A model for the attack of a nucleophile on a nitrile group: the X-ray crystal structure of 2,2′-bipyridine-3,3′-dicarbonitrile

Abstract

From analysis of the geometry of the attractive intramolecular interactions between the pyridine N atoms and the nitrile C atoms in title compound 2 it is proposed that the most favoured direction of approach of a nucleophile t o an sp C(=N) makes an angle of at least 108" t o the triple bond.

A competition between O⋯N and O⋯C through space interactions in the crystal structures of 3,3′-dinitro-2,2′-bipyridine N-oxides and N,N′-dioxides

“…Thus, a pair of interactions was observed in the dinitrile 7 with (pyridine)N … CMN separations of 2.695(2) and 2.740(2) A ånd bendings of the nitrile groups of 171.3(1)-171.6(1)u. 13 However, extension of this approach to groups with sp 2 centres attached to the 3 and 39 positions, e.g. in compounds 8 and 9 containing nitro or carboxylic ester groups, did not reveal such interactions between the pyridine nitrogen and the electron deficient group, but rather an oxygen atom from each group made a contact with the 2-carbon atom of the opposite ring (8: 2.916(2) and 2.980(2) A ˚; 9: 2.849(3) A ˚).…”

Core-Modified Phthalocyanines and Subphthalocyanines: a Synthetic Strategy towards Core-Modification and Novel Properties Arising from the Inner Ring-Expansion

“…The seven-membered-ring-containing SubPc analogues 9a and 10a were also successfully synthesized in 9.1 and 9.8 % yields, respectively, using 2,2'-biphenyldicarbonitrile [17] and 4,5-phenantherenedicarbonitrile [18] instead of 1,8-naphthalenedicarbonitrile (Scheme 4). [13,14] To our surprise, however, mixed condensation reactions with tetrafluorophthalonitrile can only provide these target core-modified compounds.…”

“…In this case, only a mono-substituted Pc analogue was obtained probably due to the severe steric effect of the large sevenmembered ring unit. Other dinitrile derivatives, such as 2,2'-bipyridyl-3,3'-dicarbonitrile and 4,5-phenanthrenedicarbonitrile [17,18] can also be utilized in place of 2,2'-biphenyldicarbonitrile to provide seven-membered ring-containing species 6 and 7, respectively (Scheme 2).…”

Interpretation of neighboring group interactions in crystal structures. A solid state and quantum-chemical study of "incipient nucleophilic attack" in 2-diazonium benzoic acid and its benzoate

“…Because of its simplicity, this model quickly was applied to related systems as well. The attack of a nucleophile on a nitrile group can be discussed from this vantage point since the C=N and C=O bonds show similar polarities (5). In fact, the concept of incipient nucleophilic attack has been broadened (6) to include not only nucleophilic attack on polar '+cx" or "YO'-multiple bonds but on all kinds of multiple bonds and to include dative bond formation as well.…”