Chlorobenzene → 1-Phenylpiperidine

HRID 1955326Notes

Reaction equation

HRID 1955326 reaction equation
CC([O-])(C)C.[Na+].[C:7]1(Cl)[CH:12]=[CH:11][CH:10]=[CH:9][CH:8]=1.[NH:14]1[CH2:19][CH2:18][CH2:17][CH2:16][CH2:15]1>C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.[Pd].[Pd].O1CCOCC1>[C:7]1([N:14]2[CH2:19][CH2:18][CH2:17][CH2:16][CH2:15]2)[CH:12]=[CH:11][CH:10]=[CH:9][CH:8]=1

Participants

6

Reactant 3

HCID 7964ChlorobenzeneHCID 8082PiperidineHCID 23676156Sodium t-butoxide

Product 1

HCID 200381-PhenylpiperidineYield 37%

Reagents, catalysts & solvents 2

HCID 9811564Bis(dibenzylideneacetone)palladiumCatalystHCID 312751,4-DioxaneSolvent

Procedure

In the drybox, 20.0 mg (0.087 mmol) of (Me2CH)PH(O)(2,4-(MeO)2C6H3) from Experiment 3, 20.0 mg (0.0218 mmol) of Pd2 (dba)3 and 3.0 mL of dioxane were loaded into a reactor (20 mL) equipped with a magnetic stir bar. The resulting mixture was stirred at room temperature for 10 min. Next, 144 mg (1.5 mmol) of NaOtBu was added into the mixture above, followed by syringing 122 μl (1.2 mmol) of PhCl, and 100 μl (1.0 mmol) of piperidine into the reactor. The resulting mixture was refluxed for 8 h. The reaction mixture was then cooled to room temperature, chromatographed on silicon gel using ethyl acetate/hexane (5% volume ratio) as eluant. The eluate was concentrated by rotary evaporation followed by high vacuum to yield 59 mg (37% yield) of 1-phenylpiperidine. It was >95% pure by 1H NMR and GC/MS. 1H NMR (500 MHz, CDCl3): δ 7.15 (m, 2H), 6.84 (m, 2H), 6.72 (m, 1H), 3.06 (t, J=5.48 Hz, 4H), 1.61 (m, 4H), 1.48 (m, 2H) ppm. 13C NMR (125 MHz, CDCl3): δ 152.3, 129.0, 119.2, 116.5, 50.7, 25.9, 24.43 ppm. MS: Calcd for C11H15N(M+): 161.3. Found: 162.3 (M+ +H).

Workup

  1. custom(20 mL) equipped with a magnetic stir bar
  2. temperatureThe resulting mixture was refluxed for 8 h
  3. temperatureThe reaction mixture was then cooled to room temperature
  4. customchromatographed on silicon gel
  5. concentrationThe eluate was concentrated by rotary evaporation

Sources & evidence

ORD record
ord-13b99bd64e374bdaaae2955496942297
Source dataset
uspto-grants-2000_09
Patent number
US06124462

Reaction notes

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