Autoxidation phases

The first term was assigned to the uncatalyzed path which includes the formation of the same reactive radical and non-radical intermediates that were reported in related studies. A clear distinction from other kinetic models is that accumulation of the disulfate radical was also postulated during the autoxidation phase (54).The continued production... 

Another catalytic system which has been successfully applied to the autoxidation of substituted toluenes involves the combination of Co/Br" with a quaternary ammonium salt as a phase transfer catalyst (ref. 20). For example, cobalt(II) chloride in combination with certain tetraalkylammonium bromides or tetraalkylphosphonium bromides afforded benzoic acid in 92 % yield from toluene at 135-160 °C and 15 bar (Fig. 19). It should be noted that this system does not require the use of acetic acid as solvent. The function of the phase transfer catalyst is presumably to solubilize the cobalt in the ArCH3 solvent via the formation of Q + [CoBr]. ... 

The speed of autoxidation was compared for different carotenoids in an aqueous model system in which the carotenoids were adsorbed onto a C-18 solid phase and exposed to a continnons flow of water saturated with oxygen at 30°C. Major products of P-carotene were identified as (Z)-isomers, 13-(Z), 9-(Z), and a di-(Z) isomer cleavage prodncts were P-apo-13-carotenone and p-apo-14 -carotenal, and also P-carotene 5,8-epoxide and P-carotene 5,8-endoperoxide. The degradation of all the carotenoids followed zero-order reaction kinetics with the following relative rates lycopene > P-cryptoxanthin > (E)-P-carotene > 9-(Z)-p-carotene. 

The liquid-phase autoxidation of cyclohexane is carried out in the presence of dissolved cobalt salts. A lot of heterogeneous catalysts were developed for this process but most catalysts lacked stability. The incorporation of cobalt ions in the framework of aluminophosphate and aluminosilicate structures opens perspectives for heterogenization of this process. CoAPO (cobalt aluminophosphate) molecular sieves were found to be active heterogeneous catalysts of this oxidation.133 Site isolation was critical to get active catalysts.134... 

Dichlorine shortens the induction period of autoxidation of paraffin wax [187] and accelerates the oxidation of hydrocarbons [109]. Difluorine is known as very active initiator of gas-phase chain reactions, for example, chlorination [188,189]. 

The catalysis of hydrocarbon liquid-phase autoxidation by transition metals is the result of the substitution of the slow bimolecular reaction (Ek 100 kJ mol-1, see Chapter 4)... 

Emulsion oxidation of alkylaromatic compounds appeared to be more efficient for the production of hydroperoxides. The first paper devoted to emulsion oxidation of cumene appeared in 1950 [1], The kinetics of emulsion oxidation of cumene was intensely studied by Kucher et al. [2-16], Autoxidation of cumene in the bulk and emulsion occurs with an induction period and autoacceleration. The simple addition of water inhibits the reaction [6], However, the addition of an aqueous solution of Na2C03 or NaOH in combination with vigorous agitation of this system accelerates the oxidation process [1-17]. The addition of an aqueous phase accelerates the oxidation and withdrawal of water retards it [6]. The addition of surfactants such as salts of fatty acids accelerates the oxidation of cumene in emulsion [3], The higher the surfactant concentration the faster the cumene autoxidation in emulsion [17]. The rates of cumene emulsion oxidation after an induction period are given below (T = 353 K, [RH] [H20] = 2 3 (v/v), p02 = 98 kPa [17]). 

The oxidation of the crystalline phase occurs 15 times more slowly than the oxidation of the amorphous phase and is likely localized in the boundary regions. The autoxidation of PE and PP occurs at the rate, which is slower at higher crystallinity of polymers and vice versa, as indicated by the amount of the oxygen consumed. Based on the evidence accumulated, it is safe to say that PE and PP are oxidized in their amorphous regions [12,33,34,42,67],... 

Metals and metal oxides, as a rule, accelerate the liquid-phase oxidation of hydrocarbons. This acceleration is produced by the initiation of free radicals via catalytic decomposition of hydroperoxides or catalysis of the reaction of RH with dioxygen (see Chapter 10). In addition to the catalytic action, a solid powder of different compounds gives evidence of the inhibiting action [1-3]. Here are a few examples. The following metals in the form of a powder retard the autoxidation of a hydrocarbon mixture (fuel T-6, at T= 398 K) Mg, Mo, Ni, Nb V, W, and Zn [4,5]. The retarding action of the following compounds was described in the literature. 

The half-order of the rate with respect to [02] and the two-term rate law were taken as evidence for a chain mechanism which involves one-electron transfer steps and proceeds via two different reaction paths. The formation of the dimer f(RS)2Cu(p-O2)Cu(RS)2] complex in the initiation phase is the core of the model, as asymmetric dissociation of this species produces two chain carriers. Earlier literature results were contested by rejecting the feasibility of a free-radical mechanism which would imply a redox shuttle between Cu(II) and Cu(I). It was assumed that the substrate remains bonded to the metal center throughout the whole process and the free thiyl radical, RS, does not form during the reaction. It was argued that if free RS radicals formed they would certainly be involved in an almost diffusion-controlled reaction with dioxygen, and the intermediate peroxo species would open alternative reaction paths to generate products other than cystine. This would clearly contradict the noted high selectivity of the autoxidation reaction. 

In Fig. 6, separate regions of bi-stability, oscillations and single stable steady-states can be noticed. This cross-shaped phase diagram is common for many non-linear chemical systems containing autocatalytic steps, and this was used as an argument to suggest that the Cu(II) ion catalyzed autoxidation of the ascorbic acid is also autocatalytic. The... 

Hydronium ion, 14 23 Hydroperoxidates, 18 411 Hydroperoxide process, for propylene oxide manufacture, 20 798, 801-806 Hydroperoxides, 14 281, 290-291 18 427-436 alkylation of, 18 445 a-oxygen-substituted, 18 448-460 chemical properties of, 18 430 433 decomposition of, 14 279 18 431-432 liquid-phase epoxidation with, 10 656 physical properties of, 18 427-430 preparation by autoxidation, 18 434 synthesis of, 18 433-435 Hydrophile-lipophile balance system,... 

Autoxidation (interaction of a substance with molecular oxygen at below 120°C without flame [1]) has often been involved in the generation of hazardous materials from reactive compounds exposed to air. Methods of inhibiting autoxidation of organic compounds in the liquid phase has been reviewed [2,3],... 

Autoxidation of secondary acetonitriles under phase-transfer catalytic conditions [2] avoids the use of hazardous and/or expensive materials required for the classical conversion of the nitriles into ketones. In the course of C-alkylation of secondary acetonitriles (see Chapter 6), it had been noted that oxidative cleavage of the nitrile group frequently occurred (Scheme 10.7) [3]. In both cases, oxidation of the anionic intermediate presumably proceeds via the peroxy derivative with the extrusion of the cyanate ion [2], Advantage of the direct oxidation reaction has been made in the synthesis of aryl ketones [3], particularly of benzoylheteroarenes. The cyanomethylheteroarenes, obtained by a photochemically induced reaction of halo-heteroarenes with phenylacetonitrile, are oxidized by air under the basic conditions. Oxidative coupling of bromoacetonitriles under basic catalytic conditions has been also observed (see Chapter 6). 

In the case of diastereomeric mixtures of chiral hydroperoxides, standard chromatography on achiral phase can be employed to separate the diastereomers. As one example for the preparation of optically pure hydroperoxides via this method, the ex-chiral pool synthesis of the pinane hydroperoxides 11 is presented by Hamann and coworkers . From (15 )-cw-pinane [(15 )-cw-10], two optically active pinane-2-hydroperoxides cA-lla and trans-llb were obtained by autoxidation according to Scheme 17. Autoxidation of (IR)-c -pinane [(17 )-cw-10] led to the formation of the two enantiomers ent-lla and ent-llh. The ratio of cis to trans products was 4/1. The diastereomers could be separated by flash chromatography to give optically pure compounds. 

For reviews of (he autoxidation of aldehydes, see Vardanyan Nalbandyan Russ. Chem. Rev. 1985, 54. 532-543 (gas phase) Sajus S6r6c de Roch, in Bamford Tipper, Ref. 37. vol. 16. 1980. pp. 89-124 (liquid phase) Maslov Blyumberg Russ. Chem. Rev. 1976, 45, 155-167 (liquid phase). For a review of photochemical oxidation of aldehydes by O . see Niclause Lcmaire Letort Adv. Pholochem. 1966, 4, 25-48. For a discussion of the mechanism of catalyzed atmospheric oxidation of aldehydes, see Larkin J. Org. Chem. 1990, 55, 1563. 

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