Methyl iodide → Fenamidone

HRID 266264Notes

Reaction equation

HRID 266264 reaction equation
[C:1]1([C@@:7]([N:13]=[C:14]=[S:15])([CH3:12])[C:8]([O:10]C)=O)[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1.[C:16]1([NH:22][NH2:23])[CH:21]=[CH:20][CH:19]=[CH:18][CH:17]=1.[CH3:24]C(C)([O-])C.[K+].CI>O1CCCC1.O>[CH3:12][C@:7]1([C:1]2[CH:2]=[CH:3][CH:4]=[CH:5][CH:6]=2)[C:8](=[O:10])[N:23]([NH:22][C:16]2[CH:21]=[CH:20][CH:19]=[CH:18][CH:17]=2)[C:14]([S:15][CH3:24])=[N:13]1

Participants

7

Reactant 4

HCID 6328Methyl iodideHCID 7516PhenylhydrazineHCID 23665647Potassium tert-butoxideHCID 57098026HCID 57098026, compound

Product 1

HCID 10403199FenamidoneYield 114.6%

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 8028TetrahydrofuranSolvent3×

Conditions

Temperature
0 °C

Procedure

682 g (3.08 mol) of methyl (+)-(2S)-2-phenyl-2-(isothiocyanato)propionate, dissolved in 4 liters of anhydrous tetrahydrofuran, are introduced into a 20 liter reactor through which passes a stream of argon. Cooling is carried out to 15° C. 343 g (3.08 mol) of phenylhydrazine, dissolved in 2 liters of tetrahydrofuran, are run in over 30 minutes, the temperature being maintained between 15° C. and 18° C. The mixture is kept stirring for 40 minutes and then cooled to 0° C. A solution of 346 g (3.08 mol) of potassium tert-butoxide in 4 liters of tetrahydrofuran is run in over 1 hour, the temperature being maintained at 0° C. The mixture is stirred for a further 2 hours at 0° C. and the formation of a pale-pink precipitate is observed. 218 ml (3.39 mol) of methyl iodide are run in over 15 minutes, the temperature being maintained between 0° C. and 3° C., and the temperature is then allowed to rise to room temperature while continuing to stir for 2 hours. The reaction mixture is poured onto 5 liters of water. After separating, the aqueous phase is extracted with 3 times 3 liters of ethyl acetate. The combined organic phases are washed with 5 liters of water, dried over magnesium sulfate and the concentrated under reduced pressure. 1099 g of a brown solid are obtained. The latter is recrystallized from 2 liters of toluene.

Workup

  1. additionare introduced into a 20 liter reactor through which
  2. temperatureCooling
  3. customis carried out to 15° C
  4. customare run in over 30 minutes
  5. temperaturethe temperature being maintained between 15° C. and 18° C
  6. customis run in over 1 hour
  7. temperaturethe temperature being maintained at 0° C
  8. stirringThe mixture is stirred for a further 2 hours at 0° C.
  9. customare run in over 15 minutes
  10. temperaturethe temperature being maintained between 0° C. and 3° C.
  11. customto rise to room temperature
  12. stirringto stir for 2 hours
  13. customAfter separating
  14. extractionthe aqueous phase is extracted with 3 times 3 liters of ethyl acetate
  15. washThe combined organic phases are washed with 5 liters of water
  16. dry with materialdried over magnesium sulfate
  17. concentrationthe concentrated under reduced pressure

Sources & evidence

ORD record
ord-f706e2a6c8694040b29f396eb3fb2ed9
Source dataset
uspto-grants-1997_07
Patent number
US05650519

Reaction notes

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