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19
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33646462923
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note
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(Z)-Biindenylidenes should be deformed to a nonplanar conformation because of the steric hindrance between the two inner peri hydrogen atoms. According to the calculations by the DFT method at the B3LYP/6-31G** level, twist angles of the central double bond of (E)- and (Z)-biindenylidenes were estimated to be 0° and 14.9°, respectively.
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20
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33646454758
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note
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The DFT calculations at the B3LYP/6-31G** level predict that the twist angles of the central double bond of (Z)-isomers of 9a, 9b, and 9c are 11.4°, 6.1°, and 8.4°, respectively, whereas those of both 9d and 9e are 0°. The corresponding angles of the (E)-isomers, (E)-9a-e, are essentially 0°.
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21
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25444522954
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Recently, the synthesis of (Z)-vinylthiophenes was reported: Hayford, A.; Kaloko, J.. Jr.; El-Kazaz, S.; Bass, G.; Harrison, C.; Corprew, T. Org. Lett. 2005, 7, 2671.
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Org. Lett.
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Hayford, A.1
Kaloko Jr., J.2
El-Kazaz, S.3
Bass, G.4
Harrison, C.5
Corprew, T.6
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23
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0031792119
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Uenishi, J.; Kawahama, R.; Yonemitsu, O.; Tsuji, J. J. Org. Chem. 1998, 63, 8965.
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Uenishi, J.1
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Tsuji, J.4
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24
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33646449838
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note
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1H NMR spectra, which showed sets of vinyl proton signals with J ∼ 16 Hz (δ 7.45 and 6.43 ppm for (E,Z)-2a and δ 7.36 and 6.38 ppm for (E,Z)-2b) and those with J ∼ 12 Hz (δ 6.96 and 5.73 ppm for (E,Z)-2a and δ 6.73 and 5.78 ppm for (E,Z)-2b).
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25
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33646448928
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note
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1H NMR spectrum of the residual fractions after isolation of pure (Z,Z)-isomer using preparative GPC. Thus, two doublet of doublet signals, due to the vinyl protons adjacent to the acetylenic carbons, with J ∼ 12 Hz (δ 5.84 and 5.71 ppm) and four doublet of doublet signals with J ∼ 16 Hz (δ 6.32, 6.25, 6.19, and 6.14 ppm) were assigned to the two (E,Z)- and (E,E)-isomers. The vinyl proton signals adjacent to aromatic rings, which appeared at lower field, were concealed by the aromatic proton signals. Simiarly, a doublet of doublet signal with J ∼ 16 Hz at δ 6.27 ppm and that with J ∼ 12 Hz at δ 5.85 ppm in the spectrum of 2d were ascribed to (E,Z)-2d.
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26
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3242689079
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Tietze, L. F.; Lücke, L. P.; Major, F.; Müller, P. Aust. J. Chem. 2004, 57, 635.
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Tietze, L.F.1
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Major, F.3
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0345686421
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Christophersen, C.; Begtrup, M.; Ebdrup, S.; Petersen, H.; Vedso, P. J. Org. Chem. 2003, 68, 9513.
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Christophersen, C.1
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Vedso, P.5
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28
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33646462489
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note
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3). It was not possible, therefore, to measure the absorption spectrum of (Z)-9a accurately.
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29
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33646440194
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note
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The low yields of 9c and 9d were partly ascribed to the decomposition of the products under the reaction conditions.
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32
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10344230249
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