An original approach to the amination of crown ethers

Full text of DOI:10.1007/s10593-010-0639-2

Chemistry of Heterocyclic Compounds, Vol. 46, No. 9 2010
LETTERS TO THE EDITOR
AN ORIGINAL APPROACH TO THE AMINATION
OF CROWN ETHERS
A. S. Lyakhovnenko1, A. V. Aksenov1*, and M. M. Kugutov1
Keywords: sodium azide, 4'-aminodibenzo[18]crown-6, dibenzo[18]crown-6, PPA, amination.
Crown ethers hold considerable importance in the study of supramolecular chemistry. Special interest is
found in methods to functionalize these compounds, for example, the techniques described by Jeong and Cho
[1]. Early we have developed a method for the direct amination of perimidines in PPA [2, 3]. In the present
work, we report the electrophilic amination of dibenzo[18]crown-6 ether 1 by this reagent system. Heating
ether 1 (0.36 g, 1 mmol) and sodium azide (0.072 g, 1.1 mmol) in PPA (2-3 g) at 90-100°C for 3 h with
monitoring by thin-layer chromatography leads to 4'-aminodibenzo[18]crown-6 (2) in 61% yield. The sample of
PPA containing 87% P2O5 was prepared according to Uhlig [4].
O
O
NH2
O
O
O
O
O
NaN3
PPA
O
O
O
O
O
2
1
Diamination products, which could not be isolated as pure products, are probably formed as side
products.
1
The H and 13C NMR spectra were taken on a JNM-ECX400 spectrometer at 400 and 100 MHz,
respectively, in CDCl3 with TMS as the internal standard. The reaction course and purity of the products were
monitored on Silufol UV-254 plates using 1:1 ethyl acetate–ethanol as the eluent.
The reaction mixture was treated with 50 ml water and brought to pH 8-9 by adding ammonium
hydroxide. The precipitate formed was filtered off. The mother liquor was extracted with three 50-ml portions of
methylene chloride. The solvent was evaporated and the residue was combined with the precipitate. The crude
product was recrystallized from butanol to give 0.226 g (61%) ether 2; mp 158-163°C (butanol)
_______
* To whom correspondence should be addressed, e-mail: k-biochem-org@stavsu.ru.
1Stavropol State University, Stavropol 355009, Russia.
__________________________________________________________________________________________
Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 9, pp. 1410-1411, September, 2010.
Original article submitted June 7, 2010.
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0009-3122/10/4608-1138©2010 Springer Science+Business Media, Inc.

1
(mp 159-163°C [1]). H NMR spectrum, , ppm (J, Hz): 3.42 (2H, br. s, NH2), 4.02 (8H, m, OCH2); 4.10 (4H,
m, OCH2); 4.16 (4H, m, OCH2); 6.21 (1H, dd, J = 8.4, J = 2.6, ArH); 6.29 (1H, d, J = 2.6, ArH); 6.88 (4H, m,
ArH); 6.70 (1H, d, J = 8.4, ArH). 13C NMR spectrum, , ppm: 68.8, 69.1, 70.1, 70.2, 70.5, 102.7, 107.5, 113.6,
113.8, 121.5, 121.6, 148.8. Found, %: C 64.14; H 6.67; N 3.69. C20H25NO6. Calculated, %: C 63.99; H 6.71;
N 3.73.
The work was carried out with the financial support of the Russian Basic Reseach Fund (grant 10-03-
00193a).
REFERENCES
1.
2.
K.-S. Jeong and Y. L. Cho, Bull. Korean Chem. Soc., 15, 705 (1994).
A. V. Aksenov, A. S. Lyakhovnenko, and N. Ts. Karaivanov, Khim. Geterotsikl. Soedin., 1091 (2009)
[Chem. Heterocycl. Comp., 45, 871 (2009)].
3.
4.
A. V. Aksenov, A. S. Lyakhovnenko, N. Ts. Karaivanov, and I. I. Levina, Khim. Geterotsikl. Soedin.,
591 (2010) [Chem. Heterocycl. Comp., 46, 468 (2010)].
F. Uhlig, Angew. Chem., 66, 435 (1954).
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