Quinuclidine → HCID 15252126, compound

HRID 1534074Notes

Reaction equation

HRID 1534074 reaction equation
[N:1]12CCC(CC1)C[CH2:2]2.[O-:9][S:10]([C:13]([F:16])([F:15])[F:14])(=[O:12])=[O:11].[F:17][N+:18]12[CH2:25][CH2:24]C([CH2:22][CH2:23]1)[CH2:20][CH2:19]2.FF.[O-:28][S:29]([C:32]([F:35])([F:34])[F:33])(=[O:31])=[O:30].C[N+]12CCN(CC1)CC2.[O-]S(C(F)(F)F)(=O)=O.[Li+]>C(#N)C>[O-:12][S:10]([C:13]([F:16])([F:15])[F:14])(=[O:11])=[O:9].[O-:31][S:29]([C:32]([F:35])([F:34])[F:33])(=[O:30])=[O:28].[F:17][N+:18]12[CH2:25][CH2:24][N+:1]([CH3:2])([CH2:22][CH2:23]1)[CH2:20][CH2:19]2

Participants

7

Reactant 5

HCID 7527QuinuclidineHCID 24524Fluorine3×HCID 2737511HCID 2737511, compoundHCID 3664839Trifluoromethanesulfonic acid, lithium saltHCID 15252130HCID 15252130, compound

Product 1

HCID 15252126HCID 15252126, compoundYield 88%

Reagents, catalysts & solvents 1

HCID 6342AcetonitrileSolvent

Procedure

Using the apparatus and techniques previously employed to convert quinuclidine to N-fluoroquinuclidinium triflate in a closed reactor (R. E. Banks et al, J. Chem. Soc., Perkin Trans. I, 1988, 2805 and R. E. Banks and I. Sharif, J. Fluorine Chem., 1988, 41, 297) a degassed solution of 1-methyl-4-aza-1-azoniabicyclo[2,2,2]octane triflate (2.18 g, 7.90 mmol) and lithium triflate (1.23 g, 7.90 mmol) in cold (-35° C.), dry acetonitrile (200 cm3), was treated with neat fluorine (less than 20 mmHg (2.7 kPa) pressure) until absorption of the fluorine became imperceptible (3 hours). The reaction mixture was allowed to warm to room temperature, filtered to remove lithium fluoride which had precipitated, and the filtrate rotary evaporated and recrystallized from methanol to give 1-fluoro-4-methyl-1,4-diazoniabicyclo [2,2,2]octane ditriflate (3.10 g, 6.98 mmol, 88%). (Found: C, 24.0; H, 3.6; F, 29.8; N, 6.4%. Calc. C, 24.3; H, 3.4; F, 29.95; N, 6.3%), m.p. 220°-222° C. δF (solution in D2O; ext. CF3CO2H ref.) 1.0 (s; CF3SO3-), 124.5 (br. m; FN+) p.p.m., δH (same solution) 3.44 (s; CH3N+), 4.43 (m; 3×CH2), 4.88 (m; 3×CH2) p.p.m. [residual H in D2O, 4.68 (s) p.p.m⟧

Workup

  1. custom(3 hours)
  2. filtrationfiltered
  3. customto remove lithium fluoride which
  4. customhad precipitated
  5. customthe filtrate rotary evaporated
  6. customrecrystallized from methanol

Sources & evidence

ORD record
ord-1ec0d40f80544f0b87c05adc135d281d
Source dataset
uspto-grants-1992_02
Patent number
US05086178

Reaction notes

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