The Journal of Organic Chemistry
Article
funnel with EtOAc (200 mL). The layers were separated and the
aqueous layer was extracted with further EtOAc (3 × 200 mL). The
combined organic layers were dried (Na2SO4), filtered and
concentrated in vacuo to yield a pale-brown oil (12.8 g), which was
purified by column chromatography (hexane) to afford 6-chloro-1H-
indene as a colorless oil (10.0 g, 82%); IR νmax (neat) 3129−2764 (C−
H), 1606 (Ar), 1583 (Ar), 1547 (Ar), 1457, 1416, 1389, 1357, 1327,
ORCID
Notes
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
■
1
1288, 1270, 1225, 1204 cm−1; H NMR (400 MHz, CDCl3) δ 7.45
Financial support from subsidy program for innovative business
promotion of Shizuoka Prefecture, Japan SAN-Pro and Japan
Trust International Research Cooperation Project is gratefully
acknowledged. We thank Mio Ohnuma and Dr. Hiroaki Sato
for conducting MALDI-MS and HR-MALDI-MS analyses,
respectively. We thank Dr. Reiko Azumi and Dr. Youfeng Yue
for helpful discussions.
(1H, br. s, CH), 7.31 (1H, d, J = 7.9 Hz, CH), 7.27−7.24 (1H, m,
CH), 6.86−6.84 (1H, m, CH), 6.58−6.56 (1H, m, CH), 3.40 (2H, s,
CH2); 13C NMR (101 MHz, CDCl3) δ 145.4 (C), 143.3 (C), 134.6
(CH), 131.4 (CH), 130.6 (C), 126.4 (CH), 124.4 (CH), 121.6 (CH),
39.0 (CH2); HRMS m/z calculated for C9H7Cl ([M]+), 150.0236;
found, 150.0237. 1H and 13C NMR data are consistent with the
literature.41
5-Chloro-indene-C60 Monoadduct. According to the general
procedure, to C60 fullerene (705 mg, 0.98 mmol) was added 6-chloro-
1H-indene (10.8 g, ∼9.9 mL, 0.072 mol, 73 equiv) and o-xylene (170.1
mL) to prepare a 5.4 mM solution in C60. The resultant mixture was
sonicated until clear (∼2 h), filtered, covered in foil and passed
through the microwave flow reactor at 0.9 mL/min heating to 190 °C
(130 W). Once stable temperature had been reached, 10 mL of
reaction mixture was discarded to waste (>1 residence time) and then
the reaction mixture was collected for 1 h (38.5 mL aliquot, overall
flow rate 0.6 mL/min). A further 0.2 mL of reaction mixture was
collected and diluted with 0.8 mL of o-xylene to prepare a 1 mM
solution. By comparison with pure 5-chloro-indene-C60 monoadduct
(IC60MA-chloro) obtained following purification (1 mM in o-xylene),
HPLC revealed a 53% yield of IC60MA-chloro. The 38.5 mL aliquot
was concentrated to dryness in vacuo. A further 2.5 mL of reaction
mixture was collected and concentrated to dryness before adding 1,3,5-
trimethoxybenzene (2.3 mg, 10 mol %). 1H NMR revealed a 51% yield
of IC60MA-chloro. Purification by column chromatography (a gradient
of CHCl3/hexane 20:1 to 5:1) gave IC60MA-chloro as a dark-brown
solid (39.5 mg, 45.3 μmol, 22% based on the theoretical max 209.4
μmol collected); IR νmax (KBr pellet) 2967−2850, 1718, 1600, 1578,
1559, 1541, 1463, 1427, 1386, 1322, 1279, 1260, 1213 cm−1; UV−vis
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ASSOCIATED CONTENT
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S
* Supporting Information
The Supporting Information is available free of charge on the
MW flow reactor details, HPLC methods, DoE studies,
MW versus thermal heating flow reaction results, HPLC
elugrams, NMR spectra and MS-MALDI spectra of
fullerene derivatives (PDF)
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AUTHOR INFORMATION
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Corresponding Authors
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F
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