NEW MONOMERS FOR FULLERENE-CONTAINING POLYMERS
181
s (3H, OCH3), 4.36 m (4H, 2CH2O), 4.96 m (1Н, OH),
5.85 d.d (1H, =CH2, J 1.3, 10.7 Hz), 6.11 d.d (1H, =CH,
J 17.5, 10.5 Hz), 6.42 d.d (1H, =CH2, J 1.3, 17.3 Hz).
13С NMR spectrum, δ, ppm: 41.14 (CH2), 52.56 (OCH3),
61.91 and 63.10 (2 OCH2), 127.89 (=CH), 131.46 (=CH2),
165.79, 166.26 and 166.69 (СО2). Found: [M – OCH3]+
185.0512. С8Н9О5. Calculated: [M – OCH3]+ 185.0444.
Mass spectrum, m/z (I rel, %): 185 [M – OCH3]+ (1), 173
(3), 156 (3), 144 (3), 117 (2), 113 (13), 101 (100), 99
(15), 86 (22), 69 (8), 59 (18), 55 (90). Found, %: С 49.81;
Н 5.72. C9H12O6. Calculated, %: С 50.00; Н 5.59.
3.30 s (2Н, С2Н2), 3.66 s (3H, OCH3), 4.06 t (2Н, ОСН2,
J 6.7 Hz), 4.85 d.d (1Н, =СН2, J 1.0, 9.2 Hz), 4.91 d.d
(1Н, =СН2, J 1.5, 17.1 Hz), 5.72 m (1Н, =СН). 13С NMR
spectrum, δ, ppm: 25.73 (СН2), 28.42, 28.88, 29.05,
29.13, 29.35, 29.40, 33.75 (СН2), 41.38 (СОСН2), 52.41
(ОСН3), 65.69 (OCH2), 114.12 (=СН), 139.14 (=СH2),
166.54 (СО2Me), 167.03 (СО2). Found, %: С 66.18;
Н 9.87. C15H26O4. Calculated, %: С 66.64; Н 9.69.
{1-Methoxycarbonyl-1-[(acryloyloxy)-
ethoxycarbonyl]-1,2-methano}-1,2-dihydro-С60-
fullerene (III). To a solution of 0.2 g (0.277 mmol) of
С60 in 30 mL of toluene was added 0.059 g (0.277 mmol)
of ester VII, 0.26 g (0.277 mmol) of diazabicyclo[4.2.0]-
undecen-7-ene (DBU), and 0.091 g (0.277 mmol) of CBr4.
The reaction mixture was stirred at room temperature for
5 min (TLC monitoring in toluene). Then the reaction
mixture was filtered, the filtrate was washed with 5%
HCl water solution, dried with MgSO4, the solvent was
distilled off. The residue was chromatographed on silica
gel (eluent toluene). We obtained 0.158 g (61%) of mono-
substituted product III and 0.04 g of unreacted fullerene.
1Н NMR spectrum, δ, ppm: 4.09 s (3Н, ОСН3), 4.56 m
(2Н, СН2О), 4.75 m (2Н, СН2О), 5.89 d (1Н, =СН2,
J 10.5 Hz), 6.14 d.d (1Н, =СН, J 10.6, 17.3 Hz), 6.48 d.d
(1Н, =СН2, J 10.7, 17.3 Hz). 13С NMR spectrum, δ, ppm:
51.73 (С1cyclopropyl), 54.12 (ОСН3), 61.87, 64.69 (2СН2О),
2-(2,2-Dichloroacetoxy)ethyl acrylate (VIII). To
a solution of 0.056 g (0.55 mmol) of compound VI in
0.5 mLof pyridine was added at cooling 0.1 g (0.68 mmol)
of dichloroacetyl chloride, and the mixture was stirred for
12 h at room temperature till the complete consumption
of initial ester (TLC monitoring). Then the mixture was
diluted with 30 mL of chloroform, washed with 5% HCl
water solution, dried with MgSO4, the solvent was dis-
tilled off. The residue was chromatographed on silica gel
(eluent CH2Cl2). Yield 0.1 g (75%). IR spectrum, ν, cm–1:
3012, 2966, 1760, 1728, 1643, 1620, 1453, 1410, 1296,
1271, 1188, 1169, 1079, 1034, 985, 970, 810, 673, 666.
1Н NMR spectrum, δ, ppm: 4.43 m (2Н, ОСН2СН2О),
4.50 m (2Н, ОСН2СН2О), 5.88 d.d (1Н, =СН2, J 1.1,
10.5 Hz), 5.97 s (1Н, СНСl2), 6.12 d.d (1Н, =СН2, J 10.5,
17.3 Hz), 6.43 d.d (1Н, =СН, J 1.2, 17.4 Hz). 13С NMR
spectrum, δ, ppm: 61.45 (CH2O), 63.73 (CHCl2), 64.63
(CH2O), 127.45 (=СН), 131.65 (=СH2), 164.32 and
165.58 (2СО2). Mass spectrum, m/z (Irel, %): 199 (0.3),
159 (1), 155 [M – 2Cl]+ (3), 141 (3), 127 (9), 111 (21),
87 (8), 85 (60), 83 (100), 76 (23). Found, %: С 36.81;
Н 3.43; Cl 30.96. C7H8Cl2O4. Calculated, %: С 37.03;
Н 3.55; Cl 31.23.
71.31 (Csp -fullerene), 127.72 (=СН), 131.88 (=СН2),
3
138.80, 139.32, 140.98 (2С), 141.91 (2С), 142.21, 142.96,
143.04 (3С), 143.10, 143.88, 143.91, 144.59, 144.66 (2С),
144.71 (3С), 144.92, 144.93, 145.08, 145.14, 145.18,
145.20, 145.22, 145.29 (2С) (Сfullerene), 163.43 (СО2),
163.88 and 165.74 (СО2). Found M+ 934.041. C69H10O6.
Calculated M 934.0477.
{1-[2-(Acryloyloxy)ethoxycarbonyl]-1-chloro-1,2-
methano}-1,2-dihydrо-С60-fullerene (IV) was obtained
similarly from 0.1 g (0.138 mmol) of С60, 0.031 g
(0.138 mmol) of ester VIII in the presence of 0.13 mL
(0.138 mmol) of DBU in 30 mL of toluene. Yield 0.06
g (46%). IR spectrum, ν, cm–1: 3432, 2927, 1743, 1723,
1666, 1506, 1427, 1405, 1302, 1264, 1174, 1114, 985,
826, 807, 658, 523. 1Н NMR spectrum, δ, ppm: 4.59 m
(2Н) and 4.81 (2Н, 2СН2О), 5.88 d.d (1Н, =СН2, J 1.1,
10.4 Hz), 6.14 d.d (1Н, =СН, J 10.5, 17.3 Hz), 6.46 d.d
(1Н, =СН2, J 1.1, 17.3 Hz). 13С NMR spectrum, δ, ppm:
61.82 and 65.24 (2СН2О), 52.87 (С1cyclopropyl), 74.90
(Undec-10-en-1-yl) methyl malonate (IX). To a
solution of 0.53 g (3.10 mmol) of 10-undecenol in 3 mL
of pyridine was added dropwise 0.51 mL (3.70 mmol)
of methylmalonyl chloride, and the mixture was stirred
at room temperature till complete consumption of initial
alcohol (TLC monitoring). Then the mixture was diluted
with 30 mL of chloroform, washed with 5% HCl water
solution, dried with MgSO4, the solvent was distilled off.
The residue was chromatographed on silica gel (eluent
petroleum ether–ethylacetate, 3 : 1). Yield 0.65 g (78%).
IR spectrum, ν, cm–1: 2974, 2926, 2855, 1741, 1641,
1435, 1418, 1362, 1240, 1198, 1171, 1117, 993, 910, 758,
723, 638. 1Н NMR spectrum, δ, ppm: 1.19 m (12Н, СН2),
1.55 t (2Н, СН2, J 7.3 Hz), 1.95 q (2Н, СН2, J 7.3 Hz),
(Csp -fullerene), 127.69 (=CH2), 131.95 (=CH), 138.78,
3
139.48, 141.18 (2С), 141.82, 142.27 (3С), 142.96, 143.05,
143.13 (2С), 143.16 (2С), 143.32, 143.77, 143.90, 144.21,
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 50 No. 2 2014