反应详情

温度

10 °C

A pre-mixed catalyst system: TMTACN (1,4,7-trimethyl-1,4,7-triazacyclononane, prepared as an approximately 60 mM solution in acetonitrile 58.4 mM, 27.3 mL, 0.006 mol eq.), manganese (II) acetate tetrahydate (150 mM, 8.0 mL, 0.0045 mol eq., prepared as a 150 mM solution in water) and equimolar ascorbic acid and sodium ascorbate (80 mM, 12.0 mL, 0.0036 mol eq., prepared as a 80 mM (of both) solution in water) was added to acetonitrile (375 mL, 5 vol) at 10° C. The combined mixture was allowed to equilibrate at 10° C. An initial charge of hydrogen peroxide (35% w/w, 15.5 g, 0.6 mol eq) was added over ten minutes. With this addition, a colour change from colourless to dark brown was noticed accompanied by an exotherm and effervescing. (For this reason it is best to carry out this experiment in a temperature controlled reaction vessel with appropriate off-gassing capability.) The combined mixture was re-cooled to 10° C. A solution of pre-prepared N,N-diallyl 4-nitrobenzenesulfonamide (75.0 g, 1.0 mol eq., see step (a) above) in acetonitrile (375 mL, 5 vol.) was added. The combined mixture was allowed to equilibrate at 10° C. Further hydrogen peroxide (35% w/w, 139.4 g, 5.4 mol eq) was added over one hour, whilst maintaining the temperature at 10° C. (The reaction requires an additional stir out at 10° C., this can be up to 16 hours.) Once completed the reaction was quenched by the addition of 10% w/w sodium sulfite (300 mL, 4 vol) over about fifteen minutes, whilst maintaining the temperature at 10° C. (the sodium sulfite was added with portion-wise monitoring for peroxide by way of a test stick). tert-Butyl methyl ether (TBME) (1.5 L, 20 vol) was added, and the resulting layers were separated. The organic layer was swapped into IMS, and the amount of solvent was reduced to about 1.05 L (14 vol.). The product precipitated on cooling to less than 10° C., and was isolated by filtration. The crude solid was washed with IMS (300 mL, 4 vol) and was then dried in a vacuum oven at 40° C. overnight to give the title compound as a white solid, 60.75 g, 73%.

1. customto equilibrate at 10° C
2. additionwas added over ten minutes
3. additionWith this addition
4. customreaction vessel with appropriate off-gassing capability
5. customto equilibrate at 10° C
6. temperaturewhilst maintaining the temperature at 10° C. (The reaction
7. customwas quenched by the addition of 10% w/w sodium sulfite (300 mL, 4 vol) over about fifteen minutes
8. temperaturewhilst maintaining the temperature at 10° C. (the sodium sulfite
9. additionwas added with portion-wise monitoring for peroxide by way of a test stick)
10. additiontert-Butyl methyl ether (TBME) (1.5 L, 20 vol) was added
11. customthe resulting layers were separated
12. customThe product precipitated
13. temperatureon cooling to less than 10° C.
14. customwas isolated by filtration
15. washThe crude solid was washed with IMS (300 mL, 4 vol)
16. customwas then dried in a vacuum oven at 40° C. overnight