Addition reactions of fluoroalkanesulfonyl azides to [60] fullerene under thermal or microwave irradiation condition

Article abstract of DOI:10.1016/j.tet.2008.09.016

The reactions of [60] fullerene with excess fluoroalkanesulfonyl azides R_fSO₂N₃ in o-dichlorobenzene under thermal or microwave irradiation condition afforded monoadduct opened [5,6]-bridged azafulleroids. While, similarly treatment of 2,2,2-trifluoroethyl azides CF₃CH₂N₃ with C₆₀ gave two monoadducts, i.e., opened [5,6]-bridged azafulleroids, closed [6,6]-bridged Aziridino-fullerene, and some multi-addition product. A general mechanism for these addition reactions was proposed.

Full text of DOI:10.1016/j.tet.2008.09.016

Tetrahedron 64 (2008) 10694–10698
Contents lists available at ScienceDirect
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Addition reactions of fluoroalkanesulfonyl azides to [60] fullerene under
thermal or microwave irradiation condition
,
b
b,
*
Ran Wu a, Xiaoyong Lu a, Yun Zhang a, Jianmin Zhang a , Wanting Xiong , Shizheng Zhu
*
a Department of Chemistry, School of Science, Shanghai University, No. 99, Shangda Road, Shanghai 200444, China
b Key Laboratory of Organofluorine Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Science, Shanghai 200032, China
a r t i c l e i n f o
a b s t r a c t
Article history:
Received 1 July 2008
Received in revised form 1 September 2008
Accepted 2 September 2008
Available online 17 September 2008
The reactions of [60] fullerene with excess fluoroalkanesulfonyl azides RfSO2N3 in o-dichlorobenzene
under thermal or microwave irradiation condition afforded monoadduct opened [5,6]-bridged aza-
fulleroids. While, similarly treatment of 2,2,2-trifluoroethyl azides CF3CH2N3 with C60 gave two mono-
adducts, i.e., opened [5,6]-bridged azafulleroids, closed [6,6]-bridged Aziridino-fullerene, and some
multi-addition product. A general mechanism for these addition reactions was proposed.
Ó 2008 Elsevier Ltd. All rights reserved.
Keywords:
[60] Fullerene
Fluoroalkylsulfonyl azides
Azafulleriod
aziridino-fullerene
Microwave irradiation
1. Introduction
Fullerene C60 was considered as electron-deficient compound,16
its reaction with 1 should be under more violent condition. As part
The reactions of organic azides with [60] fullerene have paved
the way for the synthesis of adducts with a variety of structure.1–6
The first example of reaction was reported by Wudl et al.1 Till now, it
is well established that this reaction involved a [2þ3] cycloaddition
of azide to a double bond of the fullerene with formation of in-
termediate triazoline, followed by thermal cleavage of N2 affording
the opened [5,6]-bridged azafulleroid or closed [6,6]-bridged azir-
idino-fullerene depending on the nature of the substituent of the
azide. Alternatively, nitrenes generated in situ by thermolysis or
photolysis of azides add to fullerene in [1þ2] cycloaddition yielding
closed [6,6]-aziridino-fullerene derivatives.7–9 Recently, Mattay
and Ulmer10 reported the preparation of sulfonylazafulleroid and
aziridino-fullerene derivatives by thermal reactions of excess
sulfonyl azides RSO2N3 (R: CH3, C6H5CH2, p-CH3C6H4, p-MeOC6H5)
of our continuing interest in the chemical transformation of fluo-
roalkanesulfonyl azides, we now report our preliminary in-
vestigation of the first reaction of C60 with fluorinated azides and
discuss the possible reaction mechanism.
2. Results and discussion
Thermal reaction of C60 (0.11 g, 0.14 mmol) with an equal molar
azide ICF2CF2OCF2CF2SO2N3 1a was first carried out in
Table 1
Reaction of 1a with C60 under different conditions
Entry
Reaction conditions
Yield d of
2a (%)
with C60
.
Mol.
Solvent
Temp
(ꢀC)
Time
(h)
ratioa
To the best of our knowledge no addition reaction of fluo-
roalkanesulfonyl azides RfSO2N3 1 with C60 are known. During our
study on the fluoronated sulfonyl azides 1, we found that they are
readily reacted with many aromatic compounds and electron rich
olefins such as silylenol ether, acyclic or cyclic vinylether, enamines,
etc.11–15
1
2
3
4
5
6
1
4
11
4
11
12
CBb
CB
130
130
130
160
160
160
2
de
5e
2.5
2.5
1.5
2
CB
16e
15
o-DCBc
o-DCB
o-DCB
26
30
2
a
Ratio of 1a/C60
CB: chlorobenzene.
o-DCB: o-dichlorobenzene.
Isolated yield based on the reacted C60, all reactions gave RfSO2NH2 3.
Small amount of 4.
.
b
c
d
e
* Corresponding authors.
E-mail address: zhusz@mail.sioc.ac.cn (S. Zhu).
0040-4020/$ – see front matter Ó 2008 Elsevier Ltd. All rights reserved.
doi:10.1016/j.tet.2008.09.016

R. Wu et al. / Tetrahedron 64 (2008) 10694–10698
10695
Figure 1. 13C NMR of 2a, 5a, and 5b.

10696
R. Wu et al. / Tetrahedron 64 (2008) 10694–10698
chlorobenzene (30 mL) after stirring the reaction mixture for 2 h at
130 ꢀC, the reaction was finished, chromatography on silica gel gave
unconverted C60 first, more polar products obtained by using
AcOEt/petroleum ether as elute were the corresponding fluoro-
alkane-sulfonylamine ICF2CF2OCF2CF2SO2NH2 3a and small
amount of ICF2CF2OCF2CF2SO2NH–C6H4Cl 4, which was identified
with author’s sample,15 no corresponding C60 addition product was
isolated and detected.
When the molar ratio of 1a to C60 was increased from 1:1 to 4:1
and then to 11:1, the addition product 2a was obtained and the
yield was 5% and 16%, respectively (see Table 1, entries 1–3). The
main product remained was the sulfonylamine 3a. In order to
increase the reaction temperature, o-dichlorobenzene (o-DCB) was
used as solvent. Under higher temperature (160 ꢀC) and excess
azide (up to 12 equal molar ratio), the yield of 2a was increased up
to 30% (Table 1 entry 6), it was noticed that there is no corre-
sponding N-fluoroalkanesulfonyl dichloroaniline RfSO2NHC6H3Cl2
formed.
Figure 2. UV–vis spectrum of 2a, 5a, and 5b.
The structure of 2a was identified by spectroscopic methods. The
13C NMR of 2a shows 32 signals at 125.90–149.08 ppm (Fig. 1, 13
C
NMR of 2a). In this spectrum, 28 signals have a relative intensity of 2
and the remaining 4 signals have the intensity of 1, the total in-
tegrated area for the aromatic region sums up to 60 carbon atoms.1
Because all the fullerene carbons are in the sp2 region the product
2a is the opened [5,6]-bridged azafulleroid with the Cs-symmetry
rather than the closed aziridine structure. The remaining very weak
signals are all t–t patterns and attributed to the fluorocarbon atoms
CF2. Further evidence is obtained from the UV–vis spectrum, which
is similar to pure C60, the characteristic absorption for [6,6]-closed
fullerene derivatives at 420 nm is not observed.17–19
and 5c0 as well, it was also noted that in this reaction no corre-
sponding CF3CH2NH2 was formed. The 13C NMR spectrum of 5a and
5b shows the big difference (Fig. 1, 13C NMR of 5a and 5b). The
spectrum of 5a is similar to the azafulleroid 2a exhibiting 32 signals
at 133.66–147.52 ppm for the sp2 carbons of the C60 skeleton, and
two sp3 carbon atoms at 125.06 and 54.10 ppm for CF3 and CH2.
While the spectrum of 5b exhibits only 16 peaks at 140.9–
145.2 ppm for the sp2 carbons and one peak at 82.3 ppm for the sp3
hybridized carbons of C60 skeleton, other two peaks at 125.06 and
51.35 ppm are attributed to the two sp3 carbon atoms CF3 and CH2.
This indicates for compound 5b C2v-symmetry with a [6,6] junction
on the fullerene core. The UV–vis spectrum of 5b exhibits the
typical absorption for [6,6]-bridged dihydrofullerenes including the
band at around 422 nm (Fig. 2).9,10
The 19F NMR spectrum of 2a is very similar to the starting azide
1a with a small downfield shift due to the electron-deficient in-
fluence of the carbon sphere.1 TOF mass of the monoadduct 2a
shows a weak molecular ion peak Mꢁ at m/z¼1140.8.
Under the optimum reaction conditions (Table 1, entry 6) other
fluoroalkanesulfonyl azides 1b and 1c added to C60 giving the
monoadducts [5,6]-opened ring azafulleroid 2b and 2c in 25% and
18% yield, respectively (see Table 2).
When the reaction was carried out under microwave irradiation,
however, only two monoadducts 5a (38%) and 5b (19%) were
obtained, no multi-addition product was isolated.
When the reaction of 1 with C60 in o-DCB was conducted under
microwave irradiation (700 W), the same product azafulleroids 2
and fluoroalkanesulfonyl amine 3 were isolated. The yields of 2a,
2b, and 2c were 32%, 16%, and 21%, nearly the same as the thermal
reactions, but the reaction time was shortened from 2 h to 20 min.
In contrast to the fluoroalkanesulfonyl azides 1(a–c), fourfold
excess of 2,2,2-trifluoroethyl azide CF3CH2N3 1d added to C60
affording not only two monoadducts, N-trifluoroethyl azafulleroid
5a and aziridino-fullerene 5b, but the multi-addition products 5c
All the above reaction results clearly show the difference be-
tween the fluorinated sulfonyl azides RfSO2N3 1(a–c) with their
hydrocarbon analogy RSO2N3, while the fluoroalkylazide CF3CH2N3
1d20 behaves similar to alkyl or arylazide RN3. Fluoroalkylazide 1d
added to C60 by two pathways. One is the nitrene intermediate
added to C60 in [1þ2] cycloaddition yielding aziridine fullerene 5b.
The another way is the 1d added to C60 by [3þ2] cycloaddition to
form a triazoline [A], which underwent homogeneous cleavage of
the N–N single bond giving a biradical intermediate [B], two pos-
sible routes (paths a and b) will lead to 5a and 5b as investigated by
Luh et al. (see Scheme 1).21
Table 2
In the case of fluoroalkanesulfonyl azides 1(a–c) due to the
strong electron withdrawing property of RfSO2 group, the nitrene
intermediate RfSO2N did not add to the electron-deficient carbon–
carbon double bond of C60, it transformed to the corresponding
amine RfSO2NH2 or RfSO2NHC6H4Cl (when the reaction was carried
out in C6H5Cl) (see Scheme 2). On the other hand the [3þ2] cy-
cloaddition product N-fluoroalkane-sulfonyl triazoline [A0] should
undergo N–N bond heterogeneous cleavage to give zwitterion in-
termediate [B0], which is difficult to release N2 to form a tertiary
carbon cation by an SN1 process, because both stereo and electron
effects are unfavorable, so that it did not give aziridino-fullerene
2a0. Also the intermediate [B0] could not form 2a0 by an SN2 process,
which needed a back attacking on the C1 by the nitrogen anion RNꢁ.
The only possible pathway is the attacking of the nitrogen anion
occurred on the C5 or C6 (equivalent in the monoadduct 2) fol-
lowing the departure of N2 leading to the adduct [C], which then
rearomatized to more stable product azafulleroid 2.
Reaction results of azides 2 with C60 under thermal or microwave irradiation
Entry
Reactant
Ratioa
Methodb
Time
Products
Yieldc (%)
1
2
3
4
5
6
7
1a
1a
1b
1b
1c
1c
1d
12
11
12
11
12
11
4
A
B
A
B
A
B
A
2 h
20 min
2 h
20 min
2 h
20 min
3 h
2a
2a
2b
2b
2c
2c
5a
5b
5c
5c0
5a
5b
30
32
25
16
18
21
48
16
5
12
38
19
8
1d
4
B
20 min
a
The molar ratio of azides to C60
Method A: heating in o-DCB at 160 ꢀC for 1(a–c) or 120 ꢀC for 1d; method B:
.
b
irradiated under microwave (700 W).
c
Isolated yield based on the reacted C60
.

R. Wu et al. / Tetrahedron 64 (2008) 10694–10698
10697
SO2Rf
N
N2 ,o-DCB
RfSO2N3
+
RfSO2NH2
160 °C or MWI
[5,6] - open ring
2(a-c)
1(a-c)
3
a
b
c
Rf = ICF2CF2OCF2CF2
HCF2CF2OCF2CF2
C4F9
CH2CF3
CH2CF3
N
N
CH2CF3
N
CH2CF3
N
2
N2 ,o-DCB
CF3CH3N3
120 °C or MWI
[5,6] - open ring
[6,6] - close ring
5b
5c'
1d
5a
5c
Scheme 1.
Y: CF3CH2
the alkyl or aryl azides, it reacted with C60 affording two mono-
adducts [5,6]-azafulleroid and [6,6]-aziridino-fullerene, and multi-
addition products in good yield. The present reactions afford
a convenient method to synthesize a variety of stable fluorinated
fullerene derivatives.
5b
C60
, or MW
-N2
YN3
YN
Y: RfSO2
or
YNHC6H4Cl
YNH2
(reaction carried out in C6H5Cl)
N
N2
N
N
4. Experimental
homogeneous cleavage
R
path a
-N2
R
R
N
N
4.1. General remarks
[A]
path b
-N2
[B]
R:CF3CH2
C60 was purchased from Wuhan University and in 99% purity. All
reactions were performed under nitrogen atmosphere, o-di-
chlorobenzene, chlorobenzene–carbon disulfide, toluene, and ethyl
acetate were used in AR quality. Fluoroalkanesulfonyl azides 1(a–c)22
and trifluoroethyl azide 1d20 were prepared according to the lit-
erature procedure. 1H, 13C, and 19F NMR spectra were recorded
on Bruker AM-300 or AM-400 instrument with Me4Si and CFCl3
as the internal standards, respectively. FTIR spectra were
R
N
R
N
N
R
5a
5b
[C]
+
-
N
R
obtained with
a Nicolet AV-360 spectrophotometer. UV–vis
SN1
spectra were performed with a UV-2501PC spectrophotometer.
ES-MS spectra were performed on a Q-Tof micro-instrument
and MALDI-MS spectra were performed on a Voyager-DE STR
instrument.
N
N
N
+
x
N2
heterogeneous
N-N cleavage
-
R
R
N
5
6
N R
SN2
x
2a'
A'
B'
4.2. Reaction of azide 1a with C60 in o-DCB
attack on C1
R: RfSO2
attack on C5
A solution of C60 (0.11 g, 0.14 mmol) and 1a (1.9 g, 1.68 mmol) in
30 mL of o-DCB was heated at 160 ꢀC for 2 h and the solvent was
then evaporated under reduced pressure. Chromatography on silica
gel (cyclohexane/toluene/dioxane¼6:1:0.2) gave unconverted C60
(21 mg) and 2a (38 mg 30%); more polar product ICF2CF2OCF2CF2-
SO2NH2 3a (0.9 g) was obtained by using petroleum ether/ethyl
acetate (10:1) as eluent. After isolation, product 2a was further
purified by dissolving in CS2, precipitating with n-pentane, centri-
fugation, and decanting to remove the pentane soluble
components. It was finally dried under vacuum.
R
R
N
N
5
5
6
6
C
Scheme 2. Possible mechanism for the reaction of 1 with C60 (only relevant section of
the fullerene is shown).
3. Conclusion
4.3. N-(5-Iodo-3-oxa-octafluoropentyl)sulfonyl
The reactions of fluoroalkanesulfonyl azides RfSO2N3 1(a–c)
with [60] fullerene were first investigated. In contrast to their hy-
drocarbon analogues CH3SO2N3 and C6H5CH2SO2N3, RfSO2N3 added
to C60 to give only [5,6]-azafulleroids with an open cluster struc-
ture. While their trifluoroethyl azide CF3CH2N3 behaves similar to
aza[60]fulleroid 2a
FTIR (KBr): 1631, 1410, 1332, 1293, 1138, 1030, 909, 804, 708, 617,
526 cmꢁ1
;
19F NMR (471 MHz, CS2/CDCl3¼4:1):
d
¼ꢁ64.78 (t, 2F,
3JF,F¼6.5 Hz, ICF2), ꢁ80.95 (t, 2F, JF,F¼13.5 Hz, OCF2), ꢁ85.15 to
3

10698
R. Wu et al. / Tetrahedron 64 (2008) 10694–10698
85.23 (m, 2F, CF2O), ꢁ113.60 (s, 2F, SCF2); 13C NMR (126 MHz, CS2/
4.8. Bisiminofullerene 5c
CDCl3¼4:1) ¼149.08, 147.23, 145.32, 145.01, 144.58, 144.54, 144.47,
d
144.45, 144.40, 144.35,144.27,144.02, 143.97, 143.83, 143.65, 143.49,
143.16, 143.06, 142.88, 142.01, 141.90, 140.56, 140.07, 139.76, 139.29,
138.89, 137.80, 135.91, 134.70, 134.65, 129.17, 125.90 (32C60 sp2
FTIR (KBr): 2922, 2851, 1632, 1555, 1425, 1401, 1310, 1267, 1155,
1054, 1028, 963, 849, 659, 629, 523 cmꢁ1; 1H NMR (500 MHz, CS2/
3
CDCl3¼4:1):
d
¼4.26 (q, 4H, JHF¼8.3 Hz, CH2); 13C NMR (126 MHz,
signals); UV–vis (CH2Cl2), lmax (>225 nm,
3): 492 (150), 325
CS2/CDCl3¼5:1):
d
¼147.32, 146.47, 145.20, 145.06, 144.96, 144.81,
(121,910), 257 (361,390), 227 (283,570); ES-MS: m/z observed
144.77, 144.51, 144.03, 143.38, 142.80, 142.77, 142.68, 143.66, 142.10,
141.49, 140.90, 140.67, 140.33, 140.07, 139.16, 138.65, 137.07, 136.66,
135.60,131.90,131.10,130.78 (28C60 sp2 signals), 81.69 (C60 sp3 sig-
1140.8 [M]ꢁ (calcd 1140.85).
4.4. N-(3-Oxa-1,1,2,2,4,4,5,5-octafluoropentyl)-sulfonyl
aza[60]fulleroid 2b
nals), 64.69 (CH2); 19F NMR (471 MHz, CS2/CDCl3¼4:1):
d
¼ꢁ70.07
3
(t, JHF¼8.0 Hz, CF3); UV–vis (CH2Cl2), lmax (>220 nm,
3): 772 (43),
536 (375), 330 (7315), 262 (21,666), 228 (20,253); MALDI-MS: m/z
observed 915.3 [MþH]ꢁ (calcd 914.03).
FTIR (KBr): 2921, 2852, 2638, 1540, 1410, 1326, 1283, 1177, 1139,
978, 621, 526 cmꢁ1
;
1H NMR (500 MHz, CS2/CDCl3¼4:1):
¼5.90 (t,
d
2
1H, JH,F¼52 Hz, HCF2); 19F NMR (471 MHz, CS2/CDCl3¼4:1):
4.9. Trisiminofullerene 5c0
d
¼ꢁ80.65 (t, 2F, 3JF,F¼12.2 Hz, OCF2), ꢁ88.08 to ꢁ88.14 (m, 2F, CF2O),
3
2
ꢁ113.68 (s, 2F, SCF2), ꢁ137.01 (dt, 2F, JF,F¼4.7 Hz, JH,F¼52 Hz,
FTIR (KBr): 2963, 2923, 2853, 1723, 1634, 1461, 1380, 1262, 1097,
HCF2); 13C NMR (126 MHz, CS2/CDCl3¼4:1):
d¼149.03, 147.19,
1022, 801, 701, 516 cmꢁ1
d
;
1H NMR (500 MHz, CS2/CDCl3¼4:1):
¼4.26 (q, 4H, 3JHF¼8.3 Hz, CH2), 4.36 (q, 2H, 3JHF¼8.5 Hz, CH2); 13
C
145.27, 144.97, 144.53, 144.49, 144.43, 144.40, 144.35, 144.30,
144.22, 143.98, 143.93, 143.78, 143.60, 143.45, 143.12, 143.02,
142.84, 141.97, 141.85, 140.52, 140.02, 139.71, 139.25, 139.34,
138.85, 138.39, 138.37, 137.75, 135.87, 134.60 (32C60 sp2 signals);
NMR(126 MHz, CS2/C6D6¼1:2):
d
¼148.58, 148.31, 146.66, 146.08,
145.58, 145.52, 145.16, 145.05, 144.93, 144.87, 144.61, 144.58, 144.53,
144.42, 144.28, 144.11, 143.42, 142.77, 142.45, 142.41, 141.98, 141.23,
140.54, 139.04, 137.86, 136.39,135.72, 135.46, 133.86 (30C60 sp2
signals), 82.83 (C60 sp3 signals), 65.99 (CH2); 19F NMR (471 MHz,
UV–vis (CH2Cl2), lmax (>220 nm, 3): 529 (230), 325 (114,680),
258 (350,590), 228 (254,950); ES-MS: m/z observed 1014.9 [M]ꢁ
3
3
(calcd 1014.95).
CS2/CDCl3¼4:1):
d
¼ꢁ69.60 (t, JHF¼9.4 Hz, CF3), ꢁ70.58 (t, JHF
¼
8 Hz, CF3); UV–vis (CH2Cl2), lmax (>220 nm,
3
): 536 (437), 484 (498),
4.5. N-Perfluorobutanesulfonyl aza[60]fulleroid 2c
322 (11,643), 257 (34,952), 227(34,071). ES-MS: m/z observed 1012
[MþH]ꢁ (calcd 1011.05).
FTIR (KBr): 2963, 2921, 1632, 1411, 1345, 1260, 1137, 1100, 1027,
802, 615, 526 cmꢁ1
;
19F NMR (471 MHz, CS2/CDCl3¼4:1):
¼ꢁ80.46
d
4.10. Reaction of 1a with C60 under microwave irradiation
condition
(t, 3F, 3JF,F¼9.0 Hz, CF3), ꢁ109.90 (m, 2F, CF2S), ꢁ120.43 (m, 2F, CF2),
ꢁ125.62 (m, 2F, CF2); 13C NMR (126 MHz, CS2/CDCl3¼4:1):
d
¼148.96, 147.13, 145.21, 144.92, 144.47, 144.45, 144.43, 144.36,
A solution of C60 (0.11 g, 0.14 mmol), 1a (1.76 g, 1.54 mmol), and
o-DCB (20 mL in a 50 mL three necked flask) was irradiated under
microwave (700 W) for 20 min under N2 atmosphere. As the ther-
mal reaction similar work-up gave 2a (41 mg 32%) and 3a (0.9 g),
and 18 mg of unreacted C60 was recovered.
144.34, 144.30, 144.23, 144.15, 143.92, 143.87, 143.54, 143.40, 143.13,
143.07, 142.97, 142.78, 141.92, 141.79, 140.46, 139.98, 139.68, 139.15,
138.80, 137.65, 135.81, 130.81, 129.71, 128.86 (32C60 sp2 signals);
UV–vis (CH2Cl2), lmax (>220 nm, 3): 501 (920), 492 (980), 326
(76,490), 258 (231,500), 228 (164,850), 224 (114,090); ES-MS: m/z
observed 1016.9 [M]ꢁ (calcd 1016.95).
Acknowledgements
4.6. N-1,1,1-Trifluoroethyl aza[60]fulleroid 5a
This work was supported by the National Natural Science
Foundation of China (NNSFC) (Nos. 20772078 and 20532040).
FTIR(KBr):2919,1633,1506,1427,1309,1265,1177,1154, 962, 729,
575, 525 cmꢁ1; 1H NMR (500 MHz, CS2/CDCl3¼4:1):
d
¼4.32 (q, 2H,
References and notes
3JHF¼8.5 Hz, CH2); 13C NMR (126 MHz, CS2/CDCl3¼5:1):
d
¼147.52,
144.86, 144.70, 144.61, 144.45, 144.32, 144.25, 144.16, 143.89, 143.78,
143.69, 143.57, 143.50, 143.43, 143.25, 143.13, 143.02, 142.93, 142.77,
142.58, 141.45, 140.91, 140.03, 139.51, 138.57, 138.52, 137.98, 137.94,
136.32,136.24,135.66,133.66 (32C60 sp2 signals),125.06 (CF3), 54.10
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2
(q, JCF¼33.2 Hz, CH2); 19F NMR (471 MHz, CS2/CDCl3¼4:1):
d
¼ꢁ70.63 (t, 3JHF¼8.5 Hz, CF3); UV–vis (CH2Cl2), lmax (>220 nm,
3):
784 (170), 537 (1960), 405 (7530), 329 (89,360), 258 (303,140), 222
7. Averdung, J.; Mattay, J. Tetrahedron 1996, 52, 5407–5420.
8. Averdung, J.; Jorres-Garica, G.; Laftmann, H.; Schlachter, J.; Mattay, J. Fullerene
Sci. Technol. 1996, 4, 633–654.
(212,840); MALDI-MS: m/z observed 817 [M]ꢁ (calcd 817.01).
9. Averdung, J.; Mattay, J.; Jacovi, D.; Abraham, W. Tetrahedron 1995, 51, 2543–2552.
10. Ulmer, L.; Mattay, J. Eur. J. Org. Chem. 2003, 2933–2940.
11. He, P.; Zhu, S. Z. J. Fluorine Chem. 2004, 125, 1529–1536.
12. He, P.; Zhu, S. Z. Mini-Rev. Org. Chem. 2004, 1, 417–435.
13. Zhu, S. Z.; He, P. Tetrahedron 2005, 61, 5679–5685.
14. He, P.; Zhu, S. Z. J. Fluorine Chem. 2005, 126, 825–830.
15. He, P.; Zhu, S. Z. Tetrahedron 2006, 62, 549–555.
16. Reed, C. A.; Bolskar, R. D. Chem. Rev. 2000, 100, 1075–1120.
17. Pato, M.; Wudl, Q. F.; Lucchini, V.; Maggini, M.; Stimpfe, E.; Scorrane, G.; Suznki,
J. J. Am. Chem. Soc. 1993, 115, 8479–8480.
18. Suzuki, T.; Li, Q.; Khemani, K. C.; Wudl, F. J. Am. Chem. Soc. 1992, 114, 7301–7302.
19. Isaacs, L.; Wehrsig, A.; Diederich, F. Helv. Chim. Acta 1993, 76, 1231–1250.
20. Wu, Y. M.; Deng, J.; Li, Y.; Chen, Q. Y. Synthesis 2005, 8, 1314–1318.
21. Shen, C. K. F.; Yu, H. H.; Juo, C. G.; Chien, K. M.; Her, G. R.; Luh, T. Y. Chem.dEur J.
1997, 3, 744–748.
4.7. N-(1,1,1-Trifluoroethyl)aziridino[60]fullerene 5b
FTIR (KBr): 2964, 1713, 1632, 1498, 1387, 1261, 1149, 1096, 1023,
802, 572, 523 cmꢁ1; 1H NMR (500 MHz, CS2/CDCl3¼4:1):
d
¼4.32 (q,
3
2H, JHF¼8.0 Hz, CH2); 13C NMR (126 MHz, CS2/CDCl3¼5:1):
d
¼145.16, 145.09, 144.79, 144.61, 144.44, 144.17, 144.08, 143.81,
143.68, 143.60, 143.49, 142.99, 142.73, 142.01, 141.98, 140.87 (16C60
sp2 signals), 82.31 (C60 sp3 signals), 51.35 (q, 2JCF¼32.8 Hz, CH2); 19
F
NMR (471 MHz, CS2/CDCl3¼4:1):
d
¼ꢁ69.64 (t, 3F, 3JHF¼8.9 Hz, CF3);
UV–vis (CH2Cl2), lmax (>220 nm, 3): 786 (100), 536 (690), 485
(620), 422 (1220), 404 (2620), 328 (41,640), 257 (153,110), 225
(95,900); MALDI-MS: m/z observed 817 [M]ꢁ (calcd 817.01).
22. Zhu, S. Z. J. Chem. Soc., Perkin Trans. 1 1994, 2077–2081.