Benzoyl peroxid

Such reactions can be initiated by free radicals, derived from compounds (initiators) such as benzoyl peroxide, ammonium persulphate or azobis-isobutyronitrile or by ionic mechanisms... 

Such a mechanism is supported by the fact that the reaction is accelerated by benzoyl peroxide and other radical-producing agents. It is now however considered that the function of the A -bromosuceinimide is to provide a constant, very low concentration of molecular bromine (Tedder et al,). 

Perbenzoic acid. Treatment of a cold sodium methoxide solution with a solution of pure benzoyl peroxide in chloroform affords methyl benzoate and a solution of the sodium salt of perbenzoic acid ... 

To determine the exact peroxide content of benzoyl peroxide (and of other organic peroxides) the following procedure may be employed. Place about 0 05 g. of the sample of peroxide in a glass-stoppered conical flask add 5-10 ml. of acetic anhydride (A.R. or other pure grade) and 1 g. of powdered sodium iodide. Swirl the mixture to dissolve the sodium iodide and allow the solution to stand for 5-20 minutes. Add 50-75 ml. of water, shake the mixture vigorously for about 30 seconds, and titrate the liberated iodine with standard sodium thiosulphate solution using starch as indicator. 

It is essential to use freshly recrystallised benzoyl peroxide. The commercial material usually gives poor results. Commercial benzoyl peroxide may bo recrystal, lised from a small amount of hot chloroform, or by dissolving in chloroform and precipitating with absolute methyl alcohol. 

The m.p. is not always a safe criterion of purity. Benzoyl peroxide may be analysed as follows -. Dissolve about 0-6 g., accurately weighed, of benzoyl peroxide in Is ml. of chloroform in a 350 ml. conical flask. Cool to — 5°, and add 25 ml. of 0- IN sodium methoxide solution at once with cooling and shaking. After 5 minutes at — 5°, add 100 ml. of iced water, 5 ml. of 10 per cent, sulphuric acid, and 2 g. of potassium iodide in 20 ml. of 10 per cent, sulphuric acid in the order mentioned with vigorous stirring. Titrate the liberated iodine with standard 0-lN sodium thiosulphate solution. 

Place 10 g. of hquid methyl methacrylate in a test-tube, add 10-20 mg. of benzoyl peroxide (Section IV, 196), stopper the test-tube loosely and heat in a boiling water bath. After 20-25 minutes, the hquid suddenly becomes very viscous and soon sets to a hard, colourless mass of the polymer. 

Heat 20 g. of styrene (Section IX,6) with 0 -2 g. of benzoyl peroxide (Section IV,196) on a water bath for 60-90 minutes. A glass-bke polymer (polystyrene) is produced. The polymer is soluble in benzene and in dioxan and can be precipitated from its solution by alcohol. 

They do, however, react readily, even in the dark, with sulphuryl chloride in the preaenoe of a trace of benzoyl peroxide as a catalyst (compare Section 1V,22). 

These results show that in the phenylation of thiazole with benzoyl peroxide two secondary reactions enter in competition the attack of thiazole by benzoyloxy radicals, leading to a mixture of thiazolyl benzoates, and the formation of dithiazolyle through attack of thiazole by the thiazolyl radicals resulting from hydrogen abstraction on the substrate and from the dimerization of these radicals. This last reaction is less important than in the case of thiophene but more important than in the case of pyridine (398). 

TABLE 1-56. TYPICAL PRODUCT DISTRIBUTION OF THE DECOMPOSITION AT 100°C OF BENZOYL PEROXIDE (0.02 MOLE) IN THIAZOLE (I MOLE) (397)... 

Benzoyl peroxide has been the most common source of phenyl radicals. But in reaction with thiazoles the benzoyloxy radical abstracts a hydrogen atom from the thiazole nucleus or from a methyl group in the case of methylthiazoles, giving by-products such as dithiazolyls or 2.2 -dithiazolylethane (183). The results obtained with benzoyl peroxide are summarized in Tables III-23, III-24. and III-25. 

TABLE irr-23. PHENYLATION OF THIAZOLE WITH BENZOYL PEROXIDE (183)... 

Concentration expressed in moles per mole of benzoyl peroxide used. 

TABLE 111-24. PRODUCTS FORMED BY THE DECOMPOSITION OF BENZOYL PEROXIDE IN THIAZOLE, 4-METHYLTHIAZOLE, AND 2.4-DIMETHYLTHIAZOLE WITH A MOLAR RATIO OF AND A REACTION TIME OF 20 hr AT 78°C (184)... 

The quantities of reactants and products are expressed in grams, the figures in parentheses are the yields in mole per mole of benzoyl peroxide. 

TABLE III-25. ACTTION OF BENZOYL PEROXIDE ON 4-METHYLTHlAZOLE AT 80°C UNDER NITROGEN MOLE OF PEROXIDE/MOLE OF THIAZOLE) (184. 185)... 

Benzoyl peroxide is a com monly used free radical ini tiator It has the formula O O... 

Polymerization of styrene is carried out under free radical conditions often with benzoyl peroxide as the initiator Figure 1111 illustrates a step m the growth of a poly styrene chain by a mechanism analogous to that of the polymerization of ethylene (Sec tion 6 21)... 

A certain compound A when treated with N bromosuccinimide and benzoyl peroxide under photochemical conditions in refluxing carbon tetrachloride gave 3 4 5 tnbromobenzyl bromide in excellent yield Deduce the structure of compound A... 

Benzoyl peroxide Direct sunlight, sparks and open flames, shock and friction, acids, alcohols, amines, ethers, reducing agents, polymerization catalysts, metallic naph-thenates... 

Polyethylene cross-linked by irradiation with high-energy electrons. Polysilicones cross-linked by reaction with benzoyl peroxide. 

Figure 6.3 Log-log plots of Rp versus concentration which verify the order of the kinetics with respect to the constituent varied, (a) Monomer (methyl methacrylate) concentration varied at constant initiator concentration. [Data from T. Sugimura and Y. Minoura, J. Polym. Sci. A-l 2735 (1966).] (b) Initiator concentration varied AIBN in methy methacrylate (o), benzoyl peroxide in styrene ( ), and benzoyl peroxide in methyl methacrylate ( ). (From P. J. Flory, Principles of Polymer Chemistry, copyright 1953 by Cornell University, used with permission.)...

Chlorine Benzoyl peroxide L-Ascorbic acid L-Cysteine... 

---