Decomposition of olefins

Other catalytic hydrocarbon reactions indude decomposition of olefins over a powdered nickel catalyst [84], hydrogenation of alkenes, hydrocracking of cycloalk-enes, and water-gas shift reactions [64]. 

Unfortunately, the product distribution from the decomposition of olefinic radicals cannot be predicted with any quantitative certainty. When a hydrogen atom is abstracted from an olefin, three types of radicals can be formed primary, secondary, and allylic radicals. The... 

The thermal decomposition of olefinic azides such as 5-azido-5-methylhex-l-ene (149) proceeds by way of the isolable triazoline (150), and a nitrene mechanism was ruled out, as was indicated by... 

This is the relative value of k (see Equation 4) and thus is the rate of decomposition of (olefin) PdCl . 

It is seen that the olefin content is appreciably higher as a product of this high-temperature operation than was the case from mixed-phase cracking. Actually, olefin content increases with increasing temperature up to a maximum, then decreases due to decomposition of olefins to hydrogen and methane, as shown by GrolFs results (39). 

Figure 3 also shows conversion and selectivity to C2H4 with Sn added to the Pt catalyst[15]. Both the alkane conversion and the selectivity to olefins increase significantly with added Sn. X-ray diffraction and XPS of the Pt-Sn catalyst indicate intermetallic compound formation rather than fee metal, and this surface evidently increases the alkane conversion and reduces the decomposition of olefins. 

The model of the cracking mechanism of olefins proposed by Voevodsky should lead to a strong dependence of olefin cracking products on temperature and pressure. This was not observed. The author proposes a chain olefin cracking mechanism when chains are being formed via a series of displacement and addition reactions of the radicals on w-bonds. Some influence of the paraffinic and cychparaffinic products on the kinetics and mechanism is considered. Decomposition of olefins (primary cracking products) defines the kinetic of summary reaction. 

TABLE 10 Kinetic parameters for thermal and thermo-oxidative decomposition of olefin polymers... 

The olefin hydrocarbons are not usually found in raw petroleum stocks, and hence the decomposition of olefins should properly be considered as a secondary decomposition reaction. Both hydrogenation and dehydrogenation may occur during the decomposition of olefins. Diolefins, paraffins, polymers, new olefins, hydrogen, and probably many other materials are produced. As an example of diolefin and paraffin formation, pentene-1 reacts thus ... 

Okfm Syntheses. Conversion of aldehydes and ketones to olefins by the base-catalyzed decomposition of -toluenesulfonic (Ts) acid hydrazones (10) is known as the Bamford-Stevens reaction (54,55). 

At the higher temperatures a decomposition of alkyl radicals, which is an olefin-producing variation of the -scission reaction, becomes competitive with reaction 23 (or sequence 2, 24) ... 

Classical chemiluminescence from lucigenin (20) is obtained from its reaction with hydrogen peroxide in water at a pH of about 10 Qc is reported to be about 0.5% based on lucigenin, but 1.6% based on the product A/-methylacridone which is formed in low yield (46). Lucigenin dioxetane (17) has been prepared by singlet oxygen addition to an electron-rich olefin (16) at low temperature (47). Thermal decomposition of (17) gives of 1.6% (47). 

Thermal, Thermooxidative, and Photooxidative Degradation. Polymers of a-olefins have at least one tertiary C-H bond in each monomer unit of polymer chains. As a result, these polymers are susceptible to both thermal and thermooxidative degradation. Reactivity in degradation reactions is especially significant in the case of polyolefins with branched alkyl side groups. For example, thermal decomposition of... 

In the preparation of hydroperoxides from hydrogen peroxide, dialkyl peroxides usually form as by-products from the alkylation of the hydroperoxide in the reaction mixture. The reactivity of the substrate (olefin or RX) with hydrogen peroxide is the principal restriction in the process. If elevated temperatures or strongly acidic or strongly basic conditions are required, extensive decomposition of the hydrogen peroxide and the hydroperoxide can occur. 

However, when the temperature is increased to 120°C, the principal reaction is the elimination to olefin. The thermal decomposition of dimethyl dodecyl amine oxide at 125°C in a sealed system, as opposed to a vacuum used by Cope and others, produces 2-methyl-5-decyhsoxa2ohdine, dimethyl dodecyl amine, and olefin (23). The amine oxide oxidi2es XW-diaLkylhydroxylainine to the nitrone during the pyrolysis and is reduced to a tertiary amine in the process. 

Chemical Properties. Reactions of quaternaries can be categorized iato three types (169) Hoffman eliminations, displacements, and rearrangements. Thermal decomposition of a quaternary ammonium hydroxide to an alkene, tertiary amine, and water is known as the Hoffman elimination (eq. la) (170). This reaction has not been used extensively to prepare olefins. Some cycHc olefins, however, are best prepared this way (171). Exhaustive methylation, followed by elimination, is known as the Hoffman degradation and is important ia the stmctural determination of unknown amines, especially for alkaloids (qv) (172). 

The Chugaev reaction, or thermal decomposition of the substituted esters of the xanthates, gives olefins without rearrangement (35,36). For example ... 

Alkyl boric acid esters derived from straight-chain alcohols and aryl boric acid esters are stable to relatively high temperatures. Methyl borate is stable to 470°C (11). Trialkoxyboranes from branched-chain alcohols are much less stable, and boranes from tertiary alcohols can even decompose at 100°C (12). Decomposition of branched-chain esters leads to mixtures of olefins, alcohols, and other derivatives. 

Molybdenum compounds Hydrodesulphurization and hydrotreating of petroleum Oxidation of methanol to formaldehdye Epoxidation of olefins Decomposition of alkali metal nitrides Irritation of eyes and respiratory tract Pneumoconiosis... 

Hydroboration affords an efficient preparation of the 5a-A -system (141, for example) from A" -3-ketones. Reaction with diborane followed by decomposition of the organoboron intermediate with refluxing acetic anhydride gives good yields of olefins. Ketones must be protected, and alcohols are transformed to acetates. A -7-Ketones yield 5oc-A -olefins (for example, 138). 

The Bamford-Stevens decomposition of tosylhydrazones by base has been applied to steroids, although not extensively. It has been demonstrated that the reaction proceeds via a diazo compound which undergoes rapid decomposition. The course of this decomposition depends upon the conditions in proton-donating solvents the reaction has the characteristics of a process involving carbonium ions, and olefins are formed, often accompanied by Wagner-Meerwein-type rearrangement. In aprotic solvents the diazo compound appears to give carbene intermediates which form olefins and insertion products ... 

As electrophilic substitutes for peracids, the use of borate ester induced decomposition of alkyl hydroperoxides and molybdenum VI peroxy-complexes have been reported in the recent literature. Although these reagents have led to the epoxidation of olefins in greater than 90% yield there are no reports yet of their application to steroid olefins. 

The photolytic and thermolytic decomposition of azides in the presence of olefins has been applied to aziridine synthesis. However, only a limited number of steroid aziridines have been prepared in this manner. The patent literature reports the use of cyanogen azide at ca. 50° for 24 hours in ethyl acetate for the preparation of an A-nor- and a B-norsteroidal aziridine. The addition is believed to proceed via a triazoline. The reaction of cholest-2-ene with ethyl azidoformate takes place in a nonselective manner to produce a mixture of substances, including C—H insertion products. 

The pyrolysis of perfluoro carboxylic salts can result both in mono and bimolecular products At 210-220 °C, silver salts give mostly the coupled products, at 160-165 °C in A -methylpyrrolidinone, the corresponding copper salts also give the simple decarboxylated compounds in nearly equal amounts The decomposition of the copper salts m the presence of lodobenzene at 105-125 °C results m a phenyl derivative, in addition to the olefin and coupled product [94] (equations 60-62)... 

Thermal decomposition of LiR eliminates a /6-hydrogen atom to give an olefin and LiH, a process of industrial importance for long-chain terminal alkenes. Alkenes can also be produced by treatment of ethers, the organometallic reacting here as a very strong base (proton acceptor) ... 

Thermal decomposition gives olefins, probably by rearrangement of intermediate carbenes. For example, the decomposition of 3,3-penta-methylenediazirine (68) in nitrobenzene above 160°C gives cyclohexene [Eq, (58)]. The yield as determined by bromine titration... 

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