Benzene derivatives benzylic carbons

The reaction of thiophene with the styrene-derived aziridine 44 with I11CI5 catalysis involves attack mainly at the more hindered and benzylic carbon, although ca. 10% of product formation derives from terminal attack (Scheme 33) <2002TL1565>. Similarly, In(OTf)3 can be used to promote the reaction of 44 with reactive benzenes, with the same regioselectivity <2001TL8067>. 

According to Section 4.02.3.1.8 substituents removed from the pyrazole ring by two or more saturated carbon atoms and substituents on the benzene ring of indazoles are similar in reactivity to the corresponding aromatic derivatives. For instance, chloromethyl-pyrazoles are comparable to benzyl chlorides and 5-hydroxyindazoles to /3-naphthols in their reactivity. 

Carbonylat ion of 13 4-nitrophenyloxycarbonyl chloride (J 6) in pyridine] gave a good yield of the trityl ether-carbonate 14 which was de-tritylated by hydrogenolysis (2 4) to afford the 7,8-diol-4,5-carbonate 15 in practically quantitative yield. Compound 15.. by way of its 7,8-0 -dibutylstannylidene derivative (25> 26) was regioselectively 8-0-benzylated (dibutyltin oxide, benzene, reflux then benzyl bromide, dimethyl formamide, 95 ), in fair yield (J ). Finally, the aglycon U3 was obtained in high yield by sequential 7-Q-tert.-butyldimethylsilylation (27) (compound 17) and Zemplen saponification. 

TABLE 12.4 Voltammetric Oxidation Potentials and Peak Currents (pA/mM) of Alkoxy-Substituted Benzenes, Phenols, and Benzyl Alcohols, and Their Derivatives in MeCN (0.1 M TEAP) at a Glassy-Carbon Electrode... 

Monomers Not Polymerizable by Plasma Initiation. When styrene and a-methy1styrene were subjected to plasma treatment, the monomers became yellowish and only trace amounts of insoluble films were formed. The discoloration was intensified and extensive formation of dark films were observed if carbon tetrachloride was added as the solvent. No post-polymerization was detectable for these monomers. Generally styrene and a-methylstyrene readily undergo thermal polymerization. However, no thermal polymerization was possible for these monomers after having been subjected to plasma treatment for one minute or less. It has been demonstrated from the emission spectra of glow discharge plasma of benzene (6) and its derivatives (7 ) that most of the reaction intermediates are phenyl or benzyl radicals which subsequently form a variety of compounds such as acetylene, methylacetylene, allene, fulvene, biphenyl, poly(p-phenylenes) and so forth. It is possible that styrene and a-methylstyrene also behave similarly, so that species from the monomer plasma are poor initiators for polymerization. 

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