Free radicals fragmentation

In this process, the organic halide is split into an ion and a radical fragment. Free-radical formation by oxidation of molybdenum carbonyl with carbon tetrachloride and carbon tetrabromide has been studied in detail [6]. The overall reaction may be represented as follows ... 

While this reaction with solvent continues to provide free radicals, these may be less reactive species than the original initiator fragments. We shall have more to say about the transfer of free-radical functionality to solvent in Sec. 6.8. 

The nature of the secondary reactions is uncertain. Some beheve that the primary tar components are broken down to small free radicals that recombine as they travel toward the retort exit others suggest that some components remain relatively intact except for the removal of peripheral substituent groups and that the higher molecular weight components of coal tar are, in effect, slightly altered fragments of the original coal stmcture. 

Free radicals are molecular fragments having one or more unpaired electrons, usually short-lived (milhseconds) and highly reaclive. They are detectable spectroscopically and some have been isolated. They occur as initiators and intermediates in such basic phenomena as oxidation, combustion, photolysis, and polvmerization. The rate equation of a process in which they are involved is developed on the postulate that each free radical is at equihbrium or its net rate of formation is zero. Several examples of free radical and catalytic mechanisms will be cited, aU possessing nonintegral power law or hyperbohc rate equations. 

SECTION 12.7. REARRANGEMENT AND FRAGMENTATION REACTIONS OF FREE RADICALS... 

Rearrangement and Fragmentation Reactions of Free Radicals 12.7.1. Rearrangement Reactions... 

The first step in cracking is the thermal decomposition of hydrocarbon molecules to two free radical fragments. This initiation step can occur by a homolytic carbon-carbon bond scission at any position along the hydrocarbon chain. The following represents the initiation reaction ... 

Fragmentation (mass spectrum), 410-413 Free radical, 139 Free-energy change (AG), 153 Free-energy change (AG°), standard, 153... 

The trend in relative effectiveness of RAFT agents with varying Z is rationalized in terms of interaction of Z with the C=S double bond to activate or deactivate that group towards free radical addition. Substituents that facilitate addition generally retard fragmentation. O-Alkyl xanthates (Z=0-alkyl, Table... 

Reactions that proceed photochemically do not necessarily involve observations of an excited state. Long before observations are made, the excited state may have dissociated to other fragments, such as free radicals. That is, the lifetime of many excited states is shorter than the laser excitation pulse. This statement was implied, for example, by reactions (11-46) and (11-47). In these systems one can explore the kinetics of the subsequent reactions of iodine atoms and of Mn(CO)s, a 17-electron radical. For instance, one can study... 

The selection of the thirty procedures clearly reflects the current interest of synthetic organic chemistry. Thus seven of them illustrate uses of T1(I), T1 (III), Cu(I), and Li(I), and three examples elaborate on the process now termed phase-transfer catalysis. In addition, newly developed methods involving fragmentation, sulfide contraction, and synthetically useful free radical cyclization arc covered in five procedures. Inclusion of preparations and uses of five theoretically interesting compounds demonstrates the rapid expansion of this particular area in recent years and will render these compounds more readily and consistently available. 

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