Benzoyl peroxide reaction with alcohols

It lias also been suggested that photoexcited benzoyl peroxide is somewhat more susceptible to induced decomposition processes involving electron transfer than the ground state molecule. Rosenthal et c//.15 reported on redox reactions with certain salts (including benzoate ion) and neutral molecules (e.g. alcohols). 

Bartlett and Nozaki [65] discovered the chain reaction of benzoyl peroxide decomposition in the presence of alcohols where the chain propagating step is the reaction of the ketyl radical with peroxide. 

The experimental data on the reactions of ketyl radicals with hydrogen and benzoyl peroxides were analyzed within the framework of IPM [68]. The elementary step was treated as a reaction with the dissociation of the O—H bond of the ketyl radical and formation of the same bond in acid (from acyl peroxide), alcohol (from alkyl peroxide), and water (from hydrogen peroxide). The hydroperoxyl radical also possesses the reducing activity and reacts with hydrogen peroxide by the reaction... 

The only method reported 8 for the preparation of 7-2-butoxy-norbornadiene is that described here. The general reaction of 2-butyl perbenzoate with various olefins has been described by many investigators.8 When benzoyl peroxide is used in place of 2-butyl perbenzoate under similar conditions, 7-benzoxynorbor-nadiene is obtained in 38% yield it is said to be more easily hydrolyzed to the alcohol than 7-2-butoxynorbornadiene.4... 

The methylthiomethyl (MTM) group is a related alcohol-protecting group. There are several methods for introducing the MTM group. Alkylation of an alcoholate by methylthiomethyl chloride is efficient if catalyzed by iodide ion.9 Alcohols are also converted to MTM ethers by reaction with dimethyl sulfoxide in the presence of acetic acid and acetic anhydride10 or with benzoyl peroxide and dimethyl sulfide.11 The latter two methods involve the generation of the methylthiomethylium ion by ionization of an acyloxysulfonium ion (Pummerer reaction). 

Monomer diffusion in the rubbery phase of PVC-rich reaction products is difficult, and this was demonstrated by polymerizing vinyl chloride (200 grams) at 70°C in the presence of a crude polymerizate (360 grams) containing 9% total rubber suspended in an aqueous solution of poly-(vinyl alcohol) (1.2% with respect to the polymer + monomer weight), so as to obtain a ratio of water/crude + monomer = 2.4 and by using benzoyl peroxide (0.38% with respect to the reacting monomer). 

Benzoyl peroxide is sparingly soluble in water and alcohol, but soluble in ether, benzene and chloroform. It can be prepared by reaction of benzoyl chloride with sodium peroxide. 

Manufacture. The monomer of polyvinyl chloride is gas at room temperature and has a boiling point of -13.9°C. The monomer is manufactured in two ways (1) Acetylene and HCl gas are allowed to pass over active carbon and to react with each other at 150 200 C (2) chlorine gas is allov/-ed to react on ethylene to produce C H CI CEDC) at 200 350 C to produce vinyl chloride and HCl gas. These are separated by distillation. The monomer is then polymerized in a pressure vessel the mixture of water and liquid monomer is stirred violently. Benzoyl peroxide is used as a catalyzer and polyvinyl alcohol as a dispersion agent for the reaction. 

The reagent formed by combining PhsP with benzoyl peroxide (BPO) reacts with alcohols to give benzoates in moderate to good yields. The reaction proceeds with essentially complete inversion of the configuration at the secondary carbinol stereocenters. It is noteworthy that 1,2-diols are benzoylated at the secondary hydroxy group in preference to the primary one (Scheme 46). The product ratio is practically the same as that obtained by the DEAD-PhsP procedure. Therefore, as far as benzoylation is concerned, the BPO-PhsP procedure seems attractive because the removal of hydrazine dicarboxylate from the desired product is sometimes troublesome in the DEAD-PhsP procedure. 

Pure benzaldehyde in an atmosphere of pure oxygen at 25° C. oxidizes slowly at first, passing through an induction period, then more rapidly, and finally attains a maximum rate of oxygen absorption. Treatments that serve to shorten the induction period increase the rate of oxygen absorption and vice versa. The addition of benzoyl peroxide increases the rate and the addition of benzoyl alcohol decreases it. - The period of induction has been supposed to correspond to the formation of peroxides which accumulate until the reaction undergoes autoxidation and the rate increases very rapidly. Similar phenomena have been observed with hydrocarbons. 

Extended studies on starch etherification with C2 to C5 aliphatic alkylene oxides in alkaline slurries have been performed 944,945 This reaction was subsequently re-examined for hydroxypropylation.946 No significant effects were observed as a result of using added hydrogen peroxide, benzoyl peroxide, azodiisobutyronitrile, or K2S2O8.945 In all instances, including those studied without such additives, led to water- and alcohol-soluble thermoplastic materials. Further improvements involved etherification in either acetone or butanone in the presence of aqueous NaOH. Ethylene oxide was introduced incrementally.947 Etherification of starch... 

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