Tert butyl perbenzoate

Butyl oleate, b58la tert-Butyl perbenzoate, b584 Butyl o-phthalate, dl 65 Butyl 2-propenoate, b507a... 

Sodium sulfonate 1 has previously been prepared from NaHS03 and vinyltrimethylsilane using sodium nitrite/sodium nitrate as the radical initiator.3 In the submitters hands this protocol resulted in salt 1 as a pale tan powder in only 15-53% yield if 50% (v/v) aqueous methanol is employed as solvent. The yield of 1 could be increased to 63% if 22% (v/v) aqueous methanol is employed. An advantage of this method is the elimination of a potentially explosive perester as radical initiator. However, lower yields of 1 and the subsequent lower yield of the sulfonyl chloride 2 (53% for the sulfonylation, 35% overall from vinyltrimethylsilane) make this procedure less desirable than the method presented. The use of tert-butyl perbenzoate as the radical initiator4 not only provides 1 in a higher yield, but the subsequent conversion to 2 also proceeds in better yield. 

Caution Although tert-butyl perbenzoate is one of the safest peresters/peroxides to handle, one should remain aware of the inherent shock sensitivity and instability of these compounds. Users should exercise appropriate caution during concentration procedures. 

A. Sodium p-trimethylsilylethanesulfonate (1). To a 500-mL, round-bottomed flask (Note 1) flushed with argon and equipped with a magnetic stirring bar is added vinyltrimethylsilane (28.0 mL, 18.2 g, 181 mmol), methanol (70 mL), and tert-butyl perbenzoate (0.70 mL, 0.70 g, 3.6 mmol) (Notes 2 - 4). To this solution is added a solution of sodium bisulfite, NaHSC>3, (36.1 g, 347 mmol) in 70 mL of water (Notes 5 -7). The flask is equipped with a Claisen adapter bearing an immersion thermometer and reflux condenser, and the resulting suspension is heated in an oil bath at 50°C... 

Tert-Butyl Perbenzoate Diethyl-aluminum Hydride ( )... 

Absolute and relative rates of ETR of tert-butyl perbenzoates with dimethyl sulfide at various temperatures (T = 80, 90, 100 and 110°C) were obtained. Hammett correlations at each temperature were also studied (Table 7). The Hammett slopes are positive and the reactions are better correlated with a rather than with cr. This indicates that a negative charge resides on the benzoyloxy group without conjugation with the phenyl... 

TABLE 7. Absolute rates, relative rates and Hammett correlations for ETR between tert-butyl perbenzoates and dimethyl sulfide... 

Enthalpies of ozonation, 165 Enthalpies of reactions acyl peroxides, 162-3 arene endoperoxides, 166-7 tert-butyl perbenzoate ETR reactions, 909-11... 

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