Hydrolysis hydroperoxide

Obtained synthetically by one of the following processes fusion of sodium ben-zenesulphonate with NaOH to give sodium phenate hydrolysis of chlorobenzene by dilute NaOH at 400 C and 300atm. to give sodium phenate (Dow process) catalytic vapour-phase reaction of steam and chlorobenzene at 500°C (Raschig process) direct oxidation of cumene (isopropylbenzene) to the hydroperoxide, followed by acid cleavage lo propanone and phenol catalytic liquid-phase oxidation of toluene to benzoic acid and then phenol. Where the phenate is formed, phenol is liberated by acidification. 

Many organic peroxides of metals have been hydrolyzed to alkyl hydroperoxides. The alkylperoxy derivatives of aluminum, antimony, arsenic, boron, cadmium, germanium, lead, magnesium, phosphoms, silicon, tin, and zinc yield alkyl hydroperoxides upon hydrolysis (10,33,60,61). 

Acidic hydrolysis of these hydroxyaLkyl hydroperoxides yields carboxyUc acids, whereas basic hydrolysis regenerates the parent aldehyde, hydrogen peroxide, and often other products. When derived from either aldehydes or cycHc ketones, peroxides (1, X = OH, = H, R, = alkylene or... 

The kinetics of formation and hydrolysis of /-C H OCl have been investigated (262). The chemistry of alkyl hypochlorites, /-C H OCl in particular, has been extensively explored (247). /-Butyl hypochlorite reacts with a variety of olefins via a photoinduced radical chain process to give good yields of aUyflc chlorides (263). Steroid alcohols can be oxidized and chlorinated with /-C H OCl to give good yields of ketosteroids and chlorosteroids (264) (see Steroids). /-Butyl hypochlorite is a more satisfactory reagent than HOCl for /V-chlorination of amines (265). Sulfides are oxidized in excellent yields to sulfoxides without concomitant formation of sulfones (266). 2-Amino-1, 4-quinones are rapidly chlorinated at room temperature chlorination occurs specifically at the position adjacent to the amino group (267). Anhydropenicillin is converted almost quantitatively to its 6-methoxy derivative by /-C H OCl in methanol (268). Reaction of unsaturated hydroperoxides with /-C H OCl provides monocyclic and bicycHc chloroalkyl 1,2-dioxolanes. 

Caiboo-oxygen bonds can be made using the synthetically uninteresting conversion of RMgX into ROH (shown as the firat reacdoo listed above) direct acid hydrolysis of the petxuto compound ROOMgX yields the hydroperoxide ROOM. Caibon-sulfiir bonds can be constructed using Ss to make thiols or thioethers, and similar reacdons are known for Se and Te ... 

The Dakin reaction proceeds by a mechanism analogous to that of the Baeyer-Villiger reaction. An aromatic aldehyde or ketone that is activated by a hydroxy group in the ortho or para position, e.g. salicylic aldehyde 12 (2-hydroxybenzaldehyde), reacts with hydroperoxides or alkaline hydrogen peroxide. Upon hydrolysis of the rearrangement product 13 a dihydroxybenzene, e.g. catechol 14, is obtained ... 

The last step is hydrolysis of the unstable hemiacetal. Alkoxycarbocation intermediates (73, R=alkyl) have been isolated in superacid solution at low temperatures, and their structures proved by The protonated hydroperoxides... 

Extensive studies in vitro from many groups have confirmed that exposure of LDL to a variety of pro-oxidant systems, both cell-free and cell-mediated, results in the formation of lipid hydroperoxides and peroxidation products, fragmentation of apoprotein Bioo, hydrolysis of phospholipids, oxidation of cholesterol and cholesterylesters, formation of oxysterols, preceded by consumption of a-tocopherol and accompanied by consumption of 8-carotene, the minor carotenoids and 7-tocopherol. 

R-HETE is a very potent and selective inducer of oocyte maturation [196, 199]. 8S-HETE does not show this activity. The allene oxide hydrolysis products and the hydroperoxide lyase products were not active in promoting oocyte maturation [200]. 

Alternatively the allylic hydroperoxide can undergo the so called Hock-type fragmentation621 under acid-catalyzed hydrolysis with formation of two carbonyl compounds (or moieties). The sesquiterpene (—)-geijerone has been obtained from the triene (+)-y-elemene by such a sequence (6.15) 622>. 

Acids catalyze the hydrolysis of hydroperoxides with hydrogen peroxide formation. 

Acids are well known as efficient catalysts of various heterolytic reactions (hydrolysis, esterification, enolyzation, etc. [225,226]). They catalyze the heterolytic decay of hydroperoxides formed during oxidation. For example, they catalyze the decomposition of cumyl hydroperoxide into phenol and acetone (important technological reaction) [5]. 

Hydrolysis of formed hydroperoxide and exchange reaction with H02 formation ... 

Once aryl phosphite has oxidized into phosphate followed by the catalytic decomposition of hydroperoxide [6,10,19,20], The catalyst is obviously stable, since additional hydroperoxide introduced into the system immediately breaks down [10]. Repeatedly, ROOH decomposes via the acid-catalyzed reaction with the products of phosphate hydrolysis acting as catalysts [6,10],... 

A broad spectrum of chemical reactions can be catalyzed by enzymes Hydrolysis, esterification, isomerization, addition and elimination, alkylation and dealkylation, halogenation and dehalogenation, and oxidation and reduction. The last reactions are catalyzed by redox enzymes, which are classified as oxidoreductases and divided into four categories according to the oxidant they utilize and the reactions they catalyze 1) dehydrogenases (reductases), 2) oxidases, 3) oxygenases (mono- and dioxygenases), and 4) peroxidases. The latter enzymes have received extensive attention in the last years as bio catalysts for synthetic applications. Peroxidases catalyze the oxidation of aromatic compounds, oxidation of heteroatom compounds, epoxidation, and the enantio-selective reduction of racemic hydroperoxides. In this article, a short overview... 

---