Synthesis of a phthalonitrile derivative of fullerenopyrrolidine

Article abstract of DOI:10.1007/s11172-009-0071-x

The Prato reaction was used to synthesize 2-[4-(3,4-dicyanophenoxy)phenyl]- N-methyl- 3,4-[60]fullerenopyrrolidine.

Full text of DOI:10.1007/s11172-009-0071-x

Russian Chemical Bulletin, International Edition, Vol. 58, No. 3, pp. 648—649, March, 2009
648
Synthesis of a phthalonitrile derivative of fullerenopyrrolidine
N. L. Bazyakina, O. N. Suvorova, and K. N. Maksimova
G. A. Razuvaev Institute of Organometallic Chemistry, Russian Academy of Sciences,
49 ul. Tropinina, 603950 Nizhny Novgorod, Russian Federation.
Fax: +7 (831) 462 7497. Еꢀmail: natlb@mail.ru
The Prato reaction was used to synthesize 2ꢀ[4ꢀ(3,4ꢀdicyanophenoxy)phenyl]ꢀNꢀmethylꢀ
3,4ꢀ[60]fullerenopyrrolidine.
Key words: [60]fullerene, cycloaddition reaction, phthalonitrile.
Interest in the photophysical properties of fullerene
formed upon the interaction of 4ꢀ(4ꢀformylphenoxy)ꢀ
derivatives is based on rather easy excitation of fullerene
(acceptor)—linkage—electron donor systems producing
states with charge separation. The lifetime of the excited
state can vary in a wide range depending on the type of
functional groups on fullerene and the donor properties
of the second component.1,2 Fullerene—phthalocyanine
supramolecular systems in which strong donorꢀacceptor
interactions result in longꢀlived excited states with charge
separation are intensively used now.3—6 Reactions of
cycloaddition of formylphthalocyanines to fullerene are
mainly used for the preparation of systems of this type.4
The purpose of this work is to synthesize fullereneꢀconꢀ
taining phthalonitrile for the further formation of the
fullereneꢀcontaining phthalocyanine macrocycle.
phthalonitrile with sarcosine (Scheme 1).
The reaction affords a mixture of cycloaddition
products from which the monoꢀ and diaddition products
were isolated by column chromatography. The both
compounds are brown solids stable in air and soluble in
organic solvents (toluene, chloroform). The ESI mass
spectra were obtained for both compounds. The mass
spectra of these substances contain the main peaks of
molecular ions 995 [M]–• for monosubstituted and 1270
[M]–• for disubstituted fullerenopyrrolidine phthaloꢀ
1
nitriles. The presence in the H NMR spectrum of the
monosubstituted product of signals with δ = 5.02, 5.01,
and 4.31 assigned to the pyrrolidine ring proves its formaꢀ
tion. The IR spectrum exhibits a band at 2230 cm–1 charꢀ
acteristic of the cyano group. The electronic absorption
spectrum of the synthesized fullerene derivative is characꢀ
teristic of fullerenopyrrolidines.7
2ꢀ[4ꢀ(3,4ꢀDicyanophenoxy)phenyl]ꢀNꢀmethylꢀ3,4ꢀ
fullerenopyrrolidine was synthesized by the 1,3ꢀdipolar
cycloaddition reaction of fullerene C60 with azomethine
The 1H NMR spectrum was recorded on a Bruker Avance
DPXꢀ200 instrument. Electrospray mass spectra (ESI) were
measured on a Bruker Esquire LC instrument. The electronic
absorption spectrum was obtained on a Perkin—Elmer Lambda
25 spectrometer in a 1.0ꢀcm quartz cell. The IR spectrum was
recorded on a Perkin—Elmer Spectrum 1000 spectrometer, using
KBr as an emission medium. The cycloaddition products were
separated on silica gel 60 (Merck). Sarcosine (Aldrich) was used
without additional purification. 4ꢀ(4ꢀFormylphenoxy)phthaloꢀ
nitrile was synthesized by a known procedure.8
Scheme 1
2ꢀ[4ꢀ(3,4ꢀDicyanophenoxy)phenyl]ꢀNꢀmethylꢀ3,4ꢀfullerenoꢀ
pyrrolidine. Sarcosine (0.111 g, 1.247 mmol) and 3ꢀformylꢀ
4ꢀphenoxyphthalonitrile (0.103 g, 0.416 mmol) were added
to a solution of fullerene C60 (0.3 g, 0.416 mmol) in toluene
(200 mL). The reaction mixture was stirred for 20 h with boiling,
cooled to room temperature, and filtered. The resulting solution
of the reaction products was separated on a column packed with
silica gel. Toluene was used as eluent for the isolation of
unreacted fullerene, and the desired monoaddition product was
isolated with a toluene—chloroform (1 : 1) system. After the
solvents were removed in vacuo, a solid brown product (0.109 g)
i. Toluene
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp. 631—632, March, 2009.
1066ꢀ5285/09/5803ꢀ0648 © 2009 Springer Science+Business Media, Inc.

Phthalonitrile fullerenopyrrolidine derivative
Russ.Chem.Bull., Int.Ed., Vol. 58, No. 3, March, 2009
649
was obtained. The yield was 30% (based on reacted fullerene),
m.p. > 300 °C. Found (%): C, 92.85; H, 1.21. C78H14N2O.
Calculated (%): C, 93.05; H, 1.11. 1H NMR (CDCl3), δ: 2.88
(s, 3 H, N—CH3) 4.31, 5.02 (both d, 1 H, pyrrolidine, J = 9.4 Hz);
5.01 (s, 1 H, pyrrolidine); 7.08—7.21 (m, 4 H, Ar); 7.69 (d,
1 H, Ar, J = 9.0 Hz); 8.02—7.82 (m, 2 H, Ar). UV (toluene),
3. J. Drechsel, D. Gebeyehe, M. Pfeiffer, K. Leo, Y. Hoppe,
Organic Electronics, 2004, 5, 175.
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V. Georgakilas, M. Prato, J. Am. Chem. Soc., 2005, 127, 5811.
5. A. Gouloumis, Sh. Lio, A. Sastre, P. Vazquez, L. Echegoyen,
T. Torres, Chem. Eur. J., 2000, 6, 3600.
6. M. A. Loi, P. Denk, H. Hoppe, H. Neugebaner, D. Metssener,
C. Winder, C. J. Brabes, N. S. Sariciftci, A. Gouloumis,
P. Varquez, T. Torres, Synthetic Metals, 2003, 137, 1491.
7. M. Maggini, G. Scorrano, M. Prato, J. Am. Chem. Soc., 1993,
115, 9798.
λ
max/nm: 430. IR (KBr, 4000—400 cm–1), ν/cm–1: 2922, 2851,
2230, 1590, 1562, 1500, 1484, 1462, 1425, 1353, 1331, 1307,
1277, 1247, 1201, 1177, 1163, 1122, 1089, 1030, 1015, 949, 908,
869, 850, 831, 796, 787, 746, 728, 600, 563, 525. MS (ESI—MS,
in CH2Cl2—MeOH, 1 : 10), m/z: 995 [M]–•
.
8. D. Woehle, N. Iskander, G. Graschew, H. Sinn, E. Friedrich,
W. MaierꢀBorst, J. Stern, P. Schlag, Photochem. Photobiol.,
1990, 51, 351.
This work was financially supported by the Council on
Grants at the President of the Russian Federation (Proꢀ
gram for State Support of Leading Scientific Schools of
the Russian Federation, Grant NShꢀ8017.2006.3) and in
the framework of the State Contract No. 02.442.11.7286.
References
1. G. Possamai, M. Maggini, Appl. Physics A, 2004, 79, 51.
2. E. A. Katz, Phys. Solid State, 2002, 44, 647.
Received February 22, 2008;
in revised form October 20, 2008