Supporting Information

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1 Supporting Information Synthesis and Photophysical Properties of 5-N-Arylamino-4-methylthiazoles Obtained from Direct C-H Arylations and Buchwald-Hartwig Aminations of 4-Methylthiazole Toshiaki Murai, Kirara Yamaguchi, Teppei Hayano, Toshifumi Maruyama, Koji Kawai, Hayato Kawakami, and Akira Yashita Department of Chemistry and Biomolecular Science, Faculty of Engineering, Gifu University, Yanagido, Gifu , Japan MIYOSHI OIL & FAT CO., LTD., Horikiri, Katsushika-Ku, Tokyo , Japan Table of Contents 1. X-ray Structure Analysis S3 2. Photophysical Properties S4 3. References S H NMR and 13 C NMR Spectra S4 1 H NMR and 13 C NMR Spectra of 2b S5 1 H NMR and 13 C NMR Spectra of 2c S6 1 H NMR and 13 C NMR Spectra of 2d S7 1 H NMR and 13 C NMR Spectra of 2e S8 1 H NMR and 13 C NMR Spectra of 3b S9 1 H NMR and 13 C NMR Spectra of 3c S10 1 H NMR and 13 C NMR Spectra of 3d S11 1 H NMR and 13 C NMR Spectra of 3e S12 1 H NMR and 13 C NMR Spectra of 4aa S13 S1

2 1 H NMR and 13 C NMR Spectra of 4ab S14 1 H NMR and 13 C NMR Spectra of 4b S15 1 H NMR and 13 C NMR Spectra of 4ca S16 1 H NMR and 13 C NMR Spectra of 4cd S17 1 H NMR and 13 C NMR Spectra of 4d S18 1 H NMR and 13 C NMR Spectra of 4e S19 1 H NMR and 13 C NMR Spectra of 7 S20 S2

3 1 X-ray Structure Analysis. The X-ray quality crystal was obtained by slow diffusion of pentane into toluene solution of 4d. The crystal was cut from the grown crystals and was mounted on a glass fiber. Measurements were carried out on a Rigaku/MSC Mercury CCD using a graphite-monochromator with Mo Kα radiation (λ = Å). The structure was solved by direct methods (SIR97) S1 and refined by full-matrix least-squares procedures (SHELXL-97) S2 using the Yadokari-XG S3 A stick and ball representation of 4d is shown in Figure S1. Figure S1. Molecular structure of 4d. 2 Photophysical Properties Intensity Wavelength (nm) (a) S3

4 Intensity 300 (b) Wavelength (nm) Figure S2. Change of Fluorescence spectra of 7 by adding BF 3 Et 2 O (in Et 2 O, [7] = 1x10-5 M; λ ex = 352 nm (a) and 430 nm (b). The emission wavelength of 7 shifted from 439 nm to 531 nm. Photographs of a solution of 7 and 7+BF 3 under illumination with UV light (λ ex = 365 nm). 3 References (S1) Altomare, A.; Cascarano, G. L.; Giacovazzo, C.; Guagliardi, A.; Moliterni, A. G. G.; Polidori, G.; Spagna, R. J. Appl. Cryst. 1999, 32, 115. (S2) Sheldrick, G. M. SHELXL-97, A Program for the Refinement of Crystal Structures; University of Göttingen: Göttingen, Germany, (S3) (a) Wakita, K. Yadokari-XG, Software for Crystal Structure Analyses, (b) Kabuto, C.; Akine, S.; Nemoto, T.; Kwon, E. J. Cryst. Soc. Jpn. 2009, 51, H NMR and 13 C NMR Spectra 1 H NMR and 13 C NMR spectra of all the compounds are shown from the next page. In 1 H NMR spectra () shows residual CHCl 3 from CDCl 3. S4

5 4-Methyl-2-(4-trifluoromethyl)phenylthiazole (2b) S5

6 4-Methyl-2-(3,5-bis(trifluoromethyl)phenyl)thiazole (2c) S6

7 4-Methyl-2-(4-nitro)phenylthiazole (2d) S7

8 4-Methyl-2-(2-thienyl)thiazole (2e) S8

9 5-Bromo-4-methyl-2-(4-trifluoromethyl)phenylthiazole (3b) S9

10 5-Bromo-4-methyl-2-(3,5-bis(trifluoromethyl)phenyl)thiazole (3c) S10

11 5-Bromo-4-methyl-2-(4-nitro)phenylthiazole (3d) S11

12 5-Bromo-4-methyl-2-(2-thienyl)-thiazole (3e) S12

13 4-Methyl-2-phenyl-5-methylphenylaminothiazole (4aa) S13

14 4-Methyl-2-phenyl-5-(diphenylamino)thiazole (4ab) S14

15 4-Methyl-2-(4-trifluoromethylphenyl)-5-(diphenylamino)thiazole (4b) S15

16 4-Methyl-2-(3,5-bis(trifluoromethyl)phenyl)-5-(diphenylamino)thiazole(4ca) S16

17 4-Methyl-2-(3,5-bis(trifluoromethyl)phenyl)-5-(4-dimethoxyphenylamino)thiazole (4cb) S17

18 4-Methyl-2-(4-nitrophenyl)-5-(diphenylamino)thiazole (4d) S18

19 4-Methyl-5-diphenylamino-2-(2-thienyl)thiazole (4e) S19

20 4-Methyl-2-(4-aminophenyl)-5-(diphenylamino)thiazole (7) S20