Chloranil → 4-(1,2,4,5-Tetrazin-3-yl)aniline

HRID 1395872Notes

Reaction equation

HRID 1395872 reaction equation
Cl.Cl.[NH2:3][C:4]1[CH:12]=[CH:11][C:7]([C:8]([NH2:10])=[NH:9])=[CH:6][CH:5]=1.C(O)(=O)C.[CH:17]([NH2:19])=[NH:18].NN.ClC1C(=O)C(Cl)=C(Cl)C(=O)C=1Cl>C(#N)C>[N:18]1[CH:17]=[N:19][N:10]=[C:8]([C:7]2[CH:11]=[CH:12][C:4]([NH2:3])=[CH:5][CH:6]=2)[N:9]=1

Participants

6

Reactant 4

HCID 8371ChloranilHCID 9321HydrazineHCID 756264-Amidinoaniline dihydrochlorideHCID 160693Formamidine acetate

Product 1

HCID 584902114-(1,2,4,5-Tetrazin-3-yl)anilineYield 19.1%

Reagents, catalysts & solvents 1

HCID 6342AcetonitrileSolvent

Procedure

To a mixture of 4-Aminobenzamidine dihydrochloride (1 mmol, 208 mg) and formamidine acetate (4 mmol, 416 mg) in acetonitrile (25 mL) was added anhydrous hydrazine (10 mmol, 315 uL). The solution was heated to reflux for 1 hour, cooled, and the solvent was removed by rotary evaporation. The residue was resuspended with water (25 mL) and was stirred with solid tetrachloro-1,4-benzoquinone (2 mmol, 492 mg) for 1 hour. After removal of the solids from the pink solution by filtration, the reaction was concentrated by rotary evaporation and purified by preparative HPLC using a gradient from 0-40% buffer B (buffer A is water with 0.1% TFA, and buffer B is acetonitrile with 10% water and 0.1% TFA) to afford pure 4-(1,2,4,5-tetrazin-3-yl)aniline (33 mg, 19%), as a pink solid. LRMS-ESI [M+H]+ calcd. for C8H8N5+: 174.08, found: 173.9.

Workup

  1. temperatureThe solution was heated
  2. temperatureto reflux for 1 hour
  3. temperaturecooled
  4. customthe solvent was removed by rotary evaporation
  5. customAfter removal of the solids from the pink solution
  6. filtrationby filtration
  7. concentrationthe reaction was concentrated by rotary evaporation
  8. custompurified by preparative HPLC

Sources & evidence

ORD record
ord-7bec7a2f31474e1095b1fd8fd25a7756
Source dataset
uspto-grants-2014_12
Patent number
US08900549B2

Reaction notes

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