Supporting Information Investigation of Mizoroki-Heck Coupling Polymerization as a Catalyst-Transfer Condensation Polymerization for Synthesis of Poly(p-phenylenevinylene). MASATAKA NOJIMA, RYOSUKE SAITO, YOSHIHIRO OHATA, TSUTOMU YOKOZAWA* Department of Material and Life Chemistry, Kanagawa University 3-27-1 Rokkakubashi, Kanagawa-ku, Yokohama 221-8686, Japan Synthesis of 1,4-Bis[(2-ethylhexyl)oxy]benzene (4). Hydroquinone 3 (10.14 g, 92.1 mmol) was added to a suspension of KOH powder (41.60 g, 741.0 mmol) in dry DMSO (166 mL) at room temperature, and the whole was stirred at room temperature for 1 h. 1-Bromo-2-ethylhexane (43 mL, 249.0 mmol) was added, and the reaction mixture was stirred for 20 h and finally poured into ice water. The aqueous layer was extracted with hexane, and the combined organic layers were dried over anhydrous MgSO4. After concentration in vacuo, ethyl acetate was added, and the solution was washed with water and saturated aqueous NH4Cl, and then dried over anhydrous MgSO4. The solvent and excess 1-bromo-2-ethylhexane were removed to afford 3 as a light yellow oil (31.22 g, 100%). 1H NMR (600 MHz, CDCl3) δ 6.82 (s, 4 H), 3.79 (dd, J = 5.8 and 11.7 Hz, 2 H), 3.77 (dd, J = 6.2 and 12.0 Hz, 2 H), 1.71-1.64 (m, 1 2 H), 1.51-1.30 (m, 16 H), 0.93-0.89 (m, 12 H); 13 C NMR (150 MHz, CDCl3) δ 153.4, 115.4, 71.2, 39.5, 30.5, 29.1, 23.8, 23.1, 14.1, 11.1. Synthesis of 1,4-Bis[(2-ethylhexyl)oxy]-2,5-diiodobenzene (5). Dialkoxybenzene 4 (15.0 g, 44.9 mmol), KIO3 (3.87 g, 18.1 mmol), and I2 (13.2 g, 52.1 mmol) were added to a stirred solution of acetic acid (275 mL), 96% H2SO4 (5.0 mL), and H2O (20 mL). The reaction mixture was refluxed for 16 h and then cooled to room temperature. Aqueous Na2SO4 (20 wt%) was added until the brown color of iodine disappeared, and then the mixture was extracted with hexane. The combined organic layers were filtered through Celite, dried over anhydrous MgSO4, and concentrated in vacuo. The residue was purified by means of column chromatography (SiO2, hexane) to afford 4 as a slightly yellow oil (12.56 g, 48%). 1H NMR (600 MHz, CDCl3) δ 7.16 (s, 2 H), 3.82 (dd, J = 5.4 and 9.4 Hz, 2 H), 3.80 (dd, J = 5.4 and 9.1 Hz, 2 H), 1.76-1.70 (m, 2 H), 1.58-1.26 (m, 16 H), 0.95-0.87 (m, 12 H); 13 C NMR (126 MHz, CDCl3) δ 152.8, 122.3, 86.0, 72.3, 39.4, 30.5, 29.0, 23.9, 23.0, 14.1, 11.2. Synthesis of 2,5-Bis[(2-ethylhexyl)oxy]-4-iodobenzaldehyde (6). A round-bottomed flask equipped with a three-way stopcock was heated under reduced pressure, and then cooled to room temperature under an argon atmosphere. Diiodobenzene 6 (11.02 g, 18.8 mmol) was placed in the flask, and the atmosphere in the flask was replaced with argon. Dry Et2O (35 mL) was added to the flask via a syringe, and the mixture was stirred at 0 oC. A solution of n- butyllithium (1.6 M solution in 2 hexane, 11.5 mL, 18.7 mmol) in dry Et2O (23 mL) was added dropwise via a syringe, and stirring was continued at 0 oC for 5 minutes. A solution of dry DMF (2.3 mL, 29.7 mmol) in dry Et2O (2.0 mL) was added via a syringe and the reaction mixture was stirred for 2 h at room temperature. Then, the reaction was quenched with 1 M hydrochloric acid, and the aqueous layer was extracted with diethyl ether. The combined organic layers were washed with saturated aqueous NaHCO3 and brine, dried over anhydrous MgSO4, and concentrated in vacuo. The residue was purified by means of column chromatography (SiO2, hexane/CH2Cl2 = 5/1) to afford 6 as an orange oil (7.85 g, 85%).1H NMR (500 MHz, CDCl3) δ 10.43 (s, 1 H), 7.47 (s, 1 H), 7.18 (s, 1 H), 3.93-3.87 (m, 4 H), 1.79-1.72 (m, 2 H), 1.59-1.28 (m, 16 H), 0.95-0.89 (m, 12 H); 13 C NMR (126 MHz, CDCl3) δ 189.2, 155.9, 152.2, 125.1, 124.3, 108.4, 96.7, 72.0, 71.7, 39.5, 39.3, 30.6, 30.5, 29.04, 29.01, 23.94, 23.02, 22.97, 14.08, 14.04, 11.17, 11.15. Synthesis of 1,4-Bis[(2-ethylhexyl)oxy]-2-iodo-5-vinylbenzene (1). A round-bottomed flask equipped with a three-way stopcock was heated under reduced pressure, and then cooled to room temperature under an argon atmosphere. Methyltriphenylphosphonium bromide (2.18 g, 6.09 mmol) was placed in the flask, and the atmosphere in the flask was replaced with argon. Dry THF (34 mL) was added to the flask, and the mixture was stirred at 0 oC. A solution of n-butyllithium (1.6 M solution in hexane, 3.7 mL, 6.1 mmol) was added dropwise via a syringe, and stirring was continued at 0 oC for 20 minutes. A solution of 4-iodobenzaldehyde 6 (1.95 g, 4.00 mmol) in dry THF (15.0 mL) was added via a syringe, and the reaction mixture was refluxed for 0.5 h and then cooled to room temperature. The reaction was quenched with water, and the 3 aqueous layer was extracted with Et2O. The combined organic layers were washed with water, dried over anhydrous MgSO4, and concentrated in vacuo. The residue was purified by means of column chromatography (SiO2, hexane) to afford 1 as a yellow oil (1.57 g, 38%). 1H NMR (600 MHz, CDCl3) δ 7.25 (s, 1 H), 6.97 (dd, J = 11.0 and 17.9 Hz, 1 H), 6.90 (s, 1 H), 5.74 (dd, J = 1.03 and 17.9 Hz, 1 H), 5.26 (dd, J = 1.03 and 11.0 Hz, 1 H), 3.89-3.85 (m, 2 H), 3.82-3.78 (m, 2 H), 1.77-1.70 (m, 2 H), 1.59-1.28 (m, 16 H), 0.97-0.88 (m, 12 H); 13 C NMR (150 MHz, CDCl3) δ 152.1, 151.1, 131.3, 127.6, 123.3, 114.5, 109.5, 85.8, 72.1, 71.6, 39.6, 39.5, 30.59, 30.56, 29.10, 29.06, 23.99, 23.96, 23.05, 23.02, 14.11, 14.06, 11.24, 11.16. Synthesis of 2,5-Dibromo-1,4-bis[(2-ethylhexyl)oxy]benzene (8). Compound 8 (9.25 g, 18.7 mmol) was obtained in 100% yield from 7 (5.00 g, 18.7 mmol) in a similar manner to that described for the synthesis of 4 from 3. 1 H NMR (600 MHz, CDCl3) δ 7.08 (s, 4 H), 3.81 (m, 2 H), 1.78-1.71 (m, 2 H), 1.61-1.23 (m, 16 H), 0.99-0.85 (m, 12 H); 13C NMR (126 MHz, CDCl3) δ 150.2, 1182, 111.0, 72.5, 39.4, 30.4, 29.0, 23.8, 23.0, 14.1, 11.0. Synthesis of 4-Bromo-2,5-bis[(2-ethylhexyl)oxy]benzaldehyde (9). A round-bottomed flask equipped with a three-way stopcock was heated under reduced pressure, and then cooled to room temperature under an argon atmosphere. Dibromobenzene 8 (8.51 g, 17.3 mmol) was placed in the flask, and the atmosphere in the flask was replaced with argon. Dry THF (110 mL) was added to the flask via a syringe, 4 and the mixture was stirred at -78 oC. n-Butyllithium (2.7 M solution in hexane, 8.3 mL, 22.0 mmol) was added dropwise via a syringe, and stirring was continued at -78 oC for 1 h. The reaction temperature was raised to -30 °C, and dry DMF (2.1 mL, 27.6 mmol) was added via a syringe. The reaction mixture was stirred at –30 oC for 1 h and at room temperature overnight. The reaction was quenched with 1 M hydrochloric acid, and the aqueous layer was extracted with diethyl ether. The combined organic layers were washed with saturated aqueous NaHCO3 and brine, dried over anhydrous MgSO4, and concentrated in vacuo. The residue was purified by means of column chromatography (SiO2, hexane/CH2Cl2 = 5/1) to afford 9 as a slightly yellow oil (6.22 g, 82%).1H NMR (600 MHz, CDCl3) δ10.42 (s, 1 H), 7.31 (s, 1 H), 7.24 (s, 1 H), 3.93-3.89 (m, 4 H), 1.79-1.74 (m, 2 H), 1.58-1.24 (m, 16 H), 0.96-0.87 (m, 12 H); 13 C NMR (126 MHz, CDCl3) δ 188.9, 155.9, 150.0, 124.2, 121.1, 118.3, 110.3, 72.1, 72.7, 39.4, 39.3, 30.5, 30.4, 29.03, 28.99, 23.93, 23.87, 22.99, 22.96, 14.05, 14.03, 11.12. Synthesis of 2-Bromo-1,4-bis[(2-ethylhexyl)oxy]- 5-vinylbenzene (2). Compound 2 (1.08 g, 2.46 mmol) was obtained in 82% yield from 9 (1.33 g, 3.00 mmol) in a similar manner to that described for the synthesis of 1 from 6. 1 H NMR (600 MHz, CDCl3) δ 7.05 (s, 1 H), 7.00 (s, 1 H), 6.97 (dd, J = 11.0 and 17.8 Hz, 1 H), 5.72 (dd, J = 1.1 and 17.8 Hz, 1 H), 5.27 (dd, J = 1.1 and 11.0 Hz, 1 H), 3.90-3.85 (m, 2 H), 3.83-3.78 (m, 2 H), 1.77-1.71 (m, 2 H), 1.58-1.29 (m, 16 H), 0.96-0.89 (m, 12 H); 13C NMR (150 MHz, CDCl3) δ 150.8, 149.7, 131.1, 126.6, 117.4, 114.4, 111.9, 111.2, 72.4, 71.6, 39.52, 39.51, 30.59, 30.49, 29.08, 29.06, 23.98, 23.89, 23.04, 23.01, 14.08, 14.06, 11.18, 11.15. 5 1200 3000 4000 1400 2230.17 (H/Br) 2200 2400 1600 1800 2000 2320.27 (Tolyl/Br) 2152.27 (H/H) 2230.17 (H/Br) 1961.98 (Tolyl/Br) 1871.88 (H/Br) 1793.98 (H/H) 1603.69 (Tolyl/Br) 1435.69 (H/H) 1513.59 (H/Br) (f) 3000 2000 Mass/Charge (e) Mass/Charge 2152.27 (H/H) 1800 1600 4000 Mass/Charge 2000 2000 2320.27 (Tolyl/Br) 1871.88 (H/Br) 1435.69 (H/H) 1793.98 (H/H) 1513.59 (H/Br) 1603.69 (Tolyl/Br) (d) 3000 1800 1600 Mass/Charge (c) 2000 1961.90 (Tolyl/Br) 1603.61 (Tolyl/Br) 1400 Mass/Charge 1961.98 (Tolyl/Br) 2000 1000 1871.83 (H/Br) 1513.54 (H/Br) 1155.25 (H/Br) (b) 1245.32 (Tolyl/Br) (a) 2200 Mass/Charge FIGURE S1 MALDI-TOF mass spectra of products obtained by the polymerization of 2 in the presence of 5.5 equiv of Cy2NMe and 5.0 mol% of 10 at 50 oC in THF ([2]0 = 0.25 M) for 30 min (Conv. of 2 = 85%, Mn = 1620, Mw/Mn = 1.74); (a) whole spectrum, (b) magnification between m/z = 1400-2400, 3 h (Conv. of 2 = 99%, Mn = 3270, Mw/Mn = 1.98); (c) whole spectrum, (d) magnification between m/z = 1400-2400, and 312 h (Conv. 6 of 2 = 100%, Mn = 4230, Mw/Mn = 1.99); (e) whole spectrum, (f) magnification between m/z = 1400-2400. ● ● = H/I ○ = H/H ■ = unknow-1 ◆ = unknow-2 ◇ = unknow-3 ● ● ○ ◇ ■ ■ ◇ ○ ◆ ◆ FIGURE S2 MALDI-TOF mass spectra of products obtained by the polymerization of 1 in the presence of 1.1 equiv of Cy2NMe and 5.0 mol% of bis[tri(tert-butyl)phosphine]palladium in THF ([1]0 = 0.25 M) at 50 oC for 17 h (Mn = 4120, Mw/Mn = 1.64). 7