Dimethyl Sulfide → HCID 21459871, compound

HRID 1781293Notes

Reaction equation

HRID 1781293 reaction equation
[N+]([C@@H:4]1[CH2:9][CH2:8][C:7](=[O:10])[NH:6][C@H:5]1[C:11]1[CH:16]=[CH:15][CH:14]=[CH:13][CH:12]=1)([O-])=O.ClCCl.CC(C)([O-:23])C.[K+].CSC>CO>[O:10]=[C:7]1[CH2:8][CH2:9][C:4](=[O:23])[CH:5]([C:11]2[CH:16]=[CH:15][CH:14]=[CH:13][CH:12]=2)[NH:6]1

Participants

6

Reactant 4

HCID 1068Dimethyl SulfideHCID 6344DichloromethaneHCID 1417894HCID 1417894, compoundHCID 23665647Potassium tert-butoxide

Product 1

HCID 21459871HCID 21459871, compoundYield 78.4%

Reagents, catalysts & solvents 1

HCID 887MethanolSolvent

Conditions

Temperature
0 °C

Procedure

trans-3 -Nitro-6-oxo-2-phenylpiperidine (80 g, 0.364 mol) was suspended in methanol:dichloromethane (Example 1a, 1:1, 500 ml) under nitrogen. The suspension was cooled to 0° C. and potassium t-butoxide (44.8 g, 0.4 mol) was added in portions over 30 mins. The cooling bath was then removed and the solution stirred for a further 15 mins to afford a clear yellow solution. The solution was then cooled to -78° C. and ozone bubbled through the reaction mixture for 4.5 hrs, the flow of ozone was then stopped and the mixture purged with a stream of nitrogen. Anhydrous dimethyl sulphide (53 ml, 0.73 mol) was then added dropwise and the reaction mixture allowed to warm to room temperature. The solvent was then removed at reduced pressure and the residual orange solid dissolved in dichloromethane (800 ml), washed with water (2×200 ml), dried (MgSO4), the solvent was then removed at reduced pressure. The residue was suspended in ether, filtered, and the pale yellow crystalline solid washed with ether (3×100ml) and dried under vacuum to afford 2,5-dioxo-6-phenylpiperidine (54 g, 78%): m.p. 160°-164° C.; 1H NMR (360 MHz, DMSO-d6) δ2.55-2.58 (2H, m, CH2), 2.63-2.70 (2H, m, CH2), 2.5-2.9 (4H, m, CH2CH2), 4.96 (1H, d, J=2.4 Hz, PhCH), 7.4-7.7 (5H, m, Ar), 8.2 (1H, brs, NH); m/z (CI+) 207 (M+NH4 +), 190 (M+H); Calculated for C11H11NO2C; 69.83; H, 5.86; N, 7.40%. Found C, 70.04; H, 5.77; N, 7.60%.

Workup

  1. customThe cooling bath was then removed
  2. customto afford a clear yellow solution
  3. temperatureThe solution was then cooled to -78° C.
  4. customozone bubbled through the reaction mixture for 4.5 hrs
  5. customthe mixture purged with a stream of nitrogen
  6. temperatureto warm to room temperature
  7. customThe solvent was then removed at reduced pressure
  8. dissolutionthe residual orange solid dissolved in dichloromethane (800 ml)
  9. washwashed with water (2×200 ml)
  10. dry with materialdried (MgSO4)
  11. customthe solvent was then removed at reduced pressure
  12. filtrationfiltered
  13. washthe pale yellow crystalline solid washed with ether (3×100ml)
  14. customdried under vacuum

Sources & evidence

ORD record
ord-00e070c838c440f296400559ff44fce7
Source dataset
uspto-grants-1997_05
Patent number
US05633266

Reaction notes

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