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Crystal structures and photoreactivity of trans- and cis-valerophenone diperoxides

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Abstract

The crystal structures of valerophenone diperoxides trans-1 and cis-1 were elucidated by X-ray crystallographic analysis. The 1,2,4,5-tetraoxane rings of both compounds adopt chair conformations. Intermolecular CH···O hydrogen bond, π–π, and CH/π interactions exist in cis-1, whereas only CH/π interactions exist in trans-1. In the asymmetric unit of the crystal, a half molecule exists for trans-1, while one molecule for cis-1 which shows whole-molecule disorder. Solid-state photolysis (at 254 nm) or solution-state thermolysis (at 150 °C) of trans-1 and cis-1 produced valerophenone (2) and butyl benzoate (3). Rationalization of the solid-state photoreactivity of the diperoxides by their crystal structures was attempted.

Index abstract

The crystal structure of cis-valerophenone diperoxide (cis-1) shows whole molecule disorder. Its lower photoreactivity in the solid state is explained by the locally narrow and rigid reaction cavity due to the Ph–Ph π–π overlap.

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Notes

  1. 1.

    Referring to the Cambridge Crystallographic Database (CSD Ver. 5.32), 21 crystals containing 1,2,4,5-tetraoxane have been reported. Their refcodes are as follows: AROZEM, BMTTRX, CEDDOE, DPTOCH, GAGTEO, GAGTIS, GAHXIW, IBEJAA, LEVSOV, LEVSUB, MUPTEW, QINDAS, QINDEW, QINDIA, SCHOCH10, SCHOHX10, SIFGAQ, SPOCTC10, SPOCTC10, VIBHIX, and YIZFET. We calculated the average bond lengths by using these data.

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Acknowledgments

The authors are indebted to Professor Yoshiki Matsuura (Osaka University), who first solved the crystal structure of trans-1. We also thank Dr. Sadayuki Asaoka for his assistance in doing photolysis experiments.

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Correspondence to Hiroki Takahashi.

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Takahashi, H., Ito, Y. Crystal structures and photoreactivity of trans- and cis-valerophenone diperoxides. Struct Chem 23, 441–449 (2012). https://doi.org/10.1007/s11224-011-9887-8

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Keywords

  • 1,2,4,5-Tetraoxane
  • X-ray analysis
  • Intermolecular interaction
  • Photolysis
  • Thermolysis