Naphthalene acetoxylation

Acetoxylation and nitration. It has already been mentioned that 0- and m-xylene are acetoxylated as well as nitrated by solutions of acetyl nitrate in acetic anhydride. This occurs with some other homologues of benzene, and with methyl phenethyl ether,ii but not with anisole, mesitylene or naphthalene. Results are given in table 5.4. 

Four isomers 2-nitro- bacetoxy-, 5 nitro-l acetoxyl-nitro-2 acetoxy- and, fi-n 7ro-2-acetoxy-naphthalene are described in Beil 6, 615, 616, 654 655... 

Acetoxylation of naphthalene was achieved with stoichiometric amount of Pd(OAc)2 or in a catalytic reaction using the Cu2+ + 02 system for the reoxidation of Pd(0) 786... 

Reactions of 1,4-dimethoxynaphthalene and its 2-chloro, 2-bromo, and 2-(1,3-dioxolanyl) derivatives with BAIB/TMSX (X = C1, Br) combinations in dichloromethane result in acetoxylation, monohalogenation, or dihalogenation of the more activated ring (Scheme 26) [79]. Specific outcomes depend on the naphthalene derivative and reaction conditions. It is interesting that the 2-(1,3-dioxolanyl) derivative undergoes ipso-bromination with BAIB/TMSBr, and that this mode of reactivity was not observed with 2-(l,3-dioxolanyl)-l,4-di-methoxybenzene. These reactions are mechanistically diverse. Evidence was presented that bromination occurs after the formation of molecular bromine, and that chlorination probably follows a radical pathway involving the homo-... 

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