Ferric perchlorate-mediated synthesis of 1,2-fullerenols C 60(OCOR)(OH)

Article abstract of DOI:10.1021/jo301202g

1,2-Fullerenols C₆₀(OCOR)(OH) have been facilely synthesized via the one-step reaction of [60]fullerene with acid chlorides promoted by ferric perchlorate. A possible reaction mechanism for the product formation is proposed.

Full text of DOI:10.1021/jo301202g

Note
pubs.acs.org/joc
Ferric Perchlorate-Mediated Synthesis of 1,2-Fullerenols C60(OCOR)
(OH)
Fa-Bao Li,†,‡ Xun You,† and Guan-Wu Wang*,†,§
†CAS Key Laboratory of Soft Matter Chemistry, Hefei National Laboratory for Physical Sciences at Microscale, and Department of
Chemistry, University of Science and Technology of China, Hefei, Anhui 230026, P. R. China
‡Ministry of Education Key Laboratory for the Synthesis and Application of Organic Functional Molecules and School of Chemistry
and Chemical Engineering, Hubei University, Wuhan 430062, P. R. China
§State Key Laboratory of Applied Organic Chemistry, Lanzhou University, Lanzhou, Gansu 730000, P. R. China
S
* Supporting Information
ABSTRACT: 1,2-Fullerenols C60(OCOR)(OH) have been
facilely synthesized via the one-step reaction of [60]fullerene
with acid chlorides promoted by ferric perchlorate. A possible
reaction mechanism for the product formation is proposed.
Radical reactions of fullerenes promoted by transition-metal
salts21 such as Mn(OAc)3,22 Cu(OAc)2,22d,23 Pb(OAc)4,22i,24
and TBADT[(n-Bu4N)4W10O32]25 have attracted extensive
attention. In efforts to extend the transition-metal-salt-mediated
radical reactions of fullerenes, our group recently investigated
the reactions of C60 promoted by cheap and easily available
Fe(ClO4)3. The Fe(ClO4)3-mediated reactions of C60 with
nitriles,26a aldehydes/ketones,26b malonate esters,26c arylbor-
onic acids,26d and β-keto esters26e afforded C60-fused oxazoles,
C60-fused 1,3-dioxolanes, C60-fused disubstituted lactones,
fullerenyl boronic esters, and C60-fused hemiketal and
dihydrofuran, respectively. In continuation of our interest in
Fe(ClO4)3-mediated reactions of C60, herein we describe the
Fe(ClO4)3-mediated one-step reaction of C60 with acid
chlorides to afford monohydroxylated fullerenols 1,2-
C60(OCOR)(OH).27
Initially, the reaction of C60 with 4-toluoyl chloride (1a) in
the presence of Fe(ClO4)3 by employing the direct dissolution
method26a,b was screened to obtain the optimized reaction
conditions. A mixture of Fe(ClO4)3·6H2O (0.15 mmol) and 1a
(2.5 mmol) was first heated in an oil bath preset at 60 °C for 20
min to allow ferric perchlorate to dissolve in the liquid acid
chloride. Then an o-dichlorobenzene (ODCB, 6 mL) solution
of C60 (36.0 mg, 0.05 mmol) was added. The resulting solution
was heated with vigorous stirring at the same temperature
under nitrogen atmosphere for 25 min. Much to our
satisfaction, the reaction was found to proceed well and gave
fullerenol 2a in 47% isolated yield (Table 1, entry 1). Other
reaction conditions were also examined, and the results are
summarized in Table 1. Reducing the reaction time drastically
reduced the yield of 2a (Table 1, entry 2). Increasing the
reaction temperature did not improve the yield of 2a (Table 1,
unctionalization of [60]fullerene (C60) leading to a large
Fnumber of fascinating fullerene derivatives with wide
structural diversity is the essential issue in fullerene chemistry.1
Fullerenols with hydroxy group(s) attached to the fullerene
cage were one of the first reported fullerene compounds and
exhibited biological activities.2 Mixtures of polyhydroxylated
fullerenols C60(OH)n were usually synthesized by utilizing
nitronium chemistry,3 aqueous acid reaction,4 or aqueous base
reaction.5 They could also be produced by the reaction with
8
oleum,6 nitrogen dioxide radical,7 or BH3 followed by
hydrolysis. Fullerenols with multiple addends were prepared
by the reaction of C70Cl10 with benzene/FeCl3,9 the reaction of
C60Cl6 with methyllithium followed by hydrolysis,10 the
reaction of C60 with methyllithium,11 or the transformation of
fullerene peroxides containing multiple OOtBu groups.12 The
simplest fullerene diols C60(OH)2 and C70(OH)2 could be
synthesized by the reaction of C60 and C70 with RuO4 followed
by acid hydrolysis.13 The synthesis of monohydroxylated
fullerenols with the general form of C60ROH is relatively
underdeveloped, and only a few such compounds have been
prepared by the reaction of C60 with (RFCO2)O,14 the N−O
bond cleavage of [60]fullereno[1,2d]isoxazole,15 the hydrolysis
of chlorofullerenes,16 nucleophilic substitution of C60O in the
presence of BF3·Et2O,17 the aminolysis of a C60-fused lactone,18
the reaction of C60 with water catalyzed with Cp2MCl2,19 or the
reaction of C60 with 4-substituted phenylhydrazine hydro-
chlorides in the presence of NaNO2.20 Among the reported
monohydroxylated fullerenols (C60ROH), only five of them
were formed in a 1,2-addition mode.15,17−19 In most cases, 1,2-
C60ROH were obtained by a two-step reaction15,17,18 starting
from C60. Therefore, it is still important to develop a simple and
efficient method to obtain the 1,2-addition fullerenols (1,2-
C60ROH) with different functional groups via a one-step
process from C60.
Received: June 13, 2012
Published: July 17, 2012
© 2012 American Chemical Society
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The Journal of Organic Chemistry
Note
Table 1. Reaction Conditions for the Fe(ClO4)3-Mediated
Reaction of C60 with 4-Toluoyl Chloride 1a
Table 2. Reaction Conditions and Yields for the Reaction of
a
a
C
60 with Acid Chlorides 1a−f in the Presence of Fe(ClO4)3
molar ratio
entry [C60/FEP/1a]
reaction
reaction
yield of
recovered
C60 (%)
b
c
temp (°C) time (min) 2a (%)
1
2
3
4
5
6
7
8
9
1:3:50
1:3:50
1:3:50
1:5:50
1:2:20
1:2:50
1:2:100
1:1:50
1:1:100
60
60
80
80
80
80
80
80
80
25
10
10
5
47
19
47
29
15
25
23
21
19
48
78
43
18
76
59
66
70
78
15
10
10
20
15
a
All reactions were performed under nitrogen atmosphere by the
b
direct dissolution of Fe(ClO4)3·6H2O in 1a. FEP = Fe(ClO4)3·6H2O.
c
Isolated yield.
entry 3). No improvement could be achieved by varying the
amount of 4-toluoyl chloride and Fe(ClO4)3 (Table 1, entries
4−9). Thus, the molar ratio of 1:3:50 for the reagents C60,
Fe(ClO4)3, and 1a together with the reaction temperature of 60
°C were chosen as the optimized reaction conditions.
With the optimized reaction conditions in hand, other
representative acid chlorides such as benzoyl chloride (1b), 4-
methoxybenzoyl chloride (1c), 4-chlorobenzoyl chloride (1d),
2-chlorobenzoyl chloride (1e), and cinnamoyl chloride (1f)
were employed as the substrates to obtain the desired 1,2-
fullerenols 2b, 2c, 2d, 2e, and 2f, respectively. The reaction
conditions and yields for the Fe(ClO4)3-mediated reaction of
C60 with acid chlorides 1a−f under nitrogen atmosphere are
listed in Table 2.
a
Unless otherwise indicated, all reactions were performed at 60 °C
under nitrogen atmosphere, molar ratio of C60/Fe(ClO4)3·6H2O/1 =
b
1:3:50. Isolated yield; that in parentheses was based on consumed
C60. Molar ratio of C60/Fe(ClO4)3·6H2O/1e = 1:1:50.
c
Scheme 1. Fe(ClO4)3-Mediated Reaction of C60 with Acid
Chloride 1f Affording Fullerenol 2f and C60-Fused Lactone 3
As can be seen from Table 2, aromatic acid chlorides 1a−e
with both electron-withdrawing and electron-donating groups
as well as cinnamoyl chloride 1f could be successfully utilized to
prepare 1,2-fullerenols 2a−f in 17−47% isolated yields (24−
90% based on consumed C60), comparable to the previously
reported data for most monoadducts. It should be noted that
for the Fe(ClO4)3-mediated reaction of C60 with cinnamoyl
chloride 1f, a C60-fused lactone 3 (Scheme 1) was also obtained
in 26% yield besides the expected 1,2-fullerenol 2f. Unfortu-
nately, the reaction of C60 with 4-nitrobenzoyl chloride bearing
the strong electron-withdrawing NO2 group afforded mainly
some unknown byproducts probably due to the higher
reactivity of 4-nitrobenzoyl chloride. It should be pointed out
that the use of 3 equiv of Fe(ClO4)3 for the reaction with 1e led
to a significant amount of byproducts with polarity similar to
C60, and thus, 1 equiv of Fe(ClO4)3 was required to improve
the yield and selectivity. The synthesized 1,2-fullerenols 2a−f
can be further manipulated through esterification, etherification
and arylation, as demonstrated previously by us for analogous
fullerenols.20
skeleton were located at 87.56−89.58 ppm and 83.10−85.08
ppm, close to those of other 1,2-adduct fullerene derivatives, in
which the oxygen atom is connected to the C60 skel-
eton.18,22h−j,26c No more than 29 peaks including some
overlapped ones for the 58 sp2-carbons of the C60 moiety
were observed in the range of 135−153 ppm, consistent with
the Cs symmetry of their molecular structures. As for lactone 3,
1
its H NMR spectrum displayed a singlet at 8.72 ppm for the
proton connecting to the carbon−carbon double bond moiety
besides those signals for the phenyl ring. In its 13C NMR
spectrum, there were 23 peaks including some overlapped ones
in the 135−152 ppm range for the 58 sp2-carbons of the C60
skeleton and two peaks at 96.63 and 64.90 ppm for the two sp3-
carbons of the C60 moiety, agreeing with its Cs symmetry. The
IR spectrum of lactone 3 showed an absorption at 1768 cm−1
due to the CO group. Its UV−vis spectrum exhibited a peak
at 416 nm. The peak at around 420 nm is a diagnostic
The structures of fullerenols 2a−f were fully characterized by
1
HR MS, H NMR, 13C NMR, FT-IR, and UV−vis spectra. All
1
of the H NMR spectra exhibited the expected chemical shifts
as well as the splitting patterns for all protons. In the 13C NMR
spectra of 2a−f, the peak for the CO carbon appeared at
164.19−169.43 ppm, and the two sp3-carbons of the C60
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The Journal of Organic Chemistry
Note
2.5 mmol) and ferric perchlorate hexahydrate (0.15 mmol, 0.05 mmol
in case of 1e) was added to a 50-mL round-bottom flask, which was
equipped with a reflux condenser, nitrogen inlet and outlet, and a
magnetic stirrer. The mixture was heated in an oil bath preset at 60 °C
for 20 min to allow ferric perchlorate to dissolve in the liquid acid
chloride. Then to the flask was added the o-dichlorobenzene (6 mL)
solution of C60 (36.0 mg, 0.05 mmol). The resulting solution was
heated with vigorous stirring in the oil bath at the same temperature
under nitrogen atmosphere. The reaction was carefully monitored by
thin-layer chromatography (TLC) and stopped at the designated time.
After acetic acid (1 mL) was added to the reaction solution, the
resulting mixture was directly separated on a silica gel column with
carbon disulfide/toluene as the eluent. Fullerenol 2a (2b−f) was
obtained along with unreacted C60.
absorption for the 1,2-adduct of C60, in which the oxygen atom
is directly attached to the fullerene skeleton.22h−j,26c
On the basis of the previously suggested mechanisms for the
reactions of C60 with nitriles,26a aldehydes/ketones,26b
malonate esters,26c arylboronic acids,26d and β-keto esters26e
in the presence of Fe(ClO4)3 as well as the reaction of C60 with
carboxylic acids promoted by Pb(OAc)4,22i we propose a
possible mechanism for the formation of fullerenols 2a−f and
C60-fused lactone 3 from the Fe(ClO4)3-mediated reaction of
C60 with acid chlorides (Scheme 2). A chosen acid chloride
Scheme 2. Proposed Reaction Mechanism for the Formation
of Fullerenols 2 and C60-Fused Lactone 3
Fullerenol 2a. According to the general procedure, the reaction of
C60 (36.0 mg, 0.05 mmol) with 1a (331 μL, 2.5 mmol) and
Fe(ClO4)3·6H2O (69.0 mg, 0.15 mmol) for 25 min afforded first
recovered C60 (17.1 mg, 48%) and then 2a (20.3 mg, 47%) as an
amorphous black solid: mp >300 °C; 1H NMR (300 MHz, CS2/
CDCl3) δ 8.37 (d, J = 8.1 Hz, 2H), 7.40 (d, J = 8.1 Hz, 2H), 5.21 (s,
1H), 2.53 (s, 3H); 13C NMR (75 MHz, CS2/CDCl3 with Cr(acac)3 as
relaxation reagent) (all 2C unless indicated) δ 169.43 (1C, CO),
151.15, 148.59 (1C), 148.48 (1C), 147.63, 146.49 (4C), 146.20,
146.12 (4C), 145.92, 145.46, 145.18 (4C), 145.09 (1C, aryl C),
144.87, 144.84, 144.64, 144.60, 142.59 (4C), 142.46, 142.31, 142.22,
141.54, 141.50, 141.37 (4C), 139.65, 139.14, 138.57, 136.42, 130.68
(aryl C), 129.45 (aryl C), 126.52 (1C, aryl C), 89.04 (1C, sp3-C of
C60), 85.08 (1C, sp3-C of C60), 21.93 (1C); FT-IR ν/cm−1 (KBr)
2921, 1702, 1611, 1432, 1274, 1179, 1091, 1035, 994, 922, 832, 748,
576, 526; UV−vis (CHCl3) λmax/nm (log ε) 256 (5.28), 318 (4.74),
416 (3.84), 685 (3.45); MALDI FT-ICR MS m/z calcd for C68H8O3
[M−] 872.0473, found 872.0472.
Fullerenol 2b. According to the general procedure, the reaction of
C60 (36.0 mg, 0.05 mmol) with 1b (290 μL, 2.5 mmol) and
Fe(ClO4)3·6H2O (69.0 mg, 0.15 mmol) for 10 min afforded first
recovered C60 (18.9 mg, 53%) and then 2b (18.2 mg, 42%) as an
amorphous black solid: mp >300 °C; 1H NMR (300 MHz, CS2/
DMSO-d6) δ 8.53 (s, 1H), 8.42 (d, J = 6.9 Hz, 2H), 7.67 (t, J = 7.1 Hz,
1
1H), 7.58 (t, J = 7.2 Hz, 2H); H NMR (300 MHz, CS2/CDCl3) δ
reacts with the hydrated H2O in Fe(ClO4)3·6H2O or
concomitant water in the system to produce Fe(III) complex
4 accompanied by the elimination of HClO4. Addition of
complex 4 to C60 generates fullerenyl radical 5 accompanied by
the formation of Fe(ClO4)2 and HCl. Nucleophilic addition of
H2O to fullerenyl radical 5 with the loss of H+ gives radical
anion 2•−,20,22i followed by oxidation with another molecule of
Fe(ClO4)3 to afford fullerenol 2. In the case of C60-fused
lactone 3, the first two steps are the same as those for fullerenol
2 to generate fullerene radical 5, which can undergo
intramolecular cyclization to give radical 6. Oxidation of radical
6 by a second molecule of Fe(ClO4)3 results in cation 7 along
8.48 (d, J = 7.2 Hz, 2H), 7.72 (t, J = 7.4 Hz, 1H), 7.61 (t, J = 7.5 Hz,
2H), 5.16 (s, 1H); 13C NMR (75 MHz, CS2/DMSO-d6 with Cr(acac)3
as relaxation reagent) (all 2C unless indicated) δ 164.91 (1C, CO),
152.40, 148.47, 147.51 (1C), 147.45 (1C), 145.46, 145.40, 145.08
(6C), 144.72 (4C), 144.51, 144.13 (4C), 144.05 (4C), 143.75, 141.71,
141.57, 141.42, 141.29 (4C), 140.71, 140.51 (4C), 140.38, 138.35,
137.99, 137.91, 135.37, 132.25 (1C, aryl C), 129.72 (1C, aryl C),
129.52 (aryl C), 127.71 (aryl C), 87.70 (1C, sp3-C of C60), 83.10 (1C,
sp3-C of C60); FT-IR ν/cm−1 (KBr) 2920, 1703, 1428, 1358, 1270,
1179, 1089, 1028, 993, 703, 526; UV−vis (CHCl3) λmax/nm (log ε)
256 (5.13), 318 (4.70), 417 (3.62), 685 (2.43); MALDI FT-ICR MS
m/z calcd for C67H6O3 [M−] 858.0317, found 858.0313.
Fullerenol 2c. According to the general procedure, the reaction of
C60 (36.0 mg, 0.05 mmol) with 1c (427 mg, 2.5 mmol) and
Fe(ClO4)3·6H2O (69.0 mg, 0.15 mmol) for 40 min afforded first
recovered C60 (15.9 mg, 44%) and then 2c (10.0 mg, 23%) as an
amorphous black solid: mp >300 °C; 1H NMR (300 MHz, CS2/
DMSO-d6) δ 8.44 (s, 1H), 8.36 (d, J = 8.7 Hz, 2H), 7.06 (d, J = 8.7
Hz, 2H), 3.93 (s, 3H); 13C NMR (75 MHz, CS2/DMSO-d6 with
Cr(acac)3 as relaxation reagent) (all 2C unless indicated) δ 164.80
(1C, CO), 162.22 (1C, aryl C), 152.63, 148.91, 147.66 (1C), 147.65
(1C), 145.60, 145.53, 145.23 (6C), 144.90, 144.85, 144.70, 144.27
(6C), 144.18, 143.92, 141.87, 141.72, 141.57, 141.44 (4C), 140.86,
140.65 (4C), 140.36, 138.49, 138.14, 138.00, 135.55, 131.67 (aryl C),
122.02 (1C, aryl C), 113.13 (aryl C), 87.56 (1C, sp3-C of C60), 83.28
(1C, sp3-C of C60), 54.59 (1C); FT-IR ν/cm−1 (KBr) 2925, 1704,
1605, 1510, 1460, 1328, 1263, 1167, 1099, 1035, 996, 840, 766, 526;
UV−vis (CHCl3) λmax/nm (log ε) 256 (5.04), 318 (4.60), 417 (3.66),
685 (3.31); MALDI FT-ICR MS m/z calcd for C68H8O4 [M−]
888.0423, found 888.0422.
with counteranion ClO4 and Fe(ClO4)2. Loss of H+ from
−
cation 7 leads to the formation of C60-fused lactone 3.
In summary, 1,2-fullerenols C60(OCOR)(OH) have been
effectively prepared via the reaction of C60 with acid chlorides
in the presence of Fe(ClO4)3, and they can be utilized as
precursors for further functionalization such as esterification,
etherification and arylation. The current protocol provides
facile access to 1,2-fullerenol derivatives via a one-step
procedure by using cheap and easily available acid chlorides
and Fe(ClO4)3. A possible reaction mechanism for the
formation of 1,2-fullerenols 2 and C60-fused lactone 3 has
been suggested.
EXPERIMENTAL SECTION
General Procedure for the Fe(ClO4)3-Mediated Reaction of
C60 with Acid Chlorides 1a−f. A mixture of acid chloride 1a (1b−f,
■
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Note
Fullerenol 2d. According to the general procedure, the reaction of
C60 (36.0 mg, 0.05 mmol) with 1d (318 μL, 2.5 mmol) and
Fe(ClO4)3·6H2O (69.0 mg, 0.15 mmol) for 20 min afforded first a
trace amount of recovered C60 and then 2d (10.6 mg, 24%) as an
amorphous black solid: mp >300 °C; 1H NMR (300 MHz, CS2/
DMSO-d6) δ 8.63 (s, 1H), 8.41 (d, J = 8.7 Hz, 2H), 7.59 (d, J = 8.7
Hz, 2H); 13C NMR (75 MHz, CS2/DMSO-d6 with Cr(acac)3 as
relaxation reagent) (all 2C unless indicated) δ 164.19 (1C, CO),
152.33, 148.26, 147.58 (1C), 147.51 (1C), 145.53, 145.46, 145.21,
145.15 (4C), 144.77 (4C), 144.53, 144.18 (4C), 144.06 (4C), 143.79,
141.77, 141.64, 141.49, 141.34 (4C), 140.75, 140.57 (4C), 140.40,
138.67 (1C, aryl C), 138.43, 138.05, 137.98, 135.40, 131.12 (aryl C),
128.32 (1C, aryl C), 128.03 (aryl C), 87.94 (1C, sp3-C of C60), 83.16
(1C, sp3-C of C60); FT-IR ν/cm−1 (KBr) 2923, 1708, 1594, 1428,
1401, 1270, 1091, 1041, 1016, 992, 847, 754, 527; UV−vis (CHCl3)
λmax/nm (log ε) 256 (5.12), 317 (4.65), 416 (3.85), 685 (3.42);
MALDI FT-ICR MS m/z calcd for C67H535ClO3 [M−] 891.9927,
found 891.9932.
Fullerenol 2e. According to the general procedure, the reaction of
C60 (36.0 mg, 0.05 mmol) with 1e (317 μL, 2.5 mmol) and
Fe(ClO4)3·6H2O (23.0 mg, 0.05 mmol) for 20 min afforded first
recovered C60 (23.1 mg, 64%) and then 2e (10.6 mg, 24%) as an
amorphous black solid: mp >300 °C; 1H NMR (300 MHz, CS2/
CDCl3) δ 8.42 (d, J = 8.1 Hz, 1H), 7.65−7.49 (m, 3H), 5.14 (s, 1H);
13C NMR (75 MHz, CS2/CDCl3 with Cr(acac)3 as relaxation reagent)
(all 2C unless indicated) δ 167.89 (1C, CO), 150.82, 148.66 (1C),
148.56 (1C), 147.23, 146.55 (4C), 146.29, 146.20 (4C), 146.00,
145.49, 145.25 (4C), 145.00, 144.90, 144.63 (4C), 142.65 (4C),
142.53, 142.35, 142.27, 141.59 (4C), 141.38 (4C), 139.72, 139.25,
138.63, 136.54, 134.98 (1C, aryl C), 133.64 (1C, aryl C), 132.66 (1C,
aryl C), 131.54 (1C, aryl C), 128.95 (1C, aryl C), 126.91 (1C, aryl C),
89.58 (1C, sp3-C of C60), 84.96 (1C, sp3-C of C60); FT-IR ν/cm−1
(KBr) 2922, 1701, 1590, 1467, 1431, 1357, 1291, 1244, 1102, 1041,
988, 743, 525; UV−vis (CHCl3) λmax/nm (log ε) 256 (5.04), 317
(4.60), 416 (3.75), 685 (3.36); MALDI FT-ICR MS m/z calcd for
C67H535ClO3 [M−] 891.9927, found 891.9921.
ASSOCIATED CONTENT
■
S
* Supporting Information
1H NMR and 13C NMR spectra of products 2a−f and 3. This
material is available free of charge via the Internet at http://
pubs.acs.org.
AUTHOR INFORMATION
Corresponding Author
*E-mail: gwang@ustc.edu.cn.
Notes
■
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
■
We are grateful for financial support from the National Natural
Science Foundation of China (Nos. 21132007, 20972145,
21102041), National Basic Research Program of China
(2011CB921402), and Scientific Research Foundation of
Education Commission of Hubei Province (Q20120113).
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Fullerenol 2f and C60-Fused Lactone 3. According to the
general procedure, the reaction of C60 (36.0 mg, 0.05 mmol) with 1f
(416 mg, 2.5 mmol) and Fe(ClO4)3·6H2O (69.0 mg, 0.15 mmol) for
20 min afforded first recovered C60 (18.8 mg, 52%), then 3 (11.2 mg,
26%) and 2f (7.4 mg, 17%). 2f: amorphous black solid; mp >300 °C;
1H NMR (300 MHz, CS2/CDCl3) δ 8.17 (d, J = 15.9 Hz, 1H), 7.69−
7.66 (m, 2H), 7.46−7.43 (m, 3H), 6.94 (d, J = 15.9 Hz, 1H), 5.18 (s,
1H); 13C NMR (75 MHz, CS2/CDCl3 with Cr(acac)3 as relaxation
reagent) (all 2C unless indicated) δ 169.49 (1C, CO), 151.04,
148.46 (1C), 148.37 (1C), 147.62 (1C, CH-Ph), 147.51, 146.36 (4C),
146.07, 146.00 (4C), 145.80, 145.34, 145.06 (4C), 144.97, 144.76,
144.51 (4C), 142.48 (4C), 142.35, 142.20, 142.11, 141.42, 141.38,
141.25 (4C), 139.54, 139.02, 138.37, 136.28, 133.90 (1C, aryl C),
130.87 (1C, aryl C), 128.93 (aryl C), 128.42 (aryl C), 116.81 (1C,
CH−CO), 88.74 (1C, sp3-C of C60), 84.97 (1C, sp3-C of C60); FT-IR
ν/cm−1 (KBr) 2920, 1696, 1632, 1447, 1432, 1329, 1311, 1269, 1202,
1169, 1147, 1101, 1035, 1013, 976, 918, 860, 755, 708, 598, 575, 526;
UV−vis (CHCl3) λmax/nm (log ε) 256 (4.94), 318 (4.68), 418 (3.50),
688 (2.34); MALDI FT-ICR MS m/z calcd for C69H8O3 [M−]
884.0473, found 884.0475. 3: amorphous black solid; mp >300 °C; 1H
NMR (300 MHz, CS2/CDCl3) δ 8.72 (s, 1H), 7.36−7.32 (m, 2H),
7.19−7.16 (m, 3H); 13C NMR (75 MHz, CS2/CDCl3 with Cr(acac)3
as relaxation reagent) (all 2C unless indicated) δ 168.72 (1C, CO),
151.17, 147.95 (1C), 147.42 (1C), 146.39, 146.26 (1C, CH-Ph),
145.99 (8C), 145.56, 145.48, 145.33, 145.18, 145.09, 145.03, 144.51,
144.33 (4C), 142.61 (6C), 142.14 (4C), 142.04, 141.83, 141.16,
140.98, 139.84, 138.28, 137.16, 135.17, 132.62 (1C, aryl C), 128.83
(1C, aryl C), 128.26 (aryl C), 128.15 (aryl C), 127.87 (1C, CH−CO),
96.63 (1C, sp3-C of C60), 64.90 (1C, sp3-C of C60); FT-IR ν/cm−1
(KBr) 2921, 1768, 1506, 1435, 1238, 1194, 1164, 998, 970, 967, 741,
694, 595, 575, 526; UV−vis (CHCl3) λmax/nm (log ε) 256 (4.97), 317
(4.62), 416 (3.50), 682 (2.28); MALDI FT-ICR MS m/z calcd for
C69H6O2 [M−] 866.0368, found 866.0365.
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