Supporting Information

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1 Supporting Information Convenient Synthesis of 3-Vinyl and 3-Styryl Coumarins Joana Gordo, João Avó, António J. Parola, João Carlos Lima, António Pereira* and Paula S. Branco* REQUIMTE, Departamento de Química, Faculdade de Ciências e Tecnologia, FCT, Universidade Nova de Lisboa, Portugal and Centro de Química, Departamento de Química, Universidade de Évora, Évora, Portugal General methods and experimental procedures..s2 NMR and Massa spectra.... S6 Absorption and emission spectra... S48 Fluorescence decays...s49 Absorption and 1 H NMR of irradiated 3-vinylcoumarin (2a) S51 References S52 S1

2 13 C NMR spectra of [6,7]methylenedioxy-3-vinylcoumarin (2f). Electron impact mass spectra of [6,7]methylenedioxy-3-vinylcoumarin (2f). S31

3 High resolution electron impact mass spectra of [6,7]methylenedioxy-3-vinylcoumarin (2f). 1 H NMR spectra of (E)-3-styrylcoumarin (4a). S32

4 13 C NMR spectra of (E)-3-styrylcoumarin (4a). Electron impact mas spectra of (E)-3-styrylcoumarin (4a). S33

5 1 H NMR spectra of (E)-7-methoxy-3-styrylcoumarin (4b). 13 C NMR spectra of (E)-7-methoxy-3-styrylcoumarin (4b). S34

6 Electron impact mass spectra of (E)-7-methoxy-3-styrylcoumarin (4b). High resolution electron impact mass spectra of (E)-7-methoxy-3-styrylcoumarin (4b). S35

7 1 H NMR spectra of (E)-7- diethylamino-3-styrylcoumarin (4c). 13 C NMR spectra of (E)-7- diethylamino-3-styrylcoumarin (4c). S36

8 Electron impact mass spectra of (E)-7- diethylamino-3-styrylcoumarin (4c). High resolution electron impact mass spectra of (E)-7- diethylamino-3-styrylcoumarin (4c). S37

9 1 H NMR spectra of [6,7]methylenedioxy-3-styrylcoumarin (4d). 13 C NMR spectra of [6,7]methylenedioxy-3-styrylcoumarin (4d). S38

10 Electron impact mass spectra of [6,7]methylenedioxy-3-styrylcoumarin (4d). High resolution electron impact mass spectra of [6,7]methylenedioxy-3-styrylcoumarin (4d). S39

11 1 H NMR spectra of (E)-3-(4-nitrostyryl)coumarin (4e). 13 C NMR spectra of (E)-3-(4-nitrostyryl)coumarin (4e). S4

12 Electron impact mass spectra of (E)-3-(4-nitrostyryl)coumarin (4e). High resolution electron impact mass spectra of (E)-3-(4-nitrostyryl)coumarin (4e). S41

13 1 H NMR spectra of (E)-7-methoxy-3-(4-nitrostyryl)coumarin (4f). 13 C NMR spectra of (E)-7-methoxy-3-(4-nitrostyryl)coumarin (4f). S42

14 Electron impact mass spectra of (E)-7-methoxy-3-(4-nitrostyryl)coumarin (4f). High resolution electron impact mass spectra of (E)-7-methoxy-3-(4-nitrostyryl)coumarin (4f). S43

15 1 H NMR spectra of (E)-7- diethylamino -3-(4-nitrostyryl)coumarin (4g). 13 C NMR spectra of (E)-7- diethylamino -3-(4-nitrostyryl)coumarin (4g). S44

16 Electron impact mass spectra of (E)-7- diethylamino -3-(4-nitrostyryl)coumarin (4g). High resolution electron impact mass spectra of (E)-7- diethylamino -3-(4-nitrostyryl)coumarin (4g). S45

17 1 H NMR spectra of (E)-7-methoxy-3-(2-(naphathalen-1-yl)vinyl)coumarin (4h). 13 C NMR spectra of (E)-7-methoxy-3-(2-(naphathalen-1-yl)vinyl)coumarin (4h). S46

18 Electron impact mass spectra of (E)-7-methoxy-3-(2-(naphathalen-1-yl)vinyl)coumarin (4h). High resolution electron impact mass spectra of (E)-7-methoxy-3-(2-(naphathalen-1-yl)vinyl)coumarin (4h). S47

19 Absorption and emission spectra ε / M -1 cm -1 I / a.u. ε / M -1 cm -1 I / a.u. ε / M -1 cm -1 I / a.u ε / M -1 cm -1 I / a.u. ε / M -1 cm -1 I / a.u. ε / M -1 cm -1 I / a.u Absorbance (black line) and emission (red line) spectra of 3-vinyl coumarin derivatives ε / M -1 cm -1 I / a.u. ε / M -1 cm -1 I / a.u. ε / M -1 cm -1 I / a.u ε / M -1 cm -1 I / a.u. ε / M -1 cm -1 I / a.u ε / M -1 cm -1 I / a.u. ε / M -1 cm -1 I / a.u Absorbance and emission spectra of 3-styryl coumarin derivatives S48

20 Fluorescence decays Every sample was purified by HPLC-DAD prior to fluorescence measurements, due to the fact that previously recrystallized samples yielded multiple exponential decays during fluorescence lifetime determination. Upon this purification procedure, all the compounds exhibited, generally, larger Φ F values and the fluorescence decays, in most cases, yielded bi-exponential decay laws. Table S1. Fluorescent lifetime components of 3-vinyl coumarins in acetonitrile solutions coumarin τ 1 a) [ns] α 1 τ 2 a) [ns] α 2 2a b c d e f a) Fluorescence lifetime was determined by single photon counting technique. Decays were deconvoluted from the excitation pulse using Striker s Sand program. 2 Fluorescence lifetime decays (red line) and respective fittings (black line) of 3-vinyl coumarin derivatives S49

21 Table S2. Fluorescent lifetime components of 3-styryl coumarins in acetonitrile solutions coumarin τ 1 a) [ns] α 1 τ 2 a) [ns] α 2 4a b c d e f g < a) Fluorescence lifetime was determined by single photon counting technique. Decays were deconvoluted from the excitation pulse using Striker s Sand program. 2 Fluorescence lifetime decays (red line) and respective fittings (black line) of 3-styryl coumarin derivatives S5

22 Absorption and 1 H NMR of irradiated 3-vinylcoumarin (2a) 1 irradiation at 313 nm A Spectral variation of an irradiated solution of 2a, 2.3 mm in acetonitrile. An increasing number of spectra have been omitted for clarity towards the end of the reaction. 1 H NMR spectrum of 3-vinylcoumarin (2a) irradiated for 2 minutes at 313 nm. S51

23 References 1. Arbela, I. L., J. Photochem. 198, 14, (2), Striker, G.; Subramaniam, V.; Seidel, C. A. M.; Volkmer, A., Photochromicity and fluorescence lifetimes of green fluorescent protein. Journal of Physical Chemistry B 1999, 13, (4), Smith, W. E., Formylation of Aromatic-Compounds with hexamethylenetetramine and trifluoracetic acid. J. Org. Chem. 1972, 37, (24), 3972-&. 4. Lazzarato, L.; Donnola, M.; Rolando, B.; Marini, E.; Cena, C.; Coruzzi, G.; Guaita, E.; Morini, G.; Fruttero, R.; Gasco, A.; Biondi, S.; Ongini, E., Searching for new NO-donor aspirin-like molecules: A new class of nitrooxy-acyl derivatives of salicylic acid. J. Med. Chem. 28, 51, (6), Moghaddam, F. M.; Kiamehr, M.; Khodabakhshi, M. R.; Mirjafary, Z.; Fathi, S.; Saeidian, H., A new domino Knoevenagel-hetero-Diels-Alder reaction: an efficient catalyst-free synthesis of novel thiochromone-annulated thiopyranocoumarin derivatives in aqueous medium. Tetrahedron 21, 66, (45), Minami, T.; Matsumoto, Y.; Nakamura, S.; Koyanagi, S.; Yamaguchi, M., 3-Vinylcoumarins and 3- vinylchromenes as dienes - application to the synthesis of 3,4-fused coumarins and chromenes. J. Org. Chem. 1992, 57, (1), Konigs, P.; Neumann, O.; Hackeloer, K.; Kataeva, O.; Waldvogel, S. R., Versatile one-pot synthesis of 3- alkenylcoumarins. Eur. J. Org. Chem. 28, (2), Bochkov, A. Y.; Yarovenko, V. N.; Krayushkin, M. M.; Chibisova, T. A.; Valova, T. M.; Barachevskii, V. A.; Traven, V. F.; Beletskaya, I. P., Synthesis and photoinduced fluorescence of 3-(2-hetarylethenyl)chromen-2-ones. Russ. J. Organ. Chem. 28, 44, (4), S52