Peroxybenzoic acid

Volatile solid with a pungent odor sublimes mp 41-43 C (105.8-109 E) bp 100-105T (212-221 °E) at 15 torr (partially decomposes) slightly soluble in water but mixes readily with most organic solvents. 

The toxicity of peroxybenzoic acid is very low on animals. In humans it is almost nontoxic. Peroxybenzoic acid caused skin tumor in mice on prolonged contact (NIOSH 

Its tumorigenic action was lower than that of peroxyacetic acid. Its carcinogenicity in humans is unknown. 

Peroxy linkage between benzoyl group and hydrogen 

Peroxybenzoic acid is used in organic analyses to measure the degree of unsaturation, and in making epoxides. 

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Using Figure 17 15 as a guide write a mechanism for the ] Baeyer-Villiger oxidation of cyclohexyl methyl ketone by peroxybenzoic acid J... 

It is possible to introduce this group selectively onto a primary alcohol in the presence of a secondary alcohol. The derivative is stable to KMn04, w-chloro-peroxybenzoic acid, LiAlH4, and Cr03 Pyr. Since this derivative is similar to the p-methoxyphenyl ether it should also be possible to remove it oxidatively. The GUM ethers are less stable than the MEM ethers in acid but have stability comparable to that of tlie SEM ethers. It is possible to remove the GUM ether in the presence of a MEM ether. 

Substituted peroxybenzoic acids are used for epoxidation of tnfluorovinyl alkenes with attached functional groups [7] (equation 5)... 

Benzo persaure,/. peroxybenzoic acid, perben-zoic acid. phenol, n, phenol (CaHeOH), schwarzblau, n, benzo black-blue, benzoylieren, v.t. benzoylate, introduce benzoyl into. 

Per-aciditat, /. superaeidity. -ameisensaure, /. performic (peroxyformie) acid, -benzoe-s ure, /. perbenzoic (peroxybenzoic) acid, -borsaure, /. perboric acid, -bromsiure, /. perbromic acid, -buttersaure, /. perbutyrie (peroxybutyric) acid. 

Free radical initiators can polymerize olefmic compounds. These chemical compounds have a weak covalent bond that breaks easily into two free radicals when subjected to heat. Peroxides, hydroperoxides and azo compounds are commonly used. For example, heating peroxybenzoic acid forms two free radicals, which can initiate the polymerization reaction ... 

Problem 7,14 What product would you expect from reaction of ds-2-butene with uieftt-chloro-peroxybenzoic acid Show the stereochemistry. 

Peroxybenzoic Acid Diester with Bis(1-Hydroxy-cyclohsxy ) Peroxide. See 1,1 -Bis (bsn.zovl-peroxy)-dicyclohexylperoxide in Vol 2, B135-L... 

Peroxybenzoic Acid Diester with Bi (9-Hydroxy 9-Fluorenyl) Peroxide. See 9,9 -Bis (Benzoyl-peroxy fluorenyl)-peroxide in Vol 2, B136-L... 

Peroxybenzoic Acid,- 9-Fluorenylidene Ester. See 9,9, -Bis(Benzoylperoxy)-F luorene in Vol 2, B135-R... 

The reactions of arenediazonium ions with 7V-alkyl- or 7V-arylhydroxylamines were investigated by Bamberger (1920b, and earlier papers). Mitsuhashi et al. (1965) showed that the l,3-diaryl-3-hydroxytriazenes are tautomeric with 1,3-diaryltriazene-3-oxides (Scheme 6-16). Oxidation of 1,3-diaryltriazenes with peroxybenzoic acid in ether yields the same product as that from diazonium salts and TV-arylhydroxyl-amine. The infrared spectrum of the product obtained by coupling diazotized relabeled aniline with A/-phenylhydroxylamine indicates that the diaryltriazene-oxide is the preponderant tautomer. 

Another example of substrate titration arises when peroxybenzoic acid decomposes,15... 

The pH profile for the decomposition of peroxybenzoic acid in aqueous solution at 25°C. Data are from Ref. 15. 

The solution is stirred for an additional 2 hours and is then cooled to 15°. Fifty grams of chopped ice and 75 ml. of ice-cold saturated ammonium sulfate solution are cautiously added in sequence while the temperature is maintained below 25° during the dilution (Note 4). The contents of the beaker are transferred to a separatory funnel, and the peroxybenzoic acid solution is... 

Dilution of the methanesulfonic acid is exothermic. Since peroxybenzoic acid has an appreciable solubility in aqueous methanesulfonic acid, dilution and washing are conducted with minimal quantities of saturated ammonium sulfate solution. 

In the first extraction, 90% of the available peroxybenzoic acid is extracted. The second extraction removes 7%, and the. third 2%. The first benzene extract is an approximately 40% solution of peroxybenzoic acid (2.8il/). 

A 1-ml. or 2-ml. aliquot of the benzene solution of peroxybenzoic acid is pipetted into an iodine flask, the walls of the flask are rinsed with a small quantity of chloroform, and 15 ml. of... 

The analytical method described is also used in following the consumption of peroxybenzoic acid or other peroxy acids during an oxidation reaction it has also been used in determining the conversion of other carboxylic acids to peroxy acids when solvent extraction has been used in the isolation. 

Numerous methods of preparing peroxy acids are described in the literature,2 3 and many of them have been applied to the synthesis of peroxybenzoic acid. A common way of preparing it has been by the action of sodium methoxide on benzoyl peroxide followed by acidification.3 The present method is adapted from one in a recent publication.4... 

The present procedure for peroxybenzoic acid is easier and more reliable than earlier ones. Thus that in an earlier volume of Organic Syntheses3 has been found by the submitters to be difficult to reproduce, and yields are frequently low. The modified procedure of Kolthoff, Lee, and Mairs 5 is an improvement, but it is tedious and indirect. 

Malonic acid, amino-, diethyl ester, HYDROCHLORIDE, 40, 24 Malonic acid, bts(hydroxymethyl)-, DIETHYL ETHER, 40, 27 Malonitrile, condensation with tetra-cyanoethylene, 41, 99 2-Mercaptopyrimidine, 43, 6S hydrochloride of, 43, 68 Mercuric oxide in preparation of bromo-cyclopropane, 43, 9 Mesityl isocyanide, 41,103 5-Methallyl-l,2,3,4,5-pentachlorocyclo-pentadiene, 43, 92 Methane, dimesityl-, 43, 57 Methanesiileinyl chloride, 40, 62 Methanesulfonic acid, solvent for making peroxybenzoic acid from benzoic acid, 43, 93... 

Peroxides, test for, 41, 92 Peroxy acids from carboxylic acids and 70% hydrogen peroxide, 43, 96 Peroxybenzoic acid, 43,93 iodometric analysis of, 43, 94 Peroxystearic acid, 43,96 Phenacylamine hydrochloride, 41, 82... 

Peroxybenzoic acid readily oxidizes aryl and alkyl sulphoxides in acetone, methylene chloride or chloroform solutions, to the sulphone in high yield . The reaction is second order and acid catalysed as is the reaction with peracetic acid . The rate of oxidation is about five times faster than when peracetic acid is used. Other work considering the oxidation of sulphoxides with peracids gathered kinetic evidence and showed that the reaction was indeed second order and that the reaction involved nucleophilic attack by the sulphoxide sulphur atom on the peracid moiety. A further study by the same authors showed that with benzyl and phenyl alkyl sulphoxides the rate of reaction was very sensitive to the inductive effect of the alkyl group. Support for the nucleophilic attack by the sulphur atom on the peracid in acidic solution was forthcoming from other sources . ... 

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