Nitrogen → HCID 53826978, compound

HRID 1977909Notes

Reaction equation

HRID 1977909 reaction equation
N#N.[CH2:3]([N:10]1[CH2:15][CH2:14][CH:13]([C:16]2[CH:21]=[CH:20][C:19](Br)=[CH:18][CH:17]=2)[CH2:12][CH2:11]1)[C:4]1[CH:9]=[CH:8][CH:7]=[CH:6][CH:5]=1.C([Li])CCC.[CH3:28][C:29]1[NH:30][C:31]([CH3:40])=[CH:32][C:33]=1[C:34]1[CH:39]=[CH:38][CH:37]=[CH:36][N:35]=1>CCCCCC.CCOCC>[CH2:3]([N:10]1[CH2:15][CH2:14][CH:13]([C:16]2[CH:21]=[CH:20][C:19]([C:36]3[N:35]=[C:34]([C:33]4[CH:32]=[C:31]([CH3:40])[NH:30][C:29]=4[CH3:28])[CH:39]=[CH:38][CH:37]=3)=[CH:18][CH:17]=2)[CH2:12][CH2:11]1)[C:4]1[CH:9]=[CH:8][CH:7]=[CH:6][CH:5]=1

Participants

7

Reactant 4

HCID 947NitrogenHCID 21995436HCID 21995436, compoundHCID 53980622HCID 53980622, compoundHCID 178418339Butyllithium

Product 1

HCID 53826978HCID 53826978, compoundYield 32.3%

Reagents, catalysts & solvents 2

HCID 3283Diethyl EtherSolvent2×HCID 8058HexaneSolvent

Conditions

Temperature
-70 °C

Procedure

To a 125 mL three-necked round-bottomed flask equipped with septum and N2 inlet were added 2.93 g (8.88 mmol) N-benzyl-4-(4-bromophenyl)piperidine and 30 mL dry ether. The solution was cooled to −70° C., and 6.66 mL (10.65 mmol) of a 1.6 N solution of butyl lithium in hexane added dropwise over 5 minutes. After stirring a further 5 minutes at −70° C., the solution was warmed slowly to room temperature over 25 minutes. A solution of 1.83 g (10.65 mmol) 2-(2,5-dimethylpyrrolyl)pyridine in 10 mL dry ether was then added dropwise over 5 minutes, and the reaction, which turned slowly dark red, stirred at room temperature for 3 hours. The reaction was quenched with aqueous ammonium chloride solution, partitioned between ethyl acetate and water, and the organic layer separated, washed with brine, and dried over sodium sulfate, allowing it to stand overnight to effect rearomatization of the pyridine ring. After evaporation of the solvent, the residue was chromatographed on silica gel using ethyl acetate/hexane followed by methanol/methylene chloride as eluant to afford 1.21 g (32%) of an oil.

Workup

  1. temperaturethe solution was warmed slowly to room temperature over 25 minutes
  2. customthe reaction, which
  3. stirringstirred at room temperature for 3 hours
  4. customThe reaction was quenched with aqueous ammonium chloride solution
  5. custompartitioned between ethyl acetate and water
  6. customthe organic layer separated
  7. washwashed with brine
  8. dry with materialdried over sodium sulfate
  9. waitto stand overnight
  10. customAfter evaporation of the solvent
  11. customthe residue was chromatographed on silica gel

Sources & evidence

ORD record
ord-2452c63ba038409bbfac9250be0a4b61
Source dataset
uspto-grants-2001_05
Patent number
US06235750B1

Reaction notes

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