Synthesis of novel nitroso-fulleropyrrolidines

Article abstract of DOI:10.1016/S0040-4039(02)00944-9

Novel fulleropyrrolidines containing differently head groups (-NO₂, -NH₂ -NO) spaced by a long chain from the fulleropyrrolidine moiety have been synthesised and characterised.

Full text of DOI:10.1016/S0040-4039(02)00944-9

TETRAHEDRON
LETTERS
Pergamon
Tetrahedron Letters 43 (2002) 4969–4972
Synthesis of novel nitroso-fulleropyrrolidines
Giuseppe Vasapollo,a,* Giuseppe Mele,a Luigia Longo,a Roberto Ianne,a Brian G. Gowenlockb and
Keith G. Orrellb
aDipartimento di Ingegneria dell’Innovazione, Universita` di Lecce, via Arnesano 73100 Lecce, Italy
bSchool of Chemistry, University of Exeter, Exeter EX4 4QD, UK
Received 19 April 2002; accepted 14 May 2002
Abstract—Novel fulleropyrrolidines containing differently head groups (-NO2, -NH2 -NO) spaced by a long chain from the
fulleropyrrolidine moiety have been synthesised and characterised. © 2002 Elsevier Science Ltd. All rights reserved.
The increasingly better availability of [C60] fullerene has
led to an extensive range of studies on this molecular
allotrope of carbon. Many fundamental properties of
fullerene derivatives have been discovered and
reported1 and their metal complexes evidence attractive
characteristics, such as superconductivity2–4 or charge-
transfer behaviour.5–7 It is well known also that the
ball-like structure of C60 molecules is very rigid, hydro-
phobic and exhibits peculiar properties totally different
from those of rod-like self-assembling amphiphilic
molecules.
We therefore report in this paper the preparation of
nitroso fullerene compounds together with a simple
procedure that involves the reaction sequence RNO2“
RNH2“RNO.
In particular, we report the synthesis and characterisa-
tion of the fulleropyrrolidines derivatives 1–4, 8, 9 and
of the nitroso fulleropyrrolidines 5, 6 and 10.
The compounds 1 and 2 (1: R=CH3; 2: R=C6H5) have
been prepared according to the literature (Scheme 1) by
the condensation of a-amino acids (N-methylglycine or
N-phenylglycine), with aldehydes and C60 through a
typical 1,3-dipolar addition of azomethine ylides14 gen-
erated in situ. In a typical procedure, a solution of
4-nitrobenzaldehyde (34 mg), C60 (144 mg) and N-
methylglycine (10 mg) in toluene (500 ml) was refluxed
for 24 h. After cooling the resulting solution was evap-
orated to dryness. Purification by column chromatogra-
phy (SiO2, toluene) yielded 1 (60% yield). Compound 2
(55% yield) was obtained under similar condition but
using N-phenylglycine.
Further, the use of highly organised fullerene deriva-
tives in the form of supramolecular arrays (thin films,
nanotubes, etc.) could represent new technological
potentialities and one of the most common approaches
to control the architecture of organised thin films con-
taining the fullerene moiety8,9 is the functionalisation of
C60.
On the other hand, there are many interesting studies
concerning the structure of a variety of C-nitroso com-
pounds both in the solid and in solution,10–13 but there
are no reports on C60-nitroso derivatives. The introduc-
tion of a nitroso group, as a suitable ligand for a large
variety of metals, into C60-containing structures offers
the possibility to prepare new molecules with potential
features.
N-Methyl-2-(4-aminophenyl)-fulleropyrrolidine 3 (R=
CH3) and N-phenyl-2-(4-aminophenyl)-fulleropyrro-
lidine 4 (R=C6H5) were synthesised respectively by
simple reduction of N-methyl-2-(4-nitrophenyl)-
fulleropyrrolidine 1 and N-phenyl-2-(4-nitrophenyl)-
fulleropyrrolidine 2, in chloroform, with powdered Sn
and H2O/HCl as reported in Scheme 1.
We have therefore pursued the strategy of preparing
new molecules that contain both the fullerene moiety
and the nitroso group in order to prepare nitroso
fullerene compounds with potential utility as a source
for new materials or biologically active compounds.
The compounds 5 and 6 were prepared by selective
oxidation of primary aromatic amines 3 and 4 using
H2O2 in the presence of [Mo(O)(O2)2(H2O)(hmpa)]
(hmpa=hexamethyl-phosphoramide)
through a procedure analogous to that reported by
as
catalyst
* Corresponding author. Tel.: +00-39-832-320252; fax: +00-39-832-
320279; e-mail: giuseppe.vasapollo@unile.it
0040-4039/02/$ - see front matter © 2002 Elsevier Science Ltd. All rights reserved.
PII: S0040-4039(02)00944-9

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G. Vasapollo et al. / Tetrahedron Letters 43 (2002) 4969–4972
Scheme 1.
1
Porta and co-workers.15 In a typical experiment 50 mg
of the amine 4, for example, were dissolved in chloro-
form, H2O2 (30% ww solution in water) added together
with [Mo (O)(O2)2(H2O)(hmpa)] in catalytic amount.
The mixture was stirred for 5 h at room temperature
and then filtered on a silica gel column using toluene/
petroleum ether (2/1) as eluant (>95% yield). Analytical
data for compounds 5 and 6 are consistent for the
formulation of these compounds.
The H NMR spectra of compound 10 in CDCl3 solu-
tion show typical signals of the pyrrolidino (C60)
fullerene system, as a singlet for H-2 at 4.87 ppm and
the A–B system for CH2-5, as two doublets centred at
4.97 and 4.24 ppm, respectively, with a geminal cou-
pling JAB=9.5 Hz.
Representative data for compounds 5, 6, 7, 8, 9 and 1016
N-Methyl-2-(4-nitrosophenyl)-fulleropyrrolidine (5)
FT-IR 2924, 2852, 2780, 1734, 1617, 1503, 1461, 755
A nitroso group spaced by a long alkyl chain from the
fulleropyrrolidine was also prepared, as shown in
Scheme 2.
cm−1. H NMR (CDCl3) l: 8.13 (broad signal, 2H);
1
8.00 (d, J=8.8 Hz, 2H); 5.03 (d, J=9.2 Hz, 1H);
4.80 (s, 1H); 3.75 (d, J=9.2 Hz, 1H); 2.83 (s, 3H)
ppm. LC–MS (APCI) calcd M 882 obsd 883 (M−H+)
uma.
The spacer precursor 7 was reacted in the presence of
sarcosine and C60 to give 8 in 50% isolated yield which
was reduced quantitatively to amino derivative 9 which
was then selectively oxidised to give 10 through a
sequence of reactions analogous to that for the synthe-
sis of nitroso the fulleropyrrolidines 5 and 6.
N-Phenyl-2-(4-nitrosophenyl)-fulleropyrrolidine (6)
FT-IR 2918, 2849, 1732, 1463, 1380, 1261, 1073, 1037,
The presence of a long alkyl chain groups significantly
improves its solubility in organic solvents. The incorpo-
ration of a long alkyl chain having at its end a polar
group certainly also influences the interfacial properties
of the fullerene derivatives on the water surface espe-
cially when the formation of thin films is required.
1
824, 802, 720, 755 cm−1. H NMR (CDCl3) l: 8.10 (d,
J=8.3 Hz, 2H); 7.89 (d, J=8.3 Hz, 2H); 7.73–7.35 (m,
5H); 6.17 (s, 1H); 5.68 (d, J=5 Hz, 1H); 5.02 (d, J=5
Hz, 1H) ppm. LC–MS (APCI), calcd M 944, obsd 945
(M−H+) uma.

G. Vasapollo et al. / Tetrahedron Letters 43 (2002) 4969–4972
4971
Scheme 2.
Compound 9
Compound 7
FT-IR: 3446.17, 3364.21, 2921.63, 2851.24, 2779.89,
1509.99, 1461.78, 1240.97, 1174.44, 823.46 cm−1. 1H
NMR (200 MHz, CDCl3) l: 7.71–7.67 (m, 2H), 6.96–
6.92 (m, 2H), 6.76–6.61 (m, 4H), 4.97 (d, J=9.4, 1H),
4.87 (s, 1H), 4.23 (d, J=9.4, 1H), 3.95 (t, J=6.2, 2H),
3.87 (t, J=6.5, 2H), 2.78 (s, 1H), 1.85–1.59 (m, 4H),
1.42–1.26 (m, 16H).
FT-IR: 2923.56, 2852.20, 2729.74, 1681.62, 1592.21,
1575.56, 1508.06, 1469.49, 1331.61, 1258.32, 1214.93,
1158.04, 1108.87, 996.05, 858.17, 835.03, 751.14, 653.75
1
cm−1. H NMR (200 MHz, CDCl3) l: 9.82 (s, 1H), 8.12
(d, J=9.1, 2H), 7.77 (d, J=8.6, 2H), 6.96–6.86 (m, 4H),
3.99 (t, J=6.4, 4H), 1.83–1.70 (m, 4H), 1.41–1.22 (m,
16H) ppm. 13C NMR (200 MHz, CDCl3) l: 190.48,
164.06, 131.73, 129.55, 125.63, 114.54, 114.20, 68.70,
68.22, 29.33, 29.14, 28.85, 28.77, 25.76, 25.71 ppm.
LC–MS (APCI), calcd 427 M, obsd 428 (M−H+) uma.
13C NMR (200 MHz, CDCl3) l: 167.66, 159.19, 156.39,
154.12, 153.69, 152.33, 147.27, 146.81, 146.51, 146.38,
146.28, 146.24, 146.18, 146.10, 146.07, 145.91, 145.76,
145.52, 145.48, 145.43, 145.31, 145.28, 145.25, 145.20,
145.11, 144.68, 144.60, 144.37, 143.11, 142.96, 142.64,
142.55, 142.52, 142.27, 142.24, 142.10, 142.07, 142.01,
141.95, 141.80, 141.65, 141.51, 140.13, 140.09, 139.87,
139.77, 139.55, 136.74, 136.55, 135.76, 132.32, 130.86,
130.42, 128.81, 128.66, 116.39, 115.66, 114.53, 114.37,
83.19, 77.37, 69.98, 68.96, 68.87, 67.97, 39.96, 29.68,
29.54, 29.40, 29.34, 29.26, 28.55, 26.05, 23.03, 22.67,
14.10 ppm. LC–MS (APCI), calcd M 1144, obsd 1145
(M−H+) uma.
Compound 8
FT-IR: 2922.59, 2851.24, 2788.92, 1607.38, 1591.95,
1509.99, 1462.74, 1333.53, 1260.25, 1171.54, 1109.83,
1
842.74, 752.10 cm−1. H NMR (200 MHz, CDCl3) l:
8.21–8.16 (m, 2H), 7.71–7,67 (m, 2H), 6.95–6.90 (m,
4H), 4.96 (d, J=9.4, 1H), 4.87 (s, 1H), 4.23 (d, J=9.4,
1H), 4.03 (t, J=6.4, 2H), 3.94 (t, J=6.4, 2H), 2.78 (s,
3H), 1.84–1.62 (m, 4H), 1.43–1.25 (m, 16H) ppm. 13C
NMR (200 MHz, CDCl3) l: 164.22, 159.18, 156.40,
154.14, 153.69, 147.28, 146.81, 146.52, 146.40, 146.29,
146.25, 146.19, 146.14, 146.11, 146.08, 145.92, 145.77,
145.54, 145.49, 145.44, 145.33, 145.29, 145.27, 145.22,
145.20, 145.13, 144.70, 144.59, 144.37, 143.12, 142.98,
142.66, 142.57, 142.53, 142.27, 142.25, 142.15, 142.12,
142.09, 142.02, 141.97, 141.80, 141.67, 141.51, 141.33,
140.15, 140.11, 139.87, 139.53, 136.77, 136.55, 135.79,
135.76, 130.44, 129.02, 128.73, 128.21, 125.89, 125.28,
114.54, 114.39, 83.20, 77.39, 69.99, 68.98, 68.88, 67.97,
39.97, 29.69, 29.53, 29.40, 29.31, 29.29, 28.96, 26.07,
25.90, 22.67, 14.10 ppm. LC–MS (APCI), calcd M
1174, obsd 1175 (M−H+) uma.
Compound 10
FT-IR: 2921, 2851, 2779, 1504, 1461, 1258, 1111, 838,
1
736, 619 cm−1. H NMR (200 MHz, CDCl3) l: 7.92–
7.88 (m, 2H), 7.71–7.67 (m, 2H), 7.02–6.91 (m, 4H),
4.97 (d, J=9.5 Hz, 1H), 4.87 (s, 1H), 4.24 (d, J=9.5,
1H), 4.09 (t, J=6.4, 2H), 3.95 (t, J=6.4, 2H), 2.79 (s,
3H), 1.86–1.59 (m, 4H), 1.43–1.25 (m, 16H) ppm. 13C
NMR (200 MHz, CDCl3) l: 164.24, 159.22, 154.16,
153.71, 146.17, 143.15, 142.99, 130.89, 129.03, 128.75,
128.22, 125.90, 125.30, 114.40, 114.27, 83.24, 77.41,
77.21, 68.93, 67.99, 31.93, 30.04, 29.70, 29.66, 29.53,

4972
G. Vasapollo et al. / Tetrahedron Letters 43 (2002) 4969–4972
29.40, 29.36, 28.99, 26.07, 25.92, 22.69, 14.10, 13.7
ppm. LC–MS (APCI), calcd M 1158, obsd 1159 (M−
H+) uma.
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Soc. Rev. 1990, 19, 355.
We thank MURST (Rome) for financial support
through Cofinanziamento ex-40% (Project: Fullereni).
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