Synthesis of new polyphenols containing aminoalkyl and ammonium fragments

Full text of DOI:10.1134/S1070363213010234

ISSN 1070-3632, Russian Journal of General Chemistry, 2013, Vol. 83, No. 1, pp. 130–131. © Pleiades Publishing, Ltd., 2013.
Original Russian Text © N.I. Kharitonova, A.R. Burilov, A.S. Gazizov, M.A. Pudovik, 2013, published in Zhurnal Obshchei Khimii, 2013, Vol. 83, No. 1,
pp. 138–139.
LETTERS
TO THE EDITOR
Synthesis of New Polyphenols Containing Aminoalkyl
and Ammonium Fragments
N. I. Kharitonova, A. R. Burilov, A. S. Gazizov, and M. A. Pudovik
Arbuzov Institute of Organic and Physical Chemistry, Kazan Scientific Center, Russian Academy of Sciences,
ul. Akademika Arbuzova 8, Kazan, Tatarstan, 420088 Russia
e-mail: pudovik@iopc.ru
Received July 23, 2012
DOI: 10.1134/S1070363213010234
Recently we have shown that the condensation of
resorcinol and methylresorcinol with dimethylacetal of
methylaminoacetic α-aldehyde in aqueous hydro-
chloric acid leads to the formation of the
hydrochlorides of the substituted polyphenols as the
products of the reaction between two resorcinol
molecules and one aminoacetal molecule [1]. In this
work we studied the synthetic opportunities of the
derived polyphenols. For modifications of these
compounds we used the Mannich reaction [2]. The
initial 2,2-bis(2,4-dihydroxy-3-methylphenyl)-N,N-di-
methylethylamine I was synthesized by the known
method [1, 3] starting from 2-methylresorcinol and
dimethylacetal of N,N-dimethylaminoacetaldehyde.
The reaction of I with 2 equiv of formaldehyde in the
presence of dimethylamine or morpholine results in
compounds IIa and IIb in 98 and 84% yield
respectively. In the presence of aromatic amines like
aniline, diphenylamine, or benzidine the reaction
affords a complex mixture of the unidentified products.
4
CH3
CH3
CH3
CH3
3
HO
5
OH
HO
HO
OH
OH
R
HO
OH
2
2HR + 2CH2O
+
6
8
11
1
7
9
10
R
+
+
NHMe2 Cl−
Cl−
NHMe2
II
I
13
12
12
R = NMe2 (a), N
O (b).
The obtained compounds containing three amino-
alkyl groups along with two resorcinol fragments are
of interest as new polydentate ligands [2].
of morpholine and 0.19 g of 40% formaldehyde aqueous
solution. The reaction mixture was stirred at room
temperature for 24 h and concentrated. The formed
precipitate was filtered off and dried in a vacuum
(10 h, 15 mm Hg). Yield 0.65 g (98%), mp 134°C. IR
spectrum, ν, cm–1: 1607 (Ar), 2723(NH+), 3320 (OH).
1H NMR spectrum (CD3OD), δ, ppm (J, Hz): 2.14 s
(6Н, 4СН), 2.57 s (12Н, 12СН), 2.60 s (6Н, 10СН), 3.38
d (2Н, 9СН, J 9.60), 3.89 s and 3.90 s (4Н, 11СН), 4.78
The structure and composition of the products
obtained were proved by spectroscopic methods and
elemental analysis.
2,2-Bis[2,4-dihydroxy-3-methyl-5-(morpholino-
methyl)phenyl]-N,N-dimethylethylamine hydrochloride
(IIа). To a solution of 0.5 g of 2,2-bis-(2,4-dihydroxy-
3-methylphenyl)-N,N-dimethylethylamine in a mixture
of 5 ml of ethanol and 5 ml of benzene was added 0.25 g
8
7
t (1Н, СН, J 9.54), 6.75 s (2Н, СН). Found, %: С
61.15; Н 9.01; Cl 7.60; N 8.79. С24Н38ClN3О4.
Calculated, %: С 61.59; Н 8.18; Cl 7.57; N 8.98.
130

SYNTHESIS OF NEW POLYPHENOLS CONTAINING AMINOALKYL
2,2-Bis[2,4-dihydroxy-3-methyl-5-(dimethylamino- ACKNOWLEDGMENTS
131
methyl)phenyl]-N,N-dimethylethylamine hydrochlo-
ride (IIb) was prepared similarly from 0.6 g of com-
pound I, 0.25 g of 30% dimethylamine aqueous
solution and 0.13 g of 40% formaldehyde aqueous
solution. Yield 0.66 g (84%), mp 165°C. IR spectrum,
This work was financially supported by the Russian
Foundation for Basic Research (grant no. 11-03-
00416-a).
REFERENCES
1
ν, cm–1: 1610 (Ar), 2730 (NH+), 3180 (OH). H NMR
1. Burilov, A.R., Gazizov, A.S., Volodina, Yu.M.,
Pudovik, M.A., Habicher, W.D., Baier, I., Gubaidullin, A.T.,
Litvinov, I.A., and Konovalov, A.I., Mendeleev
Commun., 2005, no. 4, p. 153.
2. Higham, Ch.S., Dowling, D.P., Shaw, J.L., Cetin, A.,
Ziegler, Ch.J., and Farrell, J.R., Tetrahedron Lett., 2006,
vol. 47, p. 4419.
3. Burilov, A.R., Gazizov, A.S., Kharitonova, N.I.,
Pudovik, M.A., Habicher, W.D., Bayer, I., and Kono-
valov, A.I., Izv. Akad. Nauk, Ser. Khim., 2007, no. 2,
p. 319.
4. Becker, H., Berger, W., Domschke, G., Fanghanel, E.,
Faust, J., Fischer, M., Gentz, F., Gewald, K., Gluch, R.,
Mayer, R., Muller, K., Pavel, D., Schmidt, H.,
Schollberg, K., Schwetlick, K., Seiler, E., and
Zeppenfeld, G., Organikum, Leipzig: Deutscher Verlag
der Wissenschaften, 1993.
4
spectrum (CD3OD), δ, ppm (J, Hz): 2.08 s (6Н, СН),
2.50–2.75 m (8Н, 12СН), 2.79 s (6Н, 10СН), 3.16 s
(4Н, 11СН), 3.17–3.68 m (8Н, 13СН), 3.85 d (2Н, 9СН,
8
7
J 9.83), 4.92 t (1Н, СН, J 7.45), 6.68 s (2Н, СН).
Found, %: С 60.72; Н 7.85; Cl 6.51; N 7.78.
С28Н42ClN3О6. Calculated, %: С 60.91; Н 7.6; Cl 6.42;
N 7.67.
1
The H NMR spectra were recorded on an Avance
600 instrument operating at 600.13 MHz the residual
protons of CD3OD serving as internal reference. The
IR spectra were registered on a UR-20 spectrometer in
the range of 400–3600 cm–1 for the samples as mulls in
mineral oil or in a thin layer. All the solvents were
purified before use [4].
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 83 No. 1 2013