Supplementary information (SI)

A comparative screeningof the catalytic activity of nanocrystallineMIIZr4(PO4)6 ceramicsin the one-pot synthesis of 1,6-Diamino-4-aryl-2-oxo-1,2-dihydropyridine-3,5-dicarbonitrile derivatives

Javad Safaei-Ghomi,* Hossein Shahbazi-Alavi,Abolfazl Ziarati

J. Safaei-Ghomi ().

Department of Organic Chemistry, Faculty of Chemistry,

University of Kashan, Kashan, 51167, I. R. Iran; e-mail:

H. Shahbazi-Alavi

Department of Organic Chemistry, Faculty of Chemistry, University of Kashan, Kashan, 51167, I. R. Iran;

Young Researchers and Elites Club, Kashan Branch, Islamic Azad University, Kashan, Iran

  1. Ziarati

School of Chemistry, College of Science, University ofTehran, Tehran 14155-6455, Iran

Spectral data

1,6-Diamino-4-(4-methylphenyl)-2-oxo-1,2-dihydropyridine-3,5-dicarbonitrile (5a) White crystals; yield: 85 %, mp 238-240 °C, IR (KBr): νmax 3403, 3455 (NH2), 3306, 3335 (NH2), 2218, 2222 (CN), 1642 (C=O), 1604 (C=C) cm-1,1H NMR (400 MHz, DMSO-d6): δ 2.28 (s, 3H, CH3), 5.65 (s, 2H, NH2), 7.33 (d, 2H, J= 8 Hz, CHAr), 7.36 (d, 2H, J= 8 Hz, CHAr), 8.49 (s, 2H, NH2) ppm; 13C NMR(100 MHz, DMSO-d6):δ 21.1, 74.4, 86.9, 115.5, 116.2, 127.3 , 128.5 , 131.2, 140.6, 156.3, 159.1, 159.6, ppm; Anal. Calcd. For C14H11N5O: C 63.39, H 4.18, N 26.40, Found C 63.15, H 4.28, N 26.34, MS (EI) (m/z): 265.

1,6-Diamino-4-(4-chlorophenyl)-2-oxo-1,2-dihydropyridine-3,5-dicarbonitrile (5b) White crystals; yield: 93 %, mp 243- 245˚C, IR (KBr): νmax 3393, 3415 (NH2), 3295, 3305 (NH2), 2215 (CN), 1672 (C=O), 1607 (C=C) cm-1, 1H NMR (400 MHz, DMSO-d6): δ 5.67 (s, 2H, NH2), 7.52 (d, 2H, J= 8 Hz, CHAr), 7.64 (d, 2H, J= 8 Hz, CHAr), 8.55 (s, 2H, NH2) ppm; 13C NMR(100 MHz, DMSO-d6): δ 74.5 , 86.5, 115.2, 116.4, 128.5, 130.2, 133.1, 135.2, 156.5, 158.4, 159.3 ppm; Anal. Calcd. For C13H8N5OCl: C 54.65, H 2.82, N 24.51, Found C 54.62, H 2.94, N 24.43,MS (EI) (m/z): 285 (is due to the 35Cl) and 287 (is due to the 37Cl).

1,6-Diamino-4-(4-nitrophenyl)-2-oxo-1,2-dihydropyridine-3,5-dicarbonitrile(5c) Yellow crystals; yield: 93 %, mp 226-228 °C, IR (KBr): νmax3285, 3393 (NH2), 3315, 3326 (NH2), 2218, 2225 (CN), 1673 (C=O), 1627 (C=C) cm-1,1H NMR (400 MHz, DMSO-d6): δ5.72 (s, 2H, NH2), 7.82 (d, 2H, J= 8.8 Hz, CHAr), 8.38 (d, 2H, J= 8.8 Hz, CHAr), 8.83 (s, 2H, NH2) ppm; 13C NMR (100MHz, DMSO-d6): δ 74.3, 86.2, 115.3, 115.5, 124.2 , 129.3, 140.8, 148.7, 156.7, 157.4, 158.6 ppm; Anal. Calcd. For C13H8N6O3: C 52.71, H 2.72, N 28.37,Found C 52.68, H 2.82, N 28.33, MS (EI) (m/z): 296.

1,6-Diamino-4-(4-methoxyphenyl)-2-oxo-1,2-dihydropyridine-3,5-dicarbonitrile (5d) Cream crystals; yield: 82%, mp 222-224 °C, IR (KBr): νmax3455, 3397 (NH2), 3272, 3221 (NH2), 2216, 2125 (CN), 1663 (C=O), 1642 (C=C) cm-1,1H NMR (400 MHz, DMSO-d6): δ 3.83 (s, 3H, OCH3), 5.64 (s, 2H, NH2), 7.08 (d, 2H, J= 7.8 Hz, CHAr), 7.44 (d, 2H, J=7.8 Hz, CHAr), 8.44 (s, 2H, NH2) ppm; 13C NMR (100 MHz, DMSO-d6): δ 56.3, 74.4, 87.3, 113.8, 115.6, 116.6, 126.4, 129.8, 156.5, 159.2, 159.4, 160.2 ppm;Anal. Calcd. ForC14H11N5O2: C 59.78, H 3.94, N 24.89,Found C 59.73, H 3.99, N 24.78,MS (EI) (m/z): 281.

1,6-Diamino-4-(2-fluorophenyl)-2-oxo-1,2-dihydropyridine-3,5-dicarbonitrile(5e)Brown crystals; yield: 90 %, mp 249-251 °C, IR (KBr): νmax3445, 3403 (NH2), 3243, 3283 (NH2), 2218 (CN), 1652 (C=O), 1630 (C=C) cm-1, 1H NMR (400 MHz, DMSO-d6): δ 5.65 (s, 2H, NH2), 7.37 (d, 1H, J= 7.2Hz, CHAr), 7.42 (d, 1H, J= 7.2Hz, CHAr), 7.49 (t, 1H, J= 8.4Hz, CHAr), 7.52 (t, 1H, J= 7.2Hz, CHAr), 8.61 (s, 2H, NH2) ppm; 13C NMR(100MHz, DMSO-d6): δ 75.4, 87.8 , 116.3, 116.5, 116.7, 122.8, 125.4, 130.7, 133.1, 154.5, 157.0, 157.1, 159.4, ppm; Anal. Calcd. For C13H8N5OF: C 57.99, H 2.99, N 26.01, Found C 57.85, H 3.04, N 25.97, MS (EI) (m/z): 269.

1,6-Diamino-4-(2-nitrophenyl)-2-oxo-1,2-dihydropyridine-3,5-dicarbonitrile (5f) Yellow crystals; yield: 88 %, mp 234-236 °C, IR (KBr): νmax3445, 3342 (NH2), 3342, 3282 (NH2), 2218 (CN), 1662 (C=O), 1594 (C=C) cm-1; 1HNMR (400 MHz, DMSO-d6): δ 5.67 (s, 2H, NH2), 7.65 (m, 4H, CHAr), 8.93 (s, 2H, NH2) ppm; 13C NMR(100 MHz, DMSO-d6): δ 74.8, 86.5, 115.3, 116.2, 123.4, 128.7, 130.2, 131.3, 134.4, 135.3, 157.5, 159.4, 160.3 ppm; Anal. Calcd. for C13H8N6O3: C 52.71, H 2.72, N 28.37, Found C 52.75, H 2.67, N 28.25, MS (EI) (m/z): 296.

1,6-Diamino-4-(4-bromophenyl)-2-oxo-1,2-dihydropyridine-3,5-dicarbonitrile (5g)

Brown crystals; yield: 89 %, mp 234-236 °C, IR (KBr): νmax 3382, 3416 (NH2), 3290, 3308 (NH2), 2216 (CN), 1668 (C=O), 1608 (C=C) cm-1, 1H NMR (400 MHz, DMSO-d6): δ 5.66 (s, 2H, NH2), 7.61-7.99 (m, 4H, CHAr), 8.53 (s, 2H, NH2) ppm; 13C NMR (100MHz, DMSO-d6): δ 74.4, 86.5, 115.2, 116.4, 128.6, 130.1, 133.3, 135.3, 156.5, 158.5, 159.2 ppm; Anal. Calcd. for C13H8N5OBr: C 47.29, H 2.44, N 21.21, Found C 47.18, H 2.35, N 21.28, MS (EI) (m/z): 329 (is due to 79Br) and 331 (is due to 81Br).

1,6-Diamino-4-phenyl-2-oxo-1,2-dihydropyridine-3,5-dicarbonitrile (5h) White crystals; yield: 88 %, mp 237-239 °C, IR (KBr,): νmax 3446, 3350 (NH2), 3245, 3316 (NH2), 2220 (CN), 1643 (C=O), 1602 (C=C) cm-1, 1H NMR (400 MHz, DMSO-d6): δ 5.64 (s, 2H, NH2), 7.45-7.55 (m, 5H, CHAr), 8.45 (s, 2H, NH2) ppm; 13C NMR (100MHz, DMSO-d6): δ 74.3, 86.3, 115.5, 1116.5, 127.8, 128.4, 130.2, 134.5, 156.6, 159.2, 159.6 ppm; Anal. Calcd. for C13H9N5O: C 62.15, H 3.61, N 27.87, Found C 62.18, H 3.53, N 27.92, MS (EI) (m/z): 251.

1,6-Diamino-4-(2-bromophenyl)-2-oxo-1,2-dihydropyridine-3,5-dicarbonitrile (5i) Brown crystals; yield: 90%, mp 231-233 °C, IR (KBr): νmax 3386, 3412 (NH2), 3291, 3301 (NH2), 2214 (CN), 1664 (C=O), 1606 (C=C) cm-1, 1H NMR (400 MHz, DMSO-d6): δ 5.69 (s, 2H, NH2), 7.79-8.63 (m, 4H, CHAr), 8.85(s, 2H, NH2) ppm; 13C NMR (100MHz, DMSO-d6): δ 74.3, 86.5, 115.2, 116.6, 128.6, 128.7, 130.1, 130.4, 133.1, 135.2, 156.4, 158.3, 159.0 ppm; Anal. Calcd. for C13H8N5OBr: C 47.29, H 2.44, N 21.21, Found C 47.22, H 2.38, N 21.24, MS (EI) (m/z): 329 (is due to 79Br) and 331 (is due to 81Br).

Fig.S1.FE-SEM image and XRD pattern of nanoMnZr4(PO4)6

Fig.S2.FE-SEM image, XRD pattern and EDS analysis of nanoFeZr4(PO4)6

Fig.S3.FE-SEM image and XRD pattern of nanoCoZr4(PO4)6

Fig.S4.FE-SEM images and XRD pattern of nanoNiZr4(PO4)6

Fig.S5.FE-SEM images and XRD pattern of nanoCuZr4(PO4)6

Fig.S6.FE-SEM images, XRD pattern and EDS analysis of nanoZnZr4(PO4)6

Fig.S7.FE-SEM images and XRD pattern of nanoCdZr4(PO4)6

1H NMR:1,6-Diamino-4-(2-fluorophenyl)-2-oxo-1,2-dihydropyridine-3,5-dicarbonitrile (5e)

1H NMR: (Expand of δ = 7-9 ppm):1,6-Diamino-4-(2-fluorophenyl)-2-oxo-1,2-dihydropyridine-3,5-dicarbonitrile (5e)

13C NMR: 1,6-Diamino-4-(2-fluorophenyl)-2-oxo-1,2-dihydropyridine-3,5-dicarbonitrile (5e)

1H NMR: 1,6-Diamino-4-(2-nitrophenyl)-2-oxo-1,2-dihydropyridine-3,5-dicarbonitrile (5f)

1H NMR:1,6-Diamino-4-(4-bromophenyl)-2-oxo-1,2-dihydropyridine-3,5-dicarbonitrile (5g)

1H NMR:1,6-Diamino-4-(2-bromophenyl)-2-oxo-1,2-dihydropyridine-3,5-dicarbonitrile (5i)

MS (EI) (m/z):1,6-Diamino-4-(2-bromophenyl)-2-oxo-1,2-dihydropyridine-3,5-dicarbonitrile (5i)

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