p-Toluenesulfonic acid → 4-(3-bromophenyl)-2,4-dihydro-3H-1,2,4-triazol-3-one

HRID 70297

Reaktionsgleichung

Reaktionsgleichung von HRID 70297
[Br:1][C:2]1[CH:3]=[C:4]([CH:6]=[CH:7][CH:8]=1)[NH2:5].[NH:9]([C:11]([O:13]C)=O)[NH2:10].[CH:15](OCC)(OCC)OCC.CC1C=CC(S(O)(=O)=O)=CC=1.C[O-].[Na+]>CO>[Br:1][C:2]1[CH:3]=[C:4]([N:5]2[CH:15]=[N:10][NH:9][C:11]2=[O:13])[CH:6]=[CH:7][CH:8]=1

Komponenten

7

Edukt 5

HCID 6101p-Toluenesulfonic acidHCID 115623-BromoanilineHCID 31214Ethyl orthoformateHCID 80519Methyl carbazateHCID 10942334Sodium Methoxide

Produkt 1

HCID 671603674-(3-bromophenyl)-2,4-dihydro-3H-1,2,4-triazol-3-one

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 887MethanolLösungsmittel

Reaktionsbedingungen

Temperatur
65 °C

Versuchsvorschrift

A mixture of 3-bromoaniline (1.0 mL, 9.18 mmol), methyl hydrazinocarboxylate (788 mg, 8.75 mmol), triethyl orthoformate (0.96 mL, 8.75 mmol), and TsOH (25 mg) in MeOH (20 mL) was stirred at 65° C. for 3 hr. After cooling to room temperature, NaOMe (1.47 g, 26.2 mmol) was added and the mixture stirred at room temperature for 16 hr. After concentration in vacuo the residue was taken up in EtOAc and H2O then acidified with 1N HCl. The aqueous phase was extracted with EtOAc and the combined organics washed with H2O then extracted twice with 1N NaOH. Combined NaOH extracts were acidified with conc. HCl and aged 5 min. Resulting solids were collected by filtration, washed with H2O and dried to give 4-(3-bromophenyl)-2,4-dihydro-3H-1,2,4-triazol-3-one as a white solid. 1H NMR (400 MHz, DMSO-d6) δ ppm 7.42-7.46 (m, 1H), 7.53 (d, J=7.8 Hz, 1H), 7.72 (d, J=7.8 Hz, 1H), 7.98 (s, 1H), 8.43 (s, 1H), 12.03 (s, 1H).

Aufarbeitung

  1. temperatureAfter cooling to room temperature
  2. stirringthe mixture stirred at room temperature for 16 hr
  3. concentrationAfter concentration in vacuo the residue
  4. extractionThe aqueous phase was extracted with EtOAc
  5. washthe combined organics washed with H2O
  6. extractionthen extracted twice with 1N NaOH
  7. customwere acidified with conc. HCl and aged 5 min
  8. customResulting solids
  9. filtrationwere collected by filtration
  10. washwashed with H2O
  11. customdried

Quellen und Nachweise

ORD-Eintrag
ord-fd66551572544a759033017f1e8c8f6f
Quelldatensatz
uspto-grants-2014_09
Patentnummer
US08822518B2

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