Synthesis of nitrobenzoazacrown compounds by ring transformations of nitrobenzocrown ethers [1]

Full text of DOI:10.1023/A:1020929303201

Russian Chemical Bulletin, International Edition, Vol. 51, No. 7, pp. 1335—1336, July, 2002
1335
Letters to the Editor
Synthesis of nitrobenzoazacrown compounds by
ring transformations of nitrobenzocrown ethers
ꢀ
S. P. Gromov, S. N. Dmitrieva, M. V. Churakova, and A. Yu. Turchanov
Center of Photochemistry, Russian Academy of Sciences,
7A ul. Novatorov, 117421 Moscow, Russian Federation.
Fax: +7 (095) 936 1255. Eꢀmail: gromov@photonics.ru
The main approach to ring construction in the modꢀ
ern chemistry of crown compounds is based on the conꢀ
densation of two acyclic derivatives (soꢀcalled 1 + 1 conꢀ
densation).1—3 At the same time, it has been shown that
many threeꢀ to sevenꢀmembered heterocycles can be not
only constructed from several fragments, but also obꢀ
tained by ring transformations including the ring openꢀ
ing and subsequent closure of a new heterocycle involvꢀ
ing intermediate acyclic compounds.4,5
There are only few examples of the opening of crown
ethers.6,7 Nevertheless, we believe that the macrocycle
opening in accessible crown ethers and the synthesis of
1—5: n = 0 (a), 1 (b), 2 (с)
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 7, pp. 1232—1233, July, 2002.
1066ꢀ5285/02/5107ꢀ1335 $27.00 © 2002 Plenum Publishing Corporation

1336
Russ.Chem.Bull., Int.Ed., Vol. 51, No. 7, July, 2002
Gromov et al.
new crown compounds from podands formed is a promꢀ
ising alternative to the current synthetic methods in the
chemistry of macroheterocyclic compounds.
This work was financially supported by the Russian
Foundation for Basic Research (Project No. 00ꢀ03ꢀ32896)
and the INTAS (2001ꢀ0267).
Earlier, we have found that the opening of nitroꢀ
benzocrown ethers 1a—c on heating them with MeNH2
gives nitrogenꢀcontaining podands 2a—c in 92—98%
yields.8,9
References
1. Host Guest Complex Chemistry Macrocycles. Synthesis, Strucꢀ
tures, Applications, Eds. F. Vögtle and E. Weber, Springer
Verlag, Berlin, 1985, Ch. 1.
2. K. E. Krakowiak, J. S. Bradshaw, and D. J. Zameckaꢀ
Krakowiak, Chem. Rev., 1989, 89, 929.
3. A. A. Formanovskii, Makrotsiklicheskie soedineniya v
analiticheskoi khimii [Macrocyclic Compounds in Analytical
Chemistry], Eds. Yu. A. Zolotov and N. M. Kuz´min, Nauka,
Moscow, 1993, Ch. 1 (in Russian).
4. H. C. van der Plas, Ring Transformations of Heterocycles,
Academic Press, London—New York, 1973, 1, 484; 2, 352.
5. A. N. Kost, S. P. Gromov, and R. S. Sagitullin, Tetrahedron,
1981, 37, 3423.
We developed a method for the cyclization of podands
2a—c into previously unknown nitro derivatives of
Nꢀmethylbenzoazacrown compounds 3a—c. The reacꢀ
tions of the podands with SOCl2 in the presence of
pyridine affords chloro derivatives 4a—c in 94—96%
yields. The Cl atom in compounds 4a—c is replaced by
an I atom in the reactions with NaI to give iodides
5a—c in 88—98% yields. When heated with NaOH or
NaH, iodides 5a—c undergo intramolecular cyclization
into nitrobenzoazacrown compounds 3a—c in 36—80%
yields.
6. E. I. Ivanov, P. B. Terent´ev, A. A. Polishchuk, K. S.
Zakharov, and B. S. Subbotin, Khim. Geterotsikl. Soedin.,
1985, 1573 [Chem. Heterocycl. Comp., 1985 (Engl. Transl.)].
7. L. Töke, I. Bitter, B. Agai, Z. Hell, E. Lindner, K. Toth,
M. Horvath, A. Szöllosy, S. Harfouch, and E. Pungor, Liebigs
Ann. Chem., 1988, 761.
8. S. P. Gromov, S. N. Dmitrieva, and V. E. Krasnovskii, Izv.
Akad. Nauk, Ser. Khim., 1997, 540 [Russ. Chem. Bull., 1997,
46, 519 (Engl. Transl.)].
The structures of all the compounds obtained were
determined using 1H and 13C NMR spectroscopy, inꢀ
cluding twoꢀdimensional NOESY spectra, and confirmed
by highꢀresolution mass spectra.
The proposed approach based on stepwise transforꢀ
mation of the macroheterocycle makes it possible to synꢀ
thesize previously unknown nitrobenzoazacrown comꢀ
pounds from accessible benzocrown ethers. The nitro
group can be reduced to an amino group and furꢀ
ther modified by the known methods to give a family
of benzoazacrown derivatives, which are promising
for use as ionꢀselective dyes and extracting agents of
metal ions.
9. S. P. Gromov and S. N. Dmitrieva, Izv. Akad. Nauk, Ser.
Khim., 1999, 542 [Russ. Chem. Bull., 1999, 48, 537 (Engl.
Transl.)].
Received March 20, 2002;
in revised form May 23, 2002