Russian Journal of Applied Chemistry, 2010, Vol. 83, No. 10, pp. 1862−1867.
Pleiades Publishing, Ltd., 2010.
Original Russian Text
I.V. Gofman, M.Ya. Goikhman, I.V. Podeshvo, E.E. Eliseeva, E.E. Bol’bat, I.V. Abalov, A.V. Yakimanskii, 2010, published in Zhurnal
Prikladnoi Khimii, 2010, Vol. 83, No. 10, pp. 1722−1727.
AND POLYMERIC MATERIALS
Films of Polyamides with Phenylpyridine Units
in the Backbone
I. V. Gofman
, M. Ya. Goikhman
, I. V. Podeshvo
, E. E. Eliseeva
, E. E. Bol’bat
I. V. Abalov
, and A. V. Yakimanskii
Institute of Macromolecular Compounds, Russian Academy of Sciences, St. Petersburg, Russia
St. Petersburg State University, St. Petersburg, Russia
Received May 5, 2010
Abstract—New polyamides derived from 2-(4-aminophenyl)-5-aminopyridine, 4,4-diaminodiphenyl ether, and
4,4'-terephthaloyloxybis(3-methoxybenzoic) acid dichloride were prepared. These polyamides are of interest
as macromolecular ligands. The deformation–strength, thermomechanical, and thermal properties of ﬁ lms of
polyamides with various content of phenylpyridine fragments were studied.
The design, synthesis, and study of properties of
new polymers containing heterorings are of much
interest for both basic and applied chemistry, because
such systems often exhibit unique properties: high
strength and heat resistance in combination with the
capability to form stable complexes with transition
metals. Among such systems, researchers’ attention has
recently been attracted by polymers containing in the
backbone  or pendant groups  2-phenylpyridine
(PP) fragments. Such polymers can act as
macromolecular ligands in formation of electrically
neutral metal–polymer complexes with Ir(III). These
compounds exhibit a unique combination of chemical
stability and luminescence and redox properties [3, 4].
Here we report on the synthesis and properties of a new
series of polyamides (PAs) containing PP units in the
Commercial solvents and chemicals were used
without additional puriﬁ cation and drying.
2-(4-Aminophenyl)-5-aminopyridine was prepared
in four steps. The ﬁ rst two steps have been implemented
for the ﬁ rst time.
1,3-Bis(piperidinyl)trimethinium perchlorate I.
To 1,1,3,3-tetramethoxypropane (14 ml, 0.085 mol),
we added with stirring 8 ml of 57% perchloric acid and
allowed the mixture to stand for 1 h at room temperature.
Then piperidine (16.8 ml, 0.17 mol) was added dropwise
with stirring and cooling on a water bath. The mixture
was stirred for 20 min, after which 10 ml of 57%
perchloric acid was added. In 20 min, the mixture was
placed for 3 h in a refrigerator for complete precipitation
of the product, after which the yellow precipitate was
ﬁ ltered off and washed with diethyl ether (2 × 5 ml).
Yield 15.8 g (61%), mp 125–128°С.
Н NMR spectrum,
δ, ppm (300 MHz, DMSO-d
): 7.67 d (J = 11.7 Hz, 2H,
), 5.78 t (J = 11.7 Hz, 1H, Н
), 3.56 m (8H,
), 1.60 m (12H, 2CH
perchlorate II. To a suspension of I (10.9 g, 0.036 mol)
in acetic anhydride (12.5 ml), cooled to 0°C, we added
dropwise with stirring nitric acid (3.0 ml, ρ = 1.4 g cm
also cooled to 0°С, maintaining the reaction mixture
temperature no higher than 3°С. The mixture was stirred
on an ice bath for 1 h. Then 10 g of ice was added, and
the pale yellow precipitate was ﬁ ltered off and washed
with ice-cold water (10 ml) and diethyl ether (2 × 5 ml).
Yield 10.5 g (83%), mp 155–157°С (dec.).
spectrum, δ, ppm (300 MHz, CDCl
): 8.42 s (2Н, Н
), 4.02–3.92 m (4Н, 2CH
N), 3.76–3.66 m (4Н,