Propylamine → N,N-dimethyl-1-phenyl-N'-propyl-cyclohexane-1,4-diamine

HRID 1179036Notes

Reaction equation

HRID 1179036 reaction equation
[CH3:1][N:2]([CH3:16])[C:3]1([C:10]2[CH:15]=[CH:14][CH:13]=[CH:12][CH:11]=2)[CH2:8][CH2:7][C:6](=O)[CH2:5][CH2:4]1.[CH2:17]([NH2:20])[CH2:18][CH3:19].C(O[BH-](OC(=O)C)OC(=O)C)(=O)C.[Na+].[OH-].[Na+]>O1CCCC1.C(O)(=O)C>[CH3:1][N:2]([CH3:16])[C:3]1([C:10]2[CH:15]=[CH:14][CH:13]=[CH:12][CH:11]=2)[CH2:8][CH2:7][CH:6]([NH:20][CH2:17][CH2:18][CH3:19])[CH2:5][CH2:4]1

Participants

7

Reactant 4

HCID 7852PropylamineHCID 14798Sodium HydroxideHCID 5049666Sodium triacetoxyborohydrideHCID 114244924-(Dimethylamino)-4-phenylcyclohexan-1-one

Product 1

HCID 9856507N,N-dimethyl-1-phenyl-N'-propyl-cyclohexane-1,4-diamine

Reagents, catalysts & solvents 2

HCID 176Acetic AcidSolventHCID 8028TetrahydrofuranSolvent

Procedure

10.0 g 4-dimethylamino-4-phenyl-cyclohexanone were dissolved in 160 ml analytical grade tetrahydrofuran, and 2.72 g n-propylamine followed by 5.97 ml glacial acetic acid were added, while stirring in an ice-bath. 13.6 g sodium triacetoxyborohydride were then added in portions in the course of 15 minutes and the mixture was subsequently stirred for approx. 65 hours. For working up, 85 ml two molar sodium hydroxide solution were added dropwise (pH>10) and the mixture was extracted three times with 100 ml diethyl ether each time. The combined organic phases were then washed twice with 100 ml water each time, dried over sodium sulfate and filtered and the filtrate was concentrated. 5.00 g of the crude product obtained (9.79 g) were chromatographed over silica gel with diethyl ether, to which one percent by volume of aqueous ammonia solution (25 wt. %) was added, and an addition of methanol increasing from one to forty per cent by volume. 2.79 g of the nonpolar and 1.33 g of the polar diastereoisomer of N,N-dimethyl-1-phenyl-N′-propyl-cyclohexane-1,4-diamine were obtained. From a sample of 356 mg of the nonpolar diastereoisomer, 253 mg of the corresponding hydrochloride were obtained as described for example 1 with water and chlorotrimethylsilane in 2-butanone.

Workup

  1. additionwere added
  2. stirringthe mixture was subsequently stirred for approx. 65 hours
  3. extractionthe mixture was extracted three times with 100 ml diethyl ether each time
  4. washThe combined organic phases were then washed twice with 100 ml water each time
  5. dry with materialdried over sodium sulfate
  6. filtrationfiltered
  7. concentrationthe filtrate was concentrated
  8. custom5.00 g of the crude product obtained (9.79 g)
  9. customwere chromatographed over silica gel with diethyl ether, to which one percent by volume of aqueous ammonia solution (25 wt. %)
  10. additionwas added
  11. additionan addition of methanol increasing from one to forty per cent by volume

Sources & evidence

ORD record
ord-eb95d64d9e8b40aab0b23c5e2f5a31d5
Source dataset
uspto-grants-2007_10
Patent number
US07276518B2

Reaction notes

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