Oxidation at room temperature

Reactions with Organic Compounds. Tetrafluoroethylene and OF2 react spontaneously to form C2F and COF2. Ethylene and OF2 may react explosively, but under controlled conditions monofluoroethane and 1,2-difluoroethane can be recovered (33). Benzene is oxidized to quinone and hydroquinone by OF2. Methanol and ethanol are oxidized at room temperature (4). Organic amines are extensively degraded by OF2 at room temperature, but primary aHphatic amines in a fluorocarbon solvent at —42°C are smoothly oxidized to the corresponding nitroso compounds (34). 

The only example of xenon in a fractional oxidation state, +, is the bright emerald green paramagnetic dixenon cation, Xe [12185-20-5]. Mixtures of xenon and fluorine gases react spontaneously with tiquid antimony pentafluoride in the dark to form solutions of XeF+ Sb2 F, in which Xe is formed as an iatermediate product that is subsequently oxidized by fluorine to the XeF+ cation (83). Spectroscopic studies have shown that xenon is oxidized at room temperature by solutions of XeF+ ia SbF solvent to give the XE cation (84). 

Oxidation. Carbon monoxide can be oxidized without a catalyst or at a controlled rate with a catalyst (eq. 4) (26). Carbon monoxide oxidation proceeds explosively if the gases are mixed stoichiometticaHy and then ignited. Surface burning will continue at temperatures above 1173 K, but the reaction is slow below 923 K without a catalyst. HopcaUte, a mixture of manganese and copper oxides, catalyzes carbon monoxide oxidation at room temperature it was used in gas masks during World War I to destroy low levels of carbon monoxide. Catalysts prepared from platinum and palladium are particularly effective for carbon monoxide oxidation at 323 K and at space velocities of 50 to 10, 000 h . Such catalysts are used in catalytic converters on automobiles (27) (see Exhaust CONTHOL, automotive). 

Secondary alcohols are oxidized at room temperature to ketones in high yields by HOCl generated in situ from aqueous NaOCl and acetic acid (109,110). Selective oxidation in the presence of a primary alcohol is possible. In methanol, aldehydes are oxidized to methyl esters (110). Under the proper conditions, alcohols can be esterified with HOCl forming isolable alkyl hypochlorites. 

The increase in thermodynamic stability of 85 is achieved by easy ring opening (01H127). This knowledge allows one to control the regioselectivity of the oxidative amination of the 6-aryl-l,2,4-tiiazine 4-oxides 53, obtaining either (i) the 5-amino-1,2,4-triazine 4-oxides 56 in the reaction of 53 with amines at low temperature in the presence of the oxidant or (ii) the 3-amino-1,2,4-triazine 4-oxides 88, provided the reaction is carried out in two steps (addition and oxidation) at room temperature or higher. 

Among the J ,J -DBFOX/Ph-transition(II) metal complex catalysts examined in nitrone cydoadditions, the anhydrous J ,J -DBFOX/Ph complex catalyst prepared from Ni(C104)2 or Fe(C104)2 provided equally excellent results. For example, in the presence of 10 mol% of the anhydrous nickel(II) complex catalyst R,R-DBFOX/Ph-Ni(C104)2, which was prepared in-situ from J ,J -DBFOX/Ph ligand, NiBr2, and 2 equimolar amounts of AgC104 in dichloromethane, the reaction of 3-crotonoyl-2-oxazolidinone with N-benzylidenemethylamine N-oxide at room temperature produced the 3,4-trans-isoxazolidine (63% yield) in near perfect endo selectivity (endo/exo=99 l) and enantioselectivity in favor for the 3S,4J ,5S enantiomer (>99% ee for the endo isomer. Scheme 7.21). The copper(II) perchlorate complex showed no catalytic activity, however, whereas the ytterbium(III) triflate complex led to the formation of racemic cycloadducts. 

The direct fluorination of sulphones has also been studied210 and this leads to oxidation. At room temperature dimethyl sulphone produced bis(trifluoromethyl)-sulphone and trifluoromethylsulphonyl fluoride in 34% and 15% yields respectively (equation 93). 

The electrochemical promotion of H2 oxidation at room temperature using aqueous alkaline solutions and finely dispersed Pt/graphite electrodes has been already described in section 10.2. Faradaic efficiency, A, values up to 20 and p values up to 5 were obtained. The dispersion of the Pt catalyst was of the order of 50%.12,13... 

Preparation of Nanosized Cold Catalysts and Oxidation at Room Temperature... 

The search for better catalysts has been facilitated in recent years by molecular modeling. We are seeing here a step change. This is the subject of Chapter 1 (Molecular Catalytic Kinetics Concepts). New types of catalysts appeared to be more selective and active than conventional ones. Tuned mesoporous catalysts, gold catalysts, and metal organic frameworks (MOFs) that are discussed in Chapter 2 (Hierarchical Porous Zeolites by Demetallation, 3 (Preparation of Nanosized Gold Catalysts and Oxidation at Room Temperature), and 4 (The Fascinating Structure... 

Stndies of the antoxidation of carotenoids in liposomal suspensions have also been performed since liposomes can mimic the environment of carotenoids in vivo. Kim et al. stndied the antoxidation of lycopene," P-carotene," and phytofluene" " in liposomal snspensions and identified oxidative cleavage compounds. Stabilities to oxidation at room temperature of various carotenoids incorporated in pig liver microsomes have also been studied." The model took into account membrane dynamics. After 3 hr of reactions, P-carotene and lycopene had completely degraded, whereas xanthophylls tested were shown to be more stable. 

Figure 9.6 Activity for CO oxidation at room temperature as a function of gold coverage on an Mo(l 12)—(8 x 2)-TiOx surface. The CO 02 ratio was 2 1 and the total pressure 5 Torr. Two discrete gold structures were investigated, (lxl) and (1 x 3). The initial turn over frequencies (TOF) over the (1 x 1) gold monolayer structure were significantly lower than that for the (1 x 3) bilayer structure. (Reproduced from Ref. 20).

When a C6D6 solution of the silylene-isocyanide complex 21 was treated with an equimolar amount of mesitonitrile oxide at room temperature, the blue color of 21 immediately disappeared, and the 29Si and 13C NMR spectra of the reaction mixture exhibited characteristic strong signals (8Si = 26.9, 8C = 184.3) assignable to those of compound 22a having a novel 1,2,4-oxazasilete ring system (Scheme 5). The oxazasilete 22a was not stable at ambient temperature, and... 

Preparation of all four diastereomers of /3-hydroxydiphenylethyl spirophosphoranes 72 via deprotonation of hydrospirophosphoranes 70 (R = H) with BuLi facilitated a subsequent mechanistic study on stereospecific alkene formation <1997TL7753, 2002CL170>. Three of the diasteromers could be formed by reacting 70 (R = H) with BuLi, followed by treatment with cis or /ra/w-stilbene oxide at room temperature (Scheme 12). 

It must be acknowledged, however, that the determination of the number of the different surface species which are formed during an adsorption process is often more difficult by means of calorimetry than by spectroscopic techniques. This may be phrased differently by saying that the resolution of spectra is usually better than the resolution of thermograms. Progress in data correction and analysis should probably improve the calorimetric results in that respect. The complex interactions with surface cations, anions, and defects which occur when carbon monoxide contacts nickel oxide at room temperature are thus revealed by the modifications of the infrared spectrum of the sample (75) but not by the differential heats of the CO-adsorption (76). Any modification of the nickel-oxide surface which alters its defect structure produces, however, a change of its energy spectrum with respect to carbon monoxide that is more clearly shown by heat-flow calorimetry (77) than by IR spectroscopy. 

The analysis of the thermograms recorded during the interaction of the successive doses of the different reactants in the sequence may also yield very relevant informations. Through the use of different techniques, it has been shown, for instance, that the different steps of the mechanism of the CO oxidation, at room temperature, at the surface of pure [TNJiO (200)3 19, 82) or lithium-doped 54) nickel oxide, may be written ... 

Fig. 33. Reaction yield as a function of time for carbon monoxide oxidation at room temperature on pure and doped nickel oxides. NiO (200), A NiO(Li) (250), O NiO (250) X NiO(Ga) (250). Reprinted from (8) with permission. Copyright 1969 by Academic Press, Inc., New York.

At temperatures near 100° Horiguchi and associates (117) have shown that CO reacts with the superoxide ion on ZnO, but the Or spectrum remained at a fixed level following the addition of a mixture of CO and 02. Hydrogen did not react with 02- at that temperature. Upon addition of nitric oxide at room temperature the Oi signal instantaneously disappeared. 

---