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1
-
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0039825089
-
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Semiempirical SCF MO calculations predict that 1 has a bond-alternating structure and is only weakly stabilized (3.4 kcal/mol) by π-electron delocalizalion: (a) Kasino, L.; Majerski, Z.; Trinajstic, N. Z Naturforsch., Teil A 1968, 23, 192.
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Kasino, L.1
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(c) Zambeili, N.; Trinaistic, N. Z. Naturforsch., Teil B 1971, 26, 1007.
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9
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(a) Chapman, O. L.; Smith, H. G.; King, R. W.; Pasto, D. J.; Stoner, M. R. J. Am. Chem. Soc. 1963, 85, 2031.
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(b) Chapman, O. L.; Busman, S. C.; Trueblood, K. N. J. Am. Chem. Soc. 1979, 101, 7067.
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For a preliminary account of a portion of this work, see: Ohkita, M.; Tsuji, T.; Nishida, S. J. Chem. Soc., Chem. Commun. 1989, 924.
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Compound 2 has previously been obtained via an independent route: Ohkita, M.; Tsuji, T.; Suzuki, M.; Murakami, M.; Nishida, S. J. Org. Chem. 1990, 55, 1506.
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21
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33947550049
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max at 355, 374, 395, 420, 442, 463, 488, and 523 nm in methylcyclohexane/isopentane (4:1) and at 352, 370, 388, 430 (sh), 447, 470, and 492 nm in ethanol. The bathochromic shifts of the absorption bands in the less polar former solvent suggest that 1 may be less polarized in the excited state than in the ground state: Bayliss, N. S.; McRae, E. G. J. Phys. Chem. 1954, 58, 1002.
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For acidity constants of carboxylic acids in organic solvents, see: (a) Calder, G. V.; Barton, T. J. J. Chem. Educ. 1971, 48, 338.
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Schuster, D.I.1
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Cyclopentenones bearing a radical stabilizing group at C-5 position undergo α-cleavage to afford the corresponding cyclopropyl ketenes: Agosta, W. C.; Smith, A. B., III J. Am. Chem. Soc. 1971, 93, 5513.
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An activation energy of 18.9 ± 0.2 kcal/mol has been reported for the thermal rearrangement of 5,5-dimethylbenzobicyclo[2.1.0]pent-2-ene to 2,2-dimethylisoindene: Dolbier, W. R., Jr.; Matsui, K.; Dewey, H. J.; Horák, D. V.; Michl, J. J. Am. Chem. Soc. 1979, 101, 2136.
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Cyclopentenones bearing an aromatic ring at C-4 position undergo di-π-methane rearrangement to yield substituted bicyclo[2.1.0]pentan-2-ones which subsequently undergo spontaneous cycloreversion to ketene derivatives at room temperature: Zimmermann, H. E.; Little, R. D. J. Am. Chem. Soc. 1974, 96, 4623.
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0345338096
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note
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Irradiation of microcrystalline 2 in a KBr pellet resulted in the [2 + 2] photodimerization.
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55
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0345338086
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Orverlay analysis (minimization of sum of non-hydrogen atom displacements) was performed on the molecular modeling system CS Chem 3D Pro V. 3.5 (CambridgeSoft Corp.; Cambridge, MA) using the PM3 optimized geometries.
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61
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0011422966
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