Water → 1-(4-Nitrobenzyl)-1H-1,2,4-triazole

HRID 862180Notes

Reaction equation

HRID 862180 reaction equation
[N+:1]([C:4]1[CH:11]=[CH:10][C:7]([CH2:8]Br)=[CH:6][CH:5]=1)([O-:3])=[O:2].N[N:13]1[CH:17]=[N:16][N:15]=[CH:14]1.O>C(O)(C)C>[N+:1]([C:4]1[CH:11]=[CH:10][C:7]([CH2:8][N:15]2[CH:14]=[N:13][CH:17]=[N:16]2)=[CH:6][CH:5]=1)([O-:3])=[O:2]

Participants

5

Reactant 3

HCID 962WaterHCID 114324-Amino-1,2,4-triazoleHCID 660114-Nitrobenzyl bromide

Product 1

HCID 64820001-(4-Nitrobenzyl)-1H-1,2,4-triazoleYield 83.3%

Reagents, catalysts & solvents 1

HCID 3776IsopropanolSolvent2×

Conditions

Temperature
-2 °C

Procedure

4-Nitrobenzyl bromide (64.22 g), 4-amino-1,2,4-triazole (26 g) and isopropyl alcohol (586 ml) were stirred together at reflux for 7% hours. The isopropanol solvent was replaced with water by using an azeotropic distillation procedure, in vacuo, on a Buchi rotary evaporator. The volume of the final aqueous slurry was 750 ml. 675 ml of this slurry was cooled to -2° C. and hydrochloric acid (50.8 ml, 12M) added over a few minutes. A solution of sodium nitrite (21.7 g) in water (86 ml) was then added dropwise, and subsurface over a 40 minute period. The temperature of the batch was kept between -2 and -1° C. during the addition and then allowed to warm to 18° C. over 30 minutes. The temperature was then increased to 28° C. and held for 1 hour and the solution treated with charcoal (4.5 g, Fisons) for 15 minutes. The charcoal was removed and the filtrate (750 ml) divided equally in two. One half of the solution was made basic with ammonia solution (22 ml) and the precipitated base collected, washed with water (2x30 ml) and dried (16 hours at 35° C. in vacuo). This gave an 83.3% yield (22.73 g) of 1-(4-nitrobenzyl)-1,2,4-triazole.

Workup

  1. temperatureat reflux for 7% hours
  2. distillationan azeotropic distillation procedure
  3. customin vacuo, on a Buchi rotary evaporator
  4. additionhydrochloric acid (50.8 ml, 12M) added over a few minutes
  5. additionA solution of sodium nitrite (21.7 g) in water (86 ml) was then added dropwise
  6. additionThe temperature of the batch was kept between -2 and -1° C. during the addition
  7. temperatureto warm to 18° C. over 30 minutes
  8. temperatureThe temperature was then increased to 28° C.
  9. waitheld for 1 hour
  10. additionthe solution treated with charcoal (4.5 g, Fisons) for 15 minutes
  11. customThe charcoal was removed
  12. customthe precipitated base collected
  13. washwashed with water (2x30 ml)
  14. customdried (16 hours at 35° C. in vacuo)

Sources & evidence

ORD record
ord-fd2583886cb843d6bed9868dc5251695
Source dataset
uspto-grants-1998_02
Patent number
US05717104

Reaction notes

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