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Supplementary Information
Double Carbonylation of Aryl Iodides with Amines under an Atmospheric Pressure of
Carbon Monoxide Using Sulfur-Modified Au-Supported Palladium
Nozomi Saito,a,c* Takahisa Taniguchi,a Naoyuki Hoshiya,b,d Satoshi Shuto,b Mitsuhiro Arisawa,b,c,e*
Yoshihiro Satoa,c*
a Laboratory of Fine Synthetic Chemistry, Faculty of Pharmaceutical Sciences, Hokkaido University,
Sapporo 060-0812, Japan
b Laboratory of Organic Chemistry for Drug Development, Faculty of Pharmaceutical Sciences,
Hokkaido University, Sapporo 060-0812, Japan
c ACT-C, Japan Science and Technology Agency (JST), Sapporo 060-0812, Japan
d Present address: Kyoto Pharmaceutical University, Misasagi, Yamashina, Kyoto 607-8412, Japan
e Present address: Graduate School of Pharmaceutical Sciences, Osaka University, 1-6 Yamada-oka,
Suita, Osaka 565-0862, Japan
S2~S13 : Experimental Procedure and Spectral Data
S14~S98 : Charts of 1H and 13C NMR spectra of α-ketoamides 3 and mono-amides 4
~ S1 ~
Electronic Supplementary Material (ESI) for Green Chemistry.This journal is © The Royal Society of Chemistry 2015
General Information
All manipulations were performed under an argon atmosphere unless stated otherwise. Solvents
were purified under argon using The Ultimate Solvent System (Glass Counter Inc.) (CH3CN, DMF,
THF, Toluene). All other solvents and reagents were purified when necessary by standard
procedures. Column chromatography was performed on silica gel 60 N (spherical, neutral; Kanto
Kagaku, 45-50 μm) with the indicated solvent as eluent. TLC and PTLC were performed on Silica
gel 60 PF254 (Merck). IR spectra were obtained on a JASCO FT/IR 460Plus spectrometer. 1H NMR
spectroscopy was recorded on JEOL ECA500 (500 MHz) NMR spectrometer. Chemical shifts are
reported in ppm from the solvent as the internal standard (CDCl3: δ = 7.26 ppm). Data are reported
as follows: chemical shift, multiplicity (s = singlet, d = doublet, t = triplet, br = broad, m =
multiplet), coupling constants (Hz) and integration. 13C NMR spectroscopy was recorded on JEOL
ECA500 (125 MHz) NMR spectrometer. Chemical shifts are reported in ppm from the solvent as
the internal standard (CDCl3: δ = 77.00 ppm). Mass spectra were obtained on JEOL JMS-T100LP
and JMS-T100GCV and JEOL JMS-FAB mate mass spectrometer, and Thermo Scientific Exactive
mass spectrometer. GC was performed using a gas chromatograph Shimadzu GC-17A equipped
with an Agilent J&W DB-5MS column and a FID detector. Sulfur-Modified Au-Supported Pd
(SAPd) Material was prepared according to the literature.1
1 M. Al-Amin, S. Arai, N. Hoshiya, T. Honma, Y. Tamenori, T. Sato, M. Yokoyama, A. Ishii, M. Takeuchi, T.Maruko, S. Shuto, M. Arisawa, J. Org. Chem. 2013, 78, 7575-7581.
~ S2 ~
Experimental Procedure for Double Carbonylation Using SAPd Shown in Scheme 1
A flame-dried test tube was charged with 1a (117.8 mg, 0.503 mmol), K2CO3 (138.7 mg, 1.00 mmol), bibenzyl (48.9 mg, 0.268 mmol, as an internal standard) and degassed DMF (3 mL). To this were added a sheet of SAPd and 2a (130.0 µL, 1.49 mmol), and the test tube was immersed in a liquid nitrogen bath. After the mixture had been frozen, the flask was evacuated to 0.05 mmHg. The flask was backfilled with CO in a plastic balloon and the frozen mixture was thawed at room temperature. Then, the resulting reaction mixture was heated at 80 °C for 24 hours and analyzed by GC with an internal standard (bibenzyl). GC Yield (3aa: 40%, 4aa: 9%, 1a: 47%). After the reaction, the immobilized Pd NPs seemed to come off the Au-mesh, and the precipitation of Pd-black was observed in the reaction mixture as following pictures.
Typical Procedure for Double Carbonylation Using SAPd (Scheme 2). A mixture of 1a (117.0 mg, 0.500 mmol), K2CO3 (137.6 mg, 1.00 mmol), bibenzyl (43.5 mg, 0.239 mmol, internal standard for GC analysis) and a sheet of SAPd in DMF (3 mL) was heated at 80 °C for 2 hours under an argon atmosphere without stirring (1 atm). After removal of SAPd from the reaction vessel, 2a (130.0 µL, 1.49 mmol) and a stirring bar were added to the vessel. The vessel was immersed in a liquid nitrogen bath. After the mixture had been frozen, the flask was evacuated to 0.05 mmHg. The flask was backfilled with CO in a plastic balloon and the frozen mixture was thawed at room temperature. Then, the resulting reaction mixture was stirred at 80 °C for 24 hours. To the mixture was added 10% HCl at 0 °C, and the aqueous layer was extracted with AcOEt. The organic layer was dried over Na2SO4 and concentrated. The residue was purified by flash column chromatography on silica gel (hexane/AcOEt = 1/1~1/2) to give 3aa (106.0 mg, 85%) as a colorless solid and 4aa (11.7 mg, 11%) as a yellow oil, respectively. 1H and 13C NMR data of 1-(4-Methoxyphenyl)-2-morpholinoethane-1,2-dione (3aa): 1H NMR (500 MHz, CDCl3) δ 7.94-7.92 (m, 2H), 6.99-6.97 (m, 2H), 3.89 (s, 3H), 3.78 (m, 4H), 3.65 (t, J = 4.9 Hz, 2H), 3.38 (t, J = 4.9 Hz, 2H); 13C NMR(125 MHz, CDCl3) δ 189.8, 165.8, 165.0, 132.1, 126.1, 114.4, 66.8, 66.7, 55.7, 46.3, 41.5. These data were identical to those reported previously.2 1H and 13C NMR data of N-(4-Methoxybenzoyl)morpholine (4aa): 1H NMR (500 MHz, CDCl3) δ 7.38-7.36 (m, 2H), 2 J. Liu, R. Zhang, S. Wang, W. Sun, C. Xia, Org. Lett. 2009, 11. 1321-1324.
~ S3 ~
6.91-6.89 (m, 2H), 3.81 (s, 3H), 3.85-3.33 (br, 8H); 13C NMR (125 MHz, CDCl3) δ 170.4, 160.8, 129.2, 127.3, 113.7, 66.9, 55.3, 48.2 (br), 43.0 (br). These data were identical to those reported previously.3
1-(4-Methoxyphenyl)-2-pyrrolidin-1-ylethane-1,2-dione (3ab) and N-(4-Methoxybenzoyl)- pyrrolidine (4ab) (Table 1, run 1). A crude product, which was obtained from 1a (117.4 mg, 0.502 mmol), K2CO3 (139.1 mg, 1.01 mmol), 2b (123.0 µL, 1.50 mmol), and bibenzyl (47.3 mg, 0.260 mmol, internal standard for GC analysis) in DMF (3 mL) at 80 °C for 24 hours, was purified by flash column chromatography on silica gel (hexane/AcOEt = 2/1~1/2) to give 3ab (95.7 mg, 82%) as a colorless solid and 4ab (10.4 mg, 10%) as a colorless solid, respectively. 1H and 13C NMR data of 3ab: 1H NMR (500 MHz, CDCl3) δ 7.93-7.90 (m, 2H), 6.93-6.91 (m, 2H), 3.83 (s, 3H), 3.59 (t, J = 6.7 Hz, 2H), 3.36 (t, J = 6.7 Hz, 2H), 1.93-1.85 (m, 4H); 13C NMR (125 MHz, CDCl3) δ 190.2, 165.2, 164.6, 132.2, 125.8, 114.1, 55.5, 46.5, 45.0, 25.8, 23.9. These data were identical to those reported previously.4 1H and 13C-NMR data of 4ab: 1H NMR (500 MHz, CDCl3) δ 7.52-7.50 (m, 2H), 6.90-6.88 (m, 2H), 3.83 (s, 3H), 3.64-3.62 (m, 2H), 3.49-3.46 (m, 2H), 1.90-1.85 (m, 4H); 13C NMR (125 MHz, CDCl3) δ 169.4, 160.7, 129.4, 129.1, 113.4, 55.3, 49.8, 46.3, 26.5, 24.4. These data were identical to those reported previously.5
1-(4-Methoxyphenyl)-2-piperidin-1-ylethane-1,2-dione (3ac) and N-(4-Methoxybenzoyl)- piperidine (4ac) (Table 1, run 2). A crude product, which was obtained from 1a (117.8 mg, 0.503 mmol), K2CO3 (137.6 mg, 0.996 mmol), bibenzyl (50.8 mg, 0.279 mmol, internal standard for GC analysis), and 2c (150.0 µL, 1.52 mmol) in DMF (3 mL) at 80 °C for 24 hours, was purified by flash column chromatography on silica gel (hexane/AcOEt = 2/1~1/2) to give 3ac (117.3 mg, 94%) as a yellow oil and 4ac (7.0 mg, 6%) as a yellow oil, respectively. 1H and 13C NMR data of 3ac: 1H NMR (500 MHz, CDCl3) δ 7.89-7.86 (m 2H), 7.00-6.93 (m, 2H), 3.85 (s, 3H), 3.67-3.64 (m, 2H), 3.26-3.24 (m, 2H), 1.66-1.64 (m, 4H), 1.51-1.49 (m, 2H); 13C NMR (125 MHz, CDCl3) δ 190.6, 165.7, 164.7, 131.9, 126.2, 114.2, 55.5, 46.9, 41.9, 26.1, 25.3, 24.3. These data were identical to those reported previously.6 1H and 13C NMR data of 4ac: 1H NMR (500 MHz, CDCl3) δ 7.36 (d, J = 8.6 Hz, 2H), 6.89 (d, J = 8.6 Hz, 2H), 3.82 (s, 3H), 3.85-3.3.21 (br, 4H), 1.85-1.40 (br, 6H); 13C NMR (125 MHz, CDCl3) δ 170.3, 160.5, 128.8, 128.6, 113.6, 55.3, 49.0 (br), 43.4 (br), 26.4 (br), 25.7 (br), 24.6. These data were identical to those reported previously.7
1-(4-Methoxyphenyl)-2-(4-methylpiperazin-1-yl)ethane-1,2-dione (3ad) and 1-(4-Methoxy- benzoyl)-4-methylpiperazine (4ad) (Table 1, run 3). A crude product, which was obtained from 1a (119.9 mg, 0.512 mmol), K2CO3 (138.4 mg, 1.00 mmol)、2d (166.0 µL, 1.50 mmol), and bibenzyl (46.8 mg, 0.257 mmol, internal standard for GC analysis) in DMF (3 mL) at 80 °C for 24 hours, was purified by flash column chromatography on silica gel (AcOEt/MeOH = 100/1~1/1) to give 3ad (115.4 mg, 86%) as a yellow oil and 4ad (13.8 mg, 11%) as a yellow oil, respectively. Spectral data of 3ad: IR (neat) 1637, 1599 cm-1; 1H NMR (500 MHz, CDCl3) δ 7.88-7.85 (m, 2H), 6.95-6.93 (m, 2H), 3.85 (s, 3H), 3.85-3.82 (m, 2H), 3.44-3.42 (m, 2H), 2.64 (t, J = 5.2 Hz, 2H), 2.52 (t, J = 5.2 Hz, 2H), 2.38 (s, 3H); 13C NMR (125 MHz, CDCl3) δ 189.8, 165.6, 164.9, 132.0, 125.8, 114.3, 55.6, 54.4, 54.0, 45.4, 45.0, 40.3; EI-LRMS m/z 262 (M+), 135; EI-HRMS calcd for 3 J. R. Martinelli, D. A. Watson, D. M. M. Freckmann, T. E. Barder, S. L. Buchwald, J. Org. Chem. 2008, 73, 7102-7107. 4 M. Iizuka, Y. Kondo, Chem. Commun. 2006, 1739-1741. 5 K. Ekoue-Kovi, C. Wolf, Org. Lett. 2007, 9, 3429-3432. 6 J. Zhang, Y. Wei, S. Lin, F. Liang, P. Liu, Org. Biomol. Chem. 2012, 10, 9237-9242. 7 J. Li, F. Xu, Y. Zhang, Q. Shen, J. Org. Chem. 2009, 74, 2575-2577.
~ S4 ~
C14H18O3N2 262.1317, found 262.1326. Spectral data of 4ad: IR (neat): 1626, 1610; 1H NMR (500 MHz, CDCl3) δ 7.38 (d, J = 8.6 Hz, 2H), 6.91 (d, J = 8.6 Hz, 2H), 3.83 (s, 3H), 3.63-3.47 (br, 4H), 2.48-2.35 (br, 4H), 2.32 (s, 3H); 13C NMR (125 MHz, CDCl3) δ 170.3, 160.9, 129.1, 128.2, 113.8, 55.4, 55.3, 55.1, 46.0; EI-LRMS m/z 234 (M+), 135; EI-HRMS calcd for C13H18N2O2 234.13683, found 234.13675.
1-(4-Methoxyphenyl)-2-(1,4-dioxa-8-azaspiro[4.5]decan-8-yl)ethane-1,2-dione (3ae) and 1-(4-Methoxybenzoyl)-4-piperidone ethylene ketal (4ae) (Table 1, run 4). A crude product, which was obtained from 1a (118.5 mg, 0.506 mmol), K2CO3 (139.7 mg, 1.01 mmol), 2e (166.0 µL, 1.50 mmol), and bibenzyl (49.6 mg, 0.272 mmol, internal standard for GC analysis) in DMF (3 mL) at 80 °C for 24 hours, was purified by flash column chromatography on silica gel (hexane/AcOEt = 2/1~1/2) to give 3ae (134.9 mg, 87%) as a colorless solid and 4ae (12.6 mg, 9%) as a colorless oil, respectively. Spectral data of 3ae: mp 127 °C (recrystallized from CHCl3/hexane); IR (film, CHCl3) 1671, 1639, 1600 cm-1; 1H NMR (500 MHz, CDCl3) δ 7.89 (d, J = 9.2 Hz, 2H), 6.95 (d, J = 9.2 Hz, 2H), 3.99-3.92 (m, 4H), 3.86 (s, 3H), 3.82 (t, J = 5.7 Hz, 2H), 3.40 (t, J = 5.7 Hz, 2H), 1.79 (t, J = 5.7 Hz, 2H), 1.66 (t, J = 5.7 Hz, 2H); 13C NMR (125 MHz, CDCl3) δ 190.3, 165.7, 164.8, 132.0, 126.1, 114.3, 106.6, 64.5, 55.6, 44.0, 39.2, 35.3, 34.6; EI-LRMS m/z 305 (M+), 135; EI-HRMS calcd for C16H19NO5 305.1263, found 305.1249. 1H and 13C NMR data of 4ae: 1H NMR (500 MHz, CDCl3) δ 7.33-7.32 (m, 2H), 6.86-6.84 (m, 2H), 3.92 (s, 4H), 3.76 (s, 3H), 3.80-3.40 (br, 4H), 1.83-1.42 (br, 4H); 13C NMR (125 MHz, CDCl3) δ 170.1, 160.5, 128.7, 127.9, 113.5, 106.8, 64.3, 55.1, 45.7 (br), 40.3 (br), 35.3 (br), 34.9 (br) These data were identical to those reported previously.8
1-[3,4-Dihydroisoquinolin-2(1H)-yl]-2-(4-methoxyphenyl)ethane-1,2-dione (3af) (Table 1, run 5). A crude product, which was 1a (117.4 mg, 0.502 mmol), K2CO3 (138.5 mg, 1.00 mmol), 2f (190.0 µL, 1.49 mmol), and bibenzyl (47.6 mg, 0.261 mmol, internal standard for GC analysis) in DMF (3 mL) at 80 °C for 24 hours, was purified by flash column chromatography on silica gel (hexane/AcOEt = 3/2~0/1) to give 3af (150.9 mg, quant) as a colorless solid. 1H and 13C NMR data of 3af: 1H NMR (500 MHz, CDCl3) δ 7.96-7.91 (m, 2H), 7.25-6.93 (m, 6H), 4.89 (s, 1.3H), 4.53 (s, 0.7H), 3.97 (t, J = 6.0 Hz, 0.7H), 3.88 (s, 1.9H), 3.86 (s, 1.1H), 3.61 (t, J = 6.0 Hz, 1.3H), 2.99 (t, J = 6.0 Hz, 0.7H), 2.85 (t, J = 6.0 Hz, 1.3H); 13C NMR (125 MHz, CDCl3) δ 190.1, 190.0, 166.4, 166.0, 164.9, 164.8, 133.4, 132.1, 131.8, 128.9, 128.7, 127.1, 126.7, 126.6, 126.5, 126.1, 126.0, 114.3, 55.6, 47.3, 43.4, 43.3, 39.2, 29.2, 28.2. These data were identical to those reported previously.9
N-Butyl-4-methoxyphenylglyoxamide (3ag) and N-Butyl-4-methoxyphenylbenzamide (4ag) (Table 1, run 6). A crude product, which was obtained from 1a (117.5 mg, 0.502 mmol), K2CO3 (139.3 mg, 1.01 mmol), 2g (148.0 µL, 1.50 mmol), and bibenyl (47.1 mg, 0.258 mmol, internal standard for GC analysis) in DMF (3 mL) at 80 °C for 24 hours, was purified by flash column chromatography on silica gel (hexane/AcOEt = 6/1) to give 3ag (87.8 mg, 74%) as a colorless solid and 4ag (23.4 mg, 22%) as a yellow oil, respectively. 1H and 13C NMR data of 3ag: 1H NMR (500 MHz, CDCl3) δ 8.42 (d, J = 8.8 Hz, 2H), 7.12 (brs, 1H), 6.95 (d, J = 8.8 Hz, 2H), 3.89 (s, 3H), 3.40-3.36 (m, 2H), 1.62-1.56 (m, 2H), 1.44-1.37 (m, 2H), 0.96 (t, J = 7.2 Hz, 3H); 13C NMR (125 MHz, CDCl3) δ 185.8, 164.6, 162.3, 133.8, 126.3, 113.7, 55.5, 39.0, 31.3, 20.0, 13.6. These data were identical to those reported previously4
1H and 13C NMR data of 4ag: 1H NMR (500 MHz,
8 D. L. Boger, M. D. Mullican, J. Org. Chem. 1984, 49, 4033-4044. 9 M. Genelot, N. Villandier, A. Bendjeriou, P. Jaithong, L. Djakovitch, V. Dufaud, Catal. Sci. Technol. 2012, 2, 1886-1893.
~ S5 ~
CDCl3) δ 7.73-7.71 (m, 2H), 6.92-6.91 (m, 2H), 6.02 (brs, 1H), 3.85 (s, 3H), 3.46-3.42 (m, 2H), 1.62-1.56 (m, 2H), 1.45-1.37 (m, 2H), 0.95 (t, J = 7.5 Hz, 3H); 13C NMR (125 MHz, CDCl3) δ 167.0, 162.0, 128.6, 127.1, 113.7, 55.4, 39.7, 31.8, 20.2, 13.8. These data were identical to those reported previously.10
2-(4-Methoxyphenyl)-2-oxo-N,N-dipropylacetamide (3ah) and 4-Methoxy-N,N-dipropyl- benzamide (4ah) (Table 1, run 7). A crude product, which was obtained from 1a (118.9 mg, 0.508 mmol), K2CO3 (139.7 mg, 1.01 mmol), 2h (205.0 µL, 1.50 mmol), and bibenzyl (48.0 mg, 0.263 mmol, internal standard for GC analysis) in DMF (3 mL) at 80 °C for 24 hours, was purified by flash column chromatography on silica gel (hexane/AcOEt = 6/1) to give 3ah (99.8 mg, 75%) as a yellow oil and 4ah (12.6 mg, 20%) as a yellow oil, respectively. Spectral data of 3ah: IR (neat) 1671, 1637, 1599 cm-1; 1H NMR (500 MHz, CDCl3) δ 7.90 (d, J = 8.9 Hz, 2H), 6.96 (d, J = 8.9 Hz, 2H), 3.88 (s, 3H), 3.44 (t, J = 7.7 Hz, 2H), 3.12 (t, J = 7.7 Hz, 2H), 1.74-1.67 (m, 2H), 1.61-1.53 (m, 2H) 0.99 (t, J = 7.5 Hz, 3H), 0.78 (t, J = 7.5 Hz, 3H); 13C NMR (125 MHz, CDCl3) δ 190.3, 167.5, 164.6, 132.0, 126.4, 114.2, 55.6, 49.3, 45.7, 21.8, 20.6, 11.4, 11.0; EI-LRMS m/z 263 (M+), 135; EI-HRMS calcd. for C15H21NO3 263.15214, found 263.15184. Spectral data of 4ah: IR data; 1630 cm-1; 1H NMR (500 MHz, CDCl3) δ 7.33-7.30 (m, 2H), 6.90-6.87 (m, 2H), 3.82 (s, 3H), 3.59-3.30 (br, 4H), 1.74-1.43 (br, 4H), 1.07-0.59 (br, 6H); 13C NMR (125 MHz, CDCl3) δ 171.7, 160.1, 129.6, 128.3, 113.6, 55.3, 50.9 (br), 46.5 (br), 21.9 (br), 20.6 (br), 11.2 (br); EI-LRMS m/z 235 (M+), 135; EI-HRMS calcd. for C14H20NO2 234.14940, found 234.14945
N-Benzyl-2-(4-methoxyphenyl)-N-methyl-2-oxoacetamide (3ai) (Table 1, run 8). A crude product, which was obtained from 1a (116.3 mg, 0.497 mmol), K2CO3 (139.2 mg, 1.01 mmol), 2i (195.0 µL, 1.51 mmol), and bibenzyl (45.6 mg, 0.250 mmol, internal standard for GC analysis) in DMF (3 mL) at 80 °C for 24 hours, was purified by flash column chromatography on silica gel (hexane/AcOEt = 4/1~1/2) followed by preparative thin-layer chromatography on silica gel (hexane/AcOEt = 3/1) to give 3ai (134.9 mg, 87%) as an colorless oil. Spectral data of 3ai: IR (neat) 1668, 1643, 1599 cm-1; 1H NMR (500 MHz, CDCl3) δ 7.97-7.92 (m, 2H), 7.40-7.25 (m, 5H) 6.99-6.97 (m, 2H), 4.72 (s, 1.1H), 4.39 (s, 0.9H), 3.88 (m, 3H), 2.97 (s, 1.4H), 2.84 (s, 1.6H); 13C NMR (125 MHz, CDCl3) δ 190.2, 167.6, 167.4, 164.8, 135.9, 135.0, 132.2, 132.1, 128.8, 128.3, 128.1, 127.8, 126.8, 126.3, 126.1, 114.3, 55.6, 53.5, 49.7, 34.5, 31.3; EI-LRMS m/z 283 (M+), 135; EI-HRMS calcd. for C17H17NO3 283.12084, found 283.12021.
N-(2-tert-Butyldimethylsiloxyethyl)-2-(4-methoxyphenyl)-N-methyl-2-oxoacetamide (3aj) (Table 1, run 9). A crude product, which was obtained from 1a (118.7 mg, 0.507 mmol), K2CO3 (141.4 mg, 1.02 mmol), 2j (342 µL, 1.50 mmol), and bibenzyl (45.8 mg, 0.251mmol, internal standard for GC analysis) in DMF (3 mL) at 80 °C for 24 hours, was purified by flash column chromatography on silica gel (hexane/AcOEt = 4/1~1/1) to give 3aj (124.3 mg, 70%) as a colorless oil. Spectral data of 3aj: IR (neat) 1672, 1646, 1600 cm-1; 1H NMR (500 MHz, CDCl3) δ 7.93-7.89 (m, 2H), 6.96-6.93 (m, 2H), 3.90 (t, J = 5.3 Hz, 1H), 3.87 (s, 3H), 3.70 (t, J = 5.7 Hz, 1H), 3.63 (t, J = 5.3 Hz, 1H), 3.34 (t, J = 5.7 Hz, 1H), 3.15-3.02 (m, 3H), 0.90-0.83 (m, 9H), 0.09--0.03 (m, 6H); 13C NMR (125 MHz, CDCl3) δ 190.5, 167.7, 167.5, 164.7, 132.2, 132.1, 126.3, 126.1, 114.2, 61.6, 61.1, 55.6, 51.8, 49.3, 37.0, 33.4, 25.8, 25.8, 18.1; EI-LRMS: m/z 351 (M+), 336, 294, 216, 135; EI-HRMS calcd. for C18H29NO4Si 354.18658, found 351.18670. 4-Methoxy-N-phenylbenzamide (4ak) (Table 1, run 10). A crude product was obtained from 1a 10 P. Nordeman, L. R. Odell, M. Larhed, J. Org. Chem. 2012, 77, 11393-11398.
~ S6 ~
(117.0 mg, 0.500 mmol), K2CO3 (138.9 mg, 1.00 mmol), 2k (140 µL, 1.54 mmol), and bibenzyl (48.8 mg, 0.268 mmol, internal standard for GC analysis) in DMF (3 mL) at 80 °C for 24 hours. The yield of 4ak was determined by 1H NMR analysis of the crude product using 1,3,5-trimethoxybenzene (δ = 6.1 ppm in CDCl3, 3H) as an internal standard (55%). Analytically pure samples were obtained by recycle preparative thin-layer chromatography on silica gel (hexane/AcOEt = 5/1).1H and 13C NMR data of 4ak: 1H NMR (500 MHz, CDCl3) δ 7.85 (d, J = 8.9 Hz, 2H), 7.70 (brs, 1H), 7.63 (d, J = 7.4 Hz), 7.39-7.36 (m, 2H), 7.16-7.13 (m, 1H), 6.99 (d, J = 8.9 Hz, 2H), 3.88 (s, 3H); 13C NMR (125 MHz, CDCl3) δ 165.2, 152.4, 138.1, 129.0, 128.9, 127.1, 124.3, 120.1, 113.9, 55.5. These data were identical to those reported previously.11
1-(3-Methoxyphenyl)-2-morpholinoethane-1,2-dione (3ba) and N-(3-Methoxybenzoyl)- morpholine (4ba) (Table 2, run 1). A crude product, which was obtained from 1b (117.2 mg, 0.502 mmol), K2CO3 (138.9 mg, 1.01 mmol), 2a (130.0 µL, 1.49 mmol), and bibenzyl (48.8 mg, 0.268 mmol) in DMF (3 mL) at 80 °C for 24 hours, was purified by flash column chromatography on silica gel (hexane/AcOEt = 2/1~1/1) to give 3ba (104.6 mg, 84%) as a colorless solid and4ba (15.6 mg, 14%) as a colorless oil, respectively. 1H and 13C NMR data of 3ba: 1H NMR (500 MHz, CDCl3) δ 7.48-7.46 (m, 2H), 7.40 (dd, J = 8.0, 8.0 Hz, 1H), 7.17 (m, 1H), 3.83 (s, 3 H), 3.78-3.74 (br, 4H), 3.62 (t, J = 4.9 Hz, 2H), 3.34 (t, J = 4.87, 2 H); 13C NMR (125 MHz, CDCl3) δ 191.0, 165.3, 160.0, 134.2, 130.1, 122.7, 121.7, 112.6, 66.6, 66.5, 55.4, 46.1, 41.5. These data were identical to those reported previously.12 1H and 13C NMR data of 4ba: 1H NMR (500 MHz, CDCl3) δ 7.31 (m, 1H), 6.96-6.94 (m, 3H). 3.81 (s, 3H), 3.87-3.26 (br, 8H); 13C NMR (125 MHz, CDCl3) δ 170.2, 159.7, 136.6, 129.7, 119.1, 115.6, 112.5, 66.9, 55.4, 48.2 (br), 42.5 (br). These data were identical to those reported previously.5
1-(2-Methoxyphenyl)-2-morpholinoethane-1,2-dione (3ca) and N-(2-Methoxybenzoyl)- morpholine (4ca) (Table 2, run 2). A crude product, which was obtained from 1c (118.1 mg, 0.502 mmol), K2CO3 (137.7 mg, 1.01 mmol), 2a (130.0 µL, 1.49 mmol), and bibenzyl (48.1 mg, 0.268 mmol, internal standard for GC analysis) in DMF (3 mL) at 80 °C for 24 hours, was purified by flash column chromatography on silica gel (hexane/AcOEt = 4/1~1/2) to give an inseparable mixture of 3ca and 4ca (97.4 mg, 3ca: 29%, 4ca: 55%) as a yellow oil. Analytically pure samples were obtained by recycle preparative thin-layer chromatography on silica gel (hexane/AcOEt = 1/1). 1H and 13C NMR data of 3ca: 1H NMR (500 MHz, CDCl3) δ 7.93 (dd, J = 7.9, 1.7 Hz, 1H), 7.58 (ddd, J = 8.7, 8.2, 1.7 Hz, 1H), 7.09 (dd, J = 8.2, 7.9 Hz, 1H), 7.00 (d, J = 8.7 Hz, 1H), 3.91 (s, 3H), 3.79 (t, J = 4.6 Hz, 2H), 3.72-3.69 (m, 4H), 3.40 (t, J = 4.6 Hz, 2H); 13C NMR (125 MHz, CDCl3) δ 190.2, 167.4, 160.1, 136.2, 131.1, 123.5, 121.5, 112.2, 66.5, 66.3, 56.2, 45.9, 41.4. These data were identical to those reported previously.2 1H and 13C NMR data of 4ca: 1H NMR (500 MHz, CDCl3) δ 7.36 (m, 1H), 7.24 (m, 1H), 7.00 (m, 1H), 6.91 (d, J = 8.6 Hz, 1H), 3.83 (s, 3H), 3.90-3.72 (m, 4H), 3.63-3.56 (m, 2H), 3.29-3.22 (m, 2H); 13C NMR (125 MHz, CDCl3) 167.8, 155.2, 130.6, 128.0, 125.2, 121.0, 110.8, 66.9, 66.8, 55.5, 47.2, 42.1. These data were identical to those reported previously.7
1-(3,5-Dimethylphenyl)-2-morpholinoethane-1,2-dione (3da) and N-(3,5-Dimethylbenzoyl)- morpholine (4da) (Table 2, run 3). A crude product, which was obtained from 1d (120.0 mg, 0.517 mmol), K2CO3 (140.9 mg, 1.02 mmol), 2a (130.0 µL, 1.49 mmol), and bibenzyl (51.8 mg,
11 E. Racine, F. Monnier, J. P. Vors, M. Taillefer, Org. Lett. 2011, 13, 2818-2821. 12 W. Wei, Y. Shao, H. Hu, F. Zhang, C. Zhang, Y. Xu, X. Wan, J. Org. Chem. 2012, 77, 7157-7165.
~ S7 ~
0.284 mmol, internal standard for GC analysis) in DMF (3 mL) at 80 °C for 24 hours, was purified by flash column chromatography on silica gel (hexane/AcOEt = 2/1~1/2) to give 3da (97.2 mg, 76%) as a white solid and 4da (7.9 mg, 7%) as a yellow amorphous solid, respectively. Spectral data of 3da: mp 101 °C (recrystallized from CHCl3/hexane); IR (film, CHCl3) 1677, 1643 cm-1; 1H NMR (500 MHz, CDCl3) δ 7.54 (s, 2H), 7.28 (s, 1H), 3.80-3.76 (m, 4H), 3.64 (t, J = 4.9 Hz, 2H), 3.35 (t, J = 4.9 Hz, 2H), 2.37 (s, 6H); 13C NMR (125 MHz, CDCl3) δ 191.6, 165.7, 138.9, 136.7, 133.0, 127.3, 66.7, 66.6, 46.2, 41.5, 21.1; EI-LRMS m/z 247 (M+), 133; EI-HRMS calcd. for C14H17NO3 247.12084, found 247.12042. 1H and 13C NMR data of 4da: 1H NMR (500 MHz, CDCl3) δ 7.04 (s, 1H), 6.99 (s, 2H), 4.01-3.24 (br, 8H), 2.33 (s, 6H); 13C NMR (125 MHz, CDCl3) δ 170.8, 138.3, 135.3, 131.3, 124.6, 66.9, 48.2, 42.5, 21.2. These data were identical to those reported previously.3
1-Morpholino-2-(3,4,5-trimethoxyphenyl)ethane-1,2-dione (3ea) and N-(3,4,5-Trimethoxy- benzoyl)morpholine (4ea) (Table 2, run 4). A crude product, which was obtained from 1e (146.9 mg, 0.496 mmol), K2CO3 (140.4 mg, 1.02 mmol), 2a (130.0 µL, 1.49 mmol), and bibenzyl (48.0 mg, 0.263 mmol) in DMF (3 mL) at 80 °C for 24 hours, was purified by flash column chromatography on silica gel (hexane/AcOEt = 2/1~1/5) to give 3ea (132.6 mg, 86%) as a colorless solid and 4ea (4.8 mg, 4%) as a yellow oil, respectively. Spectral data of 3ea: mp 133 °C (recrystallized from CHCl3/hexane); IR (film, CHCl3) 1673, 1644 cm-1; 1H NMR (500 MHz, CDCl3) δ 7.17 (s, 2H), 3.91 (s, 3H), 3.88 (s, 3H), 3.75 (s, 4H), 3.63 (t, J = 4.9 Hz, 2H), 3.35 (t, J = 4.9 Hz, 2H); 13C NMR (125 MHz, CDCl3) δ 189.9, 165.2, 153.3, 144.1, 127.9, 106.8, 66.7, 66.6, 60.9, 56.3, 46.2, 41.6; EI-LRMS m/z 309 (M+), 195; EI-HRMS calcd. for C15H19NO6 309.12124, found 309.12109. 1H NMR data of 4ea: 1H NMR (500 MHz, CDCl3) δ 6.61 (s, 2H), 3.86 (s, 6H), 3.84 (s, 3H), 3.85-3.47 (br, 8H); 13C NMR (125 MHz, CDCl3) δ 170.1, 153.3, 139.2, 130.6, 104.3, 66.9, 60.9, 56.2, 48.3 (br), 42.7 (br). These data were identical to those reported previously.13
1-Morpholino-2-phenylethane-1,2-dione (3fa) and N-Benzoylmorpholine (4fa) (Tbale 2, run 5). A crude product, which was obtained from 1f (104.2 mg, 0.511 mmol), K2CO3 (141.3 mg, 1.02 mmol), 2a (130.0 µL, 1.49 mmol), and bibenzyl (46.6 mg, 0.256 mmol, internal standard for GC analysis) in DMF (3 mL) at 80 °C for 24 hours, was purified by flash column chromatography on silica gel (hexane/AcOEt = 2/1~1/2) to give 3fa (77.7 mg, 69%) as a colorless solid and 4fa (21.1 mg, 22%) as a yellow oil, respectively. 1H and 13C NMR data of 3fa: 1H NMR (500 MHz, CDCl3) δ 7.97-7.95 (m, 2H), 7.66 (m, 1H), 7.54-7.51 (m, 2H), 3.82-3.78 (m, 4H), 3.65 (t, J = 4.7 Hz, 2H), 3.38 (t, J = 4.7 Hz, 2H); 13C NMR (125 MHz, CDCl3) δ 191.0, 165.2, 134.7, 132.7, 129.4, 128.9, 66.4, 46.0, 41.3. These data were identical to those reported previously.2 1H and 13C NMR data of 4fa: 1H NMR (500 MHz, CDCl3) δ 7.42-7.41 (m, 5H), 4.05-3.20 (br, 8H); 13C NMR (125 MHz, CDCl3) δ 170.4, 135.3, 129.9, 128.6, 127.1, 66.9, 48.2 (br), 42.5 (br). These data were identical to those reported previously.7
1-(4-Chlorophenyl)-2-morpholinoethane-1,2-dione (3ga) and N-(4-Chlorobenzoyl)morpholine (4ga) (Table 2, run 6). A crude product, which was obtained from 1g (120.2 mg, 0.504 mmol), K2CO3 (138.8 mg, 1.00 mmol), 2a (130.0 µL, 1.49 mmol), and bibenzyl (48.0 mg, 0.263 mmol, internal standard for GC analysis), DMF (3 mL) at 80 °C for 24 hours, was purified by flash column chromatography on silica gel (hexane/AcOEt = 2/1~1/2) to give 3ga (82.7 mg, 0.326 mmol, 65%) as a colorless solid and 4ga (30.6 mg, 0.136 mmol, 27%) as a colorless solid, respectively. 1H and
13 G. R. Pettit, M. P. Grealish, D. L. Herald, M. R. Boyd, E. Hamel, R. K. Pettit, J. Med. Chem. 2000, 43, 2731-2737.
~ S8 ~
13C NMR data of 3ga: 1H NMR (500 MHz, CDCl3) δ 7.91-7.88 (m, 2H), 7.50-7.47 (m, 2H), 3.79-3.75 (m, 4H), 3.65-3.63 (m, 2H), 3.38-3.36 (m, 2H); 13C NMR(125 MHz, CDCl3) δ 189.6, 164.8, 141.5, 131.4, 131.0, 129.4, 66.7, 66.6, 46.2, 41.6. These data were identical to those reported previously.2 1H and 13C NMR data of 4ga: 1H NMR (500 MHz, CDCl3) δ 7.41-7.35 (m, 4H), 4.04-3.15 (br, 8H); 13C NMR (125 MHz, CDCl3) δ 169.3, 136.0, 133.6, 128.8, 128.6, 66.8, 48.2 (br), 42.6 (br). These data were identical to those reported previously.14
1-(4-Methoxycarbonylphenyl)-2-morpholinoethane-1,2-dione (3ha) and N-(4-Methoxy- carbonylbenzoyl)morpholine (4ha) (Table 2, run 7). A crude product, which was obtained from 1h (132.5 mg, 0.506 mmol), K2CO3 (140.8 mg, 1.02 mmol), 2a (130.0 µL, 1.49 mmol), and bibenzyl (47.2 mg, 0.259 mmol, internal standard for GC analysis) in DMF (3 mL) at 80 °C for 24 hours, was purified by flash column chromatography on silica gel (hexane/AcOEt = 1/1~1/2) to give 3ha (63.9 mg, 46%) as a yellowish solid and 4ha (53.5 mg, 42%) as a yellow solid, respectively. Spectral data of 3ha: mp 139 °C (recrystallized from CHCl3/hexane); IR (film, CHCl3) 1724, 1685, 1646 cm-1; 1H NMR (500 MHz, CDCl3) δ 8.16 (d, J = 8.6 Hz, 2H), 8.02 (d, J = 8.6 Hz, 2H), 3.95 (s, 3H), 3.79 (brs, 4H), 3.66 (t, J = 4.9 Hz, 2H), 3.38 (t, J = 4.6 Hz, 2H); 13C NMR (125 MHz, CDCl3) δ 190.2, 165.8, 164.8, 136.1, 135.3, 130.1, 129.5, 66.7, 66.6, 52.6, 46.2, 41.7; EI-LRMS m/z 277 (M+), 246, 163, 135; EI-HRMS calcd. for C14H15NO5 277.09502, found 277.09458. 1H and 13C NMR data of 4ha: 1H NMR (500 MHz, CDCl3) δ 8.08 (d, J = 8.0 Hz, 2H), 7.46 (d, J = 8.0 Hz, 2H), 3.92 (s, 3H), 3.88-3.21 (br, 8H); 13C NMR (125 MHz, CDCl3) δ 169.3, 166.2, 139.5, 131.3, 129.9, 127.0, 66.8, 52.3, 48.0, 42.5. These data were identical to those reported previously.15
1-(2,2-Dimethyl-4-oxo-4H-benzo[d][1,3]dioxin-6-yl)-2-morpholinoethane-1,2-dione (3ia) and 2,2-Dimethyl-6-(morpholine-4-carbonyl)-4H-benzo[d][1,3]dioxin-4-one (4ia) (Table 2, run 8). A crude product, which was obtained from 1i (154.4 mg, 0.507 mmol), K2CO3 (142.0 mg, 1.03 mmol), 2a (130.0 µL, 1.49 mmol), and bibenzyl (51.5 mg, 0.283 mmol, internal standard for GC analysis) in DMF (3 mL) at 80 °C for 24 hours, was purified by flash column chromatography on silica gel (hexane/AcOEt = 2/1~1/5) to give 3ia (70.6 mg, 44%) as a colorless solid and 4ia (76.8 mg, 52%) as a colorless solid, respectively. Spectral data of 3ia: mp 127 °C (recrystallized from CHCl3/hexane); IR (film, CHCl3) 1747, 1682, 1644, 1612; 1H NMR (500 MHz, CDCl3) δ 8.52 (d, J = 2.3 Hz, 1H), 8.21 (dd, J = 8.6, 2.3 Hz, 1H), 7.10 (d, J = 8.6 Hz, 1H), 3.82-3.77 (m, 4H), 3.68 (t, J = 4.9 Hz, 2H), 3.41 (t, J = 4.9 Hz, 2H), 1.76 (s, 6H); 13C NMR (125 MHz, CDCl3) δ 188.4, 164.6, 160.6, 159.6, 136.9, 132.8, 128.0, 118.4, 113.4, 107.4, 66.7, 66.6, 46.3, 41.8, 25.9; EI-LRMS m/z 319 (M+), 205; EI-HRMS calcd. for C16H17NO6 319.10559, found 319.10511. Spectral data of 4ia: mp 124 °C (recrystallized from CHCl3/hexane); IR (film, CHCl3) 1743, 1632; 1H NMR (500 MHz, CDCl3) δ 7.98 (s, 1 H), 7.65 (d, J = 8.5 Hz, 1H), 7.12 (d, J = 8.5 Hz, 1H), 3.99-3.22 (br, 8H), 1.72 (s, 6H); 13C NMR (125 MHz, CDCl3) δ 168.5, 160.2, 157.0, 135.7, 129.6, 128.5, 117.8, 113.0, 106.8, 66.7, 48.3 (br), 42.8 (br), 25.7; EI-LRMS m/z 291 (M+), 205; EI-HRMS calcd. for C15H17NO5 291.11067, found 291.11070
1-Morpholino-2-(thiophen-3-yl)ethane-1,2-dione (3ja) and Morpholino(thiophen-3-yl)- methanone (4ja) (Table 2, run 9). A crude product, which was obtained from 1j (104.7 mg, 0.498 mmol), K2CO3 (138.3 mg, 1.00 mmol), 2a (130.0 µL, 1.49 mmol), and bibenzyl (48.6 mg,
14 J. Zhu, Y. Zhang, F. Shi, Y. Deng, Tetrahedron Lett. 2012, 53, 3178-3180. 15 R. Cadoni, A. Porcheddu, G. Giacomelli, L. D. Luca, Org. Lett. 2012, 14, 5014-5017.
~ S9 ~
0.267 mmol, internal standard for GC analysis) in DMF (3 mL) at 80 °C for 24 hours, was purified by flash column chromatography on silica gel (hexane/AcOEt = 2/1~1/2) to give 3ja (94.1 mg, 84%) as a colorless oil and 4ja (16.0 mg, 16%) as a colorless oil, respectively. Spectral data of 3ja: IR (film, CHCl3) 1672, 1642 cm-1; 1H NMR (500 MHz, CDCl3) δ 8.23 (dd, J = 2.9, 1.2 Hz, 1H), 7.57 (dd, J = 5.2, 1.2 Hz, 1H), 7.37 (dd, J = 5.2, 2.9 Hz, 1H), 3.77-3.72 (m, 4H), 3.65 (t, J = 4.9 Hz, 2H), 3.42 (t, J = 4.9 Hz, 2H); 13C NMR (125 MHz, CDCl3) δ 184.3, 165.1, 138.4, 136.7, 127.3, 126.8, 66.7, 66.6, 46.3, 41.7; EI-LRMS m/z 225 (M+), 111; EI-HRMS calcd. for C10H11NO3S 225.04596, found 225.04567. 1H and 13C NMR data of 4ja: 1H NMR (500 MHz, CDCl3) δ 7.52 (dd, J = 3.0, 1.2 Hz, 1H), 7.34 (dd, J = 5.0, 3.0 Hz, 1H), 7.17 (dd, J = 5.0, 1.2 Hz, 1H), 4.00-3.30 (br, 8H); 13C NMR (125 MHz, CDCl3) δ 165.7, 135.9, 126.9, 126.6, 126.1, 66.8, 47.9 (br), 42.6 (br). These data were identical to those reported previously.13
1-(1-Methyl-1H-indol-3-yl)-2-morpholinoethane-1,2-dione (3ka) and (1-Methyl-1H-indol-3-yl) (morpholino)methanone (4ka) (Table 2, run 10). A crude product, which was obtained from 1k (129.9 mg, 0.505 mmol), K2CO3 (141.8 mg, 1.03 mmol), 2a (130.0 µL, 1.49 mmol), and bibenzyl (50.4 mg, 0.277 mmol, internal standard for GC analysis) in DMF (3 mL) at 80 °C for 24 hours, was purified by flash column chromatography on silica gel (hexane/AcOEt = 4/1~1/2) to give 3ka (129.7 mg, 94%) and colorless solid 4ka (6.8 mg, 6%) as a yellowish solid. Spectral data of 3ka: mp 157 °C (recrystallized from CHCl3/hexane); IR (film, CHCl3) 1662, 1642, 1607 cm-1; 1H NMR (500 MHz, CDCl3) δ 8.21 (d, J = 1.2 Hz, 1H), 7.82 (dd, J = 8.6, 1.2 Hz, 1H), 7.34 (d, J = 8.6 Hz, 1H), 7.12 (d, J = 2.9 Hz, 1H), 6.58 (d, J = 2.9 Hz, 1H), 3.78 (s, 3H), 3.78 (s, 3H), 3.60 (t, J = 4.9 Hz, 2H), 3.36 (t, J = 4.9 Hz, 2H); 13C NMR (125 MHz, CDCl3) δ 191.5, 166.4, 139.9, 131.0, 128.0, 125.3, 124.8, 122.1, 109.8, 103.3, 66.6, 66.5, 46.2, 41.3, 32.9; EI-LRMS m/z 272 (M+), 158; EI-HRMS calcd. for C15H16N2O3 272.11609, found 272.11587. Spectral data of 4ka: mp 132 °C (recrystallized from CHCl3/hexane); IR (film, CHCl3) 1621 cm-1; 1H NMR (500 MHz, CDCl3) δ 7.70 (s, 1H), 7.32-7.27 (m, 2H), 7.08 (d, J = 3.2 Hz, 1H), 6.50 (d, J = 3.2 Hz, 1H), 3.76 (s, 3H), 3.79-3.55 (br, 8H); 13C NMR δ 171.7, 137.1, 129.9, 127.7, 126.0, 120.9, 120.4, 109.0, 101.5, 66.8, 48.2, 43.0 (br), 32.8 (br); EI-LRMS m/z 244 (M+), 158; EI-HRMS calcd. for C14H16N2O2 244.12118, found 244.12010.
1-Morpholino-2-(quinolin-6-yl)ethane-1,2-dione (3la) and Morpholino(quinolin-6-yl) methanone (4la) (Table 2, run 11). A crude product, which was obtained from 1l (128.4 mg, 0.503 mmol), K2CO3 (138.9 mg, 1.01 mmol), 2a (130.0 µL, 1.49 mmol), and bibenzyl (48.8 mg, 0.268 mmol, internal standard for GC analysis) in DMF at 80 °C for 24 hours, was purified by flash column chromatography on silica gel (hexane/AcOEt = 4/1~1/2) to give 3la (108.9 mg, 0.403 mmol, 80%) as a colorless solid and 4la (20.3 mg, 0.167 mmol, 17%) as a colorless solid, respectively. Spectral data of 3la: mp 127 °C (recrystallized from CHCl3/hexane); IR (film, CHCl3) 1680, 1645 cm-1; 1H NMR (500 MHz, CDCl3) δ 9.18 (dd, J = 4.2, 1.4 Hz, 1H), 8.45 (d, J = 1.7 Hz, 1H), 8.27 (dd, J = 8.2, 1.4 Hz, 1H), 8.23 (dd, J = 8.6, 1.7 Hz, 1H), 8.17 (d, J = 8.6 Hz, 1H), 7.49 (dd, J = 8.2, 4.2 Hz, 1H), 3.81 (s, 4H), 3.65 (t, J = 4.9 Hz, 2H), 3.41 (t, J = 4.9 Hz, 2H); 13C NMR (125 MHz, CDCl3) δ 190.3, 165.0, 153.4, 150.7, 137.7, 132.6, 130.7 (2C), 127.4 (2C), 122.3, 66.7, 66.6, 46.3, 41.7; EI-LRMS m/z 270 (M+), 156; EI-HRMS calcd. for C15H14N2O3 270.10044, found 270.10024. Spectral data of 4la: mp 121 °C (recrystallized from CHCl3/hexane); IR (film, CHCl3) 1633 cm-1; 1H NMR (500 MHz, CDCl3) δ 8.99 (brs, 1H), 8.21 (d, J = 8.0 Hz, 1H), 8.16 (d, J = 8.6 Hz, 1H), 7.93 (s, 1H), 7.73 (dd, J = 8.6, 1.7 Hz, 1H), 7.48 (m, 1H), 4.00-3.34 (br, 8H); 13C NMR (125 MHz, CDCl3) δ 169.7, 151.6, 148.4, 136.5, 133.4, 130.1 (2C), 127.8, 127.1, 122.0, 66.9, 48.3 (br), 42.7 (br); ESI-LRMS m/z 265.09 ([M+Na]+); ESI-HRMS calcd. for C14H14O2N2Na 265.09475, found 265.09476.
~ S10 ~
1-(4-Benzoylpiperazin-1-yl)-2-(naphthalen-2-yl)ethane-1,2-dione (3ml) and [4-(2-Naphthoyl) piperazin-1-yl](phenyl)methanone (4ml) (Scheme 3). A crude product, which was obtained from 1m (131.7 mg, 0.518 mmol), K2CO3 (138.2 mg, 1.00 mmol), 2l (285.6 mg, 1.50 mmol), and bibenzyl (48.7 mg, 0.267 mmol, internal standard for GC analysis) in DMF (3 mL) at 80 °C for 24 hours, was purified by flash column chromatography on silica gel (hexane/AcOEt = 4/1~2/1) to give 3ml (159.7 mg, 83%) as a colorless solid and 4ml (27.3 mg, 15%) as a colorless slid, respectively. Spectral data of 3ml: mp 144 °C (recrystallized from CHCl3/hexane); IR (film, CHCl3) 1673, 1638 cm-1; 1H NMR (500 MHz, CDCl3) δ 8.45 (s, 1H), 7.99-7.87 (m, 4H), 7.64 (m, 1H) 7.57 (m, 1H), 7.40 (s, 5H), 4.20-3.03 (br, 8H); 13C NMR (125 MHz, CDCl3) δ 191.0, 170.6, 165.6, 136.4, 134.8, 133.1, 132.3, 130.2, 129.8, 129.6, 129.2, 128.6, 127.9, 127.2, 126.9, 123.4, 47.2 (br), 45.9 (br), 42.0 (br), 41.4 (br); EI-LRMS m/z 372 (M+), 189, 155; EI-HRMS calcd. for C23H20N2O3 372.14739, found 372.14628. Spectral data of 4mk: mp 184 °C (recrystallized from CHCl3/hexane); IR (film, CHCl3) 1629 cm-1; 1H NMR (500 MHz, CDCl3) δ 7.92-7.87 (m, 4H), 7.55-7.42 (m, 8H), 4.20-3.14 (br, 8H); 13C NMR (125 MHz, CDCl3) δ 170.6, 135.1, 133.7, 132.6, 132.3, 130.1, 128.6, 128.5, 128.4, 127.8, 127.3, 127.2, 127.1, 127.0, 126.8, 124.0, 47.7 (br), 42.5 (br); EI-LRMS m/z 344 (M+), 189, 155; EI-HRMS calcd. for C22H20N2O2 344.15248, found 344.15248. Large-scale reactions. For the reaction of 1a and 2a (Scheme 4, Eq 1). A mixture of 1a (2.34 g, 10.0 mmol), K2CO3 (2.78 g, 20.1 mmol), 2a (2.6 mL, 30.1 mmol) and 2 sheets of SAPd in DMF (10 mL) was stirred at 80 °C for 24 hours. After the usual work-up, the crude product was purified by flash column chromatography on silica gel (hexane/AcOEt = 2/1~1/1) to give 3aa (2.13 g, 85%) and 4aa (105.2 mg, 5%), respectively
For the reaction of 1m and 2l (Scheme 4, Eq 2). A mixture of 1m (2.54 g, 10.0 mmol), K2CO3 (2.77 g, 20.0 mmol), 2l (5.71 g, 30.0 mmol) and 2 sheets of SAPd in DMF (10 mL) was stirred at 80 °C for 24 hours. After the usual work-up, the crude product was purified by flash column chromatography on silica gel (hexane/AcOEt = 1/1~1/2) to give 3ml (3.06 g, 82%) and 4mk (569.4 mg, 17%), respectively
~ S11 ~
Examination of reusability of SAPd (Table 3)
After the solution of 1a in DMF in the presence of K2CO3 and SAPd was heated at 80 °C for 2 hours, SAPd was removed and reused to the next reaction without purification. The yields shown in Table 3 were calculated by GC analysis using bibenzyl as an internal standard.
Run 1 cycle 1
cycle 2
cycle 3
cycle 4
cycle 5
1a (mg) 117.3 117.0 118.3 117.5 117.3 2a (µL) 130.0 130.0 130.0 130.0 130.0 bibenzyl (mg) 47.8 47.8 47.9 49.5 48.8 K2CO3 (mg) 139.0 138.0 139.5 138.3 138.2
yields (%) 3aa 88 90 90 90 89 4aa 7 7 8 8 6
Run 2 cycle 1
cycle 2
cycle 3
cycle 4
cycle 5
1a (mg) 117.8 117.5 116.7 117.2 117.1 2a (µL) 130.0 130.0 130.0 130.0 130.0 bibenzyl (mg) 47.0 46.7 50.6 47.9 48.7 K2CO3 (mg) 138.4 138.3 139.1 138.3 138.2
yields (%) 3aa 89 90 91 93 91 4aa 7 8 7 7 7
Run 3 cycle 1
cycle 2
cycle 3
cycle 4
cycle 5
1a (mg) 117.5 117.8 117.5 117.5 117.7 2a (µL) 130.0 130.0 130.0 130.0 130.0 bibenzyl (mg) 45.7 51.2 48.3 49.1 50.3 K2CO3 (mg) 139.1 138.7 138.5 138.4 138.7
yields (%) 3aa 84 84 92 90 89 4aa 6 8 6 8 7
~ S12 ~
Data of ICP-MS analysis
Amount of palladium in the reaction mixture of 1a and 2aa), and in SAPd
Amount of leached Pd (µg) in the reaction mixtureb) Immobilized Pd on SAPd (µg)
cycle 1 cycle 2 cycle 3 cycle 4 cycle 5 after use
before use
leached Pd (µg) (mol%)c)
run 1 10 (0.019)
11 (0.021)
22 (0.041)
15 (0.028)
5 (0.009) 87 408
run 2 62 (0.116)
63 (0.118)
35 (0.066)
46 (0.086)
28 (0.053) 40 338
run 3 96 (0.180)
78 (0.146)
29 (0.054)
28 (0.052)
36 (0.067) 136 329
average (µg) 56 50 28 30 23 88 358
standard deviationc) 43 35 7 16 16 48 43
a) Reaction conditions: 1a (0.5 mmol), 2a (3 equiv), K2CO3 (2 equive), bibenzyl (0.5 equiv, internal standard) DMF (3 mL), 80 °C, 24 hours b) The reaction mixture was acidified and subjected directly to ICP-MS. c) Value in parentheses indicats the loading of Pd catalyst (mol%). d) The standard deviation was calculated from three sets of samples.
~ S13 ~
PPM
PPM
PPM
PPM
10.00
10.00
10.00
10.009.50
9.50
9.50
9.509.00
9.00
9.00
9.008.50
8.50
8.50
8.508.00
8.00
8.00
8.007.50
7.50
7.50
7.507.00
7.00
7.00
7.006.50
6.50
6.50
6.506.00
6.00
6.00
6.005.50
5.50
5.50
5.505.00
5.00
5.00
5.004.50
4.50
4.50
4.504.00
4.00
4.00
4.003.50
3.50
3.50
3.503.00
3.00
3.00
3.002.50
2.50
2.50
2.502.00
2.00
2.00
2.001.50
1.50
1.50
1.501.00
1.00
1.00
1.000.50
0.50
0.50
0.500.00
0.00
0.00
0.00
2.00 2.00 2.00 2.00
2.06 2.06 2.06 2.06
3.15 3.15 3.15 3.154.12 4.12 4.12 4.12
2.07 2.07 2.07 2.07
2.04 2.04 2.04 2.04
7.938 7.938 7.938 7.9387.921 7.921 7.921 7.921
7.260 7.260 7.260 7.260
6.991 6.991 6.991 6.9916.974 6.974 6.974 6.974
3.893 3.893 3.893 3.8933.799 3.799 3.799 3.7993.784 3.784 3.784 3.7843.781 3.781 3.781 3.7813.767 3.767 3.767 3.7673.657 3.657 3.657 3.6573.648 3.648 3.648 3.6483.638 3.638 3.638 3.6383.389 3.389 3.389 3.3893.379 3.379 3.379 3.3793.370 3.370 3.370 3.370
MeO
ON
O
O
3aa
CD
Cl 3
, 500
MH
z
~ S14 ~
PPM
PPM
PPM
PPM
200
200
200
200
190
190
190
190
180
180
180
180
170
170
170
170
160
160
160
160
150
150
150
150
140
140
140
140
130
130
130
130
120
120
120
120
110
110
110
110
100
100
100
100
90
9090
90
80
8080
80
70
7070
70
60
6060
60
50
5050
50
40
4040
40
30
3030
30
20
2020
20
10
1010
10
0 000
189.800 189.800 189.800 189.800
165.773 165.773 165.773 165.773165.001 165.001 165.001 165.001
132.141 132.141 132.141 132.141
126.113 126.113 126.113 126.113
114.390 114.390 114.390 114.390
77.258 77.258 77.258 77.258 77.000 77.000 77.000 77.000 76.742 76.742 76.742 76.742
66.765 66.765 66.765 66.765 66.670 66.670 66.670 66.670
55.653 55.653 55.653 55.653
46.277 46.277 46.277 46.277
41.527 41.527 41.527 41.527
MeO
O
N
O
O
3aa
CD
Cl 3
, 125
MH
z
~ S15 ~
PPM
PPM
PPM
PPM
10.00
10.00
10.00
10.009.50
9.50
9.50
9.509.00
9.00
9.00
9.008.50
8.50
8.50
8.508.00
8.00
8.00
8.007.50
7.50
7.50
7.507.00
7.00
7.00
7.006.50
6.50
6.50
6.506.00
6.00
6.00
6.005.50
5.50
5.50
5.505.00
5.00
5.00
5.004.50
4.50
4.50
4.504.00
4.00
4.00
4.003.50
3.50
3.50
3.503.00
3.00
3.00
3.002.50
2.50
2.50
2.502.00
2.00
2.00
2.001.50
1.50
1.50
1.501.00
1.00
1.00
1.000.50
0.50
0.50
0.500.00
0.00
0.00
0.00
2.00 2.00 2.00 2.00
2.02 2.02 2.02 2.02
11.36 11.36 11.36 11.36
7.384 7.384 7.384 7.3847.378 7.378 7.378 7.3787.373 7.373 7.373 7.3737.364 7.364 7.364 7.3647.361 7.361 7.361 7.3617.260 7.260 7.260 7.2606.912 6.912 6.912 6.9126.907 6.907 6.907 6.9076.903 6.903 6.903 6.9036.894 6.894 6.894 6.8946.889 6.889 6.889 6.889
3.812 3.812 3.812 3.8123.676 3.676 3.676 3.676
MeO
O
N
O
4aa
CD
Cl 3
, 50
0 M
Hz
~ S16 ~
PPM
PPM
PPM
PPM
200
200
200
200
190
190
190
190
180
180
180
180
170
170
170
170
160
160
160
160
150
150
150
150
140
140
140
140
130
130
130
130
120
120
120
120
110
110
110
110
100
100
100
100
90
9090
90
80
8080
80
70
7070
70
60
6060
60
50
5050
50
40
4040
40
30
3030
30
20
2020
20
10
1010
10
0 000
170.371 170.371 170.371 170.371
160.842 160.842 160.842 160.842
129.156 129.156 129.156 129.156127.267 127.267 127.267 127.267
113.732 113.732 113.732 113.732
77.258 77.258 77.258 77.258 77.000 77.000 77.000 77.000 76.742 76.742 76.742 76.742
66.870 66.870 66.870 66.870
55.319 55.319 55.319 55.319
48.223 48.223 48.223 48.223
43.005 43.005 43.005 43.005
MeO
O
N
O
4aa
CD
Cl 3
, 12
5 M
Hz
~ S17 ~
PPM
PPM
PPM
PPM
10.00
10.00
10.00
10.009.50
9.50
9.50
9.509.00
9.00
9.00
9.008.50
8.50
8.50
8.508.00
8.00
8.00
8.007.50
7.50
7.50
7.507.00
7.00
7.00
7.006.50
6.50
6.50
6.506.00
6.00
6.00
6.005.50
5.50
5.50
5.505.00
5.00
5.00
5.004.50
4.50
4.50
4.504.00
4.00
4.00
4.003.50
3.50
3.50
3.503.00
3.00
3.00
3.002.50
2.50
2.50
2.502.00
2.00
2.00
2.001.50
1.50
1.50
1.501.00
1.00
1.00
1.000.50
0.50
0.50
0.500.00
0.00
0.00
0.00-0.50
-0.50
-0.50
-0.50
2.00 2.00 2.00 2.00
2.09 2.09 2.09 2.09
3.15 3.15 3.15 3.15
2.09 2.09 2.09 2.09
2.08 2.08 2.08 2.08
4.16 4.16 4.16 4.16
7.926 7.926 7.926 7.9267.921 7.921 7.921 7.9217.917 7.917 7.917 7.9177.907 7.907 7.907 7.9077.904 7.904 7.904 7.9047.898 7.898 7.898 7.8987.260 7.260 7.260 7.2606.934 6.934 6.934 6.9346.928 6.928 6.928 6.9286.924 6.924 6.924 6.9246.914 6.914 6.914 6.9146.910 6.910 6.910 6.9106.905 6.905 6.905 6.905
3.831 3.831 3.831 3.8313.601 3.601 3.601 3.6013.587 3.587 3.587 3.5873.574 3.574 3.574 3.5743.376 3.376 3.376 3.3763.363 3.363 3.363 3.3633.349 3.349 3.349 3.349
1.930 1.930 1.930 1.9301.918 1.918 1.918 1.9181.904 1.904 1.904 1.9041.898 1.898 1.898 1.8981.894 1.894 1.894 1.8941.889 1.889 1.889 1.8891.884 1.884 1.884 1.8841.880 1.880 1.880 1.8801.866 1.866 1.866 1.8661.854 1.854 1.854 1.854
MeO
O
N
O
3ab
CD
Cl 3
, 500
MH
z
~ S18 ~
PPM
PPM
PPM
PPM
200
200
200
200
190
190
190
190
180
180
180
180
170
170
170
170
160
160
160
160
150
150
150
150
140
140
140
140
130
130
130
130
120
120
120
120
110
110
110
110
100
100
100
100
90
9090
90
80
8080
80
70
7070
70
60
6060
60
50
5050
50
40
4040
40
30
3030
30
20
2020
20
10
1010
10
0 000
190.191 190.191 190.191 190.191
165.172 165.172 165.172 165.172164.610 164.610 164.610 164.610
132.170 132.170 132.170 132.170
125.769 125.769 125.769 125.769
114.104 114.104 114.104 114.104
77.258 77.258 77.258 77.258 77.000 77.000 77.000 77.000 76.742 76.742 76.742 76.742
55.491 55.491 55.491 55.491
46.535 46.535 46.535 46.535 45.018 45.018 45.018 45.018
25.751 25.751 25.751 25.751 23.881 23.881 23.881 23.881
MeO
O
N
O
3ab
CD
Cl 3
, 125
MH
z
~ S19 ~
PPM
PPM
PPM
PPM
10.00
10.00
10.00
10.009.50
9.50
9.50
9.509.00
9.00
9.00
9.008.50
8.50
8.50
8.508.00
8.00
8.00
8.007.50
7.50
7.50
7.507.00
7.00
7.00
7.006.50
6.50
6.50
6.506.00
6.00
6.00
6.005.50
5.50
5.50
5.505.00
5.00
5.00
5.004.50
4.50
4.50
4.504.00
4.00
4.00
4.003.50
3.50
3.50
3.503.00
3.00
3.00
3.002.50
2.50
2.50
2.502.00
2.00
2.00
2.001.50
1.50
1.50
1.501.00
1.00
1.00
1.000.50
0.50
0.50
0.500.00
0.00
0.00
0.00-0.50
-0.50
-0.50
-0.50
2.00 2.00 2.00 2.00
1.98 1.98 1.98 1.98
3.18 3.18 3.18 3.18
4.49 4.49 4.49 4.49
4.21 4.21 4.21 4.21
7.521 7.521 7.521 7.5217.504 7.504 7.504 7.5047.260 7.260 7.260 7.260
6.902 6.902 6.902 6.9026.884 6.884 6.884 6.884
3.828 3.828 3.828 3.8283.643 3.643 3.643 3.6433.630 3.630 3.630 3.6303.616 3.616 3.616 3.6163.487 3.487 3.487 3.4873.474 3.474 3.474 3.4743.461 3.461 3.461 3.461
1.975 1.975 1.975 1.9751.961 1.961 1.961 1.9611.947 1.947 1.947 1.9471.935 1.935 1.935 1.9351.921 1.921 1.921 1.9211.888 1.888 1.888 1.8881.876 1.876 1.876 1.8761.863 1.863 1.863 1.8631.850 1.850 1.850 1.850
MeO
O
N
4ab
CD
Cl 3
, 500
MH
z
~ S20 ~
PPM
PPM
PPM
PPM
200
200
200
200
190
190
190
190
180
180
180
180
170
170
170
170
160
160
160
160
150
150
150
150
140
140
140
140
130
130
130
130
120
120
120
120
110
110
110
110
100
100
100
100
90
9090
90
80
8080
80
70
7070
70
60
6060
60
50
5050
50
40
4040
40
30
3030
30
20
2020
20
10
1010
10
0 000
169.417 169.417 169.417 169.417
160.737 160.737 160.737 160.737
129.404 129.404 129.404 129.404129.127 129.127 129.127 129.127
113.370 113.370 113.370 113.370
77.248 77.248 77.248 77.248 77.000 77.000 77.000 77.000 76.742 76.742 76.742 76.742
55.300 55.300 55.300 55.300
49.778 49.778 49.778 49.778 46.306 46.306 46.306 46.306
26.485 26.485 26.485 26.485 24.434 24.434 24.434 24.434
MeO
O
N
4ab
CD
Cl 3
, 125
MH
z
~ S21 ~
PPM
PPM
PPM
PPM
10.00
10.00
10.00
10.009.50
9.50
9.50
9.509.00
9.00
9.00
9.008.50
8.50
8.50
8.508.00
8.00
8.00
8.007.50
7.50
7.50
7.507.00
7.00
7.00
7.006.50
6.50
6.50
6.506.00
6.00
6.00
6.005.50
5.50
5.50
5.505.00
5.00
5.00
5.004.50
4.50
4.50
4.504.00
4.00
4.00
4.003.50
3.50
3.50
3.503.00
3.00
3.00
3.002.50
2.50
2.50
2.502.00
2.00
2.00
2.001.50
1.50
1.50
1.501.00
1.00
1.00
1.000.50
0.50
0.50
0.500.00
0.00
0.00
0.00-0.50
-0.50
-0.50
-0.50
2.00 2.00 2.00 2.00
2.05 2.05 2.05 2.05
3.15 3.15 3.15 3.152.10 2.10 2.10 2.10
2.08 2.08 2.08 2.08
4.10 4.10 4.10 4.10
2.06 2.06 2.06 2.06
7.891 7.891 7.891 7.8917.885 7.885 7.885 7.8857.882 7.882 7.882 7.8827.872 7.872 7.872 7.8727.868 7.868 7.868 7.8687.862 7.862 7.862 7.8627.260 7.260 7.260 7.2606.955 6.955 6.955 6.9556.950 6.950 6.950 6.9506.945 6.945 6.945 6.9456.936 6.936 6.936 6.9366.931 6.931 6.931 6.9316.926 6.926 6.926 6.926
3.848 3.848 3.848 3.8483.665 3.665 3.665 3.6653.654 3.654 3.654 3.6543.644 3.644 3.644 3.6443.260 3.260 3.260 3.2603.248 3.248 3.248 3.2483.238 3.238 3.238 3.238
1.655 1.655 1.655 1.6551.649 1.649 1.649 1.6491.644 1.644 1.644 1.6441.511 1.511 1.511 1.5111.499 1.499 1.499 1.4991.491 1.491 1.491 1.491
MeO
O
N
O
3ac
CD
Cl 3
, 500
MH
z
~ S22 ~
PPM
PPM
PPM
PPM
200
200
200
200
190
190
190
190
180
180
180
180
170
170
170
170
160
160
160
160
150
150
150
150
140
140
140
140
130
130
130
130
120
120
120
120
110
110
110
110
100
100
100
100
90
9090
90
80
8080
80
70
7070
70
60
6060
60
50
5050
50
40
4040
40
30
3030
30
20
2020
20
10
1010
10
0 000
190.592 190.592 190.592 190.592
165.659 165.659 165.659 165.659164.657 164.657 164.657 164.657
131.864 131.864 131.864 131.864
126.189 126.189 126.189 126.189
114.190 114.190 114.190 114.190
77.248 77.248 77.248 77.248 77.000 77.000 77.000 77.000 76.742 76.742 76.742 76.742
55.520 55.520 55.520 55.520
46.926 46.926 46.926 46.926
41.928 41.928 41.928 41.928
26.104 26.104 26.104 26.104 25.340 25.340 25.340 25.340 24.263 24.263 24.263 24.263
MeO
O
N
O
3ac
CD
Cl 3
, 125
MH
z
~ S23 ~
PPM
PPM
PPM
PPM
10.00
10.00
10.00
10.009.50
9.50
9.50
9.509.00
9.00
9.00
9.008.50
8.50
8.50
8.508.00
8.00
8.00
8.007.50
7.50
7.50
7.507.00
7.00
7.00
7.006.50
6.50
6.50
6.506.00
6.00
6.00
6.005.50
5.50
5.50
5.505.00
5.00
5.00
5.004.50
4.50
4.50
4.504.00
4.00
4.00
4.003.50
3.50
3.50
3.503.00
3.00
3.00
3.002.50
2.50
2.50
2.502.00
2.00
2.00
2.001.50
1.50
1.50
1.501.00
1.00
1.00
1.000.50
0.50
0.50
0.500.00
0.00
0.00
0.00-0.50
-0.50
-0.50
-0.50
2.00 2.00 2.00 2.00
2.02 2.02 2.02 2.02
7.32 7.32 7.32 7.32
6.30 6.30 6.30 6.30
7.369 7.369 7.369 7.3697.352 7.352 7.352 7.3527.260 7.260 7.260 7.260
6.902 6.902 6.902 6.9026.884 6.884 6.884 6.884
3.820 3.820 3.820 3.8203.656 3.656 3.656 3.656
3.408 3.408 3.408 3.408
1.665 1.665 1.665 1.6651.590 1.590 1.590 1.590
MeO
O
N
4ac
CD
Cl 3
, 500
MH
z
~ S24 ~
PPM
PPM
PPM
PPM
200
200
200
200
190
190
190
190
180
180
180
180
170
170
170
170
160
160
160
160
150
150
150
150
140
140
140
140
130
130
130
130
120
120
120
120
110
110
110
110
100
100
100
100
90
9090
90
80
8080
80
70
7070
70
60
6060
60
50
5050
50
40
4040
40
30
3030
30
20
2020
20
10
1010
10
0 000
170.275 170.275 170.275 170.275
160.451 160.451 160.451 160.451
128.812 128.812 128.812 128.812128.555 128.555 128.555 128.555
113.579 113.579 113.579 113.579
77.248 77.248 77.248 77.248 77.000 77.000 77.000 77.000 76.742 76.742 76.742 76.742
55.291 55.291 55.291 55.291
48.995 48.995 48.995 48.995
43.368 43.368 43.368 43.368
26.361 26.361 26.361 26.361 25.674 25.674 25.674 25.674 24.616 24.616 24.616 24.616
MeO
O
N
4ac
CD
Cl 3
, 125
MH
z
~ S25 ~
PPM
PPM
PPM
PPM
10.00
10.00
10.00
10.009.50
9.50
9.50
9.509.00
9.00
9.00
9.008.50
8.50
8.50
8.508.00
8.00
8.00
8.007.50
7.50
7.50
7.507.00
7.00
7.00
7.006.50
6.50
6.50
6.506.00
6.00
6.00
6.005.50
5.50
5.50
5.505.00
5.00
5.00
5.004.50
4.50
4.50
4.504.00
4.00
4.00
4.003.50
3.50
3.50
3.503.00
3.00
3.00
3.002.50
2.50
2.50
2.502.00
2.00
2.00
2.001.50
1.50
1.50
1.501.00
1.00
1.00
1.000.50
0.50
0.50
0.500.00
0.00
0.00
0.00-0.50
-0.50
-0.50
-0.50
2.00 2.00 2.00 2.00
2.02 2.02 2.02 2.02
5.63 5.63 5.63 5.63
1.98 1.98 1.98 1.98
2.01 2.01 2.01 2.012.08 2.08 2.08 2.08
3.11 3.11 3.11 3.11
7.878 7.878 7.878 7.8787.873 7.873 7.873 7.8737.868 7.868 7.868 7.8687.859 7.859 7.859 7.8597.854 7.854 7.854 7.8547.849 7.849 7.849 7.8497.260 7.260 7.260 7.2606.954 6.954 6.954 6.9546.950 6.950 6.950 6.9506.945 6.945 6.945 6.9456.935 6.935 6.935 6.9356.931 6.931 6.931 6.9316.926 6.926 6.926 6.926
3.846 3.846 3.846 3.8463.829 3.829 3.829 3.8293.817 3.817 3.817 3.8173.436 3.436 3.436 3.4363.427 3.427 3.427 3.4273.417 3.417 3.417 3.417
2.648 2.648 2.648 2.6482.638 2.638 2.638 2.6382.628 2.628 2.628 2.6282.526 2.526 2.526 2.5262.515 2.515 2.515 2.5152.505 2.505 2.505 2.5052.377 2.377 2.377 2.377
MeO
ON
O
N
3ad
CD
Cl 3
, 500
MH
z
Me
~ S26 ~
PPM
PPM
PPM
PPM
200
200
200
200
190
190
190
190
180
180
180
180
170
170
170
170
160
160
160
160
150
150
150
150
140
140
140
140
130
130
130
130
120
120
120
120
110
110
110
110
100
100
100
100
90
9090
90
80
8080
80
70
7070
70
60
6060
60
50
5050
50
40
4040
40
30
3030
30
20
2020
20
10
1010
10
0 000
189.838 189.838 189.838 189.838
165.592 165.592 165.592 165.592164.934 164.934 164.934 164.934
132.046 132.046 132.046 132.046
125.827 125.827 125.827 125.827
114.333 114.333 114.333 114.333
77.248 77.248 77.248 77.248 77.000 77.000 77.000 77.000 76.742 76.742 76.742 76.742
55.577 55.577 55.577 55.577 54.423 54.423 54.423 54.423 54.013 54.013 54.013 54.013
45.371 45.371 45.371 45.371 45.008 45.008 45.008 45.008 40.325 40.325 40.325 40.325
MeO
ON
O
N
3ad
CD
Cl 3
, 125
MH
z
Me
~ S27 ~
PPM
PPM
PPM
PPM
10.00
10.00
10.00
10.009.50
9.50
9.50
9.509.00
9.00
9.00
9.008.50
8.50
8.50
8.508.00
8.00
8.00
8.007.50
7.50
7.50
7.507.00
7.00
7.00
7.006.50
6.50
6.50
6.506.00
6.00
6.00
6.005.50
5.50
5.50
5.505.00
5.00
5.00
5.004.50
4.50
4.50
4.504.00
4.00
4.00
4.003.50
3.50
3.50
3.503.00
3.00
3.00
3.002.50
2.50
2.50
2.502.00
2.00
2.00
2.001.50
1.50
1.50
1.501.00
1.00
1.00
1.000.50
0.50
0.50
0.500.00
0.00
0.00
0.00-0.50
-0.50
-0.50
-0.50
2.00 2.00 2.00 2.00
2.03 2.03 2.03 2.03
7.00 7.00 7.00 7.00
7.16 7.16 7.16 7.16
7.388 7.388 7.388 7.3887.371 7.371 7.371 7.3717.260 7.260 7.260 7.260
6.915 6.915 6.915 6.9156.898 6.898 6.898 6.898
3.831 3.831 3.831 3.831
3.633 3.633 3.633 3.633
2.412 2.412 2.412 2.4122.319 2.319 2.319 2.319
MeO
O
N
N
4ad
CD
Cl 3
, 500
MH
z
Me
~ S28 ~
PPM
PPM
PPM
PPM
200
200
200
200
190
190
190
190
180
180
180
180
170
170
170
170
160
160
160
160
150
150
150
150
140
140
140
140
130
130
130
130
120
120
120
120
110
110
110
110
100
100
100
100
90
9090
90
80
8080
80
70
7070
70
60
6060
60
50
5050
50
40
4040
40
30
3030
30
20
2020
20
10
1010
10
0 000
170.313 170.313 170.313 170.313
160.899 160.899 160.899 160.899
129.146 129.146 129.146 129.146128.173 128.173 128.173 128.173
113.808 113.808 113.808 113.808
77.258 77.258 77.258 77.258 77.000 77.000 77.000 77.000 76.742 76.742 76.742 76.742
55.367 55.367 55.367 55.367 55.348 55.348 55.348 55.348 55.148 55.148 55.148 55.148
46.020 46.020 46.020 46.020
MeO
O
N
N
4ad
CD
Cl 3
, 125
MH
z
Me
~ S29 ~
PPM
PPM
PPM
PPM
10.00
10.00
10.00
10.009.50
9.50
9.50
9.509.00
9.00
9.00
9.008.50
8.50
8.50
8.508.00
8.00
8.00
8.007.50
7.50
7.50
7.507.00
7.00
7.00
7.006.50
6.50
6.50
6.506.00
6.00
6.00
6.005.50
5.50
5.50
5.505.00
5.00
5.00
5.004.50
4.50
4.50
4.504.00
4.00
4.00
4.003.50
3.50
3.50
3.503.00
3.00
3.00
3.002.50
2.50
2.50
2.502.00
2.00
2.00
2.001.50
1.50
1.50
1.501.00
1.00
1.00
1.000.50
0.50
0.50
0.500.00
0.00
0.00
0.00-0.50
-0.50
-0.50
-0.50
2.00 2.00 2.00 2.00
2.07 2.07 2.07 2.07
4.21 4.21 4.21 4.21 3.15 3.15 3.15 3.152.05 2.05 2.05 2.05
2.07 2.07 2.07 2.07
2.24 2.24 2.24 2.242.07 2.07 2.07 2.07
7.897 7.897 7.897 7.8977.878 7.878 7.878 7.878
7.260 7.260 7.260 7.260
6.962 6.962 6.962 6.9626.944 6.944 6.944 6.944
3.990 3.990 3.990 3.9903.986 3.986 3.986 3.9863.977 3.977 3.977 3.9773.973 3.973 3.973 3.9733.969 3.969 3.969 3.9693.965 3.965 3.965 3.9653.962 3.962 3.962 3.9623.950 3.950 3.950 3.9503.948 3.948 3.948 3.9483.943 3.943 3.943 3.9433.940 3.940 3.940 3.9403.937 3.937 3.937 3.9373.927 3.927 3.927 3.9273.923 3.923 3.923 3.9233.864 3.864 3.864 3.8643.828 3.828 3.828 3.8283.816 3.816 3.816 3.8163.805 3.805 3.805 3.8053.410 3.410 3.410 3.4103.398 3.398 3.398 3.3983.387 3.387 3.387 3.387
1.803 1.803 1.803 1.8031.791 1.791 1.791 1.7911.780 1.780 1.780 1.7801.670 1.670 1.670 1.6701.659 1.659 1.659 1.6591.647 1.647 1.647 1.647
MeO
O
N
O
3ae
CD
Cl 3
, 500
MH
z
O
O
~ S30 ~
PPM
PPM
PPM
PPM
200
200
200
200
190
190
190
190
180
180
180
180
170
170
170
170
160
160
160
160
150
150
150
150
140
140
140
140
130
130
130
130
120
120
120
120
110
110
110
110
100
100
100
100
90
9090
90
80
8080
80
70
7070
70
60
6060
60
50
5050
50
40
4040
40
30
3030
30
20
2020
20
10
1010
10
0 000
190.268 190.268 190.268 190.268
165.735 165.735 165.735 165.735164.829 164.829 164.829 164.829
131.960 131.960 131.960 131.960
126.122 126.122 126.122 126.122
114.304 114.304 114.304 114.304
106.626 106.626 106.626 106.626
77.258 77.258 77.258 77.258 77.000 77.000 77.000 77.000 76.742 76.742 76.742 76.742
64.486 64.486 64.486 64.486
55.586 55.586 55.586 55.586
43.988 43.988 43.988 43.988
39.228 39.228 39.228 39.228 35.289 35.289 35.289 35.289 34.640 34.640 34.640 34.640
MeO
O
N
O
3ae
CD
Cl 3
, 125
MH
z
O
O
~ S31 ~
PPM
PPM
PPM
PPM
10.00
10.00
10.00
10.009.50
9.50
9.50
9.509.00
9.00
9.00
9.008.50
8.50
8.50
8.508.00
8.00
8.00
8.007.50
7.50
7.50
7.507.00
7.00
7.00
7.006.50
6.50
6.50
6.506.00
6.00
6.00
6.005.50
5.50
5.50
5.505.00
5.00
5.00
5.004.50
4.50
4.50
4.504.00
4.00
4.00
4.003.50
3.50
3.50
3.503.00
3.00
3.00
3.002.50
2.50
2.50
2.502.00
2.00
2.00
2.001.50
1.50
1.50
1.501.00
1.00
1.00
1.000.50
0.50
0.50
0.500.00
0.00
0.00
0.00-0.50
-0.50
-0.50
-0.50
1.97 1.97 1.97 1.97
2.00 2.00 2.00 2.00
11.14 11.14 11.14 11.14
4.00 4.00 4.00 4.00
7.333 7.333 7.333 7.3337.320 7.320 7.320 7.3207.316 7.316 7.316 7.3167.260 7.260 7.260 7.2606.863 6.863 6.863 6.8636.859 6.859 6.859 6.8596.845 6.845 6.845 6.8456.842 6.842 6.842 6.842
3.918 3.918 3.918 3.9183.764 3.764 3.764 3.764
1.666 1.666 1.666 1.666
MeO
O
N
4ae
CD
Cl 3
, 12
5 M
HzO
O
~ S32 ~
PPM
PPM
PPM
PPM
200
200
200
200
190
190
190
190
180
180
180
180
170
170
170
170
160
160
160
160
150
150
150
150
140
140
140
140
130
130
130
130
120
120
120
120
110
110
110
110
100
100
100
100
90
9090
90
80
8080
80
70
7070
70
60
6060
60
50
5050
50
40
4040
40
30
3030
30
20
2020
20
10
1010
10
0 000
170.142 170.142 170.142 170.142
160.527 160.527 160.527 160.527
128.726 128.726 128.726 128.726127.858 127.858 127.858 127.858
113.503 113.503 113.503 113.503
106.798 106.798 106.798 106.798
77.258 77.258 77.258 77.258 77.000 77.000 77.000 77.000 76.752 76.752 76.752 76.752
64.285 64.285 64.285 64.285
55.148 55.148 55.148 55.148
45.733 45.733 45.733 45.733
40.344 40.344 40.344 40.344 35.327 35.327 35.327 35.327 34.888 34.888 34.888 34.888
MeO
O
N
4ae
CD
Cl 3
, 12
5 M
HzO
O
~ S33 ~
PPM
PPM
PPM
PPM
10.00
10.00
10.00
10.009.50
9.50
9.50
9.509.00
9.00
9.00
9.008.50
8.50
8.50
8.508.00
8.00
8.00
8.007.50
7.50
7.50
7.507.00
7.00
7.00
7.006.50
6.50
6.50
6.506.00
6.00
6.00
6.005.50
5.50
5.50
5.505.00
5.00
5.00
5.004.50
4.50
4.50
4.504.00
4.00
4.00
4.003.50
3.50
3.50
3.503.00
3.00
3.00
3.002.50
2.50
2.50
2.502.00
2.00
2.00
2.001.50
1.50
1.50
1.501.00
1.00
1.00
1.000.50
0.50
0.50
0.500.00
0.00
0.00
0.00-0.50
-0.50
-0.50
-0.50
2.00 2.00 2.00 2.00
6.22 6.22 6.22 6.22
1.31 1.31 1.31 1.31
0.73 0.73 0.73 0.73
0.74 0.74 0.74 0.741.95 1.95 1.95 1.951.16 1.16 1.16 1.16
1.31 1.31 1.31 1.31
0.74 0.74 0.74 0.741.31 1.31 1.31 1.31
7.960 7.960 7.960 7.9607.954 7.954 7.954 7.9547.949 7.949 7.949 7.9497.940 7.940 7.940 7.9407.936 7.936 7.936 7.9367.930 7.930 7.930 7.9307.923 7.923 7.923 7.9237.920 7.920 7.920 7.9207.909 7.909 7.909 7.9097.906 7.906 7.906 7.9067.260 7.260 7.260 7.2607.251 7.251 7.251 7.2517.238 7.238 7.238 7.2387.233 7.233 7.233 7.2337.223 7.223 7.223 7.2237.221 7.221 7.221 7.2217.207 7.207 7.207 7.2077.195 7.195 7.195 7.1957.180 7.180 7.180 7.1807.168 7.168 7.168 7.1687.156 7.156 7.156 7.1567.151 7.151 7.151 7.1517.141 7.141 7.141 7.1417.136 7.136 7.136 7.1367.121 7.121 7.121 7.1217.107 7.107 7.107 7.1076.986 6.986 6.986 6.9866.981 6.981 6.981 6.9816.977 6.977 6.977 6.9776.967 6.967 6.967 6.9676.963 6.963 6.963 6.9636.958 6.958 6.958 6.9586.948 6.948 6.948 6.9486.945 6.945 6.945 6.9456.939 6.939 6.939 6.9396.935 6.935 6.935 6.9356.931 6.931 6.931 6.9316.926 6.926 6.926 6.9264.893 4.893 4.893 4.8934.532 4.532 4.532 4.5323.986 3.986 3.986 3.9863.974 3.974 3.974 3.9743.962 3.962 3.962 3.9623.877 3.877 3.877 3.8773.858 3.858 3.858 3.8583.622 3.622 3.622 3.6223.609 3.609 3.609 3.6093.598 3.598 3.598 3.5983.001 3.001 3.001 3.0012.988 2.988 2.988 2.9882.977 2.977 2.977 2.9772.859 2.859 2.859 2.8592.846 2.846 2.846 2.8462.835 2.835 2.835 2.835
MeO
O
N
O
3af
CD
Cl 3
, 500
MH
z
~ S34 ~
PPM
PPM
PPM
PPM
200
200
200
200
190
190
190
190
180
180
180
180
170
170
170
170
160
160
160
160
150
150
150
150
140
140
140
140
130
130
130
130
120
120
120
120
110
110
110
110
100
100
100
100
90
9090
90
80
8080
80
70
7070
70
60
6060
60
50
5050
50
40
4040
40
30
3030
30
20
2020
20
10
1010
10
0 000
190.144 190.144 190.144 190.144190.001 190.001 190.001 190.001
166.355 166.355 166.355 166.355166.040 166.040 166.040 166.040164.867 164.867 164.867 164.867164.829 164.829 164.829 164.829148.156 148.156 148.156 148.156146.201 146.201 146.201 146.201145.590 145.590 145.590 145.590134.135 134.135 134.135 134.135133.400 133.400 133.400 133.400132.122 132.122 132.122 132.122132.103 132.103 132.103 132.103131.836 131.836 131.836 131.836131.607 131.607 131.607 131.607128.879 128.879 128.879 128.879128.736 128.736 128.736 128.736127.067 127.067 127.067 127.067126.742 126.742 126.742 126.742126.695 126.695 126.695 126.695126.590 126.590 126.590 126.590126.494 126.494 126.494 126.494126.094 126.094 126.094 126.094126.008 126.008 126.008 126.008114.304 114.304 114.304 114.304114.285 114.285 114.285 114.285
77.258 77.258 77.258 77.258 77.000 77.000 77.000 77.000 76.742 76.742 76.742 76.742
55.577 55.577 55.577 55.577 55.558 55.558 55.558 55.558
47.279 47.279 47.279 47.279 43.444 43.444 43.444 43.444 43.292 43.292 43.292 43.292 39.190 39.190 39.190 39.190
29.175 29.175 29.175 29.175 28.192 28.192 28.192 28.192
MeO
O
N
O
3af
CD
Cl 3
, 125
MH
z
~ S35 ~
PPM
PPM
PPM
PPM
10.00
10.00
10.00
10.009.50
9.50
9.50
9.509.00
9.00
9.00
9.008.50
8.50
8.50
8.508.00
8.00
8.00
8.007.50
7.50
7.50
7.507.00
7.00
7.00
7.006.50
6.50
6.50
6.506.00
6.00
6.00
6.005.50
5.50
5.50
5.505.00
5.00
5.00
5.004.50
4.50
4.50
4.504.00
4.00
4.00
4.003.50
3.50
3.50
3.503.00
3.00
3.00
3.002.50
2.50
2.50
2.502.00
2.00
2.00
2.001.50
1.50
1.50
1.501.00
1.00
1.00
1.000.50
0.50
0.50
0.500.00
0.00
0.00
0.00-0.50
-0.50
-0.50
-0.50
1.94 1.94 1.94 1.94
1.01 1.01 1.01 1.012.00 2.00 2.00 2.00
3.01 3.01 3.01 3.01
2.08 2.08 2.08 2.08
5.32 5.32 5.32 5.32
3.02 3.02 3.02 3.02
8.433 8.433 8.433 8.4338.415 8.415 8.415 8.415
7.260 7.260 7.260 7.2607.117 7.117 7.117 7.1176.954 6.954 6.954 6.9546.936 6.936 6.936 6.936
3.891 3.891 3.891 3.891
3.401 3.401 3.401 3.4013.387 3.387 3.387 3.3873.374 3.374 3.374 3.3743.359 3.359 3.359 3.359
1.617 1.617 1.617 1.6171.602 1.602 1.602 1.6021.587 1.587 1.587 1.5871.572 1.572 1.572 1.5721.558 1.558 1.558 1.5581.442 1.442 1.442 1.4421.428 1.428 1.428 1.4281.413 1.413 1.413 1.4131.398 1.398 1.398 1.3981.383 1.383 1.383 1.3831.368 1.368 1.368 1.3680.969 0.969 0.969 0.9690.956 0.956 0.956 0.9560.941 0.941 0.941 0.941
MeO
OH N
O
3ag
CD
Cl 3
, 50
0 M
Hz
Me
~ S36 ~
PPM
PPM
PPM
PPM
200
200
200
200
190
190
190
190
180
180
180
180
170
170
170
170
160
160
160
160
150
150
150
150
140
140
140
140
130
130
130
130
120
120
120
120
110
110
110
110
100
100
100
100
90
9090
90
80
8080
80
70
7070
70
60
6060
60
50
5050
50
40
4040
40
30
3030
30
20
2020
20
10
1010
10
0 000
185.832 185.832 185.832 185.832
164.562 164.562 164.562 164.562162.254 162.254 162.254 162.254
133.829 133.829 133.829 133.829
126.342 126.342 126.342 126.342
113.713 113.713 113.713 113.713
77.258 77.258 77.258 77.258 77.000 77.000 77.000 77.000 76.742 76.742 76.742 76.742
55.462 55.462 55.462 55.462
39.009 39.009 39.009 39.009
31.254 31.254 31.254 31.254
19.989 19.989 19.989 19.989
13.637 13.637 13.637 13.637
MeO
OH N
O
3ag
CD
Cl 3
, 125
MH
z
Me
~ S37 ~
PPM
PPM
PPM
PPM
10.00
10.00
10.00
10.009.50
9.50
9.50
9.509.00
9.00
9.00
9.008.50
8.50
8.50
8.508.00
8.00
8.00
8.007.50
7.50
7.50
7.507.00
7.00
7.00
7.006.50
6.50
6.50
6.506.00
6.00
6.00
6.005.50
5.50
5.50
5.505.00
5.00
5.00
5.004.50
4.50
4.50
4.504.00
4.00
4.00
4.003.50
3.50
3.50
3.503.00
3.00
3.00
3.002.50
2.50
2.50
2.502.00
2.00
2.00
2.001.50
1.50
1.50
1.501.00
1.00
1.00
1.000.50
0.50
0.50
0.500.00
0.00
0.00
0.00-0.50
-0.50
-0.50
-0.50
2.00 2.00 2.00 2.00
2.04 2.04 2.04 2.04
0.95 0.95 0.95 0.95
3.12 3.12 3.12 3.12
2.06 2.06 2.06 2.06
3.02 3.02 3.02 3.022.20 2.20 2.20 2.20
3.12 3.12 3.12 3.12
7.732 7.732 7.732 7.7327.727 7.727 7.727 7.7277.718 7.718 7.718 7.7187.714 7.714 7.714 7.714
7.260 7.260 7.260 7.2606.924 6.924 6.924 6.9246.920 6.920 6.920 6.9206.911 6.911 6.911 6.9116.907 6.907 6.907 6.907
6.020 6.020 6.020 6.020
3.845 3.845 3.845 3.8453.461 3.461 3.461 3.4613.448 3.448 3.448 3.4483.436 3.436 3.436 3.4363.433 3.433 3.433 3.4333.421 3.421 3.421 3.421
1.621 1.621 1.621 1.6211.606 1.606 1.606 1.6061.591 1.591 1.591 1.5911.577 1.577 1.577 1.5771.561 1.561 1.561 1.5611.448 1.448 1.448 1.4481.433 1.433 1.433 1.4331.418 1.418 1.418 1.4181.402 1.402 1.402 1.4021.387 1.387 1.387 1.3871.372 1.372 1.372 1.3720.969 0.969 0.969 0.9690.954 0.954 0.954 0.9540.939 0.939 0.939 0.939
MeO
O
N H
4ag
CD
Cl 3
, 500
MH
z
Me
~ S38 ~
PPM
PPM
PPM
PPM
200
200
200
200
190
190
190
190
180
180
180
180
170
170
170
170
160
160
160
160
150
150
150
150
140
140
140
140
130
130
130
130
120
120
120
120
110
110
110
110
100
100
100
100
90
9090
90
80
8080
80
70
7070
70
60
6060
60
50
5050
50
40
4040
40
30
3030
30
20
2020
20
10
1010
10
0 000
166.985 166.985 166.985 166.985
161.996 161.996 161.996 161.996
128.555 128.555 128.555 128.555127.114 127.114 127.114 127.114
113.684 113.684 113.684 113.684
77.258 77.258 77.258 77.258 77.000 77.000 77.000 77.000 76.752 76.752 76.752 76.752
55.386 55.386 55.386 55.386
39.724 39.724 39.724 39.724
31.807 31.807 31.807 31.807
20.161 20.161 20.161 20.161
13.809 13.809 13.809 13.809
MeO
O
N H
4ag
CD
Cl 3
, 125
MH
z
Me
~ S39 ~
PPM
PPM
PPM
PPM
10.00
10.00
10.00
10.009.50
9.50
9.50
9.509.00
9.00
9.00
9.008.50
8.50
8.50
8.508.00
8.00
8.00
8.007.50
7.50
7.50
7.507.00
7.00
7.00
7.006.50
6.50
6.50
6.506.00
6.00
6.00
6.005.50
5.50
5.50
5.505.00
5.00
5.00
5.004.50
4.50
4.50
4.504.00
4.00
4.00
4.003.50
3.50
3.50
3.503.00
3.00
3.00
3.002.50
2.50
2.50
2.502.00
2.00
2.00
2.001.50
1.50
1.50
1.501.00
1.00
1.00
1.000.50
0.50
0.50
0.500.00
0.00
0.00
0.00-0.50
-0.50
-0.50
-0.50
2.00 2.00 2.00 2.00
2.05 2.05 2.05 2.05
3.11 3.11 3.11 3.11
2.06 2.06 2.06 2.06
2.08 2.08 2.08 2.08
4.26 4.26 4.26 4.26
3.04 3.04 3.04 3.042.92 2.92 2.92 2.92
7.906 7.906 7.906 7.9067.889 7.889 7.889 7.889
7.260 7.260 7.260 7.260
6.967 6.967 6.967 6.9676.948 6.948 6.948 6.948
3.875 3.875 3.875 3.8753.459 3.459 3.459 3.4593.444 3.444 3.444 3.4443.428 3.428 3.428 3.4283.130 3.130 3.130 3.1303.115 3.115 3.115 3.1153.099 3.099 3.099 3.099
1.740 1.740 1.740 1.7401.725 1.725 1.725 1.7251.710 1.710 1.710 1.7101.695 1.695 1.695 1.6951.680 1.680 1.680 1.6801.666 1.666 1.666 1.6661.606 1.606 1.606 1.6061.591 1.591 1.591 1.5911.576 1.576 1.576 1.5761.560 1.560 1.560 1.5601.545 1.545 1.545 1.5451.530 1.530 1.530 1.5301.001 1.001 1.001 1.0010.986 0.986 0.986 0.9860.972 0.972 0.972 0.9720.792 0.792 0.792 0.7920.777 0.777 0.777 0.7770.762 0.762 0.762 0.762
MeO
ON
O
3ah
CD
Cl 3
, 500
MH
z
Me
Me
~ S40 ~
PPM
PPM
PPM
PPM
10.00
10.00
10.00
10.009.50
9.50
9.50
9.509.00
9.00
9.00
9.008.50
8.50
8.50
8.508.00
8.00
8.00
8.007.50
7.50
7.50
7.507.00
7.00
7.00
7.006.50
6.50
6.50
6.506.00
6.00
6.00
6.005.50
5.50
5.50
5.505.00
5.00
5.00
5.004.50
4.50
4.50
4.504.00
4.00
4.00
4.003.50
3.50
3.50
3.503.00
3.00
3.00
3.002.50
2.50
2.50
2.502.00
2.00
2.00
2.001.50
1.50
1.50
1.501.00
1.00
1.00
1.000.50
0.50
0.50
0.500.00
0.00
0.00
0.00-0.50
-0.50
-0.50
-0.50
2.00 2.00 2.00 2.00
2.05 2.05 2.05 2.05
3.11 3.11 3.11 3.11
2.07 2.07 2.07 2.07
2.09 2.09 2.09 2.09
2.20 2.20 2.20 2.202.06 2.06 2.06 2.06
3.04 3.04 3.04 3.042.92 2.92 2.92 2.92
7.906 7.906 7.906 7.9067.889 7.889 7.889 7.889
7.260 7.260 7.260 7.260
6.967 6.967 6.967 6.9676.948 6.948 6.948 6.948
3.875 3.875 3.875 3.8753.459 3.459 3.459 3.4593.444 3.444 3.444 3.4443.428 3.428 3.428 3.4283.130 3.130 3.130 3.1303.115 3.115 3.115 3.1153.099 3.099 3.099 3.099
1.740 1.740 1.740 1.7401.725 1.725 1.725 1.7251.710 1.710 1.710 1.7101.695 1.695 1.695 1.6951.680 1.680 1.680 1.6801.666 1.666 1.666 1.6661.606 1.606 1.606 1.6061.591 1.591 1.591 1.5911.576 1.576 1.576 1.5761.560 1.560 1.560 1.5601.545 1.545 1.545 1.5451.530 1.530 1.530 1.5301.244 1.244 1.244 1.2441.001 1.001 1.001 1.0010.986 0.986 0.986 0.9860.972 0.972 0.972 0.9720.792 0.792 0.792 0.7920.777 0.777 0.777 0.7770.762 0.762 0.762 0.762
MeO
ON
O
3ah
CD
Cl 3
, 500
MH
z
Me
Me
~ S41 ~
PPM
PPM
PPM
PPM
200
200
200
200
190
190
190
190
180
180
180
180
170
170
170
170
160
160
160
160
150
150
150
150
140
140
140
140
130
130
130
130
120
120
120
120
110
110
110
110
100
100
100
100
90
9090
90
80
8080
80
70
7070
70
60
6060
60
50
5050
50
40
4040
40
30
3030
30
20
2020
20
10
1010
10
0 000
190.296 190.296 190.296 190.296
167.481 167.481 167.481 167.481164.610 164.610 164.610 164.610
132.027 132.027 132.027 132.027
126.418 126.418 126.418 126.418
114.190 114.190 114.190 114.190
77.258 77.258 77.258 77.258 77.000 77.000 77.000 77.000 76.752 76.752 76.752 76.752
55.577 55.577 55.577 55.577
49.301 49.301 49.301 49.301 45.743 45.743 45.743 45.743
21.773 21.773 21.773 21.773 20.590 20.590 20.590 20.590
11.395 11.395 11.395 11.395 11.004 11.004 11.004 11.004
MeO
ON
O
3ah
CD
Cl 3
, 125
MH
z
Me
Me
~ S42 ~
PPM
PPM
PPM
PPM
10.00
10.00
10.00
10.009.50
9.50
9.50
9.509.00
9.00
9.00
9.008.50
8.50
8.50
8.508.00
8.00
8.00
8.007.50
7.50
7.50
7.507.00
7.00
7.00
7.006.50
6.50
6.50
6.506.00
6.00
6.00
6.005.50
5.50
5.50
5.505.00
5.00
5.00
5.004.50
4.50
4.50
4.504.00
4.00
4.00
4.003.50
3.50
3.50
3.503.00
3.00
3.00
3.002.50
2.50
2.50
2.502.00
2.00
2.00
2.001.50
1.50
1.50
1.501.00
1.00
1.00
1.000.50
0.50
0.50
0.500.00
0.00
0.00
0.00-0.50
-0.50
-0.50
-0.50
2.00 2.00 2.00 2.00
2.02 2.02 2.02 2.02
3.10 3.10 3.10 3.10
4.38 4.38 4.38 4.38
4.33 4.33 4.33 4.33
6.36 6.36 6.36 6.36
7.328 7.328 7.328 7.3287.323 7.323 7.323 7.3237.318 7.318 7.318 7.3187.309 7.309 7.309 7.3097.305 7.305 7.305 7.3057.299 7.299 7.299 7.2997.260 7.260 7.260 7.2606.898 6.898 6.898 6.8986.894 6.894 6.894 6.8946.889 6.889 6.889 6.8896.880 6.880 6.880 6.8806.875 6.875 6.875 6.8756.869 6.869 6.869 6.869
3.818 3.818 3.818 3.818
3.412 3.412 3.412 3.412
3.206 3.206 3.206 3.206
1.642 1.642 1.642 1.6421.547 1.547 1.547 1.547
0.941 0.941 0.941 0.9410.756 0.756 0.756 0.756
MeO
O
N
4ah
CD
Cl 3
, 500
MH
z
Me
Me
~ S43 ~
PPM
PPM
PPM
PPM
200
200
200
200
190
190
190
190
180
180
180
180
170
170
170
170
160
160
160
160
150
150
150
150
140
140
140
140
130
130
130
130
120
120
120
120
110
110
110
110
100
100
100
100
90
9090
90
80
8080
80
70
7070
70
60
6060
60
50
5050
50
40
4040
40
30
3030
30
20
2020
20
10
1010
10
0 000
171.658 171.658 171.658 171.658
160.107 160.107 160.107 160.107
129.604 129.604 129.604 129.604128.297 128.297 128.297 128.297
113.560 113.560 113.560 113.560
77.258 77.258 77.258 77.258 77.000 77.000 77.000 77.000 76.742 76.742 76.742 76.742
55.253 55.253 55.253 55.253
50.855 50.855 50.855 50.855
46.458 46.458 46.458 46.458
21.945 21.945 21.945 21.945 20.638 20.638 20.638 20.638
11.224 11.224 11.224 11.224
MeO
O
N
4ah
CD
Cl 3
, 125
MH
z
Me
Me
~ S44 ~
PPM
PPM
PPM
PPM
10.00
10.00
10.00
10.009.50
9.50
9.50
9.509.00
9.00
9.00
9.008.50
8.50
8.50
8.508.00
8.00
8.00
8.007.50
7.50
7.50
7.507.00
7.00
7.00
7.006.50
6.50
6.50
6.506.00
6.00
6.00
6.005.50
5.50
5.50
5.505.00
5.00
5.00
5.004.50
4.50
4.50
4.504.00
4.00
4.00
4.003.50
3.50
3.50
3.503.00
3.00
3.00
3.002.50
2.50
2.50
2.502.00
2.00
2.00
2.001.50
1.50
1.50
1.501.00
1.00
1.00
1.000.50
0.50
0.50
0.500.00
0.00
0.00
0.00-0.50
-0.50
-0.50
-0.50
2.00 2.00 2.00 2.00
5.52 5.52 5.52 5.52
2.07 2.07 2.07 2.07
2.08 2.08 2.08 2.08
3.20 3.20 3.20 3.20
3.16 3.16 3.16 3.16
7.973 7.973 7.973 7.9737.969 7.969 7.969 7.9697.955 7.955 7.955 7.9557.949 7.949 7.949 7.9497.940 7.940 7.940 7.9407.937 7.937 7.937 7.9377.923 7.923 7.923 7.9237.399 7.399 7.399 7.3997.384 7.384 7.384 7.3847.370 7.370 7.370 7.3707.363 7.363 7.363 7.3637.350 7.350 7.350 7.3507.338 7.338 7.338 7.3387.324 7.324 7.324 7.3247.321 7.321 7.321 7.3217.309 7.309 7.309 7.3097.296 7.296 7.296 7.2967.282 7.282 7.282 7.2827.263 7.263 7.263 7.2637.260 7.260 7.260 7.2607.246 7.246 7.246 7.2466.985 6.985 6.985 6.9856.983 6.983 6.983 6.9836.967 6.967 6.967 6.9676.965 6.965 6.965 6.965
4.722 4.722 4.722 4.722
4.392 4.392 4.392 4.392
3.884 3.884 3.884 3.8843.880 3.880 3.880 3.880
2.971 2.971 2.971 2.9712.836 2.836 2.836 2.836
MeO
O
N
O
Me
3ai
CD
Cl 3
, 500
MH
z
~ S45 ~
PPM
PPM
PPM
PPM
200
200
200
200
190
190
190
190
180
180
180
180
170
170
170
170
160
160
160
160
150
150
150
150
140
140
140
140
130
130
130
130
120
120
120
120
110
110
110
110
100
100
100
100
90
9090
90
80
8080
80
70
7070
70
60
6060
60
50
5050
50
40
4040
40
30
3030
30
20
2020
20
10
1010
10
0 000
190.182 190.182 190.182 190.182
167.624 167.624 167.624 167.624167.433 167.433 167.433 167.433164.829 164.829 164.829 164.829164.810 164.810 164.810 164.810
135.861 135.861 135.861 135.861135.031 135.031 135.031 135.031132.208 132.208 132.208 132.208132.074 132.074 132.074 132.074128.822 128.822 128.822 128.822128.755 128.755 128.755 128.755128.278 128.278 128.278 128.278128.106 128.106 128.106 128.106127.792 127.792 127.792 127.792126.275 126.275 126.275 126.275126.103 126.103 126.103 126.103114.323 114.323 114.323 114.323114.266 114.266 114.266 114.266
77.258 77.258 77.258 77.258 77.000 77.000 77.000 77.000 76.752 76.752 76.752 76.752
55.606 55.606 55.606 55.606 53.526 53.526 53.526 53.526 49.730 49.730 49.730 49.730
34.469 34.469 34.469 34.469 31.273 31.273 31.273 31.273
MeO
O
N
O
Me
3ai
CD
Cl 3
, 125
MH
z
~ S46 ~
PPM
PPM
PPM
PPM
10.00
10.00
10.00
10.009.50
9.50
9.50
9.509.00
9.00
9.00
9.008.50
8.50
8.50
8.508.00
8.00
8.00
8.007.50
7.50
7.50
7.507.00
7.00
7.00
7.006.50
6.50
6.50
6.506.00
6.00
6.00
6.005.50
5.50
5.50
5.505.00
5.00
5.00
5.004.50
4.50
4.50
4.504.00
4.00
4.00
4.003.50
3.50
3.50
3.503.00
3.00
3.00
3.002.50
2.50
2.50
2.502.00
2.00
2.00
2.001.50
1.50
1.50
1.501.00
1.00
1.00
1.000.50
0.50
0.50
0.500.00
0.00
0.00
0.00-0.50
-0.50
-0.50
-0.50
2.00 2.00 2.00 2.00
2.07 2.07 2.07 2.07
1.11 1.11 1.11 1.113.02 3.02 3.02 3.020.96 0.96 0.96 0.961.02 1.02 1.02 1.02
0.97 0.97 0.97 0.97
1.47 1.47 1.47 1.471.59 1.59 1.59 1.59
9.50 9.50 9.50 9.50
6.18 6.18 6.18 6.18
7.927 7.927 7.927 7.9277.921 7.921 7.921 7.9217.915 7.915 7.915 7.9157.910 7.910 7.910 7.9107.907 7.907 7.907 7.9077.904 7.904 7.904 7.9047.897 7.897 7.897 7.8977.891 7.891 7.891 7.8917.260 7.260 7.260 7.2606.961 6.961 6.961 6.9616.957 6.957 6.957 6.9576.951 6.951 6.951 6.9516.947 6.947 6.947 6.9476.943 6.943 6.943 6.9436.937 6.937 6.937 6.9376.934 6.934 6.934 6.934
3.910 3.910 3.910 3.9103.900 3.900 3.900 3.9003.888 3.888 3.888 3.8883.872 3.872 3.872 3.8723.867 3.867 3.867 3.8673.713 3.713 3.713 3.7133.702 3.702 3.702 3.7023.690 3.690 3.690 3.6903.643 3.643 3.643 3.6433.633 3.633 3.633 3.6333.623 3.623 3.623 3.6233.351 3.351 3.351 3.3513.340 3.340 3.340 3.3403.328 3.328 3.328 3.3283.147 3.147 3.147 3.1473.018 3.018 3.018 3.018
0.896 0.896 0.896 0.8960.831 0.831 0.831 0.831
0.091 0.091 0.091 0.091-0.025 -0.025 -0.025 -0.025
MeO
ON
O
Me
3aj
CD
Cl 3
, 500
MH
z
OT
BS
~ S47 ~
PPM
PPM
PPM
PPM
200
200
200
200
190
190
190
190
180
180
180
180
170
170
170
170
160
160
160
160
150
150
150
150
140
140
140
140
130
130
130
130
120
120
120
120
110
110
110
110
100
100
100
100
90
9090
90
80
8080
80
70
7070
70
60
6060
60
50
5050
50
40
4040
40
30
3030
30
20
2020
20
10
1010
10
0 000
190.458 190.458 190.458 190.458
167.748 167.748 167.748 167.748167.509 167.509 167.509 167.509164.705 164.705 164.705 164.705
132.246 132.246 132.246 132.246132.065 132.065 132.065 132.065126.294 126.294 126.294 126.294126.113 126.113 126.113 126.113
114.247 114.247 114.247 114.247114.152 114.152 114.152 114.152
77.258 77.258 77.258 77.258 77.000 77.000 77.000 77.000 76.752 76.752 76.752 76.752
61.586 61.586 61.586 61.586 61.090 61.090 61.090 61.090
55.577 55.577 55.577 55.577 51.800 51.800 51.800 51.800 49.291 49.291 49.291 49.291
36.987 36.987 36.987 36.987 33.353 33.353 33.353 33.353
25.817 25.817 25.817 25.817 25.779 25.779 25.779 25.779
18.149 18.149 18.149 18.149
-5.497 -5.497 -5.497 -5.497 -5.602 -5.602 -5.602 -5.602
MeO
ON
O
Me
3aj
CD
Cl 3
, 125
MH
z
OT
BS
~ S48 ~
PPM
PPM
PPM
PPM
10.0
10.0
10.0
10.0
9.59.59.59.5
9.09.09.09.0
8.58.58.58.5
8.08.08.08.0
7.57.57.57.5
7.07.07.07.0
6.56.56.56.5
6.06.06.06.0
5.55.55.55.5
5.05.05.05.0
4.54.54.54.5
4.04.04.04.0
3.53.53.53.5
3.03.03.03.0
2.52.52.52.5
2.02.02.02.0
1.51.51.51.5
1.01.01.01.0
0.50.50.50.5
0.00.00.00.0
2.00 2.00 2.00 2.000.94 0.94 0.94 0.941.98 1.98 1.98 1.98
1.98 1.98 1.98 1.98
1.01 1.01 1.01 1.011.99 1.99 1.99 1.99
2.99 2.99 2.99 2.99
7.857 7.857 7.857 7.8577.839 7.839 7.839 7.8397.704 7.704 7.704 7.7047.637 7.637 7.637 7.6377.622 7.622 7.622 7.6227.388 7.388 7.388 7.3887.373 7.373 7.373 7.3737.356 7.356 7.356 7.3567.260 7.260 7.260 7.2607.158 7.158 7.158 7.1587.143 7.143 7.143 7.1437.128 7.128 7.128 7.1286.995 6.995 6.995 6.9956.977 6.977 6.977 6.977
3.882 3.882 3.882 3.882
MeO
O 4ak
CD
Cl 3
, 500
MH
z
N H
~ S49 ~
PPM
PPM
PPM
PPM
200
200
200
200
190
190
190
190
180
180
180
180
170
170
170
170
160
160
160
160
150
150
150
150
140
140
140
140
130
130
130
130
120
120
120
120
110
110
110
110
100
100
100
100
90
9090
90
80
8080
80
70
7070
70
60
6060
60
50
5050
50
40
4040
40
30
3030
30
20
2020
20
10
1010
10
0 000
165.201 165.201 165.201 165.201162.444 162.444 162.444 162.444
138.093 138.093 138.093 138.093
129.041 129.041 129.041 129.041128.888 128.888 128.888 128.888127.114 127.114 127.114 127.114124.301 124.301 124.301 124.301120.123 120.123 120.123 120.123
113.942 113.942 113.942 113.942
77.248 77.248 77.248 77.248 77.000 77.000 77.000 77.000 76.742 76.742 76.742 76.742
55.453 55.453 55.453 55.453
MeO
O 4ak
CD
Cl 3
, 125
MH
z
N H
~ S50 ~
㻼㻼㻹
㻼㻼㻹
㻼㻼㻹
㻼㻼㻹
㻝㻜㻚㻜㻜
㻝㻜㻚㻜㻜
㻝㻜㻚㻜㻜
㻝㻜㻚㻜㻜㻥㻚㻡㻜
㻥㻚㻡㻜
㻥㻚㻡㻜
㻥㻚㻡㻜㻥㻚㻜㻜
㻥㻚㻜㻜
㻥㻚㻜㻜
㻥㻚㻜㻜㻤㻚㻡㻜
㻤㻚㻡㻜
㻤㻚㻡㻜
㻤㻚㻡㻜㻤㻚㻜㻜
㻤㻚㻜㻜
㻤㻚㻜㻜
㻤㻚㻜㻜㻣㻚㻡㻜
㻣㻚㻡㻜
㻣㻚㻡㻜
㻣㻚㻡㻜㻣㻚㻜㻜
㻣㻚㻜㻜
㻣㻚㻜㻜
㻣㻚㻜㻜㻢㻚㻡㻜
㻢㻚㻡㻜
㻢㻚㻡㻜
㻢㻚㻡㻜㻢㻚㻜㻜
㻢㻚㻜㻜
㻢㻚㻜㻜
㻢㻚㻜㻜㻡㻚㻡㻜
㻡㻚㻡㻜
㻡㻚㻡㻜
㻡㻚㻡㻜㻡㻚㻜㻜
㻡㻚㻜㻜
㻡㻚㻜㻜
㻡㻚㻜㻜㻠㻚㻡㻜
㻠㻚㻡㻜
㻠㻚㻡㻜
㻠㻚㻡㻜㻠㻚㻜㻜
㻠㻚㻜㻜
㻠㻚㻜㻜
㻠㻚㻜㻜㻟㻚㻡㻜
㻟㻚㻡㻜
㻟㻚㻡㻜
㻟㻚㻡㻜㻟㻚㻜㻜
㻟㻚㻜㻜
㻟㻚㻜㻜
㻟㻚㻜㻜㻞㻚㻡㻜
㻞㻚㻡㻜
㻞㻚㻡㻜
㻞㻚㻡㻜㻞㻚㻜㻜
㻞㻚㻜㻜
㻞㻚㻜㻜
㻞㻚㻜㻜㻝㻚㻡㻜
㻝㻚㻡㻜
㻝㻚㻡㻜
㻝㻚㻡㻜㻝㻚㻜㻜
㻝㻚㻜㻜
㻝㻚㻜㻜
㻝㻚㻜㻜㻜㻚㻡㻜
㻜㻚㻡㻜
㻜㻚㻡㻜
㻜㻚㻡㻜㻜㻚㻜㻜
㻜㻚㻜㻜
㻜㻚㻜㻜
㻜㻚㻜㻜㻙㻜㻚㻡㻜
㻙㻜㻚㻡㻜
㻙㻜㻚㻡㻜
㻙㻜㻚㻡㻜
㻟㻚㻝㻟 㻟㻚㻝㻟 㻟㻚㻝㻟 㻟㻚㻝㻟
㻝㻚㻜㻜 㻝㻚㻜㻜 㻝㻚㻜㻜 㻝㻚㻜㻜
㻟㻚㻞㻤 㻟㻚㻞㻤 㻟㻚㻞㻤 㻟㻚㻞㻤㻠㻚㻟㻝 㻠㻚㻟㻝 㻠㻚㻟㻝 㻠㻚㻟㻝
㻞㻚㻝㻣 㻞㻚㻝㻣 㻞㻚㻝㻣 㻞㻚㻝㻣
㻞㻚㻝㻠 㻞㻚㻝㻠 㻞㻚㻝㻠 㻞㻚㻝㻠
㻣㻚㻠㻤㻠 㻣㻚㻠㻤㻠 㻣㻚㻠㻤㻠 㻣㻚㻠㻤㻠㻣㻚㻠㻤㻞 㻣㻚㻠㻤㻞 㻣㻚㻠㻤㻞 㻣㻚㻠㻤㻞㻣㻚㻠㻢㻢 㻣㻚㻠㻢㻢 㻣㻚㻠㻢㻢 㻣㻚㻠㻢㻢㻣㻚㻠㻢㻜 㻣㻚㻠㻢㻜 㻣㻚㻠㻢㻜 㻣㻚㻠㻢㻜㻣㻚㻠㻝㻞 㻣㻚㻠㻝㻞 㻣㻚㻠㻝㻞 㻣㻚㻠㻝㻞㻣㻚㻟㻥㻢 㻣㻚㻟㻥㻢 㻣㻚㻟㻥㻢 㻣㻚㻟㻥㻢㻣㻚㻟㻤㻜 㻣㻚㻟㻤㻜 㻣㻚㻟㻤㻜 㻣㻚㻟㻤㻜㻣㻚㻞㻢㻜 㻣㻚㻞㻢㻜 㻣㻚㻞㻢㻜 㻣㻚㻞㻢㻜㻣㻚㻝㻤㻟 㻣㻚㻝㻤㻟 㻣㻚㻝㻤㻟 㻣㻚㻝㻤㻟㻣㻚㻝㻤㻝 㻣㻚㻝㻤㻝 㻣㻚㻝㻤㻝 㻣㻚㻝㻤㻝㻣㻚㻝㻣㻢 㻣㻚㻝㻣㻢 㻣㻚㻝㻣㻢 㻣㻚㻝㻣㻢㻣㻚㻝㻢㻣 㻣㻚㻝㻢㻣 㻣㻚㻝㻢㻣 㻣㻚㻝㻢㻣㻣㻚㻝㻢㻡 㻣㻚㻝㻢㻡 㻣㻚㻝㻢㻡 㻣㻚㻝㻢㻡㻣㻚㻝㻢㻞 㻣㻚㻝㻢㻞 㻣㻚㻝㻢㻞 㻣㻚㻝㻢㻞㻣㻚㻝㻡㻥 㻣㻚㻝㻡㻥 㻣㻚㻝㻡㻥 㻣㻚㻝㻡㻥
㻟㻚㻤㻟㻠 㻟㻚㻤㻟㻠 㻟㻚㻤㻟㻠 㻟㻚㻤㻟㻠㻟㻚㻣㻤㻝 㻟㻚㻣㻤㻝 㻟㻚㻣㻤㻝 㻟㻚㻣㻤㻝㻟㻚㻣㻣㻡 㻟㻚㻣㻣㻡 㻟㻚㻣㻣㻡 㻟㻚㻣㻣㻡㻟㻚㻣㻢㻡 㻟㻚㻣㻢㻡 㻟㻚㻣㻢㻡 㻟㻚㻣㻢㻡㻟㻚㻣㻢㻜 㻟㻚㻣㻢㻜 㻟㻚㻣㻢㻜 㻟㻚㻣㻢㻜㻟㻚㻣㻡㻣 㻟㻚㻣㻡㻣 㻟㻚㻣㻡㻣 㻟㻚㻣㻡㻣㻟㻚㻣㻡㻞 㻟㻚㻣㻡㻞 㻟㻚㻣㻡㻞 㻟㻚㻣㻡㻞㻟㻚㻣㻠㻤 㻟㻚㻣㻠㻤 㻟㻚㻣㻠㻤 㻟㻚㻣㻠㻤㻟㻚㻣㻠㻞 㻟㻚㻣㻠㻞 㻟㻚㻣㻠㻞 㻟㻚㻣㻠㻞㻟㻚㻣㻟㻢 㻟㻚㻣㻟㻢 㻟㻚㻣㻟㻢 㻟㻚㻣㻟㻢㻟㻚㻢㻟㻟 㻟㻚㻢㻟㻟 㻟㻚㻢㻟㻟 㻟㻚㻢㻟㻟㻟㻚㻢㻞㻥 㻟㻚㻢㻞㻥 㻟㻚㻢㻞㻥 㻟㻚㻢㻞㻥㻟㻚㻢㻞㻟 㻟㻚㻢㻞㻟 㻟㻚㻢㻞㻟 㻟㻚㻢㻞㻟㻟㻚㻢㻝㻣 㻟㻚㻢㻝㻣 㻟㻚㻢㻝㻣 㻟㻚㻢㻝㻣㻟㻚㻢㻝㻠 㻟㻚㻢㻝㻠 㻟㻚㻢㻝㻠 㻟㻚㻢㻝㻠㻟㻚㻟㻡㻜 㻟㻚㻟㻡㻜 㻟㻚㻟㻡㻜 㻟㻚㻟㻡㻜㻟㻚㻟㻠㻣 㻟㻚㻟㻠㻣 㻟㻚㻟㻠㻣 㻟㻚㻟㻠㻣㻟㻚㻟㻠㻝 㻟㻚㻟㻠㻝 㻟㻚㻟㻠㻝 㻟㻚㻟㻠㻝㻟㻚㻟㻟㻡 㻟㻚㻟㻟㻡 㻟㻚㻟㻟㻡 㻟㻚㻟㻟㻡㻟㻚㻟㻟㻝 㻟㻚㻟㻟㻝 㻟㻚㻟㻟㻝 㻟㻚㻟㻟㻝
ON
O
O
3ba
CD
Cl 3,
500
MH
z
MeO
~ S51 ~
PPM
PPM
PPM
PPM
200
200
200
200
190
190
190
190
180
180
180
180
170
170
170
170
160
160
160
160
150
150
150
150
140
140
140
140
130
130
130
130
120
120
120
120
110
110
110
110
100
100
100
100
90
9090
90
80
8080
80
70
7070
70
60
6060
60
50
5050
50
40
4040
40
30
3030
30
20
2020
20
10
1010
10
0 000
190.993 190.993 190.993 190.993
165.296 165.296 165.296 165.296
160.022 160.022 160.022 160.022
134.192 134.192 134.192 134.192
130.052 130.052 130.052 130.052
122.698 122.698 122.698 122.698121.706 121.706 121.706 121.706
112.645 112.645 112.645 112.645
77.248 77.248 77.248 77.248 77.000 77.000 77.000 77.000 76.742 76.742 76.742 76.742
66.584 66.584 66.584 66.584 66.536 66.536 66.536 66.536
55.434 55.434 55.434 55.434
46.134 46.134 46.134 46.134
41.479 41.479 41.479 41.479
ON
O
O
3ba
CD
Cl 3
, 125
MH
z
MeO
~ S52 ~
PPM
PPM
PPM
PPM
10.00
10.00
10.00
10.009.50
9.50
9.50
9.509.00
9.00
9.00
9.008.50
8.50
8.50
8.508.00
8.00
8.00
8.007.50
7.50
7.50
7.507.00
7.00
7.00
7.006.50
6.50
6.50
6.506.00
6.00
6.00
6.005.50
5.50
5.50
5.505.00
5.00
5.00
5.004.50
4.50
4.50
4.504.00
4.00
4.00
4.003.50
3.50
3.50
3.503.00
3.00
3.00
3.002.50
2.50
2.50
2.502.00
2.00
2.00
2.001.50
1.50
1.50
1.501.00
1.00
1.00
1.000.50
0.50
0.50
0.500.00
0.00
0.00
0.00-0.50
-0.50
-0.50
-0.50
0.97 0.97 0.97 0.97
3.00 3.00 3.00 3.00
11.36 11.36 11.36 11.36
7.323 7.323 7.323 7.3237.306 7.306 7.306 7.3067.291 7.291 7.291 7.2917.260 7.260 7.260 7.2606.955 6.955 6.955 6.9556.951 6.951 6.951 6.9516.934 6.934 6.934 6.934
3.814 3.814 3.814 3.8143.808 3.808 3.808 3.8083.763 3.763 3.763 3.7633.614 3.614 3.614 3.6143.437 3.437 3.437 3.437
O
N
O
4ba
CD
Cl 3
, 500
MH
z
MeO
~ S53 ~
PPM
PPM
PPM
PPM
200
200
200
200
190
190
190
190
180
180
180
180
170
170
170
170
160
160
160
160
150
150
150
150
140
140
140
140
130
130
130
130
120
120
120
120
110
110
110
110
100
100
100
100
90
9090
90
80
8080
80
70
7070
70
60
6060
60
50
5050
50
40
4040
40
30
3030
30
20
2020
20
10
1010
10
0 000
170.161 170.161 170.161 170.161
159.688 159.688 159.688 159.688
136.595 136.595 136.595 136.595
129.661 129.661 129.661 129.661
119.054 119.054 119.054 119.054115.630 115.630 115.630 115.630112.483 112.483 112.483 112.483
77.248 77.248 77.248 77.248 77.000 77.000 77.000 77.000 76.742 76.742 76.742 76.742
66.899 66.899 66.899 66.899
55.358 55.358 55.358 55.358
48.204 48.204 48.204 48.204
42.548 42.548 42.548 42.548
O
N
O
4ba
CD
Cl 3
, 125
MH
z
MeO
~ S54 ~
PPM
PPM
PPM
PPM
10.0
10.0
10.0
10.0
9.59.59.59.5
9.09.09.09.0
8.58.58.58.5
8.08.08.08.0
7.57.57.57.5
7.07.07.07.0
6.56.56.56.5
6.06.06.06.0
5.55.55.55.5
5.05.05.05.0
4.54.54.54.5
4.04.04.04.0
3.53.53.53.5
3.03.03.03.0
2.52.52.52.5
2.02.02.02.0
1.51.51.51.5
1.01.01.01.0
0.50.50.50.5
0.00.00.00.0
-0.5
-0.5
-0.5
-0.5
1.00 1.00 1.00 1.00
1.02 1.02 1.02 1.02
0.99 0.99 0.99 0.991.03 1.03 1.03 1.03
3.23 3.23 3.23 3.232.25 2.25 2.25 2.25
4.34 4.34 4.34 4.34
2.10 2.10 2.10 2.10
7.937 7.937 7.937 7.9377.933 7.933 7.933 7.9337.921 7.921 7.921 7.9217.917 7.917 7.917 7.9177.600 7.600 7.600 7.6007.597 7.597 7.597 7.5977.583 7.583 7.583 7.5837.569 7.569 7.569 7.5697.566 7.566 7.566 7.5667.260 7.260 7.260 7.2607.107 7.107 7.107 7.1077.091 7.091 7.091 7.0917.074 7.074 7.074 7.0747.003 7.003 7.003 7.0036.987 6.987 6.987 6.987
3.909 3.909 3.909 3.9093.805 3.805 3.805 3.8053.796 3.796 3.796 3.7963.785 3.785 3.785 3.7853.728 3.728 3.728 3.7283.717 3.717 3.717 3.7173.710 3.710 3.710 3.7103.701 3.701 3.701 3.7013.690 3.690 3.690 3.6903.417 3.417 3.417 3.4173.406 3.406 3.406 3.4063.397 3.397 3.397 3.397
O
N
O
O
3ca
CD
Cl 3
, 500
MH
z
OM
e
~ S55 ~
PPM
PPM
PPM
PPM
200
200
200
200
190
190
190
190
180
180
180
180
170
170
170
170
160
160
160
160
150
150
150
150
140
140
140
140
130
130
130
130
120
120
120
120
110
110
110
110
100
100
100
100
90
9090
90
80
8080
80
70
7070
70
60
6060
60
50
5050
50
40
4040
40
30
3030
30
20
2020
20
10
1010
10
0 000
190.234 190.234 190.234 190.234
167.371 167.371 167.371 167.371
160.136 160.136 160.136 160.136
136.223 136.223 136.223 136.223
131.116 131.116 131.116 131.116
123.528 123.528 123.528 123.528121.453 121.453 121.453 121.453
112.206 112.206 112.206 112.206
77.253 77.253 77.253 77.253 77.000 77.000 77.000 77.000 76.747 76.747 76.747 76.747
66.546 66.546 66.546 66.546 66.336 66.336 66.336 66.336
56.216 56.216 56.216 56.216
45.881 45.881 45.881 45.881
41.379 41.379 41.379 41.379
O
N
O
O
3ca
CD
Cl 3
, 125
MH
z
OM
e
~ S56 ~
PPM
PPM
PPM
PPM
10.00
10.00
10.00
10.009.50
9.50
9.50
9.509.00
9.00
9.00
9.008.50
8.50
8.50
8.508.00
8.00
8.00
8.007.50
7.50
7.50
7.507.00
7.00
7.00
7.006.50
6.50
6.50
6.506.00
6.00
6.00
6.005.50
5.50
5.50
5.505.00
5.00
5.00
5.004.50
4.50
4.50
4.504.00
4.00
4.00
4.003.50
3.50
3.50
3.503.00
3.00
3.00
3.002.50
2.50
2.50
2.502.00
2.00
2.00
2.001.50
1.50
1.50
1.501.00
1.00
1.00
1.000.50
0.50
0.50
0.500.00
0.00
0.00
0.00
1.00 1.00 1.00 1.00 0.97 0.97 0.97 0.97
1.00 1.00 1.00 1.000.96 0.96 0.96 0.96
7.31 7.31 7.31 7.312.04 2.04 2.04 2.04
2.00 2.00 2.00 2.00
7.368 7.368 7.368 7.3687.364 7.364 7.364 7.3647.353 7.353 7.353 7.3537.349 7.349 7.349 7.3497.337 7.337 7.337 7.3377.333 7.333 7.333 7.3337.260 7.260 7.260 7.2607.252 7.252 7.252 7.2527.249 7.249 7.249 7.2497.236 7.236 7.236 7.2367.234 7.234 7.234 7.2347.005 7.005 7.005 7.0056.990 6.990 6.990 6.9906.975 6.975 6.975 6.9756.915 6.915 6.915 6.9156.898 6.898 6.898 6.898
3.832 3.832 3.832 3.8323.785 3.785 3.785 3.7853.765 3.765 3.765 3.7653.754 3.754 3.754 3.7543.736 3.736 3.736 3.7363.720 3.720 3.720 3.7203.628 3.628 3.628 3.6283.616 3.616 3.616 3.6163.609 3.609 3.609 3.6093.571 3.571 3.571 3.5713.564 3.564 3.564 3.5643.285 3.285 3.285 3.2853.277 3.277 3.277 3.2773.240 3.240 3.240 3.2403.230 3.230 3.230 3.2303.222 3.222 3.222 3.222
O
N
O
4ca
CD
Cl 3
, 500
MH
z
OM
e
~ S57 ~
PPM
PPM
PPM
PPM
200
200
200
200
190
190
190
190
180
180
180
180
170
170
170
170
160
160
160
160
150
150
150
150
140
140
140
140
130
130
130
130
120
120
120
120
110
110
110
110
100
100
100
100
90
9090
90
80
8080
80
70
7070
70
60
6060
60
50
5050
50
40
4040
40
30
3030
30
20
2020
20
10
1010
10
0 000
167.833 167.833 167.833 167.833
155.176 155.176 155.176 155.176
130.567 130.567 130.567 130.567128.030 128.030 128.030 128.030125.159 125.159 125.159 125.159
120.962 120.962 120.962 120.962
110.823 110.823 110.823 110.823
77.258 77.258 77.258 77.258 77.000 77.000 77.000 77.000 76.742 76.742 76.742 76.742
66.908 66.908 66.908 66.908 66.784 66.784 66.784 66.784
55.462 55.462 55.462 55.462
47.221 47.221 47.221 47.221
42.052 42.052 42.052 42.052
O
N
O
4ca
CD
Cl 3
, 125
MH
z
OM
e
~ S58 ~
PPM
PPM
PPM
PPM
10.00
10.00
10.00
10.009.50
9.50
9.50
9.509.00
9.00
9.00
9.008.50
8.50
8.50
8.508.00
8.00
8.00
8.007.50
7.50
7.50
7.507.00
7.00
7.00
7.006.50
6.50
6.50
6.506.00
6.00
6.00
6.005.50
5.50
5.50
5.505.00
5.00
5.00
5.004.50
4.50
4.50
4.504.00
4.00
4.00
4.003.50
3.50
3.50
3.503.00
3.00
3.00
3.002.50
2.50
2.50
2.502.00
2.00
2.00
2.001.50
1.50
1.50
1.501.00
1.00
1.00
1.000.50
0.50
0.50
0.500.00
0.00
0.00
0.00-0.50
-0.50
-0.50
-0.50
2.00 2.00 2.00 2.00
0.98 0.98 0.98 0.98
4.19 4.19 4.19 4.192.10 2.10 2.10 2.10
2.02 2.02 2.02 2.02
6.36 6.36 6.36 6.36
7.544 7.544 7.544 7.544
7.275 7.275 7.275 7.2757.260 7.260 7.260 7.260
3.801 3.801 3.801 3.8013.796 3.796 3.796 3.7963.782 3.782 3.782 3.7823.780 3.780 3.780 3.7803.772 3.772 3.772 3.7723.766 3.766 3.766 3.7663.759 3.759 3.759 3.7593.648 3.648 3.648 3.6483.639 3.639 3.639 3.6393.628 3.628 3.628 3.6283.362 3.362 3.362 3.3623.352 3.352 3.352 3.3523.343 3.343 3.343 3.343
2.365 2.365 2.365 2.365
O
N
O
O
3da
CD
Cl 3
, 500
MH
z
Me
Me
~ S59 ~
PPM
PPM
PPM
PPM
200
200
200
200
190
190
190
190
180
180
180
180
170
170
170
170
160
160
160
160
150
150
150
150
140
140
140
140
130
130
130
130
120
120
120
120
110
110
110
110
100
100
100
100
90
9090
90
80
8080
80
70
7070
70
60
6060
60
50
5050
50
40
4040
40
30
3030
30
20
2020
20
10
1010
10
0 000
191.574 191.574 191.574 191.574
165.659 165.659 165.659 165.659
138.866 138.866 138.866 138.866136.739 136.739 136.739 136.739132.990 132.990 132.990 132.990
127.267 127.267 127.267 127.267
77.258 77.258 77.258 77.258 77.000 77.000 77.000 77.000 76.742 76.742 76.742 76.742
66.670 66.670 66.670 66.670 66.613 66.613 66.613 66.613
46.201 46.201 46.201 46.201
41.517 41.517 41.517 41.517
21.096 21.096 21.096 21.096
O
N
O
O
3da
CD
Cl 3
, 125
MH
z
Me
Me
~ S60 ~
PPM
PPM
PPM
PPM
10.00
10.00
10.00
10.009.50
9.50
9.50
9.509.00
9.00
9.00
9.008.50
8.50
8.50
8.508.00
8.00
8.00
8.007.50
7.50
7.50
7.507.00
7.00
7.00
7.006.50
6.50
6.50
6.506.00
6.00
6.00
6.005.50
5.50
5.50
5.505.00
5.00
5.00
5.004.50
4.50
4.50
4.504.00
4.00
4.00
4.003.50
3.50
3.50
3.503.00
3.00
3.00
3.002.50
2.50
2.50
2.502.00
2.00
2.00
2.001.50
1.50
1.50
1.501.00
1.00
1.00
1.000.50
0.50
0.50
0.500.00
0.00
0.00
0.00-0.50
-0.50
-0.50
-0.50
3.00 3.00 3.00 3.00
8.47 8.47 8.47 8.47
6.37 6.37 6.37 6.37
7.260 7.260 7.260 7.2607.041 7.041 7.041 7.0416.990 6.990 6.990 6.990
3.766 3.766 3.766 3.7663.616 3.616 3.616 3.6163.447 3.447 3.447 3.447
2.327 2.327 2.327 2.327
O
N
O
4da
CD
Cl 3
, 500
MH
z
Me
Me
~ S61 ~
PPM
PPM
PPM
PPM
200
200
200
200
190
190
190
190
180
180
180
180
170
170
170
170
160
160
160
160
150
150
150
150
140
140
140
140
130
130
130
130
120
120
120
120
110
110
110
110
100
100
100
100
90
9090
90
80
8080
80
70
7070
70
60
6060
60
50
5050
50
40
4040
40
30
3030
30
20
2020
20
10
1010
10
0 000
170.781 170.781 170.781 170.781
138.255 138.255 138.255 138.255135.270 135.270 135.270 135.270
131.349 131.349 131.349 131.349
124.577 124.577 124.577 124.577
77.258 77.258 77.258 77.258 77.000 77.000 77.000 77.000 76.742 76.742 76.742 76.742
66.918 66.918 66.918 66.918
48.194 48.194 48.194 48.194
42.471 42.471 42.471 42.471
21.239 21.239 21.239 21.239
O
N
O
4da
CD
Cl 3
, 125
MH
z
Me
Me
~ S62 ~
PPM
PPM
PPM
PPM
10.00
10.00
10.00
10.009.50
9.50
9.50
9.509.00
9.00
9.00
9.008.50
8.50
8.50
8.508.00
8.00
8.00
8.007.50
7.50
7.50
7.507.00
7.00
7.00
7.006.50
6.50
6.50
6.506.00
6.00
6.00
6.005.50
5.50
5.50
5.505.00
5.00
5.00
5.004.50
4.50
4.50
4.504.00
4.00
4.00
4.003.50
3.50
3.50
3.503.00
3.00
3.00
3.002.50
2.50
2.50
2.502.00
2.00
2.00
2.001.50
1.50
1.50
1.501.00
1.00
1.00
1.000.50
0.50
0.50
0.500.00
0.00
0.00
0.00-0.50
-0.50
-0.50
-0.50
2.00 2.00 2.00 2.00
9.22 9.22 9.22 9.224.12 4.12 4.12 4.12
2.04 2.04 2.04 2.04
1.92 1.92 1.92 1.92
7.260 7.260 7.260 7.2607.174 7.174 7.174 7.174
3.908 3.908 3.908 3.9083.877 3.877 3.877 3.8773.753 3.753 3.753 3.7533.641 3.641 3.641 3.6413.636 3.636 3.636 3.6363.631 3.631 3.631 3.6313.622 3.622 3.622 3.6223.359 3.359 3.359 3.3593.349 3.349 3.349 3.3493.340 3.340 3.340 3.340
O
N
O
O
3ea
CD
Cl 3
, 125
MH
z
MeO
OM
e
MeO
~ S63 ~
PPM
PPM
PPM
PPM
200
200
200
200
190
190
190
190
180
180
180
180
170
170
170
170
160
160
160
160
150
150
150
150
140
140
140
140
130
130
130
130
120
120
120
120
110
110
110
110
100
100
100
100
90
9090
90
80
8080
80
70
7070
70
60
6060
60
50
5050
50
40
4040
40
30
3030
30
20
2020
20
10
1010
10
0 000
189.915 189.915 189.915 189.915
165.229 165.229 165.229 165.229
153.316 153.316 153.316 153.316
144.140 144.140 144.140 144.140
127.896 127.896 127.896 127.896
106.788 106.788 106.788 106.788
77.248 77.248 77.248 77.248 77.000 77.000 77.000 77.000 76.742 76.742 76.742 76.742
66.670 66.670 66.670 66.670 66.613 66.613 66.613 66.613
60.928 60.928 60.928 60.928
56.264 56.264 56.264 56.264
46.229 46.229 46.229 46.229
41.584 41.584 41.584 41.584
O
N
O
O
3ea
CD
Cl 3
, 125
MH
z
MeO
OM
e
MeO
~ S64 ~
PPM
PPM
PPM
PPM
10.00
10.00
10.00
10.009.50
9.50
9.50
9.509.00
9.00
9.00
9.008.50
8.50
8.50
8.508.00
8.00
8.00
8.007.50
7.50
7.50
7.507.00
7.00
7.00
7.006.50
6.50
6.50
6.506.00
6.00
6.00
6.005.50
5.50
5.50
5.505.00
5.00
5.00
5.004.50
4.50
4.50
4.504.00
4.00
4.00
4.003.50
3.50
3.50
3.503.00
3.00
3.00
3.002.50
2.50
2.50
2.502.00
2.00
2.00
2.001.50
1.50
1.50
1.501.00
1.00
1.00
1.000.50
0.50
0.50
0.500.00
0.00
0.00
0.00-0.50
-0.50
-0.50
-0.50
2.00 2.00 2.00 2.00
17.13 17.13 17.13 17.13
7.260 7.260 7.260 7.260
6.612 6.612 6.612 6.612
3.859 3.859 3.859 3.8593.843 3.843 3.843 3.8433.712 3.712 3.712 3.712
O
N
O
4ea
CD
Cl 3
, 500
MH
z
MeO
OM
e
MeO
~ S65 ~
PPM
PPM
PPM
PPM
200
200
200
200
190
190
190
190
180
180
180
180
170
170
170
170
160
160
160
160
150
150
150
150
140
140
140
140
130
130
130
130
120
120
120
120
110
110
110
110
100
100
100
100
90
9090
90
80
8080
80
70
7070
70
60
6060
60
50
5050
50
40
4040
40
30
3030
30
20
2020
20
10
1010
10
0 000
170.123 170.123 170.123 170.123
153.316 153.316 153.316 153.316
139.238 139.238 139.238 139.238
130.596 130.596 130.596 130.596
104.280 104.280 104.280 104.280
77.258 77.258 77.258 77.258 77.000 77.000 77.000 77.000 76.742 76.742 76.742 76.742
66.851 66.851 66.851 66.851
60.852 60.852 60.852 60.852
56.216 56.216 56.216 56.216
48.290 48.290 48.290 48.290
42.662 42.662 42.662 42.662
O
N
O
4ea
CD
Cl 3
, 125
MH
z
MeO
OM
e
MeO
~ S66 ~
PPM
PPM
PPM
PPM
10.00
10.00
10.00
10.009.50
9.50
9.50
9.509.00
9.00
9.00
9.008.50
8.50
8.50
8.508.00
8.00
8.00
8.007.50
7.50
7.50
7.507.00
7.00
7.00
7.006.50
6.50
6.50
6.506.00
6.00
6.00
6.005.50
5.50
5.50
5.505.00
5.00
5.00
5.004.50
4.50
4.50
4.504.00
4.00
4.00
4.003.50
3.50
3.50
3.503.00
3.00
3.00
3.002.50
2.50
2.50
2.502.00
2.00
2.00
2.001.50
1.50
1.50
1.501.00
1.00
1.00
1.000.50
0.50
0.50
0.500.00
0.00
0.00
0.00-0.50
-0.50
-0.50
-0.50
2.00 2.00 2.00 2.00
1.04 1.04 1.04 1.042.07 2.07 2.07 2.07
4.14 4.14 4.14 4.142.11 2.11 2.11 2.11
2.08 2.08 2.08 2.08
7.971 7.971 7.971 7.9717.957 7.957 7.957 7.9577.955 7.955 7.955 7.9557.678 7.678 7.678 7.6787.676 7.676 7.676 7.6767.663 7.663 7.663 7.6637.648 7.648 7.648 7.6487.646 7.646 7.646 7.6467.544 7.544 7.544 7.5447.541 7.541 7.541 7.5417.528 7.528 7.528 7.5287.517 7.517 7.517 7.5177.513 7.513 7.513 7.5137.260 7.260 7.260 7.260
3.820 3.820 3.820 3.8203.814 3.814 3.814 3.8143.800 3.800 3.800 3.8003.791 3.791 3.791 3.7913.779 3.779 3.779 3.7793.670 3.670 3.670 3.6703.661 3.661 3.661 3.6613.650 3.650 3.650 3.6503.397 3.397 3.397 3.3973.388 3.388 3.388 3.3883.378 3.378 3.378 3.378
ON
O
O
3fa
CD
Cl 3
, 500
MH
z
~ S67 ~
PPM
PPM
PPM
PPM
200
200
200
200
190
190
190
190
180
180
180
180
170
170
170
170
160
160
160
160
150
150
150
150
140
140
140
140
130
130
130
130
120
120
120
120
110
110
110
110
100
100
100
100
90
9090
90
80
8080
80
70
7070
70
60
6060
60
50
5050
50
40
4040
40
30
3030
30
20
2020
20
10
1010
10
0 000
190.954 190.954 190.954 190.954
165.172 165.172 165.172 165.172
134.726 134.726 134.726 134.726132.742 132.742 132.742 132.742129.365 129.365 129.365 129.365128.860 128.860 128.860 128.860
77.258 77.258 77.258 77.258 77.000 77.000 77.000 77.000 76.742 76.742 76.742 76.742
66.422 66.422 66.422 66.422 66.346 66.346 66.346 66.346
45.962 45.962 45.962 45.962
41.308 41.308 41.308 41.308
ON
O
O
3fa
CD
Cl 3
, 125
MH
z
~ S68 ~
PPM
PPM
PPM
PPM
10.00
10.00
10.00
10.009.50
9.50
9.50
9.509.00
9.00
9.00
9.008.50
8.50
8.50
8.508.00
8.00
8.00
8.007.50
7.50
7.50
7.507.00
7.00
7.00
7.006.50
6.50
6.50
6.506.00
6.00
6.00
6.005.50
5.50
5.50
5.505.00
5.00
5.00
5.004.50
4.50
4.50
4.504.00
4.00
4.00
4.003.50
3.50
3.50
3.503.00
3.00
3.00
3.002.50
2.50
2.50
2.502.00
2.00
2.00
2.001.50
1.50
1.50
1.501.00
1.00
1.00
1.000.50
0.50
0.50
0.500.00
0.00
0.00
0.00-0.50
-0.50
-0.50
-0.50
5.00 5.00 5.00 5.00
8.43 8.43 8.43 8.43
7.417 7.417 7.417 7.4177.407 7.407 7.407 7.4077.260 7.260 7.260 7.260
3.773 3.773 3.773 3.7733.625 3.625 3.625 3.6253.444 3.444 3.444 3.444
O
N
O
4fa
CD
Cl 3
, 500
MH
z
~ S69 ~
PPM
PPM
PPM
PPM
200
200
200
200
190
190
190
190
180
180
180
180
170
170
170
170
160
160
160
160
150
150
150
150
140
140
140
140
130
130
130
130
120
120
120
120
110
110
110
110
100
100
100
100
90
9090
90
80
8080
80
70
7070
70
60
6060
60
50
5050
50
40
4040
40
30
3030
30
20
2020
20
10
1010
10
0 000
170.418 170.418 170.418 170.418
135.279 135.279 135.279 135.279
129.861 129.861 129.861 129.861128.555 128.555 128.555 128.555127.067 127.067 127.067 127.067
77.258 77.258 77.258 77.258 77.000 77.000 77.000 77.000 76.752 76.752 76.752 76.752
66.889 66.889 66.889 66.889
48.194 48.194 48.194 48.194
42.471 42.471 42.471 42.471
O
N
O
4fa
CD
Cl 3
, 125
MH
z
~ S70 ~
PPM
PPM
PPM
PPM
10.00
10.00
10.00
10.009.50
9.50
9.50
9.509.00
9.00
9.00
9.008.50
8.50
8.50
8.508.00
8.00
8.00
8.007.50
7.50
7.50
7.507.00
7.00
7.00
7.006.50
6.50
6.50
6.506.00
6.00
6.00
6.005.50
5.50
5.50
5.505.00
5.00
5.00
5.004.50
4.50
4.50
4.504.00
4.00
4.00
4.003.50
3.50
3.50
3.503.00
3.00
3.00
3.002.50
2.50
2.50
2.502.00
2.00
2.00
2.001.50
1.50
1.50
1.501.00
1.00
1.00
1.000.50
0.50
0.50
0.500.00
0.00
0.00
0.00-0.50
-0.50
-0.50
-0.50
2.00 2.00 2.00 2.00
2.03 2.03 2.03 2.03
4.22 4.22 4.22 4.222.13 2.13 2.13 2.13
2.05 2.05 2.05 2.05
7.906 7.906 7.906 7.9067.901 7.901 7.901 7.9017.898 7.898 7.898 7.8987.889 7.889 7.889 7.8897.884 7.884 7.884 7.8847.880 7.880 7.880 7.8807.496 7.496 7.496 7.4967.491 7.491 7.491 7.4917.487 7.487 7.487 7.4877.478 7.478 7.478 7.4787.474 7.474 7.474 7.4747.260 7.260 7.260 7.260
3.793 3.793 3.793 3.7933.788 3.788 3.788 3.7883.777 3.777 3.777 3.7773.773 3.773 3.773 3.7733.767 3.767 3.767 3.7673.762 3.762 3.762 3.7623.752 3.752 3.752 3.7523.748 3.748 3.748 3.7483.654 3.654 3.654 3.6543.649 3.649 3.649 3.6493.643 3.643 3.643 3.6433.638 3.638 3.638 3.6383.634 3.634 3.634 3.6343.375 3.375 3.375 3.3753.365 3.365 3.365 3.3653.356 3.356 3.356 3.356
O
N
O
O
3ga
CD
Cl 3
, 500
MH
z
Cl
~ S71 ~
PPM
PPM
PPM
PPM
200
200
200
200
190
190
190
190
180
180
180
180
170
170
170
170
160
160
160
160
150
150
150
150
140
140
140
140
130
130
130
130
120
120
120
120
110
110
110
110
100
100
100
100
90
9090
90
80
8080
80
70
7070
70
60
6060
60
50
5050
50
40
4040
40
30
3030
30
20
2020
20
10
1010
10
0 000
189.648 189.648 189.648 189.648
164.829 164.829 164.829 164.829
141.546 141.546 141.546 141.546
131.397 131.397 131.397 131.397130.977 130.977 130.977 130.977129.442 129.442 129.442 129.442
77.258 77.258 77.258 77.258 77.000 77.000 77.000 77.000 76.752 76.752 76.752 76.752
66.680 66.680 66.680 66.680 66.575 66.575 66.575 66.575
46.220 46.220 46.220 46.220
41.641 41.641 41.641 41.641
O
N
O
O
3ga
CD
Cl 3
, 125
MH
z
Cl
~ S72 ~
PPM
PPM
PPM
PPM
10.00
10.00
10.00
10.009.50
9.50
9.50
9.509.00
9.00
9.00
9.008.50
8.50
8.50
8.508.00
8.00
8.00
8.007.50
7.50
7.50
7.507.00
7.00
7.00
7.006.50
6.50
6.50
6.506.00
6.00
6.00
6.005.50
5.50
5.50
5.505.00
5.00
5.00
5.004.50
4.50
4.50
4.504.00
4.00
4.00
4.003.50
3.50
3.50
3.503.00
3.00
3.00
3.002.50
2.50
2.50
2.502.00
2.00
2.00
2.001.50
1.50
1.50
1.501.00
1.00
1.00
1.000.50
0.50
0.50
0.500.00
0.00
0.00
0.00-0.50
-0.50
-0.50
-0.50
4.00 4.00 4.00 4.00
8.19 8.19 8.19 8.19
7.407 7.407 7.407 7.4077.403 7.403 7.403 7.4037.394 7.394 7.394 7.3947.389 7.389 7.389 7.3897.386 7.386 7.386 7.3867.364 7.364 7.364 7.3647.360 7.360 7.360 7.3607.352 7.352 7.352 7.3527.347 7.347 7.347 7.3477.260 7.260 7.260 7.260
3.740 3.740 3.740 3.740
3.453 3.453 3.453 3.453
O
N
O
4ga
CD
Cl 3
, 500
MH
z
Cl
~ S73 ~
PPM
PPM
PPM
PPM
200
200
200
200
190
190
190
190
180
180
180
180
170
170
170
170
160
160
160
160
150
150
150
150
140
140
140
140
130
130
130
130
120
120
120
120
110
110
110
110
100
100
100
100
90
9090
90
80
8080
80
70
7070
70
60
6060
60
50
5050
50
40
4040
40
30
3030
30
20
2020
20
10
1010
10
0 000
169.321 169.321 169.321 169.321
135.995 135.995 135.995 135.995133.591 133.591 133.591 133.591128.841 128.841 128.841 128.841128.640 128.640 128.640 128.640
77.258 77.258 77.258 77.258 77.000 77.000 77.000 77.000 76.752 76.752 76.752 76.752
66.804 66.804 66.804 66.804
48.175 48.175 48.175 48.175
42.605 42.605 42.605 42.605
O
N
O
4ga
CD
Cl 3
, 125
MH
z
Cl
~ S74 ~
PPM
PPM
PPM
PPM
10.00
10.00
10.00
10.009.50
9.50
9.50
9.509.00
9.00
9.00
9.008.50
8.50
8.50
8.508.00
8.00
8.00
8.007.50
7.50
7.50
7.507.00
7.00
7.00
7.006.50
6.50
6.50
6.506.00
6.00
6.00
6.005.50
5.50
5.50
5.505.00
5.00
5.00
5.004.50
4.50
4.50
4.504.00
4.00
4.00
4.003.50
3.50
3.50
3.503.00
3.00
3.00
3.002.50
2.50
2.50
2.502.00
2.00
2.00
2.001.50
1.50
1.50
1.501.00
1.00
1.00
1.000.50
0.50
0.50
0.500.00
0.00
0.00
0.00
2.00 2.00 2.00 2.001.99 1.99 1.99 1.99
3.03 3.03 3.03 3.034.03 4.03 4.03 4.03
2.06 2.06 2.06 2.06
1.88 1.88 1.88 1.88
8.166 8.166 8.166 8.1668.149 8.149 8.149 8.1498.025 8.025 8.025 8.0258.008 8.008 8.008 8.008
7.260 7.260 7.260 7.260
3.949 3.949 3.949 3.9493.791 3.791 3.791 3.7913.666 3.666 3.666 3.6663.656 3.656 3.656 3.6563.647 3.647 3.647 3.6473.393 3.393 3.393 3.3933.382 3.382 3.382 3.3823.373 3.373 3.373 3.373
O
N
O
O
3ha
CD
Cl 3
, 500
MH
z
MeO
2C
~ S75 ~
PPM
PPM
PPM
PPM
200
200
200
200
190
190
190
190
180
180
180
180
170
170
170
170
160
160
160
160
150
150
150
150
140
140
140
140
130
130
130
130
120
120
120
120
110
110
110
110
100
100
100
100
90
9090
90
80
8080
80
70
7070
70
60
6060
60
50
5050
50
40
4040
40
30
3030
30
20
2020
20
10
1010
10
0 000
190.210 190.210 190.210 190.210
165.792 165.792 165.792 165.792164.762 164.762 164.762 164.762
136.080 136.080 136.080 136.080135.327 135.327 135.327 135.327130.119 130.119 130.119 130.119129.547 129.547 129.547 129.547
77.258 77.258 77.258 77.258 77.000 77.000 77.000 77.000 76.752 76.752 76.752 76.752
66.680 66.680 66.680 66.680 66.594 66.594 66.594 66.594
52.611 52.611 52.611 52.611
46.229 46.229 46.229 46.229
41.699 41.699 41.699 41.699
O
N
O
O
3ha
CD
Cl 3
, 125
MH
z
MeO
2C
~ S76 ~
PPM
PPM
PPM
PPM
10.00
10.00
10.00
10.009.50
9.50
9.50
9.509.00
9.00
9.00
9.008.50
8.50
8.50
8.508.00
8.00
8.00
8.007.50
7.50
7.50
7.507.00
7.00
7.00
7.006.50
6.50
6.50
6.506.00
6.00
6.00
6.005.50
5.50
5.50
5.505.00
5.00
5.00
5.004.50
4.50
4.50
4.504.00
4.00
4.00
4.003.50
3.50
3.50
3.503.00
3.00
3.00
3.002.50
2.50
2.50
2.502.00
2.00
2.00
2.001.50
1.50
1.50
1.501.00
1.00
1.00
1.000.50
0.50
0.50
0.500.00
0.00
0.00
0.00-0.50
-0.50
-0.50
-0.50
2.00 2.00 2.00 2.00
1.97 1.97 1.97 1.97
11.09 11.09 11.09 11.09
8.087 8.087 8.087 8.0878.071 8.071 8.071 8.071
7.470 7.470 7.470 7.4707.454 7.454 7.454 7.4547.260 7.260 7.260 7.260
3.925 3.925 3.925 3.9253.776 3.776 3.776 3.7763.608 3.608 3.608 3.608
3.385 3.385 3.385 3.385
O
N
O
4ha
CD
Cl 3
, 500
MH
z
MeO
2C
~ S77 ~
PPM
PPM
PPM
PPM
200
200
200
200
190
190
190
190
180
180
180
180
170
170
170
170
160
160
160
160
150
150
150
150
140
140
140
140
130
130
130
130
120
120
120
120
110
110
110
110
100
100
100
100
90
9090
90
80
8080
80
70
7070
70
60
6060
60
50
5050
50
40
4040
40
30
3030
30
20
2020
20
10
1010
10
0 000
169.331 169.331 169.331 169.331166.212 166.212 166.212 166.212
139.524 139.524 139.524 139.524
131.292 131.292 131.292 131.292129.852 129.852 129.852 129.852127.019 127.019 127.019 127.019
77.248 77.248 77.248 77.248 77.000 77.000 77.000 77.000 76.742 76.742 76.742 76.742
66.775 66.775 66.775 66.775
52.334 52.334 52.334 52.334
48.023 48.023 48.023 48.023
42.471 42.471 42.471 42.471
O
N
O
4ha
CD
Cl 3
, 125
MH
z
MeO
2C
~ S78 ~
PPM
PPM
PPM
PPM
10.00
10.00
10.00
10.009.50
9.50
9.50
9.509.00
9.00
9.00
9.008.50
8.50
8.50
8.508.00
8.00
8.00
8.007.50
7.50
7.50
7.507.00
7.00
7.00
7.006.50
6.50
6.50
6.506.00
6.00
6.00
6.005.50
5.50
5.50
5.505.00
5.00
5.00
5.004.50
4.50
4.50
4.504.00
4.00
4.00
4.003.50
3.50
3.50
3.503.00
3.00
3.00
3.002.50
2.50
2.50
2.502.00
2.00
2.00
2.001.50
1.50
1.50
1.501.00
1.00
1.00
1.000.50
0.50
0.50
0.500.00
0.00
0.00
0.00-0.50
-0.50
-0.50
-0.50
0.92 0.92 0.92 0.92
1.00 1.00 1.00 1.00
1.02 1.02 1.02 1.02
4.16 4.16 4.16 4.162.09 2.09 2.09 2.09
2.03 2.03 2.03 2.03
6.43 6.43 6.43 6.43
8.525 8.525 8.525 8.5258.521 8.521 8.521 8.5218.216 8.216 8.216 8.2168.212 8.212 8.212 8.2128.199 8.199 8.199 8.1998.195 8.195 8.195 8.195
7.260 7.260 7.260 7.2607.109 7.109 7.109 7.1097.092 7.092 7.092 7.092
3.817 3.817 3.817 3.8173.814 3.814 3.814 3.8143.811 3.811 3.811 3.8113.806 3.806 3.806 3.8063.803 3.803 3.803 3.8033.797 3.797 3.797 3.7973.788 3.788 3.788 3.7883.782 3.782 3.782 3.7823.774 3.774 3.774 3.7743.767 3.767 3.767 3.7673.686 3.686 3.686 3.6863.675 3.675 3.675 3.6753.666 3.666 3.666 3.6663.415 3.415 3.415 3.4153.405 3.405 3.405 3.4053.396 3.396 3.396 3.3962.945 2.945 2.945 2.945
1.763 1.763 1.763 1.763
O
N
O
O
3ia
CD
Cl 3
, 500
MH
z
O
OO
~ S79 ~
PPM
PPM
PPM
PPM
200
200
200
200
190
190
190
190
180
180
180
180
170
170
170
170
160
160
160
160
150
150
150
150
140
140
140
140
130
130
130
130
120
120
120
120
110
110
110
110
100
100
100
100
90
9090
90
80
8080
80
70
7070
70
60
6060
60
50
5050
50
40
4040
40
30
3030
30
20
2020
20
10
1010
10
0 000
188.379 188.379 188.379 188.379
164.571 164.571 164.571 164.571160.613 160.613 160.613 160.613159.583 159.583 159.583 159.583
136.891 136.891 136.891 136.891
132.771 132.771 132.771 132.771
128.020 128.020 128.020 128.020
118.396 118.396 118.396 118.396
113.427 113.427 113.427 113.427
107.351 107.351 107.351 107.351
77.258 77.258 77.258 77.258 77.000 77.000 77.000 77.000 76.742 76.742 76.742 76.742
66.699 66.699 66.699 66.699 66.603 66.603 66.603 66.603
46.306 46.306 46.306 46.306
41.785 41.785 41.785 41.785
25.894 25.894 25.894 25.894
O
N
O
O
3ia
CD
Cl 3
, 125
MH
z
O
OO
~ S80 ~
PPM
PPM
PPM
PPM
10.00
10.00
10.00
10.009.50
9.50
9.50
9.509.00
9.00
9.00
9.008.50
8.50
8.50
8.508.00
8.00
8.00
8.007.50
7.50
7.50
7.507.00
7.00
7.00
7.006.50
6.50
6.50
6.506.00
6.00
6.00
6.005.50
5.50
5.50
5.505.00
5.00
5.00
5.004.50
4.50
4.50
4.504.00
4.00
4.00
4.003.50
3.50
3.50
3.503.00
3.00
3.00
3.002.50
2.50
2.50
2.502.00
2.00
2.00
2.001.50
1.50
1.50
1.501.00
1.00
1.00
1.000.50
0.50
0.50
0.500.00
0.00
0.00
0.00-0.50
-0.50
-0.50
-0.50
1.00 1.00 1.00 1.00
1.05 1.05 1.05 1.05
1.03 1.03 1.03 1.03
8.13 8.13 8.13 8.13
6.26 6.26 6.26 6.26
7.980 7.980 7.980 7.980
7.657 7.657 7.657 7.6577.640 7.640 7.640 7.640
7.260 7.260 7.260 7.2607.020 7.020 7.020 7.0207.003 7.003 7.003 7.003
3.688 3.688 3.688 3.688
1.724 1.724 1.724 1.724
N
O 4ia
CD
Cl 3
, 500
MH
z
O
OO
O
~ S81 ~
PPM
PPM
PPM
PPM
200
200
200
200
190
190
190
190
180
180
180
180
170
170
170
170
160
160
160
160
150
150
150
150
140
140
140
140
130
130
130
130
120
120
120
120
110
110
110
110
100
100
100
100
90
9090
90
80
8080
80
70
7070
70
60
6060
60
50
5050
50
40
4040
40
30
3030
30
20
2020
20
10
1010
10
0 000
168.482 168.482 168.482 168.482
160.155 160.155 160.155 160.155156.988 156.988 156.988 156.988
135.747 135.747 135.747 135.747
129.594 129.594 129.594 129.594128.545 128.545 128.545 128.545
117.805 117.805 117.805 117.805
113.045 113.045 113.045 113.045
106.836 106.836 106.836 106.836
77.248 77.248 77.248 77.248 77.000 77.000 77.000 77.000 76.742 76.742 76.742 76.742
66.699 66.699 66.699 66.699
48.347 48.347 48.347 48.347
42.776 42.776 42.776 42.776
25.732 25.732 25.732 25.732
N
O 4ia
CD
Cl 3
, 125
MH
z
O
OO
O
~ S82 ~
PPM
PPM
PPM
PPM
10.00
10.00
10.00
10.009.50
9.50
9.50
9.509.00
9.00
9.00
9.008.50
8.50
8.50
8.508.00
8.00
8.00
8.007.50
7.50
7.50
7.507.00
7.00
7.00
7.006.50
6.50
6.50
6.506.00
6.00
6.00
6.005.50
5.50
5.50
5.505.00
5.00
5.00
5.004.50
4.50
4.50
4.504.00
4.00
4.00
4.003.50
3.50
3.50
3.503.00
3.00
3.00
3.002.50
2.50
2.50
2.502.00
2.00
2.00
2.001.50
1.50
1.50
1.501.00
1.00
1.00
1.000.50
0.50
0.50
0.500.00
0.00
0.00
0.00-0.50
-0.50
-0.50
-0.50
0.93 0.93 0.93 0.93
1.00 1.00 1.00 1.000.99 0.99 0.99 0.99
4.28 4.28 4.28 4.282.17 2.17 2.17 2.172.12 2.12 2.12 2.12
8.235 8.235 8.235 8.2358.232 8.232 8.232 8.2328.229 8.229 8.229 8.2298.227 8.227 8.227 8.2277.575 7.575 7.575 7.5757.573 7.573 7.573 7.5737.565 7.565 7.565 7.5657.562 7.562 7.562 7.5627.373 7.373 7.373 7.3737.368 7.368 7.368 7.3687.363 7.363 7.363 7.3637.357 7.357 7.357 7.3577.260 7.260 7.260 7.260
3.773 3.773 3.773 3.7733.769 3.769 3.769 3.7693.765 3.765 3.765 3.7653.761 3.761 3.761 3.7613.758 3.758 3.758 3.7583.752 3.752 3.752 3.7523.740 3.740 3.740 3.7403.733 3.733 3.733 3.7333.730 3.730 3.730 3.7303.726 3.726 3.726 3.7263.722 3.722 3.722 3.7223.719 3.719 3.719 3.7193.657 3.657 3.657 3.6573.654 3.654 3.654 3.6543.648 3.648 3.648 3.6483.638 3.638 3.638 3.6383.434 3.434 3.434 3.4343.423 3.423 3.423 3.4233.414 3.414 3.414 3.414
O
N
O
O
3ja
CD
Cl 3
, 500
MH
z
S
~ S83 ~
PPM
PPM
PPM
PPM
190.0
190.0
190.0
190.0
180.0
180.0
180.0
180.0
170.0
170.0
170.0
170.0
160.0
160.0
160.0
160.0
150.0
150.0
150.0
150.0
140.0
140.0
140.0
140.0
130.0
130.0
130.0
130.0
120.0
120.0
120.0
120.0
110.0
110.0
110.0
110.0
100.0
100.0
100.0
100.0
90.0
90.0
90.0
90.0
80.0
80.0
80.0
80.0
70.0
70.0
70.0
70.0
60.0
60.0
60.0
60.0
50.0
50.0
50.0
50.0
40.0
40.0
40.0
40.0
30.0
30.0
30.0
30.0
20.0
20.0
20.0
20.0
10.0
10.0
10.0
10.0
184.253 184.253 184.253 184.253
165.071 165.071 165.071 165.071
138.420 138.420 138.420 138.420136.684 136.684 136.684 136.684
127.250 127.250 127.250 127.250126.849 126.849 126.849 126.849
77.258 77.258 77.258 77.258 77.000 77.000 77.000 77.000 76.742 76.742 76.742 76.742
66.727 66.727 66.727 66.727 66.555 66.555 66.555 66.555
46.257 46.257 46.257 46.257
41.669 41.669 41.669 41.669
O
N
O
O
3ja
CD
Cl 3
, 125
MH
z
S
~ S84 ~
PPM
PPM
PPM
PPM
10.00
10.00
10.00
10.009.50
9.50
9.50
9.509.00
9.00
9.00
9.008.50
8.50
8.50
8.508.00
8.00
8.00
8.007.50
7.50
7.50
7.507.00
7.00
7.00
7.006.50
6.50
6.50
6.506.00
6.00
6.00
6.005.50
5.50
5.50
5.505.00
5.00
5.00
5.004.50
4.50
4.50
4.504.00
4.00
4.00
4.003.50
3.50
3.50
3.503.00
3.00
3.00
3.002.50
2.50
2.50
2.502.00
2.00
2.00
2.001.50
1.50
1.50
1.501.00
1.00
1.00
1.000.50
0.50
0.50
0.500.00
0.00
0.00
0.00-0.50
-0.50
-0.50
-0.50
1.00 1.00 1.00 1.00
1.03 1.03 1.03 1.031.01 1.01 1.01 1.01
9.05 9.05 9.05 9.05
7.525 7.525 7.525 7.5257.522 7.522 7.522 7.5227.519 7.519 7.519 7.5197.517 7.517 7.517 7.5177.350 7.350 7.350 7.3507.345 7.345 7.345 7.3457.341 7.341 7.341 7.3417.334 7.334 7.334 7.3347.260 7.260 7.260 7.2607.181 7.181 7.181 7.1817.179 7.179 7.179 7.1797.171 7.171 7.171 7.1717.168 7.168 7.168 7.168
3.694 3.694 3.694 3.694
O
N
O
4ja
CD
Cl 3
, 500
MH
z
S
~ S85 ~
PPM
PPM
PPM
PPM
200
200
200
200
190
190
190
190
180
180
180
180
170
170
170
170
160
160
160
160
150
150
150
150
140
140
140
140
130
130
130
130
120
120
120
120
110
110
110
110
100
100
100
100
90
9090
90
80
8080
80
70
7070
70
60
6060
60
50
5050
50
40
4040
40
30
3030
30
20
2020
20
10
1010
10
0 000
165.735 165.735 165.735 165.735
135.851 135.851 135.851 135.851
126.905 126.905 126.905 126.905126.628 126.628 126.628 126.628126.103 126.103 126.103 126.103
77.258 77.258 77.258 77.258 77.000 77.000 77.000 77.000 76.752 76.752 76.752 76.752
66.823 66.823 66.823 66.823
47.908 47.908 47.908 47.908
42.681 42.681 42.681 42.681
O
N
O
4ja
CD
Cl 3
, 125
MH
z
S
~ S86 ~
PPM
PPM
PPM
PPM
10.00
10.00
10.00
10.009.50
9.50
9.50
9.509.00
9.00
9.00
9.008.50
8.50
8.50
8.508.00
8.00
8.00
8.007.50
7.50
7.50
7.507.00
7.00
7.00
7.006.50
6.50
6.50
6.506.00
6.00
6.00
6.005.50
5.50
5.50
5.505.00
5.00
5.00
5.004.50
4.50
4.50
4.504.00
4.00
4.00
4.003.50
3.50
3.50
3.503.00
3.00
3.00
3.002.50
2.50
2.50
2.502.00
2.00
2.00
2.001.50
1.50
1.50
1.501.00
1.00
1.00
1.000.50
0.50
0.50
0.500.00
0.00
0.00
0.00-0.50
-0.50
-0.50
-0.50
1.00 1.00 1.00 1.00
1.04 1.04 1.04 1.04
1.04 1.04 1.04 1.04
1.01 1.01 1.01 1.01
1.02 1.02 1.02 1.02
7.34 7.34 7.34 7.34
2.14 2.14 2.14 2.14
2.08 2.08 2.08 2.08
8.212 8.212 8.212 8.2128.209 8.209 8.209 8.2097.834 7.834 7.834 7.8347.830 7.830 7.830 7.8307.817 7.817 7.817 7.8177.813 7.813 7.813 7.8137.350 7.350 7.350 7.3507.333 7.333 7.333 7.3337.260 7.260 7.260 7.2607.119 7.119 7.119 7.1197.113 7.113 7.113 7.113
6.587 6.587 6.587 6.5876.582 6.582 6.582 6.5826.580 6.580 6.580 6.580
3.780 3.780 3.780 3.7803.775 3.775 3.775 3.7753.634 3.634 3.634 3.6343.607 3.607 3.607 3.6073.602 3.602 3.602 3.6023.598 3.598 3.598 3.5983.587 3.587 3.587 3.5873.368 3.368 3.368 3.3683.358 3.358 3.358 3.3583.349 3.349 3.349 3.349
O
N
O
O
3ka
CD
Cl 3
, 500
MH
z
NM
e
~ S87 ~
PPM
PPM
PPM
PPM
200
200
200
200
190
190
190
190
180
180
180
180
170
170
170
170
160
160
160
160
150
150
150
150
140
140
140
140
130
130
130
130
120
120
120
120
110
110
110
110
100
100
100
100
90
9090
90
80
8080
80
70
7070
70
60
6060
60
50
5050
50
40
4040
40
30
3030
30
20
2020
20
10
1010
10
0 000
191.517 191.517 191.517 191.517
166.393 166.393 166.393 166.393
139.867 139.867 139.867 139.867
131.006 131.006 131.006 131.006128.011 128.011 128.011 128.011125.264 125.264 125.264 125.264124.835 124.835 124.835 124.835122.097 122.097 122.097 122.097
109.783 109.783 109.783 109.783
103.326 103.326 103.326 103.326
77.248 77.248 77.248 77.248 77.000 77.000 77.000 77.000 76.742 76.742 76.742 76.742
66.575 66.575 66.575 66.575 66.508 66.508 66.508 66.508
46.153 46.153 46.153 46.153
41.308 41.308 41.308 41.308
32.942 32.942 32.942 32.942
O
N
O
O
3ka
CD
Cl 3
, 125
MH
z
NM
e
~ S88 ~
PPM
PPM
PPM
PPM
10.00
10.00
10.00
10.009.50
9.50
9.50
9.509.00
9.00
9.00
9.008.50
8.50
8.50
8.508.00
8.00
8.00
8.007.50
7.50
7.50
7.507.00
7.00
7.00
7.006.50
6.50
6.50
6.506.00
6.00
6.00
6.005.50
5.50
5.50
5.505.00
5.00
5.00
5.004.50
4.50
4.50
4.504.00
4.00
4.00
4.003.50
3.50
3.50
3.503.00
3.00
3.00
3.002.50
2.50
2.50
2.502.00
2.00
2.00
2.001.50
1.50
1.50
1.501.00
1.00
1.00
1.000.50
0.50
0.50
0.500.00
0.00
0.00
0.00-0.50
-0.50
-0.50
-0.50
1.01 1.01 1.01 1.01
2.10 2.10 2.10 2.10
1.00 1.00 1.00 1.00
1.02 1.02 1.02 1.02
11.79 11.79 11.79 11.79
7.697 7.697 7.697 7.6977.316 7.316 7.316 7.3167.300 7.300 7.300 7.3007.290 7.290 7.290 7.2907.287 7.287 7.287 7.2877.274 7.274 7.274 7.2747.270 7.270 7.270 7.2707.260 7.260 7.260 7.2607.082 7.082 7.082 7.0827.077 7.077 7.077 7.0776.503 6.503 6.503 6.5036.496 6.496 6.496 6.496
3.763 3.763 3.763 3.7633.679 3.679 3.679 3.679
N
O 4ka
CD
Cl 3
, 500
MH
z
NM
e
O
~ S89 ~
PPM
PPM
PPM
PPM
200
200
200
200
190
190
190
190
180
180
180
180
170
170
170
170
160
160
160
160
150
150
150
150
140
140
140
140
130
130
130
130
120
120
120
120
110
110
110
110
100
100
100
100
90
9090
90
80
8080
80
70
7070
70
60
6060
60
50
5050
50
40
4040
40
30
3030
30
20
2020
20
10
1010
10
0 000
171.744 171.744 171.744 171.744
137.072 137.072 137.072 137.072
129.938 129.938 129.938 129.938127.687 127.687 127.687 127.687125.951 125.951 125.951 125.951120.857 120.857 120.857 120.857120.390 120.390 120.390 120.390
109.011 109.011 109.011 109.011
101.523 101.523 101.523 101.523
77.258 77.258 77.258 77.258 77.000 77.000 77.000 77.000 76.742 76.742 76.742 76.742
66.804 66.804 66.804 66.804
48.223 48.223 48.223 48.223
43.015 43.015 43.015 43.015
32.761 32.761 32.761 32.761
N
O 4ka
CD
Cl 3
, 125
MH
z
NM
e
O
~ S90 ~
PPM
PPM
PPM
PPM
10.00
10.00
10.00
10.009.50
9.50
9.50
9.509.00
9.00
9.00
9.008.50
8.50
8.50
8.508.00
8.00
8.00
8.007.50
7.50
7.50
7.507.00
7.00
7.00
7.006.50
6.50
6.50
6.506.00
6.00
6.00
6.005.50
5.50
5.50
5.505.00
5.00
5.00
5.004.50
4.50
4.50
4.504.00
4.00
4.00
4.003.50
3.50
3.50
3.503.00
3.00
3.00
3.002.50
2.50
2.50
2.502.00
2.00
2.00
2.001.50
1.50
1.50
1.501.00
1.00
1.00
1.000.50
0.50
0.50
0.500.00
0.00
0.00
0.00-0.50
-0.50
-0.50
-0.50
1.00 1.00 1.00 1.00
1.02 1.02 1.02 1.021.03 1.03 1.03 1.03 1.02 1.02 1.02 1.020.99 0.99 0.99 0.99
1.03 1.03 1.03 1.03
4.14 4.14 4.14 4.14
2.11 2.11 2.11 2.11
2.05 2.05 2.05 2.05
9.024 9.024 9.024 9.0249.020 9.020 9.020 9.0209.015 9.015 9.015 9.0159.012 9.012 9.012 9.0128.448 8.448 8.448 8.4488.444 8.444 8.444 8.4448.279 8.279 8.279 8.2798.277 8.277 8.277 8.2778.263 8.263 8.263 8.2638.260 8.260 8.260 8.2608.237 8.237 8.237 8.2378.233 8.233 8.233 8.2338.220 8.220 8.220 8.2208.216 8.216 8.216 8.2168.183 8.183 8.183 8.1838.166 8.166 8.166 8.1667.497 7.497 7.497 7.4977.489 7.489 7.489 7.4897.481 7.481 7.481 7.4817.473 7.473 7.473 7.4737.260 7.260 7.260 7.260
3.806 3.806 3.806 3.8063.657 3.657 3.657 3.6573.648 3.648 3.648 3.6483.638 3.638 3.638 3.6383.417 3.417 3.417 3.4173.406 3.406 3.406 3.4063.397 3.397 3.397 3.397
ON
O
O
3la
CD
Cl 3
, 500
MH
z
N
~ S91 ~
PPM
PPM
PPM
PPM
200
200
200
200
190
190
190
190
180
180
180
180
170
170
170
170
160
160
160
160
150
150
150
150
140
140
140
140
130
130
130
130
120
120
120
120
110
110
110
110
100
100
100
100
90
9090
90
80
8080
80
70
7070
70
60
6060
60
50
5050
50
40
4040
40
30
3030
30
20
2020
20
10
1010
10
0 000
190.258 190.258 190.258 190.258
165.001 165.001 165.001 165.001
153.412 153.412 153.412 153.412150.655 150.655 150.655 150.655
137.683 137.683 137.683 137.683132.637 132.637 132.637 132.637130.748 130.748 130.748 130.748127.410 127.410 127.410 127.410127.372 127.372 127.372 127.372122.259 122.259 122.259 122.259
77.258 77.258 77.258 77.258 77.000 77.000 77.000 77.000 76.742 76.742 76.742 76.742
66.651 66.651 66.651 66.651 66.565 66.565 66.565 66.565
46.268 46.268 46.268 46.268
41.689 41.689 41.689 41.689
ON
O
O
3la
CD
Cl 3
, 125
MH
z
N
~ S92 ~
PPM
PPM
PPM
PPM
10.00
10.00
10.00
10.009.50
9.50
9.50
9.509.00
9.00
9.00
9.008.50
8.50
8.50
8.508.00
8.00
8.00
8.007.50
7.50
7.50
7.507.00
7.00
7.00
7.006.50
6.50
6.50
6.506.00
6.00
6.00
6.005.50
5.50
5.50
5.505.00
5.00
5.00
5.004.50
4.50
4.50
4.504.00
4.00
4.00
4.003.50
3.50
3.50
3.503.00
3.00
3.00
3.002.50
2.50
2.50
2.502.00
2.00
2.00
2.001.50
1.50
1.50
1.501.00
1.00
1.00
1.000.50
0.50
0.50
0.500.00
0.00
0.00
0.00-0.50
-0.50
-0.50
-0.50
1.00 1.00 1.00 1.00
2.17 2.17 2.17 2.17
1.07 1.07 1.07 1.07
1.11 1.11 1.11 1.11
1.06 1.06 1.06 1.06
8.93 8.93 8.93 8.93
8.989 8.989 8.989 8.989
8.214 8.214 8.214 8.2148.198 8.198 8.198 8.1988.169 8.169 8.169 8.1698.152 8.152 8.152 8.1527.930 7.930 7.930 7.9307.736 7.736 7.736 7.7367.733 7.733 7.733 7.7337.719 7.719 7.719 7.7197.716 7.716 7.716 7.7167.484 7.484 7.484 7.4847.476 7.476 7.476 7.4767.260 7.260 7.260 7.260
3.819 3.819 3.819 3.8193.660 3.660 3.660 3.6603.499 3.499 3.499 3.499
N
O 4la
CD
Cl 3
, 500
MH
zON
~ S93 ~
PPM
PPM
PPM
PPM
200
200
200
200
190
190
190
190
180
180
180
180
170
170
170
170
160
160
160
160
150
150
150
150
140
140
140
140
130
130
130
130
120
120
120
120
110
110
110
110
100
100
100
100
90
9090
90
80
8080
80
70
7070
70
60
6060
60
50
5050
50
40
4040
40
30
3030
30
20
2020
20
10
1010
10
0 000
169.674 169.674 169.674 169.674
151.647 151.647 151.647 151.647148.404 148.404 148.404 148.404
136.471 136.471 136.471 136.471133.419 133.419 133.419 133.419130.033 130.033 130.033 130.033127.782 127.782 127.782 127.782127.095 127.095 127.095 127.095121.964 121.964 121.964 121.964
77.258 77.258 77.258 77.258 77.000 77.000 77.000 77.000 76.742 76.742 76.742 76.742
66.870 66.870 66.870 66.870
48.318 48.318 48.318 48.318
42.662 42.662 42.662 42.662
N
O 4la
CD
Cl 3
, 12
5 M
HzO
N
~ S94 ~
PPM
PPM
PPM
PPM
10.0
10.0
10.0
10.0
9.59.59.59.5
9.09.09.09.0
8.58.58.58.5
8.08.08.08.0
7.57.57.57.5
7.07.07.07.0
6.56.56.56.5
6.06.06.06.0
5.55.55.55.5
5.05.05.05.0
4.54.54.54.5
4.04.04.04.0
3.53.53.53.5
3.03.03.03.0
2.52.52.52.5
2.02.02.02.0
1.51.51.51.5
1.01.01.01.0
0.50.50.50.5
0.00.00.00.0
-0.5
-0.5
-0.5
-0.5
1.00 1.00 1.00 1.00
4.08 4.08 4.08 4.08
7.15 7.15 7.15 7.15
8.29 8.29 8.29 8.29
8.453 8.453 8.453 8.4538.006 8.006 8.006 8.0067.984 7.984 7.984 7.9847.968 7.968 7.968 7.9687.906 7.906 7.906 7.9067.890 7.890 7.890 7.8907.661 7.661 7.661 7.6617.646 7.646 7.646 7.6467.602 7.602 7.602 7.6027.589 7.589 7.589 7.5897.409 7.409 7.409 7.4097.260 7.260 7.260 7.260
3.818 3.818 3.818 3.818
3.627 3.627 3.627 3.6273.465 3.465 3.465 3.465
ON
O
NB
z
3ml
CD
Cl 3
, 500
MH
z
~ S95 ~
PPM
PPM
PPM
PPM
200
200
200
200
190
190
190
190
180
180
180
180
170
170
170
170
160
160
160
160
150
150
150
150
140
140
140
140
130
130
130
130
120
120
120
120
110
110
110
110
100
100
100
100
90
9090
90
80
8080
80
70
7070
70
60
6060
60
50
5050
50
40
4040
40
30
3030
30
20
2020
20
10
1010
10
0 000
190.993 190.993 190.993 190.993
170.590 170.590 170.590 170.590
165.649 165.649 165.649 165.649
136.367 136.367 136.367 136.367134.755 134.755 134.755 134.755133.057 133.057 133.057 133.057132.284 132.284 132.284 132.284130.157 130.157 130.157 130.157129.823 129.823 129.823 129.823129.575 129.575 129.575 129.575129.184 129.184 129.184 129.184128.612 128.612 128.612 128.612127.906 127.906 127.906 127.906127.219 127.219 127.219 127.219126.971 126.971 126.971 126.971123.413 123.413 123.413 123.413
77.248 77.248 77.248 77.248 77.000 77.000 77.000 77.000 76.742 76.742 76.742 76.742
47.231 47.231 47.231 47.231 45.886 45.886 45.886 45.886 42.013 42.013 42.013 42.013 41.422 41.422 41.422 41.422
ON
O
NB
z
3ml
CD
Cl 3
, 12
5 M
Hz
~ S96 ~
PPM
PPM
PPM
PPM
10.0
10.0
10.0
10.0
9.59.59.59.5
9.09.09.09.0
8.58.58.58.5
8.08.08.08.0
7.57.57.57.5
7.07.07.07.0
6.56.56.56.5
6.06.06.06.0
5.55.55.55.5
5.05.05.05.0
4.54.54.54.5
4.04.04.04.0
3.53.53.53.5
3.03.03.03.0
2.52.52.52.5
2.02.02.02.0
1.51.51.51.5
1.01.01.01.0
0.50.50.50.5
0.00.00.00.0
-0.5
-0.5
-0.5
-0.5
4.00 4.00 4.00 4.00
7.99 7.99 7.99 7.99
7.97 7.97 7.97 7.97
7.920 7.920 7.920 7.9207.870 7.870 7.870 7.8707.550 7.550 7.550 7.5507.543 7.543 7.543 7.5437.535 7.535 7.535 7.5357.496 7.496 7.496 7.4967.479 7.479 7.479 7.4797.416 7.416 7.416 7.416
3.771 3.771 3.771 3.771
3.576 3.576 3.576 3.576
N
O 4ml
CD
Cl 3
, 500
MH
zNB
z
~ S97 ~
PPM
PPM
PPM
PPM
200
200
200
200
190
190
190
190
180
180
180
180
170
170
170
170
160
160
160
160
150
150
150
150
140
140
140
140
130
130
130
130
120
120
120
120
110
110
110
110
100
100
100
100
90
9090
90
80
8080
80
70
7070
70
60
6060
60
50
5050
50
40
4040
40
30
3030
30
20
2020
20
10
1010
10
0 000
170.638 170.638 170.638 170.638170.609 170.609 170.609 170.609
135.060 135.060 135.060 135.060133.743 133.743 133.743 133.743132.589 132.589 132.589 132.589132.303 132.303 132.303 132.303130.052 130.052 130.052 130.052128.593 128.593 128.593 128.593128.488 128.488 128.488 128.488128.354 128.354 128.354 128.354127.772 127.772 127.772 127.772127.286 127.286 127.286 127.286127.067 127.067 127.067 127.067127.009 127.009 127.009 127.009126.847 126.847 126.847 126.847124.024 124.024 124.024 124.024
77.258 77.258 77.258 77.258 77.000 77.000 77.000 77.000 76.742 76.742 76.742 76.742
47.670 47.670 47.670 47.670
42.462 42.462 42.462 42.462
N
O 4ml
CD
Cl 3
, 125
MH
zNB
z
~ S98 ~