Solid-state solvolysis induced via charge-transfer complexation by solid-phase grinding followed by contact with solvent vapor

Abstract

When 9-thienothienylfluoren-9-ol derivatives were ground together with DDQ then exposed to methanol vapor, solvolysis occurred to yield 9-methoxyfluorenes via the generation of a radical cation by solid-state single-electron transfer.

References

1. Reactivity in Molecular Crystals, ed. Y. Ohashi, VCH, Weinheim, 1993; W. Jones, in Oranic Molecular Solids, Properties and Applications, ed. W. Jones, CRN Press, NY, 1997, p. 149.
2. For a recent example, see: B. Goud and G. R. Desiraju, J. Chem. Res. (S), 1995, 244.
3. For recent examples, see: M. Kudoh, K. Naruchi, F. Akutsu and M. Miura, J. Chem. oc., Perkin Trans. 2, 1993, 555; N. B. Singh, N. P. Singh, V. A. Kumar and M. Nethaji, J. Chem. Soc., Perkin. Trans. 2, 1994, 361.
4. The photosolvolysis of fluorenols has been studied in detail. See for examples: P. Wan and E. Krogh, J. Am. Chem. Soc., 1989, 111, 4887; R. A. McClelland, N. Mathivanan and S. Steenken, J. Am. Chem. Soc., 1990, 112, 4857; A. K. Kolter and S. S. Wang, J. Am. Chem. Soc., 1963, 85, 114.
5. N. Hayashi, Y. Mazaki and K. Kobayashi, Terahedron Lett., 1994, 35, 5883.
6. DDQ has been known to catalyse the C–O bond cleavage of ethers and acetals. See for examples: A. Oku, M. Kinugasa and T. Kamada, Chem. Lett., 1993, 165; K. Tanemura, T. Suzuki and T. Horaguchi, Bull. Chem. Soc. Jpn., 1994, 67, 290; J. H. Penn and D.-L. Deng, Tetrahedron, 1992, 48, 4823.
7. A. K. Colter and S. S. Wang, J. Am. Chem. Soc., 1963, 85, 114.
8. M. Schmittel and A. Burghart, Angew. Chem., Int. Ed. Engl., 1997, 36, 2550.
9. For properties of 1c and 1d as a host compound, see: N. Hayashi, Y. Mazaki and K. Kobayashi, J. Org. Chem., 1995, 60, 6342; N. Hayashi, K. Kuruma, Y. Mazaki, T. Imakubo and K. Kobayashi, J. Am. Chem. Soc., 1998, 120, 3799 and references cited therein.
10. M. J. S. Dewar and A. Lepley, J. Am. Chem. Soc., 1961, 83, 4560; F. Toda and H. Miyamoto, Chem. Lett., 1995, 861.