Corps aromatiques nitrés. XIII. Sur la substitution du groupe nitro par oxyméthyle et oxyéthyle. A. Préparation du para‐oxyméthyl (éthyl)‐benzonitrile

Abstract

Corps aramatiques nitrks. XIII. Yur la substitution do groupe nitro par oxymbthyle et oxyktbyle. A. Prdparc4 tion du paraoxy mdt h y I (dt h y 1)befizonitrile, PAR M.M. W. REINDERS et W. E. RINGER. I) Pour les derives ortho voir la note suivante de M. W. RIIQER. 2, Ber. 18, 1492.

Aromatic Nucleophilic Substitution Reactions.

“…Section V,B). Straightforward hydrolysis or methanolysis of o-and p-dinitrobenzenes (534), o-and p-nitrobenzonitriles (465,484), s-trinitrobenzene (469), and 1,2,4-trinitrobenzene (374) has been recorded, but ethoxide tends to reduce rather than replace the nitro group in p-nitrobenzonitrile (465).…”

Direct methoxylation of nitroarenes and nitroazaarenes with alkaline methoxides via nucleophilic displacement of an aromatic hydrogen atom

“…The reaction of nitroarenes with alkoxide ions has previously been reported in a few papers, but its scope is limited and yields are often low due to the extensive formation of by-products. 3,4 It has long been known that the reaction between 1,3dinitrobenzene 1 and alkali methoxide results in the alkoxydenitration to give 3-nitroanisole 5b, since the methoxide ion is not strong enough as a base to abstract a ring hydrogen from the initial Meisenheimer adduct 2b and, therefore, it prefers to replace the nitro group as a nitrite ion from the second Meisenheimer adduct 3b which forms in equilibrium with 2b (Scheme 1). However, similar attempts to extend this methodology to the direct introduction of alkoxy groups were unsuccessful.…”

Synthesis of phenyl furyl sulfides and phenyl furyl ethers by nucleophilic substitution of nitrofurans

“…In 1891, Tiemann [3] synthesized o-and p-methoxybenzonitrile by reacting 2-chloro-4-nitrobenzaldehyde and sodium methoxide, and in 1899, Reinders and Ringer [4] synthesized the same compound from p-nitrobenzonitrile and sodium methoxide. In a 1957 study into the rate of substitution, Bunnett et al [5] reported that in reactions between pipiridine and 1,2,4-trinitrobenzene, 1-chloro-2,4-dinitrobenzene or 1-bromo-2,4-dinitrobenzene in methanol, the relative rate of substitution of the nitro group at position 1 was 200 times faster than that of chlorine or bromine.…”