Methyl (methylsulfinyl)methyl sulfide → 1-p-Nitrobenzyloxycarbonyl-4-hydroxy-4-methylsulfinylmethylthiomethylpiperidine

HRID 1252233Notes

Reaction equation

HRID 1252233 reaction equation
[CH3:1][S:2][CH2:3][S:4]([CH3:6])=[O:5].C([Li])CCC.[N+:12]([C:15]1[CH:31]=[CH:30][C:18]([CH2:19][O:20][C:21]([N:23]2[CH2:28][CH2:27][C:26](=[O:29])[CH2:25][CH2:24]2)=[O:22])=[CH:17][CH:16]=1)([O-:14])=[O:13]>O1CCCC1.CCCCCC.ClCCl.O>[N+:12]([C:15]1[CH:16]=[CH:17][C:18]([CH2:19][O:20][C:21]([N:23]2[CH2:24][CH2:25][C:26]([OH:29])([CH2:1][S:2][CH2:3][S:4]([CH3:6])=[O:5])[CH2:27][CH2:28]2)=[O:22])=[CH:30][CH:31]=1)([O-:14])=[O:13]

Participants

8

Reactant 3

HCID 99129Methyl (methylsulfinyl)methyl sulfideHCID 13292708(4-Nitrophenyl)methyl 4-oxopiperidine-1-carboxylateHCID 178418339Butyllithium

Product 1

HCID 571340091-p-Nitrobenzyloxycarbonyl-4-hydroxy-4-methylsulfinylmethylthiomethylpiperidine

Reagents, catalysts & solvents 4

HCID 962WaterSolventHCID 6344DichloromethaneSolventHCID 8028TetrahydrofuranSolvent2×HCID 8058HexaneSolvent

Procedure

To methyl methylthiomethyl sulfoxide (2.23 g) in dry tetrahydrofuran (10 ml) was added dropwise n-butyl lithium (1.15 g) in dry hexane (11.6 ml) at -60° to -70° C. under nitrogen atmosphere and the mixture was stirred for 20 minutes at the same temperature. Subsequently, 1-p-nitrobenzyloxycarbonyl-4-piperidone (5.0 g) in dry tetrahydrofuran (30 ml) was added dropwise thereto at -55° to -70° C. under nitrogen atmosphere. The reaction mixture was diluted with dichloromethane (200 ml) and water (215 ml), warmed slowly to room temperature, dried over anhydrous sodium sulfate and evaporated to give an oily residue which was then purified by silica gel chromatography to give 1-p-nitrobenzyloxycarbonyl-4-hydroxy-4-methylsulfinylmethylthiomethylpiperidine.

Workup

  1. customat -55° to -70° C.
  2. dry with materialdried over anhydrous sodium sulfate
  3. customevaporated
  4. customto give an oily residue which
  5. customwas then purified by silica gel chromatography

Sources & evidence

ORD record
ord-f2e618b6c3ab4ebdb1878a655134e8a7
Source dataset
uspto-grants-1988_05
Patent number
US04742052

Reaction notes

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