Supporting Information © Wiley-VCH 2007 69451 Weinheim, Germany

Development of a Novel Electrolytic System for Anodic Fluorination Based on Cation Exchange Reaction between Alkali Metal Fluorides and Solid-Supported Acids Toshiki Tajima,*, a Atsushi Nakajima,b Yuta Doi,b and Toshio Fuchigamib a Global Edge Institute, Tokyo Institute of Technology, Yokohama 226-8502, Japan b Department of Electronic Chemistry, Tokyo Institute of Technology, Yokohama 226- 8502, Japan

E-mail: [email protected] (T. Tajima)

1. General 1H, 13C, and 19F NMR spectra were recorded on JEOL JNM EX-270 (1H: 270 MHz, 13 19 1 13 C: 67.8 MHz, F: 254 MHz) spectrometer in CDCl3. The chemical shifts for H, C, 19 and F NMR spectra were given in d (ppm) from internal TMS, CDCl3, and monofluorobenzene (-36.5 ppm), respectively. EI mass spectra were measured with Shimadzu GCMS-QP5050A mass spectrometer. Preparative liquid chromatography was carried out using the following apparatuses: SHIMADZU LC-6AD (liquid chromatograph), SHIMADZU SPD-20A (UV detector), and SHIMADZU C-R8A (chromatopac). Cyclic voltammetry was performed by using a computer-controlled electrochemical analyzer (ALS/CH Instruments 610B), and preparative electrolyses were carried out with HOKUTO DENKO HABF-501 Potentiostat/Galvanostat.

2. Materials Ethyl a-phenylthioacetate (1), 4,4’-diisopropylbiphenyl (7), and 2,6-lutidine were purchased from Tokyo Chemical Industry and used without purification. Phenylthioacetonitrile (3) and triethylamine were purchased from Wako Pure Chemical Industries and used without purification. 4-Isopropyl-3,4-dihydro-2H-1,4-benzothiazin- 3-one (5) was synthesized according to the literature.[1] Dehydrated acetonitrile was purchased from Kanto Chemical. Potassium fluoride (KF), lithium fluoride (LiF), sodium fluoride (NaF), and cesium fluoride (CsF) were purchased from Wako Pure Chemical Industries and used without purification. Potassium hydrogen difluoride

(KHF2) was purchased from Aldrich and used without purification. Amberlyst 15Dry was purchased from Organo. 2,6-Lutidine-xHF (x=1~3) was obtained from Morita Chemical Industries (Japan).

3. Cyclic Voltammetry Cyclic voltammetry was carried out with a three-electrode system using a platinum disk (f = 0.8 mm) working electrode, a platinum wire counter electrode, and a saturated calomel electrode (SCE) as a reference electrode.

4. Spectroscopic Data The fluorinated products 2[2], 4[3], 6[1], and 8[4] were identified by reference to the literatures.

1 2,6-Lutidine-HF: H NMR (270 MHz, CDCl3) d = 14.85 (s, 1H), 7.78-7.71 (m, 1H), 13 7.20-7.16 (m, 2H), 2.63 (m, 6H) ; C NMR (67.8 MHz, CDCl3) d = 154.6, 139.1, 121.3, 19 21.2; F NMR (254 MHz, CDCl3) d = -71.9 (s).

5. References (Supporting Information) [1] A. Konno, W. Naito, T. Fuchigami, Acta Chemica Scandinavica 1999, 53, 887-891. [2] T. Fuchigami, M. Shimojo, A. Konno, K. Nakagawa, J. Org. Chem. 1990, 55, 6074- 6075. [3] T. Fuchigami, M. Shimojo, A. Konno, J. Org. Chem. 1995, 60, 3459-3464. [4] T. Tajima, H. Kurihara, A. Nakajima, T. Fuchigami, J. Electroanal. Chem. 2005, 580, 155-160.