Allyl bromide → Allylthio-2,6-dimethyl-4-heptanone

HRID 371977Notes

Reaction equation

HRID 371977 reaction equation
C[O-].[Na+].S[CH:5]([C:9](=[O:14])[CH2:10][CH:11]([CH3:13])[CH3:12])[CH:6]([CH3:8])[CH3:7].SC(S)=O.C(Br)C=C.[CH2:23]([S:26]C(C(=O)CC(C)C)C(C)C)[CH:24]=[CH2:25]>CO.Cl.O>[CH2:23]([S:26][CH2:7][CH:6]([CH3:8])[CH2:5][C:9](=[O:14])[CH2:10][CH:11]([CH3:13])[CH3:12])[CH:24]=[CH2:25]

Participants

9

Reactant 5

HCID 7841Allyl bromideHCID 422830Carbonodithioic acidHCID 10942334Sodium Methoxide3×HCID 205190993-Mercapto-2,6-dimethyl-4-heptanoneHCID 221500163-Allylthio-2,6-dimethyl-4-heptanone

Product 1

HCID 20352478Allylthio-2,6-dimethyl-4-heptanone

Reagents, catalysts & solvents 3

HCID 313Hydrochloric AcidCatalystHCID 887MethanolSolvent3×HCID 962WaterSolvent2×

Conditions

Temperature
23 °C

Procedure

Into a 25 ml, round-bottom, three-necked flask equipped with magnetic stirrer, reflux condenser, nitrogen inlet tube and cold water bath is placed a solution of 0.162 grams (0.003 moles) of sodium methoxide dissolved in 2 ml anhydrous methanol. Using the water bath the temperature of the sodium methoxide solution is reduced to 23° C. At 23° C a solution of 0.522 grams (0.003 moles) of 3-mercapto-2,6-dimethyl-4-heptanone dissolved in 3 ml anhydrous methanol is added to the sodium methoxide solution. Subsequent to the addition of the mercapto ketone, after stirring for 15 minutes at 23° C, a solution of 0.40 grams (0.0033 moles) of allyl bromide dissolved in 2 ml anhydrous methanol is added to the reaction mass with stirring. The reaction mass warms to 33° C and is continued to be stirred at 25°-33° C for a period of 2 hours. It is concentrated on a rotary evaporator using water aspirator vacuum to a volume of 3 ml, thus yielding a white slurry. Eight ml water is then added to the slurry thereby dissolving the solid therein. One drop of 10% HCl is added to the resulting material thereby reducing the pH from about 9 to about 5. The reaction mass now existing in two phases is extracted with three 8 ml volumes of methylene chloride. The extracts are combined and washed with 6 ml water and then dried over anhydrous sodium sulfate, gravity filtered and concentrated on a rotary evaporator to a weight of 0.55 grams (pale yellow oil). GLC analysis (8' × 1/4" SE-30 column), NMR, IR and mass spectral analyses of GLC isolated material confirm that the resulting product is 97% product, 3-allylthio-2,6-dimethyl-4-heptanone, having the structure: ##STR66##

Workup

  1. customInto a 25 ml, round-bottom, three-necked flask equipped with magnetic stirrer
  2. temperaturereflux condenser, nitrogen inlet tube and cold water bath
  3. customis reduced to 23° C
  4. additionis added to the reaction mass
  5. stirringwith stirring
  6. customwarms to 33° C
  7. stirringto be stirred at 25°-33° C for a period of 2 hours
  8. concentrationIt is concentrated on a rotary evaporator
  9. customthus yielding a white slurry
  10. dissolutionthereby dissolving the solid
  11. extractionis extracted with three 8 ml volumes of methylene chloride
  12. washwashed with 6 ml water
  13. dry with materialdried over anhydrous sodium sulfate, gravity
  14. filtrationfiltered
  15. concentrationconcentrated on a rotary evaporator to a weight of 0.55 grams (pale yellow oil)
  16. customGLC analysis (8' × 1/4" SE-30 column), NMR, IR and mass spectral analyses of GLC isolated material

Sources & evidence

ORD record
ord-6577729f725647419d4dabff34ecc384
Source dataset
uspto-grants-1978_05
Patent number
US04088697

Reaction notes

Loading…