Radicals ether-substituted

An Sjuyl-type (S l ) mechanism has been proposed in the synthesis of poly(2,6-dimethyl-l,4-phenylene ether) through the anion-radical polymerization of 4-bromo-2,6-dimethylphenoxide ions (204) under phase-transfer catalysed conditions269. Ions 204 are oxidized to give an oxygen radical 205. The propagation consists of the radical nucleophilic substitution by 205 at the ipso position of the bromine in 204 (equation 144). The anion-radical 206 thus formed eliminates a bromide ion to form a dimer phenoxy radical 207 (equation 145). A polymeric phenoxy radical results by continuation of this radical nucleophilic substitution. 

Chemical Properties.—Chemically the ethers are not very active nor do they lead to important derivatives. Chlorine forms substitution products in which, as in methyl ether, one to six hydrogens of the alkyl radicals are substituted. The halogen acids, especially hydriodic acid, form an alcohol by a reaction analogous to the reversion of the Williamson synthesis. 

Among nucleophiles used are enols " (including mono- and bis-TMS ethers, which are particularly favorable ) derivatives of P N and S in hydrogen sulfite dithionate and sulfide Si, Ge, Sn and alkyl or aryl in derivatives of Cd, Zn or Li . The Li reagents in particular require special experimental conditions, including dichloro methane as solvent and radical scavengers. Many nucleophiles cause electron addition to the cations, with formation of radicals. Aromatic substitutions displace not only H but SnMej or SiMe3 . Allylsilanes and trialkyl alkynylborates provide synthetically useful products. 

In synthetic contexts, thiyl radicals are known to engage in a number of useful reactions [191-198], including C-H bond abstraction [197, 199-203]. Recently, MacMillan has demonstrated the capacity of catalytically generated thiyl radicals to cleave the C-H bond of benzylic ethers for radical coupling reactions (Fig. 27) to form diaryl methanols (a) [204] or p-amino ethers (b) [205]. The light source is either a Blue LED or a Compact fluorescent lamp (CFL), as designated above. In both reactions, a wide variety of arene components and ether substitutions are tolerated to furnish a diverse set of products and only a catalytic amount of methyl thioglycolate is necessary to affect the desired C-H HAT event. In the formation of diaryl ethers (Fig. 27a), phosphate serves as the base, whereas the P-amino ether... 

The intermediacy of phenyl radicals in the thermal decomposition of aryldiazo alkyl ethers (9)" and in the products from nitrosation of 1,3-diphenyltriazene (10)" has been demonstrated. Reactions of phenyl radicals with substituted 9-methylanthracenes and 9-halogeno-anthracenes invariably give 10-phenylated products."... 

The hydrogenolyaia of cyclopropane rings (C—C bond cleavage) has been described on p, 105. In syntheses of complex molecules reductive cleavage of alcohols, epoxides, and enol ethers of 5-keto esters are the most important examples, and some selectivity rules will be given. Primary alcohols are converted into tosylates much faster than secondary alcohols. The tosylate group is substituted by hydrogen upon treatment with LiAlH (W. Zorbach, 1961). Epoxides are also easily opened by LiAlH. The hydride ion attacks the less hindered carbon atom of the epoxide (H.B. Henhest, 1956). The reduction of sterically hindered enol ethers of 9-keto esters with lithium in ammonia leads to the a,/S-unsaturated ester and subsequently to the saturated ester in reasonable yields (R.M. Coates, 1970). Tributyltin hydride reduces halides to hydrocarbons stereoselectively in a free-radical chain reaction (L.W. Menapace, 1964) and reacts only slowly with C 0 and C—C double bonds (W.T. Brady, 1970 H.G. Kuivila, 1968). 

Ethers (R —O—R ). In substitutive nomenclature, one of the possible radicals, R—O—, is stated as the prefix to the parent compound that is senior from among R or R. Examples are methoxyethane for CH3OCH2CH3 and butoxyethanol for C4Hc,0CH2CH20H. 

Partial ethers of polyhydroxy compounds may be named (1) by substitutive nomenclature or (2) by stating the name of the polyhydroxy compound followed by the name of the etherifying radical(s) followed by the word ether. For example. 

Aromatic ethers and furans undergo alkoxylation by addition upon electrolysis in an alcohol containing a suitable electrolyte.Other compounds such as aromatic hydrocarbons, alkenes, A -alkyl amides, and ethers lead to alkoxylated products by substitution. Two mechanisms for these electrochemical alkoxylations are currently discussed. The first one consists of direct oxidation of the substrate to give the radical cation which reacts with the alcohol, followed by reoxidation of the intermediate radical and either alcoholysis or elimination of a proton to the final product. In the second mechanism the primary step is the oxidation of the alcoholate to give an alkoxyl radical which then reacts with the substrate, the consequent steps then being the same as above. The formation of quinone acetals in particular seems to proceed via the second mechanism. ... 

Additions of elemental halogens to unsaturated compounds are among the most common preparations of halogenated fluoroorganics. The transformations are usually fairly clean and proceed in good yields. Besides the numerous examples of halogen addition tofluoroalkenes and fluoroalkyl-substituted alkenes, additions to perfliioropropyl vinyl ether [2] and fluormated styrenes [7, 4] have been reported. Both ionic and free-radical processes occur (equations 1 and 2)... 

The rate-determining step in the formation of the x-lithio ethers is the formation of a carbon radical as a precursor to the anion. The intermediate radical in the tetrahydropyranyl system is expected to be nonplanar, to be capable of rapid equilibration between the quasiequatorial and quasiaxial epimers, and to exist largely or entirely in the axial configuration at — 78 °C. However, treatment of the a-phenylthio ether 4 with LDMAN at higher temperature in the presence of A, A, lV, ./V -tetramethylethylenediamine leads to the more stable equatorial epimer of the lithio ether 5 and, after addition to benzaldehyde, the axial- and equatorial-substituted products were obtained in a ratio of 13 87. 

The benzoin ethers (75, R-alkyl R H) and the ot-alkyl benzoin derivatives (75, R=H, alkyl R =alkyl) undergo a-scission with sufficient facility that it is not quenched by oxygen or conventional triplet quenchers.276 This means that the initiators might be used for UV-curing in air. Unfortunately, it does not mitigate the usual effects of air as an inhibitor (Section 5.3.2). The products of a-scission (Scheme 3.53) are a benzoyl radical (13) and an ( -substituted benzyl radical (76) both of which may, in principle, initiate polymerization, 76 2"... 

Broxton and Bunnett (1979) determined the products of the reaction of 4-chloro-3-nitrobenzenediazonium ions with ethoxide ion in ethanol, which is exactly analogous to the reaction in methanol discussed earlier in this section. These authors found 12.8% 4-chloro-3-nitrophenetole, 83% 2-chloronitrobenzene, and 0.8% 2-nitrophenetole. When the reaction was carried out in C2H5OD, the first- and second-mentioned products contained 99% D and 69% D respectively. Dediazoniation in basic ethanol therefore results in a higher yield of hydro-de-diazoniation with this diazonium salt compared with the reaction in methanol. This is probably due to the slightly higher basicity of the ethoxide ion and to the more facile formation of the radical CH3-CHOH (Packer and Richardson, 1975). Broxton and McLeish (1983 c) measured the rates of (Z) — (E) interconversion for some substituted 2-chlorophenylazo ethyl ethers in ethanol. 

Bowman and Symons145 probed the stability of a series of radical anions involved in the SRN1 substitution for a-substituted aliphatic nitro-compounds [Me2C(X)N02] by studying with ESR at 77 K the succession of events following electron capture by Me2C(X)N02. The radical anions were more concentrated in an ether matrix than in an... 

Fused cyclic ethers can be derived from appropriately substituted sugars. An example is given with the stereoselective 5-exo radical cyclization of allylic... 

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