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 Production Method of Bis(trimethylsilyl) peroxide (BTMSPO)
  • Production Method of Bis(trimethylsilyl) peroxide (BTMSPO)
  • Bis(trimethylsilyl) peroxide (BTMSPO) could be produced through the following synthesis routes.

    Production Method of Bis(trimethylsilyl) peroxide (BTMSPO)

    A. Diazabicyclooctane-hydrogen peroxide (DABCO · 2H2O2) complex. A 1-L, two-necked flask, fitted with a dropping funnel, 3-cm stirring bar, and a thermometer, is charged with diazabicyclooctane (DABCO) (28.05 g, 0.25 mol) dissolved in commercial grade tetrahydrofuran (THF) (375 mL). The flask is cooled to 0°C (internal temperature, ice-salt bath), and hydrogen peroxide (49 mL of a 35% solution, 0.5 mol) (Note 4) is slowly added at such a rate that the temperature remains constant, under vigorous stirring. A precipitate appears immediately and, after completing the addition of hydrogen peroxide, stirring is continued at 0°C for 1 hr. The mixture is then filtered through a Büchner funnel and the collected precipitate washed with cold THF (3 × 50 mL) and dried under reduced pressure (2 mm, 35–40°C) in a flask for 2 hr. The yield of DABCO · 2H2O2 obtained is 28.3 g (63%), m.p. 102–105°C (sealed tube) with decomposition, softness at 80°C (lit.3 m.p. 112°C).

    B. Bis(trimethylsilyl) peroxide (BTMSPO). A 2-L, three-necked flask, containing a 3-cm stirring bar, and a thermometer, dropping funnel, and an argon inlet adapter, is maintained under a slight pressure of argon. The flask is charged with the DABCO · 2H2O2 complex (28.3 g, 0.157 mol) and DABCO (28 g, 0.25 mol). Dry dichloromethane (700 mL) is added and the mixture is cooled to 0°C. (80 mL, 0.628 mol) is added dropwise, maintaining the temperature at 0°C, and the resulting mixture is stirred for 5 hr at room temperature. The mixture is filtered through a sintered Büchner funnel and the precipitate is washed with (2 × 25 mL). The solution, transferred to a 2-L flask fitted with a vacuum-jacketed, packed column (70 cm long, 4-cm i.d.) and a distillation head equipped with a dry ice/acetone cold finger, is concentrated to ca. 80 mL under reduced pressure. Pentane (25 mL) is added to the mixture, the additional precipitate is filtered off, and the solution is transferred to a smaller flask, (500 mL). It is concentrated under reduced pressure with the distillation apparatus previously employed to give a residue of 40.1 g (71% yield) of BTMSPO as a clear colorless liquid. It is shown from multinuclear NMR to be contaminated by ca. 8% of hexamethylsiloxane.

    For synthetic purposes the BTMSPO obtained can be used without further purification; on the other hand, distillation (40°C/30 mm) or column chromatography (Florisil–eluent pentane) does not seem to improve the grade of purity. The compound can be stored under nitrogen in a refrigerator for months without any appreciable decomposition.

    Notice: The possibility of explosions when handling bis(trimethylsilyl) peroxide (BTMSPO) has been reported,2 especially in the presence of metal needles, cannulas, etc., although the product was prepared using a different procedure that included the use of 85% H2O2 and pyridine. Our method never gave rise to explosions in the general practice of an organic chemistry laboratory. Nevertheless all the reactions were carried out in safety cupboards and behind blast shields.


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