With Molecular Oxygen

Sulphites react with molecular oxygen (or air) to give sulphates, a reaction catalysed by certain ions (for example Fe, Cu, arsenate(III) ion, AsO ) and inhibited by, for example, phenol, glycerol and tin(II) ions, Sn ... 

An exception is, of course, metal-catalyzed oxidation with molecular oxygen. 

In contrast to oxidation in water, it has been found that 1-alkenes are directly oxidized with molecular oxygen in anhydrous, aprotic solvents, when a catalyst system of PdCl2(MeCN)2 and CuCl is used together with HMPA. In the absence of HMPA, no reaction takes place(100]. In the oxidation of 1-decene, the Oj uptake correlates with the amount of 2-decanone formed, and up to 0.5 mol of O2 is consumed for the production of 1 mol of the ketone. This result shows that both O atoms of molecular oxygen are incorporated into the product, and a bimetallic Pd(II) hydroperoxide coupled with a Cu salt is involved in oxidation of this type, and that the well known redox catalysis of PdXi and CuX is not always operalive[10 ]. The oxidation under anhydrous conditions is unique in terms of the regioselective formation of aldehyde 59 from X-allyl-A -methylbenzamide (58), whereas the use of aqueous DME results in the predominant formation of the methyl ketone 60. Similar results are obtained with allylic acetates and allylic carbonates[102]. The complete reversal of the regioselectivity in PdCli-catalyzed oxidation of alkenes is remarkable. 

Fig. 5. Chemistry of cyclized mbbei—bis-a2ide negative acting resist, (a) Preparation of cyclized mbber resin from polyisoprene (b) photochemistry of aromatic bis-a2ide sensiti2ers. The primary photoproduct is a highly reactive nitrene which may combine with molecular oxygen to form oxygenated products, or may react with the resin matrix by addition or insertion to form polymer—polymer linkages.

Many hydroperoxides have been prepared by autoxidation of suitable substrates with molecular oxygen (45,52,55). These reactions can be free-radical chain or nonchain processes, depending on whether triplet or singlet oxygen is involved. The free-radical process consists of three stages ... 

Other compounds, eg, azoalkanes, acetone, etc, that yield alkyl radicals either thermally or by uv irradiation have been used with molecular oxygen to prepare alkyl hydroperoxides (r56). 

Catalytic oxidation of isobutyraldehyde with air at 30—50°C gives isobutyric acid [79-31-2] ia 95% yield (5). Certain enzymes, such as horseradish peroxidase, cataly2e the reaction of isobutyraldehyde with molecular oxygen to form triplet-state acetone and formic acid with simultaneous chemiluminescence (6). 

Cobalt metal is significantly less reactive than iron and exhibits limited reactivity with molecular oxygen in air at room temperature. Upon heating, the black, mixed valence cobalt oxide [1308-06-17, Co O, forms at temperatures above 900°C the oHve green simple cobalt(II) oxide [1307-96-6] CoO, is obtained. Cobalt metal reacts with carbon dioxide at temperatures greater than 700°C to give cobalt(II) oxide and carbon monoxide. 

As shown in Fig. 12-6, hydroxyl radicals primarily add to either of the carbon atoms which form the double bond. The remaining carbon atom has an unpaired electron which combines with molecular oxygen, forming an RO2 radical. There are two types of RO2 radicals labeled C3OHO2 in Fig. 12-6. Each of these RO2 radicals reacts with NO to form NO2, and an alkoxy radical reacts with O2 to form formaldehyde, acetaldehyde, and HOj. 

The presence of oxygen can modify the course of a fiee-radical chain reaction if a radical intermediate is diverted by reaction with molecular oxygen. The oxygen molecule, with its two unpaired electrons, is extremely reactive toward most free-radical intermediates. The product which is formed is a reactive peroxyl radical, which can propagate a chain reaction leading to oxygen-containing products. 

The main product of the Elbs reaction is the 1,4-dihydroxybenzene (hydro-quinone). If the para position is already occupied by a substituent, the reaction occurs at an ortho position, leading to a catechol derivative although the yields are not as good as for a hydroquinone. Better yields of catechols 7 can be obtained by a copper-catalyzed oxidation of phenols with molecular oxygen ... 

Sulfur reacts with molecular oxygen to form compounds in which sulfur is assigned positive oxidation numbers, +4 and +6. The reactions are those used in the manufacture of sulfuric acid (see Chapter 13) ... 

The biochemical mechanism of bacterial luminescence has been studied in detail and reviewed by several authors (Hastings and Nealson, 1977 Ziegler and Baldwin, 1981 Lee et al., 1991 Baldwin and Ziegler, 1992 Tu and Mager, 1995). Bacterial luciferase catalyzes the oxidation of a long-chain aldehyde and FMNH2 with molecular oxygen, thus the enzyme can be viewed as a mixed function oxidase. The main steps of the luciferase-catalyzed luminescence are shown in Fig. 2.1. Many details of this scheme have been experimentally confirmed. 

Fig. 8.9 Possible mechanisms of the bioluminescence reaction of dinoflagellate luciferin, based on the results of the model study (Stojanovic and Kishi, 1994b Stojanovic, 1995). The luciferin might react with molecular oxygen to form the luciferin radical cation and superoxide radical anion (A), and the latter deproto-nates the radical cation at C.132 to form (B). The collapse of the radical pair might yield the excited state of the peroxide (C). Alternatively, luciferin might be directly oxygenated to give C, and C rearranges to give the excited state of the hydrate (D) by the CIEEL mechanism. Both C and D can be the light emitter.

According to the information available, it would be reasonable to consider that P. stipticus emits light when its natural luciferin is oxidized with molecular oxygen in the presence of OJ and a suitable surfactant (Shimomura et al., 1993b). Also, it seems almost certain that the natural luciferin is formed from PS-A, PS-B and a simple primary amine by the addition and condensation reactions. 

Sulphide and sulphoxide complexes have been extensively studied since cis-RuC12(DMSO)4 (DMSO, dimethyl sulphoxide, (Me)2SO) was found to have anti-tumour properties and to be a precessor for radiosensitizing agents. Such complexes can act as catalysts for the oxidation of sulphides with molecular oxygen. 

Oxygen-centered radicals are arguably the most common of initiator-derived species generated during initiation of polymerization and many studies have dealt with these species. The class includes alkoxy, hydroxy and aeyloxy radicals and tire sulfate radical anion (formed as primary radicals by homolysis of peroxides or hyponitrites) and alkylperoxy radicals (produced by the interaction of carbon-centered radicals with molecular oxygen or by the induced decomposition of hydroperoxides). 

One of the earliest examples of this methodology involves the reaction of a polymeric anion (formed by living anionic polymerization) with molecular oxygen to form a polymeric hydroperoxide which can be decomposed either thermally or, preferably, in a redox reaction to initiate block polymer formation with a second monomer (Scheme 7.25). However, the usual complications associated with initiation by hydroperoxides apply (Section 3.3.2.5). 

Enzymatic hydroxylations with molecular oxygen. V. Ullrich, Angew. Chem., Int. Ed. Engl., 1972, 11,701-712(134). 

Two examples are (1) the thermal, gas-phase decomposition of acetaldehyde at high temperatures and (2) the reaction of the hydrated 2-propylchromium ion with molecular oxygen in aqueous solution. The reactions and their rate laws are as follows ... 

TMS)3SiH as a pure material or in solution reacts spontaneously and slowly at ambient temperature with molecular oxygen from air, to form the siloxane... 

The mechanism of this unusual process has been studied in some detail. Absolute rate constants for the spontaneous reaction of (TMSlgSiH with molecular oxygen (Reaction 33) has been determined to be at 70 °C and theoretical studies elucidate the reaction coordinates. ... 

Ketones and carboxylic esters can be a hydroxylated by treatment of their enolate forms (prepared by adding the ketone or ester to LDA) with a molybdenum peroxide reagent (MoOs-pyridine-HMPA) in THF-hexane at -70°C. The enolate forms of amides and estersand the enamine derivatives of ketones can similarly be converted to their a hydroxy derivatives by reaction with molecular oxygen. The M0O5 method can also be applied to certain nitriles. Ketones have also been Qc hydroxylated by treating the corresponding silyl enol ethers with /n-chloroperoxy-... 

---