p-Bromochlorobenzene → HCID 14698740, compound

HRID 1709847Notes

Reaction equation

HRID 1709847 reaction equation
[Mg].Br[C:3]1[CH:8]=[CH:7][C:6]([Cl:9])=[CH:5][CH:4]=1.C(O[C:13]([CH:15]1[CH2:20][CH2:19][N:18]([C:21]([N:23]([CH2:26][CH3:27])[CH2:24][CH3:25])=[O:22])[CH2:17][CH2:16]1)=[O:14])C.[Cl-:28].[NH4+]>O1CCCC1>[Cl:9][C:6]1[CH:7]=[CH:8][C:3]([C:13]([C:3]2[CH:8]=[CH:7][C:6]([Cl:28])=[CH:5][CH:4]=2)([OH:14])[CH:15]2[CH2:16][CH2:17][N:18]([C:21]([N:23]([CH2:24][CH3:25])[CH2:26][CH3:27])=[O:22])[CH2:19][CH2:20]2)=[CH:4][CH:5]=1

Participants

6

Reactant 4

HCID 7806p-BromochlorobenzeneHCID 25517Ammonium ChlorideHCID 2989403HCID 2989403, compoundHCID 5462224Magnesium

Product 1

HCID 14698740HCID 14698740, compoundYield 87%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent3×

Procedure

A Grignard solution was prepared by the treatment of a slurry of 8.5 g (0.35 mole) of magnesium chips in 200 ml of dry tetrahydrofuran with a solution of 72.8 g (0.38 mole) of 1-bromo-4-chlorobenzene in 400 ml of tetrahydrofuran. After the addition was complete, the mixture was heated at reflux for 15 min to complete formation. To the Grignard solution at ambient temperature was added a solution of 38.4 g (0.15 mole) of 1-[(diethylaminocarbonyl]-4-piperidine carboxylic acid ethyl ester in 200 mo of tetrahydrofuran in a stream. The solution was stirred at ambient temperature overnight and poured into 2.5 liters of a saturated ammonium chloride solution. The layers were separated and the aqueous layer was extracted once with 500 ml of methylene chloride and once with 250 ml of methylene chloride. The combined organic layers were filtered through Celite® and the filtrate was washed successively with 500 ml of water, 750 ml of a 4% sodium hydroxide solution, 250 ml of water and 250 ml of brine. The solution was dried over sodium sulfate and concentrated under reduced pressure to give a gum which gradually crystallized. The solid was triturated with petroleum ether (30°-60° C.), collected by filtration, and dried to yield 56.7 g (87%) of title compound as a white solid. An analytical sample was recrystallized from isopropanol, mp 172°-175° C.

Workup

  1. additionAfter the addition
  2. temperaturethe mixture was heated
  3. temperatureat reflux for 15 min
  4. customThe layers were separated
  5. extractionthe aqueous layer was extracted once with 500 ml of methylene chloride and once with 250 ml of methylene chloride
  6. filtrationThe combined organic layers were filtered through Celite®
  7. washthe filtrate was washed successively with 500 ml of water, 750 ml of a 4% sodium hydroxide solution, 250 ml of water and 250 ml of brine
  8. dry with materialThe solution was dried over sodium sulfate
  9. concentrationconcentrated under reduced pressure
  10. customto give a gum which
  11. customgradually crystallized
  12. customThe solid was triturated with petroleum ether (30°-60° C.)
  13. filtrationcollected by filtration
  14. customdried

Sources & evidence

ORD record
ord-b799e08f65024de1a6d79f7dfc19534b
Source dataset
uspto-grants-1990_08
Patent number
US04950674

Reaction notes

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