CATALYTIC [2+1]-CYCLOADDITION OF ETHYL DIAZOACETATE TO FULLERENE [60]
1173
was cooled to room temperature, 8 ml of toluene was
added, and the solution was passed throgh a thin bed of
silica gel. The reaction products I–VI and C -fullerene
evaporator, the residue was dried in a vacuum and
analyzed by spectral methods.
60
The mixture of regioisomeric fullerene bis-
were separated by preparative HPLC, eluent toluene.
–1
adducts (IV). IR spectrum, cm : 1740, 1620, 1170, 1080,
1
'-Ethoxycarbonyl-(C -I )[5,6]fullero[2',3':1,9]-
1020, 780, 520. UV spectrum (CHCl ), λmax, nm: 261,
6
0
h
3
–1
1
cyclopropane (I). IR spectrum, cm : 1660, 1270, 1110,
333, 423. H NMR spectrum, δ, ppm: 1.4–1.6 m, 4.25–
1
3
040, 820, 540. UV spectrum (CHCl ), λmax, nm: 260,
4.57 m, 4.72 s, 4.80 s, 5.13 s. 13C NMR spectrum, δ,
ppm: 14.56, 15.24, 38.21, 42.57, 49.64, 62.17, 62.88, 63.57,
140–148, 164.23, 164.58, 164.80.
3
1
27, 424. H NMR spectrum, δ, ppm: 1.55 t (3H, CH ,
3
J 7 Hz), 4.50 q (2H, CH , J 7 Hz), 4.80 s (1H, CH).
2
13
C NMR spectrum, δ, ppm: 14.82, 39.48, 62.28, 70.95
The study was carried out under the financial support
of the Russian Foundation for Basic Research and the
Ministry of Science and Education (grants nos. 07-03-
3
(
sp ), 136.48, 140.84, 140.99, 141.26, 142.06, 142.18,
1
1
1
42.31, 142.52, 142.88, 143.04, 143.11, 143.13, 143.40,
43.79, 144.04, 144.48, 144.67, 144.70, 144.86, 145.12,
45.21, 145.29, 145.62, 145.86, 148.39, 164.83 (COOΕt).
Mass spectrum ES TOF, m/z (I , %): 720 (87) [C ] ,
00287, NSh-2349.2008.3).
+
rel
60
REFERENCES
+
+
8
06 (100) [M] , 828 (100) [M – H + Na] .
syn-1’a-Ethoxycarbonyl-1'a-hydro-1'a(2')-homo-
1. De la Torre, M.D.L., Tome, A.C., Silva, A.M.S., and
Cavalerio, J.A.S., Tetrahedron Lett., 2002, vol. 43, p. 4617.
2. Pellicciari, R., Annibali, D., Costantino, G., Marinozzi, M.,
and Natalini, B., Synlett., 1997, p. 1196.
3. Warton, T., Kini, U.V., Mortis, R.A., and Wilson, L.J.,
Tetrahedron Lett., 2001, vol. 42, p. 5159.
1
(
C -I )[5,6]fullerene (II). H NMR spectrum, δ, ppm:
60
h
1
7
5
1
1
1
.39 t (3H, CH , J 7 Hz), 4.25 q (2H, CH , J 7 Hz),
3 2
13
.48 s (1H, CH). C NMR spectrum, δ, ppm: 14.59,
1.83, 61.96, 131.33, 134.13, 137.19, 138.76, 138.82,
40.82, 142.01, 142.33, 142.36, 142.65, 143.55, 143.92,
44.35, 144.45, 144.73, 144.93, 145.03, 145.64, 147.70,
64.25 (COOΕt).
4. Nakamura, E., Tokuyama, H., Yamago, S., Shivaki, T., and
Sugiura, Y., Bull. Chem. Soc. Jpn., 1996, vol. 69, p. 2143.
5. Friedman, S.H., Ganapathi, P.S., Rubin, Y., and Ken-
anti-1’a-Ethoxycarbonyl-1'a-hydro-1'a(2')-homo-
yon, G.L., J. Med. Chem., 1998, vol. 41, p. 2424.
1
(
C -I )[5,6]fullerene (III). H NMR spectrum, δ,
6
0
h
6
. Dugan, L.L., Turetsky, D.M., Du, C., Lobner, D., Wheel-
er, M., Almli, C.R., Shen, C.K.-F., Luh, T.-Y., Choi, D.W.,
and Lin, T.-S., Proc. Natl. Acad. Sci. USA, 1997, vol. 94,
p. 9434.
ppm: 1.51 t (3H, CH , J 7 Hz), 4.55 q (2H, CH , J 7 Hz),
3
2
13
3
5
1
1
1
1
.82 sC (1H, CH). C NMR spectrum, δ, ppm: 14.77,
4.17, 62.60, 133.56, 134.03, 135.29, 137.90, 138.07,
38.30, 138.52, 138.54, 140.23, 141.82, 142.05, 142.21,
42.45, 142.63, 142.89, 143.03, 143.09, 143.27, 143.31,
43.40, 143.70, 143.79, 144.04, 144.66, 144.72, 144.95,
45.21, 145.27, 147.90, 168.83 (COOΕt).
7. HuangY.L., Shen, C.K., Luh, T.Y.,Yang, H.C., Hwang, K.C.,
and Chou, C.K., Eur. J. Biochem., 1998, vol. 254, p. 38.
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9. Suzuki, T., Li, Q., Khemani, K.C., Wudl, F., and Almars-
The mixture of stereo- and regioisomeric
son, O., Science, 1991, vol. 254, p. 1186.
0. Smith, A.B. III, Strongin, R.M., Brard, L., Furst, G.T.,
Romanow, W.J., Owens, K.G., Goldschimdt, R.J., and
King, R.C., J. Am. Chem. Soc., 1995, vol. 117, p. 5492.
11. Isaacs, L., Wehtsig,A., and Diederich, F., Helv. Chim. Acta,
1
fullerene bisadducts IV–VI. UV spectrum (CHCl ),
3
1
λ
, nm: 260, 327, 421. H NMR spectrum, δ, ppm:
.9–1.50 m, 3.78–4.32 m, 4.36 s, 4.37s, 4.49 s, 4.70 s,
.76 s, 5.12 s, 6.31 s, 7.05 s, 7.08 s. C NMR spectrum,
max
0
4
13
1
993, vol. 76, p. 1231.
2. Bestman, H.J. and Moll, C., Synlett., 1996, p. 729.
3. Suda, M., Synthesis, 1981, vol. 9, p. 714.
4. Dzhemilev, U.M., Dokichev, V.A., Sultanov, S.Z.,
δ, ppm: 14.55, 37.93, 41.88, 44.71, 47.06, 49.45, 51.26,
3.30, 53.68, 59.38, 61.60, 61.76, 61.90, 62.10, 62.23,
2.45, 140–148, 164.19, 164.52, 164.65, 168.05, 168.28,
1
1
1
5
6
1
9
68.54, 168.72. Mass spectrum ES TOF, m/z (I , %):
rel
Khusnutdinov, R.I., Tomilov, Yu.V., Nefedov, O.M., and
Tolstikov, G.A., Izv. Akad. Nauk SSSR, Ser. Khim., 1989,
p. 1861.
14 (100) [M – H + Na], 915 (80) [M + Na].
Thermal isomerization of open 5,6-adducts of
fullerene into the closed 6,6-cycloadduct. In a glass
reactor 20 mg of a mixture of compounds I–III or IV–
VI was dissolved in 20 ml of toluene, the solution was
refluxed for 14–20 h at the heating bath temperature not
exceeding 140°C. Toluene was distilled off on a rotary
1
5. Blickle, P., Bloch, M., and Jones, T.B., Chem. Ber., 1979,
vol. 112, p. 3691.
16. Dent, W.T., Long, R., and Wilkinson, J., J. Chem. Soc.,
1964, p. 1585.
17. Marvanov, R.M., Fakhretdinov, R.M., and Dzhemi-
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 45 No. 8 2009