<p>Isocyanate–functionalized starch as biorenewable backbone for the preparation and application of poly(ethylene imine) grafted starch</p><p>Lixia Fu and Yanqing Peng*</p><p>Shanghai Key Laboratory of Chemical Biology, School of Pharmacy, East China University of Science and Technology, Shanghai 200237, P. R. China.</p><p>Fax: +86-21-64252603</p><p>E-mail: [email protected]</p><p>1 1. 1H and 13C NMR data of products</p><p>1.1 3–phenyl–2–cyano–2–propenoic acid ethyl ester</p><p>1 m.p. 52–53 °C (from EtOH) (Lit.[1] m.p. 52–54 °C); H NMR (400 MHz, CDCl3) δ: 8.26 (s, 1H), 8.01 (d,</p><p>J = 8.0 Hz, 2H, Ar–H), 7.50 – 7.58 (m, 3H, Ar–H), 4.37 – 4.42 (m, 2H, CH2), 1.42(t, J = 7.2 Hz, 3H, CH3) 13 ppm; C NMR (100 MHz, CDCl3) δ: 162.50, 155.07, 133.32, 131.49, 131.09, 129.30, 115.51, 103.04, 62.76, 14.17 ppm; MS (EI): m/z 201.0 (M+, 100%), 172.0 (88), 156.0 (98), 128.0 (81), 102.0 (53), 77.0 (46).</p><p>1.2 3–(4–methylphenyl)–2–cyano–2–propenoic acid ethyl ester</p><p>1 m.p. 92–93 °C (from EtOH). (Lit.[2] m.p. 93–94 °C); H NMR (400 MHz, CDCl3) δ: 8.22 (s, 1H), 7.91 </p><p>(d, J = 8.0 Hz, 2H, Ar–H), 7.32(d, J = 8.0 Hz, 2H, Ar–H), 3.35 – 4.41 (m, 2H, CH2), 2.44 (s, 3H, CH3), 13 1.42 (t, J = 7.2 Hz, 3H, CH3) ppm; C NMR (100 MHz, CDCl3) δ: 162.79, 155.01, 144.67, 131.27, 130.05, 128.90, 115.80, 101.60, 62.60, 21.89, 14.20 ppm; MS (EI): m/z 215.0 (M+, 100%), 187.0 (29), 170.0 (69), 142.0 (33), 115.0 (63), 91.0 (12), 65.0 (14).</p><p>1.3 3–(2–methoxyphenyl)–2–cyano–2–propenoic acid ethyl ester</p><p>1 m.p. 86–87 °C (from EtOH). (Lit.[3] m.p. 86–88 °C); H NMR (400 MHz, CDCl3) δ: 8.68 (s, 1H), 8.22 (d, J = 8.0 Hz, 1H, Ar–H), 7.46 (t, J = 8.4 Hz, 1H, Ar–H), 7.00 (t, J = 7.6 Hz, 1H, Ar–H), 6.90 (d, J = 8.4 13 Hz, 1H, Ar–H), 4.28 – 4.33 (m, 2H, CH2), 3.83 (s, 3H, OCH3), 1.34 (t, J = 7.2 Hz, 3H, CH3) ppm; C </p><p>NMR (100 MHz, CDCl3) δ: 219.46, 162.84, 159.23, 149.80, 135.00, 129.37, 120.96, 115.93, 111.16, 102.36, 62.50, 55.77, 14.20 ppm; MS (EI): m/z 231.0 (M+, 72%), 186.0 (31), 172.0 (100), 143.0 (22), 131.0 (33), 115.0 (22), 77.0 (16).</p><p>1.4 3–(2–chlorophenyl)–2–cyano–2–propenoic acid ethyl ester</p><p>1 m.p. 50–52 °C (from EtOH). (Lit.[4] m.p. 51–52 °C); H NMR (400 MHz, CDCl3) δ: 8.70 (s, 1H), 8.25 </p><p>(d, J = 8.0 Hz, 1H, Ar–H), 7.40 – 7.53 (m, 3H, Ar–H), 4.38 – 4.44 (m, 2H, CH2), 1.43 (t, J = 7.2 Hz, 3H, 13 CH3) ppm; C NMR (100 MHz, CDCl3) δ: 161.83, 151.20, 136.45, 133.68, 130.35, 129.88, 127.48, 114.84, 106.20, 62.97, 14.15 ppm; MS (EI): m/z 235.0 (M+, 4%), 200.0 (20), 172.0 (100), 126.0 (13), 100.0 (6), 75.0 (7).</p><p>1.5 3–(4–nitrophenyl)–2–cyano–2–propenoic acid ethyl ester m.p. 167–168 °C (from EtOH). (Lit.[5] m.p. 168–170 °C); 1H NMR (400 MHz, CDCl3) δ: 8.37 (d, J = 8.8</p><p>Hz, 2H, Ar–H), 8.31 (s, 1H), 8.15 (d, J = 8.8 Hz, 2H, Ar–H), 4.40 – 4.46 (m, 2H, CH2), 1.44 (t, J = 7.2 13 Hz, 3H, CH3) ppm; C NMR (100 MHz, CDCl3) δ: 161.41, 151.75, 149.72, 136.92, 131.53, 124.331, 114.54, 107.39, 63.36, 14.11 ppm; MS (EI): m/z 246.0 (M+, 69%), 218.0 (100), 201.0 (78), 155.0 (51), 127.0 (46), 89.0 (33).</p><p>1.6 3–(3,4–dimethoxyphenyl)–2–cyano–2–propenoic acid ethyl ester</p><p>1 m.p. 154–155 °C (from EtOH). (Lit.[6] m.p. 154–156 °C); H NMR (400 MHz, CDCl3) δ: 8.16 (s, 1H), 7.80 (s, 1H, Ar–H), 7.49 (d, J = 10.0 Hz, 1H, Ar–H), 6.96 (d, J = 8.4 Hz, 1H, Ar–H), 4.35 – 4.40 (m, 2H, 13 CH2), 3.97, 3.96 (6H, 2×OCH3), 1.42 (t, J = 7.2 Hz, 3H, CH3) ppm; C NMR (100 MHz, CDCl3) δ: 163.12, 154.70, 153.70, 149.30, 127.90, 124.63, 116.38, 111.67, 110.96, 99.42, 62.47, 56.07, 14.23 ppm; MS (EI): m/z 261.0 (M+, 100%), 233.0 (22), 216.0 (16), 172.0 (16), 116.0 (10).</p><p>1.7 1,3–diphenylthiourea</p><p>2 1 m.p. 152–153 °C (from EtOH). (Lit.[7] m.p. 152–153 °C); H NMR (400 MHz, CDCl3) δ: 8.04 (s, H, 13 NH), 7.34 – 7.29 (m, 4H, Ar–H), 7.18 – 7.21 (t, J = 6.4 Hz, H, Ar–H) ppm; C NMR (100 MHz, CDCl3) δ: 77.3, 77.0, 76.7 ppm.</p><p>2. 1H and 13C NMR images of products</p><p>2.1 3–phenyl–2–cyano–2–propenoic acid ethyl ester</p><p>2.2 3–(4–methylphenyl)–2–cyano–2–propenoic acid ethyl ester</p><p>2.3 3–(2–methoxyphenyl)–2–cyano–2–propenoic acid ethyl ester</p><p>3 2.4 3–(2–chlorophenyl)–2–cyano–2–propenoic acid ethyl ester</p><p>2.5 3–(4–nitrophenyl)–2–cyano–2–propenoic acid ethyl ester</p><p>2.6 3–(3,4–dimethoxyphenyl)–2–cyano–2–propenoic acid ethyl ester</p><p>4 2.7 1,3–diphenylthiourea</p><p>3. References</p><p>[1] Yue, C.; Mao, A.; Wei, Y.; Lue, M. Catal Commun, 2008, 7, 1571.</p><p>[2] Jin, T.; Wang, X.; Liu, L.; Li, T. J Chem Res, 2006, 6, 346.</p><p>[3] Jain, A. K.; Bose, A. K. J Environ Res Devel, 2006, 2, 121.</p><p>[4] Zhang, A.; Zhang, N.; Hong, S.; Zhang, M. Synth Commun, 2009, 17, 3024.</p><p>[5] Jiang, H.; Wang, M.; Song, Z.; Gong, H. Prep Biochem Biotechnol, 2009, 2, 194.</p><p>[6] Rong, L.; Li, X.; Wang, H.; Shi, D.; Tu, S.; Zhuang, Q. Synth Commun, 2006, 16, 2407.</p><p>[7] Shahnaz P, Syed AH, Rashid K, Khalid K, Nighat A, Tahira S, Synth Commun, 2005, 35, 1663.</p><p>5</p>