2-(Ethoxymethylene)propanedinitrile → 5-amino-1-(2,5-dimethylphenyl)-1H-pyrazole-4-carbonitrile

HRID 1098201Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 1098201
Cl.[CH3:2][C:3]1[CH:8]=[CH:7][C:6]([CH3:9])=[CH:5][C:4]=1[NH:10][NH2:11].C(O[CH:15]=[C:16]([C:19]#[N:20])[C:17]#[N:18])C>CO>[NH2:20][C:19]1[N:10]([C:4]2[CH:5]=[C:6]([CH3:9])[CH:7]=[CH:8][C:3]=2[CH3:2])[N:11]=[CH:15][C:16]=1[C:17]#[N:18]

Komponenten

4

Edukt 2

HCID 671522-(Ethoxymethylene)propanedinitrileHCID 27340582,5-Dimethylphenylhydrazine hydrochloride

Produkt 1

HCID 164629665-amino-1-(2,5-dimethylphenyl)-1H-pyrazole-4-carbonitrileAusbeute 90 %

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 887MethanolLösungsmittel

Reaktionsbedingungen

Temperatur
0 °C

Versuchsvorschrift

2,5-Dimethylphenylhydrazine hydrochloride (CAS no. 56737-78-1) (10 g, 57.92 mmol) was partitioned between EtOAc (100 mL) and NaOH (2M, aq) (60 mL). The organic layer separated and washed with water (50 mL), brine (50 mL), dried (MgSO4), filtered and concentrated to afford free base of the starting material. The resultant oil was suspended in MeOH (100 mL) under nitrogen at −5° C. 2-(ethoxymethylene)malononitrile (7.07 g, 57.92 mmol) added portionwise over 5 mins and the mixture stirred at ˜0° C. for 30 mins. The reaction mixture was allowed to warm to room temperature and then heated at reflux under nitrogen for 2 hours. The reaction mixture was allowed to cool and evaporated to dryness to afford the product (11.07 g, 90%) which was used without purification. 1H NMR (400 MHz, DMSO) δ 1.98 (3H, s), 2.31 (3H, s), 6.39 (2H, s), 7.07 (1H, s), 7.21-7.28 (2H, m), 7.72 (1H, s); m/z (ES+) (M+H)+=213; HPLC tR=1.79 min.

Aufarbeitung

  1. custom56737-78-1) (10 g, 57.92 mmol) was partitioned between EtOAc (100 mL) and NaOH (2M, aq) (60 mL)
  2. customThe organic layer separated
  3. washwashed with water (50 mL), brine (50 mL)
  4. dry with materialdried (MgSO4)
  5. filtrationfiltered
  6. concentrationconcentrated
  7. customto afford free base of the starting material
  8. temperatureto warm to room temperature
  9. temperatureheated
  10. temperatureat reflux under nitrogen for 2 hours
  11. temperatureto cool
  12. customevaporated to dryness

Quellen und Nachweise

ORD-Eintrag
ord-5058b66426454d478428aae33b488dd6
Quelldatensatz
uspto-grants-2012_03
Patentnummer
US08143263B2

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