Methyl iodide → HCID 15586328, compound

HRID 1462515Notes

Reaction equation

HRID 1462515 reaction equation
C(NC(C)C)(C)C.C([Li])CCC.CN(C)C1(C2C=CC(C)=CC=2)CCC(=O)CC1.CI.[CH2:32]([CH:34]1[CH2:39][C:38]([N:47]([CH3:49])[CH3:48])([C:40]2[CH:45]=[CH:44][C:43]([CH3:46])=[CH:42][CH:41]=2)[CH2:37][CH2:36][C:35]1=[O:50])C>CCCCC.O.C1C=CC=CC=1.C(Cl)(Cl)Cl.CO.O1CCCC1>[CH3:32][CH:34]1[CH2:39][C:38]([N:47]([CH3:48])[CH3:49])([C:40]2[CH:41]=[CH:42][C:43]([CH3:46])=[CH:44][CH:45]=2)[CH2:37][CH2:36][C:35]1=[O:50]

Participants

12

Reactant 5

HCID 6328Methyl iodideHCID 7912DiisopropylamineHCID 125956434-(Dimethylamino)-4-(4-methylphenyl)cyclohexanoneHCID 13345276HCID 13345276, compoundHCID 178418339Butyllithium

Product 1

HCID 15586328HCID 15586328, compoundYield 39%

Reagents, catalysts & solvents 6

HCID 241BenzeneSolventHCID 887MethanolSolventHCID 962WaterSolventHCID 6212ChloroformSolventHCID 8003PentaneSolventHCID 8028TetrahydrofuranSolvent2×

Conditions

Temperature
25 °C

Procedure

A solution consisting of 1.02 gm. (0.010 mole) diisopropylamine in 20 ml. tetrahydrofuran was chilled in an ice:methanol bath before 6 ml. of 1.68 N butyllithium in pentane is added. To this mixture is then added a solution consisting of 2.31 gm. (0.010 mole) of 4-dimethylamino-4-(p-tolyl)cyclohexanone (prepared in Example 14) and 40 ml. tetrahydrofuran. Five minutes later, 2.82 gm. methyl iodide is added, and the mixture is stirred for 45 min. in the cold. It is allowed to warm to 25° C. and stirring is continued for 5 hours, when the reaction mixture is diluted with a mixture of water and benzene. The organic layer is separated and washed first with water and then with brine. The organic solvents are removed by evaporation under reduced pressure, and the residual waxy solid thus obtained is transferred to a column of the grade silica gel 1" by 48". The chromatogram is developed with a solvent medium consisting of 7.5% methanol in chloroform and 20-ml. fractions are collected. The fractions which contain product (as determined by TLC) are combined. The solvent is removed by evaporation under reduced pressure, and the residue thus obtained is recrystallized from diethyl ether. There is thus obtained 1.01 gm. (39% yield) of the object compound 2-ethyl-4-dimethylamino-4-(p-tolyl)cyclohexanone having a melting point at 102° to 104.5° C. NMR suggests assignment of cis relationship of 2-methyl to 4-N(CH3)2.

Workup

  1. additionTo this mixture is then added a solution
  2. customFive minutes
  3. stirringstirring
  4. waitis continued for 5 hours
  5. customThe organic layer is separated
  6. washwashed first with water
  7. customThe organic solvents are removed by evaporation under reduced pressure
  8. customthe residual waxy solid thus obtained
  9. customfractions are collected
  10. customThe solvent is removed by evaporation under reduced pressure
  11. customthe residue thus obtained
  12. customis recrystallized from diethyl ether

Sources & evidence

ORD record
ord-e5b25ab2425343ad86f6f60312a99232
Source dataset
uspto-grants-1984_07
Patent number
US04460604

Reaction notes

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