Sulfuric Acid → HCID 13216750, compound

HRID 482986Notes

Reaction equation

HRID 482986 reaction equation
[CH3:1][N:2]1[CH2:7][CH2:6][CH:5]([O:8][CH2:9][C:10]2[CH:15]=[CH:14][CH:13]=[CH:12][C:11]=2[F:16])[CH2:4][CH2:3]1.[C:17]([O-:22])(=[O:21])[C:18]([O-:20])=[O:19].S(=O)(=O)(O)O.C(=O)([O-])[O-].[Na+].[Na+]>O>[C:17]([OH:22])(=[O:21])[C:18]([OH:20])=[O:19].[O:19]=[C:18]([C:5]1([O:8][CH2:9][C:10]2[CH:15]=[CH:14][CH:13]=[CH:12][C:11]=2[F:16])[CH2:6][CH2:7][N:2]([CH3:1])[CH2:3][CH2:4]1)[CH3:17]

Participants

6

Reactant 4

HCID 1118Sulfuric AcidHCID 10340Sodium CarbonateHCID 71081OxalateHCID 20185510HCID 20185510, compound

Product 1

HCID 13216750HCID 13216750, compoundYield 59.4%

Reagents, catalysts & solvents 1

HCID 962WaterSolvent2×

Procedure

To a suspension of 1-methyl-4-(2-fluorophenylmethoxy)-piperidine (liberated from 30.6 g, 90.7 mmole, of the oxalate, and 165 ml of water was added a solution of 22 ml of conc. sulfuric acid in 53 ml of water. To the solution was added 4.0 g (13.4 mmole) of mercuric sulfate. The mixture was heated at reflux for 1.5 hr. under nitrogen and allowed to cool to room temperature. The mixture was poured into cold saturated sodium carbonate, extracted twice with ether and washed with saturated sodium chloride. The ether solution was dried over anhydrous potassium carbonate, filtered and the solvent evaporated to provide an oil. The oxalate salt was precipitated, and recrystallization from methanol/ethanol provided 21.1 g (59.4%) of 4-(1-oxoethyl)-4-(2-fluorophenylmethoxy)-1-methyl piperidine oxalate. The material appeared pure by TLC on silica gel in methanol:methylene chloride (9:1), Rf =0.4 and on alumina in ether, Rf =0.3. IR (Nujol), NMR-DMSO-d6 and MS (ci MH+ =266) are consistent with the structure, m.p.=180°-181° C.

Workup

  1. temperatureThe mixture was heated
  2. temperatureat reflux for 1.5 hr
  3. extractionextracted twice with ether
  4. washwashed with saturated sodium chloride
  5. dry with materialThe ether solution was dried over anhydrous potassium carbonate
  6. filtrationfiltered
  7. customthe solvent evaporated
  8. customto provide an oil
  9. customThe oxalate salt was precipitated
  10. customrecrystallization from methanol/ethanol

Sources & evidence

ORD record
ord-8d50ac6af86b420ab00b6276a0a38dbe
Source dataset
uspto-grants-1986_03
Patent number
US04577026

Reaction notes

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