supplementary information · 1h and 13c nmr spectra 13–39 general information all reagents and...
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Supplementary Information
Solvent-free and Efficient Synthesis of Imidazo[1,2-a]pyridine Derivatives via a One-pot Three-component Reaction
Li-Rong Wen,* Zhao-Rui Li, Ming Li,* and Han Cao
State Key Laboratory Base of Eco-Chemical Engineering, College of Chemistry and Molecular Engineering, Qingdao University of Science and Technology, Qingdao 266042, P. R. China
Contents
General information 1 Characterization data 2–11 References 11 1H and 13C NMR spectra 13–39 General Information
All reagents and solvents were obtained from commercial suppliers and used without further purification. All reagents were weighed and handled in air at room temperature. Melting points were recorded on a RY-1 microscopic melting apparatus and uncorrected. 1H NMR spectra were recorded on 500 MHz and 13C NMR spectra were recorded on 125 MHz by using a Bruker Avance 500M spectrometer. Chemical shifts were reported in parts per million (δ) relative to tetramethylsilane (TMS). IR spectra were recorded on a Nicolet iS10 FT-IR spectrometer and only major peaks are reported in cm-1. Mass spectra were performed on an Ultima Global spectrometer with an ESI source. The X-ray single-crystal diffraction was performed on Saturn 724+ instrument.
The raw materials 1a-j were synthesized according to the literatures.1~5
The raw materials 2a-f were synthesized according to the literatures.6~7
General procedure for the preparation of hexahydroimidazo[1,2-a]pyridines 4 and hexahydropyrido[1,2-a]pyridines 5 via one-pot three-component reactions
+SCH3
O S
+ R3 CHO
13
24/ 5
Et3N, 80 °C
O
R1 NH
HN
N
HNR3
SO
OR1
R2
R2
solvent-freen n
(n = 1, 2 )
General procedure for the preparation of hexahydroimidazo[1,2-a]pyridines 4 and hexahydropyrido[1,2-a] pyrimidins 5 via one-pot three-component reactions HKAs 1 (0.5 mmol), β-oxodithioesters 2 (0.5 mmol) and aldehydes 3 (0.5 mmol) were placed into a 25 mL flask, and
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the mixture was stirred for the appropriate time at 80 °C in oil bath until the HKAs 1 were completely consumed. The mixture was washed with EtOH (10 mL) three times and vacuum filtration. The crude products so obtained were recrystallized from EtOH to afford the pure products 4/5.
Characterization data
1-((6S,7S)-6-Benzoyl-7-(4-fluorophenyl)-5-thioxo-1,2,3,5,6,7-hexahydroimidazo[1,2-a]pyridin-8-yl)ethanone (4a)
N
HN
SO
OF
Primrose yellow solid; Mp 227–228 °C; IR (KBr): 1678, 1654, 1424, 1196 cm-1; 1H NMR (500 MHz, CDCl3): δ = 9.48 (s, 1H, NH), 7.01–8.04 (m, 9H, ArH), 5.29 (d, J = 1.0 Hz, 1H, CHCO), 4.49–4.54 (m, 1H, NCH2), 4.22–4.28 (m, 1H, NCH2), 4.12 (s, 1H, ArCH), 3.93–4.00 (m, 2H, NHCH2), 1.75 (s, 3H, CH3); 13C NMR (125 MHz, CDCl3): δ = 194.5, 194.0, 193.2, 163.0, 161.1, 151.9, 138.3, 134.5, 133.9, 129.2, 128.8, 128.2, 128.1, 116.3, 116.1, 87.4, 66.2, 48.3, 42.0, 26.2; HRMS (ESI-TOF+): m/z calcd for C22H20N2O2FS [(M + H)+], 395.1230; found, 395.1239. 1-((6S,7S)-6-Benzoyl-7-(4-chlorophenyl)-5-thioxo-1,2,3,5,6,7-hexahydroimidazo[1,2-a] pyridin-8-yl)ethanone (4b)
N
HN
SO
OCl
Brown yellow solid; Mp 234–235 °C; IR (KBr): 1679, 1653, 1424, 1197 cm-1; 1H NMR (500 MHz, CDCl3): δ = 9.49 (s, 1H, NH), 7.07–8.03 (m, 9H, ArH), 5.28 (d, J = 1.0 Hz, 1H, CHCO), 4.48–4.53 (m, 1H, NCH2), 4.21–4.27 (m, 1H, NCH2), 4.10 (s, 1H, ArCH), 3.90–3.99 (m, 2H, NHCH2), 1.74 (s, 3H, CH3); 13C NMR (125 MHz,CDCl3): δ = 194.3, 193.9, 193.1, 152.0, 141.1, 134.6, 133.9, 133.4, 129.4, 129.2, 128.8, 128.0, 87.1, 65.9, 48.3, 42.1, 42.0, 26.2; HRMS (ESI-TOF+): m/z calcd for C22H20N2O2SCl, [(M + H)+], 411.0934; found, 411.0942. 1-((6S,7S)-6-Benzoyl-7-(4-bromophenyl)-5-thioxo-1,2,3,5,6,7-hexahydroimidazo[1,2-a] pyridin-8-yl)ethanone (4c)
N
HN
SO
OBr
Yellow solid; Mp 229–230 °C; IR (KBr): 1679, 1654, 1424, 1197 cm-1; 1H NMR (500 MHz, CDCl3): δ = 9.49 (s, 1H, NH), 7.01–8.03 (m, 9H, ArH), 5.28 (d, J = 1.0 Hz, 1H, CHCO), 4.48–4.53 (m, 1H, NCH2), 4.21–4.27 (m, 1H, NCH2), 4.09 (s, 1H, ArCH), 3.92–4.00 (m, 2H,
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NHCH2), 1.74 (s, 3H, CH3); 13C NMR (125 MHz, CDCl3): δ = 194.4, 193.9, 193.1, 152.0, 141.6, 134.5, 133.9, 132.4, 129.2, 128.8, 128.4, 121.4, 87.0, 65.8, 48.3, 42.2, 42.0, 26.2; HRMS (ESI-TOF+): m/z calcd for C22H20N2O2SBr [(M + H)+], 455.0429; found, 455.0419. 1-((6S,7R)-6-Benzoyl-7-(2-chlorophenyl)-5-thioxo-1,2,3,5,6,7-hexahydroimidazo[1,2-a] pyridin-8-yl)ethanone (4d) and 1-((6R,7S)-6-Benzoyl-7-(2-chlorophenyl)-5-thioxo-1,2,3,5,6,7-hexahydroimidazo[1,2-a] pyridin-8-yl)ethanone (4d')
N
HN
SO
OCl
4d
N
HN
SO
OCl
4d' Brown yellow solid; Mp 200–201 °C; IR (KBr): 1677, 1654, 1425, 1201 cm-1; 1H NMR (500 MHz, CDCl3): δ = 9.51 (s, 1H, NH, 4d), 9.42 (s, 1H, NH, 4d'), 6.85–8.10 (m, 2ArH, 4d/4d'), 5.26 (d, J = 1.0 Hz, 1H, CHCO, 4d), 4.61 (d, J = 1.0 Hz, 1H, CHCO, 4d'), 4.54–4.56 (m, 1H, NCH2, 4d), 4.44–4.50 (m, 1H, NCH2, 4d'), 4.34–4.39 (m, 1H, NCH2, 4d), 4.22–4.28 (m, 1H, NCH2, 4d'), 4.11–4.18 (m, 2ArCH, 4d/4d'), 3.93–4.01 (m, 2H, NHCH2, 4d), 3.81–3.92 (m, 2H, NHCH2, 4d'), 1.90 (s, 3H, CH3, 4d), 1.75 (s, 3H, CH3, 4d'); 13C NMR (125 MHz, CDCl3): δ = 197.5, 195.4, 194.7, 194.5, 193.0, 152.5, 152.0, 140.0, 139.5, 134.9, 133.8, 133.0, 132.3, 130.1, 129.4, 128.9, 128.7, 128.5, 128.4, 127.7, 127.6, 127.3, 89.2, 87.5, 63.7, 48.5, 47.9, 47.3, 42.1, 41.8, 38.6, 34.5, 26.2, 18.4; HRMS (ESI-TOF+): m/z calcd for C22H20N2O2ClS [(M + H)+], 411.0934; found, 411.0938. 1-((6S,7S)-6-Benzoyl-7-(3-chlorophenyl)-5-thioxo-1,2,3,5,6,7-hexahydroimidazo[1,2-a] pyridin-8-yl)ethanone (4e)
N
HN
SO
OCl
Primrose yellow solid; Mp 238–239 °C; IR (KBr): 1685, 1654, 1423, 1193 cm-1; 1H NMR (500 MHz, CDCl3): δ = 9.50 (s, 1H, NH), 7.03–8.04 (m, 9H, ArH), 5.30 (d, J = 1.0 Hz, 1H, CHCO), 4.48–4.54 (m, 1H, NCH2), 4.22–4.28 (m, 1H, NCH2), 4.11 (s, 1H, ArCH), 3.93–3.98 (m, 2H, NHCH2), 1.75 (s, 3H, CH3); 13C NMR (125 MHz, CDCl3): δ = 194.3, 194.0, 193.0, 152.1, 144.6, 135.0, 134.5, 133.9, 130.6, 129.2, 128.8, 127.9, 126.8, 124.9, 86.7, 65.7, 48.3, 42.3, 42.0, 26.3; HRMS (ESI-TOF+): m/z calcd for C22H20N2O2SCl [(M + H)+], 411.0934; found, 411.0942. 1-((6S,7S)-6-Benzoyl-7-(4-nitrophenyl)-5-thioxo-1,2,3,5,6,7-hexahydroimidazo[1,2-a]pyridin-8-yl)ethanone (4f)
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N
HN
SO
OO2N
Brown yellow solid; Mp 210–211 °C; IR (KBr): 1683, 1654, 1428, 1199 cm-1; 1H NMR (500 MHz, CDCl3): δ = 9.55 (s, 1H, NH), 7.26–8.23 (m, 9H, ArH), 5.27 (d, J = 1.5 Hz, 1H, CHCO), 4.49–4.55 (m, 1H, NCH2), 4.25–4.29 (m, 1H, NCH2), 4.23 (s, 1H, ArCH), 3.97–4.01 (m, 2H, NHCH2) 1.74 (s, 3H, CH3); 13C NMR (125 MHz, CDCl3): δ = 193.9, 193.6, 192.5, 152.3, 149.9, 147.5, 134.5, 134.1, 129.3, 128.8, 127.7, 124.6, 86.4, 65.3, 48.5, 42.6, 42.1, 26.2; HRMS (ESI-TOF+): m/z calcd for C22H20N3O4S [(M + H)+], 422.1175; found, 422.1185. 1-((6S,7S)-6-Benzoyl-7-phenyl-5-thioxo-1,2,3,5,6,7-hexahydroimidazo[1,2-a]pyridin-8-yl) ethanone (4g)
N
HN
SO
O
Yellow solid; Mp 237–238 °C; IR (KBr): 1686, 1652, 1421, 1199 cm-1; 1H NMR (500 MHz, CDCl3): δ = 9.48 (s, 1H, NH), 7.13–8.06 (m, 10H, ArH), 5.33 (d, J = 1.5 Hz, 1H, CHCO), 4.49–4.55 (m, 1H, NCH2), 4.22–4.28 (m, 1H, NCH2), 4.13 (s, 1H, ArCH), 3.93–3.98 (m, 2H, NHCH2), 1.75 (s, 3H, CH3); 13C NMR (125 MHz, CDCl3): δ = 194.7, 194.2, 193.5, 151.9, 142.5, 134.5, 133.8, 129.3, 129.1, 128.8, 127.6, 126.6, 87.5, 66.0, 48.3, 42.7, 42.0, 26.3; HRMS (ESI-TOF+): m/z calcd for C22H21N2O2S [(M + H)+], 377.1324; found, 377.1315. 1-((6S,7S)-6-Benzoyl-5-thioxo-7-p-tolyl-1,2,3,5,6,7-hexahydroimidazo[1,2-a]pyridin-8-yl) ethanone (4h)
N
HN
SO
OH3C
Brown yellow solid; Mp 235–236 °C; IR (KBr): 1678, 1653, 1421, 1198 cm-1; 1H NMR (500 MHz, CDCl3): δ = 9.47 (s, 1H, NH), 7.01–8.05 (m, 9H, ArH), 5.32 (d, J = 1.0 Hz, 1H, CHCO), 4.49–4.55 (m, 1H, NCH2), 4.21–4.27 (m, 1H, NCH2), 4.10 (s, 1H, ArCH), 3.92–3.99 (m, 2H, NHCH2), 2.33 (s, 3H, ArCH3) 1.76 (s, 3H, CH3); 13C NMR (125 MHz, CDCl3): δ = 194.6, 194.3, 193.6, 151.9, 139.6, 137.2, 134.7, 133.7, 129.9, 129.1, 128.8, 126.5, 87.7, 66.3, 48.3, 42.4, 42.0, 26.2, 21.0; HRMS (ESI-TOF+): m/z calcd for C23H23N2O2S [(M + H)+], 391.1480; found, 391.1495. 1-((6S,7S)-6-Benzoyl-7-(4-methoxyphenyl)-5-thioxo-1,2,3,5,6,7-hexahydroimidazo[1,2-a] pyridin-8-yl)ethanone (4i)
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N
HN
SO
OH3CO
Primrose yellow solid; Mp 226–227 °C; IR (KBr): 1683, 1652, 1420, 1194 cm-1; 1H NMR (500 MHz, CDCl3): δ = 9.46 (s, 1H, NH), 6.85–8.05 (m, 9H, ArH), 5.32 (d, J = 1.5 Hz, 1H, CHCO), 4.49–4.53 (m, 1H, NCH2), 4.21–4.27 (m, 1H, NCH2), 4.09 (s, 1H, ArCH), 3.92–3.97 (m, 2H, NHCH2), 3.79 (s, 3H, OCH3), 1.76 (s, 3H, CH3); 13C NMR (125 MHz, CDCl3): δ = 194.6, 194.2, 193.6, 158.9, 151.9, 134.7, 134.6, 133.7, 129.1, 128.8, 127.7, 114.6, 87.8, 66.5, 55.3, 48.3, 42.0, 26.1; HRMS (ESI-TOF+): m/z calcd for C23H23N2O3S [(M + H)+], 407.1429; found, 407.1438. 1-((6S,7R)-6-Benzoyl-7-(furan-2-yl)-5-thioxo-1,2,3,5,6,7-hexahydroimidazo[1,2-a]pyridin-8- yl)ethanone (4j)
N
HN
SO
O
O
Brown yellow solid; Mp 219–220 °C; IR (KBr): 1682, 1652, 1425, 1195 cm-1; 1H NMR (500 MHz, CDCl3): δ = 9.46 (s, 1H, NH), 6.04–8.09 (m, 8H, ArH), 5.64 (d, J = 1.5 Hz, 1H, CHCO), 4.47–4.53 (m, 1H, NCH2), 4.29 (s, 1H, ArCH), 4.12–4.18 (m, 1H, NCH2), 3.85–3.94 (m, 2H, NHCH2), 1.88 (s, 3H, CH3); 13C NMR (125 MHz, CDCl3): δ = 194.1, 194.0, 193.9, 154.5, 151.9, 142.7, 134.2, 133.9, 129.1, 128.9, 110.4, 106.4, 85.3, 62.7, 48.2, 42.0, 36.7, 25.8; HRMS (ESI-TOF+): m/z calcd for C20H19N2O3S [(M + H)+], 367.1116; found, 367.1125. 1-((6S,7R)-6-Benzoyl-7-ethyl-5-thioxo-1,2,3,5,6,7-hexahydroimidazo[1,2-a]pyridin-8-yl) ethanone (4k)
N
HN
H3CH2C
SO
O
Brown yellow solid; Mp 192–193 °C; IR (KBr): 1686, 1652, 1424, 1194 cm-1; 1H NMR (500 MHz, CDCl3): δ = 9.34 (s, 1H, NH), 7.48–7.92 (m, 5H, ArH), 5.21 (d, J = 1.0 Hz, 1H, CHCO), 4.50–4.51 (m, 1H, NCH2), 4.13–4.15 (m, 1H, NCH2), 3.83–3.88 (m, 2H, NHCH2), 2.87–2.90 (m, 1H, CHCH2CH3), 1.84 (s, 3H, CH3), 1.55–1.62 (m, 2H, CHCH2CH3), 1.06 (t, J = 7.5 Hz, 3H, CHCH2CH3); 13C NMR (125 MHz, CDCl3): δ = 195.4, 194.9, 193.7, 151.5, 134.9, 133.5, 129.0, 128.5, 89.1, 63.0, 48.1, 41.9, 38.9, 29.2, 25.6, 11.2; HRMS (ESI-TOF+): m/z calcd for C18H21N2O2S [(M + H)+], 329.1324; found, 329.1329. 1-((6S,7R)-6-Benzoyl-7-isopropyl-5-thioxo-1,2,3,5,6,7-hexahydroimidazo[1,2-a]pyridin-8-yl) ethanone (4l)
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N
HN
SO
O
Brown yellow solid; Mp 185–186 °C; IR (KBr): 1682, 1655, 1429, 1196 cm-1; 1H NMR (500 MHz, CDCl3): δ = 9.46 (s, 1H, NH), 7.49–7.93 (m, 5H, ArH), 5.28 (s, 1H, CHCO), 4.52–4.57 (m, 1H, NCH2), 4.07–4.13 (m, 1H, NCH2), 3.84–3.88 (m, 2H, NHCH2), 2.76 (d, J = 6.0 Hz, 1H, CHCH(CH3)2), 1.81 (s, 3H, CH3), 1.74–1.79 (m, 1H, CHCH(CH3)2), 1.06 (d, J = 7.0 Hz, 3H, CH3CHCH3), 1.00 (d, J = 6.5 Hz, 3H, CH3CHCH3); 13C NMR (125 MHz, CDCl3): δ = 196.2, 195.3, 194.2, 151.9, 134.9, 133.5, 128.9, 128.5, 88.2, 60.7, 48.1, 43.5, 41.9, 34.3, 25.7, 20.7, 18.6; HRMS (ESI-TOF+): m/z calcd for C19H23N2O2S [(M + H)+], 343.1480; found, 343.1495. ((6S,7S)-7-Phenyl-5-thioxo-1,2,3,5,6,7-hexahydroimidazo[1,2-a]pyridine-6,8-diyl)bis (phenylmethanone) (4m)
N
HN
SO
O
Yellow solid; Mp 243–244 °C; IR (KBr): 1684, 1640, 1419, 1204 cm-1; 1H NMR (500 MHz, CDCl3): δ = 9.75 (s, 1H, NH), 6.76–7.99 (m, 15H, ArH), 5.31 (d, J = 1.5 Hz, 1H, CHCO), 4.59–4.65 (m, 1H, NCH2), 4.25–4.29 (m, 1H, NCH2), 4.24 (s, 1H, ArCH), 3.98–4.02 (m, 2H, NHCH2); 13C NMR (125 MHz, CDCl3): δ = 194.7, 194.6, 193.2, 153.5, 142.8, 140.6, 134.8, 133.7, 129.0, 128.9, 128.7, 127.7, 127.2, 126.5, 126.0, 87.5, 66.0, 48.4, 42.3, 42.1; HRMS (ESI-TOF+): m/z calcd for C27H23N2O2S [(M + H)+], 439.1480; found, 439.1466. ((6S,7S)-6-Benzoyl-7-phenyl-5-thioxo-1,2,3,5,6,7-hexahydroimidazo[1,2-a]pyridin-8-yl) (2-chlorophenyl)methanone (4n)
N
HN
SO
OCl
Brown yellow solid; Mp 225–226 °C; IR (KBr): 1681, 1648, 1417, 1208 cm-1; 1H NMR (500 MHz, CDCl3): δ = 9.72 (s, 1H, NH), 6.41–7.97 (m, 14H, ArH), 5.25 (s, 1H, CHCO), 4.58–4.63 (m, 1H, NCH2), 4.30–4.36 (m, 1H, NCH2), 3.99–4.06 (m, 2H, NHCH2), 3.81 (s, 1H, ArCH); 13C NMR (125 MHz, CDCl3): δ = 194.5, 190.7, 190.6, 153.4, 134.6, 133.7, 129.4, 129.0, 128.8, 128.7, 127.3, 126.5, 126.0, 88.3, 65.9, 48.4, 42.4, 42.3; HRMS (ESI-TOF+): m/z calcd for C27H22N2O2ClS [(M + H)+], 473.1091; found, 473.1098. ((6S,7S)-6-Benzoyl-7-phenyl-5-thioxo-1,2,3,5,6,7-hexahydroimidazo[1,2-a]pyridin-8-yl)(3- chlorophenyl)methanone (4o)
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N
HN
SO
O
Cl
Yellow solid; Mp 257–258 °C; IR (KBr): 1684, 1638, 1421, 1205 cm-1; 1H NMR (500 MHz, CDCl3): δ = 9.78 (s, 1H, NH), 6.71–7.99 (m, 14H, ArH), 5.32 (d, J = 1.5 Hz, 1H, CHCO), 4.59–4.64 (m, 1H, NCH2), 4.24–4.30 (m, 1H, NCH2), 4.18 (d, J = 1.0 Hz, 1H, ArCH), 4.00–4.03 (m, 2H, NHCH2); 13C NMR (125 MHz, CDCl3): δ = 194.6, 194.5, 191.7, 153.8, 142.5, 138.9, 134.9, 134.6, 133.9, 129.2, 129.1, 128.6, 128.0, 127.6, 127.4, 126.4, 87.2, 66.0, 48.4, 42.4, 22.2; HRMS (ESI-TOF+): m/z calcd for C27H22N2O2ClS [(M + H)+], 473.1091; found, 473.1086. ((6S,7S)-6-Benzoyl-7-phenyl-5-thioxo-1,2,3,5,6,7-hexahydroimidazo[1,2-a]pyridin-8-yl)(4- chlorophenyl)methanone (4p)
N
HN
SO
O
Cl
Yellow solid; Mp 256–257 °C; IR (KBr): 1684, 1638, 1422, 1205 cm-1; 1H NMR (500 MHz, CDCl3): δ = 9.78 (s, 1H, NH), 6.71–7.99 (m, 14H, ArH), 5.32 (s 1H, CHCO), 4.59–4.64 (m, 1H, NCH2), 4.23–4.30 (m, 1H, NCH2), 4.17 (s, 1H, ArCH), 3.99–4.05 (m, 2H, NHCH2); 13C NMR (125 MHz, CDCl3): δ = 194.6, 194.5, 191.7, 153.8, 142.5, 138.9, 134.9, 134.6, 133.9, 129.2, 129.1, 128.4, 128.0, 127.6, 127.4, 126.4, 87.2, 66.0, 48.4, 42.4, 42.2; HRMS (ESI-TOF+): m/z calcd for C27H22N2O2SCl [(M + H)+], 473.1091; found, 473.1098. ((6S,7S)-6-Benzoyl-7-phenyl-5-thioxo-1,2,3,5,6,7-hexahydroimidazo[1,2-a]pyridin-8-yl)(4- bromophenyl)methanone (4q)
N
HN
SO
O
Br
Yellow solid; Mp 250–251 °C; IR (KBr): 1683, 1643, 1417, 1201 cm-1; 1H NMR (500 MHz, CDCl3): δ = 9.78 (s, 1H, NH), 6.64–7.98 (m, 14H, ArH), 5.32 (s, 1H, CHCO), 4.59–4.64 (m, 1H, NCH2), 4.23–4.30 (m, 1H, NCH2), 4.17 (s, 1H, ArCH), 4.00–4.05 (m, 2H, NHCH2); 13C NMR (125 MHz, CDCl3): δ = 194.6, 194.5, 191.7, 153.8, 142.5, 139.3, 134.6, 133.9, 131.0, 129.2, 129.1, 128.6, 127.8, 127.4, 126.4, 123.2, 87.2, 66.0, 48.4, 42.3, 42.2; HRMS (ESI-TOF+): m/z calcd for
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C27H22N2O2BrS [(M + H)+], 517.0585; found, 517.0596. ((6S,7S)-6-Benzoyl-7-phenyl-5-thioxo-1,2,3,5,6,7-hexahydroimidazo[1,2-a]pyridin-8-yl) (p-tolyl)methanone (4r)
N
HN
SO
O
H3C
Yellow solid; Mp 259–260 °C; IR (KBr): 1684, 1637, 1421, 1204 cm-1; 1H NMR (500 MHz, CDCl3): δ = 9.76 (s, 1H, NH), 6.69–8.00 (m, 14H, ArH), 5.34 (d, J = 1.5 Hz, 1H, CHCO), 4.59–4.65 (m, 1H, NCH2), 4.32 (s, 1H, ArCH), 4.22–4.26 (m, 1H, NCH2), 3.98–4.01 (m, 2H, NHCH2), 2.21 (s, 3H, ArCH3); 13C NMR (125 MHz, CDCl3): δ = 194.6, 194.5, 193.2, 153.4, 142.7, 139.0, 137.7, 134.8, 133.6, 129.0, 128.9, 128.7, 128.4, 127.1, 126.4, 126.2, 87.5, 65.8, 48.4, 42.2, 42.0, 21.2; HRMS (ESI-TOF+): m/z calcd for C28H25N2O2S [(M + H)+], 453.1637; found, 453.1645. ((6S,7S)-6-Benzoyl-7-phenyl-5-thioxo-1,2,3,5,6,7-hexahydroimidazo[1,2-a]pyridin-8-yl)(4- methoxyphenyl)methanone (4s)
N
HN
SO
O
H3CO
Yellow solid; Mp 251–252 °C; IR (KBr): 1685, 1641, 1419, 1202 cm-1; 1H NMR (500 MHz, CDCl3): δ = 9.75 (s, 1H, NH), 6.48–8.00 (m, 14H, ArH), 5.35 (d, J = 1.5 Hz, 1H, CHCO), 4.58–4.63 (m, 1H, NCH2), 4.35 (d, J = 1.0 Hz, 1H, ArCH), 4.21–4.27 (m, 1H, NCH2), 3.96–4.00 (m, 2H, NHCH2), 3.70 (s, 3H, OCH3); 13C NMR (125 MHz, CDCl3): δ = 194.6, 194.5, 192.6, 160.2, 153.4, 142.8, 134.8, 133.7, 133.2, 129.1, 129.0, 128.7, 128.1, 127.2, 126.5, 113.1, 87.4, 66.0, 55.1, 48.4, 42.4, 42.1; HRMS (ESI-TOF+): m/z calcd for C28H25N2O3S [(M + H)+], 469.1586; found, 469.1595. ((6S,7S)-8-Benzoyl-7-phenyl-5-thioxo-1,2,3,5,6,7-hexahydroimidazo[1,2-a]pyridin-6-yl)(4- chlorophenyl)methanone (4t)
N
HN
SO
O
Cl
Yellow solid; Mp 265–266 °C; IR (KBr): 1686, 1639, 1417, 1204 cm-1; 1H NMR (500 MHz,
8
Electronic Supplementary Material (ESI) for Green ChemistryThis journal is © The Royal Society of Chemistry 2012
CDCl3): δ = 9.75 (s, 1H, NH), 6.78–7.92 (m, 14H, ArH), 5.24 (d, J = 1.5 Hz, 1H, CHCO), 4.58–4.64 (m, 1H, NCH2), 4.24–4.30 (m, 1H, NCH2), 4.17 (d, J = 1.0 Hz, 1H, ArCH), 3.99–4.03 (m, 2H, NHCH2); 13C NMR (125 MHz, CDCl3): δ = 194.0, 193.4, 193.2, 153.4, 142.6, 140.5, 140.3, 133.0, 130.0, 129.3, 129.0, 127.8, 127.3, 126.3, 125.9, 87.3, 65.9, 48.4, 42.4, 42.1; HRMS (ESI-TOF+): m/z calcd for C27H22N2O2ClS [(M + H)+], 473.1091; found, 473.1082. ((6S,7S)-8-Benzoyl-7-phenyl-5-thioxo-1,2,3,5,6,7-hexahydroimidazo[1,2-a]pyridin-6-yl)(4- bromophenyl)methanone (4u)
N
HN
SO
O
Br
Brown yellow solid; Mp 249–250 °C; IR (KBr): 1684, 1637, 1416, 1202 cm-1; 1H NMR (500 MHz, CDCl3): δ = 9.75 (s, 1H, NH), 6.77–7.89 (m, 14H, ArH), 5.26 (d, J = 1.5 Hz, 1H, CHCO), 4.58–4.60 (m, 1H, NCH2), 4.24–4.27 (m, 1H, NCH2), 4.16 (d, J = 0.5 Hz, 1H, ArCH), 3.97–4.00 (m, 2H, NHCH2); 13C NMR (125 MHz, CDCl3): δ = 194.8, 194.1, 193.3, 153.5, 147.3, 142.9, 142.6, 140.6, 133.6, 132.4, 130.8, 130.2, 129.1, 129.0, 127.9, 127.4, 127.3, 126.5, 126.1, 126.0 125.3, 87.4, 65.7, 48.5, 42.6, 42.2; HRMS (ESI-TOF+): m/z calcd for C27H22N2O2BrS [(M + H)+], 517.0585; found, 517.0575. ((6S,7S)-8-Benzoyl-7-phenyl-5-thioxo-1,2,3,5,6,7-hexahydroimidazo[1,2-a]pyridin-6-yl) (p-tolyl)methanone (4v)
N
HN
SO
O
H3C
Yellow solid; Mp 253–254 °C; IR (KBr): 1683, 1642, 1420, 1196 cm-1; 1H NMR (500 MHz, CDCl3): δ = 9.76 (s, 1H, NH), 6.78–7.89 (m, 14H, ArH), 5.29 (d, J = 1.5 Hz, 1H, CHCO), 4.59–4.63 (m, 1H, NCH2), 4.25–4.28 (m, 1H, NCH2), 4.24 (d, J = 1.0 Hz, 1H, ArCH), 3.99–4.02 (m, 2H, NHCH2); 13C NMR (125 MHz, CDCl3): δ = 194.9, 194.2, 193.2, 153.5, 144.7, 142.8, 140.6, 132.6, 129.7, 128.9, 128.8, 127.7, 127.1, 126.5, 126.1, 87.5, 65.8, 48.3, 42.4, 42.1, 21.7; HRMS (ESI-TOF+): m/z calcd for C28H25N2O2S [(M + H)+], 453.1637; found, 453.1629. ((6S,7S)-8-Benzoyl-7-phenyl-5-thioxo-1,2,3,5,6,7-hexahydroimidazo[1,2-a]pyridin-6-yl)(4- methoxyphenyl)methanone (4w)
N
HN
SO
O
H3CO
9
Electronic Supplementary Material (ESI) for Green ChemistryThis journal is © The Royal Society of Chemistry 2012
Brown yellow solid; Mp 243–244 °C; IR (KBr): 1677, 1645, 1420, 1205 cm-1; 1H NMR (500 MHz, CDCl3): δ = 9.75 (s, 1H, NH), 6.80–8.00 (m, 14H, ArH), 5.27 (d, J = 1.5 Hz, 1H, CHCO), 4.60–4.62 (m, 1H, NCH2), 4.24–4.28 (m, 1H, NCH2), 4.23 (s, 1H, ArCH), 3.99–4.02 (m, 2H, NHCH2), 3.91 (s, 3H, OCH3); 13C NMR (125 MHz, CDCl3): δ = 195.1, 193.3, 193.1, 153.5, 143.0, 140.7, 131.2, 129.0, 127.9, 127.4, 127.2, 126.5, 126.2, 123.3, 114.3, 87.7, 65.6, 55.7, 48.6, 42.6, 42.2; HRMS (ESI-TOF+): m/z calcd for C28H25N2O3S [(M + H)+], 469.1586; found, 469.1586. ((6S,7S)-8-(4-Chlorobenzoyl)-7-phenyl-5-thioxo-1,2,3,5,6,7-hexahydroimidazo[1,2-a]pyridin-6-yl)(4-fluorophenyl)methanone (4x)
N
HN
SO
O
F
Cl
Yellow solid; Mp 248–249 °C; IR (KBr): 1686, 1637, 1417, 1202 cm-1; 1H NMR (500 MHz, CDCl3): δ = 9.80 (s, 1H, NH), 6.73–8.02 (m, 13H, ArH), 5.26 (d, J = 1.5 Hz, 1H, CHCO), 4.58–4.61 (m, 1H, NCH2), 4.25–4.28 (m, 1H, NCH2), 4.14 (d, J = 1.0 Hz, 1H, ArCH), 3.99–4.03 (m, 2H, NHCH2); 13C NMR (125 MHz, CDCl3): δ = 194.7, 194.1, 193.4, 167.2, 165.2, 153.8, 147.5, 142.6, 139.0, 134.9, 131.4, 131.1, 130.7, 129.1, 128.1, 127.4, 126.5, 125.4, 116.3, 87.4, 65.9, 48.5, 42.6, 42.2; HRMS (ESI-TOF+): m/z calcd for C27H21N2O2FClS [(M + H)+], 491.0996; found, 491.0985. ((6S,7S)-7-(4-Chlorophenyl)-5-thioxo-1,2,3,5,6,7-hexahydroimidazo[1,2-a]pyridine-6,8-diyl) bis(phenylmethanone) (4y)
N
HN
SO
OCl
Yellow solid; Mp 255–256 °C; IR (KBr): 1683, 1643, 1419, 1204 cm-1; 1H NMR (500 MHz, CDCl3): δ = 9.74 (s, 1H, NH), 6.75–7.97 (m, 14H, ArH), 5.25 (d, J = 1.5 Hz, 1H, CHCO), 4.59–4.64 (m, 1H, NCH2), 4.24–4.30 (m, 1H, NCH2), 4.21 (d, J = 0.5 Hz, 1H, ArCH), 4.00–4.03 (m, 2H, NHCH2); 13C NMR (125 MHz, CDCl3): δ = 194.4, 194.3, 193.2, 153.4, 141.2, 140.4, 134.6, 133.8, 133.0, 129.1, 129.0, 128.6, 127.9, 125.9, 87.1, 65.8, 48.4, 42.2, 41.8; HRMS (ESI-TOF+): m/z calcd for C27H22N2O2SCl [(M + H)+], 473.1091; found, 473.1075. ((7S,8S)-9-(2-Chlorobenzoyl)-8-phenyl-6-thioxo-2,3,4,6,7,8-hexahydro-1H-pyrido[1,2-a] pyrimidin-7-yl)(p-tolyl)methanone (5a) and (S,Z)-(2-Chlorophenyl)(7-(hydroxy(p-tolyl)methylene)-8-phenyl-6-thioxo-2,3,4,6,7,8- hexahydro-1H-pyrido[1,2-a]pyrimidin-9-yl)methanone (5a')
10
Electronic Supplementary Material (ESI) for Green ChemistryThis journal is © The Royal Society of Chemistry 2012
N
SO
O
H3C
Cl
HN
5a
N
SOH
O
H3C
Cl
HN
5a' Yellow solid; Mp 203–204 °C; IR (KBr): 1679, 1620, 1391, 1158 cm-1; 1H NMR (500 MHz, CDCl3): δ = 12.79 (s, 1H, NH), 6.15–7.88 (m, 13H, ArH), 5.39 (s, 1H, CHCO), 4.79–4.81 (m, 1H, NCH2), 4.11–4.16 (m, 1H, NCH2), 4.00 (s, 0.4H, ArCH, 5a'), 3.71 (s, 0.6H, ArCH, 5a), 3.67 (s, 2H, NHCH2), 2.44–2.50 (d, J = 29.0 Hz, 3H, ArCH3), 2.34–2.37 (m, 1H, CH2CH2CH2), 2.23–2.26 (m, 1H, CH2CH2CH2), 1.64 (s, OH, 5a', exchanged by D2O); 13C NMR (125 MHz, CDCl3): δ = 199.7, 199.3, 194.3, 193.4, 188.4, 155.1, 144.5, 142.5, 141.2, 139.7, 132.1, 131.1, 129.7, 129.5, 128.9, 128.7, 128.4, 127.5, 127.1, 126.8, 125.8, 125.6, 89.9, 89.6, 67.7, 67.1, 46.8, 41.6, 41.4, 38.9, 21.7, 21.6; HRMS (ESI-TOF+): m/z calcd for C29H26N2O2SCl [(M + H)+], 501.1404; found, 501.1415. ((7S,8S)-9-(2,4-Dichlorobenzoyl)-8-phenyl-6-thioxo-2,3,4,6,7,8-hexahydro-1H-pyrido[1,2-a] pyrimidin-7-yl)(p-tolyl)methanone (5b) and (S,Z)-(2,4-Dichlorophenyl)(7-(hydroxy(p-tolyl)methylene)-8-phenyl-6-thioxo-2,3,4,6,7,8- hexahydro-1H-pyrido[1,2-a]pyrimidin-9-yl)methanone (5b')
N
SO
O
H3C
Cl
HN
Cl
5b
N
SOH
O
H3C
Cl
HN
Cl
5b' Yellow solid; Mp 223–224 °C; IR (KBr): 1678, 1622, 1377, 1185 cm-1; 1H NMR (500 MHz, CDCl3): δ = 12.75 (s, 1H, NH), 6.09–7.86 (m, 12H, ArH), 5.40 (s, 1H, CHCO), 4.76–4.80 (m, 1H, NCH2), 4.11–4.14 (m, 1H, NCH2), 3.95 (s, 0.4H, ArCH, 5b'), 3.66 (s, 0.6H, ArCH, 5b), 3.66 (s, 2H, NHCH2), 2.45–2.51 (d, J = 27.0 Hz, 3H, ArCH3), 2.35 (m, 1H, CH2CH2CH2), 2.23 (m, 1H, CH2CH2CH2); 13C NMR (125 MHz, CDCl3): δ = 199.6, 199.2, 194.2, 193.3, 155.2, 144.7, 142.3, 140.8, 138.2, 137.9, 134.0, 132.0, 130.7, 129.6, 128.8, 128.4, 127.7, 127.3, 126.7, 126.2, 89.8, 89.6, 67.7, 67.1, 46.8, 41.5, 39.0, 21.7, 21.5; HRMS (ESI-TOF+): m/z calcd for C29H25N2O2SCl2 [(M + H)+], 535.1014; found, 535.1024. References 1. (a) L. S. Geoffroy, C. Alain, K. Gilbert, Synthetic Communications. 2005, 35, 693–699. (b) M.
M. E. Ahmed, A. M. Abdussalam, A. A. Hatif, Synthetic Communications. 1997, 27(14), 2433–2444.
2. (a) A. V. N. Reddy, S. N. Maiti, I. P. Singh, G. Micetich, Synth. Commun. 1989, 19, 3021−3025. (b) H. Foks, D. Pancechowska-Ksepko, M. Janowiec, Z. Zwolska, E. Augustynowicz-Kopec, Phosphorus, Sulfur Silicon Relat. Elem. 2005, 180, 2291−2297.
3. M.-X. Zhao, M.-X. Wang, Z.-T. Huang, Tetrahedron 2002, 58, 1309−1316. 4. (a) Z.-T. Huang, M.-X. Wang, Synthesis 1992, 12, 1273−1276. (b) Z.-J. Li, D. Charles, Synth.
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Electronic Supplementary Material (ESI) for Green ChemistryThis journal is © The Royal Society of Chemistry 2012
Commun. 2001, 31, 527−533. 5. (a) Z.-T. Huang, P.-C. Zhang, Chem. Ber. 1989, 122, 2011–2016. (b) Z.-T. Huang, X. Shi,
Synthesis 1990, 2, 162–167. 6. (a) R. K. Ali, F. M. Mehdi, Journal of the Chinese Chemical Society, 2008, 55, 639–642. (b) T.
Bahman, A. R. Kiasat, J. Chem. Researchs, 1998, 455. (c) R. K. Ali, K. Foad, S. Ali, Synthetic Communications, 2008, 38, 1057–1063. (d) K. Riza, R. B. Nicholas, J. Org. Chem. 1981, 46, 197–201. (e) S. Mohammad, A. Zeinab, M. Barahman, SYNTHESIS, 2010, 3, 0392–0394.
7. (a) G. Singh, S. S. Bhattacharjee, H. Ila, H. Junjappa, Communications Synthesis 1982, 693-694. (b) R. Samuel, C. V. Asokan, S. Suma, P. Chandran, S. Retnamma, E. R. Anabha, Tetrahedron Letters 2007, 48, 8376–8378. (c) K. N. Satheesh, C. V. Asokan, Synthetic Communications, 1999, 29(5), 791–798.
12
Electronic Supplementary Material (ESI) for Green ChemistryThis journal is © The Royal Society of Chemistry 2012
1H and 13C NMR spectra
N
HN
SO
OF
1H and 13C NMR spectra of 4a
10 9 8 7 6 5 4 3 2 1 ppm
0.001
1.746
3.933
3.943
3.951
3.968
3.985
4.005
4.122
4.216
4.232
4.236
4.241
4.252
4.257
4.260
4.276
4.489
4.499
4.507
4.515
4.524
4.532
4.542
5.294
5.296
7.012
7.016
7.029
7.046
7.097
7.107
7.114
7.124
7.560
7.575
7.591
7.659
7.674
7.689
8.023
8.024
8.039
9.483
3.009
2.095
1.028
1.021
1.010
1.000
2.039
1.947
1.975
1.015
1.992
0.854
NAME LZR-2-fEXPNO 1PROCNO 1Date_ 20110530Time 16.21INSTRUM av500PROBHD 5 mm PABBO BB-PULPROG zg30TD 32768SOLVENT CDCl3NS 4DS 1SWH 10000.000 HzFIDRES 0.305176 HzAQ 1.6385000 secRG 406DW 50.000 usecDE 6.00 usecTE 295.9 KD1 2.00000000 secTD0 1
======== CHANNEL f1 ========NUC1 1HP1 13.50 usecPL1 2.20 dBSFO1 500.0335010 MHzSI 16384SF 500.0300082 MHzWDW EMSSB 0LB 0.30 HzGB 0PC 2.00
LZR-2-f 1H 1D 2011 05 30
7.07.27.47.67.88.08.2 ppm
200 180 160 140 120 100 80 60 40 20 ppm
26.230
41.984
48.344
66.156
87.379
116.078
116.250
128.172
128.234
128.779
129.180
133.900
134.515
138.278
151.935
161.052
163.013
193.244
194.040
194.473
LZR-2-F 13C 1D 2011 05 27
NAME LZR-2-fEXPNO 2PROCNO 1Date_ 20110531Time 20.51INSTRUM av500PROBHD 5 mm PABBO BB-PULPROG zgpg30TD 65536SOLVENT CDCl3NS 944DS 2SWH 32679.738 HzFIDRES 0.498653 HzAQ 1.0027661 secRG 18400DW 15.300 usecDE 6.00 usecTE 297.2 KD1 2.00000000 secd11 0.03000000 secDELTA 1.89999998 secTD0 1
======== CHANNEL f1 ========NUC1 13CP1 9.60 usecPL1 2.00 dBSFO1 125.7464750 MHz
======== CHANNEL f2 ========CPDPRG2 waltz16NUC2 1HPCPD2 80.00 usecPL2 2.60 dBPL12 17.66 dBPL13 17.66 dBSFO2 500.0355000 MHzSI 32768SF 125.7326470 MHzWDW EMSSB 0LB 6.00 HzGB 0PC 2.00
13
Electronic Supplementary Material (ESI) for Green ChemistryThis journal is © The Royal Society of Chemistry 2012
N
HN
SO
OCl
1H and 13C NMR spectra of 4b
10 9 8 7 6 5 4 3 2 1 ppm
-0.006
1.735
3.904
3.914
3.924
3.934
3.942
3.957
3.975
3.994
4.103
4.205
4.220
4.224
4.230
4.240
4.246
4.249
4.265
4.475
4.485
4.493
4.502
4.510
4.519
4.528
5.277
5.279
7.067
7.084
7.259
7.297
7.301
7.314
7.319
7.553
7.568
7.584
7.652
7.667
7.682
8.010
8.013
8.027
9.485
3.211
2.227
1.147
1.108
1.097
1.088
2.166
2.107
2.147
1.090
2.150
1.000
NAME LZR-2-BEXPNO 1PROCNO 1Date_ 20110410Time 19.36INSTRUM av500PROBHD 5 mm PABBO BB-PULPROG zg30TD 32768SOLVENT CDCl3NS 4DS 1SWH 10000.000 HzFIDRES 0.305176 HzAQ 1.6385000 secRG 256DW 50.000 usecDE 6.00 usecTE 293.6 KD1 2.00000000 secTD0 1
======== CHANNEL f1 ========NUC1 1HP1 13.50 usecPL1 2.20 dBSFO1 500.0335010 MHzSI 16384SF 500.0300106 MHzWDW EMSSB 0LB 0.30 HzGB 0PC 4.00
LZR-2-B 1H 1D 2011 04 10
7.07.27.47.67.88.08.2 ppm
200 180 160 140 120 100 80 60 40 20 ppm
26.179
42.019
42.126
48.339
65.936
87.080
128.004
128.759
129.169
129.434
133.374
133.874
134.551
141.088
151.997
193.093
193.941
194.313
LZR-2-B 13C 1D 2011 04 11
NAME LZR-2-BEXPNO 2PROCNO 1Date_ 20110411Time 16.25INSTRUM av500PROBHD 5 mm PABBO BB-PULPROG zgpg30TD 65536SOLVENT CDCl3NS 802DS 2SWH 32679.738 HzFIDRES 0.498653 HzAQ 1.0027661 secRG 18400DW 15.300 usecDE 6.00 usecTE 296.6 KD1 2.00000000 secd11 0.03000000 secDELTA 1.89999998 secTD0 1
======== CHANNEL f1 ========NUC1 13CP1 9.60 usecPL1 2.00 dBSFO1 125.7464750 MHz
======== CHANNEL f2 ========CPDPRG2 waltz16NUC2 1HPCPD2 80.00 usecPL2 2.60 dBPL12 17.66 dBPL13 17.66 dBSFO2 500.0355000 MHzSI 32768SF 125.7326470 MHzWDW EMSSB 0LB 5.00 HzGB 0PC 2.00
14
Electronic Supplementary Material (ESI) for Green ChemistryThis journal is © The Royal Society of Chemistry 2012
N
HN
SO
OBr
1H and 13C NMR spectra of 4c
10 9 8 7 6 5 4 3 2 1 ppm
0.000
1.740
3.922
3.931
3.941
3.949
3.964
3.982
4.002
4.091
4.209
4.225
4.229
4.234
4.244
4.250
4.254
4.270
4.481
4.491
4.499
4.507
4.516
4.524
4.534
5.279
5.281
7.013
7.030
7.451
7.456
7.459
7.473
7.477
7.558
7.573
7.588
7.658
7.673
7.688
8.013
8.015
8.030
9.489
2.973
2.047
1.014
1.015
1.001
0.991
1.989
1.971
1.979
1.000
1.959
0.898
NAME LZR-2-EEXPNO 1PROCNO 1Date_ 20110511Time 9.39INSTRUM av500PROBHD 5 mm PABBO BB-PULPROG zg30TD 32768SOLVENT CDCl3NS 4DS 1SWH 10000.000 HzFIDRES 0.305176 HzAQ 1.6385000 secRG 406DW 50.000 usecDE 6.00 usecTE 295.3 KD1 2.00000000 secTD0 1
======== CHANNEL f1 ========NUC1 1HP1 13.50 usecPL1 2.20 dBSFO1 500.0335010 MHzSI 16384SF 500.0300082 MHzWDW EMSSB 0LB 0.30 HzGB 0PC 2.00
LZR-2-E 1H 1D 2011 05 11
7.07.27.47.67.88.08.2 ppm
200 180 160 140 120 100 80 60 40 20 ppm
26.230
42.031
42.184
48.345
65.803
86.977
121.438
128.362
128.776
129.199
132.396
133.936
134.459
141.589
151.995
193.051
193.927
194.357
LZR-2-E 13C 1D 2011 05 13
NAME LZR-2-EEXPNO 2PROCNO 1Date_ 20110513Time 16.16INSTRUM av500PROBHD 5 mm PABBO BB-PULPROG zgpg30TD 65536SOLVENT CDCl3NS 576DS 2SWH 32679.738 HzFIDRES 0.498653 HzAQ 1.0027661 secRG 18400DW 15.300 usecDE 6.00 usecTE 297.8 KD1 2.00000000 secd11 0.03000000 secDELTA 1.89999998 secTD0 1
======== CHANNEL f1 ========NUC1 13CP1 9.60 usecPL1 2.00 dBSFO1 125.7464750 MHz
======== CHANNEL f2 ========CPDPRG2 waltz16NUC2 1HPCPD2 80.00 usecPL2 2.60 dBPL12 17.66 dBPL13 17.66 dBSFO2 500.0355000 MHzSI 32768SF 125.7326470 MHzWDW EMSSB 0LB 6.00 HzGB 0PC 2.00
15
Electronic Supplementary Material (ESI) for Green ChemistryThis journal is © The Royal Society of Chemistry 2012
N
HN
SO
OCl
4d
N
HN
SO
OCl
4d' 1H and 13C NMR spectra of 4d/4d'
10 9 8 7 6 5 4 3 2 1 ppm
1.751
1.896
3.252
3.268
3.460
3.463
3.494
3.497
3.834
3.851
3.870
3.941
3.952
3.960
3.971
3.988
4.248
4.264
4.470
4.539
4.542
4.555
4.558
4.612
4.614
5.261
5.263
6.853
6.857
6.868
6.932
6.937
7.130
7.143
7.185
7.197
7.372
7.387
7.397
7.410
7.507
7.522
7.538
7.622
7.636
8.089
8.104
9.507
3.114
2.640
0.888
0.890
1.843
2.196
0.924
1.094
0.904
1.096
0.876
1.044
1.035
0.835
1.022
1.897
2.001
1.877
2.114
1.049
2.103
0.805
1.000
NAME LZR-2-IEXPNO 1PROCNO 1Date_ 20110622Time 16.46INSTRUM av500PROBHD 5 mm PABBO BB-PULPROG zg30TD 32768SOLVENT CDCl3NS 4DS 1SWH 10000.000 HzFIDRES 0.305176 HzAQ 1.6385000 secRG 228DW 50.000 usecDE 6.00 usecTE 297.6 KD1 2.00000000 secTD0 1
======== CHANNEL f1 ========NUC1 1HP1 13.50 usecPL1 2.20 dBSFO1 500.0335010 MHzSI 16384SF 500.0300076 MHzWDW EMSSB 0LB 0.30 HzGB 0PC 2.00
LZR-2-I 1H 1D 2011 06 22
7.07.27.47.67.88.08.28.4 ppm
20406080100120140160180200 ppm
18.423
26.169
34.457
38.628
41.806
42.097
47.282
47.880
48.454
63.700
87.450
89.174
127.272
127.607
127.712
128.422
128.545
128.729
128.872
129.439
130.110
132.330
132.961
133.806
134.905
139.503
140.048
152.002
152.528
192.971
194.462
194.657
195.410
197.507
LZR-2-I 13C 1D 2011 10 27
NAME LZR-2-IEXPNO 2PROCNO 1Date_ 20111027Time 16.07INSTRUM av500PROBHD 5 mm PABBO BB-PULPROG zgpg30TD 65536SOLVENT CDCl3NS 1177DS 2SWH 32679.738 HzFIDRES 0.498653 HzAQ 1.0027661 secRG 18400DW 15.300 usecDE 6.00 usecTE 296.3 KD1 2.00000000 secd11 0.03000000 secDELTA 1.89999998 secTD0 1
======== CHANNEL f1 ========NUC1 13CP1 9.60 usecPL1 2.00 dBSFO1 125.7464750 MHz
======== CHANNEL f2 ========CPDPRG2 waltz16NUC2 1HPCPD2 80.00 usecPL2 2.60 dBPL12 17.66 dBPL13 17.66 dBSFO2 500.0355000 MHzSI 32768SF 125.7326437 MHzWDW EMSSB 0LB 10.00 HzGB 0PC 1.00
16
Electronic Supplementary Material (ESI) for Green ChemistryThis journal is © The Royal Society of Chemistry 2012
N
HN
SO
OCl
1H and 13C NMR spectra of 4e
10 9 8 7 6 5 4 3 2 1 ppm
0.000
1.745
3.933
3.941
3.950
3.961
3.966
3.982
4.107
4.222
4.237
4.241
4.247
4.257
4.263
4.266
4.282
4.482
4.493
4.499
4.509
4.518
4.525
4.535
5.301
5.303
7.025
7.039
7.103
7.241
7.244
7.247
7.257
7.260
7.263
7.267
7.282
7.298
7.566
7.581
7.596
7.662
7.676
7.691
8.022
8.024
8.039
9.504
3.610
2.426
1.221
1.244
1.216
1.196
1.191
1.141
3.030
2.413
1.186
2.426
1.000
NAME LZR-2-KEXPNO 1PROCNO 1Date_ 20110622Time 16.53INSTRUM av500PROBHD 5 mm PABBO BB-PULPROG zg30TD 32768SOLVENT CDCl3NS 4DS 1SWH 10000.000 HzFIDRES 0.305176 HzAQ 1.6385000 secRG 228DW 50.000 usecDE 6.00 usecTE 297.6 KD1 2.00000000 secTD0 1
======== CHANNEL f1 ========NUC1 1HP1 13.50 usecPL1 2.20 dBSFO1 500.0335010 MHzSI 16384SF 500.0300089 MHzWDW EMSSB 0LB 0.30 HzGB 0PC 2.00
LZR-2-K 1H 1D 2011 06 22
7.07.27.47.67.88.08.2 ppm
200 180 160 140 120 100 80 60 40 20 ppm
26.250
42.039
42.335
48.341
65.739
86.740
124.887
126.808
127.880
128.785
129.217
130.589
133.945
134.462
135.034
144.626
152.067
193.014
193.972
194.332
LZR-2-K 13C 1D 2011 06 27
NAME LZR-2-KEXPNO 2PROCNO 1Date_ 20110627Time 21.34INSTRUM av500PROBHD 5 mm PABBO BB-PULPROG zgpg30TD 65536SOLVENT CDCl3NS 307DS 2SWH 32679.738 HzFIDRES 0.498653 HzAQ 1.0027661 secRG 18400DW 15.300 usecDE 6.00 usecTE 298.0 KD1 2.00000000 secd11 0.03000000 secDELTA 1.89999998 secTD0 1
======== CHANNEL f1 ========NUC1 13CP1 9.60 usecPL1 2.00 dBSFO1 125.7464750 MHz
======== CHANNEL f2 ========CPDPRG2 waltz16NUC2 1HPCPD2 80.00 usecPL2 2.60 dBPL12 17.66 dBPL13 17.66 dBSFO2 500.0355000 MHzSI 32768SF 125.7326470 MHzWDW EMSSB 0LB 6.00 HzGB 0PC 2.00
17
Electronic Supplementary Material (ESI) for Green ChemistryThis journal is © The Royal Society of Chemistry 2012
N
HN
SO
OO2N
1H and 13C NMR spectra of 4f
9 8 7 6 5 4 3 2 1 ppm
0.000
0.006
1.737
3.966
3.977
3.986
3.994
4.011
4.235
4.252
4.256
4.261
4.271
4.277
4.281
4.297
4.492
4.503
4.510
4.519
4.528
4.535
4.546
5.274
5.277
7.262
7.313
7.330
7.577
7.593
7.608
7.681
7.696
7.710
8.016
8.031
8.212
8.229
9.548
2.973
2.084
1.131
0.919
1.018
0.994
2.002
2.016
1.000
2.000
1.841
0.834
NAME LZR-2-JEXPNO 1PROCNO 1Date_ 20110906Time 16.43INSTRUM av500PROBHD 5 mm PABBO BB-PULPROG zg30TD 32768SOLVENT CDCl3NS 8DS 1SWH 10000.000 HzFIDRES 0.305176 HzAQ 1.6385000 secRG 575DW 50.000 usecDE 6.00 usecTE 297.9 KD1 2.00000000 secTD0 1
======== CHANNEL f1 ========NUC1 1HP1 13.50 usecPL1 2.20 dBSFO1 500.0335010 MHzSI 16384SF 500.0300094 MHzWDW EMSSB 0LB 0.30 HzGB 0PC 2.00
LZR-2-J 1H 2011 09 06
7.27.47.67.88.08.28.4 ppm
20406080100120140160180200 ppm
26.169
42.135
42.604
48.463
65.314
86.430
124.656
127.707
128.789
129.326
134.101
134.525
147.487
149.964
152.281
192.524
193.575
193.923
LZR-2-J 13C 1D 2011 09 11
NAME LZR-2-JEXPNO 2PROCNO 1Date_ 20110911Time 11.01INSTRUM av500PROBHD 5 mm PABBO BB-PULPROG zgpg30TD 65536SOLVENT CDCl3NS 6541DS 2SWH 32679.738 HzFIDRES 0.498653 HzAQ 1.0027661 secRG 18400DW 15.300 usecDE 6.00 usecTE 298.4 KD1 2.00000000 secd11 0.03000000 secDELTA 1.89999998 secTD0 1
======== CHANNEL f1 ========NUC1 13CP1 9.60 usecPL1 2.00 dBSFO1 125.7464750 MHz
======== CHANNEL f2 ========CPDPRG2 waltz16NUC2 1HPCPD2 80.00 usecPL2 2.60 dBPL12 17.66 dBPL13 17.66 dBSFO2 500.0355000 MHzSI 32768SF 125.7326387 MHzWDW EMSSB 0LB 6.00 HzGB 0PC 2.00
18
Electronic Supplementary Material (ESI) for Green ChemistryThis journal is © The Royal Society of Chemistry 2012
N
HN
SO
O
1H and 13C NMR spectra of 4g
11 10 9 8 7 6 5 4 3 2 1 ppm
1.753
3.930
3.940
3.948
3.963
3.981
4.129
4.219
4.235
4.238
4.244
4.254
4.260
4.264
4.279
4.495
4.504
4.513
4.521
4.530
4.538
4.548
5.333
5.336
7.126
7.141
7.250
7.259
7.265
7.269
7.280
7.320
7.336
7.350
7.556
7.559
7.571
7.587
7.652
7.655
7.667
7.680
7.682
8.040
8.042
8.057
9.482
3.034
2.100
1.025
1.032
1.024
1.000
1.993
1.939
1.981
2.000
1.004
2.003
0.815
NAME LZR-2-CEXPNO 1PROCNO 1Date_ 20110428Time 20.27INSTRUM av500PROBHD 5 mm PABBO BB-PULPROG zg30TD 32768SOLVENT CDCl3NS 4DS 1SWH 10000.000 HzFIDRES 0.305176 HzAQ 1.6385000 secRG 456DW 50.000 usecDE 6.00 usecTE 295.4 KD1 2.00000000 secTD0 1
======== CHANNEL f1 ========NUC1 1HP1 13.50 usecPL1 2.20 dBSFO1 500.0335010 MHzSI 16384SF 500.0300106 MHzWDW EMSSB 0LB 0.30 HzGB 0PC 10.00
LZR-2-C 1H 1D 2011 04 28
7.27.47.67.88.08.2 ppm
20406080100120140160180200 ppm
26.297
42.009
42.705
48.320
66.041
87.494
126.624
127.566
128.841
129.138
129.269
133.836
134.534
142.539
151.928
193.478
194.207
194.649
LZR-2-C 13C 1D 2011 04 29
NAME LZR-2-CEXPNO 2PROCNO 1Date_ 20110429Time 16.48INSTRUM av500PROBHD 5 mm PABBO BB-PULPROG zgpg30TD 65536SOLVENT CDCl3NS 2440DS 2SWH 32679.738 HzFIDRES 0.498653 HzAQ 1.0027661 secRG 18400DW 15.300 usecDE 6.00 usecTE 297.9 KD1 2.00000000 secd11 0.03000000 secDELTA 1.89999998 secTD0 1
======== CHANNEL f1 ========NUC1 13CP1 9.60 usecPL1 2.00 dBSFO1 125.7464750 MHz
======== CHANNEL f2 ========CPDPRG2 waltz16NUC2 1HPCPD2 80.00 usecPL2 2.60 dBPL12 17.66 dBPL13 17.66 dBSFO2 500.0355000 MHzSI 32768SF 125.7326470 MHzWDW EMSSB 0LB 5.00 HzGB 0PC 2.00
19
Electronic Supplementary Material (ESI) for Green ChemistryThis journal is © The Royal Society of Chemistry 2012
N
HN
SO
OH3C
1H and 13C NMR spectra of 4h
9 8 7 6 5 4 3 2 1 ppm
1.757
2.328
3.924
3.934
3.942
3.958
3.976
3.995
4.102
4.210
4.226
4.230
4.235
4.245
4.251
4.255
4.271
4.492
4.501
4.509
4.518
4.526
4.535
4.544
5.320
5.322
7.014
7.030
7.126
7.142
7.264
7.553
7.568
7.584
7.650
7.652
7.664
7.677
7.679
8.037
8.039
8.054
9.465
3.021
2.967
2.067
0.984
1.033
1.013
1.011
2.021
2.003
2.013
1.002
2.000
0.900
NAME LZR-2-DEXPNO 1PROCNO 1Date_ 20110511Time 9.46INSTRUM av500PROBHD 5 mm PABBO BB-PULPROG zg30TD 32768SOLVENT CDCl3NS 4DS 1SWH 10000.000 HzFIDRES 0.305176 HzAQ 1.6385000 secRG 406DW 50.000 usecDE 6.00 usecTE 295.3 KD1 2.00000000 secTD0 1
======== CHANNEL f1 ========NUC1 1HP1 13.50 usecPL1 2.20 dBSFO1 500.0335010 MHzSI 16384SF 500.0300082 MHzWDW EMSSB 0LB 0.30 HzGB 0PC 2.00
LZR-2-D 1H 1D 2011 05 11
6.87.07.27.47.67.88.08.2 ppm
200 180 160 140 120 100 80 60 40 20 ppm
20.953
26.166
41.979
42.359
48.297
66.317
87.702
126.470
128.802
129.064
129.894
133.700
134.699
137.179
139.564
151.904
193.620
194.253
194.604
LZR-2-D 13C 1D 2011 05 13
NAME LZR-2-DEXPNO 2PROCNO 1Date_ 20110513Time 14.29INSTRUM av500PROBHD 5 mm PABBO BB-PULPROG zgpg30TD 65536SOLVENT CDCl3NS 3599DS 2SWH 32679.738 HzFIDRES 0.498653 HzAQ 1.0027661 secRG 18400DW 15.300 usecDE 6.00 usecTE 300.2 KD1 2.00000000 secd11 0.03000000 secDELTA 1.89999998 secTD0 1
======== CHANNEL f1 ========NUC1 13CP1 9.60 usecPL1 2.00 dBSFO1 125.7464750 MHz
======== CHANNEL f2 ========CPDPRG2 waltz16NUC2 1HPCPD2 80.00 usecPL2 2.60 dBPL12 17.66 dBPL13 17.66 dBSFO2 500.0355000 MHzSI 32768SF 125.7326470 MHzWDW EMSSB 0LB 6.00 HzGB 0PC 2.00
20
Electronic Supplementary Material (ESI) for Green ChemistryThis journal is © The Royal Society of Chemistry 2012
N
HN
SO
OH3CO
1H and 13C NMR spectra of 4i
10 9 8 7 6 5 4 3 2 1 ppm
0.003
1.758
3.793
3.918
3.928
3.938
3.947
3.955
3.972
4.093
4.208
4.224
4.228
4.233
4.244
4.249
4.253
4.269
4.487
4.497
4.505
4.514
4.522
4.530
5.318
5.321
6.847
6.853
6.856
6.866
6.870
6.876
7.043
7.049
7.053
7.066
7.551
7.554
7.566
7.582
7.647
7.649
7.662
7.677
8.033
8.036
8.050
9.457
3.015
3.117
2.109
1.028
1.029
1.024
1.018
2.017
2.035
1.999
1.000
2.022
0.878
NAME LZR-2-hEXPNO 1PROCNO 1Date_ 20110519Time 20.06INSTRUM av500PROBHD 5 mm PABBO BB-PULPROG zg30TD 32768SOLVENT CDCl3NS 4DS 1SWH 10000.000 HzFIDRES 0.305176 HzAQ 1.6385000 secRG 406DW 50.000 usecDE 6.00 usecTE 299.1 KD1 2.00000000 secTD0 1
======== CHANNEL f1 ========NUC1 1HP1 13.50 usecPL1 2.20 dBSFO1 500.0335010 MHzSI 16384SF 500.0300082 MHzWDW EMSSB 0LB 0.30 HzGB 0PC 2.00
LZR-2-h 1H 1D 2011 05 19
6.87.07.27.47.67.88.0 ppm
200 180 160 140 120 100 80 60 40 20 ppm
26.143
41.981
48.312
55.264
66.508
87.838
114.622
127.654
128.790
129.070
133.701
134.587
134.726
151.848
158.940
193.637
194.243
194.625
LZR-2-h 13C 1D 2011 05 23
NAME LZR-2-hEXPNO 2PROCNO 1Date_ 20110523Time 17.31INSTRUM av500PROBHD 5 mm PABBO BB-PULPROG zgpg30TD 65536SOLVENT CDCl3NS 1178DS 2SWH 32679.738 HzFIDRES 0.498653 HzAQ 1.0027661 secRG 18400DW 15.300 usecDE 6.00 usecTE 299.4 KD1 2.00000000 secd11 0.03000000 secDELTA 1.89999998 secTD0 1
======== CHANNEL f1 ========NUC1 13CP1 9.60 usecPL1 2.00 dBSFO1 125.7464750 MHz
======== CHANNEL f2 ========CPDPRG2 waltz16NUC2 1HPCPD2 80.00 usecPL2 2.60 dBPL12 17.66 dBPL13 17.66 dBSFO2 500.0355000 MHzSI 32768SF 125.7326470 MHzWDW EMSSB 0LB 6.00 HzGB 0PC 2.00
21
Electronic Supplementary Material (ESI) for Green ChemistryThis journal is © The Royal Society of Chemistry 2012
N
HN
SO
O
O
1H and 13C NMR spectra of 4j
10 9 8 7 6 5 4 3 2 1 ppm
-0.003
1.876
3.846
3.856
3.865
3.876
3.885
3.903
3.919
3.939
4.124
4.140
4.144
4.149
4.160
4.165
4.169
4.184
4.289
4.473
4.483
4.492
4.500
4.508
4.517
4.527
5.640
5.643
6.035
6.042
6.269
6.273
6.275
6.279
7.264
7.406
7.408
7.535
7.551
7.566
7.632
7.647
7.662
8.071
8.073
8.088
9.456
3.014
2.106
1.046
0.977
1.037
0.974
0.940
0.937
0.902
2.010
1.000
2.016
0.866
NAME LZR-2-OEXPNO 1PROCNO 1Date_ 20110705Time 19.39INSTRUM av500PROBHD 5 mm PABBO BB-PULPROG zg30TD 32768SOLVENT CDCl3NS 4DS 1SWH 10000.000 HzFIDRES 0.305176 HzAQ 1.6385000 secRG 228DW 50.000 usecDE 6.00 usecTE 295.7 KD1 2.00000000 secTD0 1
======== CHANNEL f1 ========NUC1 1HP1 13.50 usecPL1 2.20 dBSFO1 500.0335010 MHzSI 16384SF 500.0300082 MHzWDW EMSSB 0LB 0.30 HzGB 0PC 2.00
LZR-2-O 1H 1D 2011 07 05
7.27.47.67.88.08.2 ppm
200 180 160 140 120 100 80 60 40 20 ppm
25.806
36.654
41.958
48.221
62.648
85.256
106.392
110.359
128.866
129.118
133.927
134.222
142.697
151.944
154.471
193.926
193.975
194.143
LZR-2-O 13C 1D 2011 07 07
NAME LZR-2-OEXPNO 2PROCNO 1Date_ 20110707Time 16.12INSTRUM av500PROBHD 5 mm PABBO BB-PULPROG zgpg30TD 65536SOLVENT CDCl3NS 8030DS 2SWH 32679.738 HzFIDRES 0.498653 HzAQ 1.0027661 secRG 18400DW 15.300 usecDE 6.00 usecTE 298.8 KD1 2.00000000 secd11 0.03000000 secDELTA 1.89999998 secTD0 1
======== CHANNEL f1 ========NUC1 13CP1 9.60 usecPL1 2.00 dBSFO1 125.7464750 MHz
======== CHANNEL f2 ========CPDPRG2 waltz16NUC2 1HPCPD2 80.00 usecPL2 2.60 dBPL12 17.66 dBPL13 17.66 dBSFO2 500.0355000 MHzSI 32768SF 125.7326470 MHzWDW EMSSB 0LB 5.00 HzGB 0PC 2.00
22
Electronic Supplementary Material (ESI) for Green ChemistryThis journal is © The Royal Society of Chemistry 2012
N
HN
H3CH2C
SO
O
1H and 13C NMR spectra of 4k
9 8 7 6 5 4 3 2 1 ppm
-0.009
1.049
1.064
1.079
1.550
1.566
1.581
1.590
1.601
1.605
1.616
1.842
2.874
2.877
2.885
2.888
2.890
2.893
2.902
2.904
3.829
3.839
3.848
3.864
3.881
4.125
4.129
4.134
4.150
4.154
4.501
4.510
5.213
5.215
7.264
7.481
7.484
7.496
7.512
7.587
7.589
7.602
7.617
7.895
7.898
7.912
7.914
9.343
3.122
2.132
3.006
1.020
2.125
1.045
1.045
1.004
2.050
1.000
2.044
0.860
NAME LZR-2-PEXPNO 1PROCNO 1Date_ 20110705Time 19.46INSTRUM av500PROBHD 5 mm PABBO BB-PULPROG zg30TD 32768SOLVENT CDCl3NS 4DS 1SWH 10000.000 HzFIDRES 0.305176 HzAQ 1.6385000 secRG 228DW 50.000 usecDE 6.00 usecTE 295.6 KD1 2.00000000 secTD0 1
======== CHANNEL f1 ========NUC1 1HP1 13.50 usecPL1 2.20 dBSFO1 500.0335010 MHzSI 16384SF 500.0300082 MHzWDW EMSSB 0LB 0.30 HzGB 0PC 2.00
LZR-2-P 1H 1D 2011 07 05
7.37.47.57.67.77.87.98.08.1 ppm
20406080100120140160180200 ppm
11.224
25.594
29.230
38.852
41.912
48.144
62.964
89.051
128.449
128.952
133.524
134.869
151.522
193.717
194.932
195.356
LZR-2-P 13C 1D 2011 07 08
NAME LZR-2-PEXPNO 2PROCNO 1Date_ 20110708Time 10.16INSTRUM av500PROBHD 5 mm PABBO BB-PULPROG zgpg30TD 65536SOLVENT CDCl3NS 552DS 2SWH 32679.738 HzFIDRES 0.498653 HzAQ 1.0027661 secRG 18400DW 15.300 usecDE 6.00 usecTE 299.7 KD1 2.00000000 secd11 0.03000000 secDELTA 1.89999998 secTD0 1
======== CHANNEL f1 ========NUC1 13CP1 9.60 usecPL1 2.00 dBSFO1 125.7464750 MHz
======== CHANNEL f2 ========CPDPRG2 waltz16NUC2 1HPCPD2 80.00 usecPL2 2.60 dBPL12 17.66 dBPL13 17.66 dBSFO2 500.0355000 MHzSI 32768SF 125.7326470 MHzWDW EMSSB 0LB 6.00 HzGB 0PC 2.00
23
Electronic Supplementary Material (ESI) for Green ChemistryThis journal is © The Royal Society of Chemistry 2012
N
HN
SO
O
1H and 13C NMR spectra of 4l
9 8 7 6 5 4 3 2 1 ppm
0.991
1.004
1.051
1.065
1.735
1.754
1.767
1.781
1.794
1.814
2.755
2.767
3.842
3.852
3.860
3.872
3.876
4.069
4.087
4.094
4.106
4.112
4.130
4.523
4.535
4.538
4.548
4.559
4.564
4.574
5.284
7.269
7.488
7.504
7.519
7.593
7.608
7.622
7.908
7.924
9.461
3.293
3.268
1.096
3.398
1.084
2.139
1.095
1.082
1.079
2.198
1.082
2.148
1.000
NAME LZR-2-QEXPNO 1PROCNO 1Date_ 20110713Time 19.33INSTRUM av500PROBHD 5 mm PABBO BB-PULPROG zg30TD 32768SOLVENT CDCl3NS 4DS 1SWH 10000.000 HzFIDRES 0.305176 HzAQ 1.6385000 secRG 287DW 50.000 usecDE 6.00 usecTE 297.1 KD1 2.00000000 secTD0 1
======== CHANNEL f1 ========NUC1 1HP1 13.50 usecPL1 2.20 dBSFO1 500.0335010 MHzSI 16384SF 500.0300060 MHzWDW EMSSB 0LB 0.30 HzGB 0PC 2.00
LZR-2-Q 1H 1D 2011 07 13
7.27.37.47.57.67.77.87.98.0 ppm
200 180 160 140 120 100 80 60 40 20 ppm
18.596
20.726
25.705
34.282
41.879
43.544
48.075
60.709
88.192
128.475
128.937
133.465
134.923
151.897
194.149
195.269
196.167
LZR-2-Q 13C 1D 2011 07 15
NAME LZR-2-QEXPNO 2PROCNO 1Date_ 20110715Time 9.53INSTRUM av500PROBHD 5 mm PABBO BB-PULPROG zgpg30TD 65536SOLVENT CDCl3NS 386DS 2SWH 32679.738 HzFIDRES 0.498653 HzAQ 1.0027661 secRG 18400DW 15.300 usecDE 6.00 usecTE 298.0 KD1 2.00000000 secd11 0.03000000 secDELTA 1.89999998 secTD0 1
======== CHANNEL f1 ========NUC1 13CP1 9.60 usecPL1 2.00 dBSFO1 125.7464750 MHz
======== CHANNEL f2 ========CPDPRG2 waltz16NUC2 1HPCPD2 80.00 usecPL2 2.60 dBPL12 17.66 dBPL13 17.66 dBSFO2 500.0355000 MHzSI 32768SF 125.7326470 MHzWDW EMSSB 0LB 6.00 HzGB 0PC 2.00
24
Electronic Supplementary Material (ESI) for Green ChemistryThis journal is © The Royal Society of Chemistry 2012
N
HN
SO
O
1H and 13C NMR spectra of 4m
10 9 8 7 6 5 4 3 2 1 ppm
3.983
3.994
4.000
4.013
4.016
4.241
4.248
4.252
4.257
4.268
4.275
4.293
4.594
4.606
4.609
4.620
4.630
4.635
4.646
5.315
5.318
6.756
6.771
6.875
6.888
6.958
6.974
6.989
7.139
7.154
7.186
7.200
7.208
7.223
7.236
7.259
7.509
7.524
7.540
7.631
7.646
7.972
7.987
9.752
2.034
1.088
0.872
1.023
1.015
2.000
1.999
2.023
1.131
2.901
2.029
1.025
2.038
0.892
NAME LZR-2-AEXPNO 1PROCNO 1Date_ 20110319Time 16.08INSTRUM av500PROBHD 5 mm PABBO BB-PULPROG zg30TD 32768SOLVENT CDCl3NS 8DS 1SWH 10000.000 HzFIDRES 0.305176 HzAQ 1.6385000 secRG 256DW 50.000 usecDE 6.00 usecTE 293.9 KD1 2.00000000 secTD0 1
======== CHANNEL f1 ========NUC1 1HP1 13.50 usecPL1 2.20 dBSFO1 500.0335010 MHzSI 16384SF 500.0300106 MHzWDW EMSSB 0LB 0.30 HzGB 0PC 4.00
LZR-1-A 1H 1D 2011 03 19
6.87.07.27.47.67.88.0 ppm
20406080100120140160180200 ppm
42.123
42.316
48.379
65.999
87.506
126.028
126.471
127.189
127.741
128.652
128.923
129.036
133.657
134.807
140.570
142.749
153.476
193.230
194.570
194.676
LZR-2-A 13C 1D 2011 05 30
NAME LZR-2-AEXPNO 2PROCNO 1Date_ 20110530Time 17.49INSTRUM av500PROBHD 5 mm PABBO BB-PULPROG zgpg30TD 65536SOLVENT CDCl3NS 1672DS 2SWH 32679.738 HzFIDRES 0.498653 HzAQ 1.0027661 secRG 16400DW 15.300 usecDE 6.00 usecTE 298.6 KD1 2.00000000 secd11 0.03000000 secDELTA 1.89999998 secTD0 1
======== CHANNEL f1 ========NUC1 13CP1 9.60 usecPL1 2.00 dBSFO1 125.7464750 MHz
======== CHANNEL f2 ========CPDPRG2 waltz16NUC2 1HPCPD2 80.00 usecPL2 2.20 dBPL12 17.66 dBPL13 17.66 dBSFO2 500.0355000 MHzSI 32768SF 125.7326470 MHzWDW EMSSB 0LB 6.00 HzGB 0PC 2.00
25
Electronic Supplementary Material (ESI) for Green ChemistryThis journal is © The Royal Society of Chemistry 2012
N
HN
SO
OCl
1H and 13C NMR spectra of 4n
10 9 8 7 6 5 4 3 2 1 ppm
3.805
3.992
4.012
4.022
4.031
4.043
4.063
4.299
4.320
4.340
4.359
4.577
4.587
4.595
4.603
4.611
4.620
4.630
5.250
6.410
6.732
6.787
7.044
7.060
7.074
7.090
7.167
7.174
7.260
7.495
7.509
7.523
7.620
7.633
7.958
7.973
9.723
0.915
2.191
1.046
1.050
1.036
1.003
3.097
2.096
3.123
2.071
1.049
2.084
1.000
NAME LZR-2-REXPNO 1PROCNO 1Date_ 20110713Time 19.38INSTRUM av500PROBHD 5 mm PABBO BB-PULPROG zg30TD 32768SOLVENT CDCl3NS 4DS 1SWH 10000.000 HzFIDRES 0.305176 HzAQ 1.6385000 secRG 287DW 50.000 usecDE 6.00 usecTE 297.1 KD1 2.00000000 secTD0 1
======== CHANNEL f1 ========NUC1 1HP1 13.50 usecPL1 2.20 dBSFO1 500.0335010 MHzSI 16384SF 500.0300103 MHzWDW EMSSB 0LB 0.30 HzGB 0PC 2.00
LZR-2-R 1H 1D 2011 07 13
6.46.66.87.07.27.47.67.88.08.2 ppm
200 180 160 140 120 100 80 60 40 20 ppm
42.247
42.425
48.407
65.889
88.315
126.034
126.515
127.263
128.794
128.847
128.972
129.384
133.733
134.553
153.382
190.642
190.653
194.583
LZR-2-R 13C 1D 2011 07 15
NAME LZR-2-REXPNO 2PROCNO 1Date_ 20110715Time 12.21INSTRUM av500PROBHD 5 mm PABBO BB-PULPROG zgpg30TD 65536SOLVENT CDCl3NS 1210DS 2SWH 32679.738 HzFIDRES 0.498653 HzAQ 1.0027661 secRG 18400DW 15.300 usecDE 6.00 usecTE 298.9 KD1 2.00000000 secd11 0.03000000 secDELTA 1.89999998 secTD0 1
======== CHANNEL f1 ========NUC1 13CP1 9.60 usecPL1 2.00 dBSFO1 125.7464750 MHz
======== CHANNEL f2 ========CPDPRG2 waltz16NUC2 1HPCPD2 80.00 usecPL2 2.60 dBPL12 17.66 dBPL13 17.66 dBSFO2 500.0355000 MHzSI 32768SF 125.7326470 MHzWDW EMSSB 0LB 6.00 HzGB 0PC 2.00
26
Electronic Supplementary Material (ESI) for Green ChemistryThis journal is © The Royal Society of Chemistry 2012
N
HN
SO
O
Cl
1H and 13C NMR spectra of 4o
10 9 8 7 6 5 4 3 2 1 ppm
0.003
3.999
4.010
4.017
4.033
4.177
4.179
4.239
4.256
4.259
4.265
4.276
4.282
4.301
4.593
4.606
4.609
4.619
4.630
4.635
5.322
5.325
6.707
6.720
6.724
6.912
6.926
6.953
6.956
6.970
7.212
7.217
7.226
7.241
7.256
7.264
7.269
7.272
7.530
7.545
7.561
7.657
7.672
7.687
7.972
7.974
7.989
9.778
2.323
1.156
1.193
1.180
1.151
2.288
2.320
2.308
1.052
0.875
1.033
2.357
1.169
2.366
1.000
NAME LZR-2-MEXPNO 1PROCNO 1Date_ 20110628Time 19.13INSTRUM av500PROBHD 5 mm PABBO BB-PULPROG zg30TD 32768SOLVENT CDCl3NS 4DS 1SWH 10000.000 HzFIDRES 0.305176 HzAQ 1.6385000 secRG 362DW 50.000 usecDE 6.00 usecTE 296.2 KD1 2.00000000 secTD0 1
======== CHANNEL f1 ========NUC1 1HP1 13.50 usecPL1 2.20 dBSFO1 500.0335010 MHzSI 16384SF 500.0300082 MHzWDW EMSSB 0LB 0.30 HzGB 0PC 2.00
LZR-2-M 1H 1D 2011 06 28
6.87.07.27.47.67.88.0 ppm
200 180 160 140 120 100 80 60 40 20 ppm
42.178
42.353
48.376
66.003
87.217
126.433
127.388
127.583
128.029
128.642
129.092
129.172
133.881
134.606
134.868
138.893
142.456
153.802
191.691
194.554
194.586
lzr-2-m 13C 1D 2011 07 01
NAME LZR-2-MEXPNO 2PROCNO 1Date_ 20110701Time 19.39INSTRUM av500PROBHD 5 mm PABBO BB-PULPROG zgpg30TD 65536SOLVENT CDCl3NS 1162DS 2SWH 32679.738 HzFIDRES 0.498653 HzAQ 1.0027661 secRG 10300DW 15.300 usecDE 6.00 usecTE 296.9 KD1 2.00000000 secd11 0.03000000 secDELTA 1.89999998 secTD0 1
======== CHANNEL f1 ========NUC1 13CP1 9.60 usecPL1 2.00 dBSFO1 125.7464750 MHz
======== CHANNEL f2 ========CPDPRG2 waltz16NUC2 1HPCPD2 80.00 usecPL2 2.60 dBPL12 17.66 dBPL13 17.66 dBSFO2 500.0355000 MHzSI 32768SF 125.7326470 MHzWDW EMSSB 0LB 6.00 HzGB 0PC 1.00
27
Electronic Supplementary Material (ESI) for Green ChemistryThis journal is © The Royal Society of Chemistry 2012
N
HN
SO
O
Cl
1H and 13C NMR spectra of 4p
10 9 8 7 6 5 4 3 2 1 ppm
0.000
3.993
4.011
4.024
4.047
4.174
4.235
4.253
4.277
4.296
4.588
4.602
4.614
4.625
4.641
5.319
6.705
6.721
6.909
6.923
6.950
6.966
7.049
7.194
7.208
7.222
7.237
7.252
7.261
7.525
7.541
7.556
7.652
7.667
7.681
7.970
7.985
9.775
2.045
0.990
1.021
1.017
0.998
1.967
3.905
3.734
2.008
1.006
2.000
0.854
NAME LZR-2-LEXPNO 1PROCNO 1Date_ 20110622Time 16.58INSTRUM av500PROBHD 5 mm PABBO BB-PULPROG zg30TD 32768SOLVENT CDCl3NS 4DS 1SWH 10000.000 HzFIDRES 0.305176 HzAQ 1.6385000 secRG 406DW 50.000 usecDE 6.00 usecTE 297.6 KD1 2.00000000 secTD0 1
======== CHANNEL f1 ========NUC1 1HP1 13.50 usecPL1 2.20 dBSFO1 500.0335010 MHzSI 16384SF 500.0300101 MHzWDW EMSSB 0LB 0.30 HzGB 0PC 2.00
LZR-2-L 1H 1D 2011 06 22
6.66.87.07.27.47.67.88.08.2 ppm
200 180 160 140 120 100 80 60 40 20 ppm
42.172
42.357
48.375
66.018
87.216
126.445
127.382
127.591
128.017
128.637
129.094
129.164
133.865
134.631
134.872
138.907
142.462
153.800
191.673
194.539
194.579
LZR-2-L 13C 1D 2011 06 28
NAME LZR-2-LEXPNO 2PROCNO 1Date_ 20110628Time 15.18INSTRUM av500PROBHD 5 mm PABBO BB-PULPROG zgpg30TD 65536SOLVENT CDCl3NS 453DS 2SWH 32679.738 HzFIDRES 0.498653 HzAQ 1.0027661 secRG 18400DW 15.300 usecDE 6.00 usecTE 297.8 KD1 2.00000000 secd11 0.03000000 secDELTA 1.89999998 secTD0 1
======== CHANNEL f1 ========NUC1 13CP1 9.60 usecPL1 2.00 dBSFO1 125.7464750 MHz
======== CHANNEL f2 ========CPDPRG2 waltz16NUC2 1HPCPD2 80.00 usecPL2 2.60 dBPL12 17.66 dBPL13 17.66 dBSFO2 500.0355000 MHzSI 32768SF 125.7326470 MHzWDW EMSSB 0LB 6.00 HzGB 0PC 2.00
28
Electronic Supplementary Material (ESI) for Green ChemistryThis journal is © The Royal Society of Chemistry 2012
N
HN
SO
O
Br
1H and 13C NMR spectra of 4q
10 9 8 7 6 5 4 3 2 1 ppm
0.000
3.995
4.013
4.026
4.050
4.169
4.234
4.252
4.259
4.277
4.295
4.588
4.601
4.614
4.625
4.641
5.320
6.640
6.657
6.912
6.926
7.003
7.109
7.125
7.195
7.210
7.224
7.239
7.255
7.261
7.485
7.501
7.527
7.543
7.558
7.656
7.670
7.684
7.699
7.968
7.984
9.778
2.019
1.009
1.010
1.056
1.025
1.987
1.993
2.063
4.162
1.978
1.076
2.000
0.900
NAME LZR-2-TEXPNO 1PROCNO 1Date_ 20110713Time 19.42INSTRUM av500PROBHD 5 mm PABBO BB-PULPROG zg30TD 32768SOLVENT CDCl3NS 4DS 1SWH 10000.000 HzFIDRES 0.305176 HzAQ 1.6385000 secRG 645DW 50.000 usecDE 6.00 usecTE 297.1 KD1 2.00000000 secTD0 1
======== CHANNEL f1 ========NUC1 1HP1 13.50 usecPL1 2.20 dBSFO1 500.0335010 MHzSI 16384SF 500.0300098 MHzWDW EMSSB 0LB 0.30 HzGB 0PC 2.00
LZR-2-T 1H 1D 2011 07 13
6.87.07.27.47.67.88.0 ppm
20406080100120140160180200 ppm
42.186
42.337
48.377
66.020
87.204
123.199
126.436
127.397
127.832
128.641
129.107
129.188
130.968
133.892
134.620
139.355
142.460
153.841
191.677
194.540
194.590
LZR-2-T 13C 1D 2011 07 15
NAME LZR-2-TEXPNO 2PROCNO 1Date_ 20110715Time 10.28INSTRUM av500PROBHD 5 mm PABBO BB-PULPROG zgpg30TD 65536SOLVENT CDCl3NS 933DS 2SWH 32679.738 HzFIDRES 0.498653 HzAQ 1.0027661 secRG 18400DW 15.300 usecDE 6.00 usecTE 298.6 KD1 2.00000000 secd11 0.03000000 secDELTA 1.89999998 secTD0 1
======== CHANNEL f1 ========NUC1 13CP1 9.60 usecPL1 2.00 dBSFO1 125.7464750 MHz
======== CHANNEL f2 ========CPDPRG2 waltz16NUC2 1HPCPD2 80.00 usecPL2 2.60 dBPL12 17.66 dBPL13 17.66 dBSFO2 500.0355000 MHzSI 32768SF 125.7326470 MHzWDW EMSSB 0LB 6.00 HzGB 0PC 2.00
29
Electronic Supplementary Material (ESI) for Green ChemistryThis journal is © The Royal Society of Chemistry 2012
N
HN
SO
O
H3C
1H and 13C NMR spectra of 4r
10 9 8 7 6 5 4 3 2 1 ppm
0.005
2.214
3.977
3.987
3.994
4.005
4.010
4.221
4.238
4.240
4.246
4.264
4.320
4.593
4.604
4.609
4.620
4.629
4.635
5.343
5.346
6.692
6.708
6.777
6.792
6.920
6.934
7.191
7.195
7.202
7.204
7.219
7.231
7.234
7.245
7.248
7.250
7.264
7.523
7.538
7.553
7.645
7.660
7.674
7.987
7.989
8.004
9.760
3.030
2.041
1.060
0.993
1.024
1.018
2.000
2.000
1.994
3.185
2.014
0.997
2.000
0.778
NAME LZR-2-UEXPNO 1PROCNO 1Date_ 20110816Time 16.57INSTRUM av500PROBHD 5 mm PABBO BB-PULPROG zg30TD 32768SOLVENT CDCl3NS 4DS 1SWH 10000.000 HzFIDRES 0.305176 HzAQ 1.6385000 secRG 362DW 50.000 usecDE 6.00 usecTE 297.7 KD1 2.00000000 secTD0 1
======== CHANNEL f1 ========NUC1 1HP1 13.50 usecPL1 2.20 dBSFO1 500.0335010 MHzSI 16384SF 500.0300082 MHzWDW EMSSB 0LB 0.30 HzGB 0PC 2.00
LZR-2-U 1H 1D 2011 08 16
6.66.87.07.27.47.67.88.08.2 ppm
200 180 160 140 120 100 80 60 40 20 ppm
21.232
42.094
42.221
48.398
65.884
87.488
126.220
126.491
127.164
128.396
128.688
128.931
129.077
133.684
134.813
137.726
139.000
142.766
153.435
193.261
194.579
194.674
LZR-2-U 13C 1D 2011 08 18
NAME LZR-2-UEXPNO 2PROCNO 1Date_ 20110818Time 10.23INSTRUM av500PROBHD 5 mm PABBO BB-PULPROG zgpg30TD 65536SOLVENT CDCl3NS 1501DS 2SWH 32679.738 HzFIDRES 0.498653 HzAQ 1.0027661 secRG 18400DW 15.300 usecDE 6.00 usecTE 299.1 KD1 2.00000000 secd11 0.03000000 secDELTA 1.89999998 secTD0 1
======== CHANNEL f1 ========NUC1 13CP1 9.60 usecPL1 2.00 dBSFO1 125.7464750 MHz
======== CHANNEL f2 ========CPDPRG2 waltz16NUC2 1HPCPD2 80.00 usecPL2 2.60 dBPL12 17.66 dBPL13 17.66 dBSFO2 500.0355000 MHzSI 32768SF 125.7326470 MHzWDW EMSSB 0LB 6.00 HzGB 0PC 2.00
30
Electronic Supplementary Material (ESI) for Green ChemistryThis journal is © The Royal Society of Chemistry 2012
N
HN
SO
O
H3CO
1H and 13C NMR spectra of 4s
10 9 8 7 6 5 4 3 2 1 ppm
3.702
3.955
3.966
3.972
3.987
4.210
4.227
4.229
4.235
4.247
4.253
4.271
4.348
4.350
4.585
4.598
4.600
4.611
4.621
4.626
5.350
5.353
6.484
6.490
6.493
6.504
6.507
6.513
6.781
6.786
6.790
6.803
6.944
6.959
7.196
7.229
7.241
7.244
7.255
7.519
7.535
7.550
7.635
7.650
7.664
7.992
7.995
9.749
2.986
2.030
1.028
1.000
1.007
1.000
1.990
2.008
2.001
3.203
1.980
1.005
2.004
0.937
NAME LZR-2-NEXPNO 1PROCNO 1Date_ 20110628Time 19.18INSTRUM av500PROBHD 5 mm PABBO BB-PULPROG zg30TD 32768SOLVENT CDCl3NS 4DS 1SWH 10000.000 HzFIDRES 0.305176 HzAQ 1.6385000 secRG 228DW 50.000 usecDE 6.00 usecTE 296.2 KD1 2.00000000 secTD0 1
======== CHANNEL f1 ========NUC1 1HP1 13.50 usecPL1 2.20 dBSFO1 500.0335010 MHzSI 16384SF 500.0300082 MHzWDW EMSSB 0LB 0.30 HzGB 0PC 2.00
LZR-2-N 1H 1D 2011 06 28
6.66.87.07.27.47.67.88.0 ppm
20406080100120140160180200 ppm
42.075
42.374
48.433
55.142
65.949
87.411
113.066
126.494
127.211
128.083
128.685
128.995
129.104
133.173
133.700
134.821
142.802
153.439
160.184
192.587
194.586
194.593
lzr-2-N 13C 1D 2011 07 02
NAME LZR-2-NEXPNO 2PROCNO 1Date_ 20110702Time 18.17INSTRUM av500PROBHD 5 mm PABBO BB-PULPROG zgpg30TD 65536SOLVENT CDCl3NS 1293DS 2SWH 32679.738 HzFIDRES 0.498653 HzAQ 1.0027661 secRG 18400DW 15.300 usecDE 6.00 usecTE 301.0 KD1 2.00000000 secd11 0.03000000 secDELTA 1.89999998 secTD0 1
======== CHANNEL f1 ========NUC1 13CP1 9.60 usecPL1 2.00 dBSFO1 125.7464750 MHz
======== CHANNEL f2 ========CPDPRG2 waltz16NUC2 1HPCPD2 80.00 usecPL2 2.60 dBPL12 17.66 dBPL13 17.66 dBSFO2 500.0355000 MHzSI 32768SF 125.7326470 MHzWDW EMSSB 0LB 6.00 HzGB 0PC 1.00
31
Electronic Supplementary Material (ESI) for Green ChemistryThis journal is © The Royal Society of Chemistry 2012
N
HN
SO
O
Cl
1H and 13C NMR spectra of 4t
11 10 9 8 7 6 5 4 3 2 1 ppm
-0.002
3.993
4.005
4.010
4.025
4.170
4.172
4.237
4.255
4.262
4.273
4.280
4.298
4.581
4.595
4.607
4.621
4.634
5.237
5.240
6.782
6.796
6.861
6.874
6.877
7.018
7.033
7.049
7.188
7.202
7.214
7.219
7.234
7.243
7.247
7.252
7.264
7.486
7.489
7.500
7.503
7.508
7.880
7.901
7.904
7.915
7.918
9.754
2.038
0.986
1.065
1.012
0.996
1.945
1.939
2.000
4.083
1.875
2.000
0.746
NAME LZR-2-VEXPNO 1PROCNO 1Date_ 20110816Time 17.01INSTRUM av500PROBHD 5 mm PABBO BB-PULPROG zg30TD 32768SOLVENT CDCl3NS 4DS 1SWH 10000.000 HzFIDRES 0.305176 HzAQ 1.6385000 secRG 362DW 50.000 usecDE 6.00 usecTE 297.6 KD1 2.00000000 secTD0 1
======== CHANNEL f1 ========NUC1 1HP1 13.50 usecPL1 2.20 dBSFO1 500.0335010 MHzSI 16384SF 500.0300082 MHzWDW EMSSB 0LB 0.30 HzGB 0PC 2.00
LZR-2-V 1H 1D 2011 08 16
6.87.07.27.47.67.88.0 ppm
200 180 160 140 120 100 80 60 40 20 ppm
42.132
42.392
48.396
65.882
87.393
125.944
126.450
127.322
127.815
129.017
129.370
130.052
133.062
140.321
140.499
142.577
153.386
193.205
193.433
194.064
LZR-2-V 13C 1D 2011 08 18
NAME LZR-2-VEXPNO 2PROCNO 1Date_ 20110818Time 15.22INSTRUM av500PROBHD 5 mm PABBO BB-PULPROG zgpg30TD 65536SOLVENT CDCl3NS 2334DS 2SWH 32679.738 HzFIDRES 0.498653 HzAQ 1.0027661 secRG 18400DW 15.300 usecDE 6.00 usecTE 299.5 KD1 2.00000000 secd11 0.03000000 secDELTA 1.89999998 secTD0 1
======== CHANNEL f1 ========NUC1 13CP1 9.60 usecPL1 2.00 dBSFO1 125.7464750 MHz
======== CHANNEL f2 ========CPDPRG2 waltz16NUC2 1HPCPD2 80.00 usecPL2 2.60 dBPL12 17.66 dBPL13 17.66 dBSFO2 500.0355000 MHzSI 32768SF 125.7326470 MHzWDW EMSSB 0LB 6.00 HzGB 0PC 2.00
32
Electronic Supplementary Material (ESI) for Green ChemistryThis journal is © The Royal Society of Chemistry 2012
N
HN
SO
O
Br
1H and 13C NMR spectra of 4u
10 9 8 7 6 5 4 3 2 1 ppm
0.000
3.971
3.979
3.987
4.003
4.162
4.163
4.224
4.240
4.248
4.266
4.580
4.592
4.604
5.223
5.226
5.258
5.261
6.770
6.786
6.799
6.856
6.870
6.885
6.998
7.014
7.030
7.046
7.169
7.184
7.204
7.213
7.216
7.227
7.232
7.259
7.300
7.317
7.645
7.659
7.662
7.814
7.831
7.876
7.879
7.890
7.893
9.755
2.232
1.238
1.048
1.129
1.034
2.098
2.193
2.189
4.498
0.984
1.086
1.058
1.000
0.958
NAME LZR-2-XEXPNO 1PROCNO 1Date_ 20110906Time 16.50INSTRUM av500PROBHD 5 mm PABBO BB-PULPROG zg30TD 32768SOLVENT CDCl3NS 8DS 1SWH 10000.000 HzFIDRES 0.305176 HzAQ 1.6385000 secRG 256DW 50.000 usecDE 6.00 usecTE 297.9 KD1 2.00000000 secTD0 1
======== CHANNEL f1 ========NUC1 1HP1 13.50 usecPL1 2.20 dBSFO1 500.0335010 MHzSI 16384SF 500.0300107 MHzWDW EMSSB 0LB 0.30 HzGB 0PC 2.00
LZR-2-X 1H 2011 09 06
6.66.87.07.27.47.67.88.0 ppm
20406080100120140160180200 ppm
42.195
42.567
48.465
65.740
87.426
125.317
125.998
126.136
126.527
127.270
127.392
127.874
129.010
129.088
130.181
130.765
132.439
133.554
140.553
142.612
142.874
147.253
153.451
193.257
194.095
194.815
LZR-2-X 13C 1D 2011 09 09
NAME LZR-2-XEXPNO 2PROCNO 1Date_ 20110909Time 18.05INSTRUM av500PROBHD 5 mm PABBO BB-PULPROG zgpg30TD 65536SOLVENT CDCl3NS 1613DS 2SWH 32679.738 HzFIDRES 0.498653 HzAQ 1.0027661 secRG 18400DW 15.300 usecDE 6.00 usecTE 299.1 KD1 2.00000000 secd11 0.03000000 secDELTA 1.89999998 secTD0 1
======== CHANNEL f1 ========NUC1 13CP1 9.60 usecPL1 2.00 dBSFO1 125.7464750 MHz
======== CHANNEL f2 ========CPDPRG2 waltz16NUC2 1HPCPD2 80.00 usecPL2 2.60 dBPL12 17.66 dBPL13 17.66 dBSFO2 500.0355000 MHzSI 32768SF 125.7326387 MHzWDW EMSSB 0LB 6.00 HzGB 0PC 2.00
33
Electronic Supplementary Material (ESI) for Green ChemistryThis journal is © The Royal Society of Chemistry 2012
N
HN
SO
O
H3C
1H and 13C NMR spectra of 4v
10 9 8 7 6 5 4 3 2 1 ppm
0.005
3.985
3.994
4.002
4.013
4.019
4.242
4.244
4.250
4.254
4.259
4.277
4.592
4.603
4.608
4.619
4.628
4.633
5.294
5.297
6.776
6.778
6.793
6.875
6.889
6.891
6.972
6.987
7.003
7.154
7.156
7.169
7.185
7.191
7.196
7.199
7.202
7.207
7.222
7.231
7.235
7.239
7.264
7.312
7.329
7.873
7.890
9.757
2.990
2.112
0.905
0.930
1.042
1.035
2.009
2.040
2.107
4.128
1.978
2.000
0.805
NAME LZR-2-WEXPNO 1PROCNO 1Date_ 20110816Time 17.05INSTRUM av500PROBHD 5 mm PABBO BB-PULPROG zg30TD 32768SOLVENT CDCl3NS 4DS 1SWH 10000.000 HzFIDRES 0.305176 HzAQ 1.6385000 secRG 362DW 50.000 usecDE 6.00 usecTE 297.6 KD1 2.00000000 secTD0 1
======== CHANNEL f1 ========NUC1 1HP1 13.50 usecPL1 2.20 dBSFO1 500.0335010 MHzSI 16384SF 500.0300082 MHzWDW EMSSB 0LB 0.30 HzGB 0PC 2.00
LZR-2-W 1H 1D 2011 08 16
6.87.07.27.47.67.88.0 ppm
20406080100120140160180200 ppm
21.693
42.123
42.404
48.388
65.825
87.584
126.098
126.480
127.160
127.733
128.833
128.913
129.727
132.144
140.597
142.852
144.738
153.490
193.222
194.197
194.924
LZR-2-W 13C 1D 2011 08 18
NAME LZR-2-WEXPNO 2PROCNO 1Date_ 20110818Time 15.11INSTRUM av500PROBHD 5 mm PABBO BB-PULPROG zgpg30TD 65536SOLVENT CDCl3NS 4115DS 2SWH 32679.738 HzFIDRES 0.498653 HzAQ 1.0027661 secRG 18400DW 15.300 usecDE 6.00 usecTE 299.7 KD1 2.00000000 secd11 0.03000000 secDELTA 1.89999998 secTD0 1
======== CHANNEL f1 ========NUC1 13CP1 9.60 usecPL1 2.00 dBSFO1 125.7464750 MHz
======== CHANNEL f2 ========CPDPRG2 waltz16NUC2 1HPCPD2 80.00 usecPL2 2.60 dBPL12 17.66 dBPL13 17.66 dBSFO2 500.0355000 MHzSI 32768SF 125.7326470 MHzWDW EMSSB 0LB 6.00 HzGB 0PC 2.00
34
Electronic Supplementary Material (ESI) for Green ChemistryThis journal is © The Royal Society of Chemistry 2012
N
HN
SO
O
H3CO
1H and 13C NMR spectra of 4w
10 9 8 7 6 5 4 3 2 1 ppm
-0.006
0.000
0.007
3.914
3.986
3.989
3.997
4.006
4.016
4.023
4.235
4.244
4.246
4.251
4.260
4.277
4.601
4.606
4.617
5.276
5.279
6.800
6.802
6.816
6.875
6.889
6.892
6.982
6.995
7.000
7.010
7.026
7.163
7.166
7.178
7.184
7.190
7.194
7.197
7.200
7.206
7.221
7.234
7.238
7.261
7.961
7.979
9.750
3.023
1.923
0.995
0.819
1.034
0.993
1.996
2.000
4.231
4.283
1.981
0.871
NAME LZR-2-YEXPNO 1PROCNO 1Date_ 20110906Time 17.00INSTRUM av500PROBHD 5 mm PABBO BB-PULPROG zg30TD 32768SOLVENT CDCl3NS 8DS 1SWH 10000.000 HzFIDRES 0.305176 HzAQ 1.6385000 secRG 575DW 50.000 usecDE 6.00 usecTE 297.9 KD1 2.00000000 secTD0 1
======== CHANNEL f1 ========NUC1 1HP1 13.50 usecPL1 2.20 dBSFO1 500.0335010 MHzSI 16384SF 500.0300097 MHzWDW EMSSB 0LB 0.30 HzGB 0PC 2.00
LZR-2-Y 1H 2011 09 06
6.87.07.27.47.67.88.08.2 ppm
20406080100120140160180200 ppm
42.196
42.623
48.646
55.696
65.566
87.656
114.332
123.310
126.199
126.548
127.229
127.433
127.900
128.968
131.170
140.711
142.979
153.521
193.079
193.289
195.146
LZR-2-Y 13C 1D 2011 09 11
NAME LZR-2-YEXPNO 2PROCNO 1Date_ 20110911Time 18.47INSTRUM av500PROBHD 5 mm PABBO BB-PULPROG zgpg30TD 65536SOLVENT CDCl3NS 2739DS 2SWH 32679.738 HzFIDRES 0.498653 HzAQ 1.0027661 secRG 18400DW 15.300 usecDE 6.00 usecTE 299.3 KD1 2.00000000 secd11 0.03000000 secDELTA 1.89999998 secTD0 1
======== CHANNEL f1 ========NUC1 13CP1 9.60 usecPL1 2.00 dBSFO1 125.7464750 MHz
======== CHANNEL f2 ========CPDPRG2 waltz16NUC2 1HPCPD2 80.00 usecPL2 2.60 dBPL12 17.66 dBPL13 17.66 dBSFO2 500.0355000 MHzSI 32768SF 125.7326387 MHzWDW EMSSB 0LB 6.00 HzGB 0PC 1.00
35
Electronic Supplementary Material (ESI) for Green ChemistryThis journal is © The Royal Society of Chemistry 2012
N
HN
SO
O
F
Cl
1H and 13C NMR spectra of 4x
10 9 8 7 6 5 4 3 2 1 ppm
3.986
3.994
4.004
4.011
4.026
4.111
4.113
4.142
4.144
4.254
4.261
4.272
4.279
4.583
4.590
4.596
4.602
4.609
5.259
5.262
6.732
6.736
6.749
6.766
6.896
6.910
6.922
6.992
7.008
7.024
7.189
7.206
7.219
7.223
7.230
7.248
7.253
7.260
7.270
7.309
7.326
7.869
7.886
7.996
8.007
8.011
8.021
9.799
2.014
1.009
1.045
1.022
0.938
1.980
2.000
1.971
4.969
0.825
0.831
1.169
0.866
NAME LZR-2-ZEXPNO 1PROCNO 1Date_ 20110906Time 16.55INSTRUM av500PROBHD 5 mm PABBO BB-PULPROG zg30TD 32768SOLVENT CDCl3NS 8DS 1SWH 10000.000 HzFIDRES 0.305176 HzAQ 1.6385000 secRG 256DW 50.000 usecDE 6.00 usecTE 297.9 KD1 2.00000000 secTD0 1
======== CHANNEL f1 ========NUC1 1HP1 13.50 usecPL1 2.20 dBSFO1 500.0335010 MHzSI 16384SF 500.0300101 MHzWDW EMSSB 0LB 0.30 HzGB 0PC 2.00
LZR-2-Z 1H 2011 09 06
6.87.07.27.47.67.88.0 ppm
200 180 160 140 120 100 80 60 40 20 ppm
42.218
42.595
48.460
65.894
87.367
116.281
125.404
126.501
127.409
128.096
129.130
130.719
131.113
131.411
134.939
139.044
142.619
147.485
153.803
165.163
167.206
193.408
194.077
194.677
LZR-2-Z 13C 1D 2011 09 13
NAME LZR-2-ZEXPNO 2PROCNO 1Date_ 20110913Time 11.16INSTRUM av500PROBHD 5 mm PABBO BB-PULPROG zgpg30TD 65536SOLVENT CDCl3NS 3861DS 2SWH 32679.738 HzFIDRES 0.498653 HzAQ 1.0027661 secRG 1620DW 15.300 usecDE 6.00 usecTE 300.5 KD1 2.00000000 secd11 0.03000000 secDELTA 1.89999998 secTD0 1
======== CHANNEL f1 ========NUC1 13CP1 9.60 usecPL1 2.00 dBSFO1 125.7464750 MHz
======== CHANNEL f2 ========CPDPRG2 waltz16NUC2 1HPCPD2 80.00 usecPL2 2.60 dBPL12 17.66 dBPL13 17.66 dBSFO2 500.0355000 MHzSI 32768SF 125.7326387 MHzWDW EMSSB 0LB 6.00 HzGB 0PC 2.00
36
Electronic Supplementary Material (ESI) for Green ChemistryThis journal is © The Royal Society of Chemistry 2012
N
HN
SO
OCl
1H and 13C NMR spectra of 4y
10 9 8 7 6 5 4 3 2 1 ppm
3.995
4.006
4.013
4.028
4.213
4.214
4.237
4.254
4.256
4.262
4.273
4.280
4.298
4.587
4.602
4.613
4.624
4.628
4.640
5.250
5.253
6.745
6.759
6.799
6.816
6.979
6.994
7.010
7.155
7.170
7.183
7.200
7.205
7.264
7.519
7.534
7.550
7.644
7.659
7.674
7.950
7.952
7.967
9.736
2.035
0.979
0.990
1.003
1.000
3.946
2.000
2.938
1.991
1.006
2.003
0.844
NAME LZR-3-aEXPNO 1PROCNO 1Date_ 20110530Time 16.26INSTRUM av500PROBHD 5 mm PABBO BB-PULPROG zg30TD 32768SOLVENT CDCl3NS 4DS 1SWH 10000.000 HzFIDRES 0.305176 HzAQ 1.6385000 secRG 406DW 50.000 usecDE 6.00 usecTE 295.9 KD1 2.00000000 secTD0 1
======== CHANNEL f1 ========NUC1 1HP1 13.50 usecPL1 2.20 dBSFO1 500.0335010 MHzSI 16384SF 500.0300082 MHzWDW EMSSB 0LB 0.30 HzGB 0PC 2.00
LZR-3-a 1H 1D 2011 05 30
6.87.07.27.47.67.88.0 ppm
20406080100120140160180200 ppm
41.762
42.150
48.421
65.816
87.048
125.895
127.869
128.625
128.994
129.124
132.997
133.809
134.639
140.394
141.224
153.417
193.169
194.275
194.368
LZR-3-a 13C 1D 2011 06 03
NAME LZR-3-aEXPNO 2PROCNO 1Date_ 20110603Time 16.40INSTRUM av500PROBHD 5 mm PABBO BB-PULPROG zgpg30TD 65536SOLVENT CDCl3NS 628DS 2SWH 32679.738 HzFIDRES 0.498653 HzAQ 1.0027661 secRG 18400DW 15.300 usecDE 6.00 usecTE 297.5 KD1 2.00000000 secd11 0.03000000 secDELTA 1.89999998 secTD0 1
======== CHANNEL f1 ========NUC1 13CP1 9.60 usecPL1 2.00 dBSFO1 125.7464750 MHz
======== CHANNEL f2 ========CPDPRG2 waltz16NUC2 1HPCPD2 80.00 usecPL2 2.60 dBPL12 17.66 dBPL13 17.66 dBSFO2 500.0355000 MHzSI 32768SF 125.7326470 MHzWDW EMSSB 0LB 6.00 HzGB 0PC 2.00
37
Electronic Supplementary Material (ESI) for Green ChemistryThis journal is © The Royal Society of Chemistry 2012
N
SO
O
H3C
Cl
HN
5a
N
SOH
O
H3C
Cl
HN
5a' 1H and 13C NMR spectra of 5a/5a'
13 12 11 10 9 8 7 6 5 4 3 2 1 0 ppm
1.641
2.239
2.363
2.443
2.501
3.667
3.707
4.000
4.114
4.120
4.128
4.149
4.160
4.790
4.799
4.813
5.390
6.156
6.169
6.356
6.374
6.543
6.555
6.571
6.756
6.769
6.785
6.830
6.842
6.917
6.927
7.002
7.018
7.035
7.179
7.193
7.206
7.220
7.261
7.281
7.338
7.352
7.842
7.860
7.883
12.787
0.785
1.107
1.170
3.208
1.996
0.572
0.442
1.109
1.025
1.000
0.397
0.524
0.415
0.580
1.189
0.968
2.111
3.321
0.608
0.971
1.990
0.834
NAME LZR-A-1EXPNO 1PROCNO 1Date_ 20110928Time 15.37INSTRUM av500PROBHD 5 mm PABBO BB-PULPROG zg30TD 32768SOLVENT CDCl3NS 8DS 1SWH 10000.000 HzFIDRES 0.305176 HzAQ 1.6385000 secRG 406DW 50.000 usecDE 6.00 usecTE 296.9 KD1 2.00000000 secTD0 1
======== CHANNEL f1 ========NUC1 1HP1 13.50 usecPL1 2.20 dBSFO1 500.0335010 MHzSI 16384SF 500.0300101 MHzWDW EMSSB 0LB 0.30 HzGB 0PC 2.00
LZR-A-1 1H 2011 09 28
6.06.57.07.58.0 ppm 3.84.04.2 ppm
30405060708090100110120130140150160170180190200 ppm
21.564
21.718
38.943
41.377
41.564
46.840
67.148
67.688
89.648
89.945
125.584
125.838
126.752
127.126
127.512
128.393
128.690
128.910
129.527
129.747
131.121
132.147
139.696
141.162
142.482
144.534
155.088
188.436
193.420
194.300
199.284
199.724
LZR-A-1 13C 1D 2011 10 03
NAME LZR-A-1EXPNO 2PROCNO 1Date_ 20111003Time 11.09INSTRUM av500PROBHD 5 mm PABBO BB-PULPROG zgpg30TD 65536SOLVENT CDCl3NS 11478DS 2SWH 32679.738 HzFIDRES 0.498653 HzAQ 1.0027661 secRG 18400DW 15.300 usecDE 6.00 usecTE 296.6 KD1 2.00000000 secd11 0.03000000 secDELTA 1.89999998 secTD0 1
======== CHANNEL f1 ========NUC1 13CP1 9.60 usecPL1 2.00 dBSFO1 125.7464750 MHz
======== CHANNEL f2 ========CPDPRG2 waltz16NUC2 1HPCPD2 80.00 usecPL2 2.60 dBPL12 17.66 dBPL13 17.66 dBSFO2 500.0355000 MHzSI 32768SF 125.7326437 MHzWDW EMSSB 0LB 10.00 HzGB 0PC 1.00
38
Electronic Supplementary Material (ESI) for Green ChemistryThis journal is © The Royal Society of Chemistry 2012
N
SO
O
H3C
Cl
HN
Cl
5b
N
SOH
O
H3C
Cl
HN
Cl
5b' 1H and 13C NMR spectra of 5b/5b'
13 12 11 10 9 8 7 6 5 4 3 2 1 ppm
2.225
2.233
2.353
2.455
2.509
3.663
3.949
4.108
4.120
4.130
4.138
4.143
4.755
4.762
4.779
4.789
4.802
5.403
6.086
6.099
6.283
6.299
6.526
6.542
6.749
6.765
6.864
6.876
6.942
7.066
7.193
7.214
7.229
7.259
7.283
7.297
7.350
7.845
7.858
12.751
1.000
1.063
2.956
2.638
0.409
1.027
1.008
1.000
0.412
0.560
0.385
0.579
1.258
0.723
0.960
2.955
1.102
0.842
1.980
0.907
NAME LZR-A-2EXPNO 1PROCNO 1Date_ 20110929Time 15.42INSTRUM av500PROBHD 5 mm PABBO BB-PULPROG zg30TD 32768SOLVENT CDCl3NS 4DS 1SWH 10000.000 HzFIDRES 0.305176 HzAQ 1.6385000 secRG 287DW 50.000 usecDE 6.00 usecTE 299.7 KD1 2.00000000 secTD0 1
======== CHANNEL f1 ========NUC1 1HP1 13.50 usecPL1 2.20 dBSFO1 500.0335010 MHzSI 16384SF 500.0300107 MHzWDW EMSSB 0LB 0.30 HzGB 0PC 2.00
LZR-A-2 1H 2011 09 29
6.57.07.58.0 ppm
30405060708090100110120130140150160170180190200 ppm
21.466
21.698
38.950
41.499
46.787
67.115
67.684
89.571
89.845
126.162
126.688
127.257
127.721
128.353
128.837
129.617
130.712
131.976
133.977
137.853
138.190
140.845
142.298
144.721
155.190
186.957
193.340
194.161
199.154
199.596
LZR-A-2 13C 1D 2011 10 03
NAME LZR-A-2EXPNO 2PROCNO 1Date_ 20111004Time 9.51INSTRUM av500PROBHD 5 mm PABBO BB-PULPROG zgpg30TD 65536SOLVENT CDCl3NS 14827DS 2SWH 32679.738 HzFIDRES 0.498653 HzAQ 1.0027661 secRG 18400DW 15.300 usecDE 6.00 usecTE 299.7 KD1 2.00000000 secd11 0.03000000 secDELTA 1.89999998 secTD0 1
======== CHANNEL f1 ========NUC1 13CP1 9.60 usecPL1 2.00 dBSFO1 125.7464750 MHz
======== CHANNEL f2 ========CPDPRG2 waltz16NUC2 1HPCPD2 80.00 usecPL2 2.60 dBPL12 17.66 dBPL13 17.66 dBSFO2 500.0355000 MHzSI 32768SF 125.7326464 MHzWDW EMSSB 0LB 6.00 HzGB 0PC 2.00
39
Electronic Supplementary Material (ESI) for Green ChemistryThis journal is © The Royal Society of Chemistry 2012