Dimethylamine → HCID 54507421, compound

HRID 262996Notes

Reaction equation

HRID 262996 reaction equation
CO[CH:3]1[CH2:8][CH2:7][CH2:6][C:5](=[O:9])[C:4]1=[CH:10][C:11]1[CH:16]=[CH:15][CH:14]=[CH:13][CH:12]=1.[CH3:17][NH:18][CH3:19].[H-].[H-].[H-].[H-].[Li+].[Al+3].[OH-].[Na+].C[CH2:29][O:30]CC>>[CH3:17][N:18]([CH3:19])[CH:10]([C@H:4]1[CH2:3][CH2:8][CH2:7][CH2:6][C@H:5]1[OH:9])[C:11]1[CH:12]=[CH:13][CH:14]=[C:15]([O:30][CH3:29])[CH:16]=1

Participants

6

Reactant 5

HCID 674DimethylamineHCID 3283Diethyl Ether2×HCID 14798Sodium HydroxideHCID 21226445Aluminium lithium hydrideHCID 68643022HCID 68643022, compound

Product 1

HCID 54507421HCID 54507421, compound

Procedure

A solution of m-methoxybenzalcyclohexanone (50 g. 2.31×10-1 moles) in ether (50 ml.) was cooled to -5° in a pressure bottle and treated with 20 ml. dimethylamine (3×10-1 moles). The bottle was stoppered and left at room temperature during 60 hours. The above reaction was performed in duplicate (IR monitoring indicates the mixture attains an equilibrium concentration in which the β-dimethylamino ketone addition product is favored over the m-methoxybenzalcyclohexanone by a ratio of ca. 2:1). The combined total reaction mixtures were added dropwise under nitrogen to a stirred suspension of LiAlH4 (20 g.) in ether (1.2 liters) and the mixture was refluxed during 4 hours. The ice cooled reaction mixture was treated with 3% aqueous NaOH solution (100 ml.) and filtered. The precipitated solids were washed with boiling ether and the combined filtrates evaporated to approximately 1 liter. The ether layer was extracted (twice) with an excess of dilute HCl followed by a water extraction. The combined aqueous extracts were back extracted with ether, basified with 50% NaOH and extracted with ether (twice). The ether layers were washed with brine and evaporated to an oil (50 g.) shown by glc to consist predominantly (96%) of two components. 32 g. of the residue were chromatographed on a Woelm alumina column (900 g. neutral activity Grade III), built in benzene-hexane (1:1). Benzene-hexane fractions (1:1 and 2:1) eluted the major component trans-2-(α-dimethylamino-m-methoxybenzyl)cyclohexanol (20 g.) NMR (CDCl3): δ 2.28 (6H singlet N(CH3)2), 3.0 (1H doublet J= 3 cps CH N(Me)2), 3.3-3.7 (1H broad multiplet CH(OH)), 3.8 (3H singlet OCH3) ppm.

Workup

  1. additiontreated with 20 ml
  2. customThe above reaction
  3. concentrationan equilibrium concentration in which
  4. additionthe β-dimethylamino ketone addition product
  5. customThe combined total reaction mixtures
  6. temperaturethe mixture was refluxed during 4 hours
  7. customreaction mixture
  8. filtrationfiltered
  9. washThe precipitated solids were washed with boiling ether
  10. customthe combined filtrates evaporated to approximately 1 liter
  11. extractionThe ether layer was extracted (twice) with an excess of dilute HCl
  12. extractionfollowed by a water extraction
  13. extractionThe combined aqueous extracts were back extracted with ether
  14. extractionextracted with ether (twice)
  15. washThe ether layers were washed with brine
  16. customevaporated to an oil (50 g.)
  17. customof the residue were chromatographed on a Woelm alumina column (900 g. neutral activity Grade III)
  18. washBenzene-hexane fractions (1:1 and 2:1) eluted the major component trans-2-(α-dimethylamino-m-methoxybenzyl)cyclohexanol (20 g.) NMR (CDCl3): δ 2.28 (6H singlet N(CH3)2), 3.0 (1H doublet J= 3 cps CH N(Me)2), 3.3-3.7 (1H broad multiplet CH(OH)), 3.8 (3H singlet OCH3) ppm

Sources & evidence

ORD record
ord-59bd6a82a2d747f2af373e7c278862ed
Source dataset
uspto-grants-1979_05
Patent number
US04155935

Reaction notes

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