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ring was found to lower the photocycloreversion quantum yields.
Furthermore, 3b was thermally stable even at 100 °C in
acetonitrile.34
3. Conclusion
We found that the closed-ring isomer of the diarylperfluoro-
cyclopentene bearing diethylamino group causes the substitution
reaction with primary alcohols at room temperature. The reaction
products with methanol and ethylene glycol were isolated and
their structures were identified by 1H NMR, mass spectrometry,
and X-ray crystallographic analysis. It was revealed that two fluo-
rine atoms were replaced with alkoxy groups. The absorption max-
ima of the alkoxy-substituted diarylethenes were shifted to shorter
wavelength compared with the original diarylperfluorocyclopen-
tene. In addition, the photocycloreversion quantum yields de-
creased with the substitution of the alkoxy groups. We have
succeeded in changing a photochromic system by the substitution
reaction with the alcohols under the mild condition.
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32. 2a: 1H NMR (300 MHz, CDCl3): d = 1.18 (t, J = 7.2 Hz, 6H, CH2CH3), 1.92 (s, 3H,
CH3), 1.95 (s, 3H, CH3), 3.38 (q, J = 7.2 Hz, 4H, CH2CH3), 3.74 (s, 3H, OCH3), 6.65
(d, J = 8.8 Hz, 2H, aromatic H), 7.08 (s, 1H, thienyl H), 7.29–7.40 (m, 6H,
aromatic H), 7.54 (d, J = 8.8 Hz, 2H, aromatic H). MS m/z = 603 (M+).
3a: 1H NMR (300 MHz, CDCl3): d = 1.18 (t, J = 7.2 Hz, 6H, CH2CH3), 1.92 (s, 3H,
CH3), 1.95 (s, 3H, CH3), 3.38 (q, J = 7.2 Hz, 4H, CH2CH3), 3.39 (s, 6H, OCH3), 6.65
(d, J = 8.8 Hz, 2H, aromatic H), 7.08 (s, 1H, thienyl H), 7.29–7.40 (m, 6H,
aromatic H), 7.54 (d, J = 8.8 Hz, 2H, aromatic H). MS m/z = 615 (M+).
33. 4b was obtained by the substitution reaction of 1b with ethylene glycol. Upon
irradiation with visible light before the HPLC analysis, 4b changed to 4a.
4a: 1H NMR (300 MHz, CDCl3): d = 1.18 (t, J = 7.2 Hz, 6H, CH2CH3), 1.92 (s, 3H,
CH3), 1.95 (s, 3H, CH3), 3.38 (q, J = 7.2 Hz, 4H, CH2CH3), 4.13 (m, 4H, OCH2CH2O),
6.65 (d, J = 8.8 Hz, 2H, aromatic H), 7.08 (s, 1H, thienyl H), 7.29–7.40 (m, 6H,
aromatic H), 7.54 (d, J = 8.8 Hz, 2H, aromatic H). MS m/z = 613 (M+).
34. The thermal cycloreversion reaction of 3b proceeded in only less than 1% for
5 h at 100 °C in acetonitrile, whereas 1b changed to 1a in 20% conversion under
the same conditions.
Acknowledgments
This work was partly supported by a Grant-in-Aid for Scientific
Research on Priority Area ‘Strong Photon-Molecule Coupling Fields’
(470) (No. 21020032) from the Ministry of Education, Culture,
Sports, Science, and Technology of Japan.
References and notes
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Elsevier: Amsterdam, 2003.