Water → Tropenol 9-fluorofluorene-9-carboxylate

HRID 33415Notes

Reaction equation

HRID 33415 reaction equation
COCCN(S(F)(F)[F:11])CCOC.[C@@:14]12([OH:23])[N:21]([CH3:22])[C@@H:18]([CH2:19][CH2:20]1)[CH2:17][CH:16]=[CH:15]2.O[C:25]1([C:38]([O-:40])=[O:39])[C:37]2[CH:36]=[CH:35][CH:34]=[CH:33][C:32]=2[C:31]2[C:26]1=[CH:27][CH:28]=[CH:29][CH:30]=2.O.C([O-])(O)=O.[Na+]>ClCCl>[C@@:14]12([OH:23])[N:21]([CH3:22])[C@@H:18]([CH2:19][CH2:20]1)[CH2:17][CH:16]=[CH:15]2.[F:11][C:25]1([C:38]([O-:40])=[O:39])[C:37]2[CH:36]=[CH:35][CH:34]=[CH:33][C:32]=2[C:31]2[C:26]1=[CH:27][CH:28]=[CH:29][CH:30]=2

Participants

6

Reactant 4

HCID 962WaterHCID 516892Sodium BicarbonateHCID 2734690(Bis(2-methoxyethyl)amino)sulfur trifluorideHCID 86593872Tropenol 9-hydroxyfluorene-9-carboxylate

Product 1

HCID 86593873Tropenol 9-fluorofluorene-9-carboxylate

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent2×

Procedure

1.66 mL (0.009 mol) of bis-(2-methoxyethyl)aminosulfur trifluoride are placed in 10 mL dichloromethane and within 20 minutes at 15°-20° C., a solution of 2.4 g (0.007 mol) of 4a in 25 mL dichloromethane is added dropwise thereto. The mixture is stirred for 20 hours at ambient temperature, cooled to 0° C., and carefully combined with 80 mL of water with thorough stirring. Then the mixture is carefully adjusted to pH 8 with aqueous NaHCO3 solution, the organic phase is separated off, the aqueous phase is extracted again with dichloromethane, the combined organic phases are washed with water, dried over magnesium sulfate, and evaporated to dryness. The hydrochloride is precipitated and recrystallized from acetonitrile-diethyl ether. Then the free base is liberated again using 10% aqueous sodium carbonate solution. Yield: 1.05 g bright yellow crystals (53% of theoretical yield).

Workup

  1. temperaturecooled to 0° C.
  2. customthe organic phase is separated off
  3. extractionthe aqueous phase is extracted again with dichloromethane
  4. washthe combined organic phases are washed with water
  5. dry with materialdried over magnesium sulfate
  6. customevaporated to dryness
  7. customThe hydrochloride is precipitated
  8. customrecrystallized from acetonitrile-diethyl ether

Sources & evidence

ORD record
ord-3b0cf7fbe1d142a6b74aa89d3a600a16
Source dataset
uspto-grants-2008_09
Patent number
US07429600B2

Reaction notes

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