Synthesis and properties of new triazole methanofullerenes under the "click-chemistry" conditions

Article abstract of DOI:10.1007/s11172-012-0159-6

The "click-chemistry" methods were used for the first time to synthesize new 1,2,3-triazole derivatives of fullerene, promising for the study of their biological activity, as well as for the preparation of new fullerene-containing materials on their basis

Full text of DOI:10.1007/s11172-012-0159-6

Russian Chemical Bulletin, International Edition, Vol. 61, No. 6, pp. 1169—1175, June, 2012
1169
Synthesis and properties of new triazole methanofullerenes
under the "clickꢀchemistry" conditions
V. P. Gubskaya, Sh. K. Latypov, F. G. Sibgatullina, A. A. Balandina, T. A. Zhelonkina,
G. M. Fazleeva, L. N. Islamova, D. R. Sharafutdinova, I. A. Nuretdinov, and O. G. Sinyashin
A. E. Arbuzov Institute of Organic and Physical Chemistry, Kazan Scientific Center of the Russian Academy of Sciences,
8 ul. Akad. Arbuzova, 420088 Kazan, Russian Federation.
Fax: +7 (843 2) 75 2253. Eꢀmail: in@iopc.ru
The "clickꢀchemistry" methods were used for the first time to synthesize new 1,2,3ꢀtriazole
derivatives of fullerene, promising for the study of their biological activity, as well as for the
preparation of new fullereneꢀcontaining materials on their basis. The purity and composition of
the compounds synthesized were confirmed by MALDIꢀTOF mass spectrometry and HPLC,
their structures were confirmed by a combination of 2D NMR homoꢀ and heteronuclear
correlation.
Key words: "clickꢀchemistry", alkyne methanofullerenes, 1,2,3ꢀtriazole derivatives of
fullerene, highꢀperformance liquid chromatography, 2D NMR homoꢀ and heteronuclear corꢀ
relation.
In the last years, the soꢀcalled "clickꢀchemistry" reacꢀ
tions attracted great attention of researchers. In the
works,1,2 it was independently shown that the reactions of
azides with alkynes3 in the presence of CuI as a catalyst
proceeded under mild conditions by the pattern of 1,3ꢀdiꢀ
polar cycloaddition and exclusively furnished 1,4ꢀdisubꢀ
stituted 1,2,3ꢀtriazoles in high yields. The practical interꢀ
est to these reactions is explained by the fact that many
known 1,2,3ꢀtriazoles possess various biological activity,
including the antiꢀHIV activity.4—7
A possibility of the formation of fullerene derivatives
containing 1,2,3ꢀtriazole fragments is studied poorly.
While the "clickꢀchemistry" approach turned out to be
a powerful method for the preparation of different triꢀ
azoleꢀcontaining organic compounds, its compatibility
with the fullerene derivatives was not so obvious, since
organic azides can also undergo a [3+2] cycloaddition at
the double bonds of fullerene.8,9 Among seldom examples
are the works,10,11 in which efficient methods for the synꢀ
thesis of fullerene triazole hexakisꢀadducts and triazoleꢀ
porphirineꢀfullerene diads were developed using the "clickꢀ
chemistry" reactions. A number of unique triazole derivaꢀ
tives of fullerene were obtained, promising for the practiꢀ
cal application.
reaction, starting from fullerene C60 and triazole derivaꢀ
tives containing active methylene groups; 2) the synthesis
of methanofullerene derivatives containing acetylenic
bonds with subsequent formation of the heterocycle under
the "clickꢀchemistry" conditions.
Results and Discussion
The starting phosphorylated alkyne 1 was obtained by
the reaction of propargyl chloroacetate with triethyl phosꢀ
phite in the benzene solution upon reflux. Subsequent
heterocyclization of compound 1 was carried out under
the "clickꢀchemistry" conditions using benzylazide and
CuI as a catalyst. The reaction course was monitored by
IR spectra of the reaction mixture. The disappearance of
the band at 2096 cm–1 characteristic of the azide group
indicated the conversion of the starting alkyne 1 to the
corresponding triazole 2 (Scheme 1).
Scheme 1
Taking into account the actuality of development of
new materials and biologically active compounds based
on fullerene, we applied the "clickꢀchemistry" method for
the preparation of new phosphorylated and malonate
methanofullerenes containing 1,2,3ꢀtriazole fragments. To
accomplish this, we used two approaches: 1) the synthesis
of 1,2,3ꢀtriazole fullerene derivatives by the Bingel—Hirsch
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 6, pp. 1158—1163, June, 2012.
1066ꢀ5285/12/6106ꢀ1169 © 2012 Springer Science+Business Media, Inc.

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Russ.Chem.Bull., Int.Ed., Vol. 61, No. 6, June, 2012
Gubskaya et al.
Scheme 2
13
C: R2 = 0.994 (1), 0.996 (2); 15N: R2 = 0.995 (2)
Fig. 1. The principal heteronuclear correlations (shown with
arrows from the 1H to the X nucleus). The correlation coeffiꢀ
cients between the experimental and calculated chemical shifts
are given.
The structure of compounds 1 and 2 unambiguously
was established using a number of 2D NMR correlation
methods (1H—1H, 1H—13C, 1H—15N, and 1H—31P)12
.
The principal HMBC correlations for compounds 1 and 2
are shown in Fig. 1. Besides this, the agreement between
the experimental and the calculated13 13C and 15N (GIAO
DFT) chemical shifts for compound 2 (see Figs 1 and 2)
additionally confirms the structure suggested.
The reaction of fullerene C60 and compounds 1 and 2
in the presence of tetrabromomethane and 1,8ꢀdiazabiꢀ
cyclo[5.4.0]undecꢀ7ꢀene (DBU) under the Bingel—Hirsch
reaction conditions14,15 furnished the corresponding phosꢀ
phorylated methanofullerenes 3 and 4 containing the
alkyne and the triazole fragments, respectively (Scheme 2).
These reactions take place at room temperature. The yields
of compounds 3 and 4 after their isolation by column
chromatography on SiO2 were 41 and 25.2%, respectively,
if calculated based on the converted fullerene.
Compound 4 was also obtained by an alternative methꢀ
od from methanofullerene 3 containing acetylene bonds
and benzylazide in the presence of a (EtO)3P•CuI cataꢀ
lyst, i.e. under the "clickꢀchemistry" reaction conditions
(Scheme 3).
The reaction course was monitored by highꢀperforꢀ
mance liquid chromatography (HPLC) (Fig. 3). As it is
(13C)calc
(15N)calc
a
b
360
320
280
130
90
50
50
90
130
(13C)exp
280
320
(15N)exp
Fig. 2. The correlation of the experimental and the calculated chemical shifts 13C (a) and 15N (b) for compound 2; R2 = 0.996 (a)
and 0.995 (b).

New triazole fullerene derivatives
Russ.Chem.Bull., Int.Ed., Vol. 61, No. 6, June, 2012
1171
I
characteristic of the addition of the methano fragment at
the closed 6,6ꢀbond of the fullerene sphere.
c
4
The IR spectra of compounds 3 and 4 exhibit an abꢀ
sorption band in the region 527 cm–1 characteristic of
vibrations of the bonds of the fullerene framework, whereꢀ
as vibrational bands of the carbonyl and the phosphoryl
groups are found in the region 1733 and 1262 cm–1, reꢀ
spectively. A vibrational band at 2121 cm–1 characteristic
of the CH group at the triple bond was found for methaꢀ
nofullerene 3 containing an alkyne fragment, for methaꢀ
nofullerene 4, a weak vibrational band of the CH group in
3
3
b
the triazole ring was found at 3140 cm–1
.
In the MALDIꢀTOF mass spectra of compounds 3
and 4, peaks of the protonated molecular ions [MH]+ with
m/z 953.05 and 1086.1, respectively, are present, which
confirms the composition of the molecules under study.
Finally, the structures of compounds 3 and 4 were
confirmed based on the data of 1D and 2D NMR correlaꢀ
tion experiments.12 The principal HMBCꢀcorrelations,
which allowed us to establish the structures of the addends
in compounds 3 and 4, are shown in Fig. 4.
С60
4
a
The 13C NMR spectra of compounds 3 and 4, besides
the signals of the addend, exhibit a number of lines in the
region indicative for the C atoms of the fullerene sphere
( 148—136 and ~70). The presence of the spinꢀspin couꢀ
pling constants from the phosphorus nuclei to the carbon
nuclei of the fullerene C(1)/C(6) atoms16 indicates the
addition of the addend to the fullerene sphere. In this case,
the chemical shifts for C(1)/C(6) ( 70.10 and 70.24 for 3
and 4, respectively) allows us to suggest a close character
of the cycloaddition at the 6—6 bond.
2
4
6
8
10
12
tR/min
Fig. 3. The chromatogram (HPLC) for the reaction mixture
obtained in the synthesis of compound 4 by the Bingel—Hirsch
reaction (a) and for the starting compound 3 (b), as well as for
the reaction mixture in the synthesis of product 4 by the "clickꢀ
chemistry" (c) (a Partisil5ꢀODS(C18) column; eluent toluene—
acetonitrile (1 : 1); UV detector,  = 328 nm); I is the intensity.
We also obtained dipropargyl malonate 5 (see Ref. 17)
and a derived from it alkyne methanofullerene 6. The reꢀ
Scheme 3
seen from Fig. 3, a, the Bingel—Hirsch reaction, besides
the main product 4, formed many polycycloaddition prodꢀ
ucts, which decreased the yield of compound 4 (25%).
The reaction of methanofullerene 3 with benzylazide
under the "clickꢀchemistry" conditions required only mild
conditions and gave high yield of compound 4 (~89%). An
increase in the reaction time led to a complete conversion
of phosphorylated alkyne methanofullerene 3 to the triꢀ
azole methanofullerene 4, with the benzylazide itself beꢀ
ing unreactive with fullerene C60 under these conditions.
The structures of compounds obtained were confirmed
by the spectral data, their composition was confirmed by
MALDIꢀTOF mass spectrometry.
The UV spectra of methanofullerenes 3 and 4 exhibit
absorption bands of the fullerene framework at 258, 326,
431, 492, and 696 nm. The absorption band at 431 nm is
Fig. 4. The principal heteronuclear correlations (shown with
arrows from the 1H to the X nucleus) for compounds 3 and 4 (the
upper part of the fullerene sphere is shown schematically).

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Russ.Chem.Bull., Int.Ed., Vol. 61, No. 6, June, 2012
Gubskaya et al.
Scheme 4
R = CH2Ph
action of compound 6 with benzylazide in the presence
of the catalyst (EtO)3P•CuI led to the formation of the
triazole methanofullerene 7 (Scheme 4). Compounds 6
and 7 were isolated by column chromatography on silica
gel in 46 and 44% yields, respectively. Spectral characꢀ
teristics of compound 5 corresponded to the literature
data.17 The structures of the obtained compounds 6 and 7
were also confirmed by a combination of spectroscopic
methods.
The mass spectra of compounds 6 and 7exhibited peaks of
the molecular ions with m/z 898.02 and 1065.1 [M + H]+,
respectively, which confirmed the composition of the
methanofullerenes under study.
A number of 1D and 2D NMR correlation experiꢀ
ments were used to confirm the structures of compounds
6 and 7, as well.
The 1D 13C NMR spectra of compounds 6 and 7 exꢀ
hibited 17 signals with  145—136 in the region indicative
for the sp2ꢀhybridized C atoms of the fullerene sphere, as
well as the signals for the sp3ꢀhybridized atoms C(1)/C(6)
( ~71). The chemical shift for the C(1)/C(6) (70.9 and
71.2 for 6 and 7, respectively) indicated a closed character
1
of cycloaddition at the 6—6ꢀbond. The H NMR spectra
of compounds 6 and 7 and the principal HMBC correlaꢀ
tions characteristic of them, which allowed us to establish
the structures of the addends, are shown in Fig. 5.
a
CDCl3
NCH
Ph
OCH2
CH(5)ta
7.5
7.0
6.5
6.0
5.5
5.0
4.5
4.0
3.5
3.0

b
OCH2
CH
7.5
7.0
6.5
6.0
5.5
5.0
4.5
4.0
3.5
3.0

1
Fig. 5. The H NMR spectra and the principal heteronuclear correlations for compounds 6 (a) and 7 (b) (only the upper part of the
fullerene sphere and a one part of the attached fragment are shown schematically); CH(5)ta is the signal for triazole.

New triazole fullerene derivatives
Russ.Chem.Bull., Int.Ed., Vol. 61, No. 6, June, 2012
1173
(MALDIꢀTOF), found: m/z 367.370 [M]+. C16H22N3O5P. Calꢀ
culated: M = 367.373. IR (in KBr pellet), /cm–1: 490, 606, 725,
810, 889, 973, 1029, 1117, 1164, 1262 (P=O), 1369, 1394, 1456,
1498, 1559, 1608, 1733 (C=O), 2912, 2940, 2985, 3140. 31P NMR,
: 18.88. H NMR (CDCl3), : 1.35 (t, 6 H, J = 7.2 Hz); 3.10
(d, 2 H, JPCH = 21.5 Hz); 4.14 (m, 4 H); 5.32 (s, 2 H); 5.67 (s, 2 H);
In conclusion, we obtained new alkyne and triazole
derivatives of fullerene C60 and showed that in the prepaꢀ
ration of triazoleꢀcontaining methanofullerenes, the cycloꢀ
addition of azides and alkynes by the "clickꢀchemistry"
reaction was preferable as compared to the Bingel—Hirsch
reaction, since it led to the formation of only the target
compound in high yield. In this case, fullerene did not
react with azide under the indicated conditions.
1
7.48 (m, 5 H); 7.97 (s, 1 H).
61ꢀ(Propargyloxycarbonyl)ꢀ61ꢀ(diethoxyphosphoryl)methꢀ
ano[60]fullerene (3). A solution of compound 1 (0.1053 g,
0.45 mmol) in toluene, CBr4 (0.1494 g, 0.45 mmol) in toluene,
and DBU (0.0685 g, 0.45 mmol) were sequentially added to
a solution of fullerene C60 (0.216 g, 0.3 mmol) in toluene
(150 mL). The reaction mixture was stirred for 9 h at 28—30 C.
The reaction progress was monitored by HPLC. Then, the reacꢀ
tion mixture was acidified with three drops of 1 M H2SO4 and
the solution obtained was washed with water (2×30 mL). The
organic layer was concentrated in vacuo and the residue was
deposited on a column with SiO2. Unreacted C60 (15.7 mg) was
isolated by elution with a mixture of toluene—hexane (20 : 20, v/v).
Elution with a mixture of toluene—acetonitrile (40 : 0.5, v/v) led
to the isolation of compound 3 (99.3 mg, 42%, the yield was
calculated based on the consumed fullerene C60), as well as to
a mixture of bisꢀadducts. MS (MALDIꢀTOF): m/z 952.02.
C69H13O5P. Calculated: M = 952.05. UV (CH2Cl2), max/nm
(): 327 (15 905), 430 (3848), 492 (2107), 696 (142). IR (in KBr
pellet), /cm–1: 488, 525, 573, 669, 708, 740, 800, 950, 1010,
1042, 1173, 1220, 1259 (P=O), 1367, 1428, 1534, 1738 (C=O),
2922, 2980. 1H NMR (CDCl3), : 1.58 (t, 6 H, J = 7.2 Hz); 2.61
(t, 1 H, J = 2.7 Hz); 4.37 (m, 4 H); 5.06 (d, 2 H, J = 2.3 Hz).
31P {1H} NMR (CDCl3), : 10.76. 13C NMR (CDCl3), : 15.26,
16.11, 16.95, 17.80, 47.71—48.79 (J = 164 Hz); 53.33, 54.35,
55.35, 63.55, 64.65, 65.64, 70,04, 75.39, 76.32, 77.89, 77.07,
70.75, 137.08, 140.82, 140.85, 140.92, 141.82, 141.98, 142.14,
142.18, 142.70, 142.94, 142.95, 143.05, 143.13, 143.81, 143.96,
144.49, 144.59, 144.70, 144.81, 144.86, 144.89, 144.93, 144.98,
145.13, 145.24, 145.28, 147.08 (3JCP = 3 Hz); 163.55.
61ꢀ[(1ꢀBenzylꢀ1,2,3ꢀtriazolꢀ4ꢀyl)methoxycarbonyl]ꢀ61ꢀ(diꢀ
ethoxyphosphoryl)methano[60]fullerene (4). Method A (the Binꢀ
gel—Hirsch reaction). A solution of compound 2 (0.1519 g,
0.41 mmol) in toluene, CBr4 (0.1375 g, 0.41 mmol) in toluene,
and DBU (0.0630 g, 0.41 mmol) were sequentially added to
a solution of fullerene C60 (0.198 g, 0.27 mmol) in toluene
(200 mL). The reaction mixture was stirred for 42 h at ~20 C.
The reaction progress was monitored by HPLC. Then, the reacꢀ
tion mixture was acidified with three drops of 1 M H2SO4, the
solution obtained was washed with water (2×30 mL). The organꢀ
ic layer was concentrated in vacuo, and the residue was depositꢀ
ed on a column with SiO2. Unreacted C60 (15.7 mg) was isolated
by elution with a mixture of toluene—hexane (30 : 10, v/v). Eluꢀ
tion with a mixture of toluene—acetonitrile (38 : 2, v/v) led to
the isolation of compound 4 (58 mg, 25%, the yield was calculatꢀ
ed based on the consumed fullerene C60), as well as a mixture of
bisꢀadducts.
Experimental
Analysis by HPLC was performed on an Agilent Technoloꢀ
gies 1200 Series chromatograph with a UV detector, using colꢀ
umns with a C18 reversed phase (Partisilꢀ5 ODSꢀ3) and toluꢀ
ene—MeCN (1 : 1, v/v) as an eluent. Organic solvents were dried
and distilled before use. Fullerene C60 (99.9%) was purchased
from Fulleren Tsentr Inc., Nizhny Novgorod. All chemical maꢀ
nipulations were performed under dry argon.
UV spectra were recorded on a Specord Mꢀ40 spectroꢀ
photometer in dichloromethane, IR spectra were recorded on
a BrukerꢀVector 22 Fourierꢀtransform spectrometer (Bruker).
Mass spectra were recorded on a MALDIꢀTOF mass specꢀ
trometer.
1D and 2D NMR experiments (1H, 13C, and 31P) were perꢀ
formed on an Avanceꢀ400 (Bruker) (1H, 400.1 MHz; 13C,
100.6 MHz; 15N, 40.5 MHz; 31P, 161.9 MHz) spectrometer at
30 C, using residual signals of CDCl3 as a reference ( 7.26
H
and  77.0). Chemical shifts of 15N and 31P were determined
C
relative to the signals of the external standard CD3CN ( 0.0)
N
or H3PO4 ( 0.0), respectively.
P
NMR chemical shifts for compounds 1 and 2 were calculꢀ
ated by the GIAO B3LYP/6ꢀ31G(d) method, using the
GAUSSIAN 98 program package.18
Diethyl (propargyloxycarbonylmethyl)phosphonate (1). Proꢀ
pargyl chloroacetate (5 g, 0.037 mol) in anhydrous benzene
(5 mL) was added dropwise to a refluxed solution of triethyl
phosphite (6.3 g, 0.037 mol) in benzene (5 mL) and the reflux
was continued for 6 h. Then, the solvent was evaporated to obꢀ
tain a crude product (7.8 g), which after distillation in vacuo at
126—130 C (2 Torr) yielded compound 1 (5 g, 57%) as a dense
oil, nD 1.4550, d4 1.1715. IR (in KBr pellet), /cm–1: 494,
617, 708, 784, 887, 975, 1027, 1114, 1164, 1261 (P=O); 1370,
1394, 1444, 1479, 1642, 1744 (C=O); 2126 (—C=CH); 2912,
2936, 2986. 31P NMR, : 18.75. 1H NMR (CDCl3), : 1.24
(t, 6 H, J = 7.3 Hz); 2.45 (t, 1 H, J = 2.7 Hz); 2.93 (d, 2 H,
J = 21.7 Hz); 4.075 (m, 4 H); 4.62 (d, 2 H, J = 2.9 Hz).
20
20
Diethyl [(1ꢀbenzylꢀ1,2,3ꢀtriazolꢀ4ꢀyl)methoxycarbonylmeꢀ
thyl]phosphonate (2). Compound 1 (0.5 g, 2.1 mmol) in anꢀ
hydrous benzene (10 mL) was placed into a flatꢀbottom flask,
followed by addition of benzylazide (0.28 g, 2 mmol) and a triꢀ
ethyl phosphite complex with CuI (0.15 g, 4.2 mmol). The reacꢀ
tion mixture was stirred at ~20 C for 7 days using a magnetic
stirrer. The reaction progress was monitored recording IR specꢀ
tra of the reaction mixture and observing decrease in intensity of
the band characteristic of the azide group (2098 cm–1). Comꢀ
pound 2 was purified by column chromatography on SiO2. Unꢀ
reacted benzylazide and the CuI complex were isolated by eluꢀ
tion with a mixture of benzene—ethyl acetate (5 : 2). Eluꢀ
tion with ethyl alcohol gave compound 2 (0.5 g, 64.1%). MS
Method B (clickꢀchemistry). A mixture of compound 3 (0.04 g,
0.04 mmol), benzylazide (PhCH2N3) (5.6 mg, 0.04 mmol), and
the catalyst (EtO)3P•CuI (2.9 g, 0.008 mmol) in anhydrous tolꢀ
uene (20 mL) was stirred for 74 h at ~20 C. The reaction progress
was monitored by HPLC. Compound 4 (33.9 mg, 89%) was
isolated by column chromatography on silica gel with a mixture
of toluene—acetonitrile (38 : 2, v/v). MS (MALDIꢀTOF): m/z
1086.12 [M + H]+. C76H20O5PN3. Calculated: M = 1085.11.

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Gubskaya et al.
UV (CH2Cl2), max/nm (): 326 (14 803), 429 (4127), 491 (2087),
696 (132). IR (in KBr pellet), /cm–1: 525, 575, 588, 703, 725,
801, 979, 1016, 1044, 1095, 1176, 1220, 1264 (P=O), 1367, 1428,
1495, 1737 (C=O), 2923, 3140. 31P {1H} NMR (CDCl3), : 11.00.
1H NMR (CDCl3), : 1.45 (t, 6 H, J = 7.0 Hz); 4.45 (m, 4 H);
5.51 (s, 2 H); 5.59 (s, 2 H); 7.28—7.78 (m, 5 H); 7.67 (s, 1 H).
13C NMR (CDCl3), : 16.46, 22.59, 31.52, 47.52, 49.14, 54.36,
60.04, 64.53, 64.59, 70.12, 70.16, 109.94, 128.22, 128.95, 129.20,
130.00, 132.34, 136.62, 137.58, 140.78, 140.82, 140.85, 141.67,
141.79, 142.07, 142.15, 142.21, 142.64, 142.92, 142.94, 143.03,
143.05, 143.11, 143.77, 143.94, 144.25, 144.55, 144.60, 144.62,
144.65, 144.79, 144.83, 144.89, 145.11, 145.21, 145.24, 147.14
(3JP,C = 3 Hz), 163.55.
search 7P and 22P) and the Russian Foundation for Basic
Research (Project No. 09ꢀ03ꢀ00123ꢀa).
The structures of compounds were studied in the NMR
Department of the Federal Community spectroanalytical
center of physicochemical studies of structure, properties,
and composition of compounds and materials (TsKP
SATs) and Federal TsKP of physicochemical studies of
compounds and materials (FTsKP FKhI) (State Contracts
of the Ministry of Education and Science of the Russian
Federation Nos 02.451.11.7036 and 02.451.11.7019).
References
61ꢀBis(propargyloxycarbonyl)methano[60]fullerene (6). A soꢀ
lution of freshly distilled dipropargyl malonate 5 (0.113 g,
0.63 mmol) in toluene, CBr4 (0.208 g, 0.63 mmol) in toluene,
and DBU (0.095 g, 0.63 mmol) were sequentially added to
a solution of fullerene C60 (0.3 g, 0.42 mmol) in anhydrous
dichlorobenzene (35 mL) with stirring. The reaction mixture
was stirred for 10 h at ~20 C. The reaction progress was moniꢀ
tored by HPLC. Then, the reaction mixture was acidified with
three drops of 1 M H2SO4, the solution was washed with water
(2×10 mL). The organic layer was concentrated in vacuo and the
residue was deposited on a column with SiO2. Unreacted C60
(121.5 mg) was isolated by elution with hexane. Elution with
a mixture of toluene—hexane (1 : 1) gave compound 6 (102.3 mg,
46%, the yield was calculated based on the consumed fulꢀ
lerene C60), as well as a mixture of bisꢀadducts (93 mg). MS
(MALDIꢀTOF): m/z 898.02. C69H13O5P. Calculated: M = 898.05.
UV (CH2Cl2), max/nm (): 327 (15 905), 430 (3848), 492 (2107),
696 (142). IR (a suspension in Nujol), /cm–1: 527, 579, 672,
724, 970, 1001, 1059, 1096, 1182, 1199, 1225, 1266, 1367, 1428,
1539, 1649, 1747 (C=O), 2129, 3291. 1H NMR (CDCl3), : 2.65
(t, 2 H, J = 2.4 Hz); 5.10 (d, 4 H, J = 2.4 Hz). 13C NMR
(CDCl3), : 50.63 (C61), 54.52 (OCH2), 70.90 (sp3), 76.28, 76.55,
139.25, 140.96, 141.81, 142.18, 142.98, 143.00, 143.04, 143.86,
144.60, 144.67, 144.69, 144.93, 145.04, 145.18, 145.28, 162.55.
61ꢀBis[(1ꢀbenzylꢀ1,2,3ꢀtriazolꢀ4ꢀyl)methoxycarbonyl]methꢀ
ano[60]fullerene (7). A mixture of compound 6 (0.059 g,
0.066 mmol), benzylazide (PhCH2N3) (0.017 g, 0.065 mmol),
and the catalyst (EtO)3P•CuI (0.0047 g, 0.013 mmol) in anꢀ
hydrous toluene (25 mL) was stirred for 105 h at ~20 C. The
reaction progress was monitored by HPLC. Compound 6
(4.02 mg) was isolated by column chromatography on silica gel
eluting with a mixture of toluene—hexane (30 : 10, v/v), comꢀ
pound 7 (31.4 mg, 44%) was isolated by eluting with a mixture of
toluene—hexane—MeCN (40 : 4 : 2.5, v/v). MS (MALDIꢀTOF):
m/z 1165.49 [M + H]+. C83H20N6O4. Calculated: M = 1164.16.
UV (CH2Cl2), max/nm (): 3268 (14 950), 428 (4104), 492
(2093), 697 (112). IR (a suspension in Nujol), /cm–1: 526, 580,
723, 817, 997, 1026, 1050, 1113, 1156, 1182, 1205, 1228, 1263,
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1745 (C=O), 3141. H NMR (CDCl3), : 5.52 (s, 4 H, OCH2);
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This work was financially supported by the Presidium
of Russian Academy of Sciences (Program for Basic Reꢀ

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Received December 12, 2011;
in revised form February 20, 2012