1,2,4,5-Tetrazine → 1,2,4,5-Tetrazine

HRID 586296Notes

Reaction equation

HRID 586296 reaction equation
[F:1][C:2]1[CH:7]=[CH:6][C:5]([N+:8]([O-:10])=[O:9])=[CH:4][C:3]=1[C:11]#[C:12][Si:13]([CH3:16])([CH3:15])[CH3:14].[N:17]1[CH:22]=[N:21][N:20]=[CH:19][N:18]=1>O1CCOCC1>[N:17]1[CH:22]=[N:21][N:20]=[CH:19][N:18]=1.[F:1][C:2]1[CH:7]=[CH:6][C:5]([N+:8]([O-:10])=[O:9])=[CH:4][C:3]=1[C:11]1[C:12]([Si:13]([CH3:15])([CH3:14])[CH3:16])=[CH:19][N:18]=[N:17][CH:22]=1

Participants

5

Reactant 2

HCID 92631,2,4,5-TetrazineHCID 12687357((2-Fluoro-5-nitrophenyl)ethynyl)trimethylsilane

Product 2

HCID 92631,2,4,5-TetrazineHCID 223295324-(2-Fluoro-5-nitrophenyl)-5-trimethylsilanylpyridazine

Reagents, catalysts & solvents 1

HCID 312751,4-DioxaneSolvent

Procedure

A solution of 1,2,4,5-tetrazine (0.53 M in dichloromethane) was prepared by the method of H. C. van der Plas et al. (J. Heterocycl. Chem., 1987, 24, 545-548). (2-Fluoro-5-nitrophenylethynyl)trimethylsilane (8.8 g, 37.1 mmol) and 1,4-dioxane were added to a solution of 1,2,4,5-tetrazine (35 ml, 18.6 mmol, 0.53 M in dichloromethane). The dichloromethane was distilled off and the dioxane solution was stirred at reflux for 36 h. The solvent was removed to leave a brown oil. Purification by chromatography (silica gel, 0-1% MeOH/CH2Cl2) gave 4-(2-fluoro-5-nitrophenyl)-5-trimethylsilanylpyridazine as a brown oil: MS (ES+) m/z 292 [M+H]+ and 249 [M−3CH2]+.

Workup

  1. distillationThe dichloromethane was distilled off
  2. temperatureat reflux for 36 h
  3. customThe solvent was removed
  4. customto leave a brown oil
  5. customPurification by chromatography (silica gel, 0-1% MeOH/CH2Cl2)

Sources & evidence

ORD record
ord-ab6954b384b84f9e84cd340adb5e9598
Source dataset
uspto-grants-2005_08
Patent number
US06936608B2

Reaction notes

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