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2CO is 68 kcal/mol; thus, the sensitized process is energywise feasible.
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1H NMR spectroscopy; the product ratio was ca. 91:9.
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3643085352
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note
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Although for the corresponding spirocyclopropane-substituted 1,3 diradical the housane persists (ref 17), the failure to observe the housane 2 derives presumably from the fact that epoxide ring is cleaved ca. 100 times faster than the cyclopropane ring (ref 18).
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For dipolar character in singlet diradicals see (a) Salem, L.; Row and C. Angew. Chem., Int. Ed. Engl. 1972, 11, 92. (b) Jean, Y.; Salem, L. J. Chem. Soc., Chem. Commun. 1971, 382. (c) Horsley, J.A.; Jean Y., Moser, C.; Salem, L.; Sevens, R. M.; Wright, J. S. J. Am. Chem. Soc. 1972, 94, 279.
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For dipolar character in singlet diradicals see (a) Salem, L.; Row and C. Angew. Chem., Int. Ed. Engl. 1972, 11, 92. (b) Jean, Y.; Salem, L. J. Chem. Soc., Chem. Commun. 1971, 382. (c) Horsley, J.A.; Jean Y., Moser, C.; Salem, L.; Sevens, R. M.; Wright, J. S. J. Am. Chem. Soc. 1972, 94, 279.
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52
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10 analogue (-23.0 kcal/mol, ref 31).
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For stereoelectronic effects on cyclopropane-ring cleavage, see (a) Kochi, J. K.; Krusic, P. J.; Eaton, D. R. J. Am. Chem. Soc. 1969, 91, 1877. (b) Friedrich, E. C. J. Org. Chem. 1969, 34, 528. (c) Friedrich, E. C.; Holmstead, R. L. J. Org. Chem. 1971, 36, 971. (d) Friedrich, E. C.; Holmstead, R. L. J. Org. Chem. 1972, 37, 2546. (e) Reference 20d.
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For stereoelectronic effects on cyclopropane-ring cleavage, see (a) Kochi, J. K.; Krusic, P. J.; Eaton, D. R. J. Am. Chem. Soc. 1969, 91, 1877. (b) Friedrich, E. C. J. Org. Chem. 1969, 34, 528. (c) Friedrich, E. C.; Holmstead, R. L. J. Org. Chem. 1971, 36, 971. (d) Friedrich, E. C.; Holmstead, R. L. J. Org. Chem. 1972, 37, 2546. (e) Reference 20d.
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