Benzoyl, determination

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. 

Several triazinyl ketones isomerize to 4-acetamidopyrimidines. TTiis is seen in the C-acylation of 2,4,6-trimethyl-l,3,5-triazine (708) with benzoyl chloride in the presence of sodium amide to give the ketone (709) which undergoes a Dimroth-like rearrangement in boiling water to afford A-(2-methyl-6-phenylpyrimidin-4-yl)acetamide (710) it can be seen that the acylating agent determines the identity of the 6-substituent 64JHC145). 

The reactivities of benzoyltrimethylhydrazine (428) and l-benzoyl-2-methylpyrazoline (429) towards methyl iodide have been discussed in connection with the corresponding geometries determined by X-ray crystallography (81JOC2490). 

Steric fectors clearly enter into determining the ortho para ratio. The hindered 2,4,6-trimethylbenzoyl group is introduced with a 50 1 preference for the para position. Similarly, in the benzoylation of alkylbenzenes by benzoyl chloride-aluminum chloride, the amount of ortho product decreases (10.3%, 6.0%, 3.1%, 0.6%, respectively) as the branching of the alkyl group is increased along the series methyl, ethyl, i-propyl, t-butyl. ... 

Oxidation of ecgonine (2) by means of chromium trioxide was found to afford a keto acid (3). This was formulated as shown based on the fact that the compound undergoes ready themnal decarboxylation to tropinone (4)The latter had been obtained earlier from degradative studies in connection with the structural determination of atropine (5) and its structure established independently. Confirmation for the structure came from the finding that carbonation of the enolate of tropinone does in fact lead back to ecgonine. Reduction, esterification with methanol followed by benzoylation then affords cocaine. 

The polymerization of vinyl monomers on the surface of silica can be induced also by free radical initiators such as azo-bis-isobutyronitrile (AIBN), di-tert-butylperoxide, benzoyl peroxide etc. The selection of initiator type and method of its introduction in polymerizable systems are determined by the nature of monomers and tasks of investigations. Usually, the following procedures are used ... 

Yamase and Goto406 determined first- and second-order rate coefficients for the aluminium chloride-catalysed reaction of halide derivatives of benzoic acid (lO5 = F, 1.73 Cl, 4.49 Br, 4.35 I, 0.81) and phenylacetic acid (105fc2 = F, 12 Cl, 21 Br, 9 I, 6) with benzene. The maxima in the rates for the acid chloride are best accommodated by the assumption that a highly (but not completely) polarised complex takes part in the transition state. Polarisation of such a complex would be aided by electron supply, and consistently, the acetyl halides are about a hundred times as reactive as the benzoyl compounds (see p. 180, also Tables 105 and 108). 

Subsequently rates of benzoylation of a range of aromatics were determined under the same conditions (Table 105)407. The high negative entropy of activation is consistent with the high degree of ordering required for the polarised acyl chloride-aluminium chloride complex to be the electrophile. 

The use of ethylene dichloride as solvent was extended by Brown et al. 11 to the determination of the kinetics of benzoylation of other aromatics, using benzoyl chloride catalysed by aluminium chloride, and the data are included in Table 109 the relative reactivities are thus benzene, 1.0 toluene, 117 o-xylene, 1,393 m-xylene, 3,960 and p-xylene, 243 and these values are closely similar to those obtained with nitrobenzene as solvent. No exact comparison of the coefficients with those of Corriu et al. 16 is possible because of the different temperatures employed, but the rates appear to be comparable for the two sets of data after allowing for reasonable temperature dependencies. 

The greater steric hindrance to acetylation was also shown by a comparison of the rate of (103At2) of acetylation of toluene (0.763), ethylbenzene (0.660), i-propylbenzene (0.606) and f-butylbenzene (0.462) with those (determined by the competition method) for benzoylation both sets of data (Table 112) were obtained with dichloroethane as solvent at 25 °C, all reagent concentrations being 0.1 A/421. Relative rates of acylation other aromatics under the same conditions have also been obtained and are given in Table 113422. The different steric requirements for acetylation and benzoylation are further shown by the following respective relative rates for acylation of naphthalene derivatives in chloroform at 0 °C naphthalene (1 position) 1.00,1.00, (2 position) 0.31,0.04 2,3-dimethylnaphthalene (1 position) 1.59, 172, (5 position) 7.14, 38.2, (6 position) 3.68, 7.7422a. 

If the rate constant kd for spontaneous decomposition of the initiator is known, the efficiency / of initiation may be determined. (This is a refinement of the molecular weight method set forth in Sec. Ic) The spontaneous decomposition rate of benzoyl peroxide in styrene, according to the work of Swain, Stockmayer, and Clarke is 3.2X10- sec. at 60°C. Hence the efficiency of initiation of the polymerization of styrene by benzoyl peroxide at 60°C is indicated to be about 0.60. 

Polymer extracts are frequently examined using GC-MS. Pierre and van Bree [257] have identified nonylphenol from the antioxidant TNPP, a hindered bisphenol antioxidant, the plasticiser DOP, and two peroxide catalyst residues (cumol and 2-phenyl-2-propanol) from an ABS terpolymer extract. Tetramethylsuccino-dinitrile (TMSDN) has been determined quantitatively using specific-ion GC-MS in extracts of polymers prepared using azobisisobutyronitrile TMSDN is highly volatile. Peroxides (e.g. benzoyl or lauroylperoxide) produce acids as residues which may be detected by MS by methylation of the evaporated extract prior to GC-MS examination [258]. GC-MS techniques are... 

However, the reaction rate is not uniform. The maximum reaction rate must be known to calculate the area needed for heat exchange. This can and should be determined in a laboratory. For the suspension polymerization of polystyrene at 80°C using 0.5% benzoyl peroxide in an inert atmosphere, the reaction takes 4.5 hr to reach completion and the maximum conversion rate is 20% in 0.5 hr.24 Although... 

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