Bis trimethylsilyl peroxide

Martin G. Banwell Jens Renner The Australian National University, Canberra, ACT, Australia 

Form Supplied in colorless oil used as an anhydrous and protected form of hydrogen peroxide 10% solution in hexane or in CH2CI2. 

Preparative Methods obtained in 80-96% yields by reaction of chlorotrimethylsilane with l,4-diazabicyclo[2.2.2]octane-(H202)2, hexamethylenetetramine-H202, or hydrogen peroxide-urea in CH2CI2.  

Handling, Storage, and Precautions thermally stable can be handled in the pure state and distilled rearranges at 150-180 °C. = 

Academia Sinica National Tsing Hua University, Taiwan, Republic of China 

---

H2O2 in the presence of HE/BE acts as an effective and economical reagent for aromatic hydroxylation (163). Hydroxylations of phenols and amines in similar high acidity media are very effective (163). Xylenes were hydroxylated by bis(trimethylsilyl) peroxide and AlCl in poor yields (164). 

Further improvement of this process was accomplished by Yudin and Sharpless by use of the stoichiometric oxidant bis(trimethylsilyl) peroxide (BTSP, Scheme 12.7) [28],... 

Table 12.2 Epoxidation of olefins with bis(trimethylsilyl) peroxide (BTSP) catalyzed by high-valent oxorhenium deri-vatives> bl...

S-adenosylmethionine 406 biosynthesis of epoxide 349 bis(trimethylsilyl) peroxide (BTSP) 448, 450 bis(trimethylsilyl)urea 449 bis-oxepane ring 281... 

Lithiomethyl)quinoxahne (87) with bis(trimethylsilyl) peroxide (88) gave 2-ethylquinoxaline (89) (lithiation by LiNPr, THF then synthonj, —78°C, N2, 2 h 40%) several homologs likewise. ... 

Although bis(trimethylsilyl)peroxide (BTSP) 1949 is considered in a review to be quite stable [137], some minor accidents with its use have been reported [138]. It is usually prepared from 85% H2O2 and Me3SiCl (TCS) 14 in ether-pyridine... 

Conversion of sulfones such as 1955 into their a-sulfonyl anions by treatment with n-BuIi at -78°C in THF then addition of bis(trimethylsilyl)peroxide (BTSP) 1949 afford, via intermediates such as 1956, aldehydes or ketones such as cyclohexanone and HMDSO 7 [146]. This reaction has subsequently been applied to the synthesis of aldehydes [147]. After hthiation with -BuLi thioethers such as phenyl benzyl sulfide 1957 react with BTSP 1949 to give mixtures of the O-silyl 1958 and C-silyl 1959 products [148]. On treatment with -BuLi at -30°C the a,a-bis-(trimethylsilyl)dimethylsulfide 1960 is, hkewise, converted into its anion, which reacts with 1949 to give the a-trimethylsilyloxy sulfide 1961 and MesSiOLi 98 [149] (Scheme 12.41). 

Bis(trimethylsilyl)peroxide (1) can be used to produce phosphine oxides stereospecifically from either phosphines (with retention) or phosphine sulphides (with inversion).1 A variety of organoelement substituted pentadienes, including the phosphine oxides (2) and (3),... 

Prepared in situ from trihalocyclopropanes. Bis(trimethylsilyl)peroxide. 

Yudin and Sharpless reported on the utilization of much cheaper, readily available inorganic Re catalysts [Re207, ReOsfOH), ReOs (0.5-1 mol%)] in combination with bis(trimethylsilyl) peroxide as oxidant and 0.5-1 mol% of pyridine (equation 52) . In this oxidation process high epoxide yields (78-96%) were obtained using CH2CI2 or THF as solvent. Traces of water or other protic species have been found to be essential for rapid turnover and accelerate the reaction. 

The oxidation of substituted pyridines to iV-oxides was reported by Sharpless and coworkers to proceed with yields between 78 and 99% (Scheme 154). A variety of substituents like electron donor as well as acceptor groups and alkenyl substituents are tolerated. In 1998, Sharpless and coworkers reported an alternative method for the preparation of pyridine-A-oxides in which the MTO/H2O2 catalyst could be replaced by cheaper inorganic rhenium derivatives (ReOs, Re207, HOReOs) in the presence of bis(trimethylsilyl) peroxide (equation 73). Yields of the prepared A-oxides after simple workup (filtration and bulb to bulb distillation) ranged from 70-98%. Molecular sieves slowed down the reaction while small amounts of water (0-15%) were essential for the reaction. Both electron-poor or electron-rich pyridines give high yields of their A-oxides and while para-... 

Silicon and gennaninm peroxides TABLE 15. Oxidation of disilanes with bis(trimethylsilyl) peroxide... 

Bis(trifluoromethyl) peroxycarbonate, 705 Bis(trifluoromethyl) peroxydicarbonate, 705 Bis(trifluoromethyl) trioxide IR spectrum, 740 O NMR spectroscopy, 182 Bis(trifluoromethyl) tiioxydicarbonate, 740 Bis(trimethylsilyl) monoperoxysulfate Baeyer-Vilhger oxidation, 785 catalytic epoxidation, 791-2 Bis(trimethylsilyl) peroxide (BTSP) alcohol oxidation, 787-90 alkyne reactions, 800 aromatic compounds, 794-5 Baeyer-Vilhger ketone oxidation, 784-7 demethylation, 798... 

Bromopyrogallol Red, hydrogen peroxide determination, 628-9 Bronchial epithehal cells, IR spectrophotometry, 683 Br0nsted acids, olefin epoxidation, 471 BSA see Bovine semm albumin BTSP see Bis(trimethylsilyl) peroxide 2-Butanone peroxide, hydroperoxide determination, 686, 688, 689 -2-Butene, final ozonide, 721 t-Butoxy free radical, a-methylstyrene dimer reaction, 697... 

Cumyl propyl peroxide, determination, 708 Curing processes, 692, 707 Curtin-Hammett principle, electron-poor alkene photooxygenation, 877 Cyanine dye, TBARS assay, 667 Cyanohydrins, bis(trimethylsilyl) peroxide reactions, 797... 

---