Oxidation, of alkanes

Draw a chair conformation of cyclohexane with one CH3CH2 group and one CH3 group that fits each description  

In Chapter 3 we learned that a functional group contains a heteroatom or n bond and constitutes the reactive part of a molecule. Alkanes are the only family of organic molecules that have no functional group, and therefore, alkanes undergo few reactions. In fact, alkanes are inert to reaction unless forcing conditions are used. 

In Chapter 4, we consider only one reaction of alkanes—combustion. Combustion is an oxidation-reduction reaction. 

Compounds that contain many C-H bonds and few C-Z bonds are said to be in a reduced state, whereas those that contain few C-H bonds and more C-Z bonds are in a more oxidized state. CH4 is thus highly reduced, while CO2 is highly oxidized. 

Oxidation and reduction are opposite processes. As in acid-base reactions, there are always two components in these reactions. One component is oxidized and one is reduced. 

Oxidation of unfunctionalized alkanes is notoriously difficult to perform selectively, because breaking of a C-H bond is required. Although oxidation is thermodynamically favourable, there are limited kinetic pathways for reaction to occur. For most alkanes, the hydrogens are not labile, and, as the carbon atom cannot expand its valence electron shell beyond eight electrons, there is no mechanism for electrophilic or nucleophilic substitution short of using extreme (superacid or superbase) conditions. Alkane oxidations are therefore normally radical processes, and thus difficult to control in terms of selectivity. Nonetheless, some oxidations of alkanes have been performed under supercritical conditions, although it is probable that these actually proceed via radical mechanisms. 

Classical autoxidation of tertiary C-H bonds in alkanes can afford the corresponding hydroperoxides in high selectivities. This is applied industrially in the conversion of pinane to the corresponding hydroperoxide, an intermediate in the manufacture of pinanol (Fig. 4.43). 

More reactive hydroperoxides can be converted selectively to alcohols via the method of Bashkirov (Fig. 4.44), where a boric acid ester protects the product from further oxidation and thus increases the selectivity [121]. The method is used to convert C10-C20 paraffins to alcohols which are used as detergents and surfactants, for the oxidation of cyclohexane (see elsewhere) and cyclododecane to cyclododecanol (cyclododecanone) for the manufacture of nylon-12. 

Recently the Co/Mn/N-hydroxyphthalimide (NHPI) systems of Ishii have been added to the list of aerobic oxidations of hydrocarbons, including both aromatic side chains and alkanes. For example, toluene was oxidized to benzoic acid at 25°C [125] and cyclohexane afforded adipic acid in 73% selectivity at 73% conversion [126], see Fig. 4.46. A related system, employing N-hydroxysac-charine, instead of NHPI was reported for the selective oxidation of large ring cycloalkanes [127]. 

Manganese Catalysts for the Oxidation of Alkanes, Alcjohols, and Aldehydes 

In general, the focus on alkane oxidation has been on C—H activation of standard alkane substrates however, recently focus has shifted toward selective reactions on real synthetic targets. An impressive example of this can be seen in the report of Chen and White employing an iron-based catalyst and H2O2 as the terminal oxidant [139]. More recently, Macleod et al. have used the Jacobsen salen catalyst to achieve selective 

C H activation of phannaceutical intermediates including phenylethylmalondia-mide, primidone, and phenobarbital 140]. 

Although focused on the oxidation of alkenes, de Boer et cd. [117] noted in their report from 2005 that [Mn (p-0)3(tmtacn)2] together with 1 mol% of CCI3CO2H was moderately effective in the oxidation of linear and cyclic alkanes with H2O2, for example, with cydooctane 50% conversion to cyclooctanone with 1.3 equiv. H2O2. Unfortunately, the high activity of this class of complex for alcohol oxidation predudes selective C H oxidation to the alcohol (see below). 

Abstract This chapter covers oxidation of C-H and C-C bonds in alkanes. Section 4.1 concerns oxidation of C-H bonds aldehydes and other CH species (4.1.1), methylene (-CH groups) (4.1.2) and methyl (-CH ) groups (4.1.3). This is followed by the oxidation of cyclic alkanes (4.1.4) and large-scale alkane oxidations (4.1.5). Alkane oxidations not considered here but covered in Chapter 1 are hsted in Section 4.1.6. The final section (4.2) concerns oxidative cleavage of C-C bonds. 

Because Z is more electronegative than C, replacing C-H bonds with C—Z bonds decreases the electron density around C. Loss of electron density = oxidation. 

Despite the fact that several related complexes of other metals have been described [30], only Mn triazacyclononane derivatives have been fixed onto soluble polymers and successfully applied in alkane oxidation so far [31]. 

Acetic Acid. Although at the time of this writing Monsanto s Rh-catalyzed methanol carbonylation (see Section 7.2.4) is the predominant process in the manufacture of acetic acid, providing about 95% of the world s production, some acetic acid is still produced by the air oxidation of n-butane or light naphtha. n-Butane is used mainly in the United States, whereas light naphtha fractions from petroleum refining are the main feedstock in Europe. 

Noncatalytic oxidation to produce acetic acid can be carried out in the gas phase (350-400°C, 5-10 atm) or in the liquid phase (150-200°C). Liquid-phase catalytic oxidations are operated under similar mild conditions. Conditions for the oxidation of naphtha are usually more severe than those for n-butane, and the process gives more complex product mixtures.865-869 Cobalt and other transition-metal salts (Mn, Ni, Cr) are used as catalysts, although cobalt acetate is preferred. In the oxidation carried out in acetic acid solution at almost total conversion, carbon oxides, carboxylic acids and esters, and carbonyl compounds are the major byproducts. Acetic acid is produced in moderate yields (40-60%) and the economy of the process depends largely on the sale of the byproducts (propionic acid, 2-butanone). 

A radical chain reaction to yield sec-butyl hydroperoxide (105) as intermediate is operative17,870 [Eq. (9.163)]. Metal ions play a role in decomposition of the latter by P cleavage [Eq. (9.164)]  

Acetaldehyde thus formed is oxidized in situ to acetic acid. Decomposition may also take place through other pathways. Ethyl alcohol can be an important primary product which cooxidizes rapidly.870 871 

Oxidation of butane and butenes to maleic anhydride is discussed in connection with the synthesis of maleic anhydride (see Section 9.5.4.). 

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Raw Material and Energy Aspects to Pyridine Manufacture. The majority of pyridine and pyridine derivatives are based on raw materials like aldehydes or ketones. These are petroleum-derived starting materials and their manufacture entails cracking and distillation of alkanes and alkenes, and oxidation of alkanes, alkenes, or alcohols. Ammonia is usually the source of the nitrogen atom in pyridine compounds. Gas-phase synthesis of pyridines requires high temperatures (350—550°C) and is therefore somewhat energy intensive. 

Precious Meta.1 Ca.ta.lysts, Precious metals are deposited throughout the TWC-activated coating layer. Rhodium plays an important role ia the reduction of NO, and is combiaed with platinum and/or palladium for the oxidation of HC and CO. Only a small amount of these expensive materials is used (31) (see Platinum-GROUP metals). The metals are dispersed on the high surface area particles as precious metal solutions, and then reduced to small metal crystals by various techniques. Catalytic reactions occur on the precious metal surfaces. Whereas metal within the crystal caimot directly participate ia the catalytic process, it can play a role when surface metal oxides are influenced through strong metal to support reactions (SMSI) (32,33). Some exhaust gas reactions, for instance the oxidation of alkanes, require larger Pt crystals than other reactions, such as the oxidation of CO (34). 

Oxidative reactions frequently represent a convenient preparative route to synthetic intermediates and end products This chapter includes oxidations of alkanes and cycloalkanes, alkenes and cycloalkenes, dienes, aromatic fluorocarbons, alcohols, phenols, ethers, aldehydes and ketones, carboxylic acids, nitrogen compounds, and organophosphorus, -sulfur, -selenium, -iodine, and -boron compounds... 

The equilibrium (1) at the electrode surface will lie to the right, i.e. the reduction of O will occur if the electrode potential is set at a value more cathodic than E. Conversely, the oxidation of R would require the potential to be more anodic than F/ . Since the potential range in certain solvents can extend from — 3-0 V to + 3-5 V, the driving force for an oxidation or a reduction is of the order of 3 eV or 260 kJ moR and experience shows that this is sufficient for the oxidation and reduction of most organic compounds, including many which are resistant to chemical redox reagents. For example, the electrochemical oxidation of alkanes and alkenes to carbonium ions is possible in several systems... 

In the same spirit DFT studies on peroxo-complexes in titanosilicalite-1 catalyst were performed [3]. This topic was selected since Ti-containing porous silicates exhibited excellent catalytic activities in the oxidation of various organic compounds in the presence of hydrogen peroxide under mild conditions. Catalytic reactions include epoxidation of alkenes, oxidation of alkanes, alcohols, amines, hydroxylation of aromatics, and ammoximation of ketones. The studies comprised detailed analysis of the activated adsorption of hydrogen peroxide with... 

Recently, Nam, Fukuzumi, and coworkers succeed in an iron-catalyzed oxidation of alkanes using Ce(IV) and water. Here, the generation of the reactive nonheme iron (IV) 0x0 complex is proposed, which subsequently oxidized the respective alkane (Scheme 16) [104]. With the corresponding iron(II) complex of the pentadentate ligand 31, it was possible to achieve oxidation of ethylbenzene to acetophenone (9 TON). 0 labeling studies indicated that water is the oxygen source. 

The large amounts of natural gas (mainly methane) found worldwide have led to extentive research programs in the area of the direct conversion of methane [1-3]. Ihe oxidative transformation of methane (OTM) is an important route for the effective utilization of the abundant natural gas resources. How to increase catalyst activity is a common problem on the activation of methane. The oxidation of methane over transition m al oxides is always high active, but its main product is CO2, namely the product of deep oxidation. It is because transition metal oxides have high oxidative activity. So, they were usually used as the main corrqtonent of catalysts for the conqilete oxidation of alkane[4]. The strong oxidative activity of CH4 over tran on metal oxides such as NiO indicates that the activation of C-H bond over transition metal oxides is much easier than that over alkaline earth metal oxides and rare earth metal oxides. Furthermore, the activation of C-H bond is the key step of OTM reaction. It is the reason that we use transition metal oxides as the mam conq>onent of the OTM catalysts. However, we have to reahze that the selectivity of OTM over transition metal oxides is poor. 

ROO- + Au -OH — ROOM Au"-0 Scheme 2.8 Oxidation of alkanes with hydrogen peroxide catalyzed by gold(lll) and gold(l) complexes. 

Au "=0 species are postulated, inter alia, as active intermediates in the oxidation of alkanes with hydrogen peroxide catalyzed by gold(III) and gold(I) complexes [115]. The reaction sequence is proposed in Scheme 2.8. 

In yet another version of adopting a biphase system, oxidation of alkanes with rert-butyl hydroperoxide has been conducted with an aqueous phase. Launay et al. (1998) have developed an efficient and highly selective conversion of cyclo-octane to cyclo-octanone using Ru colloidial particles formed in situ from RuCli. 5H2O. The aqueous phase can be recycled. 

The most extensive studies of alkane reactions in aqueous media are on the oxygenation reaction. In fact, nature has used monooxygenase (found in mammalian tissue) and other enzymes to catalyze the oxidation of alkanes to give alcohols in aqueous environments at ambient... 

TABLE 2.1 Oxidation of Alkanes with Ozone Catalyzed by Li12[Mnn2-ZnW(ZnW9034)2] in 40 percent t-BuOH-Water ... 

FIGURE 6.12 Suggested radical mechanism for oxidation of alkanes.33 36 55... 

Iron N,N -bis(2-pyridinecarboxamide) complexes encaged in zeolite Y were used for the partial oxidation of alkanes.99 Epoxidation with manganese N,N -bis(2-pyridinecarboxamide) complexes encapsulated in zeolite Y was also reported.100... 

Due to the high initiation rate and low (room) temperature, chains for oxidation of alkanes are short and many products are formed by disproportionation of peroxyl and hydroperoxyl radicals. The G values of the products of radiolytic oxidation of four alkanes are given in the following table [233] ... 

The oxidation of primary and secondary alcohols in the presence of 1-naphthylamine, 2-naphthylamine, or phenyl-1-naphthylamine is characterized by the high values of the inhibition coefficient / > 10 [1-7], Alkylperoxyl, a-ketoperoxyl radicals, and (3-hydroxyperoxyl radicals, like the peroxyl radicals derived from tertiary alcohols, appeared to be incapable of reducing the aminyl radicals formed from aromatic amines. For example, when the oxidation of tert-butanol is inhibited by 1-naphthylamine, the coefficient /is equal to 2, which coincides with the value found in the inhibited oxidation of alkanes [3], However, the addition of hydrogen peroxide to the tert-butanol getting oxidized helps to perform the cyclic chain termination mechanism (1-naphthylamine as the inhibitor, T = 393 K, cumyl peroxide as initiator, p02 = 98 kPa [8]). This is due to the participation of the formed hydroperoxyl radical in the chain termination ... 

The titanosilicate version of UTD-1 has been shown to be an effective catalyst for the oxidation of alkanes, alkenes, and alcohols (77-79) by using peroxides as the oxidant. The large pores of Ti-UTD-1 readily accommodate large molecules such as 2,6-di-ferf-butylphenol (2,6-DTBP). The bulky 2,6-DTBP substrate can be converted to the corresponding quinone with activity and selectivity comparable to the mesoporous catalysts Ti-MCM-41 and Ti-HMS (80), where HMS = hexagonal mesoporous silica. Both Ti-UTD-1 and UTD-1 have also been prepared as oriented thin films via a laser ablation technique (81-85). Continuous UTD-1 membranes with the channels oriented normal to the substrate surface have been employed in a catalytic oxidation-separation process (82). At room temperature, a cyclohexene-ferf-butylhydroperoxide was passed through the membrane and epoxidation products were trapped on the down stream side. The UTD-1 membranes supported on metal frits have also been evaluated for the separation of linear paraffins and aromatics (83). In a model separation of n-hexane and toluene, enhanced permeation of the linear alkane was observed. Oriented UTD-1 films have also been evenly coated on small 3D objects such as glass and metal beads (84, 85). 

The supported Co2+-substituted Wells-Dawson POM, Cs6H2[P2W17061Co(OH2)], on silica was stable up to 773 K and catalyzed the heterogeneous oxidation of various aldehydes to the corresponding carboxylic acids with 02 as a sole oxidant [116], The H5PV2Mo10O40 POM, impregnated onto meso-porous MCM-41, catalyzed the aerobic oxidation of alkanes and alkenes using isobutyraldehyde as a... 

The oxidation of alkanes involves what is formally the insertion of an oxygen atom into a carbon-hydrogen bond (Fig. 4.41), although the reality of the mechanism is considerably more complex. 

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