A new synthesis of aryl hetaryl ketones via S_RN1 reactions of halogenated heterocycles with potassiophenylacetonitrile followed by phase‐transfer catalyzed decyanation

Abstract

Reaction of halogenated pyridines, quinolines, pyrimidines, and pyrazines with potassiophenylacetonitrile (5) in liquid ammonia under near‐uv irradiation affords secondary nitriles, which then undergo oxidative decyanation under phase‐transfer catalytic conditions to afford aryl hetaryl ketones in excellent yields.

Difluoromethylation of some C–H acids with chlorodifluoromethane under conditions of phase transfer catalysis (PTC)

“…Oxidation of 2-arylalkanenitrles (including 1a) with oxygen under PTC conditions to the corresponding phenones is firmly established [27][28][29]. Reactions of 1a carried out either in the presence of more diluted sodium hydroxide solutions or in different solvents and temperatures gave usually lower content of 2a in the reaction mixtures ( Table 2, entries 2-6).…”

Phase-Transfer-Catalyzed Oxidations

“…Aryl pyridinyl ketones were prepared in a two-step PTe procedure involving first alkylation of phenylacetonitrile, then oxidation of the resulting nitrile with air [212]: • DHDMAC = dihexadecyldimethylanunonium chloride.…”

2-Cyanomethylbenzaldehyde – useful substrate for preparation of some 1,3-di- and 1,2,3-trisubstituted naphthalenes or substituted 1-cyanobenzobicyclo[2.2.2]octenes

“…It is well established that PTC oxidation of α-arylalkanenitriles with dioxygen leads to the formation of corresponding phenones. [14][15][16] In the case of 5, this reaction should give 3-aroyl-1-naphthols (by an oxidationtautomerization route), which in fact were not formed. On the other hand, 2-substituted derivatives of 1,4-dicyano-1,2-dihydronaphthalene treated with 5% ethanolic potassium hydroxide were dehydrogenated into 1,4-dicyanonaphthalenes in low yield, but aromatization comprised mainly elimination of hydrogen cyanide.…”