Supplementary Information · 1H and 13C NMR spectra 13–39 General Information All reagents and...

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

1

Electronic Supplementary Material (ESI) for Green ChemistryThis journal is © The Royal Society of Chemistry 2012

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,

2


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)

3


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)

4


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)

5


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)

6


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

7


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


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


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


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.

11


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


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


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


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



14


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


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



15


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


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



16


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


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



17


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


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



18


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


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



19


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


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



20


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


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



21


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


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



22


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


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



23


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


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



24


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


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



25


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


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



26


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


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



27


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


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



28


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


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



29


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


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



30


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


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



31


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


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



32


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


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



33


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


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



34


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


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



35


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


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



36


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


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



37


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


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



38


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


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



39


Supplementary Information · 1H and 13C NMR spectra 13–39 General Information All reagents and...

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