Chemistry - An Asian Journal
10.1002/asia.201500079
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CDCl3, 25 °C, C6F6): =–61.52 (m, 6F; CF3), –62.33 (br. sept,
J(F,F)=11.0, 6F; CF3), –62.50 (m, 6F; CF3), –69.60 ppm (q, J(F,F)=10.6
Hz, 6F; CF3); UV/Vis (toluene): λmax=365, 412, 471, 518, 558 nm; MALDI
MS: m/z (%): 1639.0 (5) [M–CF3–], 1652.3 (11) [M*–CF3–], 1708.0 (100)
[M–].
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Compound III, C70(CF3)8[CH(CO2Et)2]H: tR 4.7 min (Cosmosil
Buckyprep 4.6 mm I.D. × 25 cm, toluene–hexane, 1:1 (v/v), 1 mL min–1);
1H NMR (400.3 MHz, CDCl3, 25 °C, TMS): =5.91 (s, 1H, Ccage–H), 4.91
(q, J(H,F)=2.7 Hz, 1H; CH(CO2Et)2), 4.46 (dq, 3J(H,H)=7.1 Hz,
2J(H,H)=10.8 Hz, 1H; CH2), 4.36 (dq, 3J(H,H)=7.1 Hz, 2J(H,H)=10.8 Hz,
1H; CH2), 4.33 (dq, 3J(H,H)=7.1 Hz, 2J(H,H)=11.0 Hz, 1H; CH2), 4.31 (dq,
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3
3J(H,H)=7.1 Hz, 2J(H,H)=11.0 Hz, 1H; CH2), 1.39 (t, J(H,H)=7.1 Hz, 3H;
CH3), 1.29 (t, 3J(H,H)=7.1 Hz, 3H; CH3); 19F NMR (376.5 MHz, CDCl3,
25 °C, C6F6): =–57.95 (sept, J(F,F)=13.1, 3F; CF3), –60.75 (3F, sept,
J(F,F)=13.7 Hz, CF3), –61.30 (sept, J(F,F)=13.2 Hz, 3F; CF3), –62.11
(sept, J(F,F)=12.8 Hz, 6F; CF3), –62.39 (sept, J(F,F)=12.8 Hz, 3F; CF3),
–63.45 (sept, J(F,F)=13.2 Hz, 3F; CF3), –63.87 (dq, J(F,F)=13.2 Hz and
J(H,F)=2.7 Hz, 3F; CF3), –71.80 ppm (q, J(F,F)=12.1 Hz, 3F; CF3);
UV/Vis (toluene): λmax=305, 394, 417, 452 nm; MALDI MS: m/z (%):
1393.0 (100) [M–{CH(CO2Et)2}–], 1552.0 (5) [M–].
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30–31.
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N. S. Ovchinnikova, A. A. Goryunkov, P. A. Khavrel, N. M. Belov, M. G.
Apenova, I. N. Ioffe, M. A. Yurovskaya, S. I. Troyanov, L. N. Sidorov, E.
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Compound IV, С70(CF3)8[C(CO2Et)2]: tR 5.3 min (Cosmosil Buckyprep
4.6 mm I.D. × 25 cm, toluene–hexane, 1:1 (v/v), 1 mL min–1); 1H NMR
(400.3 MHz, CDCl3, 25 °C, TMS): =4.49 (dq, 3J(H,H)=7.1 Hz,
2J(H,H)=10.6, 2H; CH2), 4.45 (dq, 3J(H,H)=7.1 Hz, 2J(H,H)=10.6 Hz, 2H;
CH2), 1.41 (t, 3J(H,H)=7.1 Hz, 3H; CH3), 1.32 ppm (t, 3J(H,H)=7.1 Hz, 3H;
CH3); 19F NMR (376.5 MHz, CDCl3, 25 °C, C6F6): =–61.30 (m, 6F; CF3),
–61.60 (sept, J(F,F)=13.5 Hz, 3F; CF3), –62.36 (m, 6F; CF3), –62.78
(sept, J(F,F)=12.4 Hz, 3F; CF3), –68.83 (q, J(F,F)=11.0 Hz, 3F; CF3), –
69.07 ppm (br. q, J(F,F)=10.4 Hz, 3F; CF3); UV/Vis (toluene): λmax=388,
417, 458, 484, 516, 564, 612 nm; MALDI MS: m/z (%): 1481.0 (4) [M–
CF3–], 1494.3 (6) [M*–CF3–], 1550.0 (100) [M–].
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Acknowledgements
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The authors are grateful Sergey A. Sokolov for HRMS analysis.
This work was partially supported by the Russian Foundation for
Basic Research (projects nos. 12-03-31513, 13-03-00311, 15-
03-05083) and the Ministry of Education and Science of the
Russian Federation (project MD-5540.2013.3). The reported
study was supported by the Supercomputing Center of
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Notes
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‡ Hereinafter, the isomeric names are given in the following format:
“symmetry–notation of the addittion pattern–composition”, e.g. Cs-p7-
C70(CF3)8. Abbrevations used in the notation for the addition patterns: p,
para, and m, meta, denote C6(CF3)2 hexagon with 1,4- and 1,3-situated CF3
groups, respectively; superscript denotes the number of similar edge-
sharing fragments in a chain, a discontinuity in an addition pattern is
denoted by comma.
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Keywords: nucleophilic cyclopropanation • reaction mechanism
• trifluoromethylfullerenes • DFT calculations • structure
elucidation
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