Diethyl Ether → HCID 20295623, compound

HRID 1389868Notes

Reaction equation

HRID 1389868 reaction equation
[Mg].Br[C:3]1[C:12]2[C:7](=[CH:8][CH:9]=[CH:10][CH:11]=2)[C:6]([Cl:13])=[CH:5][CH:4]=1.[N:14]1[CH:19]=[CH:18][C:17]([C:20]#N)=[CH:16][CH:15]=1.[Cl-].[NH4+].[H][H].CC[O:28]CC>C(Br)C.C1C=CC=CC=1.[Rh]>[ClH:13].[Cl:13][C:6]1[C:7]2[C:12](=[CH:11][CH:10]=[CH:9][CH:8]=2)[C:3]([CH:20]([CH:17]2[CH2:18][CH2:19][NH:14][CH2:15][CH2:16]2)[OH:28])=[CH:4][CH:5]=1

Participants

10

Reactant 6

HCID 3283Diethyl Ether3×HCID 75064-CyanopyridineHCID 25517Ammonium ChlorideHCID 37455621-bromo-4-chloronaphthaleneHCID 5462224MagnesiumHCID 178418361HCID 178418361, compound

Product 1

HCID 20295623HCID 20295623, compound

Reagents, catalysts & solvents 3

HCID 6332Ethyl BromideCatalystHCID 23948RhodiumCatalystHCID 241BenzeneSolvent

Procedure

To a flask containing 1.8 g (72 mmoles) of magnesium turnings and 20 ml of anhydrous ether under nitrogen is added 10 drops of ethyl bromide. The ether is heated to reflux and a solution of 10 g (50 mmoles) of 1-bromo-4-chloronaphthalene in 150 ml of dry ether added gradually during 30 minutes and refluxing continued for 8 hours. 60 g (58 mmoles) of 4-pyridinecarbonitrile in 100 ml of benzene is added gradually and the solution refluxed for 3 hours and the adduct decomposed by addition of saturated ammonium chloride solution. The resulting 4-(4-chloro-1-naphthoyl)pyridine is extracted into ether and the organic phase washed with brine and dried over magnesium sulfate. The ether is removed in vacuo and the residue dissolved in methanol and reduced by reaction with 200 mmoles of hydrogen gas in the presence of a rhodium catalyst. The catalyst is filtered off, an excess of alcoholic hydrochloride acid is added, and the solution concentrated in vacuo. The residue is recrystallized from isopropanol to yield α-(4-chloro-1-naphthyl)-4-piperidinemethanol hydrochloride.

Workup

  1. temperatureto reflux
  2. temperaturerefluxing
  3. temperaturethe solution refluxed for 3 hours
  4. extractionThe resulting 4-(4-chloro-1-naphthoyl)pyridine is extracted into ether
  5. washthe organic phase washed with brine
  6. dry with materialdried over magnesium sulfate
  7. customThe ether is removed in vacuo
  8. dissolutionthe residue dissolved in methanol
  9. filtrationThe catalyst is filtered off
  10. additionan excess of alcoholic hydrochloride acid is added
  11. concentrationthe solution concentrated in vacuo
  12. customThe residue is recrystallized from isopropanol

Sources & evidence

ORD record
ord-243ffe69515744229eab3e22d55cfbae
Source dataset
uspto-grants-1981_01
Patent number
US04246268

Reaction notes

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