Homolysis

Some systematic studies on the different reaction schemes and how they are realized in organic reactions were performed some time ago [18]. Reactions used in organic synthesis were analyzed thoroughly in order to identify which reaction schemes occur. The analysis was restricted to reactions that shift electrons in pairs, as either a bonding or a free electron pair. Thus, only polar or heteiolytic and concerted reactions were considered. However, it must be emphasized that the reaction schemes list only the overall change in the distribution of bonds and ftee electron pairs, and make no specific statements on a reaction mechanism. Thus, reactions that proceed mechanistically through homolysis might be included in the overall reaction scheme. 

The more stable the radical the lower the energy required to generate it by C—H bond homolysis... 

As the table indicates C—H bond dissociation energies m alkanes are approxi mately 375 to 435 kJ/mol (90-105 kcal/mol) Homolysis of the H—CH3 bond m methane gives methyl radical and requires 435 kJ/mol (104 kcal/mol) The dissociation energy of the H—CH2CH3 bond m ethane which gives a primary radical is somewhat less (410 kJ/mol or 98 kcal/mol) and is consistent with the notion that ethyl radical (primary) is more stable than methyl... 

In discussing mechanism (5.F) in the last chapter we noted that the entrapment of two reactive species in the same solvent cage may be considered a transition state in the reaction of these species. Reactions such as the thermal homolysis of peroxides and azo compounds result in the formation of two radicals already trapped together in a cage that promotes direct recombination, as with the 2-cyanopropyl radicals from 2,2 -azobisisobutyronitrile (AIBN),... 

Irradiation of ethyleneimine (341,342) with light of short wavelength ia the gas phase has been carried out direcdy and with sensitization (343—349). Photolysis products found were hydrogen, nitrogen, ethylene, ammonium, saturated hydrocarbons (methane, ethane, propane, / -butane), and the dimer of the ethyleneimino radical. The nature and the amount of the reaction products is highly dependent on the conditions used. For example, the photoproducts identified ia a fast flow photoreactor iacluded hydrocyanic acid and acetonitrile (345), ia addition to those found ia a steady state system. The reaction of hydrogen radicals with ethyleneimine results ia the formation of hydrocyanic acid ia addition to methane (350). Important processes ia the photolysis of ethyleneimine are nitrene extmsion and homolysis of the N—H bond, as suggested and simulated by ab initio SCF calculations (351). The occurrence of ethyleneimine as an iatermediate ia the photolytic formation of hydrocyanic acid from acetylene and ammonia ia the atmosphere of the planet Jupiter has been postulated (352), but is disputed (353). 

Hydroperoxides are photo- and thermally sensitive and undergo initial oxygen—oxygen bond homolysis, and they are readily attacked by free radicals undergoing induced decompositions (eqs. 8—10). 

Therefore, first-order, decomposition rates for alkyl hydroperoxides, ie, from oxygen—oxygen bond homolysis, are vaUd only if induced decomposition reactions... 

Chemical Properties. Acychc di-Z f/-alkyl peroxides efftciendy generate alkoxy free radicals by thermal or photolytic homolysis. 

Thermal decomposition of dihydroperoxides results in initial homolysis of an oxygen—oxygen bond foUowed by carbon—oxygen and carbon—carbon bond cleavages to yield mixtures of carbonyl compounds (ketones, aldehydes), esters, carboxyHc acids, hydrocarbons, and hydrogen peroxide. 

The alkyl peroxyesters undergo homolysis, thermally and photochemically, to generate free radicals (168,213,229—232) ... 

Table 15 shows that peroxyester stabiUty decreases for the alkyl groups in the following order tert — butyl > tert — amyl > tert — octyl > tert — cumyl > 3 — hydroxy — 1,1 dimethylbutyl. The order of activity of the R group in peroxyesters is also observed in other alkyl peroxides. Peroxyesters derived from benzoic acids and non-abranched carboxyUc acids are more stable than those derived from mono-a-branched acids which are more stable than those derived from di-a-branched acids (19,21,168). The size of the a-branch also is important, since steric acceleration of homolysis occurs with increasing branch size (236). Suitably substituted peroxyesters show rate enhancements because of anchimeric assistance (168,213,237). 

The second mechanism, proposed by Mayo (116), involves the Diels-Alder reaction of two styrene molecules to form a reactive dimer (DH) followed by a molecular assisted homolysis between DH and another styrene molecule. 

Decomposition of Thiols. Thiols decompose by two principal paths (i43— i45). These are the carbon—sulfur bond homolysis and the unimolecular decomposition to alkene and hydrogen sulfide. For methanethiol, the only available route is homolysis, as in reaction 29. For ethanethiol, the favored route is formation of ethylene and hydrogen sulfide via the unimolecular process, as in reaction 30. 

C—N bond homolysis may be the initial step in the conversion of (396) into the phenylazopyrazole (402), a product which is believed to arise by interaction of ground-state pyrazole with a photochemically generated phenyldiazonium ion (76CC685). 

Oxirane on thermolysis or photolysis suffers C—O homolysis to give a plethora of products (Scheme 2). Substituted oxiranes behave similarly on thermolysis although some C—C cleavage is observed (Scheme 3). Cyclopentene and cyclohexene oxides undergo only C—O cleavage (Scheme 4). 

The amount of induced decomposition that occurs depends on the concentration and reactivity of the radical intermediates and the susceptibility of the substrate to radical attack. The radical X- may be formed from the peroxide, but it can also be derived from subsequent reactions with the solvent. For this reason, both the structure of the peroxide and the nature of the reaction medium are important in determining the extent of induced decomposition, relative to unimolecular homolysis. 

The radical X is formed by homolysis of the X—R bond either thermally or photolytically. In the reactions of alcohols with lead tetraacetate evidence suggests that the X—R bond (X = 0, R = Pb(OAc)3) has ionic character. In this case the oxy radical is formed by a one electron transfer (thermally or photochemically induced) from oxygen to lead. 

In most cases the carbon radical formed in the hydrogen abstraction step 2 will react with the radical R formed in the homolysis of the X—R bond. However, a cage reaction does not seem to be involved in this step. This has been established in the nitrite photolysis and probably applies to hypohalites as well. In the lead tetraacetate reaction, the steps following the oxyradical formation leading to tetrahydrofuran derivatives are less clear. 

The homolysis of tertiary hypochlorites for the production of oxy radicals is well known." The ease with which secondary hypohalites decompose to ketones has hampered the application of hypohalites for transannular reactions. However the tendency for the base-catalyzed heterolytic decomposition decreases as one passes from hypochlorites to hypobromites tohypoidites. Therefore the suitability of hypohalites for functionalization at the angular positions in steroids should increase in the same order. Since hypoidites (or iodine) do not react readily with ketones or carbon-carbon double bonds under neutral conditions hypoiodite reactions are more generally applicable than hypochlorite or hypobromite decompositions. 

The solvents generally used for the haloamine homolysis are 84 % or greater concentrated sulfuric acid or mixtures of acetic and sulfuric acid. The use of trifluoroacetic acid has also given excellent results. 

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