TBHP tert-butyl hydroperoxide

A recent stndy (13,27) describes the use of Co-Si-TUD-1 for the liquid-phase oxidation of cyclohexane. Several other metals were tested as well. TBHP (tert-butyl hydroperoxide) was used as an oxidant and the reactions were carried out at 70°C. Oxidation of cyclohexane was carried out using 20 ml of a mixture of cyclohexane, 35mol% TBHP and 1 g of chlorobenzene as internal standard, in combination with the catalyst (0.1 mmol of active metal pretreated overnight at 180°C). Identification of the products was carried out using GC-MS. The concentration of carboxylic side products was determined by GC analysis from separate samples after conversion into the respective methyl esters. Evolution and consumption of molecular oxygen was monitored volumetrically with an attached gas burette. All mass balances were 92% or better. 

The scope of metal-mediated asymmetric epoxidation of allylic alcohols was remarkably enhanced by a new titanium system introduced by Katsuki and Sharpless epoxidation of allylic alcohols using a titanium(IV) isopropoxide, dialkyl tartrate (DAT), and TBHP (TBHP = tert-butyl-hydroperoxide) proceeds with high enantioselectivity and good chemical yield, regardless of... 

Table 11.7 Epoxidation of cyclohexene with TBHP (tert-butyl hydroperoxide) using selected species [31] .

MeCN, acetonitrile PhMe toluene TBHP, tert-butyl hydroperoxide. 

CPBA, chloroperbenzoic add NMO, N-methylmorpholine-N-oxide PPNO, 4-phenylp)nidine-N-oxide TBHP, tert-butyl hydroperoxide BINOL, l,l -bi-2-naphthol CMHP, cumene hydroperoxide. 

TBHP = tert-butyl hydroperoxide Scheme 11 Synthesis of ethyl menthyl (methylsulfinyl)methylphosphonates 33... 

Li and co-workers developed a CDC allylic alleviation between allylic sp C-H and methylenic sp C-H bonds. By using a combination of CuBr and C0CI2 as the catalyst and a stoichiometric amount of TBHP (tert-butyl hydroperoxide) as the oxidant, various 1,3-dicarbonyl compounds reacted smoothly with cyclohexene and gave the desired products in moderate yields (Scheme 5.3). Sensitive substituents such as chloro and bromo were tolerated under the optimized reaction conditions. Other cyclic alkenes including diallylic systems were also transformed into the desired products when... 

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