Sodium Hydroxide → 2-(4-Bromophenethyl)-phenethylamine

HRID 1288546Notes

Reaction equation

HRID 1288546 reaction equation
[H-].[Al+3].[Li+].[H-].[H-].[H-].[Br:7][C:8]1[CH:24]=[CH:23][C:11]([CH2:12][CH2:13][C:14]2[CH:19]=[CH:18][CH:17]=[CH:16][C:15]=2[CH2:20][C:21]#[N:22])=[CH:10][CH:9]=1.[OH-].[Na+].C(O)(=O)/C=C\C(O)=O>CO.O.CCOCC>[Br:7][C:8]1[CH:9]=[CH:10][C:11]([CH2:12][CH2:13][C:14]2[CH:19]=[CH:18][CH:17]=[CH:16][C:15]=2[CH2:20][CH2:21][NH2:22])=[CH:23][CH:24]=1

Participants

8

Reactant 4

HCID 14798Sodium HydroxideHCID 444266Maleic AcidHCID 21226445Aluminium lithium hydrideHCID 543480192-(4-Bromophenethyl)-phenylacetonitrile

Product 1

HCID 215028722-(4-Bromophenethyl)-phenethylamine

Reagents, catalysts & solvents 3

HCID 887MethanolSolventHCID 962WaterSolvent2×HCID 3283Diethyl EtherSolvent2×

Procedure

Lithium aluminum hydride, 0.61 g. (0.016 mole), is weighed under nitrogen, transferred to a dry, nitrogen-flushed reaction flask and suspended in 50 ml. of absolute ether. The mixture is stirred at reflux for 30 minutes, then cooled to room temperature and a solution of 2.4 g. (0.008 mole) of 2-(4-bromophenethyl)-phenylacetonitrile in 30 ml. of absolute ether is added dropwise. After 16 hours at reflux, the cooled mixture is hydrolyzed by the successive dropwise addition of 0.7 ml. of water, 0.7 ml. of 20% aqueous sodium hydroxide, and 1.5 ml. of water. The ethereal layer is separated and stirred with 18 ml. of 3N hydrochloric acid. The hydrochloride salt of the product separates, m.p. 148°-153° C. (cloudy melt). Repeated recrystallizations from absolute ethanol-ether and from water yield purified material, m.p. 148°-150° C. (cloudy melt). The hydrochloride is converted to the base by rendering an aqueous solution strongly alkaline. The oily base is extracted into benzene. Evaporation of the washed and dried benzene extract under reduced pressure leaves the product as the residual oil. The base may be converted to the hydrogen maleate salt by treating a solution in methanol with a slight excess of maleic acid. Dilution with absolute ether precipitates the hydrogen maleate in white crystals, m.p. 158°-160° C.

Workup

  1. customflushed
  2. customreaction flask
  3. temperatureat reflux for 30 minutes
  4. temperatureAfter 16 hours at reflux
  5. additionthe cooled mixture is hydrolyzed by the successive dropwise addition of 0.7 ml
  6. customThe ethereal layer is separated
  7. stirringstirred with 18 ml
  8. customrecrystallizations from absolute ethanol-ether
  9. customfrom water yield
  10. custompurified material, m.p. 148°-150° C. (cloudy melt)
  11. extractionThe oily base is extracted into benzene
  12. customEvaporation of the
  13. washwashed
  14. extractiondried benzene extract under reduced pressure
  15. customleaves the product as the residual oil
  16. customDilution with absolute ether precipitates the hydrogen maleate in white crystals, m.p. 158°-160° C.

Sources & evidence

ORD record
ord-a7bbab3bb0d74ba3a7eeef32d928b978
Source dataset
uspto-grants-1976_10
Patent number
US03988454

Reaction notes

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