Synthesis of fullerene-containing methacrylates

Article abstract of DOI:10.1016/j.mencom.2012.06.009

The Bingel-Hirsch reaction between fullerene C60 and 2-methacryloyloxyethyl methyl malonate or 2-methacryloyloxyethyl dichloroacetate afforded the corresponding monocyclopropanation products.

Full text of DOI:10.1016/j.mencom.2012.06.009

Mendeleev
Communications
Mendeleev Commun., 2012, 22, 199–200
Synthesis of fullerene-containing methacrylates
a
b
b
Seda A. Torosyan, Yulia N. Biglova, Vladimir V. Mikheev,
b
a
a
Zarina T. Khalitova, Fanuza A. Gimalova and Mansur S. Miftakhov*
a
b
Institute of Organic Chemistry, Ufa Scientific Centre of the Russian Academy of Sciences, 450054 Ufa,
Russian Federation. Fax: +7 347 235 6066; e-mail: bioreg@anrb.ru
Department of Chemistry, Bashkir State University, 450074 Ufa, Russian Federation
DOI: 10.1016/j.mencom.2012.06.009
The Bingel–Hirsch reaction between fullerene C60 and 2-methacryloyloxyethyl methyl malonate or 2-methacryloyloxyethyl dichloro-
acetate afforded the corresponding monocyclopropanation products.
1
Fullerene C60 exhibits electron-withdrawing properties and is
used in the composite materials that show high-temperature super-
3
, CBr4,
2
conductivity, as electron-accepting components of plastic solar
DBU, PhMe
CO Me
O
2
3
–7
8
Me
CH2
batteries, etc.
O
4
6%
O
In this paper, we report the syntheses of new methacrylate
†
O
monomers 1 and 2 (Scheme 1) containing covalently attached
fullerene C60 in the side chain. Compounds 1 and 2 were accessed
by cyclopropanation of fullerene C60 with reactants 3 and 4 (for
their formulae see Scheme 2) according to the Bingel–Hirsch
1
9
reaction. Note that the coupling C60 + 4 did not require the use
of CBr4.
4
, DBU,
Compound 5 was obtained by controlled esterification of
methacrylic acid with ethylene glycol.10 Esterification of hydroxy
group in compound 5 with methyl hydrogen malonate by the
Cl
O
O
PhMe
Me
CH2
5
9%
O
11
‡
O
Mitsunobu reaction proceeded smoothly (method i, Scheme 2).
2
†
NMR spectra were recorded on a Bruker AM-300 spectrometer at
1
13
3
00 ( H) and 75.47 MHz ( C) and a Bruker AVANCE-500 spectrometer
Scheme 1
1
13
at 500 ( H) and 125.77 MHz ( C), using TMS as the internal standard.
IR spectra were measured on an IR Prestige-21 Fourier Transform Shimadzu
spectrophotometer using samples prepared as thin films or dispersed in
Nujol. Mass spectra were recorded on a MALDI Voyager-D STR TOF
spectrometer. Elemental analyses of the compounds obtained match the
calculated values. The progress of reactions was monitored by TLC on
Sorbfil plates (Russia); spots were detected by calcinations or by treatment
with an alkaline solution of potassium permanganate. The products were
isolated by column chromatography on silica gel (30–60 g of sorbent per
gram of substrate); freshly distilled solvents were used as the eluents.
O
Me
O
OMe
O
i or ii
CH2
O
O
O
3
4
Me
OH
O
O
Cl
CH2
iii
Me
O
5
O
Cl
{
(1-Methoxycarbonyl)-1-[2-(methacryloyloxy)ethyloxycarbonyl]-1,2-
CH2
O
methane}-1,2-dihydro-C -fullerene 1. Fullerene C (0.1 g, 0.14 mmol)
60
60
was dissolved in toluene (30 ml); CBr (0.045 g, 0.14 mmol), compound 3
4
(
0
0.03 g, 0.14 mmol) and diazabicyclo[4.2.0]undec-7-ene (DBU) (0.13 g,
.14 mmol) were added, and the mixture was stirred for 5 min at room
Scheme 2 Reagents and conditions: i, MeO CCH CO H, DIAD, PPh ,
2
2
2
3
THF (55%); ii, MeO CCH C(O)Cl, Py (57%); iii, Cl CHC(O)Cl, Py, room
temperature. The mixture was filtered, the filtrate was washed with 5%
hydrochloric acid, dried with MgSO and concentrated, and the residue was
2
2
2
temperature (75%).
4
treated with column chromatography on silica gel using toluene–light
petroleum (4:1) as the eluent to give 0.060 g (46%) of monoadduct 1 and
{1-Chloro-1-[2-(methacryloyloxy)ethyloxycarbonyl]-1,2-methane}-
–1
0
2
1
3
.04 g of non-reacted C . Dark brown powder. Mp > 360°C. IR (n/cm ):
980, 2953, 2924, 1746, 1719, 1452, 1433, 1319, 1296, 1267, 1234, 1213,
1,2-dihydro-C -fullerene 2 was obtained similarly to compound 1 from
60
60
C60 (0.1 g, 0.14 mmol), compound 4 (0.034 g, 0.14 mmol) and DBU
163, 1111, 1095, 943, 813, 756, 667, 527. UV (CHCl , lmax/nm): 257,
(0.13 ml, 0.14 mmol) in toluene (30 ml). Yield 0.075 g (59%). Dark brown
3
1
1
26, 425. H NMR (CDCl ) d: 1.97 (s, 3H, Me), 4.01 (s, 3H, OMe), 4.55
powder, mp > 300°C. UV (CHCl , l /nm): 257, 325, 425. H NMR
3
3
max
(
t, 2H, CH O, J 4.4 Hz), 4.75 (m, 2H, CH O, J 4.5 Hz), 5.62 (br.s, 1H) and
(CDCl ) d: 2.01 (s, 3H, Me), 4.64 and 4.87 (2m, 2×2H, 2CH O), 5.66 (t,
2
2
3
2
13
1
13
6
5
1
.17 (s, 1H, =CH2). C NMR (CDCl ) d: 18.31 (Me), 53.80 (Ccycloprop.),
1H, =CH , J 1.5 Hz) and 6.15 (s, 1H, =CH ). C NMR (CDCl ), d: 18.26
3
2
2
3
sp3
1
sp3
4.11 (OMe), 62.05, 64.80 (2CH O), 71.30 (Cfullerene), 126.57 (=CH2),
(Me), 52.76 (C
), 61.91, 65.22 (2CH O), 74.81 (Cfullerene), 126.61
2
cycloprop. 2
35.67 (=CMe), 138.78, 139.27, 140.97, 141.19, 142.19, 142.94, 143.02
(=CH ), 135.56 (=CMe), 138.58, 139.37, 141.07, 141.09, 141.73, 142.16
2
(
1
3C), 143.07, 143.85, 143.89, 144.56, 144.63, 144.65, 144.69, 144.91,
(2C), 142.19, 142.85, 142.94, 143.04 (3C), 143.06, 143.21, 143.66, 143.78,
144.10, 144.27, 144.37, 144.52, 144.66, 144.72, 144.75 (3C), 144.80,
144.88, 145.16, 145.17, 145.21, 145.30 (Cfullerene), 163.88 and 166.95 (CO2).
45.06, 145.11, 145.14, 145.20, 145.27 (Cfullerene), 163.46 (CO ), 163.90
2
+
and 166.99 (CO ). MS, m/z: 948.061 [M ] (calc. for C H O , m/z:
9
2
70 12
6
+
48.0634).
MS, m/z: 924.051 [M ] (calc. for C H ClO , m/z: 924.019).
68
9
4
©
2012 Mendeleev Communications. All rights reserved.
– 199 –

Mendeleev Commun., 2012, 22, 199–200
5 Ch.-Y. Chang, Ch.-E. Wu, Sh.-Y. Chen, C. Cui,Y.-J. Cheng, Ch.-S. Hsu,
However, the use of methyl malonate chloride (method ii) was
more practical for it provided almost the same yield of the
product 3. For the preparation of compound 4, we used the
corresponding acid chloride (method iii).
The electron-withdrawing properties of fullerene C60 moieties
in methanefullerenes 1 and 2 are further enhanced by additional
inductive effects of the ester group and the Cl atom, respectively,
which seems promising for practical use. The monomers 1 and 2
will be tested in polymerization and copolymerization reactions.
Y.-L. Wang and Y. Li, Angew. Chem. Int. Ed., 2011, 50, 9368.
D. Guidi, B. M. Illescas, C. M. Atienza, M. Wielopolski and N. Martin,
Chem. Soc. Rev., 2009, 38, 1587.
P. A. Troshin and N. S. Sariciftci, in Supramolecular Chemistry: From
Molecules to Nanomaterials, eds. J. W. Steed and P. A. Gale, John Wiley &
Sons, Ltd., Chichester, UK, 2012, p. 2725.
6
7
8 P. A. Troshin, R. N. Lyubovskaya and V. F. Razumov, Rossiiskie Nano-
tekhnologii, 2008, 3, 6 (in Russian).
9
X. Camps and A. Hirsch, J. Chem. Soc., Perkin Trans. 1, 1997, 1595.
0 K. Ramalinga, P. Vijayalakshmi and T. N. B. Kaimal, Tetrahedron Lett.,
002, 43, 879.
1 O. Mitsunobu and M. Eguchi, Bull. Chem. Soc. Jpn., 1971, 44, 3427.
1
1
2
The authors are grateful to Professor L. M. Khalilov and V. M.
Yanybin for recording MALDI TOF mass spectra.
References
1
2
3
4
F. Zhou, C. Jehoulet and A. J. Bard, J. Am Chem. Soc., 1992, 114,
1004.
A. Hebard, M. Rossienski, R. Haddon, D. Murphy, S. Glarum, T. Palstra,
A. Ramires and A. Kortan, Nature, 1991, 350, 600.
K. Moriwaki, F. Matsumoto, Y. Takao, D. Shimizu and T. Ohno,
Tetrahedron, 2010, 66, 7316.
1
Received: 23rd January 2012; Com. 12/3866
-Methacryloyloxyethyl dichloroacetate 4. iii) Dichloroacetyl chloride
2
(
(
0.1 g, 0.68 mmol) was added with cooling to a solution of compound 5
0.056 g, 0.55 mmol) in pyridine (0.5 ml) and the mixture was stirred at
Y.-J. Cheng, Sh.-H. Yang and Ch.-S. Hsu, Chem. Rev., 2009, 109, 5868.
room temperature for 12 h until the starting compound was consumed
the progress of the reaction was monitored by TLC). The mixture was then
diluted with CH Cl (30 ml), washed with 5% HCl to remove pyridine,
(
‡
2
-Methacryloyloxyethyl methyl malonate 3. i) Diisopropyl diazo-
2
2
dicarboxylate (0.424 g, 2.10 mmol) and PPh (0.55 g, 2.10 mmol) were
and dried with MgSO ; the solvent was evaporated. The product was
3
4
added with stirring in an argon flow to a solution of compound 5 (0.27 g,
purified on a column with SiO using CH Cl as the eluent. Yield 75%
2
2
2
–1
2
.60 mmol) and methyl hydrogen malonate (0.3 g, 2.50 mmol) in THF
(0.1 g). IR (n/cm ): 3013, 2963, 1769, 1751, 1718, 1635, 1454, 1369,
1
(
5 ml) and the mixture was stirred at room temperature until the starting
1323, 1296, 1159, 1055, 1031, 966, 945, 814. H NMR (CDCl ) d: 1.90
3
compound was consumed (the progress of the reaction was monitored by
TLC). The solvent was then removed on a rotary evaporator. The residue
was purified on a column with SiO using CH Cl –MeOH (20:1) as the
(t, 3H, Me, J 1.1 Hz), 4.40 and 4.50 (2m, 2×2H, OCH CH O), 5.57 (t,
2
2
1
3
1H, =CH , J 1.4 Hz), 5.96 (s, 1H, CHCl ), 6.09 (s, 1H, =CH ). C NMR
2
2
2
(CDCl ) d: 18.15 (Me), 61.59 (CH O), 63.93 (CHCl ), 64.81 (CH O), 126.40
2
2
2
3
2
2
2
eluent.Yield 55% (0.25 g). ii) Methyl malonate chloride (0.25 g, 1.83 mmol)
(=CH ) and 135.57 (=CMe), 164.32 and 166.86 (2CO ).
2
2
was added to a solution of compound 5 (0.2 g, 1.52 mmol) in pyridine
2-Hydroxyethyl methacrylate 5. Ethylene glycol (105.4 ml, 1.7 mol)
and iodine (0.1 g) were added to methacrylic acid (15 ml, 0.17 mol) and
the mixture was refluxed for 4 h. After cooling of the mixture, a solution
of NaCl was added. The mixture was extracted with CH Cl , the combined
(
3 ml) and the mixture was stirred at room temperature until the starting
compound was consumed (TLC control). The mixture was then diluted
with chloroform (30 ml), washed with 5% HCl and dried with MgSO4;
the solvent was evaporated. The product was purified on a column with
2
2
organic layers were washed with 5% aqueous Na S O and with saturated
2
2
3
SiO using EtOAc–light petroleum (1:3) as the eluent. Yield 57% (0.19 g).
IR (n/cm ): 2958, 2932, 2895, 1757, 1718, 1638, 1439, 1412, 1371, 1338,
NaCl solutions and then dried with MgSO . The solvent was distilled off
2
4
–1
in a rotary evaporator and the product was purified by distillation in vacuo.
–1
1
7
321, 1298, 1279, 1161, 1151, 1055, 1039, 1024, 949, 851, 815, 785, 851,
Bp 83–85°C (20 Torr). Yield 85%. IR (n/cm ): 3425, 2957, 2930, 2884,
1
1
58, 656, 603, 581, 521, 482. H NMR (CDCl ) d: 1.96 (t, 3H, Me, J 1.0
1714, 1635, 1454, 1321, 1298, 1170, 1080, 1033, 945, 903, 816. H NMR
3
and 1.6 Hz), 3.45 (s, 2H, CH ), 3.75 (s, 3H, OMe), 4.40 (m, 4H, 2CH O),
(CDCl ) d: 1.90 (t, 3H, Me, J 1.3 Hz), 3.80 (t, 2H, CH O, J 6.5 Hz), 4.25
2
2
3
2
13
5
.61 (t, 1H, =CH , J 1.6 Hz), 6.15 (s, 1H, =CH ). C NMR (CDCl ) d:
(t, 2H, CH O, J 6.5 Hz), 5.10 (t, 1H, =CH , J 1.3 Hz), 6.10 (s, 1H, =CH ).
2
2
3
2
2
2
13
1
8.06 (Me), 40.97 (CH ), 52.38 (OMe), 61.90 and 62.91 (2OCH ), 126.00
C NMR (CDCl ) d: 18.20 (Me), 61.01 and 66.24 (2OCH ), 126.01 (=CH ),
3 2 2
2
2
(
=CH ), 135.64 (=CMe), 166.10, 166.53 and 166.84 (CO ).
135.90 (=CMe), 167.73 (CO2).
2
2
–
200 –