Trifluoroacetic acid → HCID 19802616, compound

HRID 1645823Notes

Reaction equation

HRID 1645823 reaction equation
C([SiH](CC)CC)C.O[C:9]1([C:17]2[CH:22]=[CH:21][C:20]([O:23][CH3:24])=[CH:19][CH:18]=2)[CH:14]2[CH2:15][CH2:16][N:11]([CH2:12][CH2:13]2)[CH2:10]1.[C:25](=[O:28])([O-:27])O.[Na+].FC(F)(F)[C:32]([OH:34])=[O:33]>>[C:32]([OH:34])(=[O:33])[C:25]([OH:27])=[O:28].[CH3:24][O:23][C:20]1[CH:21]=[CH:22][C:17]([CH:9]2[CH:14]3[CH2:13][CH2:12][N:11]([CH2:16][CH2:15]3)[CH2:10]2)=[CH:18][CH:19]=1

Participants

5

Reactant 4

HCID 6422Trifluoroacetic acidHCID 12052TriethylsilaneHCID 516892Sodium BicarbonateHCID 15121263HCID 15121263, compound

Product 1

HCID 19802616HCID 19802616, compound

Procedure

Triethylsilane (3.8 mL, 0.024 mol) was added to a stirred solution of 3-hydroxy-3-(4-methoxyphenyl)quinuclidine (1.0 g, 0.0048 mol, prepared as in Example 2) in trifluoroacetic acid (10 mL). After 20 hours at 50° C. the solution was cooled to 5° C. and basified to pH9 with saturated sodium hydrogen carbonate solution. The mixture was extracted with dichloromethane (3× 100 mL), then the combined organics were dried (sodium sulphate) then evaporated to dryness. The crude product was purified by flash chromatography on silica using dichloromethane/methanol (20:1) to afford the title compound free base (0.86 g, 83%). The hydrogen oxalate salt had mp 104° C.-106° C. (acetone). Rf =0.77 in dichlormethane/methanol (20:1) on alumina plates; 1H NMR (360 MHz, D2O) δ 1.75-1.87 (1H, m), 1.88-1.92 (1H, m) and 2.03-2.17 (2H, m, 5-CH2 and 8-CH2); 2.22-2.24 (1H, m, 4-CH); 3.29-3.63 (6H, m, 2-CH2, 6-CH2 and 7-CH2); 3.70-3.79 (1H, m, 3-CH); 3.83 (3H, s, OCH3); 7.03 (2H, d, J=9 Hz, 2×Ar-H); 7.34 (2 H, d, J=9 Hz, 2×Ar-H); MS, m/z 217 for M+ of free base. (Found: C, 61.86; H, 61.86; H, 6.81; N, 4.50.C14H19NO.C2H2O4.0.25 H2O requires C, 61.62; H, 6.95; N, 4.49%).

Workup

  1. extractionThe mixture was extracted with dichloromethane (3× 100 mL)
  2. dry with materialthe combined organics were dried (sodium sulphate)
  3. customthen evaporated to dryness
  4. customThe crude product was purified by flash chromatography on silica

Sources & evidence

ORD record
ord-44c86fbc81c74ebe99aa841914a3ec7c
Source dataset
uspto-grants-1993_01
Patent number
US05177084

Reaction notes

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