2-Ethynyl-1,3,5-trimethylbenzene → 1,3,4-Tris(2,4,6-trimethylphenyl)-1H-1,2,3-triazolium hexafluorophosphate

HRID 1477256Notes

Reaction equation

HRID 1477256 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].[C:22]1([CH3:32])[CH:27]=[C:26]([CH3:28])[CH:25]=[C:24]([CH3:29])[C:23]=1[C:30]#[CH:31].ClOC(C)(C)C.[F:39][P-:40]([F:45])([F:44])([F:43])([F:42])[F:41].[K+]>ClCCl>[F:39][P-:40]([F:45])([F:44])([F:43])([F:42])[F:41].[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]=[C:30]([C:23]2[C:24]([CH3:29])=[CH:25][C:26]([CH3:28])=[CH:27][C:22]=2[CH3:32])[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 1366102-Ethynyl-1,3,5-trimethylbenzeneHCID 521297Tert-Butyl hypochloriteHCID 153301851,3-DimesityltriazeneHCID 23688904Potassium hexafluorophosphate

Product 1

HCID 866913221,3,4-Tris(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 mesitylacetylene 9b (5.76 g, 40 mmol) 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. Volatiles are evaporated under reduced pressure, and the crude solid is redissolved in acetone (50 mL), to which is then added potassium hexafluorophosphate (3.68 g, 20 mmol). The mixture is stirred at room temperature for ca. 1 hour, filtered, and the solid residue is washed with dichloromethane. The collected filtrate is 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 10bb as an off-white solid (10.10 g, 88%). Analytical samples were obtained after recrystallization by vapor diffusion of diethyl ether in an acetonitrile solution of 10bb. 1H-NMR (CD3CN, 300 MHz): δ=8.94 (s, 1H), 7.27 (s, 2H), 7.10 (s, 2H), 7.05 (s, 2H), 2.43 (s, 3H), 2.31 (s, 3H), 2.28 (s, 3H), 2.25 (s, 6H), 2.17 (s, 6H), 2.06 (s, 6H). 13C-NMR (CD3CN, 75 MHz): δ=145.2, 144.5, 144.3, 143.9, 139.6, 135.7, 135.2, 132.4, 131.7, 131.5, 131.3, 131.1, 130.9, 119.0, 21.5, 21.4, 21.3, 19.1, 17.9. HR-MS (ESI): Calcd. for C29H34N3 [M+]: 424.2747. found 424.2758.

Workup

  1. customVolatiles are evaporated under reduced pressure
  2. dissolutionthe crude solid is redissolved in acetone (50 mL), to which
  3. stirringThe mixture is stirred at room temperature for ca. 1 hour
  4. filtrationfiltered
  5. washthe solid residue is washed with dichloromethane
  6. customThe collected filtrate is evaporated under reduced pressure
  7. additionDiethyl ether is then added
  8. customthe mixture is vigorously triturated for ca. 1 hour
  9. filtrationFiltration
  10. washwashing with copious quantities of diethyl ether
  11. customafford
  12. dry with materialafter drying under vacuum, triazolium salt 10bb as an off-white solid (10.10 g, 88%)
  13. customAnalytical samples were obtained
  14. customafter recrystallization by vapor diffusion of diethyl ether in an acetonitrile solution of 10bb

Sources & evidence

ORD record
ord-0e847f23365e40d09214eef4fb9c0131
Source dataset
uspto-grants-2016_08
Patent number
US09403781B2

Reaction notes

Loading…