Benzynes anion-radicals

The neat resin preparation for PPS is quite compHcated, despite the fact that the overall polymerization reaction appears to be simple. Several commercial PPS polymerization processes that feature some steps in common have been described (1,2). At least three different mechanisms have been pubUshed in an attempt to describe the basic reaction of a sodium sulfide equivalent and -dichlorobenzene these are S Ar (13,16,19), radical cation (20,21), and Buimett s (22) Sj l radical anion (23—25) mechanisms. The benzyne mechanism was ruled out (16) based on the observation that the para-substitution pattern of the monomer, -dichlorobenzene, is retained in the repeating unit of the polymer. Demonstration that the step-growth polymerization of sodium sulfide and /)-dichlorohenzene proceeds via the S Ar mechanism is fairly recent (1991) (26). Eurther complexity in the polymerization is the incorporation of comonomers that alter the polymer stmcture, thereby modifying the properties of the polymer. Additionally, post-polymerization treatments can be utilized, which modify the properties of the polymer. Preparation of the neat resin is an area of significant latitude and extreme importance for the end user. 

Intra-complex TMS+ abstraction by F yields the trimethylenemethane radical anion 33. Similarly, a number of other (mostly aromatic) distonic radical anions have been generated. Using the same approach, several other highly unsaturated distonic negative ions, such as the benzyne radical anions, were also studied164. 

The distonic radical anions of o-, m-, and p-benzyne were crucial intermediates in an elegant determination of the S,T splitting of the corresponding benzynes. The ions are accessible by well-estabhshed (routine) gas-phase reactions o-benzyne... 

A variation on the aryne mechanism for nucleophilic aromatic substitution (discussed above, Scheme 2.8) is the SrnI mechanism (see also Chapter 10). Product analysis, with or without radical initiation or radical inhibition, played a crucial role in establishing a radical anion mechanism [21]. The four isomeric bromo- and chloro-trimethylbenzenes (23-X and 25-X, Scheme 2.9) reacted with potassium amide in liquid ammonia, as expected for the benzyne mechanism, giving the same product ratio of 25-NH2/23-NH2 = 1.46. As the benzyne intermediate (24) is unsymmetrical, a 1 1 product ratio is not observed. 

Aromatic compounds are dechlorinated by the general mechanism shown in Sch. 1. Electron transfer to a ir-antibonding orbital forms an aromatic radical anion, which then ejects Cl" to give an aromatic radical. This radical picks up a second electron to give a very basic cx-anion, which abstracts a proton either from NH3 or from a more acidic source like water, when water is present. If water is not present, then an NH2 anion can be formed. The presence of ME can lead to the formation of aminated products via the benzyne mechanism. Aminated products were formed in dry NH3 but not when water was present [24], A further reduction via radical anion formation and proton abstraction can give dihydroaromatics or tetrahydroaromatics, or dimerization may occur. In soils, both water and... 

Excited radical anions may be created in a medium which is only slightly reducing, which is not always the case in the presence of anions or by direct electrochemistry. If, for instance, o-dibromobenzene is electrochemically reduced, benzene is the product, obtained via bromobenzene radical and benzyne, since the second electron uptake cannot be avoided [181]. 

Another reaction that cannot be an SN2, because of the impossibility of carrying it out on an aryl halide, is the displacement from the aryl bromide 7.187. The mechanism is an Sr jI reaction (see p. 147), involving an electron transfer from the enolate 7.186 to the halide 7.187. The radical anion 7.189 loses the bromide ion to give the aryl radical 7.190, and this couples with the radical 7.188 derived from the nucleophile to give the ketone 7.191.252 The m-mcthyl group shows that the reaction did not take place by way of a benzyne. 

Such results indicate that, from a mechanistic point of view, it is not a matter of a simple aromatic nucleophilic substitution (in any case very difficult if not yi benzyne), but more probably of a radical substitution on an activated complex of the TCDD (SRNl mechanism) (1 ) this mechanism is favoured by the fact that the radical anion of TCDD is particularly stabilized (IJ). How this radical anion is generated from the initiator peroxide and how it reacts with the hydrogen donor (PEG or the solvent) is not at this moment clear however, interesting to note, degradation of TCDD by u.v. irradiation leads to the same intermediate compounds. 

Deoxygenation of 1,4-epoxy-1,4-dihydronaphthalenes. The Diels—Alder adducts of benzynes with furanes can be aromatized by this radical anion in... 

Cyclopentadienyl anion Bicyclo [1,1,1] -propellane Pentadienyl radical p-Benzyne m-Benzyne 0- Benzyne Cyclopentene Bicyclo [1,1,1] -pentane... 

Early on, it was demonstrated that aromatic nitro compounds may form radical anions in alkaline solutions [4], with the possibilities of photochemical reactions [5]. There followed the development of the radical chain mechanism [6]. An interesting early danonstration of reaction by this mechanism was in the reaction of ort/io-halogenoanisoles with potassium amide in liquid ammonia [7]. Reaction by the benzyne mechanism gives predominantly the uiera-substituted product due to the electronic influence of the methoxy group. Howeva, with an access of potassium metal, which promotes electron transfer, the pathway predominates yielding ort/io-anisidine, as shown in Scheme 6.4. The mechanism now forms an important synthetic pathway, and this and other homolytic processes are covered in Chapters 9 and 10. 

To the more usual homolytic fragmentation of aryl halides (from the excited state or from the radical anion, the well known SrnI reaction, for a recent example see the arylation of aromatics), the heterolytic version of the reaction which produces phenyl cations has more recently joined. A theroretic study on the photodissociation of fluorinated iodobenzenes has been published. The perfluoroallgrlation of various alkenes has been obtained by irradiation in the presence of iodoperfluorobutane. The formation of phenyl cations is exemplified in many arylation reactions and, in the case of o-chlorostannane, also a benzyne has been reported. In the field of polymer chemistry, iodonium salts are model cationic photoinitiators. In particular the truxene-acridine/diphenyl iodonium salt/9-vinylcarbazole combination is able to promote the ringopening polymerization of an epoxide, whereas the truxene AD/allq l halide/amine system is very efficient in initiating the radical photopolymerization of an acrylate. ... 

Transposition of substituents takes place from aromatic compounds based on ortho effects from hydroxyphenyl ketones via assumed nucleophilic attack on the carbonyl carbon atom of the phenoxide site to give a tight tetravalent intermediate that promptly decomposes through benzyne neutral release and formation of a carboxylate anion (Scheme 17.19a). This reaction is hindered from meta- and para-substituted phenols. Alternatively, radical alkane loss is also observed that can be rationalized by considering the formation of an ion-neutral complex (Scheme 17.19b) comprised of quinone-like and alkylide groups. The relatively low ionization energy allows the generation of odd-electron quinone-like species and the elimination of the alkane radical (Scheme 17.19b). 

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