Isocyanate Functionalized Starch As Biorenewable Backbone for the Preparation and Application

Isocyanate–functionalized starch as biorenewable backbone for the preparation and application of poly(ethylene imine) grafted starch

Lixia Fu and Yanqing Peng*

Shanghai Key Laboratory of Chemical Biology, School of Pharmacy, East China University of Science and Technology, Shanghai 200237, P. R. China.

Fax: +86-21-64252603

E-mail: [email protected]

1 1. 1H and 13C NMR data of products

1.1 3–phenyl–2–cyano–2–propenoic acid ethyl ester

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,

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).

1.2 3–(4–methylphenyl)–2–cyano–2–propenoic acid ethyl ester

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

(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).

1.3 3–(2–methoxyphenyl)–2–cyano–2–propenoic acid ethyl ester

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

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).

1.4 3–(2–chlorophenyl)–2–cyano–2–propenoic acid ethyl ester

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

(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).

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

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).

1.6 3–(3,4–dimethoxyphenyl)–2–cyano–2–propenoic acid ethyl ester

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).

1.7 1,3–diphenylthiourea

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.

2. 1H and 13C NMR images of products

2.1 3–phenyl–2–cyano–2–propenoic acid ethyl ester

2.2 3–(4–methylphenyl)–2–cyano–2–propenoic acid ethyl ester

2.3 3–(2–methoxyphenyl)–2–cyano–2–propenoic acid ethyl ester

3 2.4 3–(2–chlorophenyl)–2–cyano–2–propenoic acid ethyl ester

2.5 3–(4–nitrophenyl)–2–cyano–2–propenoic acid ethyl ester

2.6 3–(3,4–dimethoxyphenyl)–2–cyano–2–propenoic acid ethyl ester

4 2.7 1,3–diphenylthiourea

3. References

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[2] Jin, T.; Wang, X.; Liu, L.; Li, T. J Chem Res, 2006, 6, 346.

[3] Jain, A. K.; Bose, A. K. J Environ Res Devel, 2006, 2, 121.

[4] Zhang, A.; Zhang, N.; Hong, S.; Zhang, M. Synth Commun, 2009, 17, 3024.

[5] Jiang, H.; Wang, M.; Song, Z.; Gong, H. Prep Biochem Biotechnol, 2009, 2, 194.

[6] Rong, L.; Li, X.; Wang, H.; Shi, D.; Tu, S.; Zhuang, Q. Synth Commun, 2006, 16, 2407.

[7] Shahnaz P, Syed AH, Rashid K, Khalid K, Nighat A, Tahira S, Synth Commun, 2005, 35, 1663.