Benzylamine → N,N-dimethyl-N'-benzyl-1,2-cyclohexanediamine

HRID 614567Notes

Reaction equation

HRID 614567 reaction equation
[CH3:1][N:2]([CH3:10])[C@@H:3]1[CH2:8][CH2:7][CH2:6][CH2:5][C@H:4]1O.[H-].[Na+].CS(Cl)(=O)=O.[CH2:18]([NH2:25])[C:19]1[CH:24]=[CH:23][CH:22]=[CH:21][CH:20]=1>C1COCC1>[CH3:1][N:2]([CH3:10])[CH:3]1[CH2:8][CH2:7][CH2:6][CH2:5][CH:4]1[NH:25][CH2:18][C:19]1[CH:24]=[CH:23][CH:22]=[CH:21][CH:20]=1

Participants

6

Reactant 4

HCID 7504BenzylamineHCID 24758Sodium hydrideHCID 31297Methanesulfonyl chlorideHCID 15560793rac-(1R,2R)-2-(dimethylamino)cyclohexan-1-ol

Product 1

HCID 11264769N,N-dimethyl-N'-benzyl-1,2-cyclohexanediamineYield 65%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Procedure

A solution of trans-2-dimethylaminocyclohexanol (58 g., 0.405 mole) prepared in Part A in 80 ml. of THF is added during 10 min. to a suspension of NaH (17.05 g., 0.405 mole of 57% dispersion in mineral oil) in 240 ml. of THF and the mixture is refluxed for 3 hours. It is cooled to 10° and methanesulfonyl chloride (46.39 g., 0.405 mole) added dropwise during 30 min., keeping the temperature below 10°. Benzylamine (86.79 g., 0.81 mole) is then added during 5 min., the solvent evaporated, and heating continued at 95° for 16 hr. NaOH (500 ml. of 20% solution) is added and the mixture heated at 95° for 1 hr., cooled, and extracted with ether (5 × 100 ml.). The ether solution is extracted with 10% HCl (6 × 100 ml.) and backwashed once with ether (discard). The acid extract is cooled, basified with 20% NaOH, and extracted with ether. The ether solution is washed with H2O, saturated salt solution, dried (MgSO4) and evaporated. Distillation at 0.4 mm gives 61 g. (65% yield) of N,N-dimethyl-N'-benzyl-1,2-cyclohexanediamine, b.p. 112°. It is identical by tlc to the sample prepared by the reaction of benzylamine with trans-2-chloro-1-dimethylaminocyclohexane (Procedure III).

Workup

  1. temperatureIt is cooled to 10°
  2. customthe temperature below 10°
  3. customthe solvent evaporated
  4. temperatureheating
  5. additionNaOH (500 ml. of 20% solution) is added
  6. temperaturethe mixture heated at 95° for 1 hr
  7. temperature, cooled
  8. extractionextracted with ether (5 × 100 ml.)
  9. extractionThe ether solution is extracted with 10% HCl (6 × 100 ml.)
  10. extractionThe acid extract
  11. temperatureis cooled
  12. extractionextracted with ether
  13. washThe ether solution is washed with H2O, saturated salt solution
  14. dry with materialdried (MgSO4)
  15. customevaporated
  16. distillationDistillation at 0.4 mm
  17. customgives 61 g

Sources & evidence

ORD record
ord-9d7c5478a062422ea0759abc7263259f
Source dataset
uspto-grants-1979_03
Patent number
US04145435

Reaction notes

Loading…