Summary of Oxidation Reactions

As it is clear from the preceding paragraphs, there are four different positions where X -phosphorins are attached by oxidants  

1) Phosphorus H2O2, halogens, diazonium salts lead to 1.1-substituted X -phos-phorins or to rearranged 2-hydrophosphinic acids. 

2) Phosphorus anri C-4 oxygen, nitric acid, chlorine in excess. Sensitized oxygen leads to 1.4 addition product 80, oxygen in benzene solution to 4.4 -peroxy phosphinic acid 68. With nitric acid, halogen in excess or autoxidation of 2- 

3) Phosphorus C-4 in aryl ring at C—4 aryl diazonium salt in excess. 

The cyclic 4-hydroxy-phosphinic acid esters yield diastereoisomers which show remarkable differences in H-NMR, in some cases also in IR or in mass spectra. 

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Table 13, presents a summary of oxidation reactions catalyzed by heteropoly compounds. Vapor-phase... 

A summary of oxidation reactions of aliphatic hydrocarbons is given in Table 8. 

A summary of oxidation-reduction half-reactions arranged in order of decreasing oxidation strength and useful for selecting reagent systems. 

Figure 4.17 Summary of oxidation number changes by reaction stage for labelled atoms in Scheme 4.9 for triclosan synthesis.

Although no reported work is available on vinyl acetylene oxidation, oxidation by O would probably lead primarily to the formation of CO, H2, and acetylene (via an intermediate methyl acetylene) [37], The oxidation of vinyl acetylene, or the cyclopentadienyl radical shown earlier, requires the formation of an adduct [as shown in reaction (3.142)]. When OH forms the adduct, the reaction is so exothermic that it drives the system back to the initial reacting species. Thus, O atoms become the primary oxidizing species in the reaction steps. This factor may explain why the fuel decay and intermediate species formed in rich and lean oxidation experiments follow the same trend, although rich experiments show much slower rates [65] because the concentrations of oxygen atoms are lower. Figure 3.13 is a summary of the reaction steps that form the general mechanism of benzene and the phenyl radical oxidation based on a modified version of a model proposed by Emdee et al. [61, 66], Other models of benzene oxidation [67, 68, which are based on Ref. [61], place emphasis on different reactions. 

I able 6.1 Summary of the reactions for the synthesis of oxides nanopartieJe by difTcrcnl methods... 

Table 11 Summary of the reaction products generated via the deprotonation of styrene oxide 83 in a microflow reactor (RT = 24 s, —78 °C)...

Figure 3. Summary of the reaction paths for the electrochemical oxidation of NADH. The potentials given are referred to SCE at pH 7.0. Reproduced with permission from ref. 35. Copyright 1991 Elsevier Science Publishers.

Reaction (147) is the dominant means of oxidizing benzyl radicals. It is a slow step, so the oxidation of toluene is overall slower than that of benzene, even though the induction period for toluene is shorter. The oxidation of the phenyl radical has been discussed, so one can complete the mechanism of the oxidation of toluene by referring to that section. Figure 12 from Ref. [66] is an appropriate summary of the reactions. 

Reaction of a lubricating oil with white phosphorus at 150-300 °C followed by oxidation with air gives a solution of oil soluble phosphorus compounds, believed to contain phosphonic add groups A summary of the reaction of unsaturated compounds with phosphorus is given in Table 5. 

A summary of the reactions of the /1-oxidation of saturated fatty acids is shown in Figure 12.6. The pathway begins with an oxidation-reduction reaction, catalyzed by acyl-CoA dehydrogenase (an inner mitochondrial membrane flavo-protein), in which one hydrogen atom each is removed from the a- and /1-carbons and transferred to the enzyme-bound FAD ... 

An excellent summary of the reactions of nitric oxide is given by T. Moeller, /, Chem, Educ., 23 (1946), 441, 542. 

The study aids for this chapter include key terms and concepts (which are hyperlinked to the Glossary from the bold, blue terms in the WileyPLUS version of the book at wileyplus.com) and Synthetic Connections summaries of oxidation, reduction, and carbon—carbon bond-forming reactions related to alcohol and carbonyl compounds. 

In summary, any primary alcohol will undergo the following sequence of oxidation reactions ... 

Aerobic transformation of uric acid to allantoin (equation 119) is catalyzed by uricase, an enzyme widely distributed throughout the phylogenetic scale, which participates in the final degradation of purines (246,472). It catalyzes oxidation of uric acid only (396) substituted uric acids are not attacked. The course of oxidation is complex, the number of products and their relative proportions being dependent upon conditions of reaction. A summary of these reactions is given in Figure 33 (36,43,96,130-132,181,592). 

EVANS provides a summary of the reactions of organometallics with oxide surfaces that lead to well-defined surface species including mononuclear and polynuclear complexes and monometallic and bimetallic particles. These surface reactions are described by the same principles encountered in molecular chemistry the reaction classes include nucleophilic attack at the ligands, electrophilic attack at the metal-carbon bond, oxidative addition, Lewis base adduct formation, redox reactions, etc. The synthesis of well-defined reactive sites on surfaces by these organometallic routes will facilitate the study of elementary steps in surface chemistry. 

Table 6 presents a summary of the oxidation—reduction characteristics of actinide ions (12—14,17,20). The disproportionation reactions of UO2, Pu , PUO2, and AmO are very compHcated and have been studied extensively. In the case of plutonium, the situation is especially complex four oxidation states of plutonium [(111), (IV), (V), and (VI) ] can exist together ia aqueous solution ia equiUbrium with each other at appreciable concentrations. 

The optical absorption spectra of Pu ions in aqueous solution show sharp bands in the wavelength region 400—1100 nm (Fig. 4). The maxima of some of these bands can be used to determine the concentration of Pu ions in each oxidation state (III—VI), thus quantitative deterrninations of oxidation—reduction equiUbria and kinetics are possible. A comprehensive summary of kinetic data of oxidation—reduction reactions is available (101) as are the reduction kinetics of Pu + (aq) (84). 

In equation 1, the Grignard reagent, C H MgBr, plays a dual role as reducing agent and the source of the arene compound (see Grignard reaction). The Cr(CO)g is recovered from an apparent phenyl chromium intermediate by the addition of water (19,20). Other routes to chromium hexacarbonyl are possible, and an excellent summary of chromium carbonyl and derivatives can be found in reference 2. The only access to the less stable Cr(—II) and Cr(—I) oxidation states is by reduction of Cr(CO)g. 

The as-spun acrylic fibers must be thermally stabilized in order to preserve the molecular structure generated as the fibers are drawn. This is typically performed in air at temperatures between 200 and 400°C [8]. Control of the heating rate is essential, since the stabilization reactions are highly exothermic. Therefore, the time required to adequately stabilize PAN fibers can be several hours, but will depend on the size of the fibers, as well as on the composition of the oxidizing atmosphere. Their are numerous reactions that occur during this stabilization process, including oxidation, nitrile cyclization, and saturated carbon bond dehydration [7]. A summary of several fimctional groups which appear in stabilized PAN fiber can be seen in Fig. 3. 

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