Tert-Butyl hypochlorite → 1,3,4-Tris(2,6-difluorophenyl)-1H-1,2,3-triazolium hexafluorophosphate

HRID 1477261Notes

Reaction equation

HRID 1477261 reaction equation
[F:1][C:2]1[CH:7]=[CH:6][CH:5]=[C:4]([F:8])[C:3]=1[N:9]=[N:10][NH:11][C:12]1[C:17]([F:18])=[CH:16][CH:15]=[CH:14][C:13]=1[F:19].[F:20][P-:21]([F:26])([F:25])([F:24])([F:23])[F:22].[K+].Br/[CH:29]=[CH:30]\[C:31]1[C:36]([F:37])=[CH:35][CH:34]=[CH:33][C:32]=1[F:38].ClOC(C)(C)C>ClCCl>[F:20][P-:21]([F:26])([F:25])([F:24])([F:23])[F:22].[F:1][C:2]1[CH:7]=[CH:6][CH:5]=[C:4]([F:8])[C:3]=1[NH+:9]1[CH:29]=[C:30]([C:31]2[C:36]([F:37])=[CH:35][CH:34]=[CH:33][C:32]=2[F:38])[N:11]([C:12]2[C:13]([F:19])=[CH:14][CH:15]=[CH:16][C:17]=2[F:18])[NH:10]1

Participants

6

Reactant 4

HCID 521297Tert-Butyl hypochloriteHCID 23688904Potassium hexafluorophosphateHCID 674691621,3-Bis(2,6-difluorophenyl)triazeneHCID 86691330HCID 86691330, compound

Product 1

HCID 866913281,3,4-Tris(2,6-difluorophenyl)-1H-1,2,3-triazolium hexafluorophosphate

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

To a stirred suspension of triazene 8d (808 mg, 3 mmol) and anhydrous potassium hexafluorophosphate (750 mg, 4 mmol) and (Z)-1-Bromo-2-(2,6-difluorophenyl)ethene 11q (1.32 g, 6 mmol) in dry dichloromethane (20 mL) in the dark at −78° C. is added tert-butyl hypochlorite (500 μL, 4.4 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 10dq as an off-white solid (1.45 g, 88%). Analytical samples were obtained after recrystallization by vapor diffusion of diethyl ether in an acetonitrile solution of 10dq. 1H-NMR ((CD3)2SO, 300 MHz): δ=10.37 (s, 1H), 8.05-7.90 (m, 2H), 7.89-7.81 (m, 1H), 7.69 (t, J=8.9 Hz, 2H), 7.61 (t, J=8.9 Hz, 2H), 7.44 (t, J=8.9 Hz, 2H). 13C-NMR (((CD3)2SO, 75 MHz): δ=159.4 (dd, J=253, 4 Hz), 155.7 (d, J=257 Hz), 155.3 (d, J=257 Hz), 137.1 (2t, J=10 Hz), 136.2, 135.9 (t, J=10 Hz), 134.6, 114.0 (d, J=18 Hz), 113.8 (d, J=18 Hz), 113.0 (d, J=20 Hz), 112.6 (t, J=14 Hz), 110.3 (t, J=15 Hz), 99.1 (t, J=18 Hz). 19F-NMR (CD3CN, 282 MHz): δ=−71.9 (d, J=705 Hz, 6F), −110.3 (2F), −118.8 (2F), −119.0 (2F). HR-MS (ESI): Calcd. for C20H10F6N3 [M+]: 406.0773. found 406.0784.

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 10dq as an off-white solid (1.45 g, 88%)
  11. customAnalytical samples were obtained
  12. customafter recrystallization by vapor diffusion of diethyl ether in an acetonitrile solution of 10dq

Sources & evidence

ORD record
ord-93ac63098d87430181b5815ef3268c1b
Source dataset
uspto-grants-2016_08
Patent number
US09403781B2

Reaction notes

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