1-(2-Bromoethyl)-4-chlorobenzene → HCID 13971552, compound

HRID 745549Notes

Reaction equation

HRID 745549 reaction equation
[Mg].[Cl:2][C:3]1[CH:11]=[CH:10][C:6]([CH2:7][CH2:8]Br)=[CH:5][CH:4]=1.[CH2:12]=[C:13]1[C:18](=[O:19])[CH:17]2[CH2:20][CH2:21][N:14]1[CH2:15][CH2:16]2>C(OCC)C.[Cu]Cl>[ClH:2].[Cl:2][C:3]1[CH:11]=[CH:10][C:6]([CH2:7][CH2:8][CH2:12][CH:13]2[C:18](=[O:19])[CH:17]3[CH2:20][CH2:21][N:14]2[CH2:15][CH2:16]3)=[CH:5][CH:4]=1

Participants

6

Reactant 3

HCID 230291-(2-Bromoethyl)-4-chlorobenzeneHCID 3229732-Methylene-3-quinuclidoneHCID 5462224Magnesium

Product 1

HCID 13971552HCID 13971552, compound

Reagents, catalysts & solvents 2

HCID 62652Cuprous chlorideCatalystHCID 3283Diethyl EtherSolvent2×

Procedure

To 3.30 g (0.136 mole) magnesium turnings in 50 ml anhydrous diethyl ether under nitrogen, add 28.6 g (0.13 mole) p-chlorophenethyl bromide slowly. Allow the reaction mixture to reflux gently with mechanical stirring for 11/2 hours. Chill the reaction mixture on an ice/MeOH bath and add 1.29 g (0.013 mole) copper (I) chloride. Suspend 10.3 g (0.067 mole) 2-methylene-3-quinuclidinone in 30 ml diethyl ether and add dropwise to the chilled reaction mixture. Heat to reflux for an additional 2 hours. Follow progress of the reaction by thin-layer chromatography on silica gel (methanol:NH4OH, 9:1). When complete, quench the cooled reaction mixture with 25 ml saturated ammonium chloride solution. Filter the 2-phase reaction mixture and separate the layers. Wash the aqueous phase with 1×50 ml diethyl ether. Combine diethyl ether layers and dry over potassium carbonate. Remove solvents in vacuo to obtain the free base of the title compound. Dissolve the residue in 25 ml diethyl ether and acidify with HCl gas. Collect the title compound via filtration.

Workup

  1. temperatureto reflux gently
  2. temperatureChill the reaction mixture on an ice/MeOH bath
  3. additionadd dropwise to the chilled reaction mixture
  4. temperatureHeat
  5. temperatureto reflux for an additional 2 hours
  6. customprogress of the reaction by thin-layer chromatography on silica gel (methanol:NH4OH, 9:1)
  7. customWhen complete, quench
  8. customthe cooled reaction mixture with 25 ml saturated ammonium chloride solution
  9. filtrationFilter the 2-phase reaction mixture
  10. customseparate the layers
  11. washWash the aqueous phase with 1×50 ml diethyl ether
  12. dry with materialCombine diethyl ether layers and dry over potassium carbonate

Sources & evidence

ORD record
ord-2b2dd8efa3a4478c9d36e2b3df41da20
Source dataset
uspto-grants-1986_07
Patent number
US04599344

Reaction notes

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