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to obtain the desired product. All isolated products matched
spectroscopic data reported previously in the literature (see ESI).
2011, 21, 3443e3447.
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9336e9344.
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4.4. Oxidation of hydrocarbons possessing methyl or
methylene groups
In a typical preparation, a 7.5 mL vial was charged with GO
(100 mg), substrate (50 mg), CHCl3 (0.5 mL) and a magnetic stir bar.
The vial was then sealed with a Teflon-lined cap under ambient at-
mosphere and heated at 70 ꢀC,120 ꢀC or 120 ꢀC for 24 h. The reaction
mixture was then cooled to room temperature and washed with
CH2Cl2 (50 mL). The filtrate was collected and the solvent was re-
moved under vacuum to obtain the crude product, which was then
purified by silica chromatography (CH2Cl2, hexanes, EtOAc/CH2Cl2 or
CH2Cl2/hexanes as the eluent). The oxidation reactions involving tol-
uene, 4-nitrotoluene, cyclohexadiene, cyclohexene, and cyclohexane
were performed using CDCl3 instead of CHCl3 and conversions were
determined directly by 1H NMR spectroscopy. All products matched
spectroscopic data reported previously in the literature (see ESI).
13. (a) Baeckvall, J. E.; Akermark, B.; Ljunggren, S. O. J. Am. Chem. Soc. 1979, 101,
2411e2416; (b) Smidt, J.; Hafner, W.; Jira, R.; Sedlmeier, J.; Sieber, R.; Ruttinger,
R.; Kojer, H. Angew. Chem. 1959, 71, 176e182.
14. In order to determine whether a transition metal impurity in the GO was re-
sponsible for the observed reactivity, the as-prepared GO was analyzed by
atomic absorption (AA) spectrometry and inductively coupled plasma mass
spectrometry (ICP-MS). No measurable manganese (used in the preparation of
GO) was observed via AA, and the Mn content (analyzed at a concentration of 0.
05 mg mLꢂ1 in a 1% aqueous HNO3 solution) was measured to be 76 ppb via
ICP-MS. Other metal impurities found in low concentrations include: Al
(25 ppb), Ba (1 ppb), and Pb (1 ppb).
15. In addition to the desired product, analysis of the resulting crude reaction
mixture via 1H NMR spectroscopy revealed the presence of cis-stilbene, trans-
stilbene (7%), a small amount of benzaldehyde (4%) and benzoic acid (<2%) as
by-products.
16. trans-Stilbene was found to be unreactive under the conditions described
herein.
17. Under these conditions, we surmise that the increased yields of un-
functionalized stilbenes may be due to side reactions of GO with the functional
groups present on the derivatives of cis-stilbene. The use of lower GO loadings
or lower temperatures may minimize these side reactions, though such varia-
tions have not been exhaustively explored.
Acknowledgements
We gratefully acknowledge support for this work provided by
the National Science Foundation (grant No. DMR-0907324) and the
Robert A. Welch Foundation (grant No. F-1621). These data include
MOL files and InChIKeys of the most important compounds de-
scribed in this article.
18. (a) Astin, S.; Moulds, L. de V.; Riley, H. L. J. Chem. Soc. 1935, 901e904; (b) Fir-
ouzabadi, H.; Sardarian, A. R.; Moosavipour, H.; Afshari, G. M. Synthesis 1986,
285e288.
Supplementary data
19. GO loadings of less than 200 wt % were found to be ineffective in the ox-
idation of the hydrocarbons bearing methyl or methylene groups shown in
Table 4.
Supplementary data related to this article can be found online at
20. Analysis by FT-IR (KBr) and powder conductivity of the GO recovered after re-
action with diphenylmethane revealed that the carbon material was reduced,
consistent with our previous results (see the Supplementary data, Figs. S1eS3,).11
21. Similar reactivity was observed when multi-walled carbon nanotubes
(MWCNTs) were used to effect the oxidative dehydrogenation of 9,10-
dihydroanthracene.23,26
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