Olefins radical reaction

In principle, this degradation can continue until the residual radical contains only hydrogen or methyl groups attached to the carbon with the odd electron. Those radicals which stiU contain a carbon—carbon bond can form an olefin via reaction 23 (or sequence 2, 24). Methyl radicals are a special case with limited options. 

A typical example of a nonpolymeric chain-propagating radical reaction is the anti-Markovnikov addition of hydrogen sulfide to a terminal olefin. The mechanism involves alternating abstraction and addition reactions in the propagating steps ... 

Nitrations are highly exothermic, ie, ca 126 kj/mol (30 kcal/mol). However, the heat of reaction varies with the hydrocarbon that is nitrated. The mechanism of a nitration depends on the reactants and the operating conditions. The reactions usually are either ionic or free-radical. Ionic nitrations are commonly used for aromatics many heterocycHcs hydroxyl compounds, eg, simple alcohols, glycols, glycerol, and cellulose and amines. Nitration of paraffins, cycloparaffins, and olefins frequentiy involves a free-radical reaction. Aromatic compounds and other hydrocarbons sometimes can be nitrated by free-radical reactions, but generally such reactions are less successful. 

Commercial phosphine derivatives are produced either by the acid-cataly2ed addition of phosphine to an aldehyde or by free-radical addition to olefins, particulady a-olefins. The reactions usually take place in an autoclave under moderate pressures (<4 MPa (580 psi)) and at temperatures between 60 and 100°C. 

This reaction proceeds through a chain mechanism. Free-radical additions to 1-butene, as in the case of HBr, RSH, and H2S to other olefins (19—21), can be expected to yield terminally substituted derivatives. Some polymerization reactions are also free-radical reactions. 

This is an exothermic reaction, and both homogeneous (radical or cationic) and heterogeneous (soHd catalyst) initiators are used. The products range in molecular weight from below 1000 to a few million (see Olefin polymers). Reaction mechanisms and reactor designs have been extensively discussed (10-12). 

Stannanes also add across double bonds offiuonnated olefins in a free radical reaction Trimethylstannane undergoes stereospecific addition to hexafluorocyclo-butene to afford trans 1,2,3,3,4,4 hexafluoro 1 (trimethylstannyl)cyclobutane [5] (equation 1)... 

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. 

B) is a 1,2-disubstituted olefin and is generally unre-active in free-radical reactions. 

The free-radical reaction may be equally initiated by photoactivated sulfur dioxide (3S02)442 (equation 79). On the other hand, polysulfones are obtained by radical copolymerization of appropriate olefins with sulfur dioxide443-449, and similarly, uptake of sulfur dioxide by a radical-pair formed by nitrogen extrusion from an azo compound yields the corresponding sulfone450 (equation 80). Correspondingly, alkylbenzenes, dibenzoyl peroxide, and sulfur dioxide yield sulfones under thermal conditions451... 

Few CIDNP studies on free radical reactions with olefins and related unsaturated molecules have been reported, and relatively little chemically useful information seems to have been derived, despite the potential relevance in polymerizing systems. Thus CIDNP has been reported in the decomposition of benzoyl peroxide in the presence of styrene and... 

The (TMS)3Si radical addition to terminal alkenes or alkynes, followed by radical cyclization to oxime ethers, were also studied (Reaction 50). The radical reactions proceeded effectively by the use of triethylborane as a radical initiator to provide the functionalized pyrrolidines via a carbon-carbon bond-forming process. Yields of 79 and 63% are obtained for oxime ethers connected with an olefin or propargyl group, respectively. 

In view of the extensive and fruitful results described above, redox reactions of small ring compounds provide a variety of versatile synthetic methods. In particular, transition metal-induced redox reactions play an important role in this area. Transition metal intermediates such as metallacycles, carbene complexes, 71-allyl complexes, transition metal enolates are involved, allowing further transformations, for example, insertion of olefins and carbon monoxide. Two-electron- and one-electron-mediated transformations are complementary to each other although the latter radical reactions have been less thoroughly investigated. 

Epoxides will also participate in radical reactions and this usually results in ring opening of the epoxide. The addition of a radical derived from xanthate 38 to butadiene monoepoxide provides the addition product 39 in good yields as an E/Z mixture of olefins <06AG(I)6520>. This reaction presumably proceeds through the addition of the xanthate-derived radical to the olefin, which then opens the epoxide. 

The same group recently disclosed a related free radical process, namely an efficient one-pot sequence comprising a homolytic aromatic substitution followed by an ionic Homer-Wadsworth-Emmons olefination, for the production of a small library of a,/3-unsaturated oxindoles (Scheme 6.164) [311]. Suitable TEMPO-derived alkoxy-amine precursors were exposed to microwave irradiation in N,N-dimethylformam-ide for 2 min to generate an oxindole intermediate via a radical reaction pathway (intramolecular homolytic aromatic substitution). After the addition of potassium tert-butoxide base (1.2 equivalents) and a suitable aromatic aldehyde (10-20 equivalents), the mixture was further exposed to microwave irradiation at 180 °C for 6 min to provide the a,jS-unsaturated oxindoles in moderate to high overall yields. A number of related oxindoles were also prepared via the same one-pot radical/ionic pathway (Scheme 6.164). 

Besides the mirror and addition reactions already discussed, gas phase radicals dimerize, disproportionate, transfer hydrogen, and polymerize olefins. Similar reactions in the liquid phase are an indication (but not proof) of free radical intermediates. 

Scheme 12.21. Selective formation of a tetrasubstituted olefin by a tandem radical reaction.

The first reactions of fluorinated olefins in C02 reported by DeSimone et al. involved the free-radical telomerization of 1,1 -difluoroethylene29 and tetrafluor-oethylene.30 This work demonstrated the feasibility of carrying out free-radical reactions of highly electrophilic species in solvents other than expensive fluorocarbons and environmentally detrimental chlorofluorocarbons. The work has since been more broadly applied to the synthesis of tetrafluoroethylene-based, nonaqueous grades of fluoropolymers,31,32 such as poly(tetrafluoroethylene-co-peduoropropylvinyl ether) (Scheme 2). These reactions were typically carried out at between 20 and 40% solids in C02 at initial pressures of between 100 and 150 bars, and 30-35°C (Table 10.1). 

Use of the kinetic advantage method thus points clearly to the occurrence of chemical catalysis with the low-valent metalloporphyrins. This is confirmed by repeating, with iron(I) octaethylporphyrin and cobalt (I) etioporphyrin, the stereochemical experiments carried out earlier with the anion radical of 1,4-diacetylbenzene. Complete stereospecificity is observed in both cases The meso isomer of 4,5-dibromooctane is converted totally into the c/.v-olcfin the d,l isomer is converted totally into the trans-olefin. The reaction again exhibits a clear antiperiplanar preference. 

In one of the earliest investigations of spin trapping, olefin polymerization was employed to demonstrate the utility of the method as a qualitative probe for free-radical reactions (Chalfont et al., 1968). The polymerization of styrene, initiated by t-butoxyl radicals, proved to be an excellent system with which to obtain spectra attributable to spin adducts with MNP (a) of the initiator radical... 

Although thiolacetic acid additions are free-radical reactions (60), it was found recently that the addition to electron-poor olefins can be base catalyzed (61) (eqs. [14], [15]). Thus the (S)-(-) adduct is obtained with an e.e. of 54% when cyclohexenone is treated with thiolacetic acid in benzene in the presence of catalytic amounts of cinchonine. The reaction appears to be quite general, although very high e.e. s (>80%) have not yet been achieved. 

Cobaloxime(I), electrochemically regenerated from chloro(pyridine)-cobaloxime (III) (232), has been employed as a mediator in the reductive cleavage of the C—Br bond of 2-bromoalkyl 2-alkynyl ethers (253), giving (254) through radical trapping ofthe internal olefin (Scheme 95) [390]. An interesting feature of the radical cyclization (253) (254) is the reaction in methanol, unlike the trialkyltin hydride-promoted radical reactions that need an aprotic nonpolar solvent. An improved procedure for the electroreductive radical cyclization of (253) has been attained by the combined use of cobaloxime(III) (232) and a zinc plate as a sacrificial anode in an undivided cell [391]. The procedure is advantageous in terms of the turnover of the catalyst and the convenience of the operation. 

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