Solvent-free reactions of fullerenes with diethyl bromomalonate in the presence of inorganic bases under high-speed vibration milling conditions

Article abstract of DOI:10.1081/SCC-120030320

Solvent-free reactions of C₆₀ and C₇₀ with diethyl bromomalonate in the presence of various inorganic bases were investigated under the high-speed vibration milling (HSVM) conditions, and are shown to give methanofullerenes 1 and 2 in good to excellent yields based on consumed fullerenes. Several weak inorganic bases were found to be quite effective in promoting the solvent-free mechanochemical Bingel reactions of C₆₀ and C₇₀ under the HSVM conditions. Among the studied bases, sodium acetate gave the highest yield of monoadducts, while potassium carbonate afforded a considerable amount of bisadducts for both C₆₀ and C ₇₀.

Full text of DOI:10.1081/SCC-120030320

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Solvent‐Free Reactions of Fullerenes with Diethyl
Bromomalonate in the Presence of Inorganic Bases
Under High‐Speed Vibration Milling Conditions
a
a b
a
a b
a
Ru‐Fang Peng , Guan‐Wu Wang
, Ye‐Bing Shen , Yu‐Jin Li
, Ting‐Hu Zhang ,
a b
c
c
You‐Cheng Liu
, Yasujiro Murata & Koichi Komatsu
a
Department of Chemistry , University of Science and Technology of China , Hefei,
Anhui, 230026, P.R. China
b
State Key Laboratory of Applied Organic Chemistry , Lanzhou University , Lanzhou,
Gansu, P.R. China
c
Institute for Chemical Research , Kyoto University , Uji, Kyoto, Japan
Published online: 20 Aug 2006.
To cite this article: Ru‐Fang Peng , Guan‐Wu Wang , Ye‐Bing Shen , Yu‐Jin Li , Ting‐Hu Zhang , You‐Cheng Liu , Yasujiro
Murata & Koichi Komatsu (2004) Solvent‐Free Reactions of Fullerenes with Diethyl Bromomalonate in the Presence of
Inorganic Bases Under High‐Speed Vibration Milling Conditions, Synthetic Communications: An International Journal for
Rapid Communication of Synthetic Organic Chemistry, 34:11, 2117-2126, DOI: 10.1081/SCC-120030320
To link to this article: http://dx.doi.org/10.1081/SCC-120030320
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w
SYNTHETIC COMMUNICATIONS
Vol. 34, No. 11, pp. 2117–2126, 2004
Solvent-Free Reactions of Fullerenes with
Diethyl Bromomalonate in the Presence
of Inorganic Bases Under High-Speed
Vibration Milling Conditions
1
Ru-Fang Peng, Guan-Wu Wang,
,#
1,2,*
1
Ye-Bing Shen,
1,2
Yu-Jin Li, Ting-Hu Zhang, You-Cheng Liu,
1
,2
1
3
3
Yasujiro Murata, and Koichi Komatsu
1
Department of Chemistry, University of Science and
Technology of China, Hefei, Anhui, P.R. China
2
State Key Laboratory of Applied Organic Chemistry,
Lanzhou University, Lanzhou, Gansu, P.R. China
3
Institute for Chemical Research, Kyoto University,
Uji, Kyoto, Japan
ABSTRACT
Solvent-free reactions of C60 and C70 with diethyl bromomalonate in the
presence of various inorganic bases were investigated under the high-
#
Visiting Scholar from College of Material Sciences, Southwest University of Science
and Technology.
Correspondence: Guan-Wu Wang, Department of Chemistry, University of Science
*
and Technology of China, Hefei, Anhui 230026, P.R. China; E-mail: gwang@ustc.
edu.cn.
2
117
DOI: 10.1081/SCC-120030320
0039-7911 (Print); 1532-2432 (Online)
www.dekker.com
Copyright # 2004 by Marcel Dekker, Inc.

ORDER
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2
118
Peng et al.
speed vibration milling (HSVM) conditions, and are shown to give
methanofullerenes 1 and 2 in good to excellent yields based on consumed
fullerenes. Several weak inorganic bases were found to be quite effective
in promoting the solvent-free mechanochemical Bingel reactions of
C60 and C70 under the HSVM conditions. Among the studied bases,
sodium acetate gave the highest yield of monoadducts, while potassium
carbonate afforded a considerable amount of bisadducts for both C60
and C70
.
Key Words: Diethyl bromomalonate; Fullerenes; High-speed vibration
milling; Bingel reaction.
INTRODUCTION
Solvent-free organic reactions are currently attracting much interest of
chemists because of their prevention of pollution, low costs, and simplicity
[
1]
in the procedure. In fullerene chemistry, the functionalization by solid-
state reaction using a high-speed vibration milling (HSVM) technique has
been developed and continues to be of interest due to its high efficiency com-
pared to the liquid-phase reaction, and more importantly because of the feasi-
bility of obtaining some novel products which cannot be obtained in the
liquid-phase reaction. The HSVM technique was first applied to the solvent-
[2]
free Reformatsky-type reaction of C60 in 1996, since then it has been suc-
cessfully utilized in a number of mechanochemical reactions of fuller-
[
3–14]
enes.
the presence of organic base such as 1,8-diazabicyclo[5,4,0]undec-7-ene
Reaction of C60 or C70 with a-halo esters or a-halo ketones in
[15]
(
DBU) in organic solvents, known as Bingel reaction,
is one of the most
frequently used reactions in fullerene chemistry to synthesize various cyclo-
propanated fullerene derivatives. However, when we tried to apply our
HSVM technique to the solvent-free reaction of C60 with diethyl bromomalo-
nate in the presence of DBU, no reaction took place at all. Instead, the usage of
inorganic base such as Na CO afforded the expected cyclopropanated deriva-
2
3
[
16]
tive of C60 satisfactorily.
This result led us to investigate the HSVM reac-
tion of C60 as well as C70 with diethyl bromomalonate in the presence of
various inorganic bases to find the best auxiliary base in the solvent-free Bingel
reaction.
The reaction of C60 with diethyl bromomalonate under HSVM conditions
was found to give methanofullerene 1 in the presence of various inorganic
bases (Sch. 1).
The optimized yields of methanofullerene 1 and reaction conditions for
the HSVM reaction of C60 with diethyl bromomalonate in the presence of
different inorganic bases are summarized in Table 1.

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Reactions of Fullerenes with Diethyl Bromomalonate
2119
Scheme 1. The reaction of C60 with diethyl bromomalonate under HSVM conditions.
From Table 1, it can be seen that the HSVM reaction of C60 with
diethyl bromomalonate with NaOAc, Na CO , NaHCO , Ca(OH) , and
2
3
3
2
.
Na B O 10H O as the auxiliary base gave very good yield of methanoful-
2
4
7
2
lerene 1 (45–94% based on consumed C ) compared with the Bingel reac-
6
0
[15]
tion conducted in toluene with NaH as the base (45%). The usage of
K CO led to the formation of a large amount (35%) of bisadducts, thus
2
3
making the yield of monoadduct lower than that with Na CO used as a
2
3
base. The poor yields of the Bingel reaction product with NaOH and
KOH as the base are probably due to the side reactions such as direct
addition of hydroxy group(s) to C60 and the HBr elimination from diethyl
bromomalonate. The latter side reaction was verified by the formation of
[
17]
tetrakis(ethoxycarbonyl)ethylene
diethyl bromomalonate with NaOH or KOH under the HSVM conditions
Sch. 2).
We also extended the solid-state Bingel reaction under the HSVM
in high yield from the reaction of
(
conditions to C70 (Sch. 3). The examined bases are those used for the Bingel
Table 1. Results of the solid-state Bingel reaction of C60: yields of methanofullerene
1, reaction conditions, and the used inorganic bases.
Reaction
time (hr)
Yield of
1 (%)
Recovered
C60 (%)
a
Entry
Base
Ratio
1
2
3
4
5
6
7
8
9
NaOAc
Na CO
1 : 1 : 2
1 : 1 : 1
1 : 1 : 4
1 : 1 : 2
1 : 1 : 2
1 : 1 : 1
1
59
51
48
45
44
35
41
49
36
43
34
79
77
78
0.5
1
2
3
NaHCO
Ca(OH)
3
2
1
.
Na
2
B
4
O
7
10H
2
O
1
b
K CO
2
0.5
0.5
0.5
1
29
3
NaOH
KOH
Alkaline Al O
1 : 1.5 : 1.5
1 : 1 : 2
1 : 1 : 4
11
17
10
2
3
a
Molar ratio of C60 : diethyl bromomalonate : base.
3
b
5% of bisadducts were obtained.

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2
120
Peng et al.
Scheme 2. Reaction of diethyl bromomalonate in the presence of alkali hydroxide
under HSVM conditions.
reaction of C60 under the HSVM conditions except NaOH, KOH, and alkaline
Al O which gave poor results. The HSVM reaction of C70 with
2
3
diethyl bromomalonate selectively gave only one isomer of methanofullerene
, which resulted from the reaction at the most reactive bond (C1–C2) of C .
2
7
0
It is quite remarkable that the formation of the other three possible positional
isomers was not observed at all. The optimized yields of methanofullerene 2
and reaction conditions for the HSVM reaction of C70 with diethyl bromoma-
lonate in the presence of various inorganic bases are listed in Table 2.
Similarly to the HSVM Bingel reaction of C , the usage of NaOAc
6
0
afforded the highest yield (74%) of methanofullerene 2 for the reaction of
C70 with diethyl bromomalonate, and the utilization of K CO led to the
2
3
formation of a relatively large amount of bisadduct. The exact reason for
the favorable bisadduct formation in the Bingel reaction of both C60 and
C70 with the use of K CO is not clear for the moment.
2
3
The bisadducts obtained from the Bingel reaction of C70 with diethyl bro-
momalonate and K CO consist of three isomers 3a, 3b, and 3c (Fig. 1), which
were isolated by column chromatography in a ratio of 1.3 : 2.8 : 1. These three
2
3
1
isomers were characterized by H NMR, MS, and UV-VIS spectroscopy. The
UV-VIS spectra of 3a–c (Fig. 2) resemble those of tetrakis[(ethoxycarbonyl)-
methyl]1,2 : 67,68-bis(methano)[70]fullerene-71,71,72,72-tetracarboxylate,
tetrakis[(ethoxycarbonyl)methyl]1,2 : 56,57-bis(methano)[70]fullerene-71,71,
7
2,72-tetracarboxylate, and tetrakis[(ethoxycarbonyl)methyl]1,2 : 41,58-bis
thus supporting the
[18]
(methano)[70]fullerene-71,71,72,72-tetracarboxylate,
assigned structures.
Scheme 3. The reaction of C70 with diethyl bromomalonate under HSVM conditions.

ORDER
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Reactions of Fullerenes with Diethyl Bromomalonate
2121
Table 2. Results of the solid-state Bingel reaction of C70: yields of methanofullerene
2
and reaction conditions and the used inorganic bases.
Reaction
time (hr)
Yield of
2 (%)
Recovered
C
a
Entry
Base
Ratio
70 (%)
1
2
3
4
5
6
NaOAc
Na CO
1 : 1 : 2
1 : 1.5 : 1.5
1 : 1 : 4
1 : 1 : 2
1 : 1 : 2
1 : 1 : 1
1
74
53
44
57
52
22
28
54
24
45
34
0.5
1
2
3
NaHCO
Ca(OH)
3
2
1
.
Na B O 10H O
1
0.5
2
4
7
2
b
K CO
2
33
3
a
Molar ratio of C70 : diethyl bromomalonate : base.
9% of bisadducts were obtained.
b
2
The advantage of this solid-state reaction lies in the possibility of con-
ducting the fullerene reactions in a relatively large-scale. In fact, when the
solid-state Bingel reaction under the HSVM conditions using 0.5 g of C /
6
0
C70 mixture (82 : 18 by weight) together with diethyl bromomalonate and
Na CO was allowed to proceed for 1 hr, monoadducts of C and C70 were
2
3
60
obtained as the main products (44%) along with some of bisadduct isomers
19%). If one uses a solubilizing group such as long alkyl chains incorporated
(
in malonate, there would be no need for chromatographic separation but only
by washing of the crude product mixtures with solvent such as toluene or ethyl
acetate, the reaction product could be selectively separated out from
unchanged C /C , which is relatively insoluble.
6
0
70
In summary, the present work demonstrate that the reaction of C60 or C70
with diethyl bromomalonate does in fact proceed without any solvent only
Figure 1. Structures of bisadduct isomers 3a–c of C .
7
0

ORDER
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2
122
Peng et al.
Figure 2. UV–VIS spectra of bisadduct isomers 3a–c of C70 in n-hexane.
when inorganic bases instead of organic base, such as DBU, is used under
solid-state mechanochemical reaction conditions such as HSVM. Particularly,
weak inorganic bases were found to be generally effective in promoting the
solvent-free Bingel reactions of C60 and C70 under the HSVM conditions.
Among the investigated inorganic bases, NaOAc gave the highest yields of
monoadducts, while K CO was found to give a large amount of bisadducts
2
3
for the reactions of both C60 and C70.
EXPERIMENTAL
C60 (.99.9%) and C70 (98%) were purchased from 3D Carbon Cluster
Material Co. of Wuhan University in China. A mixture of C60 and C70
(
82 : 18) was purchased from Matsubo Co., Japan.
The solid-state HSVM reaction was conducted as has been already
[
4]
reported.
General Procedure for the Solid-State HSVM Bingel Reaction
of Fullerenes
A mixture of C60 or C70 (0.02 mmol), diethyl bromomalonate, and an
inorganic base in a certain molar ratio was vigorously shaken by HSVM at
a rate of 3500 cycles per minute for a specific time. The resulting mixture
was washed out with toluene and the collected washings were evaporated in
vacuo. The residue was chromatographed over a silica gel column with CS2

ORDER
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Reactions of Fullerenes with Diethyl Bromomalonate
2123
as an eluent to give unchanged C60 or C , and then with toluene as an eluent
70
to give the monoadduct of the Bingel product, followed by bisadduct isomers
in the case when K CO was used as the base.
2
3
The results of the reaction of C60 with diethyl bromomalonate in the pre-
sence of various inorganic bases are given in Table 1. The cyclopropanated
C60 derivative 1 was characterized by the following spectral data and ident-
[
15]
ified by the comparison of these data with the reported data.
n 2979, 2930, 1746, 1462, 1429, 1388, 1367, 1295, 1267, 1235, 1207, 1184,
1: IR (KBr)
2
097, 1061, 1021, 863, 740, 706, 580, 552, 528 cm ; H NMR (300 MHz,
1 1
1
1
3
CS –CDCl ) d 4.51 (q, J ¼ 7 Hz, 4H), 1.48 (t, J ¼ 7 Hz, 6H); C NMR
2
3
(
75 MHz, CS –CDCl ) d 162.66 (2C, CO), 145.03 (4C), 144.97 (4C),
2 3
144.88 (4C), 144.86 (4C), 144.57 (2C), 144.40 (4C), 144.34 (4C), 143.61
(
4C), 142.83 (2C), 142.81 (2C), 142.74 (4C), 142.72 (4C), 141.96 (4C),
3
41.58 (4C), 140.69 (4C), 138.81 (4C), 71.31 (2C, sp -C of C ), 62.96
1
60
(
lmax 256, 326, 424 nm; APCI MS m/z 878 (M ).
4C, OCH ), 51.86 (2C, CCO ), 14.19 (4C, OCH CH ); UV–VIS (n-C H )
2 2 2 3 6 14
2
The results of the reaction of C70 with diethyl bromomalonate in the pre-
sence of various inorganic bases are listed in Table 2. Methanofullerene 2 was
separated in the same way as described above and its identity was confirmed
[
15]
by its spectral data.
2: IR (KBr) n 2972, 2920, 1744, 1511, 1427, 1226,
2
092, 1016, 795, 672, 577, 534, 459 cm . H NMR (300 MHz, CDCl ) d
1 1
1
4
3
3
.52 (m, 4H), 1.49 (t, J ¼ 7 Hz, 6H); UV–VIS (n-C H ) l
235, 323,
6
14
max
2
51, 367, 400, 457, 537, 607, 658 nm; APCI MS m/z 998 (M ).
Reaction of C70 with Diethyl Bromomalonate and K CO
2
3
A mixture of C70 (16.8 mg, 0.02 mmol), diethyl bromomalonate (3.7 mL,
.02 mmol), and K CO (2.8 mg, 0.02 mmol) was vigorously shaken by
0
2
3
HSVM for 30 min. The resulting mixture was washed out with toluene and
the collected washings were evaporated in vacuo. The residue was chromato-
graphed over a silica gel column with CS as an eluent to give recovered C
2
70
(
5.7 mg, 34%), and then careful elution with toluene as an eluent afforded
methanofullerene 2 (6.6 mg, 33%) and three bisadduct isomers eluted in the
order of 3a (1.7 mg, 7%), 3b (3.7 mg, 16%), and 3c (1.3 mg, 6%). The struc-
[18]
ture of 3a, 3b, and 3c was deduced based on the elution order and the simi-
larity of the UV–VIS spectrum of each compound with the corresponding
bisadduct isomers obtained from the liquid-phase Bingel reaction of C with
70
[18]
other bromomalonate esters.
1
3
a: H NMR (300 MHz, CDCl ) d 4.51 (q, J ¼ 7 Hz, 4H), 4.50
3
(
q, J ¼ 7 Hz, 2H), 4.49 (q, J ¼ 7 Hz, 2H), 1.47 (t, J ¼ 7 Hz, 6H), 1.46

ORDER
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2
124
Peng et al.
236, 259, 284, 343, 364, 398, 434,
max
(
t, J ¼ 7 Hz, 6H); UV-VIS (n-C H ) l
6
14
2
4
48, 469, 519, 633, 685 nm; APCI MS m/z 1156 (M ).
1
3
b: H NMR (300 MHz, CDCl ) d 4.53 (q, J ¼ 7 Hz, 4H), 4.51
3
(
q, J ¼ 7 Hz, 4H), 1.49 (t, J ¼ 7 Hz, 6H), 1.47 (t, J ¼ 7 Hz, 6H); UV–VIS
6 14 max
2
(n-C H ) l
229, 254, 326, 395, 432, 463, 526, 650 nm; APCI MS m/z
1
156 (M ).
1
3
c: H NMR (300 MHz, CDCl ) d 4.53 (q, J ¼ 7 Hz, 8H), 1.49
3
(
t, J ¼ 7 Hz, 12H); UV-VIS (n-C H ) l
227, 269, 330, 369, 396, 423,
6
14
max
2
71, 531, 663 nm; APCI MS m/z 1156 (M ).
4
Reaction of Diethyl Bromomalonate with NaOH or KOH
A mixture of diethyl bromomalonate (24 mg, 0.1 mmol) and NaOH
4 mg, 0.1 mmol) was shaken for 15 min under the HSVM conditions. The
(
combined reaction mixture from five runs was washed with water and dried
[17]
in vacuo to give tetrakis(ethoxycarbonyl)ethylene
(69 mg, 86%): m.p.
5
1
3–558C; IR (KBr) n 2988, 2974, 2943, 1728, 1485, 1455, 1367, 1252,
095, 1025, 860, 810, 772, 720, 592, 537 cm
2
1
1
; H NMR (300 MHz,
CDCl ) d 4.31 (q, J ¼ 7 Hz, 8H), 1.31 (t, J ¼ 7 Hz, 12H).
3
The same procedure for the HSVM reaction of diethyl bromomalonate
with KOH afforded tetrakis(ethoxycarbonyl)ethylene in 89% yield.
Large-Scale Reaction of C /C Mixture with Diethyl
0
6
70
Bromomalonate and Na CO
2
3
After a reaction was conducted with a mixture of C /C [82 : 18,
6
0
70
0.502 g, 0.68 mmol (averaged molecular weight 741.6)], diethyl
bromomalonate (0.16 g, 0.67 mmol), and Na CO (0.073 g, 0.69 mmol) under
2
3
the HSVM solid-state conditions for 1 hr, the HPLC analysis of the reaction
mixture on a Buckyprep column with toluene as an eluent showed the pre-
sence of 51% monoadduct and 15% bisadduct of C /C as well as 33%
6
0
70
unreacted C /C . The unreacted diethyl bromomalonate and some by-pro-
6
0
70
ducts were washed out with pentane (2 Â 40 mL). The crude product was dis-
solved in 40 mL of CS and transferred to the top of a silica gel column
2
(
elution with CS . Elution with CS –toluene (7 : 3) afforded monoadducts 1
20 mm  250 mm). Unreacted C /C (170 mg, 34%) was recovered by
2 2
6
0
70
and 2 (269 mg, 44%), and bisadducts (137 mg, 19%) of C /C were eluted
6
0
70
by toluene–EtOAc (9 : 1) as dark brown solids.

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Reactions of Fullerenes with Diethyl Bromomalonate
ACKNOWLEDGMENTS
2125
We are grateful for financial support from the National Science Fund for
Distinguished Young Scholars (21025205), Hundred Talents Program of the
Chineese Academy of Sciences, Anhui Provincial Natural Science Foundation
(
00045306), and Anhui Provincial Bureau of Personnel Affairs (2001Z019).
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Received in Japan September 30, 2003

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