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(Z)-[6]Paracycloph-3-ene^†

Corresponding Author

Dr. Yoshito Tobe

Department of Applied Fine Chemistry, Faculty of Engineering Osaka University, Suita, Osaka 565 (Japan)

Department of Applied Fine Chemistry, Faculty of Engineering Osaka University, Suita, Osaka 565 (Japan)Search for more papers by this author

Ken-ichi Ueda,

Ken-ichi Ueda

Department of Applied Fine Chemistry, Faculty of Engineering Osaka University, Suita, Osaka 565 (Japan)

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Dr. Kiyomi Kakiuchi,

Dr. Kiyomi Kakiuchi

Department of Applied Fine Chemistry, Faculty of Engineering Osaka University, Suita, Osaka 565 (Japan)

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Dr. Yoshinobu Odaira,

Dr. Yoshinobu Odaira

Department of Applied Fine Chemistry, Faculty of Engineering Osaka University, Suita, Osaka 565 (Japan)

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Dr. Yoshito Tobe,

Corresponding Author

Dr. Yoshito Tobe

Department of Applied Fine Chemistry, Faculty of Engineering Osaka University, Suita, Osaka 565 (Japan)

Department of Applied Fine Chemistry, Faculty of Engineering Osaka University, Suita, Osaka 565 (Japan)Search for more papers by this author

Ken-ichi Ueda,

Ken-ichi Ueda

Department of Applied Fine Chemistry, Faculty of Engineering Osaka University, Suita, Osaka 565 (Japan)

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Dr. Kiyomi Kakiuchi,

Dr. Kiyomi Kakiuchi

Department of Applied Fine Chemistry, Faculty of Engineering Osaka University, Suita, Osaka 565 (Japan)

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Dr. Yoshinobu Odaira,

Dr. Yoshinobu Odaira

Department of Applied Fine Chemistry, Faculty of Engineering Osaka University, Suita, Osaka 565 (Japan)

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First published: April 1986

https://doi.org/10.1002/anie.198603691

Citations: 6

^†

We are grateful to Dr. Y. Takai of the Institute of Scientific and Industrial Research, Osaka University for measuring the ¹H-NMR spectrum and for valuable discussions.

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The smallest isoiable paracyclophane, the title compound 1, was obtained by thermal valence isomerization of the Dewar benzene isomer 2. The ¹H-NMR and, in particular, the UV spectra indicate that the benzene ring in 1 deviates much more strongly from planarity than in [6]paracyclophane.

References

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7 IR: v̄ = 790, 730, 690 cm⁻¹; MS: m/z 158 (M^⊕, 10%), 104 (M^⊕-C₄H₆, 100%): ¹H-NMR (360 MHz, CDCl₃): δ = 7.20 (2H, dd, ⁴J = 1.0, ⁵J = 0.9 Hz, H⁸, H⁹), 7.07 (2H, dd, ⁴J = 1.0, ⁵J = 0.9 Hz, H¹¹, H¹²), 4.68 (2H, XX' of AA'BB'XX', ³J = 12.2, ³J = 11.9, ³J ≈ 5, ⁴J = −0.8, ⁴J ≈ −1Hz, H⁴, H⁴), 2.79 (2H, ddd, ²J = 12.0, ³J = 3.5, ³J = 3.5 Hz, H¹, H⁶), 2.26 (2H, ddd, ²J = 12.0, ³J = 12.0, ³J = 3.0 Hz, H¹, H⁶), 1.88 (2H, m, H²′, H⁵′), 1.01 (2H, m, H², H⁵). Upon irradiation at δ = 4.68, the multiplets at 1.88 and 1.01 changed into ddd with ²j = 12.0, ³J = 3.5, ³J = 3.0 Hz and ²J = 12.0, ³j = 12.0, ³j = 3.5 Hz, respectively. ¹³C-NMR (CDCl₃): δ = 142.9 (s), 136.0 (d), 132.1 (d), 132.0 (d), 35.8 (t), 34.2 (t).
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8 [6]Paracycophane: UV (hexane): λ_max = 299 (ϵ = 460), 251 (6500), and 214 (17000) nm.
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Volume25, Issue4

April 1986

Pages 369-371

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