Russian Journal of Applied Chemistry, 2010, Vol. 83, No. 5, pp. 926−928.
Pleiades Publishing, Ltd., 2010.
Original Russian Text
T.N. Gavrishova, V.M. Li, M.F. Budyka, 2010, published in Zhurnal Prikladnoi Khimii, 2010, Vol. 83, No. 5, pp. 873−875.
Synthesis of Di- and Triazido Derivatives
T. N. Gavrishova, V. M. Li, and M. F. Budyka
Institute of Chemical Physics Problems, Russian Academy of Sciences, Chernogolovka, Russia
Received November 16, 2009
Abstract—The possibility of obtaining new di- and triazidophenylpyridines: 4-phenyl-2,6-bis(4-azidophenyl)
pyridine and 2,4,6-tris(4-azidophenyl)pyridine by a three-stage synthesis from commercially available compounds
Aromatic azides, owing to their photochemical activ-
ity, are widely used for obtaining heterocyclic compounds
, photoresists , monomers , and as photoafﬁ ne
Recently attention of a number of researchers is
attracted by heteroaromatic polyazides. Di- and triazi-
dopyridines are used to generate quintet dinitrenes and
septet trinitrenes [5, 6], and azidotriazines are applied as
high-energy compounds [7, 8].
Using commercially available compounds (nitroaceto-
phenone and a corresponding benzaldehyde), in the present
work we have synthesized in three-stages di- and triazido
derivatives of 2,4,6-triphenylpyridine (TPP) with azido
groups in the para-position of phenyl rings: 4-phenyl-
2,6-bis (4-azidophenyl)pyridine (IIIa) and 2,4,6-tris(4-
azidophenyl)-pyridine (IIIb) (see the scheme).
These compounds are of interest for the study of the
size effect in aromatic azides  and a selective pho-
tolysis of nonequivalent azido groups , they can be
used as a support for obtaining cross-linked polymers
and dendrimers . High-spin polynitrenes, products
of the photolysis of azides (IIIa) and (IIIb) are interest-
ing subjects for studying regularities in the interaction
of nitrene centers through an aromatic π-system and the
effects of mutual orientation of nitrene centers on the
spin-spin interaction .
To construct the triphenylpyridine framework, we used
Kronke’s reaction, which is a modiﬁ cation of the synthesis
of pyridines after Chichibabin . The method consists
in the condensation of arylalcylketones with aromatic al-
dehydes in the presence of ammonium acetate in ice acetic
acid . To reduce the reaction duration and to increase
R = H, R' – NO
(Ia); R = H, R' – NH
(IIa); R = H, R' – N
(IIIa); R = R' =
(Ib); R = R' = NH
(IIb); R = R' = N