Reactions with lead oxides

Nehlsen et al.140 reported a developing process for the removal of thiols from a hydrocarbon stream by a heterogeneous reaction with lead oxide at a temperature <50 °C. The principle is heterogeneous reaction of thiols with lead oxide to form insoluble lead thiolates, which is then separated from the hydrocarbon stream. They claimed that the process allows the original thiols to be recovered for other uses, and the lead is also recovered and recycled. Experimental recovery of the lead for recycling exceeds 94%. Thiols are recovered with typical yields of 80%-90%. 

Nehlsen, J.P., Benziger, J.B., and Kevrekidis, I.G. A process for the removal of thiols from a hydrocarbon stream by a heterogeneous reaction with lead oxide. Energy Fuels, 2004, 18, 721. 

Reaction with Meta/ Oxides. The reaction of hydrogen chloride with the transition-metal oxides at elevated temperatures has been studied extensively. Fe202 reacts readily at temperatures as low as 300°C to produce FeCl and water. The heavier transition-metal oxides require a higher reaction temperature, and the primary reaction product is usually the corresponding oxychlorides. Similar reactions are reported for many other metal oxides, such as Sb202, BeO, AI2O2, andTi02, which lead to the formation of relatively volatile chlorides or oxychlorides. 

Although some of the oxidative ring closures described above, e.g. reactions with lead tetraacetate (Section 4.03.4.1.2), may actually involve radical intermediates, little use has been made of this reaction type in the synthesis of five-membered rings with two or more heteroatoms. Radical intermediates involved in photochemical transformations are described in Section 4.03.9. Free radical substitutions are described in the various monograph chapters. 

Diphenylbutadiene has been obtained from phenylacetic acid and cinnamaldehyde with lead oxide, by the dehydrogenation of l,4-diphenyl-2-butene with butyllithium, and by the coupling reaction of benzenediazonium chloride and cinnamyl-ideneacetic acid." The present method gives better yields than those previously reported, is adaptable to the preparation of a variety of substituted bistyryls, and is relatively easy to carry out. 

Shock-modified zirconia powder was reacted with lead oxide in controlled differential thermal analysis (DTA) experiments and compared to the unmodified material by Hankey and co-workers [82H01]. This reaction yields... 

Fig. 7.10. The solid state reactivity of shock-modified zirconia with lead oxide as studied with differential thermal analysis (DTA) shows both a reduction in onset temperature and apparent increase in reaction rate. The shock-modified material has a behavior much like the much higher specific surface powder shown in B (after Hankey et al. [82H01]).

The oxidative cleavage of the central carbon-carbon bond in a vicinal diol 1, by reaction with lead tetraacetate or periodic acid, yields two carbonyl compounds 2 and 3 as products. 

Furthermore reactions with difluorophosphoric anhydride are of some importance (55). The easy cleavage of the P—0—P-bridge in reactions with organometallic oxides (17) and halides (18) leads to derivatives of difluorophosphoric acid in a very mild way ... 

The losses of lead as litharge (PbO) can be minimized if the impurity elements could be oxidized at an oxygen potential lower than that which causes the oxidation of lead. This can be achieved if the activities of the oxides of the impurity elements in the slag are decreased, for example, by the addition of an oxide which reacts very much more strongly with the oxides of the impurities than it does with lead oxide. Sodium hydroxide is a useful reagent for this purpose and sodium nitrate can be used as the source of oxygen. The reaction involved in this process, known as the Harris process, can be formally written as... 

The formation of silaneselone 57 was evidenced by the trapping reaction with mesitonitrile oxide leading to the corresponding cycloadduct 58 and was also supported by the observation of a remarkably downfield 29Si chemical shift (8Si = 174) indicative of the Si=Se double bond of 57. Although this direct selenation of silylene 55 with an equimolar amount of selenium was not reproducible, the use of excess amount of elemental selenium resulted in the formation of a new cyclic diselenide, diselenasilirane 59, as a stable compound (8Si = -44 and... 

Functionalization of these reactive anionic chain ends can be achieved by a variety of methods all based on the general concepts of carbanion chemistry. For example, reaction with C02 or succinnic anhydride leads to the carboxy terminated derivatives [10], while hydroxy-terminated polymers can be easily obtained by reaction with ethylene oxide (Scheme 3) [11]. In select functionalization reactions, such as alkylation with p-vinyl benzyl chloride, the nucleophilicity of the carbanionic species may be necessary and this can be achieved by reaction of the chain end with 1,1-diphenylethene followed by functionalization [12,13]. 

The polymerization of 2.4.6-trichlorophenol with lead oxide and silver oxide has also been investigated by Hedayatullah and Denivelle (40) and Muller (65) has also oxidized a number of polyhalophenols and looked at the intermediates in the reaction in order to develop a mechanism for the reaction. 

Apoptosis is induced by various intra- and extracellular stimuli, and recently nitric oxide was reported to induce apoptosis in cultured cerebellar granule cells and cultured cortical neurons. The toxicity of nitric oxide is mainly ascribed to peroxynitrite, a reaction product of nitric oxide with superoxide (Figure 13.8). Cells producing an increased amount of SOD (superoxide, superoxide oxidoreductase EC 1.15.1.1) are resistant to nitric oxide-mediated apoptosis. In contrast, superoxide levels that have been increased by downregulation of Cu,Zn-SOD lead to apoptotic cell death in PC 12 cells, which required the reaction with nitric oxide to generate peroxynitrite. Peroxynitrite itself was found to induce apoptosis in PC12 cells and in cultured cortical neurons. 

The redistribution reaction in lead compounds is straightforward and there are no appreciable side reactions. It is normally carried out commercially in the liquid phase at substantially room temperature. However, a catalyst is required to effect the reaction with lead compounds. A number of catalysts have been patented, but the exact procedure as practiced commercially has never been revealed. Among the effective catalysts are activated alumina and other activated metal oxides, triethyllead chloride, triethyllead iodide, phosphorus trichloride, arsenic trichloride, bismuth trichloride, iron(III)chloride, zirconium(IV)-chloride, tin(IV)chloride, zinc chloride, zinc fluoride, mercury(II)chloride, boron trifluoride, aluminum chloride, aluminum bromide, dimethyl-aluminum chloride, and platinum(IV)chloride 43,70-72,79,80,97,117, 131,31s) A separate catalyst compound is not required for the exchange between R.jPb and R3PbX compounds however, this type of uncatalyzed exchange is rather slow. Again, the products are practically a random mixture. 

The isomers of the now very popular dioxiranes, carbonyl oxides, are much less well-known species. However, the reaction of both isomers with two aliphatic thioketones was investigated [258]. A clear cut difference in reactivity was observed, with dioxiranes leading expectedly to the sulfines, while 5-membered ring thio-ozonides were produced from the reactions with carbonyl oxides, thus proving the possibility of a dipolar cycloaddition. 

The unsymmetrical isomers of trinitrotoluene also give specific reactions with sodium carbonate and with lead oxide. The former also affects the ignition temperatures of the isomers. The corresponding data are tabulated below, in Table 80 (after Brunswig [141]). 

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