Synthesis of Polycyano-Substituted Azulenes via Direct Oxidative Cyanation Reaction

Abstract

The synthesis of dicyano-, tricyano-, and tetracyanoazulenes substituted on both rings via direct oxidative cyanation reaction is described. 1-Cyanoazulene or 1,3-dicyanoazulene treated with tetraethylammonium cyanide (Et 4 N + CN -) and subsequently with DDQ or para-chloranil were transformed stepwise into the desired polycyano-substituted azulenes. Scheme 3Downloaded by: University of Pittsburgh. Copyrighted material.Counterion Et 4 N + (for both 9a, 10a): d = 3.02 (q, 2 H, J = 7.3 Hz, CH 2 ), 1.25 (t, 3 H, J = 7.3 Hz, CH 3 ). Adduct 11aMixture of 9 with TEAC, at r.t.

Superacidity of P(OH)3 and SO(OH)2 derivatives of cyclopentadiene and vinylcyclopentadiene in the gas phase: A computational DFT analysis

“…The latter has a number of favorable consequences, including a low nucleophilicity and a weakly coordinating ability of the conjugate base anions. In this context, and since the chemistry of the cyano group is known, attempts to synthesize and prepare some of the acids proposed here are highly recommended.…”

Alkynylazulenes as Building Blocks for Highly Unsaturated Scaffolds

“…Makosza et al reported the synthesis of 1-cyano-6-trimethylsilylethynylazulene (48) in 97% yield from 1-cyanoazulene (47) by firstly vicarious nucleophilic substitution (VNS) hydroxylation at 6-position to give 6-hydroxyazulene-1-carbonitrile followed by 6-O-sulphonylation to afford the corresponding trifluorome-thanesulfonate derivative and subsequent reaction with TMSA under Sonogashira conditions (Scheme 8). [46]…”