Potassium Carbonate → 1-N-Phenoxycarbonyl-4-ethynyl-4-(4-fluoro-2-nitrophenoxy)piperidine

HRID 1193552Notes

Reaction equation

HRID 1193552 reaction equation
C(=O)([O-])[O-].[K+].[K+].C[N:8]1[CH2:13][CH2:12][C:11]([C:25]#[CH:26])([O:14][C:15]2[CH:20]=[CH:19][C:18]([F:21])=[CH:17][C:16]=2[N+:22]([O-:24])=[O:23])[CH2:10][CH2:9]1.[C:27]1([O:33][C:34](Cl)=[O:35])[CH:32]=[CH:31][CH:30]=[CH:29][CH:28]=1>ClCCl.CCOCC>[O:33]([C:34]([N:8]1[CH2:13][CH2:12][C:11]([C:25]#[CH:26])([O:14][C:15]2[CH:20]=[CH:19][C:18]([F:21])=[CH:17][C:16]=2[N+:22]([O-:24])=[O:23])[CH2:10][CH2:9]1)=[O:35])[C:27]1[CH:32]=[CH:31][CH:30]=[CH:29][CH:28]=1

Participants

6

Reactant 3

HCID 11430Potassium CarbonateHCID 15891Phenyl chloroformateHCID 14281483N-Methyl-4-ethynyl-4-(4-fluoro-2-nitrophenoxy)piperidine

Product 1

HCID 142814891-N-Phenoxycarbonyl-4-ethynyl-4-(4-fluoro-2-nitrophenoxy)piperidineYield 74.1%

Reagents, catalysts & solvents 2

HCID 3283Diethyl EtherSolventHCID 6344DichloromethaneSolvent2×

Procedure

To a stirred suspension of 5.01 g of potassium carbonate, 50 ml of dichloromethane (dried over anhydrous magnesium sulfate) and 10.1 g of 1-N-methyl-4-ethynyl-4-(4-fluoro-2-nitrophenoxy)piperidine was added dropwise a solution of 5.66 g of phenylchloroformate in 50 ml of dichloromethane (dried over anhydrous magnesium sulfate). The mixture was stirred 12 hr at ambient temperature and 6 hr at reflux under nitrogen. The suspension was poured onto ice, extracted with dichloromethane, washed with 15% sodium hydroxide solution, 1N hydrochloric acid and saturated sodium chloride solution. The dichloromethane solution was dried over anhydrous sodium sulfate, filtered and the solvent evaporated to provide an oil. The oil was dissolved in ether, washed with water, 1N hydrochloric acid and saturated sodium chloride solution. The solution was dried over anhydrous sodium sulfate, filtered and the solvent evaporated to provide an oil. The oil was dried overnight at room temperature (1 mm) during which time it crystallized to provide 10.3 g (73.8%) of product. Recrystallization from cyclohexane/ethyl acetate provided the analytical sample, mp 82°-83°.

Workup

  1. temperatureat reflux under nitrogen
  2. additionThe suspension was poured onto ice
  3. extractionextracted with dichloromethane
  4. washwashed with 15% sodium hydroxide solution, 1N hydrochloric acid and saturated sodium chloride solution
  5. dry with materialThe dichloromethane solution was dried over anhydrous sodium sulfate
  6. filtrationfiltered
  7. customthe solvent evaporated
  8. customto provide an oil
  9. washwashed with water, 1N hydrochloric acid and saturated sodium chloride solution
  10. dry with materialThe solution was dried over anhydrous sodium sulfate
  11. filtrationfiltered
  12. customthe solvent evaporated
  13. customto provide an oil
  14. customThe oil was dried overnight at room temperature (1 mm) during which time it
  15. customcrystallized

Sources & evidence

ORD record
ord-e9c64de71001470a8295513b51b4cb88
Source dataset
uspto-grants-1989_03
Patent number
US04810792

Reaction notes

Loading…