Methyl iodide → HCID 15586325, compound

HRID 543859Notes

Reaction equation

HRID 543859 reaction equation
[CH:1](NC(C)C)(C)C.C([Li])CCC.[Cl:13][C:14]1[CH:19]=[CH:18][C:17]([C:20]2([N:27]([CH3:29])[CH3:28])[CH2:25][CH2:24][C:23](=[O:26])[CH2:22][CH2:21]2)=[CH:16][CH:15]=1.CI.[Cl-].[NH4+]>CCCCC.C(Cl)Cl.CO.C1C=CC=CC=1.O1CCCC1>[Cl:13][C:14]1[CH:15]=[CH:16][C:17]([C:20]2([N:27]([CH3:29])[CH3:28])[CH2:21][CH2:22][C:23](=[O:26])[CH:24]([CH3:1])[CH2:25]2)=[CH:18][CH:19]=1

Participants

11

Reactant 5

HCID 6328Methyl iodideHCID 7912DiisopropylamineHCID 25517Ammonium ChlorideHCID 125956504-(4-Chlorophenyl)-4-(dimethylamino)cyclohexan-1-oneHCID 178418339Butyllithium

Product 1

HCID 15586325HCID 15586325, compound

Reagents, catalysts & solvents 5

HCID 241BenzeneSolventHCID 887MethanolSolvent2×HCID 6344DichloromethaneSolvent2×HCID 8003PentaneSolventHCID 8028TetrahydrofuranSolvent2×

Conditions

Temperature
25 °C

Procedure

A solution consisting of 0.51 gm. (0.005 mole) diisopropylamine in 10 ml. tetrahydrofuran is chilled in an ice: methanol bath and 3 ml. of 1.68 N butyllithium in pentane is added. To this mixture is then added a solution consisting of 1.25 gm. (0.005 mole) 4(p-chlorophenyl)-4-dimethylaminocyclohexanone (prepared in Preparation I, above) in 20 ml. tetrahydrofuran. After 5 min. stirring, 1.42 gm. methyl iodide is added. The reaction mixture is stirred for another 30 min. in the cold, and then it is allowed to warm up to 25° C. Stirring is continued for 21/2 hours when 20 ml. saturated aqueous ammonium chloride is added. Benzene is also added. The organic solvent phase is separated, washed initially with water and then with brine. The organic solvents are removed by evaporation under reduced pressure. The residue thus obtained is transferred to a chromatographic column containing 200 ml. silica gel. The chromatogram is developed with 2 liters of a mixture of 3% methanol in methylene chloride followed by 2 liters of a mixture of 5% methanol in methylene chloride. Fractions which are shown by TLC to contain product are collected and combined. The solvents are removed by evaporation under reduced pressure giving the desired 4-(p-chlorophenyl)-2-methyl-4-dimethylaminocyclohexanone. The compound is recrystallized from diethyl ether to give an analytical sample having a melting point at 110° to 111° C. This is recognized to be the cis isomer with respect to the 4-amino substituent, by NMR spectroscopy.

Workup

  1. additionTo this mixture is then added a solution
  2. stirringThe reaction mixture is stirred for another 30 min. in the cold, and then it
  3. stirringStirring
  4. custom2 hours when 20 ml
  5. customThe organic solvent phase is separated
  6. washwashed initially with water
  7. customThe organic solvents are removed by evaporation under reduced pressure
  8. customThe residue thus obtained
  9. additioncontaining 200 ml
  10. customare collected
  11. customThe solvents are removed by evaporation under reduced pressure

Sources & evidence

ORD record
ord-733f0fca7d43456d8813e1cecd0aa0bf
Source dataset
uspto-grants-1984_05
Patent number
US04447454

Reaction notes

Loading…