Reaction #56465

Reaction equation

1,1,2-trichlorobutadiene

water

triethylamine

isobutyric acid dimethylamide

→

1,1,2-trichlorobutadiene

dimethylamine

Solvents

methylene chloride

methylene chloride

Conditions

Workup

1. 1
   Otherprepared
2. 2
   Temperaturewhile cooling
3. 3
   Temperaturethe mixture was then heated
4. 4
   Temperaturerefluxed for 1 hour
5. 5
   TemperatureAfter heating
6. 6
   Temperatureunder reflux for 5 hours
7. 7
   workup.STIRRINGthe mixture was stirred overnight (15 hours)
8. 8
   OtherSeparating the phases
9. 9
   Dryingdrying the organic phase over sodium sulphate
10. 10
    workup.DISTILLATIONto fractional distillation

Procedure

50.0 g (0.5 mol) of triethylamine in 100 ml of methylene chloride was added dropwise to 350 ml of the solution, prepared according to Example 7a, of the amide chloride of isobutyric acid dimethylamide in methylene chloride at 20° C., while cooling and stirring, and the mixture was then heated and refluxed for 1 hour. Thereafter, 75.0 g (0.55 mol) of zinc chloride were added at 10° C. and 79.0 g (0.5 mol) of 1,1,2-trichlorobutadiene were added dropwise to the reaction solution in the course of 60 minutes. After heating under reflux for 5 hours, 400 ml of water were added to the reaction solution and the mixture was stirred overnight (15 hours). Separating the phases and drying the organic phase over sodium sulphate and subjecting it to fractional distillation gave 10.5 g of 1,1,2-trichlorobutadiene, 11.5 g of isobutryic acid dimethylamine and 66.8 g (59%, relative to isobutyric acid dimethylamine employed) of the ketone of boiling point 112°-117° C./10 mm Hg and refractive index nD20 of 1.509.

Source