Hydrogen peroxide cyclohexanone

Certain ketones, eg, cyclohexanone, react with hydrogen peroxide in the presence of ammonia, yielding 1,2,4-dioxazohdines (159) ... 

The spiro peroxide A, which is readily prepared from cyclohexanone and hydrogen peroxide, decomposes thermally to give substantial amounts of cyclodecane (B) and... 

The preparation of Pans-1,2-cyclohexanediol by oxidation of cyclohexene with peroxyformic acid and subsequent hydrolysis of the diol monoformate has been described, and other methods for the preparation of both cis- and trans-l,2-cyclohexanediols were cited. Subsequently the trans diol has been prepared by oxidation of cyclohexene with various peroxy acids, with hydrogen peroxide and selenium dioxide, and with iodine and silver acetate by the Prevost reaction. Alternative methods for preparing the trans isomer are hydroboration of various enol derivatives of cyclohexanone and reduction of Pans-2-cyclohexen-l-ol epoxide with lithium aluminum hydride. cis-1,2-Cyclohexanediol has been prepared by cis hydroxylation of cyclohexene with various reagents or catalysts derived from osmium tetroxide, by solvolysis of Pans-2-halocyclohexanol esters in a manner similar to the Woodward-Prevost reaction, by reduction of cis-2-cyclohexen-l-ol epoxide with lithium aluminum hydride, and by oxymercuration of 2-cyclohexen-l-ol with mercury(II) trifluoro-acetate in the presence of ehloral and subsequent reduction. ... 

New materials are also finding application in the area of catalysis reiated to the Chemicals industry. For example, microporous [10] materials which have titanium incorporated into the framework structure (e.g. so-calied TS-1) show selective oxidation behaviour with aqueous hydrogen peroxide as oxidizing agent (Figure 5). Two processes based on these new catalytic materials have now been developed and commercialized by ENl. These include the selective oxidation of phenol to catechol and hydroquinone and the ammoxidation of cyclohexanone to e-caproiactam. 

The effect of the nitric acid/hydrogen peroxide mixture on acetone when it is hot gives rise to an explosive oxidation, especially when the medium is confined. This situation also applies to a large number of ketones, and in particular, cyclic ketones. Cyclic di- and triperoxides form compounds that detonate, if there is no strict and very delicate thermal control. Accidents have been reported with butanone, 3-pentanone, cyclopentanone, cyclohexanone and methylcyclo-hexanones. 

This appears to be a main constituent of commercial cyclohexanone peroxide together with the bis(hydroperoxy) peroxide (below), and is also known to be hazardous [1], Prepared from cyclohexanone and 30% hydrogen peroxide in presence of hydrochloric acid catalyst, it must be kept moist after isolation as it may explode on drying out [2],... 

Ketones play an important role in the decomposition of peroxides to form radicals in alcohols undergoing oxidation. The formed hydroxyhydroperoxide decomposes to form radicals more rapidly than hydrogen peroxide. With an increase in the ketone concentration, there is an increase in the proportion of peroxide in the form of hydroxyhydroperoxide, with the corresponding increase in the rate of formation of radicals. This was proved by the acceptor radical method in the cyclohexanol-cyclohexanone-hydrogen peroxide system [59], The equilibrium constant was found to be K — 0.10 L mol 1 (373 K), 0.11 L mol 1 (383 K), and 0.12 L mol 1 (393 K). The rate constant of free radical generation results in the formation of cyclohexylhydroxy hydroperoxide decomposition and was found to be ki = 2.2 x 104 exp(—67.8/7 7) s 1 [59]. 

Copper(II) sulfate Cumene hydroperoxide Cyanides Cyclohexanol Cyclohexanone Decaborane-14 Diazomethane 1,1-Dichloroethylene Dimethylformamide Hydroxylamine, magnesium Acids (inorganic or organic) Acids, water or steam, fluorine, magnesium, nitric acid and nitrates, nitrites Oxidants Hydrogen peroxide, nitric acid Dimethyl sulfoxide, ethers, halocarbons Alkali metals, calcium sulfate Air, chlorotrifluoroethylene, ozone, perchloryl fluoride Halocarbons, inorganic and organic nitrates, bromine, chromium(VI) oxide, aluminum trimethyl, phosphorus trioxide... 

Acyl nitroso compounds (3, Scheme 7.2) contain a nitroso group (-N=0) directly attached to a carbonyl carbon. Oxidation of an N-acyl hydroxylamine derivative provides the most direct method for the preparation of acyl C-nitroso compounds [10]. Treatment of hydroxamic acids, N-hydroxy carbamates or N-hydroxyureas with sodium periodate or tetra-alkyl ammonium periodate salts results in the formation of the corresponding acyl nitroso species (Scheme 7.2) [11-14]. Other oxidants including the Dess-Martin periodinane and both ruthenium (II) and iridium (I) based species efficiently convert N-acyl hydroxylamines to the corresponding acyl nitroso compounds [15-18]. The Swern oxidation also provides a useful alternative procedure for the oxidative preparation of acyl nitroso species [19]. Horseradish peroxidase (HRP) catalyzed oxidation of N-hydroxyurea with hydrogen peroxide forms an acyl nitroso species, which can be trapped with 1, 3-cyclohexanone, giving evidence of the formation of these species with enzymatic oxidants [20]. 

Methylenecyclohexane oxide has been prepared by the oxidation of methylenecyclohexane with benzonitrile-hydrogen peroxide or with peracetic acid by treatment of 1-chlorocyclo-hexylmethanol with aqueous potassium hydroxide and by the reaction of dimethylsulfonium methylide with cyclohexanone. This reaction illustrates a general method for the conversion of ketones and aldehydes into oxiranes using the methylene-transfer reagent dimethyloxosulfonium methylide. The yields of oxiranes are usually high, and the crude products, in most cases, are of sufficient purity to be used in subsequent reactions (e.g., rearrangement to aldehydes) without further purification. 

O3yhydroperoxides. Peroxides of the oxyhydro type are obtained by the addition of hydrogen peroxide to ketones. High yields of alkyl radicals are then often obtained by reaction with ferrous salts. 1-Meth-oxycyclohexyl hydroperoxide is easily obtained from cyclohexanone and hydrogen peroxide in methanol. It gives rise to the 5-(methoxy-carbonyl)-pentyl radical, which has been used to alkylate protonated heteroaromatic bases in high yield [Eq. (6)]. 

In 2003, Velusamy and Punniyamurthy reported on a copper(II)-catalyzed C—H oxidation of alkylbenzenes and cyclohexane to the corresponding ketones with 30% hydrogen peroxide (Scheme 131). The reaction was catalyzed by the copper complex 192a depicted in Scheme 131 and yields were high in the case of alkylbenzenes (82-89%) whereas cyclohexanone was obtained with a low yield of 18%. Chemoselectivity was very high in every case neither aromatic oxidation nor oxidation at another position of the alkyl chain was observed. 

The selective oxidation of saturated hydrocarbons is a reaction of high industrial importance. Besides a variety of other oxidants, hydrogen peroxide as a very clean oxidant has also been used for these purposes . As an example, in 1989 Moiseev and coworkers reported on the vanadium(V)-catalyzed oxidation of cyclohexane with hydrogen peroxide (Scheme 146) . When the reaction was carried out in acetic acid cyclohexanol and cyclohexanone were formed, bnt conversions were very poor and did not exceed 13%. Employing CF3COOH as solvent, complete conversions could be obtained within 5 min-ntes. Here, cyclohexyl trifluoroacetate was the main product (85% of the products formed) resulting from the reaction of cyclohexanol (the primary product of the oxidation) with CF3COOH. 

In 2001, Albrecht Berkessel and Nadine Vogl reported on the Baeyer-Villiger oxidation with hydrogen peroxide in 1,1,1,3,3,3-hexafluoroisopropanol (HFIP) as solvent in the presence of Brpnsted acid catalysts such as para-toluenesulfonic acid (equation 85) . Under these conditions cyclohexanone could be selectively transformed into the corresponding lactone within 40 min at 60 °C with a yield of 92%. Mechanistic investigations of Berkessel and coworkers revealed that this reaction in HFIP proceeds by a new mechanism, via spiro-bisperoxide 234 as intermediate, which then rearranges to form the lactone. The study illustrates the importance of HFIP as solvent for the reaction, which presumably allows the cationic rearrangement of the tetroxane intermediates. 

The process starts from tricyclohexylidene triperoxide which is obtained by oxidation of cyclohexanone with hydrogen peroxide. Pyrolysis leads to a mixture of 1,16-hexadecanolide and cyclopentadecane. The latter is oxidized by oxygen under boric acid catalysis to cyclopentadecanol which is subsequently oxidized to cyclopentadecanone [124,124a]. 

Cyclohexanone Peroxide. The compn of peroxides obtd from the interaction of cyclohexanone other cyclic ketones with hydrogen peroxides has been a controversial matter. Milas (Ref 3) claimed to have obtd from an ethereal soln of H202 cyclohexanone ... 

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