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Reaction of C602- with Organic Halides Revisited in DMF: Proton Transfer from Water to RC60- and Unexpected Formation of 1,2-Dihydro[60]fullerenes.
- Source :
-
Journal of Organic Chemistry . 6/18/2010, Vol. 75 Issue 12, p4086-4094. 9p. - Publication Year :
- 2010
-
Abstract
- The reactions of dianionic C60 with organic halides, which have been studied extensively in benzonitrile (PhCN), are revisited in a different solvent medium, N,N-dimethylformamide (DMF), by using ArCH2Br (Ar = Ph, C6H4CH3, C6H4Br). Interestingly, instead of the 1,4-R2C60 adducts, which are the typical products when the reactions are carried out in PhCN, the 1,2-dihydro[60]fullerenes (1,2-HRC60) have been obtained as the major products in DMF, except for the case of o-CH3C6H4CH2Br probably due to the steric effect. The obtained 1,2-dihydro[6Q]fullerenes have been characterized with single-crystal diffraction, 1H and 13C NMR, high-resolution mass spectrometry (HRMS), and UV-vis. Further examination with deuterated reagents including PhCD2Br, DMF-d7, and D2O has revealed that the fullerenyl hydrogen of 1,2-dihydrofullerenes originates from traces of water residue in DMF. When the reaction is re-examined in PhCN with the addition of an excessive amount of water, the yield of I ,2-dihydrofullerene increases significantly, but is still lower compared with that obtained in DMF, demonstrating a considerable solvent effect on the reactivity of C602-. A possible mechanism accounting for such a difference is proposed. The work has presented an alternative protocol for effective preparation of 1,2-dihydro[60]fullerenes, and may also provide clues toward a better understanding of the proton transfer process for anionic C60-mediated reducing reactions involving H2O. [ABSTRACT FROM AUTHOR]
Details
- Language :
- English
- ISSN :
- 00223263
- Volume :
- 75
- Issue :
- 12
- Database :
- Academic Search Index
- Journal :
- Journal of Organic Chemistry
- Publication Type :
- Academic Journal
- Accession number :
- 53482354
- Full Text :
- https://doi.org/10.1021/jo100430a