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

HRID 1372340Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 1372340
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

Komponenten

4

Edukt 2

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

Produkt 1

HCID 210697671-(2-Bromo-5-fluorophenyl)-3,5-dimethyl-1H-1,2,4-triazoleAusbeute 89,6 %

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 1049PyridineLösungsmittel

Versuchsvorschrift

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.

Aufarbeitung

  1. temperatureheated at 125–130° C. under nitrogen for 2 h
  2. temperatureAfter cooling the mixture
  3. concentrationwas concentrated in vacuo to dryness
  4. additionthe residue diluted with EtOAc (100 mL)
  5. washwas washed with water (50 mL)
  6. dry with materialwith brine (30 mL), dried (Na2SO4)
  7. filtrationfiltered
  8. concentrationconcentrated

Quellen und Nachweise

ORD-Eintrag
ord-752b5fc5e93140c9bf3ac1a55fb7d090
Quelldatensatz
uspto-grants-2007_01
Patentnummer
US07157447B2

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