Preparation and characterization of sulfonyl-azafulleroid and sulfonylaziridino-fullerene derivatives

Article abstract of DOI:10.1002/ejoc.200300122

Thermolysis of several sulfonyl azides in the presence of C₆₀ leads either to aza[60]fulleroids or to mixtures of aza[60]-fulleroids and corresponding aziridino-fullerenes, depending on the substituent at the sulfonyl group. In all cases, 1,2-c

Full text of DOI:10.1002/ejoc.200300122

FULL PAPER
Preparation and Characterization of Sulfonyl-Azafulleroid and
Sulfonylaziridino-Fullerene Derivatives
[a]
[a]
Lars Ulmer and Jochen Mattay*
Keywords: Fullerenes / Azo compounds / Photochemistry / Rearrangement / Cyclic voltammetry
Thermolysis of several sulfonyl azides in the presence of C60
leads either to aza[60]fulleroids or to mixtures of aza[60]-
fulleroids and corresponding aziridino-fullerenes, depending
on the substituent at the sulfonyl group. In all cases, 1,2-
yields azafulleroids with C
measurements revealed that there is no significant change of
electrochemical properties compared to C60 and C70
s
-symmetry. Cyclic-voltammetric
.
closed aziridino-fullerenes can be obtained from azafullero- ( Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim,
ids by irradiation. Addition of sulfonyl azides to C70 only
Germany, 2003)
Introduction
with the formation of intermediate triazolines, followed by
thermal cleavage of N . Depending on the nature of the
2
The thermal reaction of organic azides with fullerenes is substituent the nitrogen release affords different ratios of
a versatile route to provide stable cluster opened [5,6]- opened [5,6]-bridged azafulleroid to closed [6,6]-bridged
bridged iminofullerenes (azafulleroids).[1Ϫ12] Alternatively, aziridino-fullerene. Photochemical release of nitrogen pre-
cluster opened monofunctionalized fullerene derivatives dominantly leads to aziridino-fullerenes with closed fuller-
[
2,9Ϫ11]
(
fulleroids) are accessible by thermal reactions of diazo ene framework.
[13Ϫ20]
compounds with fullerenes.
To the best of our knowl-
Nitrenes generated in situ by photolysis or thermolysis
edge, no other examples of cluster opened monoadducts of of azides add to fullerenes in [2ϩ1] cycloadditons yielding
C60 and C70 are known. However, fulleroids containing at exclusively closed [6,6]-bridged aziridino-fullerenes.[9,10,23]
least one substituent such as a phenyl- or alkoxycarbonyl
group are thermally convertible to the corresponding [6,6]-
bridged
isomers with closed fullerene frame- Results and Discussion
[
2,5Ϫ8,11,13,17,21,22]
work.
The synthesis of azafulleroids is achieved by [3ϩ2] cyclo-
We investigated addition reactions of several sulfonyl az-
additions of azides to a [6,6] double bond of the fullerene ides 1aϪd to C60 and C , photochemical rearrangements
70
Scheme 1. Formation of (sulfonylimino)fullerenes by addition of sulfonyl azides to C60
and the electrochemical properties of the synthesized fuller-
ene derivatives.
[
a]
Organische Chemie I, Fakultät für Chemie, Universität
Bielefeld,
Universitätsstr. 25, 33615 Bielefeld, Germany
E-mail: mattay@uni-bielefeld.de
The preparation of the sulfonylimino[60]fullerenes 2a؊d,
a؊b was achieved by thermal reaction of sulfonyl azides
3
1aϪd with C60 for 2 h as shown in Scheme 1. The sulfonyl
Eur. J. Org. Chem. 2003, 2933Ϫ2940
DOI: 10.1002/ejoc.200300122
 2003 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
2933

L. Ulmer, J. Mattay
FULL PAPER
azides were prepared by reaction of the corresponding sul-
fonyl chlorides with sodium azide.[
24]
Chromatography on silica gel yielded unconverted C60
(1st fraction) and mixtures of azafulleroid/aziridino-fuller-
ene (2a/3a and 2b/3b) or only azafulleroids (2c,d) in Ͼ 25%
yield, respectively. Separation of the azafulleroid/aziridino-
fullerene mixtures has been accomplished by second chro-
matography on silica gel (2a/3a) or by HPLC (Bucky
Clutcher I) (2b/3b). Azafulleroids are isolated in 11% (2a)
and 7% (2b) yield and aziridino-fullerenes are isolated in
1
2% (3a) and 10% (3b) yield.
The structures of the [5,6]-opened azafulleroids 2aϪd
Scheme 2. Photochemical rearrangement of azafulleroids to azirid-
ino-fullerenes
have been identified by standard spectroscopic methods.
MALDI-TOF mass spectra show for all monoadducts the
molecular ion peaks at m/z ϭ 813 (2a/3a), 889 (2b/3b and
These results clearly show differences between reaction of
alkylated (1a, 1b) and arylated sulfonyl azides (1c, 1d) with
fullerenes. Addition of arylated sulfonyl azides exclusively
results in the formation of azafulleroids whereas addition
of alkylated sulfonylazides yields both, azafulleroids and
aziridino-fullerenes in nearly the same ratio. The decisive
step seems to be the nitrogen release from the intermediate
triazoline. Luh et al. suggested the following mechanism for
nitrogen release from triazolinofullerenes: homolytic cleav-
age of the NϪN single bond of triazolines with formation
of an amino/diazenyl diradical, which stabilizes by addition
of the amino radical center to either C-6 or C-2 followed
2c/3c) and 905 (2d/3d) together with peaks at m/z ϭ 720
1
3
owing to the fragment C . The C NMR spectra of 2aϪd
show 32 signals at δ ϭ 115Ϫ155 ppm for the sp carbons
of the C60 skeleton. The number of signals and the absence
of signals in the range of δ ϭ 60Ϫ80 ppm indicate both a
6
0
2
3
[
5,6]-opened structure without sp carbons in the fullerene
framework and C -symmetry. The remaining signals are at-
tributed to the aromatic and aliphatic carbon atoms of the
functional groups as well as the signals of the H NMR
spectra. Further evidence is obtained from the UV/Vis spec-
tra which are similar to the spectrum of pure C . The
s
1
60
[
11]
by N -release and electrocyclic ring opening.
Following
characteristic absorption for [6,6]-closed fullerene deriva-
2
tives at 420 nm are not observed.[
14Ϫ17]
this mechanism, differences in reactivity result from stabiliz-
ing effects in the diradical species. Ouchi, Ito and co-work-
ers also observed a large substituent effect on the photoch-
The 13C NMR spectra of the aziridino-fullerenes 3a,b
show only 17 signals for the C60 skeleton [16 between δ ϭ
1
[
25]
3
emical rearrangement of N-aryl-aza[60]fulleroids.
15 and 155 ppm and one for the sp hybridized carbons at
In contrast to C60 monofunctionalization of C70 leads to
mixtures of regioisomers due to lower symmetry and to dif-
ferences in reactivity between the various double bonds.
There are each four different [6,6] (IϪIV) and [5,6] ring fu-
sions (VϪVIII) (Scheme 3). Double bonds in the pole re-
gion are more reactive (I, II) which is explained by the
greater curvature and the resulting higher bonding tension.
Therefore addition reactions theoretically could lead to
eight regioisomeric monoadducts. Four of them have a [6,6]
junction and four have a [5,6] junction. Additions to the
δ ϭ 79.48 ppm (3a) and 79.06 ppm (3b), respectively]. This
indicates for both derivatives C -symmetry with a [6,6]
junction on the fullerene core. The UV/Vis spectra exhibits
the typical bands of [6,6]-bridged dihydrofullerenes includ-
ing the band at around 420 nm.
To synthesize the corresponding aziridino-fullerenes 3c
and 3d solutions of the azafulleroids 2c and 2d, respectively,
in oxygen free 1,1,2,2-tetrachloroethane were irradiated for
2
v
2
h in pyrex tubes (of, 10 mL) using a RPR 100 Rayonet
Photochemical Chamber Reactor equipped with RPR-4190
[
6,6] bonds result in closed structures which could be dis-
˚
A lamps (Scheme 2). Chromatography on silica gel yielded
13
tinguished by C NMR spectroscopy. Functionalization at
small amounts of unconverted azafulleroid and the ful-
leroaziridine derivatives (3c, 3d) in Ͼ 40% yield. The other
azafulleroids (2a, 2b) can be converted into the correspond-
ing aziridino-fullerenes (3a, 3b) by irradiation under same
bond I and II leads to C -symmetrical adducts with each
s
1
13
conditions as well. The H, C NMR and UV/Vis spectra
of these compounds are identical to the ones described
above.
The 13C NMR spectra of 3c and 3d show 16 signals at
2
1
20Ϫ150 ppm for the sp carbons of the fullerene core and
only one signal [δ ϭ 80.01 ppm (3c) and δ ϭ 80.17 ppm
3
(
3d)] for the sp hybridized carbons in the fullerene frame-
work, indicating C2v symmetry with a [6,6] junction on the
fullerene core. Further evidence is obtained from UV/Vis
spectra which displays the characteristic absorption for 1,2
adducts at around 420 nm.
Scheme 3. A: Eight distinct sets of bonds of C70: [6,6]- (IϪIV) and
[
5,6] bonds (VϪVIII). B: Partial numbering of some carbon atoms
[21]
corresponding the IUPAC.
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 2003 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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Eur. J. Org. Chem. 2003, 2933Ϫ2940

Sulfonyl-Azafulleroid and Sulfonylaziridino-Fullerene Derivatives
2
FULL PAPER
3
3
7 signals in the region for sp hybridized fullerene carbon of δ ϭ 115Ϫ155 ppm and 1 single intensity sp resonance
atoms. Due to different bridgehead atoms in the fullerene assigned to the methyl group. The presence of only one sp3
core it is possible to distinguish between these closed Cs- resonance indicates that this isomer is a fulleroid, and the
symmetrical adducts. 1,2 adducts (bond I) show two differ- number of resonances indicates a structure with C -sym-
s
3
ent signals for the two non equivalent sp hybridized car- metry. There are two possible fulleroids with C -symmetry
s
bons while at [5,6] adducts (bond II) display only one signal of 4a: one formed by [3ϩ2] cycloddition of methylsulfonyl
1
3
for the two equivalent bridgehead atoms. C NMR spectra azide to the C1ϪC2 double bond followed by nitrogen re-
of C70 derivatives functionalized at bond III show 70 signal lease and rearrangement to the C2ϪC3 position with an
because of the C -symmetry fullerene derivatives. Additions opened cluster structure. The second possible structure is
1
13
to bond IV result in C -symmetrical adducts of which
C
formed by [3ϩ2] cycloddition of methylsulfonyl azide to the
2
v
NMR spectra show only 21 signals for the fullerene C7ϪC21 double bond. Decomposition of the triazoline and
[
4,7,18,26Ϫ32]
carbons.
rearrangement to the C7ϪC8 position leads also to an
C70 adducts with junctions to [5,6] ring fusions (VϪVIII) opened cluster structure. We tentatively assigned 4a to a
can be synthesized accordingly to the [60]fulleroid deriva- C2ϪC3 azafulleroid structure due to the higher reactivity
tives. First, azides are added to C70 with formation of tri- of the C1ϪC2 double bond in the most curved surface.
azolino derivatives. Nitrogen release and a norcaradiene re-
The 13C NMR spectra of 4c, 5c, 4d and 5d indicate ful-
arrangement leads now to aza[70]fulleroid. Depending on leroid structures with a plane of symmetry for all as well.
3
the first addition step, four different regioisomers are pos- Each spectrum displays one single intensity sp resonance
2
sible. Two of these isomers, the C2ϪC3 and the C7ϪC8 assigned to the corresponding methyl group and 41 sp res-
fulleroid, have a plane of symmetry whereas the two other onances, four assigned to the phenyl group and 37 assigned
ones, functionalized at bonds VI and VII, are C -symmetri- to the fullerene carbons. These patterns are indicative of Cs-
1
cal. The C - and the C -symmetrical fulleroids could not be symmetrical fulleroid structures. Since the polar region of
s
1
1
3
distinguished from each other by C NMR spectroscopy C70 is the more reactive area of the fullerene, we assume the
2
due to the same number of signals in the region for sp
major products 4c and 4d to be formed upon addition to
the C2ϪC3 bond. Consequently, the minor products 5c and
hybridized fullerene carbon atoms.[
4,7,18,26Ϫ32]
Thermolysis of sulfonyl azides 1a, 1c, and 1d in the pres- 5d must be functionalized at the C7ϪC8 bond. The UV/Vis
ence of C70 in 1,2-dichlorobenzene for 3 h at 160 °C leads spectra of the fulleroids 4a, 4c and 4d are similar to each
to aza[70]fulleroids. In case of methylsulfonyl azide (1a) other and the spectra of all five monofunctionalised
only one aza[70]fulleroid besides several by-products in Ͻ aza[70]fulleroids are similar to the one of C .
70
3% was obtained whereas addition of 1c and 1d resulted in
These results suggest that sulfonyl azides are suitable to
the formation of two isomeric azafulleroids (Scheme 4).
synthesize aza[70]fulleroids, with a C2ϪC3 junction as well
Chromatography on silica gel with toluene/cyclohexane as with a C7ϪC8 junction. There are only few examples
yielded unconverted C70 (1st fraction) and mixtures of aza- of C70 derivatives containing a C7ϪC8 junction reported
[
31,32]
fulleroids and by-products. Separation of the azafulleroids so far.
was carried out by second chromatography on silica gel The electrochemical behavior of the sulfonyliminofuller-
with toluene/cyclohexane (1:2). Azafulleroids were isolated enes was studied by cyclic voltammetry and compared to
in 12% (4a), 9% (4c), 6% (5c), 10% (4d) and 7% (5d) yield, that of C60 and C70 in order to determine the extent of
and their molecular formulae were confirmed by mass spec- electronic interaction between addend and fullerene core.
trometry.
The measurements were performed in o-dichlorobenzene
Addition product 4a displays a 13C NMR spectrum com- with 0.1  (Bu N)BF as supporting electrolyte. The data
4
4
2
prised of 38 resonances, 37 sp resonances in the region for the C60 derivatives are listed in Table 1.
Scheme 4. Formation of aza[70]fulleroids by addition of sulfonyl azides
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 2003 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
2935

L. Ulmer, J. Mattay
FULL PAPER
ϩ
Table 1. E1/2 values (mV vs. Fc/Fc ) of C60 and several sulfonylimino[60]fullerenes (E1/2 ϭ (Ered ϩ Ereox)/2, Ered and Ereox peak potentials;
E ϭ Ereox ϩ Ered
∆
)
Compound
1st reduction potential,
2nd reduction potential,
3rd reduction potential,
E1/2 (∆E)/[mV]
1
2
3
E1/2 (∆E)/[mV]
E1/2 (∆E)/[mV]
C
60
a
Ϫ1050 (63)
Ϫ1086 (72)
Ϫ1088 (82)
Ϫ1084 (85)
Ϫ1088 (76)
Ϫ1070 (85)
Ϫ1080 (68)
Ϫ1450 (67)
Ϫ1464 (74)
Ϫ1476 (82)
Ϫ1460 (87)
1466 (80)
Ϫ1454 (90)
Ϫ1470 (68)
Ϫ1915 (65)
Ϫ1930 (74)
Ϫ1934 (86)
Ϫ1922 (88)
Ϫ1932 (85)
Ϫ1911 (90)
Ϫ1926 (72)
2
3
2
3
2
3
a
c
c
d
d
ϩ
Table 2. E1/2 values (mV vs. Fc/Fc ) of C60 and several sulfonylimino[70]fullerenes (E1/2 ϭ (Ered ϩ Ereox)/2, Ered and Ereox peak potentials;
∆E ϭ Ereox ϩ Ered)
Compound
1st reduction potential,
2nd reduction potential,
3rd reduction potential,
E1/2 (∆E)
1
2
3
E1/2 (∆E)
E1/2 (∆E)
C
70
a
Ϫ1066 (63)
Ϫ1070 (72)
Ϫ1076 (85)
Ϫ1064 (76)
Ϫ1054 (85)
Ϫ1066 (68)
Ϫ1442 (67)
Ϫ1428 (74)
Ϫ1454 (87)
Ϫ1412 (80)
Ϫ1422 (90)
Ϫ1430 (68)
Ϫ1846 (65)
Ϫ1846 (74)
Ϫ1855 (88)
Ϫ1832 (85)
Ϫ1826 (90)
Ϫ1840 (72)
4
4
5
4
5
c
c
d
d
All compounds exhibit three well defined, single electron, the investigated region for both, the C60 and C70 deriva-
quasireversible waves[33,34] and retain the electronic proper- tives.
ties of C . The reduction potentials are slightly shifted to-
6
0
ward more negative values than in C60 itself. However, the
effect of functionalization is large for the first reduction
step for all derivatives. Among them the methoxy sulfonyl
group causes the smallest effect. This behaviour is observed
in most [60]fullerene derivatives, of which cyclic voltammo-
grams are typically characterised by small shifts to more
Experimental Section
General Remarks: C60 and C70 were used in gold grade (Hoechst,
Ն 99.4%). All reactions were performed under argon. o-Dichloro-
benzene was of purum grade (Ն 98%), toluene, carbon disulfide,
acetonitrile and 1,1,2,2-tetrachloroethane were used in per analysis
negative values of the reduction potentials due to an in- quality. Cyclohexane was used freshly distilled. Removal of all sol-
crease of electron density.[
14Ϫ18,35Ϫ38]
vents was carried out under reduced pressure. The solutions were
The data for the C70 derivatives are listed in Table 2. irradiated in pyrex tubes (of, 10 mL) in a RPR-100 Rayonet Photo-
˚
chemical Chamber Reactor with RPR-4190 A lamps. Analytical
These compounds exhibit three well defined, single elec-
high performance liquid chromatography (HPLC) was performed
tron, quasireversible reduction steps and retain the elec-
by using a C18-reversed phase column (Macherey ET 250/4 Nucleo-
tronic properties of C . Though the effect of functionaliz-
7
0
sil 100Ϫ5) and toluene/acetonitrile (1:1.1) as liquid phase (UV/Vis
ation on the potentials is not uniform. These results are in
agreement with other [70]fullerene derivatives.[
detection at 300 nm Kontron HPLC detector 432), flow
39,40,41]
Ϫ1
1.1 mL·min
(Merck L-6000 pump). For preparative HPLC a
Bucky Clutcher column (Regis, precolumn 50 ϫ 10.0 mm, column
˚
2
50 ϫ 21.1 mm, Bucky Clutcher I, 10 µm, 100 A), an Abimed-
Conclusion
Gilson Spectrochrom detector (UV/Vis detection at 300 nm) and a
Kontron HPLC pump 420 (flow: 10 mL·min ) were used. Column
Ϫ1
Thermolysis of sulfonyl azides has been shown to be a chromatography was performed on silica gel (MachereyϪNagel,
6
3Ϫ200 µm and 40Ϫ60 µm). After isolation, products were purified
versatile procedure for the formation of monofunctional-
ized aza[60]fulleroids with an opened cluster structure. The
corresponding aziridino-fullerenes are accessible by photo-
by dissolving in CS , precipitating with n-pentane, centrifugation
and decanting to remove the pentane soluble components. It was
finally dried under vacuum. Matrix laser desorption time-of-flight
mass spectra (MALDI-TOF) were recorded with a Voyager
2
chemical rearrangement. Addition of sulfonyl azides to C70
TM
DE
leads to the formation of fulleroid structures as well. Sur-
prisingly, the functionalization occurs at the pole region
with most curved surface as well as at the relatively flat
instrument (PE Biosystems, nitrogen laser, λ ϭ 337 nm, matrix:
-[(2E)-3-(4-tert-butylphenyl)-2-methylprop-2-enylidene]malono-
dinitrile (DCTB), linear mode). Relative intensities are given in per-
2
midsection. The influence of sulfonylimino groups on the centages. NMR spectra were recorded with Bruker AM 300 and
electronic properties of the fullerene seems to be small in DRX 500 spectrometers. Chemical shift data are reported relative
2936
 2003 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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Eur. J. Org. Chem. 2003, 2933Ϫ2940

Sulfonyl-Azafulleroid and Sulfonylaziridino-Fullerene Derivatives
FULL PAPER
to solvent peak as reference. Fourier tranform infrared spectra were
recorded with a PerkinϪElmer 1600-FTIR spetrometer. UV/Vis
spectra were performed with a PerkinϪElmer Lambda 40 spectro-
photometer.
144.78, 144.46, 144.38, 144.35, 144.33, 144.31, 144.28, 144.26,
144.16, 144.01, 143.82, 143.65, 143.51, 143.26, 143.24, 143.12,
143.07, 142.86, 141.96, 141.83, 140.36, 140.25, 139.81, 138.90,
2
138.85, 138.77, 138.10, 136.44, 135.07, 134.05 (32 C60 sp signals),
1
4
1
2
31.47 (C-5Ј, C-9Ј), 129.40 (C-7Ј), 129.10 (C-6Ј, C-8Ј), 127.98 (C-
Ј) 60.85 (C-3Ј) ppm. FT-IR (KBr): ν˜ ϭ 2918 m (CH
), 1508 s,
): λmax (Ͼ
40 nm, ε) ϭ 260 (144000), 325 (48000) nm. MS (MALDI-TOF,
Electrochemical Measurements: The electrochemical studies were
carried out in o-dichlorobenzene (per analysis quality, water-free).
The supporting electrolyte was (Bu N)BF (0.1 ). All measure-
4 4
2
Ϫ1
2 2
355 s, 1153 s, 694 s, 528 m cm . UV/Vis (CH Cl
ments were carried out using a K0264 three-electrode cell. The
working electrode was a Pt-electrode (diameter 2 mm), the auxiliary
electrode a Pt-wire, and the reference electrode a Ag-wire (pseudo-
Ϫ
neg. ion-mode, DCTB, 15 kV): m/z (%) ϭ 889 (100) [M] (calcd.
Ϫ
889.03), 734 (25) [M Ϫ C
7 7 2
H NO S] .
ϩ
1
reference electrode). All potentials in the text are given vs. Fc/Fc
2nd Fraction, N-(Benzylsulfonylaziridino)[2Ј,3Ј:1,2][60]fullerene: H
used as internal standard. The cell was connected to a com-
puterized PAR 273 A (EG&G Princton Applied Research, USA).
NMR (500.13 MHz, CS /CD Cl , 4:1): δ ϭ 7.78Ϫ7.77 (m, 2 H, 8Ј-
H, 10Ј-H), 7.53Ϫ7.48 (m, 3 H, 7Ј-H, 9Ј-H, 11Ј-H), 4.83 (s, 3 H, 5Ј-
2
2
2
1
3
H) ppm. C NMR (125.76 MHz, CS
2
/CD
2 2
Cl , 5:1): δ ϭ 145.47,
Reaction of C60 with Methylsulfonyl Azide (1a): A solution of C60
1
1
1
6
1
2
45.32, 145.21, 144.68, 144.37, 144.13, 144.08, 143.39, 143.26,
43.25, 142.92, 142.38, 141.99, 141.23, 141.01 (15 C60 sp signals),
31.61 (C-7Ј, C-11Ј), 129.60 (C-9Ј), 129.50 (C-8Ј, C-10Ј), 127.99 (C-
(216 mg, 0.30 mmol) and methylsulfonyl azide (1a, 0.75 g,
2
6.2 mmol) in 50 mL 1,2-dichlorobenzene was heated at 160 °C for
2
h. The solvent was then evaporated under reduced pressure.
Ј) 61.95 (C-5Ј) ppm. FT-IR (KBr): ν˜ ϭ 2918 m (CH
152 s, 818 m, 696 m, 525 m cm . UV/Vis (CH Cl
2 2
), 1341 s,
): λmax (Ͼ
40 nm, ε) ϭ 254 (106000), 322 (32000), 407 (200), 422 (1250) nm.
2
Chromatography on silica gel 60 (toluene/cyclohexane, 1:1) gave
Ϫ1
85 mg (39%) of unconverted C60 and 85 mg of a mixture of 2a and
3a. The solution of the mixture was reduced to 20 mL and second
MS (MALDI-TOF, pos. ion-mode, DCTB, 15 kV): m/z (%) ϭ 889
chromatography on silica gel 40 (toluene/cyclohexane, 1:1) gave
0 mg (12%) of 3a (1st fraction) and 26 mg (11%) of 2a (2nd frac-
tion).
ϩ
(
100) [M] (calcd. 889.03).
3
Reaction of C60 with (4-Methylphenyl)sulfonyl Azide (1c): A solu-
tion of C60 (216 mg, 0.30 mmol) and (4-methylphenyl)sulfonyl az-
ide (1c, 1.2 g, 6.0 mmol) in 50 mL 1,2-dichlorobenzene was heated
at 160 °C for 2 h. The solvent was then evaporated under reduced
pressure. Chromatography on silica gel 60 (toluene/cyclohexane,
1
st Fraction, N-(Methylsulfonyl)aziridino[2Ј,3Ј:1,2][60]fullerene: 1
NMR (500.13 MHz, CS /CD Cl , 5:1): δ ϭ 3.72 (s, 3 H, 5Ј-H)
ppm. 13C NMR (125.76 MHz, CS
/CD Cl , 5:1): δ ϭ 145.47,
45.32, 145.25, 145.18, 144.68, 144.30, 144.15, 144.07, 143.41,
H
2
2
2
2
2
2
1
1
1:1) gave 83 mg (38%) of unconverted C60 (1st fraction) and 75 mg
2
43.31, 143.28, 142.98, 142.35, 142.05, 141.16, 129.16 (16 C60 sp
(
28%) of 2c (2nd fraction).
signals), 79.48 (C-1, C-2), 43.08 (C-5Ј) ppm. FT-IR (KBr): ν˜ ϭ
2nd Fraction, 1,6-[N-(4Ј-Methylphenylsulfonyl)]aza[60]fulleroid: 1H
Ϫ1
2
(
(
922 m (CH
CH Cl ): λmax (Ͼ 220 nm, ε) ϭ 254 (90100), 323 (27700), 402 sh
2400), 410 (2100), 422 (1500), 484 (1100), 600 sh (450), 680 (130)
3
), 1348 s, 1161 s, 955 m, 816 m, 698 m cm . UV/Vis
3
NMR (500.13 MHz, CS
8
2
/CD
2
Cl
2
, 4:1): δ ϭ 8.02 (d,
J
H,H
ϭ
2
2
3
.4 Hz, 2 H, 4Ј-H, 8Ј-H), 7.42 (d, JH,H ϭ 8.4 Hz, 2 H, 5Ј-H, 7Ј-
H), 2.55 (s, 3 H, 9Ј-H) ppm. 13C NMR (125.76 MHz, CS
/CD Cl
5:1): δ ϭ 148.20, 147.15, 144.68, 144.53, 144.14, 143.99, 143.96,
2
2
2
,
nm. MS (MALDI-TOF, neg. ion-mode, DCTB, 15 kV): m/z (%) ϭ
Ϫ
Ϫ
8
13 (100) [M] (calcd. 812.99), 720 (56) [M Ϫ CH
3 2
NO S] .
1
1
1
43.89, 143.81, 143.77, 143.62, 143.50, 143.45, 143.25, 143.04,
42.82, 142.79, 142.67, 142.52, 141.50, 141.46, 139.89, 139.54,
1
2
nd Fraction, 1,6-(N-Methylsulfonyl)aza[60]fulleroid: H NMR
1
3
(500.13 MHz, CS
2
/CD
2
Cl
/CD
44.61, 144.46, 144.39, 144.38, 144.36, 144.29, 144.08, 143.91,
2
, 5:1): δ ϭ 3.49 (s, 3 H, C-3Ј) ppm.
C
39.29, 138.40, 138.14, 137.71, 137.68, 135.31, 134.62, 133.69 (31
NMR (125.76 MHz, CS
2
2
Cl , 5:1): δ ϭ 147.86, 147.44, 144.72,
2
2
C
60 sp signals), 135.47 (C-6Ј), 129.68 (C-5Ј, C-7Ј), 128.77 (C-4Ј,
1
1
1
1
3
C-8Ј), 21.66 (C-9Ј) ppm. FT-IR (KBr): nu(tilde ϭ 2913 m (CH ),
43.90, 143.70, 143.56, 143.21, 143.05, 142.00, 141.90, 141.20,
40.41, 140.11, 140.08, 138.99, 138.88, 138.81, 138.12, 135.86,
35.13, 133.87, 128.44, 127.19, 125.55 (32 C60 sp signals), 41.36
Ϫ1
1
508 s, 1338 s, 1261 m, 1165 s, 1086 s, 807 s, 644 m, 525 s cm
UV/Vis (CH Cl ): λmax (Ͼ 240 nm, ε) ϭ 259 (56000), 326 (18250)
nm. MS (MALDI-TOF, pos. ion-mode, DCTB, 15 kV): m/z (%) ϭ
.
2
2
2
(
C-3Ј) ppm. FT-IR (KBr): ν˜ ϭ 2922 m (CH
m, 769 m cm . UV/Vis (CH Cl
2 2
(
3
), 1357 s, 1162 s, 955
): λmax (Ͼ 220 nm, ε) ϭ 258
94000), 327 (30100), 525 (830), 595 sh (590) nm. MS (MALDI-
ϩ
ϩ
8
7 7 2
89 (100) [M] (calcd. 889.03), 720 (46) [M Ϫ C H NO S] .
Ϫ1
Reaction of C60 with (4-Methoxyphenyl)sulfonyl Azide (1d): A solu-
tion of C60 (216 mg, 0.30 mmol) and (4-methoxyphenyl)sulfonyl az-
ide (1d, 1.3 g, 6.1 mmol) in 50 mL 1,2-dichlorobenzene was heated
at 160 °C for 2 h. The solvent was then evaporated under reduced
pressure. Chromatography on silica gel 60 (toluene/cyclohexane,
Ϫ
TOF, neg. ion-mode, DCTB, 15 kV): m/z (%) ϭ 813 (100) [M]
Ϫ
(
calcd. 812.99), 720 (45) [M Ϫ CH
3 2
NO S] .
Reaction of C60 with Benzylsulfonyl Azide (1b): A solution of C60
(216 mg, 0.30 mmol) and benylsulfonyl azide (1b, 1.2 g, 6.0 mmol) 2:1) gave 75 mg (35%) of unconverted C60 and 90 mg of 2d polluted
in 70 mL 1,2-dichlorobenzene was heated for 15 min under reflux.
The solvent was then evaporated under reduced pressure. Chroma-
with polar by-products. The solution of 2d then was reduced to
20 mL. Chromatography on silica gel 40 (toluene/cyclohexane, 1:1)
tography on silica gel 60 (toluene/cyclohexane, 1:1) gave 90 mg gave 84 mg (31%) of 2d.
(
42%) of unconverted C60 and 72 mg of a mixture of 2b and 3b.
2
nd Fraction, 1,6-[N-(4Ј-Methoxyphenylsulfonyl)]aza[60]fulleroid:
The solution of the mixture was reduced to 20 mL. Chromatogra-
phy with HPLC (Bucky Clutcher I) (toluene/cyclohexane, 10:1)
gave 18 mg (7%) of 2b (1st fraction) and 26 mg (10%) of 3b (2nd
fraction).
1
3
H NMR (500.13 MHz, CS
.0 Hz, 2 H, 4Ј-H, 8Ј-H), 7.05 (d, JH,H ϭ 9.0 Hz, 2 H, 5Ј-H, 7Ј-
H), 3.95 (s, 3 H, 10Ј-H) ppm. 13C NMR (125.76 MHz, CS
/CD Cl
:1): δ ϭ 163.63 (C-6Ј), 148.19, 147.24, 144.56, 144.16, 144.05,
2 2 2
/CD Cl , 5:1): δ ϭ 8.02 (d, JH,H ϭ
3
9
2
2
2
,
5
1
(
st Fraction, 1,6-(N-Benzylsulfonyl)aza[60]fulleroid: 1H NMR
500.13 MHz, CS /CD Cl , 4:1): δ ϭ 7.56Ϫ7.54 (m, 2 H, 6Ј-H, 8Ј-
144.02, 143.94, 143.84, 143.82, 143.75, 143.66, 143.55, 143.50,
143.30, 143.08, 142.90, 142.89, 142.86, 142.85, 142.59, 142.53,
2
2
2
H), 7.47Ϫ7.45 (m, 3 H, 7Ј-H, 5Ј-H, 9Ј-H), 4.71 (s, 2 H, 3Ј-H) ppm. 141.55, 141.50, 139.90, 139.60, 139.36, 138.48, 138.19, 137.80,
13
2
C NMR (125.76 MHz, CS
2
/CD
2
Cl
2
, 5:1): δ ϭ 147.35, 147.16, 137.68, 135.33, 134.71, 134.11, 131.04 (32 C60 sp signals, C-3Ј, C-
Eur. J. Org. Chem. 2003, 2933Ϫ2940
www.eurjoc.org  2003 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim 2937

L. Ulmer, J. Mattay
FULL PAPER
4
Ј, C-8Ј), 114.18 (C-5Ј, C-7Ј), 55.30 (C-10Ј) ppm. FT-IR (KBr): s, 1261 s, 1159 s, 1088 s, 1024 m, 803 m, 683 m, 612 m cmϪ1. UV/
ν˜ ϭ 2930 s (CH
), 1740 m, 1592 m, 1494 m, 1261 s, 1159 s, 1088 Vis (CH Cl ): λmax (Ͼ 220 nm, ε) ϭ 256 (91300), 323 (32600), 411
s, 1024 m, 803 m, 683 m, 612 m cm . UV/Vis (CH ): λmax (Ͼ (2100), 423 (1400) nm. MS (MALDI-TOF, neg. ion-mode, DCTB,
20 nm, ε) ϭ 258 (92500), 325 (33000) nm. MS (MALDI-TOF, 15 kV): m/z (%) ϭ 905 (100) [M] (calcd. 905.02), 720 (15) [M
3
2
2
Ϫ1
2
Cl
2
Ϫ
2
Ϫ
Ϫ
7 7 3
neg. ion-mode, DCTB, 15 kV): m/z (%) ϭ 905 (100) [M] (calcd. Ϫ C H NO S] .
Ϫ
7 7 3
905.02), 720 (20) [M Ϫ C H NO S] .
Reaction of C70 with Methylsulfonyl Azide (1a): A solution of C70
(252 mg, 0.300 mmol) and methylsulfonyl azide (1a, 0.75 g,
6.2 mmol) in 70 mL 1,2-dichlorobenzene was heated at 160 °C for
Photochemical Rearrangements of Azafulleroids to the Correspond-
ing Aziridino-fullerenes
3
h. The solvent was then evaporated under reduced pressure.
Synthesis of N-(Methylsulfonyl)aziridino[2Ј,3Ј:1,2][60]fullerene (3a):
A solution of 1,6-(N-methylsulfonyl)aza[60]fulleroid (2a, 65 mg,
Chromatography on silica gel 40 (toluene/cyclohexane, 1:1) gave
unconverted C70 and a mixture of several products. The solution
of the product mixture was reduced to 10 mL and flash chromatog-
raphy on silica gel 40 (toluene/cyclohexane, 1:2) gave 34 mg (12%)
of 4a (4th fraction).
0
5
.08 mmol) in 60 mL 1,1,2,2-tetrachlorethane was irradiated for
h. The solvent was evaporated under reduced pressure. Chroma-
tography on silica gel 40 (toluene/cyclohexane, 1:2) gave 26 mg
40%) of 3a (1st fraction) and 13 mg (20%) not consumed 2a.
(
4
th Fraction, 2,3-(N-Methylsulfonyl)aza[70]fulleroid: 1H NMR
(500.13 MHz, CS /CD Cl , 5:1): δ ϭ 3.09 (s, 3 H, 3Ј-H) ppm.
NMR (125.76 MHz, CS /CD Cl , 5:1): δ ϭ 151.65, 150.63, 149.92,
2 2 2
149.57, 149.50, 149.48, 148.73, 148.56, 148.38, 147.64, 147.53,
147.51, 147.47, 147.07, 146.03, 145.50, 145.24, 145.20, 145.12,
144.77, 144.63, 144.33, 144.32, 143.45, 139.99, 139.30, 138.62,
137.41, 131.95, 131.08, 130.99, 130.35, 128.86, 128.12, 127.47,
125.78, 116.84 (37 C70 sp signals), 40.58 (C-3Ј) ppm. FT-IR (KBr):
ν˜ ϭ 2927 s (CH ), 1424 m, 1350 m, 1160 s, 958 m cm . UV/Vis
1
3
Synthesis of N-(Benzylylsulfonyl)aziridino[2Ј,3Ј:1,2][60]fullerene
3b): A solution of 1,6-(N-benzylsulfonyl)aza[60]fulleroid (2b,
5 mg, 0.02 mmol) in 20 mL 1,1,2,2-tetrachlorethane was ir-
C
2
2
2
(
1
radiated for 4 h. The solvent was evaporated under reduced press-
ure, and the residue was filtered through silica gel with toluene.
Chromatography with HPLC (Bucky Clutcher I) (toluene/cyclohex-
ane, 10:1) gave 8 mg (53%) of 3b (1st fraction) and 3 mg (20%) not
consumed 2b (2nd fraction).
2
Ϫ1
3
(
(
CH
2 2
Cl ): λmax (Ͼ 220 nm, ε) ϭ 242 (191000), 333 (36000), 366
Synthesis of N-(4Ј-Methylphenylsulfonyl)aziridino[2Ј,3Ј:1,2][60]ful-
lerene (3c): A solution of 1,6-[N-(4Ј-methylphenylsulfonyl)]aza[60]f-
ulleroid (2c, 75 mg, 0.08 mmol) in 60 mL 1,1,2,2-tetrachlorethane
was irradiated for 6 h. The solvent was evaporated under reduced
pressure, and the residue was filtered through silica gel with tolu-
ene. Chromatography with HPLC (Bucky Clutcher I) (toluene/
21000), 384 (35000), 485 (18000) nm. MS (MALDI-TOF, neg. ion-
Ϫ
mode, DCTB, 15 kV): m/z (%) ϭ 933 (100) [M] (calcd. 932.99),
8
Ϫ
3 2
40 (35) [M Ϫ CH NO S] .
Reaction of C70 with (4-Methylphenyl)sulfonyl Azide (1c): A solu-
tion of C70 (252 mg, 0.300 mmol) and (4-methylphenyl)sulfonyl az-
cyclohexane, 8:1) gave 31 mg (41%) of 3c (1st fraction) and 17 mg ide (1c, 1.2 g, 6.0 mmol) in 70 mL 1,2-dichlorobenzene was heated
(23%) not consumed 2c (2nd fraction).
at 160 °C for 3 h. The solvent was then evaporated under reduced
pressure. Chromatography on silica gel 40 (toluene/cyclohexane,
1
st Fraction, N-(4Ј-Methylphenylsulfonyl)aziridino[2Ј,3Ј:1,2][60]ful-
1:1) gave unconverted C70 and a mixture of several products. The
1
lerene: H NMR (500.13 MHz, CS
2
2 2
/CD Cl , 4:1): δ ϭ 8.24 (d,
solution of the product mixture was reduced to 10 mL and flash
chromatography on silica gel 40 (toluene/cyclohexane, 1:2) gave
3
3
J
H,H ϭ 8.5 Hz, 2 H, 4Ј-H, 8Ј-H), 7.59 (d, JH,H ϭ 8.5 Hz, 2 H, 5Ј-
13
H, 7Ј-H), 2.66 (s, 3 H, 10Ј-H) ppm. C NMR (125.76 MHz, CS
CD Cl , 4:1): δ ϭ 145.70, 145.48, 145.32, 145.23, 145.16, 144.69,
2 2
2
/
19 mg (6%) of 5c (3rd fraction) and 28 mg (9%) of 4c (4th fraction).
3
rd Fraction, 7,8-[N-(4Ј-Methylphenylsulfonyl)]aza[70]fulleroid: 1H
1
1
1
9
1
44.36, 144.17, 144.09, 143.49, 143.34, 143.29, 142.98, 142.37,
42.07, 141.51, 141.11 (16 C60 sp signals, C-3Ј), 136.07 (C-6Ј),
3
2
NMR (500.13 MHz, CS /CD Cl , 4:1): δ ϭ 8.33 (d, JH,H
ϭ
2
2
2
3
8
.2 Hz, 2 H, 4Ј-H, 8Ј-H), 7.62 (d, JH,H ϭ 8.2 Hz, 2 H, 5Ј-H, 7Ј-
H), 2.68 (s, 3 H, 9Ј-H) ppm. 13C NMR (125.76 MHz, CS
/CD Cl
4:1): δ ϭ 151.93, 150.59, 150.45, 150.27, 148.59, 148.53, 148.12,
30.34 (C-5Ј, C-7Ј), 128.77 (C-4Ј, C-8Ј), 80.01 (C-1,C-2), 22.19 (C-
2
,
Ј) ppm. FT-IR (KBr): ν˜ ϭ 2922 s (CH
166 s, 1085 m, 808 m, 674 m, 592 m, 526 m cm . UV/Vis
Cl ): λmax (Ͼ 220 nm, ε) ϭ 231 (71000), 251 (94000), 321
32000), 410 (2100), 422 (1500) nm. MS (MALDI-TOF, pos. ion-
), 1636 s, 1508 m, 1344 s,
2
2
3
Ϫ1
1
1
48.09, 147.98, 147.89, 147.56, 147.47, 147.35, 147.33, 147.31,
46.78, 146.26, 146.11, 145.41, 145.32, 145.21, 145.13, 144.86,
(CH
2
2
(
ϩ
144.13, 144.02, 143.83, 143.41, 142.68, 140.37, 136.31, 134.96,
mode, DCTB, 15 kV): m/z (%) ϭ 889 (100) [M] (calcd. 889.03).
2
134.28, 133.02, 132.55, 132.43, 131.90, 128.72, 123.83 (37 C70 sp
Synthesis of N-(4Ј-Methoxyphenylsulfonyl)aziridino[2Ј,3Ј:1,2][60]-
fullerene (3d): A solution of 1,6-[N-(4Ј-methoxyphenylsulfonyl)]-
aza[60]fulleroid (2d, 85 mg, 0.09 mmol) in 80 mL of 1,1,2,2-tetra-
chlorethane was irradiated for 6 h. The solvent was evaporated un- 220 nm, ε) ϭ 237 (183000), 333 (39000), 473 (20000) nm. MS
der reduced pressure. Chromatography on silica gel 40 (toluene/ (MALDI-TOF, pos. ion-mode, DCTB, 15 kV): m/z (%) ϭ 1010
signals, C-3Ј), 135.36 (C-6Ј), 130.37 (C-5Ј, C-7Ј), 129.83 (C-4Ј, C-
8Ј), 22.28 (C-9Ј) ppm. FT-IR (KBr): ν˜ ϭ 2918 s (CH ), 1654 s,
3
Ϫ1
2
2
max
1261 s, 1165 w, 1090 s, 802 s cm . UV/Vis (CH Cl ): λ (Ͼ
ϩ
cyclohexane, 1:2) gave 36 mg (42%) of 3d (1st fraction) and 16 mg
19%) not consumed 2d.
(100) [M] (calcd. 1009.02).
(
4
th Fraction, 2,3-(N-Methylsulfonyl)aza[70]fulleroid: 1H NMR
3
1
st Fraction, N-(4Ј-Methoxyphenylsulfonyl)aziridino[2Ј,3Ј:1,2][60]-
(500.13 MHz, CS
2
/CD
2
Cl
2
, 4:1): δ ϭ 7.81 (d, JH,H ϭ 8.1 Hz, 2 H,
1
3
fullerene: H NMR (500.13 MHz, CS
2
/CD
2
3
Cl
2
, 5:1): δ ϭ 8.29 (d, 4Ј-H, 8Ј-H), 7.36 (d, JH,H ϭ 8.1 Hz, 2 H, 5Ј-H, 7Ј-H), 2.55 (s, 3 H,
H,H ϭ 9.0 Hz, 2 H, 4Ј-H, 8Ј-H), 7.21 (d, JH,H ϭ 9.0 Hz, 2 H, 5Ј- /CD Cl , 4:1): δ ϭ 151.95,
9Ј-H) ppm. 13C NMR (125.76 MHz, CS
150.88, 150.64, 150.27, 149.83, 149.80, 149.79, 149.10, 148.83,
, 5:1): δ ϭ 164.47 (C-6Ј), 145.44, 145.27, 145.18, 145.11, 148.68, 147.87, 147.86, 147.75, 147.66, 147.36, 146.33, 145.63,
44.66, 144.30, 144.13, 144.05, 143.50, 143.30, 143.25, 142.95, 145.48, 145.47, 145.34, 145.25, 145.10, 145.04, 144.90, 144.70,
3
J
2
2
2
13
H, 7Ј-H), 4.02 (s, 3 H, 10Ј-H) ppm. C NMR (125.76 MHz, CS
CD Cl
1
1
2
/
2
2
2
42.33, 142.00, 141.49, 141.06, 130.98, 129.63 (16 C60 sp signals,
144.58, 144.53, 143.74, 139.97, 138.88, 138.83, 138.48, 138.22,
2
C-3Ј, C-4Ј, C-8Ј), 114.81 (C-5Ј, C-7Ј), 80.17 (C-1,C-2), 55.75 (C-
132.24, 131.34, 131.27, 126.05, 117.36 (37 C70 sp signals, C-3Ј),
1
0Ј) ppm. FT-IR (KBr): ν˜ ϭ 2928 s (CH
), 1738 m, 1594 m, 1344 135.13 (C-6Ј), 129.97 (C-5Ј, C-7Ј), 128.98 (C-4Ј, C-8Ј), 22.04 (C-9Ј)
3
2938
 2003 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjoc.org
Eur. J. Org. Chem. 2003, 2933Ϫ2940

Sulfonyl-Azafulleroid and Sulfonylaziridino-Fullerene Derivatives
FULL PAPER
[
[
5]
6]
ppm. FT-IR (KBr): ν˜ ϭ 2922 s (CH
281 s, 1163 s, 1085 m, 793 m, 671 m, 656 m, 573 s, 562 s, 524 m
), 1718 m, 1420 m, 1341 m,
T. Grösser, M. Prato, V. Lucchini, A. Hirsch, F. Wudl, Angew.
Chem. 1995, 107, 1462Ϫ1464; Angew. Chem. Int. Ed. Engl.
1995, 34, 1343.
3
1
Ϫ1
cm . UV/Vis (CH
2 2
Cl ): λmax (Ͼ 220 nm, ε) ϭ 240 (235000), 333
G. Schick, T. Grösser, A. Hirsch, Chem. Commun. 1995,
(
54000), 384 (49000), 486 (28000) nm. MS (MALDI-TOF, neg. ion-
2289Ϫ2290.
Ϫ
mode, DCTB, 15 kV): m/z (%) ϭ 1010 (100) [M] (calcd. 1009.02),
8
[
[
7]
8]
B. Nuber, A. Hirsch, Full. Sci. Techn. 1996, 4, 715Ϫ728.
Ϫ
7 7 2
54 (13) [M Ϫ C H O S] .
G. Schick, A. Hirsch, H. Mauser, T. Clark, Chem. Eur. J. 1996,
2, 935Ϫ943.
Reaction of C70 with (4-Methoxyphenyl)sulfonyl Azide (1d): A solu-
tion of C70 (252 mg, 0.300 mmol) and (4-methoxyphenyl)sulfonyl
azide (1d, 1.3 g, 6.1 mmol) in 70 mL 1,2-dichlorobenzene was
heated at 160 °C for 3 h. The solvent was then evaporated under
reduced pressure. Chromatography on silica gel 40 (toluene/cyclo-
hexane, 1:1) gave unconverted C70 and a mixture of several prod-
ucts. The solution of the product mixture was reduced to 20 mL
and flash chromatography on silica gel 40 (toluene/cyclohexane,
[
9]
J. Averdung, J. Mattay, Tetrahedron 1996, 52, 5407Ϫ5420.
J. Averdung, G. Torres-Garcia, H. Luftmann, I. Schlachter, J.
Mattay, Full. Sci. Techn. 1996, 4, 633Ϫ654.
Shen, K.-F. C. H. Yu, C.-G. Juo, K.-M. Chien, G.-R. Her, T.-
Y. Luh, Chem. Eur. J. 1997, 3, 744Ϫ748.
M. Casas, M. Duran, J. Mestres, N. Mart ´ı n, M. Sol a` , J. Org.
Chem. 2001, 66, 433Ϫ442.
F. Diederich, L. Isaacs, D. Philp, Chem. Soc. Rev. 1994, 23,
243Ϫ255.
[10]
[11]
[12]
[13]
1:2) gave 22 mg (7%) of 5d (1st fraction) and 31 mg (10%) of 4d
[14]
(2nd fraction).
T. Suzuki, Q. Li, K. C. Khemani, F. Wudl, Ö. Almarsson, J.
Am. Chem. Soc. 1992, 114, 7300Ϫ7301.
T. Suzuki, Q. Li, K. C. Khemani, F. Wudl, J. Am. Chem. Soc.
1
1
st Fraction, 7,8-[N-(4Ј-Methoxyphenylsulfonyl)]aza[70]fulleroid: H
[15]
[16]
3
2 2 2 H,H
NMR (500.13 MHz, CS /CD Cl , 5:1): δ ϭ 8.37 (d, J ϭ
1992, 114, 7301Ϫ7302.
3
9
.0 Hz, 2 H, 4Ј-H, 8Ј-H), 7.29 (d, JH,H ϭ 9.0 Hz, 2 H, 5Ј-H, 7Ј-
H), 4.04 (s, 3 H, 10Ј-H) ppm. 13C NMR (125.76 MHz, CS
/CD Cl
:1): δ ϭ 163.95 (C-6Ј), 151.58, 150.24, 149.93, 148.25, 148.19,
47.79, 147.74, 147.63, 147.56, 147.23, 147.09, 147.00, 146.98,
46.95, 146.46, 145.92, 145.76, 145.05, 144.98, 144.79, 144.52,
43.68, 143.65, 143.49, 143.08, 142.34, 140.03, 136.01, 134.58,
32.69, 132.20, 132.08, 131.73, 131.55, 128.84, 128.38, 128.09,
M. Prato, V. Lucchini, M. Maggini, E. Stimpfl, G. Scorrano,
M. Eiermann, T. Suzuki, F. Wudl, J. Am. Chem. Soc. 1993,
115, 8479Ϫ8480.
2
2
2
,
5
1
1
1
1
1
[
[
17]
18]
L. Isaacs, A. Wehrsig, F. Diederich, Helv. Chim. Acta 1993,
76, 1231Ϫ1250.
A. B. Smith, III, R. M. Strongin, L. Brard, G. T. Furst, W. J.
Romanow, K. G. Owens, R. J. Goldschmidt, R. C. King, J.
Am. Chem. Soc. 1995, 117, 5492Ϫ5502.
2
25.19, 123.64 (37 C70 sp signals, C-3Ј, C-4Ј, C-8Ј), 114.53 (C-5Ј,
[19]
R. A. Janssen, J. C. Hummelen, F. Wudl, J. Am. Chem. Soc.
C-7Ј), 55.43 (C-10Ј) ppm. FT-IR (KBr): ν˜ ϭ 2925 s (CH
), 1735 s,
3
1
995, 117, 544Ϫ545.
1
701 m, 1592 m, 1453 m, 1430 s, 1262 m, 1159 s, 1087 s, 672 m
[20]
[21]
G. Schick, A. Hirsch, Tetrahedron 1998, 54, 4283Ϫ4296.
P. Ceroni, F. Conti, C. Corvaja, M. Maggini, F. Paolucci, S.
Roffia, G. Scorrano, A. Toffoletti, J. Phys. Chem. A 2000,
104, 156Ϫ163.
Ϫ1
cm . UV/Vis (CH
2 2
Cl ): λmax (Ͼ 220 nm, ε) ϭ 240 (205000), 3343
(
41000), 387 (38000), 460 (21000) nm. MS (MALDI-TOF, neg. ion-
Ϫ
mode, DCTB, 15 kV): m/z (%) ϭ 1025 (100) [M] (calcd. 1025.02),
8
Ϫ
[22]
[23]
[24]
40 (30) [M Ϫ C
7
H
7
NO
3
S] .
M. H. Hall, H. Lu, P. B. Shevlin, J. Am. Chem. Soc. 2001,
123, 1349Ϫ1354.
2
nd Fraction, 2,3-[N-(4Ј-Methoxyphenylsulfonyl)]aza[70]fulleroid:
J. Averdung, J. Mattay, D. Jacobi, W. Abraham, Tetrahedron
995, 51, 2543Ϫ2552.
1
3
H NMR (500.13 MHz, CS
.0 Hz, 2 H, 4Ј-H, 8Ј-H), 7.02 (d, JH,H ϭ 9.0 Hz, 2 H, 5Ј-H, 7Ј-
H), 3.96 (s, 3 H, 10Ј-H) ppm. 13C NMR (125.76 MHz, CS
/CD Cl
:1): δ ϭ 163.73 (C-6Ј), 151.62, 150.54, 150.31, 149.95, 149.49,
2 2 2
/CD Cl , 5:1): δ ϭ 7.87 (d, JH,H ϭ
1
3
9
L. F. Tietze, F. Eicher, Reaktionen und Synthesen im org. chem.
Praktikum, 2nd ed., Georg Thieme Verlag, Stuttgart, New
York, 1991, S. 270Ϫ271.
2
2
2
,
5
1
1
1
1
1
[
[
25]
26]
49.47, 149.45, 148.78, 148.50, 148.34, 147.53, 147.42, 147.33,
47.03, 146.00, 145.30, 145.13, 145.02, 144.92, 144.78, 144.56,
44.38, 144.23, 144.18, 143.39, 139.51, 138.55, 138.43, 138.17,
37.85, 131.90, 131.00, 130.93, 130.92, 128.82, 128.06, 125.73,
A. Ouchi, R. Hatsuda, B. Z. S. Awen, M. Sakuragi, R. Ogura,
T. Ishii, Y. Araki, O. Ito, J. Am. Chem. Soc. 2002, 124,
1
3364Ϫ13365.
T. Akasaka, E. Mitsuhida, W. Ando, J. Am. Chem. Soc. 1994,
16, 2627Ϫ2628.
1
2
25.16, 117.24 (37 C70 sp signals, C-3Ј, C-4Ј, C-8Ј), 114.14 (C-5Ј,
[
[
27]
28]
S. R. Wilson, Q. Lu, J. Org. Chem. 1995, 60, 6496Ϫ6498.
A. Hermann, M. Rüttimann, C. Thilgen, F. Diederich, Helv.
Chim. Acta 1995, 78, 1673Ϫ1704.
A. B. Smith, III, R. M. Strongin, L. Brard, G. T. Furst, J. H.
Atkins, W. J. Romanow, J. Org. Chem. 1996, 61, 1904Ϫ1905.
H. Irngartinger, C.-M. Köhler, G. Baum, D. Fenske, Liebigs.
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C-7Ј), 55.37 (C-10Ј) ppm. FT-IR (KBr): ν˜ ϭ 2926 s (CH
), 1592
3
m, 1447 s, 1408 m, 1361 m, 1261 m, 1158 s, 1128 m, 1093 s, 1032
Ϫ1
m, 832 m, 673 s cm . UV/Vis (CH
42 (210000), 333 (42000), 367 (23000), 384 (41000), 486 (22000)
nm. MS (MALDI-TOF, neg. ion-mode, DCTB, 15 kV): m/z (%) ϭ
2
Cl
2
): λmax (Ͼ 220 nm, ε) ϭ
[29]
[30]
2
Ϫ
Ϫ
1
7 7 3
025 (100) [M] (calcd. 1025.02), 840 (45) [M Ϫ C H NO S] .
[
[
31]
32]
Acknowledgments
We gratefully acknowledge financial support by the Department of
Science and Research NRW (MSWF), the Fonds der Chemischen
Industrie (FCI) and the Innovationsfond der Universität Bielefeld.
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