1,3,5-Triazine → 1-(2-bromo-5-fluorophenyl)-1H-1,2,4-triazole

HRID 1726670Notes

Reaction equation

HRID 1726670 reaction equation
Cl.[Br:2][C:3]1[CH:8]=[CH:7][C:6]([F:9])=[CH:5][C:4]=1[NH:10][NH2:11].[N:12]1[CH:17]=NC=N[CH:13]=1>CCO>[Br:2][C:3]1[CH:8]=[CH:7][C:6]([F:9])=[CH:5][C:4]=1[N:10]1[CH:17]=[N:12][CH:13]=[N:11]1

Participants

4

Reactant 2

HCID 92621,3,5-TriazineHCID 21069774(2-Bromo-5-fluorophenyl)hydrazine hydrochloride

Product 1

HCID 210697651-(2-bromo-5-fluorophenyl)-1H-1,2,4-triazoleYield 61.3%

Reagents, catalysts & solvents 1

HCID 702EthanolSolvent

Conditions

Temperature
90 °C

Procedure

Prepared according to the procedure described in J. Org. Chem., 1956, 21, 1037. A stirred mixture of (2-bromo-5-fluoro-phenyl)-hydrazine hydrochloride (31.9 g, 0.132 mol) and s-triazine (10.7 g, 0.132 mol; Aldrich) in EtOH (250 mL) was heated at 90° C. for 3 h. After cooling, the insoluble material was filtered off and the filtrate was concentrated. The residue was partitioned between CH2Cl2 (200 mL) and water (200 mL), and the aqueous phase was extracted once more with CH2Cl2 and the combined extracts were dried (MgSO4), filtered and concentrated to a red semi-solid which was triturated with hexanes to give 19.6 g of the title compound as an orange solid: HPLC rt=1.68 min. LC/MS m/z 242 (M+H); 1H NMR (CDCl3, 500 MHz) δ ppm 7.02-7.15 (1H, m, 5-CH), 7.29 (1H, dd, J=8.4, 2.9 Hz, 3-CH), 7.68 (1H, dd, J=8.8, 5.5 Hz, 6-CH), 8.10 (1H, s, 8-CH), 8.54 (1H, s, 7-CH); 13C NMR (CDCl3, 125.8 Hz) δ ppm 112.54, 112.57 (d, J=1.5 Hz, 1-C), 115.68, 115.88 (d, J=25 Hz, 3-CH), 118.07, 118.25 (d, J=22 Hz, 5-CH), 135.11, 135.18 (d, J=8.6 Hz, 6-CH), 137.43, 137.52 (d, J=11 Hz, 2-C), 144.4 (7-CH), 152.6 (8-CH), 160.95, 162.94 (d, J=251 Hz, 4-CF); HRMS (ESI) calcd for C8H6BrN3 (M+H) 241.9727; found 241.9733 (δ 1.6 ppm); UV (MeOH) λmax 275 nm (ε1.45×103); Anal. calcd for C8H5BrFN3: C, 39.69; H, 2.08; N, 17.36; found C, 39.63; H, 1.83; N, 17.22.

Workup

  1. customPrepared
  2. temperatureAfter cooling
  3. filtrationthe insoluble material was filtered off
  4. concentrationthe filtrate was concentrated
  5. customThe residue was partitioned between CH2Cl2 (200 mL) and water (200 mL)
  6. extractionthe aqueous phase was extracted once more with CH2Cl2
  7. dry with materialthe combined extracts were dried (MgSO4)
  8. filtrationfiltered
  9. concentrationconcentrated to a red semi-solid which
  10. customwas triturated with hexanes

Sources & evidence

ORD record
ord-e3b4f0e708e549b2a97a106c96367704
Source dataset
uspto-grants-2009_02
Patent number
US07491819B1

Reaction notes

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