Hydrocarbon-based radicals

The addition of perfluoroalkyl iodides to simple olefins has been quite successful under aqueous conditions to synthesize fluorinated hydrocarbons.119 In addition to carbon-based radicals, other radicals such as sulfur-based radicals, generated from RSH-type precursors (R = alkyl, acyl) with AIBN, also smoothly add to a-allylglycines protected at none, one, or both of the amino acid functions (NH2 and/or CO2H). Optimal results were obtained when both the unsaturated amino... 

Damall, K.R., Lloyd, A.C., Winer, A.M., Pitts, J.N. (1976) Reactivity scale for atmospheric hydrocarbons based on reaction with hydroxyl radicals. Environ. Sci. Technol. 10, 692-696. 

Unlike hydrocarbon-based fuels like methane and gasoline, coal has never been subjected to a comprehensive mechanistic analysis, due to the complexity of its molecular structure. However, coal s complex structure consists of various mono-cyclic units that can be explored aromatic hydrocarbons and heteroaromatic rings are recurring units in coal s structure, even while the overall structure varies geographically. Understanding low- and high-temperature oxidation reactions for these subunits and their reactive radical intermediates will facilitate a better understanding of their chemistry in combustion. 

Darnall, K. R., A. C. Lloyd, A. M. Winer, and J. N. Pitts, Jr., Reactivity Scale for Atmospheric Hydrocarbons Based on Reaction with Hydroxyl Radical, Environ. Sci. TechnoL, 10, 692-696 (1976). 

Interest in synthetic naphthenic acid has grown as the supply of product has fluctuated, Oxidation of naphthene-based hydrocarbons, free-radical addition of carboxylic acids to olefins, and addition of unsatnrated fatty acids to cycloparaflins have been studied but not commercialized. 

Slobodin et al. [39] confirmed that thermal decomposition of EPR (equimolar ratio) began at 170 °C and ceased at 360 C. A total 93.66% condensate products, 5.2% gas and 1.14% carbonaceous residue were obtained, mainly at 235 °C. The composition of the gaseous portion, determined by GLC was ethane-ethylene 1.25%, propane 0.81%, propylene 0.98%, butane-butylene 0.99% and butadiene 0.99% by wt. of EPR. The liquid products were separated into five fractions with boiling ranges of 100 C, 100-150 C, 150-200 °C, 200-250 °C, and >250 °C. The fractionation yielded pentane, 1-pentene, 2-methylbutane, 2-methyl-l-butene, 2-methyl-2-butene, isoprene and piperylene of C5 hydrocarbon and hexane, 1-hexane, 2-methylpentane of Cg hydrocarbons. Based on these data, the thermal degradation was proposed to proceed via a free-radical mechanism. A free radical CH3... 

Pathway (b) is always the minor channel. For small hydrocarbon peroxy radicals the branching ratio kjk increases from <0.014 for R = C2H5 to approximately 0.2 for n-hexane. As the hydrocarbon grows further, a branching ratio of kf,/k = 0.4 is approached (e.g., for n-octane) [12]. With respect to the HCFC-based peroxy radical plus NO reactions, there have been no reports of either a pressure dependence to the reaction or of observations of alkyl nitrate formation. Most of the studies base the conclusion that channel (b) is insignificant on the observation that the NO2 produced approximately equals the initial peroxy radical concentration. 

Nakasuji K, Kubo T (2004) Multi-stage amphoteric redox hydrocarbons based on a phenalenyl radical. Bull Chem Soc Jpn 77 1791-1801... 

Flowever, in order to deliver on its promise and maximize its impact on the broader field of chemistry, the methodology of reaction dynamics must be extended toward more complex reactions involving polyatomic molecules and radicals for which even the primary products may not be known. There certainly have been examples of this notably the crossed molecular beams work by Lee [59] on the reactions of O atoms with a series of hydrocarbons. In such cases the spectroscopy of the products is often too complicated to investigate using laser-based techniques, but the recent marriage of intense syncluotron radiation light sources with state-of-the-art scattering instruments holds considerable promise for the elucidation of the bimolecular and photodissociation dynamics of these more complex species. 

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