Bromoethene → 1,3-Bis(2,4,6-trimethylphenyl)-1H-1,2,3-triazolium hexafluorophosphate

HRID 1477257Notes

Reaction equation

HRID 1477257 reaction equation
[C:1]1([CH3:21])[CH:6]=[C:5]([CH3:7])[CH:4]=[C:3]([CH3:8])[C:2]=1[N:9]=[N:10][NH:11][C:12]1[C:17]([CH3:18])=[CH:16][C:15]([CH3:19])=[CH:14][C:13]=1[CH3:20].[F:22][P-:23]([F:28])([F:27])([F:26])([F:25])[F:24].[K+].[CH:30](Br)=[CH2:31].ClOC(C)(C)C>ClCCl>[F:22][P-:23]([F:28])([F:27])([F:26])([F:25])[F:24].[CH3:21][C:1]1[CH:6]=[C:5]([CH3:7])[CH:4]=[C:3]([CH3:8])[C:2]=1[NH+:9]1[CH:31]=[CH:30][N:11]([C:12]2[C:13]([CH3:20])=[CH:14][C:15]([CH3:19])=[CH:16][C:17]=2[CH3:18])[NH:10]1

Participants

6

Reactant 4

HCID 11641BromoetheneHCID 521297Tert-Butyl hypochloriteHCID 153301851,3-DimesityltriazeneHCID 23688904Potassium hexafluorophosphate

Product 1

HCID 866913231,3-Bis(2,4,6-trimethylphenyl)-1H-1,2,3-triazolium hexafluorophosphate

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

To a stirred suspension of triazene 8b (5.63 g, 20 mmol) and anhydrous potassium hexafluorophosphate (3.68 g, 20 mmol) and excess vinyl bromide 11e (10 mL) in dry dichloromethane (100 mL) in the dark at 78° C. is added tert-butyl hypochlorite (3.33 mL, 30 mmol), upon which the mixture instantly darkens. The mixture is stirred overnight as it is slowly allowed to warm to room temperature. The contents are then filtered, and the solid residue is washed with dichloromethane. The filtrate is collected, and volatiles are evaporated under reduced pressure. Diethyl ether is then added, and the mixture is vigorously triturated for ca. 1 hour, with occasional scratching of the glass surfaces to ensure efficient mixing. Filtration and washing with copious quantities of diethyl ether afford, after drying under vacuum, triazolium salt 10be as an off-white solid (8.21 g, 91%). 1H-NMR (CD3CN, 300 MHz): δ=8.82 (s, 2H), 7.21 (s, 4H), 2.40 (s, 6H), 2.09 (s, 12H). 13C-NMR (CD3CN, 75 MHz): δ=144.3, 135.7, 135.1, 132.3, 130.9, 21.4, 17.5. HR-MS (ESI): Calcd. for C20H24N3 [M+]: 306.1965. found 306.1973.

Workup

  1. filtrationThe contents are then filtered
  2. washthe solid residue is washed with dichloromethane
  3. customThe filtrate is collected
  4. customvolatiles are evaporated under reduced pressure
  5. additionDiethyl ether is then added
  6. customthe mixture is vigorously triturated for ca. 1 hour
  7. filtrationFiltration
  8. washwashing with copious quantities of diethyl ether
  9. customafford
  10. dry with materialafter drying under vacuum, triazolium salt 10be as an off-white solid (8.21 g, 91%)

Sources & evidence

ORD record
ord-3c215f82b5a34cd9899a9b47cee14787
Source dataset
uspto-grants-2016_08
Patent number
US09403781B2

Reaction notes

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