N-methyl-2-(phenylthio)benzamide → N-Methyl-2-(phenylthio)benzylamine

HRID 973253Notes

Reaction equation

HRID 973253 reaction equation
[H-].[Al+3].[Li+].[H-].[H-].[H-].[Cl-].[Al+3].[Cl-].[Cl-].[CH3:11][NH:12][C:13](=O)[C:14]1[CH:19]=[CH:18][CH:17]=[CH:16][C:15]=1[S:20][C:21]1[CH:26]=[CH:25][CH:24]=[CH:23][CH:22]=1.C(O)(=O)/C=C\C(O)=O.C(O)(=O)/C=C\C([O-])=O>C(O)C.O.CCOCC>[CH3:11][NH:12][CH2:13][C:14]1[CH:19]=[CH:18][CH:17]=[CH:16][C:15]=1[S:20][C:21]1[CH:26]=[CH:25][CH:24]=[CH:23][CH:22]=1

Participants

9

Reactant 5

HCID 320119N-methyl-2-(phenylthio)benzamideHCID 444266Maleic AcidHCID 6451240Aluminum(III) ChlorideHCID 11966254Hydrogen maleateHCID 21226445Aluminium lithium hydride

Product 1

HCID 14400280N-Methyl-2-(phenylthio)benzylamine

Reagents, catalysts & solvents 3

HCID 702EthanolSolventHCID 962WaterSolventHCID 3283Diethyl EtherSolvent3×

Procedure

Lithium aluminum hydride, 1.52 h. (0.04 mole), is weighed under nitrogen, transferred to a dry nitrogen-flushed reaction flask, and suspended in 50 ml. of absolute ether. A solution of 5.34 g. (0.04 mole) of aluminum chloride in 60 ml. of absolute ether is added dropwise. The mixture, containing a while precipitate, is stirred at room temperature while a solution of 4.87 g. (0.02 mole) of N-methyl-2-(phenylthio)benzamide in 1 1. of absolute ether is added dropwise. The mixture is stirred at reflux for about 18 hours. After cooling, hydrolysis is effected by the dropwise addition of 60 ml. of water. After decantation of the ethereal layer and washing of the gelatinous precipitate with boiling ether, the precipitate is suspended in 40 ml. of 40% aqueous sodium hydroxide and 200 ml. of water. The mixture is extracted repeatedly with ether-benzene (1:1). Evaporation of solvents under reduced pressure from the washed and dried organic extract leaves the product as the residual oil. The base is converted to the hydrogen maleate salt by treating an ethereal solution with a slight excess of maleic acid dissolved in absolute ethanol. The hydrogen maleate separates in white crystals, m.p. 121°-122.5° C. The melting point is unchanged upon further recrystallization.

Workup

  1. customflushed
  2. customreaction flask
  3. additionThe mixture, containing a while precipitate
  4. stirringThe mixture is stirred
  5. temperatureat reflux for about 18 hours
  6. temperatureAfter cooling
  7. customhydrolysis
  8. additionis effected by the dropwise addition of 60 ml
  9. washAfter decantation of the ethereal layer and washing of the gelatinous precipitate with boiling ether
  10. extractionThe mixture is extracted repeatedly with ether-benzene (1:1)
  11. customEvaporation of solvents under reduced pressure from the
  12. washwashed
  13. extractiondried organic extract
  14. customleaves the product as the residual oil
  15. customThe melting point is unchanged upon further recrystallization

Sources & evidence

ORD record
ord-da70d7dfb9fb44d69e307b8b576cc8a5
Source dataset
uspto-grants-1977_10
Patent number
US04055665

Reaction notes

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