Triphenylphosphine → 3-(4-Bromo-2,6-dimethylphenoxymethyl)-1-methylpiperidine

HRID 1384979Notes

Reaction equation

HRID 1384979 reaction equation
[OH:1][CH2:2][CH:3]1[CH2:8][CH2:7][CH2:6][N:5]([CH3:9])[CH2:4]1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.[Br:29][C:30]1[CH:35]=[C:34]([CH3:36])[C:33](O)=[C:32]([CH3:38])[CH:31]=1.N(C(OCC)=O)=NC(OCC)=O>O1CCCC1>[Br:29][C:30]1[CH:35]=[C:34]([CH3:36])[C:33]([O:1][CH2:2][CH:3]2[CH2:8][CH2:7][CH2:6][N:5]([CH3:9])[CH2:4]2)=[C:32]([CH3:38])[CH:31]=1

Participants

6

Reactant 4

HCID 11776TriphenylphosphineHCID 169194-Bromo-2,6-dimethylphenolHCID 97998(1-Methyl-3-piperidyl)methanolHCID 220568ethyl N-ethoxycarbonyliminocarbamate

Product 1

HCID 99486563-(4-Bromo-2,6-dimethylphenoxymethyl)-1-methylpiperidineYield 66.2%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Conditions

Temperature
0 °C

Procedure

3-Hydroxymethyl-1-methylpiperidine (0.4 mL, 3.14 mmol) and triphenylphosphine (1.01 g, 3.85 mmol) were added to a solution of 4-bromo-2,6-dimethylphenol (517 mg, 2.57 mmol) in tetrahydrofuran (10 mL) at 0° C. under dry nitrogen, followed by the dropwise addition of diethyl azodicarboxylate (0.57 mL, 3.60 mmol). The mixture was stirred at 0° C. for 4 hours and the solvent removed in vacuo. The residue was purified on silica gel, eluting with 5% methanol in dichloromethane containing 0.25% ammonium hydroxide, to give 3-(4-bromo-2,6-dimethylphenoxymethyl)-1-methylpiperidine as an oil (531 mg, 66%).

Workup

  1. customthe solvent removed in vacuo
  2. customThe residue was purified on silica gel
  3. washeluting with 5% methanol in dichloromethane containing 0.25% ammonium hydroxide

Sources & evidence

ORD record
ord-398eaab2aa0c4960b356c18f8627fb95
Source dataset
uspto-grants-2001_07
Patent number
US06262078B1

Reaction notes

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