Biphenyl → HCID 23459454, compound

HRID 2287118Notes

Reaction equation

HRID 2287118 reaction equation
[C:1]1([C:7]2[CH:12]=[CH:11][CH:10]=[CH:9][CH:8]=2)[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1.[Li].Cl.Cl[CH2:16][CH:17]([N:19]([CH3:21])[CH3:20])[CH3:18].[Cl-].[NH4+]>C(Cl)Cl.CO.CCOCC>[CH3:16][CH:17]([N:19]([CH3:21])[CH3:20])[CH2:18][C:1]1([C:7]2[CH:8]=[CH:9][CH:10]=[CH:11][CH:12]=2)[CH:6]=[CH:5][CH2:4][CH:3]=[CH:2]1

Participants

7

Reactant 4

HCID 7095BiphenylHCID 25517Ammonium ChlorideHCID 284272-Propanamine, 1-chloro-N,N-dimethyl-, hydrochloride (1:1)HCID 3028194Lithium

Product 1

HCID 23459454HCID 23459454, compound

Reagents, catalysts & solvents 2

HCID 3283Diethyl EtherSolventHCID 21226129Dichloromethane methanolSolvent

Conditions

Temperature
-70 °C

Procedure

46.1 g. of biphenyl in 400 ml. of absolute ether are added at about -33° C. while stirring to 600 ml. of dry, condensed ammonia. 4.2 g. of lithium wire (about 2 cm long pieces, de-greased with cyclohexane) are then added at about -50° C. within 15 minutes. The mixture is held at boiling temperature for 2 hours. It is then cooled to about -70° C. and 15.8 g. of racemic 2-chloro-N,N,1-trimethylethylamine hydrochloride are added portionwise over a period of 10 minutes. The mixture is again warmed to boiling temperature (about -33° C.) and stirred at this temperature for 2 hours. 32 g. of ammonium chloride are then added and the ammonia is distilled off. Subsequently, the mixture is worked-up aqueous: the ether solution is washed with water. The aqueous phase is adjusted to a pH greater than 12 with sodium hydroxide solution and extracted further twice with ether. The ether phases are combined and extracted twice with 2 N aqueous hydrochloric acid. The acid extracts are again made alkaline and extracted with ether. The ether phases are dried, filtered and concentrated. There is obtained an oily product which, after chromatography on a 20-fold amount of silica gel using methylene chloride/methanol (10:1) as the solvent, yields α,N,N-trimethyl-1-phenyl-2,5-cyclohexadien-1-ethylamine. This product is dissolved in ether and converted with hydrogen chloride into the hydrochloride which is recrystallized from methylene chloride/ether. The product has a melting point of 158°-159° C.

Workup

  1. customof dry
  2. customcondensed ammonia
  3. customfor 2 hours
  4. temperatureThe mixture is again warmed
  5. customtemperature (about -33° C.)
  6. stirringstirred at this temperature for 2 hours
  7. distillationthe ammonia is distilled off
  8. washthe ether solution is washed with water
  9. extractionextracted further twice with ether
  10. extractionextracted twice with 2 N aqueous hydrochloric acid
  11. extractionextracted with ether
  12. dry with materialThe ether phases are dried
  13. filtrationfiltered
  14. concentrationconcentrated
  15. customThere is obtained an oily product which

Sources & evidence

ORD record
ord-dee73c7e4c5e4944ae165cb5c5f70fc2
Source dataset
uspto-grants-1981_05
Patent number
US04269788

Reaction notes

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