53. Some guanyl- and guanido-naphthalenes. Group migration in cyanonaphthalenes

The Preparation of Nitriles.

“…Thus, potassium acenaphthene-3-sulfonate and potassium ferrocyanide give acenaphthylene as the main product (443). King and Wright have shown that migrations of the nitrile group from the ß-to the «-position of the naphthalene nucleus sometimes occur in this synthesis (311). When sodium 2-naphthonitrile-7-sulfonate or the 2,7-naphthalenedisulfonate is treated with potassium cyanide, some 1,7dicyanonaphthalene is obtained together with the 2,7-derivative.…”

The Chemistry of Imidates.

“…Extending his investigations, Pinner (260) discovered that phthalonitrile gave rise to a monoimidate salt only, and King and Wright (178) found that whereas both cyano groups of 2,7-dicyanonaphthalene underwent conversion into the imidate, only the 7-cyano group of 1,7-dicyanonaphthalene was reactive under the conditions of the Pinner synthesis. Other examples of this proximity effect were discovered by Lander and Jewson (199), who failed to convert o-chlorobenzonitrile into an imidate, and by Guy and Paris (123), who were similarly unsuccessful in the case of o-cyanobenzenesulfonamide.…”

“…but, although many diamidines of potential trypanocidal action have been synthesized via diimidates, the imidates themselves have not been well characterized (12,178).…”

“…The reaction is normally carried out at 0°C., and anhydrous chloroform (12), nitrobenzene (12), dioxane (38,178), dimethyl Cellosolve (349), and, in particular, benzene (7,12,252) and ether (228,252,275) have been used as diluents. It has been established, however, that use of a solvent may be detrimental to the yield and that better results accrue in certain cases when the anhydrous diluent is added after several days or when the imidate is on the point of crystallization (222,285,308).…”

Aromatic Nucleophilic Substitution Reactions.

“…In the course of preparation of some dicyanonaphthalenes by cyanide fusion of cyanonaphthalenesulfonic acids or naphthalenedisulfonic acids, King and Wright (328)…”