1,4,7-trimethyl-1,4,7-triazonane

Conditions: temp:10.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: 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%. to equilibrate at 10° C was added over ten minutes With this addition reaction vessel with appropriate off-gassing capability to equilibrate at 10° C whilst maintaining the temperature at 10° C. (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 the resulting layers were separated The product precipitated on cooling to less than 10° C. was isolated by filtration The crude solid was washed with IMS (300 mL, 4 vol) was then dried in a vacuum oven at 40° C. overnight

Conditions: temp:140.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To a magnetically stirred 500-mL flask containing 106 mL of concentrated sulfuric acid and 19 ml of milli-Q water was added 100 g (0.17 mol) of Ts3 -TACN over a few minutes. A large portion of the Ts3 -TACN floated on top of the mixture. The reaction mixture was heated in a 140° C. oil bath. After stirring vigorously for 15 minutes, the material dissolved in the acid. Heating was continued for a total of 6 hours. A 5-L flask equipped with an overhead stirrer and a condenser was cooled to 0° C. and charged with 308 g of 50% NaOH and 125 mL of water. The alkaline solution was vigorously stirred and the sulfuric acid mixture was added through an addition funnel over a 45-minute period (conducted by transferring about 20 mL aliquots into the addition funnel). The resulting mixture was intended to have a pH of 7. the reaction was maintained at 0° C. and 225 mL of 37% formaldehyde and 225 mL of 88% formic acid were added sequentially. The mixture was heated to an internal temperature of 90° C. The evolution of CO2 was moderate. The reaction was heated at this temperature for 14 hours. The reaction was cooled to 0° C. and 490 g of 50% NaOH was added over a 35-minute period through an addition funnel. The resulting slurry showed a pH of 14 (indicator paper). About 400 mL of hexane were added and the mixture was stirred for 2 minutes. The reaction mixture was filtered and the crystalline material on the grit was washed with an additional 150 mL of hexane. The organic phase of the mother liquor was separated and the aqueous portion was extracted with 200 mL of hexane. The combined extracts were dried over a small amount of Na2SO4, filtered, and concentrated to yield 25.34 g (88%) of MeTACN as a very light yellow liquid. The material was stored in a tightly-capped brown glass bottle at 0° C. the material dissolved in the acid Heating was continued for a total of 6 hours A 5-L flask equipped with an overhead stirrer and a condenser was cooled to 0° C. The alkaline solution was vigorously stirred the reaction was maintained at 0° C. The mixture was heated to an internal temperature of 90° C The reaction was heated at this temperature for 14 hours The reaction was cooled to 0° C. the mixture was stirred for 2 minutes The reaction mixture was filtered the crystalline material on the grit was washed with an additional 150 mL of hexane The organic phase of the mother liquor was separated the aqueous portion was extracted with 200 mL of hexane The combined extracts were dried over a small amount of Na2SO4 filtered concentrated to yield 25.34 g (88%) of MeTACN as a very light yellow liquid was stored in a tightly-capped brown glass bottle at 0° C.

Conditions: temp:10.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: 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%. to equilibrate at 10° C was added over ten minutes With this addition reaction vessel with appropriate off-gassing capability to equilibrate at 10° C whilst maintaining the temperature at 10° C. (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 the resulting layers were separated The product precipitated on cooling to less than 10° C. was isolated by filtration The crude solid was washed with IMS (300 mL, 4 vol) was then dried in a vacuum oven at 40° C. overnight