반응 #459952

반응 방정식

hydrogen peroxide

trifluoroacetic anhydride

disodium hydrogen phosphate

1,1-dinitro-1-cyano-3-butene

→

1,1-dinitro-1-cyano-3-butene

1,1-dinitro-1-cyano-3,4-epoxybutane

수율 63.0%

용매

methylene chloride

water

methylene chloride

반응 조건

후처리

1. 1
   workup.ADDITIONThis reagent was added over a 35 minute period to
2. 2
   workup.ADDITIONmixture of 8.2 g, 0.048 moles
3. 3
   기타After this mild exothermic reaction
4. 4
   온도the solution was heated
5. 5
   온도under reflux for 21/2 hours
6. 6
   workup.DISSOLUTIONhad dissolved
7. 7
   기타The organic layer was separated
8. 8
   추출the aqueous layer was extracted with 2-10 ml portions of methylene chloride
9. 9
   세척The combined methylene chloride extracts were washed with 15 ml of 10% sodium bicarbonate solution
10. 10
    건조dried over magnesium sulfate
11. 11
    기타The solvent was removed at reduced pressure

실험 절차

A solution of peroxytrifluoracetic acid was prepared from 1.70 ml, 0.062 moles, of 90% hydrogen peroxide, 10.5 ml, 0.074 moles, of trifluoroacetic anhydride, and 12 ml of methylene chloride. This reagent was added over a 35 minute period to a well stirred, boiling mixture of 8.2 g, 0.048 moles, of 1,1-dinitro-1-cyano-3-butene, 50 ml of methylene chloride, and 27.5 g, 0.192 moles, of disodium hydrogen phosphate. After this mild exothermic reaction had subsided, the solution was heated under reflux for 21/2 hours. The resulting mixture was stirred with 75 ml of water until all the inorganic salts had dissolved. The organic layer was separated and the aqueous layer was extracted with 2-10 ml portions of methylene chloride. The combined methylene chloride extracts were washed with 15 ml of 10% sodium bicarbonate solution and dried over magnesium sulfate. The solvent was removed at reduced pressure and the residual liquid was fractionated through a small Vigreux column to yield 3.6 g of unreacted 1,1-dinitro-1-cyano-3-butene and 3.17 g (63% yield) of 1,1-dinitro-1-cyano-3,4-epoxybutane, b.p. 62°-64°/0.005 mm., N25D 1.4672. The infrared spectrum was consistent with the assigned structure.

출처