=2[Cl:7])[C:11]=1[C:12]#[N:13]

Participants

4

Reactant 2

HCID 180892,4-Dichlorobenzylidenemalononitrile2×HCID 178418311HCID 178418311, compound

Product 1

HCID 67214669HCID 67214669, compound

Reagents, catalysts & solvents 1

HCID 1049PyridineSolvent

Procedure

A solution of 157 mg (1.87 mmol) of 3-amino-1,2,4-triazole and 417 mg (1.87 mmol) of (2,4-dichlorobenzylidene)malononitrile (Intermediate 1) in 4.7 mL of anhydrous pyridine was stirred at reflux under air for 22 h and then cooled and concentrated in vacuo. The residue was partitioned between 5% aqueous citric acid solution and a 1:1 mixture of ethyl acetate and tetrahydrofuran. The organic phase was washed once more with the citric acid solution and then (after addition of some more tetrahydrofuran) with saturated aqueous sodium chloride solution. The combined aqueous fractions were re-extracted with a 2:3 mixture of ethyl acetate and tetrahydrofuran. The combined organics were dried over magnesium sulfate, filtered, and concentrated in vacuo. Purification of the residue by flash chromatography on silica gel (gradient elution with 2-3% methanol in dichloromethane) afforded the title compound as an amber-colored glass, which was used without further purification. LC-MS 305 (M+1).

Workup

  1. temperatureat reflux under air for 22 h
  2. temperaturecooled
  3. concentrationconcentrated in vacuo
  4. customThe residue was partitioned between 5% aqueous citric acid solution
  5. additiona 1:1 mixture of ethyl acetate and tetrahydrofuran
  6. washThe organic phase was washed once more with the citric acid solution
  7. addition(after addition of some more tetrahydrofuran) with saturated aqueous sodium chloride solution
  8. extractionThe combined aqueous fractions were re-extracted with a 2:3 mixture of ethyl acetate and tetrahydrofuran
  9. dry with materialThe combined organics were dried over magnesium sulfate
  10. filtrationfiltered
  11. concentrationconcentrated in vacuo
  12. customPurification of the residue by flash chromatography on silica gel (gradient elution with 2-3% methanol in dichloromethane)

Sources & evidence

ORD record
ord-824442a376914a49905f406c5c9eb7af
Source dataset
uspto-grants-2011_06
Patent number
US07956061B2

Reaction notes

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