Acetic Acid → 3-(methylsulfanyl)cyclohexanone

HRID 423958Notes

Reaction equation

HRID 423958 reaction equation
[C:1]1(=[O:7])[CH2:6][CH2:5][CH2:4][CH:3]=[CH:2]1.C(O)(=O)C.[CH3:12][S-:13].[Na+]>C1(C)C=CC=CC=1>[CH3:12][S:13][CH:3]1[CH2:4][CH2:5][CH2:6][C:1](=[O:7])[CH2:2]1

Participants

5

Reactant 3

HCID 176Acetic AcidHCID 135942-Cyclohexen-1-oneHCID 4378561Sodium methanethiolate

Product 1

HCID 2875743-(methylsulfanyl)cyclohexanoneYield 86.2%

Reagents, catalysts & solvents 1

HCID 1140TolueneSolvent

Procedure

Cyclohex-2-enone (3.80 g, 95% Aldrich, 39.5 mmol uncorrected), toluene (15.31 g, HPLC grade) and glacial acetic acid (2.85 g, 47.4 mmoles, 1.20 eq, 99.7+% Aldrich) were combined in a 50 mL 3-necked round bottom flask equipped with a magnetic stirrer, reflux condenser with nitrogen oil bubbler vented to a bleach scrubber, thermometer with Therm-o-watch controller and septum. To the stirred solution was added 15 wt % sodium thiomethoxide (19.4 g of solution, 2.91 g, 41.5 mmol, 1.05 eq of NaSCH3) in portions via syringe during 19 min. The reaction temperature increased from 28.0° C. to 36.4° C. during the addition. The two-phase mixture was stirred at ambient temperature overnight. The reaction mixture was heated to about 50° C. and stirred for 7.5 h. The mixture was then allowed to cool to room temperature with stirring overnight. The phases were allowed to settle for 30 min. The lower aqueous phase was removed. The upper organic phase was washed with water (2×10 mL), dried through a cone of anhydrous magnesium sulfate and concentrated on the rotary evaporator (29 in. Hg vacuum/48° C.) to afford 4.91 g of 3-(methylthio)cyclohexanone as a clear pale yellow oil. Area % conversion by GC 95%. Raw area % 91.1%. Mass recovery 86%.

Workup

  1. customequipped with a magnetic stirrer
  2. temperaturereflux condenser with nitrogen oil bubbler
  3. temperatureThe reaction temperature increased from 28.0° C. to 36.4° C. during the addition
  4. temperatureThe reaction mixture was heated to about 50° C.
  5. stirringstirred for 7.5 h
  6. temperatureto cool to room temperature
  7. stirringwith stirring overnight
  8. waitto settle for 30 min
  9. customThe lower aqueous phase was removed
  10. washThe upper organic phase was washed with water (2×10 mL)
  11. dry with materialdried through a cone of anhydrous magnesium sulfate
  12. concentrationconcentrated on the rotary evaporator (29 in. Hg vacuum/48° C.)

Sources & evidence

ORD record
ord-9cfd20a3bf37487ab89834528fccc68c
Source dataset
uspto-grants-2012_01
Patent number
US08101803B2

Reaction notes

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