Reacción #50128

Ecuación de reacción

tetramine

hexamethylenetetramine

1,2-Dichloroethane

4-propionyloxy-2-methyl-1-chloro-2-butene

( i )

4-propionyloxy-2-methyl-1-chloro-2-butene

→

4-propionyloxy-2-methyl-2-buten-1-al

Rendimiento 26.8%

Disolventes

water

water

Condiciones de reacción

Tratamiento posterior

1. 1
   Otrowere removed by extraction
2. 2
   workup.ADDITION1,2-Dichloroethane (400 ml) was further added to the aqueous layer that
3. 3
   Lavadohad been washed
4. 4
   workup.STIRRINGthe mixture was stirred at 60° C. for 4 hours
5. 5
   OtroAfter completion of the reaction
6. 6
   Otrothe 1,2-dichloroethane layer was separated
7. 7
   workup.ADDITION1,2-dichloroethane (250 ml) was further added to the aqueous layer for extraction
8. 8
   Secadodried over anhydrous sodium sulfate
9. 9
   OtroThe 1,2-dichloroethane was evaporated under reduced pressure
10. 10
    Otrothe residue was purified by silica gel column chromatography (ethyl acetate-hexane (=1:5))

Procedimiento

The crude 4-propionyloxy-2-methyl-1-chloro-2-butene (64.0 g, 0.362 mol) obtained in the above (i) was added to a solution of hexamethylenetetramine (50.9 g, 0.363 mol) in water (345 ml), and the mixture was stirred at 35° C. for 4 hours to prepare a tetramine salt. 1,2-Dichloroethane (200 ml) was added to the reaction mixture, and compounds insoluble in water were removed by extraction. 1,2-Dichloroethane (400 ml) was further added to the aqueous layer that had been washed, and the mixture was stirred at 60° C. for 4 hours to hydrolyze the tetramine salt. After completion of the reaction, the 1,2-dichloroethane layer was separated, and 1,2-dichloroethane (250 ml) was further added to the aqueous layer for extraction. The 1,2-dichloroethane layers were combined and dried over anhydrous sodium sulfate. The 1,2-dichloroethane was evaporated under reduced pressure, and the residue was purified by silica gel column chromatography (ethyl acetate-hexane (=1:5)) to give 4-propionyloxy-2-methyl-2-buten-1-al (15.2 g, 0.0973 mol, Yield: 26.8% ).

Fuente