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

HRID 471830

반응식

HRID 471830 반응식
[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

참가 물질

7

반응물 5

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

생성물 1

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

시약·촉매·용매 1

HCID 887Methanol용매

반응 조건

온도
65 °C

실험 절차

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).

후처리

  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

출처 및 근거

ORD 기록
ord-c60b08e596864811872f14e2940d85b9
출처 데이터셋
uspto-grants-2014_01
특허 번호
US08633175B2

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