A New Modified Electrophilic Cyanation of Aromatics with Activated Aryl Cyanates

3,4-Dihydro-benz[1,3]oxazine Derivatives from 2-Acyl(or aroyl)-cyanatobenzenes

“…Recently we were able to show that 3-or 4-acyl(or benzoy1)-cyanatobenzenes react, using Friedel-Crafts conditions, with electron-rich aromatics under cyanation. This reaction proceeds with high para-selectivity leading to carbonitriles in moderate to good yields [12]. However, cyanatobenzenes 2 substituted in ortho position to the carbonyl group show a different reaction behaviour.…”

Acylated cyanatoarenes - reagents for convenient cyanations

“…The reaction is carried out with A1C13 + HCl as catalyst. Moderate to good yields of isolated carbonitriles 8 are obtained by treating the aromatic compounds with 1 or 2a at 0 to 5°C [24].…”

“…Recently, we described the improved cyanation of aromatics, enamines and 1,3-dicarbonyl compounds using cyanatoarenes which are activated by carbonyl groups. We have found that cyanatoanthraquinone 1 and acylsubstituted cyanatobenzenes 2a, 2b act as convenient and powerful reagents for the introduction of hitrile functions [23,24]. The reagent of choice is determined by factors such as workingup procedures.…”

“…The yields obtained are only moderate [5, 21, 221. Despite the usefulness of the reagents mentioned above there are several factors limiting their general application, for example toxical or irritating activities, difficult accessibility, thermal instability, or small yields in some cases [12, 141. Recently, we described the improved cyanation of aromatics, enamines and 1,3-dicarbonyl compounds using cyanatoarenes which are activated by carbonyl groups. We have found that cyanatoanthraquinone 1 and acylsubstituted cyanatobenzenes 2a, 2b act as convenient and powerful reagents for the introduction of hitrile functions [23,24]. The reagent of choice is determined by factors such as workingup procedures.…”