None were significantly different

None were significantly different. 4. (Table S1). Data reduction was carried out using the SAINT program [46]. Semi-empirical absorption corrections were applied based on comparative reflections using SADABS [47]. The structure answer and refinements were performed with the SHELXS-97 and SHELXL-2013 program packages [48]. 2.2. Syntheses 2.2.1. General Procedure for the Synthesis of 1-Substituted 2-Methyl-3-hydroxypyridin-4-(1H)-thiones (1dC1f) A solution of 1aC1c (1 equiv.) and Lawessons reagent (1.5 equiv.) in tetrahydrofuran was heated at 60 C for 4C6 h. After the completion of the reaction, the reaction combination was cooled and concentrated under reduced pressure. The pure product was isolated by column chromatography on silica gel using dichloromethane as the eluent. A solution of the product in methanol (MeOH)/dichloromethane (DCM) was kept at 4 C. After 12 h, needle-like crystals created, which were filtered, washed with chilly methanol, and dried under vacuum. 2.2.2. 1-Benzyl-2-methyl-3-hydroxypyridin-4(1H)-thione, 1d Compound 1d was synthesized according to the general process using 1a (2.15 g, 10 mmol) and Lawessons reagent (6.0 g, 15 mmol). Yield: 61% (1.42 g), MS (ESI+); = 232.0783 [M + H]+. Anal. found: C, 66.04; H, 6.01; N, 5.62; Calc. for C13H13NOS0.25H2O: C, 66.21; H, 5.77; N, 5.94. 1H NMR (400.13 MHz, DMSO-= 2.31 (s, 3H, H-7), 5.46 (s, 2H, H-N), 6.94C7.85 (m, 7H, H-5, H-Ph, H-6) ppm. 2.2.3. 1-Ethylbenzyl-2-methyl-3-hydroxypyridin-4(1H)-thione, 1e Compound 1e was synthesized according to the general process using 1b (2.45 g, 10 mmol) and Lawessons reagent (6.0 g, 15 mmol). Yield: 60% (1.48 g), MS (ESI+); = 268.0767 [M + Na]+. Anal. found: C, 66.04; H, 6.01; N, 5.62; Calc. for C14H15NOS0.5H2O: C, 66.11; H, 6.34; N, 5.51. 1H NMR (400.13 MHz, DMSO-= 2.41 (s, 3H, H-7), 3.05 (t, 2H, H-Ph, 3= 7 Hz), 4.36 (t, 2H, H-N, 3= 7 Hz), 7.21C7.32 (m, 6H, H-5, H-Ph), 7.54 (d, 1H, H-6, 3= 7 Hz) ppm. 2.2.4. 1-(p-Methylbenzyl)-2-methyl-3-hydroxypyridin-4(1H)-thione, 1f Compound 1f was synthesized according to the general process using 1c (2.45 g, 10 mmol) and Lawessons reagent (6.0 g, 15 mmol). Yield: 65% (1.59 g), MS (ESI+); = CB 300919 268.0771 [M + Na]+. Anal. found: C, 60.09; H, 6.43; N, 5.22; Calc. for C14H15NOS2H2O: C, 59.75; H, 6.81; N, 4.98. 1H NMR (400.13 MHz, MeOH-= 2.01 (s, 3H, H-Ph), 2.39 (s, 3H, H-7), 5.42 (s, 2H, H-N), 7.11C7.15 (m, 2H, H-Ph), 7.36C7.40 (m, 2H, H-Ph), 7.47 (d, 1H, H-5, 3= 7 Hz), 7.65 (d, 1H, H-6, 3= 7 Hz) ppm. 2.3. General Procedure for the Synthesis of Ru(6-p-Cymene) Complexes (= 450.1013 [M ? Cl]+ (calcd. 450.1008). Anal. found: C, 52.63; H, 4.86; N, 2.70; Calc. for C23H26ClNO2Ru0.6CH2Cl2: C, 52.89; H, 5.12; N, 2.61. 1H NMR (400.13 MHz, MeOH-= 1.32 (d, 6H, H-15/H-17, 3= 7 Hz), 2.25 (s, 3H, H-7), 2.33 (s, 3H, H-14), 2.81C2.87 (m, 1H, H-16), 5.32 (s, 2H, N-CH2), 5.42 (d, 2H, H-9/H-13, 3= 6 Hz), 5.65 (d, 2H, H-10/H-12, 3= 6 Hz), 6.57 (d, 1H, H-5,), 7.01 (d, 2H, Ph, 3= 7 Hz), 7.28C7.37 (m, CB 300919 3H, Ph), 7.55 (d, 1H, H-6, 3= 7 Hz) ppm. 13C1H NMR (100.61 MHz, MeOH-= 12.1 (C-7), 18.4 (C-15,C-17), 22.6 (C-14), 32.4 (C-16), 59.1 (C-Ph), 78.9 (C-9/C-13), 80.6 (C-10/C-12), 97.0 (C-11), 100.0 (C-8), 110.4 (C-5), 127.4 (C-Ph), 129.3 (C-Ph), 130.2 (C-Ph), 135.7 (C-6), 135.8 (C-2), 137.0 (C-Ph), 160.9 (C-3), 175.7 (C-4) ppm. 2.3.2. [Chlorido3-oxo-1-ethylbenzyl-2-methylpyridin-4(1H)-onato-2O,O(6-p-cymene)ruthenium(II)], 2b Complex 2b was synthesized from bis[dichlorido(6-p-cymene)ruthenium(II)] (159 mg, 0.26 mmol, 1b (119 mg, 0.52 mmol), and NaOMe (34 mg, 0.63 mmol). Yield: 37% (104 mg), MS (ESI+); = 464.1159 [M ? Cl]+ (calcd. 464.1165). Anal. found: C, 56.41; H, 5.36; N, 3.10; Calc. for C24H28ClNO2Ru0.5H2O: C, 56.74; CB 300919 H, 5.75; N, 2.76. 1H NMR (400.13 MHz, CDCl3, 25 C): = 1.28 (d, 3H, H-15/H-17, 3= 7 Hz), 1.32 (d, 3H, H-15/H-17, 3= 7 Hz), 2.31 (s, 3H, H-7), 2.43 (s, H-14), 2.91 (m, 1H, H-16), 2.95 (t, 2H, Ph-CH2, 3= 7 Hz), 4.02 (q, 2H, N-CH2, 3= 7 Hz, 2= 16 Hz), 5.24 (d, 1H, H-9/H-13, 3= 6 Hz), 5.29 (d, 1H, H-9/H-13, 3= 6 Hz), 5.43 (d, 1H, H-10/H-12, 3= 6 Hz), 5.49 (d, 1H, H-10/H-12, 3= 6 Hz), 6.32 (d, 1H, H-5, 3= 7 Hz), 6.70 (d, 1H, H-6, 3= 7 Hz), 7.00C7.03 (m, 2H, Ph), 7.23C7.29 (m, 3H, Ph) ppm. 13C1H NMR (100.61.The crystallization from a methanol/dichloromethane combination gave pure products in good yields. carried out using the SAINT program [46]. Semi-empirical absorption corrections were applied based on comparative reflections using SADABS [47]. The structure answer and refinements were performed with the SHELXS-97 and SHELXL-2013 program packages [48]. 2.2. Syntheses 2.2.1. General Procedure for the Synthesis of 1-Substituted 2-Methyl-3-hydroxypyridin-4-(1H)-thiones CB 300919 (1dC1f) A solution of 1aC1c (1 equiv.) and Lawessons reagent (1.5 equiv.) in tetrahydrofuran was heated at 60 C for 4C6 h. After the completion of the reaction, the reaction combination was cooled and concentrated under reduced pressure. The real product was isolated by column chromatography on silica gel using dichloromethane as the eluent. A solution of the product in methanol (MeOH)/dichloromethane (DCM) was kept at 4 C. After 12 h, needle-like crystals created, which were filtered, washed with chilly methanol, and dried under vacuum. 2.2.2. 1-Benzyl-2-methyl-3-hydroxypyridin-4(1H)-thione, 1d Compound 1d was synthesized according to the general process using 1a (2.15 g, 10 mmol) and Lawessons reagent (6.0 g, 15 mmol). Yield: 61% (1.42 g), MS (ESI+); = 232.0783 [M + H]+. Anal. found: C, 66.04; H, 6.01; N, 5.62; Calc. for C13H13NOS0.25H2O: C, 66.21; H, 5.77; N, 5.94. 1H NMR (400.13 MHz, DMSO-= 2.31 (s, 3H, H-7), 5.46 (s, 2H, H-N), 6.94C7.85 (m, 7H, H-5, H-Ph, H-6) ppm. 2.2.3. 1-Ethylbenzyl-2-methyl-3-hydroxypyridin-4(1H)-thione, 1e Compound 1e was synthesized according to the general process using 1b (2.45 g, 10 mmol) and Lawessons reagent (6.0 g, 15 mmol). Yield: 60% (1.48 g), MS (ESI+); = 268.0767 [M + Na]+. Anal. found: C, 66.04; H, 6.01; N, 5.62; Calc. for C14H15NOS0.5H2O: C, 66.11; H, 6.34; N, 5.51. 1H NMR (400.13 MHz, DMSO-= 2.41 (s, 3H, H-7), 3.05 (t, 2H, H-Ph, 3= 7 Hz), 4.36 (t, 2H, H-N, 3= 7 Hz), 7.21C7.32 (m, 6H, H-5, H-Ph), 7.54 (d, 1H, H-6, 3= 7 Hz) ppm. 2.2.4. 1-(p-Methylbenzyl)-2-methyl-3-hydroxypyridin-4(1H)-thione, 1f Compound 1f was synthesized according to the general process using 1c (2.45 g, 10 mmol) and Lawessons reagent (6.0 g, 15 mmol). Yield: 65% (1.59 g), MS (ESI+); = 268.0771 [M RICTOR + Na]+. Anal. found: C, 60.09; H, 6.43; N, CB 300919 5.22; Calc. for C14H15NOS2H2O: C, 59.75; H, 6.81; N, 4.98. 1H NMR (400.13 MHz, MeOH-= 2.01 (s, 3H, H-Ph), 2.39 (s, 3H, H-7), 5.42 (s, 2H, H-N), 7.11C7.15 (m, 2H, H-Ph), 7.36C7.40 (m, 2H, H-Ph), 7.47 (d, 1H, H-5, 3= 7 Hz), 7.65 (d, 1H, H-6, 3= 7 Hz) ppm. 2.3. General Procedure for the Synthesis of Ru(6-p-Cymene) Complexes (= 450.1013 [M ? Cl]+ (calcd. 450.1008). Anal. found: C, 52.63; H, 4.86; N, 2.70; Calc. for C23H26ClNO2Ru0.6CH2Cl2: C, 52.89; H, 5.12; N, 2.61. 1H NMR (400.13 MHz, MeOH-= 1.32 (d, 6H, H-15/H-17, 3= 7 Hz), 2.25 (s, 3H, H-7), 2.33 (s, 3H, H-14), 2.81C2.87 (m, 1H, H-16), 5.32 (s, 2H, N-CH2), 5.42 (d, 2H, H-9/H-13, 3= 6 Hz), 5.65 (d, 2H, H-10/H-12, 3= 6 Hz), 6.57 (d, 1H, H-5,), 7.01 (d, 2H, Ph, 3= 7 Hz), 7.28C7.37 (m, 3H, Ph), 7.55 (d, 1H, H-6, 3= 7 Hz) ppm. 13C1H NMR (100.61 MHz, MeOH-= 12.1 (C-7), 18.4 (C-15,C-17), 22.6 (C-14), 32.4 (C-16), 59.1 (C-Ph), 78.9 (C-9/C-13), 80.6 (C-10/C-12), 97.0 (C-11), 100.0 (C-8), 110.4 (C-5), 127.4 (C-Ph), 129.3 (C-Ph), 130.2 (C-Ph), 135.7 (C-6), 135.8 (C-2), 137.0 (C-Ph), 160.9 (C-3), 175.7 (C-4) ppm. 2.3.2. [Chlorido3-oxo-1-ethylbenzyl-2-methylpyridin-4(1H)-onato-2O,O(6-p-cymene)ruthenium(II)], 2b Complex 2b was synthesized from bis[dichlorido(6-p-cymene)ruthenium(II)] (159 mg, 0.26 mmol, 1b (119 mg, 0.52 mmol), and NaOMe (34 mg, 0.63 mmol). Yield:.

Related Posts