Allyl bromide → 1,3-Bis(2,4,6-trimethylphenyl)-4-methyl-1H-1,2,3-triazolium hexafluorophosphate

HRID 1477258Notes

Reaction equation

HRID 1477258 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+].[CH2:30](Br)[CH:31]=[CH2:32].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:30]=[C:31]([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 7841Allyl bromideHCID 521297Tert-Butyl hypochloriteHCID 153301851,3-DimesityltriazeneHCID 23688904Potassium hexafluorophosphate

Product 1

HCID 1317364831,3-Bis(2,4,6-trimethylphenyl)-4-methyl-1H-1,2,3-triazolium hexafluorophosphate

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

To a stirred suspension of triazene 8b (1.70 g, 6 mmol) and anhydrous potassium hexafluorophosphate (1.10 g, 6 mmol) and allyl bromide 12 (1.04 mL, 12 mmol) in dry dichloromethane (20 mL) in the dark at −78° C. is added tert-butyl hypochlorite (1.0 mL, 9 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 affords the crude dihydrotriazolium salt 13 as a beige solid (3.02 g, ˜92%), which is contaminated by ca. 30% of the aromatized triazolium salt 10bi. 1H-NMR (CDCl3, 300 MHz): δ=7.07 (s, 2H), 7.06 (s, 2H), 6.03 (t, J=12.7 Hz), 5.20 (t, J=14.9 Hz, 1H), 4.85 (t, J=12.5 Hz, 1H), 3.91 (dd, J=12.8, 2.5 Hz, 1H), 3.68 (d, J=12.6 Hz, 1H), 2.45-2.36 (m, 18H). 13C-NMR (CDCl3, 75 MHz): δ=142.8, 142.6, 135.9, 134.8, 134.3, 134.1, 132.2, 131.2, 130.5, 128.8, 68.3, 59.1, 30.1, 21.3, 21.2, 19.0, 18.7, 17.8. Calcd. for C21H27BrN3 [M+]: 400.1383. found 400.1400.

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

Sources & evidence

ORD record
ord-ceda6f149e4f4c93a34ff6caa1bdad1e
Source dataset
uspto-grants-2016_08
Patent number
US09403781B2

Reaction notes

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