Diacetamide → 1-(2-Bromo-5-fluorophenyl)-3,5-dimethyl-1H-1,2,4-triazole

HRID 1726669

반응식

HRID 1726669 반응식
Cl.[Br:2][C:3]1[CH:8]=[CH:7][C:6]([F:9])=[CH:5][C:4]=1[NH:10][NH2:11].[CH3:12][C:13]([NH:15][C:16]([CH3:18])=O)=O>N1C=CC=CC=1>[Br:2][C:3]1[CH:8]=[CH:7][C:6]([F:9])=[CH:5][C:4]=1[N:10]1[C:16]([CH3:18])=[N:15][C:13]([CH3:12])=[N:11]1

참가 물질

4

반응물 2

HCID 12263DiacetamideHCID 21069774(2-Bromo-5-fluorophenyl)hydrazine hydrochloride

생성물 1

HCID 210697671-(2-Bromo-5-fluorophenyl)-3,5-dimethyl-1H-1,2,4-triazole수율 89.6%

시약·촉매·용매 1

HCID 1049Pyridine용매

반응 조건

온도
127.5 °C

실험 절차

A mixture of 1-(2-bromo-5-fluoro-phenyl)-hydrazine hydrochloride (24.15 g, 100 mmol) and diacetamide (10.1 g, 100 mmol; Aldrich) in anhydrous pyridine (100 mL) was stirred in an oil bath heated at 125-130° C. under nitrogen for 2 h. After cooling the mixture was concentrated in vacuo to dryness, and the residue diluted with EtOAc (100 mL) was washed with water (50 mL), and then with brine (30 mL), dried (Na2SO4), filtered and concentrated to obtain 24.2 g of the title compound as a brownish oil: HPLC rt=1.59 min. LC/MS m/z 270/272 (M+H); 1H NMR (CDCl3, 500 MHz) δ ppm 2.30 (3H, s, 9-Me), 2.39 (3H, s, 10-Me), 7.10-7.15 (2H, m, 3,5-CH), 7.67 (1H, dd, J=8.5, 5.5 Hz, 6-H); 13C NMR (CDCl3, 125.8 Hz) δ ppm 12.4 (9-CH3), 13.8 (10-Me), 116.5 (d, J=4 Hz, 1-C), 117.2, (d, J=24 Hz, 3-CH), 118.9 (d, J=22 Hz, 5-CH), 134.7 (d, J=8.5 Hz, 6-CH), 137.8 (d, J=10 Hz, 2-C), 153.9 (7-C), 160.9 (8-C), 161.8 (d, J=251 Hz, 4-CF); HRMS (ESI) calcd for C10H10BrFN3 (M+H) 270.0042, found 270.0048 (δ+2.2 ppm). This triazole was also prepared in 62% yield from 1-(2-bromo-5-fluoro-phenyl)-hydrazine hydrochloride and 2,4,6-trimethyl-s-triazine by refluxing them in EtOH.

후처리

  1. temperatureAfter cooling the mixture
  2. concentrationwas concentrated in vacuo to dryness
  3. additionthe residue diluted with EtOAc (100 mL)
  4. washwas washed with water (50 mL)
  5. dry with materialwith brine (30 mL), dried (Na2SO4)
  6. filtrationfiltered
  7. concentrationconcentrated

출처 및 근거

ORD 기록
ord-8d577fdb8cb04c5a96397a24cb80ab75
출처 데이터셋
uspto-grants-2009_02
특허 번호
US07491819B1

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