Hydroperoxy methyl

Cleavage of acid-labile protective groups.1 The reaction of H202 (70%, FMC) and CI3CCOOH in CH2C12/(-butyl alcohol converts a dimethyl acetal (1) into a hydroperoxy methyl acetal (a), which can be isolated but which for convenience (and safety) is reduced to the aldehyde 2 in 80% overall yield. The same conditions can effect oxidative cleavage of tetrahydropyranyl and trityl ethers. 

Hydroperoxy methyl HO-OCH2 -24.6 -102.9 Derived This volume... 

Little is known about the existence of alkyl hydrotetraoxides, R—OOOOH. There is some kinetic evidence supporting methyl hydrotetraoxide [23594-84-5] as a very labile intermediate in the reaction of methylperoxy radical, , and hydroperoxy radical, OOH (63). 

Commercially available MEKP formulations are mixtures of the dihydroperoxide (1), where X = OOH R = H, R = methyl, and R = ethyl (2,2-dihydroperoxybutane [2625-67 ]) and dialkyl peroxide (2), where X = OOH, Y = OOH, R = methyl, and R = ethyl (di(2-hydroperoxy-2-butyl) peroxide [126-76-1J). These formulations are widely used as free-radical initiators in the metal-promoted cure of unsaturated polyester resins at about 20°C. 

The reaction rate of fumarate polyester polymers with styrene is 20 times that of similar maleate polymers. Commercial phthaHc and isophthaHc resins usually have fumarate levels in excess of 95% and demonstrate full hardness and property development when catalyzed and cured. The addition polymerization reaction between the fumarate polyester polymer and styrene monomer is initiated by free-radical catalysts, commercially usually benzoyl peroxide (BPO) and methyl ethyl ketone peroxide (MEKP), which can be dissociated by heat or redox metal activators into peroxy and hydroperoxy free radicals. 

Bis-hydroperoxy diisopropylidene peroxide Barium methyl peroxide... 

Hydroperoxy-2-methyl- 570 2-Hydroperoxy-2-phenyl- 570, 680 2-Hydroximino- 376, 613 2-Hydroximino-l-aryl- 379f 2-Hydroximino-l.3-diaryl- 379f. 

Dimethyl peroxide Diethyl peroxide Di-t-butyl-di-peroxyphthalate Difuroyl peroxide Dibenzoyl peroxide Dimeric ethylidene peroxide Dimeric acetone peroxide Dimeric cyclohexanone peroxide Diozonide of phorone Dimethyl ketone peroxide Ethyl hydroperoxide Ethylene ozonide Hydroxymethyl methyl peroxide Hydroxymethyl hydroperoxide 1-Hydroxyethyl ethyl peroxide 1 -Hydroperoxy-1 -acetoxycyclodecan-6-one Isopropyl percarbonate Isopropyl hydroperoxide Methyl ethyl ketone peroxide Methyl hydroperoxide Methyl ethyl peroxide Monoperoxy succinic acid Nonanoyl peroxide (75% hydrocarbon solution) 1-Naphthoyl peroxide Oxalic acid ester of t-butyl hydroperoxide Ozonide of maleic anhydride Phenylhydrazone hydroperoxide Polymeric butadiene peroxide Polymeric isoprene peroxide Polymeric dimethylbutadiene peroxide Polymeric peroxides of methacrylic acid esters and styrene... 

Additional hypotheses concerning prostaglandin biosynthesis in P. homomalla resulted from isolation of 11R-HETE (76) from the polar lipid fraction [95]. Apparently, 11R-HETE (76) is also a minor product of incubations of arachidonic acid with acetone powder preparations of P. homomalla [95], In this alternate hypothesis (Scheme 8), an 11-hydroxy or 11-hydroperoxy-8,9-allene oxide intermediate is formed from a sequence of oxidations at C8 and Cll. Opening of the allene oxide to a transient C8 earboeation induces eycli-zation with a consequent addition of water to C15. This proposed pathway leads initially to formation of PGE2 (16 or 38), which following acetylation, elimination of acetic acid from Cl 1-12, and esterification, forms the observed major natural product in the coral, 15-acetoxy methyl PGA2 (36 or 54). Notably, if... 

Bis(2-hydroperoxy-4-methyl-2-pentyl) peroxide, 3566 1,2- or l,4-Bis(2-hydroperoxy-2-propyl)benzene, 3542... 

Bis(2-hydroperoxy-4-methyl-2-pentyl) peroxide, 3566 2-(4-Bromophenyl)-2-propyl l-( 1,1-dimethyl-2-pentyn-4-enyl) peroxide, 3709 2-(4-Chlorophenyl)-2-propyl l-( 1,1-dimethyl-2-pentyn-4-enyl) peroxide, 3711... 

The methyl radical rapidly (in 10 s) combines with oxygen to form the methylperoxy radical, CH3O3. A recent study has confirmed that nitric oxide is oxidized by methylperoxy, although the rate constant is still unknown. The meffioxy radical, CH3O, should then react predominantly with oxygen to form formaldehyde, CHjO, and hydroperoxy radical. The net result of this sequence is the oxidation of one molecule of nitric oxide to nitrogen dioxide and the conversion of an alkyl radical into a hydro-... 

A molecular entity having an unpaired electron. Free radicals are usually short-hved and are highly reactive. Examples include methyl radical ( CH3), hydroxyl radical ( OH), nitric oxide (NO ), hydroperoxy radical (HOO ), and the sodium atom (Na). Note that, since there is at least one unpaired electron, a free radical has... 

Dihydro-6-hydroperoxy-5-hydroxy-5-methyl-2,4(li/,3 )- pyiimidinedione (FUFDIT) 1.451 1.394 105.8 86... 

Methyl 2-(2-hydroperoxy-2,4,4-triphenyl-3-oxetanyhdene)acetate (MIWPEN) 1.471 1.400 11.8 100... 

The three solid phase tetralin and decalin hydroperoxides have enthalpies of reaction that are surprisingly comparable, —93.9 6.4 kJmoR, despite the sometimes large error bars associated with either the peroxide or corresponding alcohol and their differences in structure. Notably, the gas phase reaction enthalpy for the cumyl hydroperoxide is nearly identical to the solid phase reaction enthalpy for the 1-methyl-1-tetralin hydroperoxide, —87.0kJmoR, for these structurally similar compounds and supports the hypothesis that the gas and condensed phase formal reaction enthalpies are nearly the same for all compounds. Flowever, for 2,5-dimethylhexane-2,5-dihydroperoxide, the enthalpies of reaction 5 per hydroperoxy group for the solid and gaseous phase are not close —57 and —76 kJmoR, respectively. Compare them with the enthalpies of reaction for ferf-butyl hydroperoxide of —66 (Iq) and —67 or —78 (g) kJmoR. For the unsaturated counterpart, 2,5-dimethylhex-3-yne-2,5-dihydroperoxide, the solid and gas phase enthalpies of reaction per hydroperoxy group are —64.2 kJmoR and —74.6 kJmoR, respectively. 

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