Radical acceptor

The mechanism of the Patemo-Biichi reaction is not well understood, and while a general pathway has been proposed and widely aceepted, it is apparent that it does not represent the full scope of reactions. Biichi originally proposed that the reaction occurred by light catalyzed stimulation of the carbonyl moiety 1 into an excited singlet state 4. Inter-system crossing then led to a triplet state diradical 5 which could be quenched by olefinic radical acceptors. Intermediate diradical 6 has been quenched or trapped by other radical acceptors and is generally felt to be on the reaction path of the large majority of Patemo-Biichi reactions. Diradical 6 then recombines to form product oxetane 3. 

The inertia of (TMS)3SiH toward azides allows this functionality to be used as a radical acceptor. An example is given in Reaction (52) where the amine product was tosylated before work-up. 

The reactivity of oxime ethers as radical acceptors is enhanced by Lewis acids, BF3 being the most effective.343... 

Generally radical acceptors or oxidation catalysts, which effectively remove free radicals formed during milling and mixing procedures. Inter-macromolecular action leads to reduction of the entanglements between polymer molecules. Chemically activated zinc soaps. 

Little used organic acceptors for these reactions, also [53,54], The use of a glycal as the radical source together with a functionalized enone as the radical acceptor is remarkable. Enones are swiftly reduced by Cp2TiCT [55] and thus epoxide activation must be considered as even more efficient. The product of the addition constitutes a valuable intermediate en route to derivatives of thyrsiferiol. 

The above-mentioned important and impressive applications of titanocene mediated and catalyzed epoxide opening have been achieved by using the already classical 5-exo, 6-exo and 6-endo cyclizations with alkenes or alkynes as radical acceptors. Besides these achievements, the high chemoselectiv-ity of radical generation and slow reduction of the intermediate radicals by Cp2TiCl has resulted in some remarkable novel methodology. 

In general, aldehydes constitute the more efficient radical acceptors. Surprisingly, when enones were employed as radical acceptors 1,2-addition to the carbonyl group was in some cases preferred over the conjugate 1,4-addition [116]. 

The catalytic conditions are well suited for the preparation of cyclopropanes provided that a, /J-unsaturated carbonyl compounds are employed as radical acceptors (formation of electrophilic radicals after cyclization) as shown in Scheme 32 [123]. 

The above-mentioned multi-component catalytic systems are of synthetic potential in radical reactions. The generated ketyl radicals are able to undergo the inter- and intra-molecular coupling with a variety of radical acceptors. 

Tetralin has been shown to undergo thermal dehydrogenation to naphthalene and rearrangement to methyl indan in either the absence or presence of free radical acceptors [ 1, 2]. The presence of free radical acceptors usually accelerates the rearrangement reaction. Even with alkylated Tetralins>... 

Sym-octahydrophenanthrene (HgPh) would be expected to follow the same rearrangement-dehydrogenation reactions as Tetralin, except with more isomer and product possibilities. The reactions shown in Figure 1 illustrate the many structures expected from sym-HgPh in the presence of free radical acceptors. Unlike Tetralin, hydrophenanthrenes have multiple structures which each, in turn, form various isomers. The amounts of these isomers are dependent upon the type of hydrogen-transfer reactions and the environment of the system. 

Moreover, alkynes instead of alkenes can be used as ketyl radical acceptors, and it was also demonstrated that the organosamarium species of type 2-740 can be trapped with an electrophile, such as acetone. 

If the attacking radical contains an adequately placed radical acceptor functionality, the possibility of a radical cycloaddition is provided, offering a procedure to construct cyclic products from acyclic precursors. For this type of ring-forming process, in which two molecular fragments are united with the formation of two new bonds, the term annulation has been adopted (Scheme 3.3). 

N-Aziridinylimines are valuable substrates for domino radical cydizations since they are able to serve simultaneously as radical acceptors and donors. They allow a versatile and general construction of quaternary carbon centers from carbonyl compounds [33]. By employing this methodology, an elegant and stereoselective synthesis of ( )-modhephene (3-70), one of the rare naturally occurring [3.3.3]propellanes,... 

Xanthates serve as a reliable source of electrophilic radicals, and this was exploited by Zard and coworkers for a short synthesis of ( )-matrine (3-304), a naturally occurring alkaloid which has been claimed to have anti-ulcerogenic and anticancer properties [116]. Heating a mixture of xanthate 3-299 and the radical acceptor 3-300 (3 equiv.) in benzene in the presence of lauroyl peroxide as initiator, gave 3-301 in 30% yield and a 3 1 mixture of the tetracylic products 3-302 and 3-303 in 18% yield (Scheme 3.76) [117]. The three compounds could be converted into the... 

The problem of retention of asymmetry of the formed free radical in the fast geminate recombination of radicals was studied by photolysis of the optically active azo-compound PhMeCH—N=NCH2Ph [88,89]. The radical pair of two alkyl radicals was initiated by the photolysis of the azo-compound in benzene in the presence of 2-nitroso-2-methylpropane as a free radical acceptor. The yield of the radical pair combination product was found to be 28%. This product PhMeEtCCH2Ph was found to be composed of 31% 5,5 -(-)(double retention), 48% meso (one inversion), and 21% R.R(+) double inversion. These results were interpreted in terms of the competition between recombination (kc), diffusion (kD), and rotation (kml) of one of the optically active radicals with respect to another. The analysis of these data gave kxo[Pg.126]

The introduction of a free radical acceptor (scavenger) helps to measure the probability (e) of radical pairs to escape from geminate combination and diffuse out of the cage. The value of e for the fixed initiator or photoinitiator depends on the viscosity 17 of the solvent. The following empirical dependence for the photodecomposition of initiators was found... 

This reaction was proposed by Farmer [44]. Miller and Mayo observed this reaction experimentally in oxidized styrene [45]. The rate constant of this reaction was measured by the free radical acceptor method by Denisova and Denisov [46]. This reaction is endothermic. The activation energies of these reactions are sufficiently higher than their enthalpy values. 

The formation of radicals from hydrogen peroxide in cyclohexanol was measured by the free radical acceptor method [60] the effective rate constant of initiation was found to be equal to ki = 9.0 x 106 exp(—90.3/RT) s 1. For the first-order decomposition of H2O2 in an alcohol medium, the following reactions were discussed. 

Chain generation by the reaction of diacetals of different structures with dioxygen was studied by the method of free radical acceptors. Free radical generation was found to occur with the rate constant [68]... 

Tin(II) was found to be oxidized by dioxygen via the chain branching mechanism [156-162]. The oxidation rate is v = k[02]2 in organic solvents and v = [Sn(II)]1/2[02]1/2 in aqueous solutions. The reaction, under certain conditions, has an induction period. Free radical acceptors retard this reaction. The following kinetic scheme was proposed for tin(II) oxidation by dioxygen. 

By the free radical acceptor method in the decomposition of cumyl hydroperoxide catalyzed by Fe203 (343 K, 0.25 g cm-3 Fe203, ionol as acceptor of free radicals [257])... 

Rate Constants of Hydroperoxide Group Decomposition into Free Radicals Measured by Kinetics of Autoxidation and by Free Radical Acceptor Method... 

The study of POOH decay in the presence and absence of a free radical acceptor. In the absence of an inhibitor, the decay of POOH proceeds homolytically and under the action of radicals. 

Hydroperoxides oxidize aromatic amines more readily than analogous phenols. Thus, at 368 K cumyl hydroperoxide oxidizes a-naphthylamine and a-naphthol with ku = 1.4 x 10 4 and 1.7 x 10 5L mol-1 s 1, respectively [115,118], The oxidation of amines with hydroperoxides occurs apparently by chain mechanism, since the step of free radical generation proceeds much more slowly. This was proved in experiments on amines oxidation by cumyl hydroperoxide in the presence of /V,/V -diphcnyl-l, 4-phcnylcnediamine (QH2) as a radical acceptor [125]. The following reactions were supposed to occur in solution (80% decane and 20% chlorobenzene) ... 

At the same time, quinones do not practically retard oxidation of hydrocarbons, since alkyl radicals react very rapidly with dioxygen (see Chapter 4) to give alkylperoxyl radicals, which scarcely react with quinones. Quinones exhibit their inhibiting properties as alkyl radical acceptors only in the oxidation of polymers (see Chapter 19). However, quinones were found to decelerate the oxidation of alcohols very efficiently and for long periods by ensuring cyclic chain termination via the following reactions [31-34] ... 

The concurrent slow homolytic reaction gives rise to free radicals [14]. The occurrence of the homolytic reaction can be revealed by the consumption of free radical acceptors [8,15], CL [16], or NMR spectroscopy [17,18]. The introduction of phosphite into the hydroperoxide-containing cumene causes an initiation, pro-oxidative effect related to the formation of free radicals [6]. The yield of radicals from aliphatic phosphites is much lower (0.01-0.02%) than that from aromatic phosphites (up to 5%) [17]. The homolytic reaction of phosphites with hydroperoxide has a higher activation energy than the heterolytic reaction, which results in the predominance of the former reaction at elevated temperatures. 

These reactions produce free radicals, as follows from the fact of consumption of free radical acceptor [42]. The oxidation of ethylbenzene in the presence of thiophenol is accompanied by CL induced by peroxyl radicals of ethylbenzene [43]. Dilauryl dithiopropionate induces the pro-oxidative effect in the oxidation of cumene in the presence of cumyl hydroperoxide [44] provided that the latter is added at a sufficiently high proportion ([sulfide]/[ROOH] > 2). By analogy with similar systems, it can be suggested that sulfide should react with ROOH both heterolytically (the major reaction) and homolytically producing free radicals. When dilauryl dithiopropionate reacts with cumyl hydroperoxide in chlorobenzene, the rate constants of these reactions (molecular m and homolytic i) in chlorobenzene are [42]... 

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