Bis- 3,3 -peroxide

This highly active epoxidation system, based on the controlled hydrolysis of BTSP with a catalytic amount of water, maximizes the formation of the Re monoperoxide complex at the expense of the more thermodynamically stable bis (peroxide) (Scheme 12.8). BTSP is very stable and can be prepared in molar amounts... 

The reaction of 8 with oxygen (Scheme 1) leads to the bis-carbonyl-0-oxide 10 and can be seen either as a reaction of two carbene centers or as a reaction of two radical centers, giving a bis-peroxide. The IR and UV data suggest that there is little interaction between the two carbonyl centers via the linker. 

Sensitized photooxidation of benzhydrylidenecydobutane. Addition of singlet oxygen to a conjugated ethylenic-aromatic system. Determination of the structure of the bis-peroxide formed. Tetrahedron Letters, 13 (34), 3583-3586. 

Fig. 52 Pd(II)-catalyzed tandem bis(peroxidation)/cyclization reactions of W-arylacrylamides...

Recently An et al. disclosed a palladium(II)-catalyzed bis(peroxidation)/cycli-zation method for the synthesis of 3-(peroxymethyl)-3-peroxyoxindoles 209 from N - ar y 1 aery I a m i d e s 208 (Fig. 52) [235]. Using 5 mol% of Pd(OAc)2 in the presence of terf-butyl hydroperoxide, 46-96% of products 209 were obtained. The reactions were proposed to involve a Pd-catalyzed radical bis(peroxidation) of the acrylic unit [236] followed by a two-electron directed cyclometalation/reductive elimination reaction of intermediate bis(peroxide) 208A. 

Some more compliated cases of reactions of bis-peroxides have also been reported (eq. 16,17). It was proposed ( ) on the basis of a large negative AST that the reaction in eq. 17 proceeds by the 3-bond path indicated. 

Isopropylidene or benzylidene 2-hydrazinoselenazole derivatives can be converted to highly colored 2.2 -dioxo-A-3,3 -biselenazol-5,5 -inylidene-bis-hydrazones (Table X-11) by oxidation with ferric chloride and hydrogen peroxide i33). 

PEROXIDES AND PEROXIDE COMPOUNDS - ORGANIC PEROXIDES] (Vol 18) Bis(2,4-di-tert-butylphenyl)pentaerythritoldiphosphite [26741-53-7]... 

The perfluoroalkane sulfonic acids were fkst reported ki 1954. Trifluoromethanesulfonic acid was obtained by the oxidation of bis(ttifluoromethyl thio) mercury with aqueous hydrogen peroxide (1). The preparation of a series of perfluoroalkanesulfonic acids derived from electrochemical fluotination (ECF) of alkane sulfonyl haUdes was also disclosed ki the same year (2). The synthetic operations employed when the perfluoroalkanesulfonic acid is derived from electrochemical fluotination, which is the best method of preparation, are shown ki equations 1—3. 

Solution polymerization of VDE in fluorinated and fluorochlorinated hydrocarbons such as CEC-113 and initiated with organic peroxides (99), especially bis(perfluoropropionyl) peroxide (100), has been claimed. Radiation-induced polymerization of VDE has also been investigated (101,102). Alkylboron compounds activated by oxygen initiate VDE polymerization in water or organic solvents (103,104). Microwave-stimulated, low pressure plasma polymerization of VDE gives polymer film that is <10 pm thick (105). Highly regular PVDE polymer with minimized defect stmcture was synthesized and claimed (106). Perdeuterated PVDE has also been prepared and described (107). 

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). 

Bis (trimethyl silyl) peroxide (CH2)3SiOOSi(CH2)3 can be used with triflic acid (CF SO H) and acts as an effective hydroxylating agent of aromatics such as toluene, mesitylene and naphthalene (165). Sodium perborate (a safe and inexpensive commercial chemical) can be used in conjunction with the triflic acid to hydroxylate aromatics (166). 

Mesityl Oxide. Mesityl oxide (MSO) (4-metliyl-3-penten-2-one) is an oily colorless liquid with an unpleasant odor. It exhibits the versatiUty and unusual reactivity associated with conjugated a,P unsaturated carbonyl compounds (172). On standing ia air, mesityl oxide slowly forms bis(3,5,5-trimethyl-l,2-dioxolanyl)-3-peroxide (173). 

The first detailed investigation of the reaction kinetics was reported in 1984 (68). The reaction of bis(pentachlorophenyl) oxalate [1173-75-7] (PCPO) and hydrogen peroxide cataly2ed by sodium saUcylate in chlorobenzene produced chemiluminescence from diphenylamine (DPA) as a simple time—intensity profile from which a chemiluminescence decay rate constant could be determined. These studies demonstrated a first-order dependence for both PCPO and hydrogen peroxide and a zero-order dependence on the fluorescer in accord with an earher study (9). Furthermore, the chemiluminescence quantum efficiencies Qc) are dependent on the ease of oxidation of the fluorescer, an unstable, short-hved intermediate (r = 0.5 /is) serves as the chemical activator, and such a short-hved species "is not consistent with attempts to identify a relatively stable dioxetane as the intermediate" (68). 

Hydrogen peroxide has also been analy2ed by its chemiluminescent reaction with bis(2,4,6-trichlorophenyl) oxalate and perylene in a buffered (pH 4—10) aqueous ethyl acetate—methanol solution (284). Using a flow system, intensity was linear from the detection limit of 7 x 10 M to at least 10 M. 

Such copolymers of oxygen have been prepared from styrene, a-methylstyrene, indene, ketenes, butadiene, isoprene, l,l-diphen5iethylene, methyl methacrjiate, methyl acrylate, acrylonitrile, and vinyl chloride (44,66,109). 1,3-Dienes, such as butadiene, yield randomly distributed 1,2- and 1,4-copolymers. Oxygen pressure and olefin stmcture are important factors in these reactions for example, other products, eg, carbonyl compounds, epoxides, etc, can form at low oxygen pressures. Polymers possessing dialkyl peroxide moieties in the polymer backbone have also been prepared by base-catalyzed condensations of di(hydroxy-/ f2 -alkyl) peroxides with dibasic acid chlorides or bis(chloroformates) (110). 

Organomineral peroxides of antimony arsenic, boron, magnesium, tin, cadmium, lead, silicon, and 2inc have been prepared by autoxidation and some are Hsted in Table 3 (33,44,60,93,115). For example, dimethyl cadmium reacts with oxygen to form methylperoxy methyl cadmium [69331-62-0] and bis(methylperoxy) cadmium. 

Polymeric -peroxides (3) from hydrogen peroxide and lower carbon ketones have been separated by paper or column chromatography and have been characterized by conversion to the bis(p-(nitro)peroxybenzoates). Oligomeric peroxides (3, R = methyl, R = ethyl, n = 1-4) from methyl ethyl ketone have been separated and interconverted by suitable treatment with ketone and hydrogen peroxide (44). 

Bis(carbamoyl) peroxides of the foUowiag structure were prepared by reaction of the corresponding carbamoyl chlorides and hydrogen peroxide—urea complex in the presence of pyridine (211). 

In another method, phosgene is gradually passed into 1,2-propylene glycol (9). The chloroformate is washed, dried, and distilled at 266 Pa (2 mm Hg) and added slowly to a mixture of aHyl alcohol and pyridine below 15°C. The purified monomer 1,2-propylene glycol bis(aHyl carbonate) (C H O ) heated with lauroyl peroxide at 70°C gives a hard clear, polymer. 

Trifluoromethanesulfonic acid, also known as triflic acid [1493-13-6] is widely used ia organic syntheses and has been thoroughly reviewed (93,94). It was first prepared ia 1954 via the oxidation of bis(trifluoromethylthio)mercury with hydrogen peroxide [7722-84-1] (95). Several other routes of preparation have been disclosed (96—98). The acid exhibits excellent thermal and hydrolytic stabiUty, it is not readily oxidized or reduced, nor is it prone to fluoride anion generation. 

Dithionite is a stronger reducing agent than sulfite. Many metal ions, eg, Cu", Ag", Pb ", Sb ", and Bi ", are reduced to the metal, whereas TiO " is reduced to (346). Dithionite readily reduces iodine, peroxides, ferric salts, and oxygen. Some of the decolorizing appHcations of dithionite, eg, in clay bleaching, are based on the reduction of ferric iron. 

The thermal fragmentation of unsaturated bicyclic 1,4-peroxides, often readily made from 1,4-dienes (Scheme 84), has become an important route to novel bis(oxiranes) (80T833, 81CRV91). 

Bis-(chloromethyl)oxacyclobutane [78-71-7] M 155.0, m 18.9 . Shaken with aqueous NaHC03 or FeS04 to remove peroxides. Separated, dried with anhydrous Na2S04, then distd under reduced pressure from a little CaH2 [Dainton, Ivin and Walmsley Trans Faraday Sac 65 17884 I960],... 

---