Peroxide groups

S. Patai, ed.. The Chemistry of Peroxides, John Wiley Sons, Inc., New York, 1983 S. Patai, ed.. Supplement E2 The Chemistry of FLydroyyl, Ether and Peroxide Groups,John Wiley Sons, Inc., New York, 1993. 

A peroxide oi peioxo compound contains at least one pair of oxygen atoms, bound by a single covalent bond, in which each oxygen atom has an oxidation number of —. The peroxide group can be attached to a metal, M, through one (1) or two (2) oxygen atoms, or it can bridge two metals (3) ... 

Peroxomonosulfuric acid [7722-86-3] H2SO, when pure, forms colorless crystals that melt with decomposition at 45°C. One of its protons is strong, as ia sulfuric acid, but its other proton, which is on the peroxide group, is weak (pH = 9.4). Peroxomonosulfuric acid is a strong oxidi2iag agent ... 

Diperoxyketals in which the peroxide groups are in a ring are among the most thermally stable organic peroxides, eg, 3,3,6,6,9,9-hexamethyl-l,2,4,5-tetraoxacydononane(10) which has 10-h HLT = 141" C in benzene. 

ANALYSIS OF PEROXIDE GROUPS IN POLYMERS BY CHROMATOGRAPHY AND THERMOGRAVIMETRY... 

Content of prime - tertiary peroxide groups was measured by the quantity of products of complete decay, which were measured by chromatography. It is known that the main contents in products of the complete decay of Oct-MA-TBPMM samples are acetone and 2,2-dimethylpropanol, which arise in reactions of chain fragmentation of tert-butylperoxy radical or in reaction of chain transfer of this radical. In this case the sum of acetone and 2,2-dimethylpropanol molecules is equal to the quantity of peroxide groups in polymer. As an internal standard we used chloroform. 

Macrobisperoxides contain peroxide groups in both ends of the main chain. The first example of macro-... 

Cationic polymerization of tetrahydrofuran with the or bis(3,5-di-bromomethyl) benzoyl peroxide and AgPp6 pairs of 4,4 -bromomethyl benzoyl peroxide and AgPp6 yield active poly-THP having peroxide group in the main... 

Entries 15 to 18 are examples of use of iodocyclization in multistep syntheses. In Entry 15, iodolactonization was followed by elimination of HI from the bicyclic lactone. In Entry 16, a cyclic peroxide group remained unaffected by the standard iodolactonization and subsequent Bu3SnH reductive deiodination. (See Section 5.5 for... 

There has been a DFT (BLYP/6-31G ) study of the TS and its relationship to the enantioselectivity of the reaction.59 The strategy used was to build up the model by successively adding components. First the titanium coordination sphere, including an alkene and peroxide group, was modeled (Figure 12.4a). In Figure 12.4b, the diol... 

Peroxidic groups in oxidized polyolefins have frequently been employed as sources of free radicals to allow grafting of vinyl monomers to polyolefins (2f[). Some of the products from the gas reactions also have interesting potential as reactive sites. For example, chloroformate groups are well known to react with alcohols, and amines 2J[). Thus chloroformate groups could be useful for example in coupling highly oriented polyolefin fibres to resins such as epoxy based systems. 

The oxidation of naphthalic acid (1,8-naphthalenedicarboxylic acid) by peroxide, rather surprisingly, does not proceed by formation of a cyclic peroxide but rather via a dioxirane [53] (a three-membered ring containing a carbon atom and a peroxide group). CL is observed from this reaction. 

In reactions of decay of alkyl radicals with the peroxide group (see 2.4.4) ... 

The amount of lsO in the carbonyl group of peroxide was found to decrease with time of decomposition, and amount of lsO in the peroxide group was found to increase (isooctane, 353 K, [MeCOOOCOMe]0 = 0.05 mol L-1 [79]) ... 

S. W. Slayden and J. F. Liebman, in The Chemistry of Functional Groups, Supplement E2 The Chemistry of Hydroxyl, Ether and Peroxide Groups (Ed. S. Patai), Wiley, Chichester, 1993. 

Temperature = 25°C pressure = 1 bar a-CsN bond not included -NsO bond not included c No ring deformation correction d No cyclopropane ring in method e-C=N- bond not included f Some nitrogen groups not in table 8 No peroxide group in table h Average deviation from experimental values... 

The results of a number of tests such as those described in Chapter 2 led to classifications for the peroxide group. These tests included the determination of the hazards of decomposition (deflagration and detonation), bum rate, fire hazard, and reactivity hazards. Five different classes were formulated, as listed in the NFPA 43B Hazard Class, from the test results. Emergency procedures have been established for these five classes. 

For over 20 years two improvised explosives containing the peroxide group have been of constant concern to legal authorities. Both triacetonetriperoxide (TATP) (2) and hexamethylenetriperoxide diamine (HMTD) (3) are easily prepared from readily available starting materials. Both compounds have been encountered for the first time by the Israel Police in the late 1970s and early 1980s [60], but... 

Weatherburn and co-workers prepared the first and only trinuclear Mn3 complex, [Mn3O(OAc)2(O2)(dien)3]l3 H2O 0.33CH3OH (104), which has a bridging peroxide group (triangular c. Figure 21). This complex was prepared from the reaction of either Mn(OAc)2 or Mn(OAc)3 with dien in methanol under reflux. The Mn" Mn separations in (104) are 3.32(3) A and 3.14(4) A. 

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