Sodium methanethiolate → HCID 22622431, compound

HRID 840428Notes

Reaction equation

HRID 840428 reaction equation
[CH3:1][S-:2].[Na+].Cl[CH2:5][C:6]1[CH:11]=[CH:10][CH:9]=[CH:8][C:7]=1[CH:12]1[CH2:17][CH2:16][N:15]([NH:18][C:19]([O:21][C:22]([CH3:25])([CH3:24])[CH3:23])=[O:20])[CH2:14][CH2:13]1>CC(C)=O.C(=O)(O)[O-].[Na+].C(OCC)C>[CH3:1][S:2][CH2:5][C:6]1[CH:11]=[CH:10][CH:9]=[CH:8][C:7]=1[CH:12]1[CH2:17][CH2:16][N:15]([NH:18][C:19]([O:21][C:22]([CH3:25])([CH3:24])[CH3:23])=[O:20])[CH2:14][CH2:13]1

Participants

6

Reactant 2

HCID 4378561Sodium methanethiolateHCID 22622364HCID 22622364, compound

Product 1

HCID 22622431HCID 22622431, compoundYield 52.4%

Reagents, catalysts & solvents 3

HCID 180AcetoneSolventHCID 3283Diethyl EtherSolventHCID 516892Sodium BicarbonateSolvent

Procedure

Sodium thiomethoxide (0.220 g) tetra-n-butylammonium bromide (0.100 g) and tert-butyl 4-(2-chloromethylphenyl)piperidinecarbamate (0.867 g) were combined in acetone (20 mL) under nitrogen and stirred for 6 h, then heated under reflux for 90 min. The reaction was diluted with aqueous sodium bicarbonate and diethyl ether. The organic phase was dried and evaporated and the residue purified by chromatography (6:1 hexanes:ethyl acetate) to give tert-butyl 4-(2-methylthiomethylphenyl)piperidinecarbamate (0.471 g) as a yellow oil. MS: m/z222 (M-Boc). 1H NMR (CDCl3) δ 7.18 (m, 4H, Ar—H), 3.68 (s, 2H, Ar—CH2—S), 3.04 (m, 1H), 2.80 (m,3H), 2.04 (s, 3H, S—CH3), 1.70 (m, 5H), 1.49 (s, 9H). This material was N-deprotected with HCl according to the conditions described for Example 21d to afford 4-(2-methylthiomethylphenyl)piperidine. 1H NMR (CDC13) δ 7.30 (m, 4H, Ar—H), 3.77 (s, 2H), 3.63 (m, 2H), 3.10 (m, 3H), 2.25 (m, 2H), 2.04 (s, 3H, S—CH3), 1.95 (m, 2H).

Workup

  1. temperatureheated
  2. temperatureunder reflux for 90 min
  3. customThe organic phase was dried
  4. customevaporated
  5. customthe residue purified by chromatography (6:1 hexanes:ethyl acetate)

Sources & evidence

ORD record
ord-81f50a063c2d464fa08c3ae9be8f9932
Source dataset
uspto-grants-2002_04
Patent number
US06365602B1

Reaction notes

Loading…