Formation directe des β‐alkylhydroxylamines

The Principle of Vinylogy.

“…An extremely interesting comparison of these vinylogs was made by Angelí (5), who pointed out that in NO, NO, NO, NO, (ortho or para) Angelí (1) showed also that p-nitrotoluene was converted by the action of nitrous acid to the oxime analogous to the nitrolic acid derived from nitromethane in the same manner: The replacement of a nitro group in o-dinitrobenzene by a hydroxyl group (51), an amino group (52), or a methoxyl group (54) takes place when the dinitro compound is treated, respectively, with aqueous alkali, ammonia, or sodium methoxide. Similar reactions take place with p-dinitrobenzene (54). m-Dinitrobenzene, on the other hand, resists the action of such reagents; heating with solid potassium hydroxide fails to displace the nitro groups.…”

“…With p-chlorobenzaldehyde lepidine gives a 70 per cent yield of p-chlorobenzallepidine (30). When treated with benzaldehyde 2-phenyllepidine gives a 54 per cent yield of the corresponding benzal derivative (40).…”

Aromatic Nucleophilic Substitution Reactions.

“…It is therefore to be expected that the phenomenon of the declining rate coefficient should be more pronounced at higher temperatures, and this has been observed (283). Also, the reaction of alcoholic ammonia with p-dinitrobenzene produces p-nitroaniline at low temperatures and p-nitrophenetole at elevated temperatures (377).…”

Metallic Salts of Alcohols and Alcohol Analogs.

“…Presumably tetraalkylammonium alphyl oxides (274,272,397,1,189), tetraalkylammonium (146) and tetraalkylarsonium (121a) salts of alkanes, and hydrazinium methoxide (82) can exist only at low temperatures. The reactions which should give rise to them at higher ones yield only decomposition products.…”