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Photochromic dithienylethenes with extended π-systems

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Abstract

The syntheses and photochromic properties of six new photochromic dithienylethenes with differently substituted conjugated double bonds at the thiophene units are presented.

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Notes and references

  1. M. Irie, Chem. Rev., 2000, 100, 1658.

    Google Scholar 

  2. A. Osuka, D. Fujikane, H. Shinmori, S. Kobatake and M. Irie, J. Org. Chem., 2001, 66, 3913.

    Article  CAS  Google Scholar 

  3. Compound 5 was purchased from Aldrich. Compounds 6 and 7 were prepared by reacting equimolar amounts of the corresponding bromo-compound with triphenylphosphine in boiling toluene overnight. After cooling to room temperature, the precipitate is filtered, washed with cyclohexane and dried in air. The phosphonium salts 6 and 7 were obtained in 90% and 95% yield.

  4. G. Belluci, C. Chiappe and G. L. Moro, Tetrahedron Lett., 1996, 37, 4225.

    Article  Google Scholar 

  5. Data for 2: reaction time 3 h, yield 63%, δH(500 MHz, CDCl3) 1.96 (6H, s, CH3), 3.81 (6H, s, OCH3), 6.16 (2H, d, J 15.8, ArCH=CH), 7.20 (2H, s, ArH), 7.69 (2H, d, J 15.8, ArCH?CH); δC (125 MHz, CDCl3) 14.8, 26.9, 51.8, 117.5, 125.7, 130.4, 136.1, 137.7, 144.8, 166.8; ESI-HRMS: m/z calc. for C23H18O4S2F6Na+: 559.04429 ([M + Na]+), found: 559.04405. 3: reaction time 1.5 h, yield 60% as a mixture of isomers; E,E,E,E-isomer separated by column chromatography on silica gel eluting with cyclohexane-ethyl acetate 9:1 (v/v): δH(500 MHz, CDCl3) 1.29 (6 H, t, J 7.1, OCH2CH3), 1.90 (6 H, s, CH3), 4.20 (4H, q, J 7.1, OCH2CH3), 5.94 (2H, d, J 15.1, ArCH=CH), 6.53 (2H, dd, J 15.1 and 11.3, ArCH=CH), 6.87 (2H, d, J 15.1, EtO2CCH=CH), 7.02 (2H, s, ArH), 7.33 (2H, dd, J 15.1 and 11.3, EtO2CCH=CH); δC(125 MHz, CDCl3) 14.3, 14.8, 60.4, 121.7, 124.2, 125.7, 126.5, 127.7, 128.1, 131.5,139.2,139.6, 143.1, 143.4, 166.8; ESI-HRMS: m/z calc. for C29H26O4S2F6Na+: 639.10689 ([M + Na]+), found: 639.10681. Data for 4: reaction time 3 h; yield 80% as a mixture of isomers; Z,Z-isomer separated by column chromatography on silica gel eluting with cyclohexane-ethyl acetate 9:1 (v/v). The NMR spectra show signals of another isomer (20% by integration, δ values not given): δH(500 MHz, CDCl3) 1.39 (6 H, t, J 7.1, OCH2CH3), 1.73 (6 H, s, CH3), 4.37 (4H, q, J 7.1, OCH2CH3), 6.55 (2H, d, J 11.9, CH=CHPhCO2Et), 6.62 (2H, d, J 11.9, CH=CHPhCO2Et), 6.9 (2H, s, ArH), 7.37 (4H, d, J 8.2, ArH), 8.00 (4H, d, J 8.2, ArH); δC(125 MHz, CDCl3) 14.3, 14.4, 61.0, 123.9, 124.3, 126.1, 128.2, 128.6, 128.7, 129.7, 129.8, 130.0, 137.3, 141.6, 142.3, 166.3; ESI-HRMS: m/z calc. for C37H30O4S2F6Na+: 739.13819 ([M + Na]+), found: 739.13686.

  6. L. N. Lucas, J. van Esch, R. M. Kellogg and B. L. Feringa, Chem. Commun., 1998, 2313.

    Google Scholar 

  7. Data for 9: reaction time 24 h; crude product purified by column chromatography on silica gel eluting with cyclohexane-ethyl acetate 4:1 (v/v), yield 20%: δH(500 MHz, CDCl3) 1.93 (6 H, s, CH3), 2.03 (2H, m, CH2CH2CH2), 2.74 (4H, m, CH2CH2CH2), 3.73 (6 H, s, OCH3), 6.01 (2H, d, J 15.7, ArCH2=CH2), 6.87 (2H, s, ArH), 7.60 (2H, d, J 15.7, ArCH2=CH2); δC (125 MHz, CDCl3): 14.8, 22.9, 38.3, 51.6, 115.3, 132.3, 134.6, 135.6, 136.7, 137.4, 138.9, 167.4; EI-HRMS: m/z calc. for C23H24O4S2: 428.11160, found: C23H24O4S2: 428.11020. Data for 10: reaction time 24 h, yield 22% as a mixture of isomers which were separated by column chromatography on silica gel eluting with cyclohexane-ethyl acetate 9:1 (v/v): Data for (E,Z,E,E-isomer): δH(500 MHz, CDCl3) 1.28 (6 H, dt, J 6.9, CH2CH3), 1.92 (3H, s, CH3), 1.94 (3H, s, CH3), 2.03 (2H, m, CH2CH2CH2), 2.75 (4H, m, CH2CH2CH2), 4.20 (4H, m, CH2CH3), 5.87 (1H, d, J 15.1, ArCH=CH), 5.96 (1H, d, J 15.1, ArCH=CH), 6.08 (1H, dd, J 11.4, ArCH=CH) 6.45 (1H, dd, J 15.1, ArCH=CH) 6.59 (1H, d, J 11.4, CH=CHCO2Et) 6.76 (1H, s, ArH) 6.77 (1H, s, ArH) 6.84 (1H, d, J 15.1, CH=CHCO2Et), 7.32 (1H, dd, J 15.1, CH=CHCO2Et), 7.98 (1H, dd, J 15.1, CH=CHCO2Et); δC (125 MHz, CDCl3): 14.3, 14.5, 14.8, 22.9, 26.9, 38.4, 38.5, 60.3, 60.4, 120.1, 122.7, 1123.2, 124.6, 129.5, 130.0, 131.7, 133.1, 134.5, 135.5, 135.9, 136.6, 137.1, 137.4, 138.6, 140.2, 144.3, 167.0, 167.2; EI-HRMS: m/z calc. for C29H32O4S2: 508.17420, found C29H32O4S2: 508.17530. Data for 11: reaction time 12 h; yield 33% as a mixture of isomers which were partially separated by column chromatography on silica gel eluting with cyclohexane-ethyl acetate 9:1 (v/v): δH(E,E-isomer)(500 MHz, CDCl3) 1.37 (6H, t, J 6.9 CH2CH3), 1.96 (6 H, s, CH3), 2.04 (2H, m, CH2CH2CH2), 2.77 (4H, m, CH2CH2CH2), 4.35 (4H, q, J 6.9, CH2CH3), 6.75 (2H, d, J 16.3, ArCH2=CH2), 6.78 (2H, s, ArH), 7.17 (2H, d, J 16.3, ArCH2=CH2), 7.44 (4H, d, J 8.5 ArH), 7.96 (4H, d, J 8.5, ArH) EI-HRMS: m/z calc. for C37H36O4S2: 608.20550, found C37H36O4S2: 608.20670.

  8. Compound 9 does not give significant amounts of closed-ring isomer even after irradiation with 420 nm light for several minutes.

  9. For example: comparison of the absorption spectra of the pure E,E,E,E- and E,Z,E,E-isomers of compound 10 (purity checked by NMR) do not show any differences.

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  1. Organische Chemie I, Universität Bielefeld, Postfach 100131, 33501, Bielefeld, Germany

    Oliver Tosic, Kai Altenhöner & Jochen Mattay

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  1. Oliver Tosic
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  2. Kai Altenhöner
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  3. Jochen Mattay
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Correspondence to Jochen Mattay.

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This paper is part of a themed issue on synthetic and natural photoswitches.

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Tosic, O., Altenhöner, K. & Mattay, J. Photochromic dithienylethenes with extended π-systems. Photochem Photobiol Sci 9, 128–130 (2010). https://doi.org/10.1039/b9pp00100j

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