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

HRID 70297

反応式

HRID 70297 の反応式
[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

参加物

7

反応物 5

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

生成物 1

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

試薬・触媒・溶媒 1

HCID 887Methanol溶媒

反応条件

温度
65 °C

実験手順

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).

後処理

  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

出典と根拠

ORDレコード
ord-fd66551572544a759033017f1e8c8f6f
出典データセット
uspto-grants-2014_09
特許番号
US08822518B2

関連ノート

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