Cyclohexanol, decomposition

Riboflavin forms fine yellow to orange-yeUow needles with a bitter taste from 2 N acetic acid, alcohol, water, or pyridine. It melts with decomposition at 278—279°C (darkens at ca 240°C). The solubihty of riboflavin in water is 10—13 mg/100 mL at 25—27.5°C, and in absolute ethanol 4.5 mg/100 mL at 27.5°C it is slightly soluble in amyl alcohol, cyclohexanol, benzyl alcohol, amyl acetate, and phenol, but insoluble in ether, chloroform, acetone, and benzene. It is very soluble in dilute alkah, but these solutions are unstable. Various polymorphic crystalline forms of riboflavin exhibit variations in physical properties. In aqueous nicotinamide solution at pH 5, solubihty increases from 0.1 to 2.5% as the nicotinamide concentration increases from 5 to 50% (9). 

A direct attack on the diazirine ring was observed only by use of almost concentrated sulfuric acid or strong Lewis acids, e.g. aluminum chloride in the case of (208). Some hydrazine was found together with cyclohexanone and cyclohexanol after decomposition of the spirodiazirine (189) with 80% sulfuric acid (B-67MI50800). 

The reaction rates cannot be set as high as intrinsically possible by the kinetics, because otherwise heat removal due to the large reaction enthalpies (500-550 kj mol ) will become a major problem [17, 60, 61]. For this reason, the hydrogen supply is restricted, thereby controlling the reaction rate. Otherwise, decomposition of nitrobenzene or of partially hydrogenated intermediates can occur ]60], The reaction involves various elemental reactions with different intermediates which can react with each other ]60], At short reaction times, the intermediates can be identified, while complete conversion is achieved at long reaction times. The product aniline itself can react further to give side products such as cyclohexanol, cyclohexylamine and other species. 

Let us compare the ratio of radicals in oxidized 2-propanol and cyclohexanol at different temperatures when oxidation occurs with long chains and chain initiation and termination do not influence the stationary state concentration of radicals. The values of the rate constants of the reactions of peroxyl radicals (kp) with alcohol and decomposition of the alkylhydroxy-peroxyl radical (k ) are taken from Table 7.4 and Table 7.5. 

The formation of radicals from hydrogen peroxide in cyclohexanol was measured by the free radical acceptor method [60] the effective rate constant of initiation was found to be equal to ki = 9.0 x 106 exp(—90.3/RT) s 1. For the first-order decomposition of H2O2 in an alcohol medium, the following reactions were discussed. 

In addition to hydroperoxide decomposition by the reaction of the first-order bimolecular decomposition was observed in cyclohexanol at [H202] > 1 M [60], The bimolecular radical generation occurs with the rate constant k 6.8 x 108 exp(—121.7/R7) L mol-1 s-1. The following mechanism was suggested as the most probable. 

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]. 

The reverse micelles stabilized by SDS retard the autoxidation of ethylbenzene [27]. It was proved that the SDS micelles catalyze hydroperoxide decomposition without the formation of free radicals. The introduction of cyclohexanol and cyclohexanone in the system decreases the rate of hydroperoxide decay (ethylbenzene, 363 K, [SDS] = 10 3mol L [cyclohexanol] =0.03 mol L-1, and [cyclohexanone] = 0.01 mol L 1 [27]). Such an effect proves that the decay of MePhCHOOH proceeds in the layer of polar molecules surrounding the micelle. The addition of alcohol or ketone lowers the hydroperoxide concentration in such a layer and, therefore, retards hydroperoxide decomposition. The surfactant AOT apparently creates such a layer around water moleculesthat is very thick and creates difficulties for the penetration of hydroperoxide molecules close to polar water. The phenomenology of micellar catalysis is close to that of heterogeneous catalysis and inhibition (see Chapters 10 and 20). 

The goal here was to find new solid catalysts for cyclohexyl hydroperoxide (chhp) decomposition in cyclohexanol and cyclohexanone. The requirement list had foreseen a study on silica-supported metals of groups 4 and 5 and the need for a heterogeneous catalyst without metal Bxiviation. 

While some phenol is produced by the nucleophilic substitution of chlorine in chlorobenzene by the hydroxyl group (structure 17.17), most is produced by the acidic decomposition of cumene hydroperoxide (structure 17.18) that also gives acetone along with the phenol. Some of the new processes for synthesizing phenol are the dehydrogenation of cyclohexanol, the decarboxylation of benzoic acid, and the hydrogen peroxide hydroxylation of benzene. 

The decarboxylation of decanedioic acid was studied in co-oxidation with cyclohexanol [106]. This reaction was seen to proceed through the attack of radicals (H02 and cyclohexyl-hydroxyperoxyl radical), see Chapter 7) on the C—H bonds of the acid and decomposition of the formed hydroperoxide. It was found that kpl2 = 3.8 x 104 exp(-50.2/7 7 ) L mol-1 s-1 and kd = 1.4 x 1015 exp(—108.8/ ) s The quasistationary concentration of the intermediate hydroperoxide decomposing with the formation of C02 was estimated to be as small as... 

Iron(III) weso-tetraphenylporphyrin chloride [Fe(TPP)Cl] will induce the autoxidation of cyclohexene at atmospheric pressure and room temperature via a free radical chain process.210 The iron-bridged dimer [Fe(TPP)]2 0 is apparently the catalytic species since it is formed rapidly from Fe(TPP)Cl after the 2-3 hr induction period. In a separate study, cyclohexene hydroperoxide was found to be catalytically decomposed by Fe(TPP)Cl to cyclohexanol, cyclohexanone, and cyclohexene oxide in yields comparable to those obtained in the direct autoxidation of cyclohexene. However, [Fe(TPP)] 20 is not formed in the hydroperoxide reaction. Furthermore, the catalytic decomposition of the hydroperoxide by Fe(TPP)Cl did not initiate the autoxidation of cyclohexene since the autoxidation still had a 2-3 hr induction period. Inhibitors such as 4-tert-butylcatechol quenched the autoxidation but had no effect on the decom-... 

The oxidized dimer, [Fe2(TPA)20(0Ac)]3+, 41, was shown to be an efficient catalyst for cyclohexane oxidation using tert-BuOOH as a source of oxygen (69). This catalyst reacts in CH3CN to yield cyclohexanol (9 equiv), cyclohexanone (11 equiv), and (tert-butylperoxy)cyclohexane (16 equiv) in 0.25 h at ambient temperatures and pressures under an inert atmosphere. The catalyst is not degraded during the catalytic reaction as determined by spectroscopic measurements and the fact that it can maintain its turnover efficiency with subsequent additions of oxidant. Solvent effects on product distribution were significant benzo-nitrile favored the hydroxylated products at the expense of (tert-butyl-peroxy)cyclohexane, whereas pyridine had the opposite effect. Addition of the two-electron oxidant trap, dimethyl sulfide, to the catalytic system completely suppressed the formation of cyclohexanol and cyclohexanone, but had no effect on the production of (tert-butylper-oxy)cyclohexane. These and other studies suggested that cyclohexanol and cyclohexanone must arise from an oxidant different from that responsible for the formation of (tert-butylperoxy)cyclohexane. Thus, two modes of tert-BuOOH decomposition were postulated a heterolytic... 

Other work in which migratory aptitudes have been compared has involved the formation of the azide (or its conjugate acid) in situ from the corresponding alcohol or olefin, and its decomposition without isolation (the Schmidt reaction). For example, 1-substituted cyclohexanols underwent predominantly ring expansion when the 1-substituent was methyl, ethyl or cyclohexyT. A series of tertiary carbinols were studied in which it was found that the migration tendency was in the order Ph i-Pr CgHii Et The products of... 

The synthesis of cyclohexanone, which is an intermediate in the manufacture of nylon 6 and nylon 6,6 is an important industrial process [1], One of the major current routes for the synthesis of cyclohexanone is the liquid-phase autoxidation of cyclohexane at 125-160 °C and 10 bar followed by the selective decomposition of the intermediate cyclohexyl hydroperoxide, using a soluble cobalt catalyst, to a mixture of cyclohexanol and cyclohexanone [2]. These severe conditions are necessary due to the low reactivity of cyclohexane towards autoxidation. Due to the high reactivity of the products in the autoxidation step conversions must be kept low (<10%) [3,4]. Heterogeneous catalysts potentially offer several advantages over their homogeneous counterparts, for example, ease of recovery and recycling and enhanced stability. Recently we found that chromium substituted aluminophosphate-5 and chromium substituted silicalite-1 (CrS-1) are active, selective and recyclable catalysts for the decomposition of cyclohexyl hydroperoxide to cyclohexanone [5j. 

To investigate the mechanism of the reaction, a decomposition experiment was carried out in the presence of cyclohexanol to see if cyclohexanone, which is the intermolecular oxidation product of cyclohexanol and cyclohexene hydroperoxide, was formed (Table 2). To compare the oxidizability of cyclohexanol and 2-cyclohexen-l-ol, oxidation of both substrates were carried out with CrAPO-5 as catalyst and tert-butyl hydroperoxide (TBHP) as oxidant (Table 2). 

Oxidation of cyclohexanol and 2-cyclohexen-l-ol with TBHP over CrAPO-5 and the decomposition of cyclohexenyl hydroperoxide in the presence of cyclohexanol. 

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