1) Proton NMR spectroscopy was used to analyze the ligands H2L1-H2L4. Sharp singlets corresponding to various protons including the quinoline nitrogen, imine nitrogen, and azomethine protons were observed.
2) Ligands H2L1-H2L4 were prepared by refluxing equimolar solutions of 6-methyl-2-oxo-1,2-dihydroquinoline-3-carboxaldehyde and various thiosemicarbazides.
3) Yields and melting points are reported for each ligand. Characteristic IR, UV-Vis, and 1H NMR spectral data are also reported.
Tetrahedron Letters Volume 40 Issue 5 1999 (Doi 10.1016/s0040-4039 (98) 02540-4) Francisco JoséRomero-Salguero Jean-Marie Lehn - Synthesis of Multitopic Bidentate Ligands Based On Alternating Py
1) Proton NMR spectroscopy was used to analyze the ligands H2L1-H2L4. Sharp singlets corresponding to various protons including the quinoline nitrogen, imine nitrogen, and azomethine protons were observed.
2) Ligands H2L1-H2L4 were prepared by refluxing equimolar solutions of 6-methyl-2-oxo-1,2-dihydroquinoline-3-carboxaldehyde and various thiosemicarbazides.
3) Yields and melting points are reported for each ligand. Characteristic IR, UV-Vis, and 1H NMR spectral data are also reported.
1) Proton NMR spectroscopy was used to analyze the ligands H2L1-H2L4. Sharp singlets corresponding to various protons including the quinoline nitrogen, imine nitrogen, and azomethine protons were observed.
2) Ligands H2L1-H2L4 were prepared by refluxing equimolar solutions of 6-methyl-2-oxo-1,2-dihydroquinoline-3-carboxaldehyde and various thiosemicarbazides.
3) Yields and melting points are reported for each ligand. Characteristic IR, UV-Vis, and 1H NMR spectral data are also reported.
1) Proton NMR spectroscopy was used to analyze the ligands H2L1-H2L4. Sharp singlets corresponding to various protons including the quinoline nitrogen, imine nitrogen, and azomethine protons were observed.
2) Ligands H2L1-H2L4 were prepared by refluxing equimolar solutions of 6-methyl-2-oxo-1,2-dihydroquinoline-3-carboxaldehyde and various thiosemicarbazides.
3) Yields and melting points are reported for each ligand. Characteristic IR, UV-Vis, and 1H NMR spectral data are also reported.
The 1H-NMR spectra of the ligands (H2L1-4) have been recorded in DMSO,FIGURE S1-S4. The spectra of ligands displayed a sharp singlet atδ 11.92–12.03 and δ 11.62–11.96 ppm corresponding to quinoline nitrogen N(1)H and imine nitrogen N(3)H protons respectively.[37] In addition, all the ligands (except H2L3) showed a sharp singlet at δ 8.38– 8.69 ppmcorresponding to azomethine (HC=N) proton respectively. [38]However, in the ligand H2L3 azomethine (HC=N) and terminal N(4)H protons mixed together and appeared as multiplet at δ 8.57-8.59 ppm.[39,46]Although, a doublet appeared at δ 8.25–8.30 ppm in ligandH2L1, which was assigned to terminal N(4)H2 protons respectively. Whereas, a doublet appeared at δ8.56–8.57 ppm ranges corresponding to terminal NH proton ofthe ligandH2L2,and a sharp singlet atδ 8.80 ppm in ligand H2L4 has been assigned to terminal NH proton.[39] A sharp singlet appeared at δ 8.07–8.26 ppm for C(4)H protons in all the ligands (except ligand H2L4). In ligand H2L4,a sharp doublet appeared at δ 7.58-7.59 ppm corresponding to C(7) proton. The N(4) terminal phenyl protons were observed as multiplet in the ranges ofδ7.34-7.40 and 7.20-7.24 ppm. [47] In addition, the ligands (H2L1-4) exhibited a sharp signal at δ 7.40-7.57 ppm for C(5)H protons. While, a doublet was observed at δ 7.33- 7.35 and 7.34-7.35 ppm ranges was attributed to C(7)H protons of the ligandsH2L2and H2L3respectively and a pentet at δ 7.33-7.35 ppm was assigned for C(7)H protons of ligand H2L1.In addition, the ligands H2L2 and H2L3showed doublets for C(8)H protons at δ 7.20-7.22 ppm and in H2L1, a sharp singlet correspondingto C(8) proton was observed at δ 7.19 ppm. However, a doublet was observed at δ 3.03-3.04 ppm corresponding to terminal methyl protons in ligand H2L2. In ligand H2L3, a pentet and a triplet at δ 3.58-3.63 and 1.15-1.18 ppm corresponding to terminal methylene and methyl protons respectively. [48]In addition, the ligand H2L1showed a triplet at δ 2.48-2.49 ppm for C(6)H methyl protons, however this proton was observed as doublet at δ 2.490-2.493 ppm in the ligand H2L2.Further, the pentet observed at δ 2.48-2.49 ppm in ligand H2L3andH2L3 has been assigned for C(6)H methyl protons.[49] Preparation of 4(N)-substituted thiosemicarbazide ligands [H2-6MOQtsc-R] (Where R= H or CH3 or C2H5 or C6H5)(H2L1-4) Ligand [H2-6MOQtsc-H]H2L1was prepared by refluxing the equimolarsolution of 4N-thiosemicarbazide (0.242 g, 2.6 mmol) and 6-methyl-2-oxo-1,2-dihydroquinoline-3- carboxaldehyde (0.5 g, 2.6 mmol) in 20 cm 3 of methanol and refluxed for 30 minutes. During which a yellow colour precipitate was formed, then the reaction mixture was cooled to room temperature and the product formed was filtered, washed several times with cold methanol, and dried under vacuum. Other ligands (H2L2-4)were also prepared by adopting the comparable procedure by using respective thiosemicarbazides i.e., methylthiosemicarbazide (0.2794 g, 2.6 mmol), ethylthiosemicarbazide (0.3167 g, 2.6 mmol), phenylthiosemicarbazide (0.444 g, 2.6 mmol) as given in Scheme 1. [H2-6MOQtsc-H](H2L1): Yield: 83 %, Mp: >265 °C. Selected IR bands (‘ν’ in cm-1): 1655 (C=O); 1563 (C=N); 866 (C=S). UV-Vis (DMSO), λmax: 266 (87,934) (dm3mol−1cm−1)nm (n→л* transition); 360 (14,146) (dm3 mol−1cm−1)nm (n→л* transition); 1H NMR (500 MHz, DMSO-d6): (δ, ppm): 11.92 (s, 1H, N(1)H); 11.62 (s, 1H, N(3)H); 8.69 (s, 1H, -CH=N); 8.25-8.30 (d, 2H, J=20 Hz,N(4)H2); 8.07 (s, 1H, C(4)H); 7.40 (s, 1H, C(5)H); 7.33-7.35 (p, 1H, J=10 Hz, C(7)H); 7.19 (s, 1H, C(8)H); 2.48-2.49 (t, 3H, J=5 Hz, C(6)H, -CH3). [H2-6MOQtsc-Me](H2L2): Yield: 87 %, Mp: >267 °C. Selected IR bands (‘ν’ in cm-1): 1643 (C=O); 1603 (C=N); 856 (C=S). UV-Vis (DMSO), λmax: 267 (10,793) (dm3 mol−1cm−1)nm (n→л* transition); 360 (17,355) (dm3 mol−1cm−1)nm (n→л* transition); 1 H NMR (500 MHz, DMSO-d6): (δ, ppm): 11.94 (s, 1H, N(1)H); 11.68 (s, 1H, N(3)H); 8.60 (s, 1H, -CH=N); 8.56-8.57 (d, 1H, J=5 Hz, N(4)H); 8.26 (s, 1H, C(4)H); 7.42 (s, 1H, C(5)H); 7.33-7.35 (d, 1H, J=10 Hz, C(7)H); 7.20-7.22 (d, 1H, J=10 Hz,C(8)H); 3.08-3.04 (d, 3H, J=20 Hz terminal -CH3); 2.490-2.493 (d, 3H, J=1.5 Hz C(6)H, -CH3). [H2-6MOQtsc-Et](H2L3): Yield: 81 %, Mp: >265 °C. Selected IR bands (‘ν’ in cm-1): 1645 (C=O); 1598 (C=N); 858 (C=S). UV-Vis (DMSO), λmax: 267 (13,549) (dm3 mol−1cm−1)nm (n→л* transition); 361 (16,430) (dm3 mol−1cm−1)nm (n→л* transition); 1 H NMR (500 MHz, DMSO-d6): (δ, ppm): 11.94 (s, 1H, N(1)H); 11.62 (s, 1H, N(3)H); 8.57- 8.59 (m, 2H, J=10 Hz, -CH=N & N(4)H); 8.26 (s, 1H, C(4)H); 7.45 (s, 1H, C(5)H); 7.34- 7.35 (d, 1H, J=5 Hz, C(7)H); 7.20-7.22 (d, 1H, J=10 Hz, C(8)H); 3.58-3.63 (p, 2H, J=25 Hz, terminal –CH2); 1.15-1.18 (t, 3H, J=15 Hz, terminal -CH3); 2.48-2.49 (p, 3H, J=5 Hz C(6)H, -CH3). [H2-6MOQtsc-Ph](H2L4): Yield: 85 %, Mp: >267 °C. Selected IR bands (‘ν’ in cm-1): 1651 (C=O); 1541 (C=N); 852 (C=S). UV-Vis (DMSO), λmax: 270 (13,549) (dm3 mol−1cm−1)nm (n→л* transition); 360 (16,430) (dm3 mol−1cm−1)nm (n→л* transition); 1 H NMR (500 MHz, DMSO-d6): (δ, ppm): 12.03 (s, 1H, N(1)H); 11.96 (s, 1H, N(3)H); 8.80 (s, 1H, N(4)H); 8.38 (s, 1H, -CH=N); 7.57 (s, 1H, -C(5)H); 7.58-7.59 (d, 1H, C(7)); 7.45 (s, 1H, C(8)); 7.34-7.40 (m, 3H, terminal phenyl protons); 7.20-7.24 (m, 2H, terminal phenyl protons); terminal -CH3); 2.48-2.49 (p, 3H, J=5 Hz C(6)H, -CH3).
Tetrahedron Letters Volume 40 Issue 5 1999 (Doi 10.1016/s0040-4039 (98) 02540-4) Francisco JoséRomero-Salguero Jean-Marie Lehn - Synthesis of Multitopic Bidentate Ligands Based On Alternating Py