Preparation and Rearrangement of N-Vinyl Nitrones: Synthesis of Spiroisoxazolines and Fluorene-Tethered Isoxazoles Dong-Liang Mo, Donald A. Wink, Laura L. Anderson* Department of Chemistry, University of Illinois, Chicago, 845 W. Taylor St., Chicago, IL 60607-7061
[email protected] Supporting Information:
Contents: I.
General Experimental Information
S-2
II.
Synthesis of N-Vinyl Nitrones 3 via Copper-Mediated Coupling of Fluorenone Oxime 1 and Vinyl Boronic Acids 2 (Scheme 2)
S-3
III.
Synthesis of Spiroisoxazolines 3 via Thermal Rearrangement of Fluorenone S-10 N-Vinyl Nitrones (Table 2)
IV.
Additions and Rearrangements of N-Vinyl Nitrones: Preparation of S-15 Fluorene-Tethered Isoxazoles (Table 3)
V.
Independent Synthesis of Nitrone 3b
S-19
VI.
Mechanistic Discussion
S-21
VII
Three-Dimensional Representations of 3g and 5m as Determined by X-Ray S-22 Crystallography
VIII. References
S-23
IX.
1
H, 13C, and DEPT Data for Fluorene N-Vinyl Nitrones 3
S-24
X.
1
H, 13C, and DEPT Data for Spiroisoxazolines 5
S-69
XI.
1
H, 13C, and DEPT Data for 6-14
S-98
XII.
1
H, 13C, and DEPT Data for 4, S-1, and S-2
S-124
I. General Experimental Information. 1
H NMR and 13C NMR spectra were recorded at ambient temperature using 500 MHz spectrometers. The data are reported as follows: chemical shift in ppm from internal tetramethylsilane on the scale, multiplicity (br = broad, s = singlet, d = doublet, t = triplet, q = quartet, m = multiplet), coupling constants (Hz), and integration. High resolution mass spectra were acquired on an LTQ FT spectrometer, and were obtained by peak matching. Melting points are reported uncorrected. Analytical thin layer chromatography was performed on 0.25 mm extra hard silica gel plates with UV254 fluorescent indicator. Medium pressure liquid chromatography was performed using force flow of the indicated solvent system down columns packed with 60Å (40 – 60 µm) mesh silica gel (SiO2). Unless otherwise noted, all reagents and solvents were obtained from commercial sources and, where appropriate, purified prior to use. THF, CH2Cl2, and toluene were dried by filtration through alumina according to the procedure of Grubbs.1 Vinyl boronic acids were prepared according to literature procedures and used without further purification.2
II. Synthesis of N-Vinyl Nitrones 3 via Copper-Mediated Coupling of Fluorenone Oxime 1 and Vinyl Boronic Acids 2 (Scheme 2).
General Procedure A. A scintillation vial was charged with 9H-fluoren-9-one oxime 1 (1 equiv), vinyl boronic acid 2 (3 equiv), Cu(OAc)2 (2 equiv), and anhydrous Na2SO4 (8-9 equiv). These solids were then diluted with 1,2-dichloroethane (DCE) to form a 0.1 M solution of 9H-fluoren-9-one oxime. Pyridine (10 equiv) was added to the resulting slurry via syringe. The scintillation vial was then capped with a septum pierced with a ventilation needle and the reaction mixture was stirred at 25 ºC for 18 h. DCE and pyridine were then removed under reduced pressure and the crude reaction mixture was purified by medium pressure chromatography (1:20-1:3; ethyl acetate:hexanes) to give 3 as a yellow oil or solid.
Nitrone 3a: General procedure A was employed using the following reagents: 9H-fluoren-9-one oxime 1 (0.059 g; 0.30 mmol), (Z)-hex-3-en-3-ylboronic acid 2a (0.115 g, 0.899 mmol), Cu(OAc)2 (0.108 g, 0.595 mmol), Na2SO4 (0.360 g, 2.53 mmol), and pyridine (0.240 mL, 2.97 mmol). General procedure A afforded 3a as a yellow oil (0.051 g, 61%) after purification using medium pressure chromatography (1:10; ethyl acetate: hexanes). 1H NMR (500 MHz; CDCl3): δ 8.87 (d, J = 7.5 Hz, 1H), 7.70-7.68 (m, 3H), 7.47-7.44 (m, 1H), 7.40 (t, J = 7.5 Hz, 1H), 7.34-7.31 (m, 1H), 7.21-7.18 (m, 1H), 5.75 (t, J = 7.5 Hz, 1H), 2.87-2.83 (m, 1H), 2.60-2.55 (m, 1H), 2.33-2.28 (m, 2H), 1.18 (t, J = 7.5 Hz, 3H), 1.14 (t, J = 7.5 Hz, 3H); 13C NMR (125 MHz, CDCl3): δ 146.6, 144.0, 139.3, 138.7, 132.5, 130.9, 130.8, 129.0, 128.9, 129.8, 127.1, 124.4, 124.2, 120.3, 119.4, 21.8, 20.6, 13.0, 11.6; IR (thin film) 3053, 2966, 2926, 2872, 1606, 1526, 1446, 1336, 1256, 1209, 773, 725 cm-1; HRMS (ESI) m/z calcd. for C19H20NO (M+H)+ 278.1545, found 278.1541.
Nitrone 3b: General procedure A was employed using the following reagents: 9H-fluoren-9-one oxime 1 (0.059 g; 0.30 mmol), cyclohexenylboronic acid 2b (0.113 g, 0.897 mmol), Cu(OAc)2 (0.108 g, 0.595 mmol), Na2SO4 (0.360 g, 2.53 mmol), and pyridine (0.240 mL, 2.97 mmol). General procedure A
afforded 3b as a yellow solid (0.070 g, 84%) after purification using medium pressure chromatography (1:10; ethyl acetate: hexanes). 1H NMR (500 MHz; CDCl3): δ 8.85 (d, J = 8.0 Hz, 1H), 7.68-7.63 (m, 3H), 7.46-7.43 (m, 1H), 7.39 (t, J = 7.5 Hz, 1H), 7.34 (t, J = 7.5 Hz, 1H), 7.25-7.22 (m, 1H), 6.05-6.04 (m, 1H), 2.85-2.81 (m, 1H), 2.40-2.31 (m, 3H), 1.97-1.93 (m, 2H), 1.83-1.80 (m, 2H); 13C NMR (125 MHz, CDCl3): δ 145.3, 143.5, 139.2, 138.8, 132.4, 130.8, 130.6, 128.9, 128.8, 127.4, 127.0, 124.9, 123.9, 120.3, 119.4, 25.4, 24.2, 22.2, 21.2; IR (thin film) 3057, 2934, 2857, 1606, 1529, 1446, 1249, 1209, 769, 725 cm-1; HRMS (ESI) m/z calcd. for C19H18NO (M+H)+ 276.1388, found 276.1396; mp 176-177 ºC. Nitrone 3b (using 1.5 equiv of 2b): General procedure A was employed using the following reagents: 9H-fluoren-9-one oxime 1 (0.059 g; 0.30 mmol), cyclohexenylboronic acid 2b (0.057 g, 0.45 mmol), Cu(OAc)2 (0.108 g, 0.595 mmol), Na2SO4 (0.360 g, 2.53 mmol), and pyridine (0.240 mL, 2.97 mmol). General procedure A afforded 3b as a yellow solid (0.044 g, 53%) after purification using medium pressure chromatography (1:10; ethyl acetate: hexanes).
Nitrone 3c (using 2 equiv of 2c): General procedure A was employed using the following reagents: 9Hfluoren-9-one oxime 1 (0.059 g; 0.30 mmol), Z-2-buten-2-yl boronic acid 2c (0.060 g, 0.60 mmol), Cu(OAc)2 (0.108 g, 0.595 mmol), Na2SO4 (0.360 g, 2.53 mmol), and pyridine (0.240 mL, 2.97 mmol). General procedure A afforded 3c as a yellow oil (0.045 g, 60%) after purification using medium pressure chromatography (1:10; ethyl acetate: hexanes). 1H NMR (500 MHz; CDCl3): δ 8.84 (d, J = 7.5 Hz, 1H), 7.67-7.65 (m, 2H), 7.49 (d, J = 7.5 Hz, 1H), 7.44-7.41 (m, 1H), 7.38 (t, J = 7.5 Hz, 1H), 7.33-7.30 (m, 1H), 7.23 (t, J = 7.5 Hz, 1H), 5.84 (q, J = 6.5 Hz, 1H), 2.22 (s, 3H), 1.86 (d, J = 6.0 Hz, 3H); 13C NMR (125 MHz, CDCl3): δ 143.2, 142.9, 139.2, 138.8, 132.4, 130.8, 130.6, 129.0, 128.8, 127.5, 127.0, 123.8, 123.0, 120.3, 119.5, 13.9, 12.9; IR (thin film) 3053, 2919, 2850, 1606, 1529, 1446, 1253, 1206, 696, 769, 732 cm-1; HRMS (ESI) m/z calcd. for C17H16NO (M+H)+ 250.1232, found 250.1223.
Nitrone 3d: General procedure A was employed using the following reagents: 9H-fluoren-9-one oxime 1 (0.059 g; 0.30 mmol), cyclopentenylboronic acid 2d (0.100 g, 0.893 mmol), Cu(OAc)2 (0.108 g, 0.595 mmol), Na2SO4 (0.360 g, 2.53 mmol), and pyridine (0.240 mL, 2.97 mmol). General procedure A afforded 3d as a yellow solid (0.058 g, 74%) after purification using medium pressure chromatography (1:10; ethyl acetate: hexanes). 1H NMR (500 MHz; CDCl3): δ 8.86 (d, J = 7.0 Hz, 1H), 7.67-7.66 (m, 2H), 7.56 (d, J = 8.0 Hz, 1H), 7.46 (t, J = 7.0 Hz, 1H), 7.39-7.31 (m, 2H), 7.23 (t, J = 7.0 Hz, 1H), 6.04-6.03 (m, 1H), 2.93-2.90 (m, 2H), 2.68-2.65 (m, 2H), 2.27-2.24 (m, 2H); 13C NMR (125 MHz, CDCl3): δ 147.5, 144.8, 139.3, 138.8, 132.2, 131.0, 130.4, 129.2, 128.8, 127.5, 127.4, 127.1, 123.6, 120.4, 119.5, 31.6,
31.1, 22.4; IR (thin film) 2963, 2923, 2854, 1602, 1536, 1442, 1256, 1206, 769, 725 cm-1; HRMS (ESI) m/z calcd. for C18H16NO (M+H)+ 262.1232, found 262.1228; mp 123-124 ºC.
Nitrone 3e: General procedure A was employed using the following reagents: 9H-fluoren-9-one oxime 1 (0.059 g; 0.30 mmol), (Z)-cycloheptenylboronic acid 2e (0.113 g, 0.807 mmol), Cu(OAc)2 (0.108 g, 0.595 mmol), Na2SO4 (0.360 g, 2.53 mmol), and pyridine (0.240 mL, 2.97 mmol). General procedure A afforded 3e as a yellow solid (0.068g, 78%) after purification using medium pressure chromatography (1:10; ethyl acetate: hexanes). 1H NMR (500 MHz; CDCl3): δ 8.84 (d, J = 7.0 Hz, 1H), 7.73 (d, J = 8.5 Hz, 1H), 7.68 (d, J = 7.0 Hz, 2H), 7.45 (t, J = 7.0 Hz, 1H), 7.39 (t, J = 7.0 Hz, 1H), 7.34 (t, J = 7.5 Hz, 1H), 7.25 (t, J = 7.5 Hz, 1H), 6.15-6.12 (m, 1H), 2.81-2.78 (m, 1H), 2.68-2.63 (m, 1H), 2.36-2.33 (m, 2H), 1.97-1.95 (m, 2H), 1.89-1.87 (m, 2H), 1.79-1.72 (m, 2H); 13C NMR (125 MHz, CDCl3): δ 149.2, 142.9, 139.2, 138.8, 132.6, 130.9, 130.8, 129.1, 128.9, 128.8, 127.3, 127.0, 123.9, 120.3, 119.4, 31.6, 30.7, 27.3, 26.7, 26.3; IR (thin film) 3054, 2921, 2852, 1603, 1527, 1442, 1341, 1252, 768, 727 cm-1; HRMS (ESI) m/z calcd. for C20H20NO (M+H)+ 290.1545, found 290.1539; mp 143-144 ºC.
Nitrone 3f: General procedure A was employed using the following reagents: 9H-fluoren-9-one oxime 1 (0.059 g; 0.30 mmol), 3,6-dihydro-2H-pyran-4-ylboronic acid 2f (0.115 g, 0.899 mmol), Cu(OAc)2 (0.108 g, 0.595 mmol), Na2SO4 (0.360 g, 2.53 mmol), and pyridine (0.240 mL, 2.97 mmol). General procedure A afforded 3f as a yellow solid (0.068 g, 81%) after purification using medium pressure chromatography (1:3; ethyl acetate: hexanes). 1H NMR (500 MHz; CDCl3): δ 8.83 (d, J = 7.5 Hz, 1H), 7.71-7.67 (m, 3H), 7.48-7.45 (m, 1H), 7.40-7.33 (m, 2H), 7.27-7.24 (m, 1H), 6.10-6.09 (m, 1H), 4.41-4.37 (m, 2H), 4.234.20 (m, 1H), 3.92-3.91 (m, 1H), 2.90-2.81 (m, 1H), 2.70-2.67 (m, 1H); 13C NMR (125 MHz, CDCl3): δ 144.3, 142.1, 139.3, 139.0, 132.1, 131.2, 130.3, 129.3, 128.8, 127.8, 127.0, 124.1, 123.3, 120.4, 119.5, 64.3, 64.4, 25.7; IR (thin film) 3053, 2930, 2860, 1606, 1533, 1438, 1344, 1256, 1206, 769, 725 cm-1; HRMS (ESI) m/z calcd. for C18H16NO2 (M+H)+ 278.1811, found 278.1173; mp 180-181 ºC.
Nitrone 3g: General procedure A was employed using the following reagents: 9H-fluoren-9-one oxime 1 (0.059 g; 0.30 mmol), 1,4-dioxaspiro[4.5]dec-7-en-8-ylboronic acid 2g (0.165 g, 0.897 mmol), Cu(OAc)2 (0.108 g, 0.595 mmol), Na2SO4 (0.360 g, 2.53 mmol), and pyridine (0.240 mL, 2.97 mmol). General procedure A afforded 3g as a yellow solid (0.073 g, 72%) after purification using medium pressure chromatography (1:3; ethyl acetate: hexanes). 1H NMR (500 MHz; CDCl3): δ 8.84 (d, J = 7.0 Hz, 1H), 7.96 (d, J = 7.5 Hz, 1H), 7.66-7.64 (m, 2H), 7.45-7.42 (m, 1H), 7.38-7.35 (m, 1H), 7.33-7.30 (m, 1H), 7.24-7.21 (m, 1H), 5.92-5.91 (m, 1H), 4.10-4.03 (m, 4H), 2.97-2.93 (m, 1H), 2.67-2.57 (m, 2H), 2.432.39 (m, 1H), 2.08-2.04 (m, 2H); 13C NMR (125 MHz, CDCl3): δ 144.5, 144.3, 139.1, 139.0, 132.3, 131.0, 130.6, 129.0, 128.7, 127.8, 127.0, 124.7, 122.2, 120.1, 119.5, 106.9, 64.8, 64.6, 34.7, 30.7, 24.5; IR (thin film) 3061, 2952, 2883, 1606, 1529, 1449, 1118, 1063, 769, 732 cm-1; HRMS (ESI) m/z calcd. for C21H20NO3 (M+H)+ 334.1443, found 334.1447; mp 195-197 ºC.
Nitrone 3h: General procedure A was employed using the following reagents: 9H-fluoren-9-one oxime 1 (0.059 g; 0.30 mmol), 4-phenylcyclohex-1-enylboronic acid 2h (0.164 g, 0.812 mmol), Cu(OAc)2 (0.108 g, 0.595 mmol), Na2SO4 (0.360 g, 2.53 mmol), and pyridine (0.240 mL, 2.97 mmol). General procedure A afforded 3h as a yellow solid (0.083 g, 78%) after purification using medium pressure chromatography (1:10; ethyl acetate: hexanes). Nitrone 3h was isolated as a mixture of C(vinyl)–N bond rotomers which were only distinguishable by 13C NMR spectroscopy. 1H NMR (500 MHz; CDCl3): δ 8.88 (d, J = 7.0 Hz, 1H), 7.78 (d, J = 7.0 Hz, 1H), 7.72 (t, J = 6.5 Hz, 2H), 7.49 (t, J = 7.0 Hz, 1H), 7.42-7.33 (m, 6H), 7.317.27 (m, 2H), 6.15-6.14 (m, 1H), 2.95-2.07 (m, 2H), 2.64-2.47 (m, 3H), 2.28-2.23 (m, 1H), 2.15-2.12 (m, 1H); 13C NMR (125 MHz, CDCl3) rotomer A: δ 145.3, 139.4, 138.9, 132.4, 131.0, 130.6, 129.1, 128.9, 128.7, 127.5, 127.1, 126.8, 126.7, 124.6, 124.5, 124.0, 123.6, 120.4, 119.5, 39.4, 32.3, 29.6, 26.9; 13C NMR (125 MHz, CDCl3) rotomer B: δ 145.1, 139.3, 138.9, 132.4, 131.0, 130.6, 129.1, 128.9, 128.7, 127.5, 127.1, 126.8, 126.7, 124.6, 124.5, 124.0, 123.6, 120.4, 119.5, 38.6, 32.1, 29.4, 25.7; IR (thin film) 3057, 3022, 2918, 2836, 1603, 1531, 1445, 1245, 699, 679 cm-1; HRMS (ESI) m/z calcd. for C25H22NO (M+H)+ 352.1701, found 352.1711; mp 175-176 ºC.
Nitrone 3i: General procedure A was employed using the following reagents: 9H-fluoren-9-one oxime 1 (0.059 g; 0.30 mmol), 4-tert-butylcyclohex-1-enylboronic acid 2i (0.164 g, 0.901 mmol), Cu(OAc)2 (0.108 g, 0.595 mmol), Na2SO4 (0.360 g, 2.53 mmol), and pyridine (0.240 mL, 2.97 mmol). General procedure A afforded 3i as a yellow solid (0.071 g, 71%) after purification using medium pressure
chromatography (1:10; ethyl acetate: hexanes). Nitrone 3i was a mixture of C(vinyl)–N bond rotomers which were only distinguishable by 13C NMR spectroscopy. 1H NMR (500 MHz; CDCl3): δ 8.84 (d, J = 7.0 Hz, 1H), 7.68-7.76 (m, 3H), 7.45 (t, J = 7.5 Hz, 1H), 7.39 (t, J = 7.5 Hz, 1H), 7.34 (t, J = 7.5 Hz, 1H), 7.26-7.25 (m, 1H), 6.05-6.03 (m, 1H), 2.89-2.86 (m, 1H), 2.43-2.31 (m, 2H), 2.15-2.20 (m, 2H), 1.551.54 (m, 2H), 0.97 (s, 9H); 13C NMR (125 MHz, CDCl3) rotomer A: δ 145.3, 143.9, 139.3, 138.8, 132.4, 130.8, 128.9, 128.8, 127.5, 127.0, 125.2, 124.0, 123.6, 120.3, 119.4, 43.6, 32.4, 27.4, 27.2, 26.2, 23.8; 13C NMR (125 MHz, CDCl3) rotomer B: δ 145.1, 143.3, 139.1, 138.8, 132.4, 130.7, 128.9, 128.8, 127.5, 127.0, 125.1, 124.1, 123.6, 120.3, 119.4, 42.7, 32.2, 27.4, 27.2, 25.9, 23.8; IR (thin film) 3053, 2955, 2868, 1609, 1526, 1446, 1336, 1253, 1209, 776, 728 cm-1; HRMS (ESI) m/z calcd. for C23H26NO (M+H)+ 332.2014, found 332.2019; mp 186-187 ºC.
Nitrone 3j: General procedure A was employed with the following reagents: 9H-fluoren-9-one oxime 1 (0.059 g; 0.30 mmol), 2-phenyl-vinyl boronic acid 2j (0.120 g, 0.811 mmol), Cu(OAc)2 (0.108 g, 0.595 mmol), Na2SO4 (0.360 g, 2.53 mmol), and pyridine (0.240 mL, 2.97 mmol). General procedure A afforded 3i as a yellow oil (0.061 g, 68%) after purification using medium pressure chromatography (1:10; ethyl acetate: hexanes). 1H NMR (500 MHz; CDCl3): δ 8.90 (d, J = 7.5 Hz, 1H), 8.30 (d, J = 13.5 Hz, 1H), 7.90 (d, J = 13.5 Hz, 1H), 7.72-7.66 (m, 3H), 7.61-7.59 (m, 2H), 7.47-7.30 (m, 7H); 13C NMR (125 MHz, CDCl3): δ 145.5, 139.7, 138.8, 133.4, 133.1, 132.7, 131.6, 131.1, 130.2, 129.9, 129.4, 129.2, 129.0, 128.0, 127.8, 127.5, 125.0, 120.9, 119.7; IR (thin film) 3060, 3029, 2924, 2870, 1601, 1509, 1448, 1248, 987, 728 cm-1; HRMS (ESI) m/z calcd. for C21H16NO (M+H)+ 298.1232, found 298.1235.
Nitrone 3k: General procedure A was employed using the following reagents: 9H-fluoren-9-one oxime 1 (0.059 g; 0.30 mmol), 1-hexenylboronic acid 2k (0.115 g, 0.899 mmol), Cu(OAc)2 (0.108 g, 0.595 mmol), Na2SO4 (0.360 g, 2.53 mmol), and pyridine (0.240 mL, 2.97 mmol). General procedure A afforded 3k as a yellow oil (0.072 g, 86%) after purification using medium pressure chromatography (1:10; ethyl acetate: hexanes). 1H NMR (500 MHz; CDCl3): δ 8.85 (d, J = 8.0 Hz, 1H), 7.71-7.59 (m, 4H), 7.53 (t, J = 7.0 Hz, 1H), 7.38-7.35 (m, 2H), 7.31 (t, J = 7.0 Hz, 1H), 7.03-7.00 (m, 1H), 2.41-2.37 (m, 2H), 1.61-1.55 (m, 2H), 1.47-1.43 (m, 2H), 0.98 (t, J = 7.5 Hz, 3H); 13C NMR (125 MHz, CDCl3): δ 144.1, 139.5, 138.7, 134.6, 134.2, 133.1, 130.8, 130.3, 129.2, 128.9, 127.6, 127.3, 124.9, 120.7, 119.6, 30.7, 29.3, 22.3, 13.8; IR (thin film) 3053, 2955, 2924, 2859, 1509, 1452, 1268, 1211, 983, 769, 722 cm-1; HRMS (ESI) m/z calcd. for C19H20NO (M+H)+ 278.1545, found 278.1538. Nitrone 3k (using 1.5 equiv of 2k): General procedure A was employed using the following reagents: 9H-fluoren-9-one oxime 1 (0.059 g; 0.30 mmol), 1-hexenylboronic acid 2k (0.058 g, 0.453 mmol),
Cu(OAc)2 (0.108 g, 0.595 mmol), Na2SO4 (0.360 g, 2.53 mmol), and pyridine (0.240 mL, 2.97 mmol). General procedure A afforded 3b as a yellow solid (0.060 g, 72%) after purification using medium pressure chromatography (1:10; ethyl acetate: hexanes).
Nitrone 3l: General procedure A was employed using the following reagents: 9H-fluoren-9-one oxime 1 (0.059 g; 0.30 mmol), (Z)-1-phenylbut-1-enylboronic acid 2l (0.158 g, 0.898 mmol), Cu(OAc)2 (0.108 g, 0.595 mmol), Na2SO4 (0.360 g, 2.53 mmol), and pyridine (0.240 mL, 2.97 mmol). General procedure A afforded 3l as a yellow solid (0.056 g, 57%) after purification using medium pressure chromatography (1:10; ethyl acetate: hexanes). 1H NMR (500 MHz; CDCl3): δ 8.91 (d, J = 7.5 Hz, 1H), 7.74-7.69 (m, 3H), 7.58 (d, J = 7.5 Hz, 2H), 7.48-7.46 (m, 1H), 7.41-7.31 (m, 5H), 7.21 (t, J = 7.5 Hz, 1H), 6.10 (t, J = 7.5 Hz, 1H), 2.55-2.53 (m, 2H), 1.19 (t, J = 7.5 Hz, 3H); 13C NMR (125 MHz, CDCl3): δ 144.8, 139.3, 139.0, 132.5, 131.8, 131.4, 131.3, 131.1, 131.0, 130.7, 129.1, 128.9, 128.8, 128.7, 127.4, 127.2, 124.4, 120.3, 119.5, 21.8, 13.2; IR (thin film) 3024, 2926, 2860, 1602, 1526, 1496, 1446, 1253, 1030, 728, 689 cm-1; HRMS (ESI) m/z calcd. for C23H20NO (M+H)+ 326.1545, found 326.1553; mp 43-44 ºC.
Nitrone 3m: General procedure A: 9H-fluoren-9-one oxime 1 (0.059 g; 0.30 mmol), (Z)-1-(4nitrophenyl)hex-1-enylboronic acid 2m (0.224 g, 0.899 mmol), Cu(OAc)2 (0.108 g, 0.595 mmol), Na2SO4 (0.360 g, 2.53 mmol), and pyridine (0.240 mL, 2.97 mmol) afforded 3m as a yellow solid (0.067 g, 56%) after purification using medium pressure chromatography (1:10; ethyl acetate: hexanes). 1H NMR (500 MHz; CDCl3): δ 8.86 (d, J = 8.0 Hz, 1H), 8.25 (d, J = 8.0 Hz, 2H), 7.77 (d, J = 8.5 Hz, 2H), 7.70 (d, J = 7.5 Hz, 2H), 7.60 (d, J = 8.0 Hz, 1H), 7.49-7.47 (m, 1H), 7.41-7.38 (m, 1H), 7.36 (t, J = 7.5 Hz, 1H), 7.21 (t, J = 7.5 Hz, 1H), 6.32 (t, J = 7.5 Hz, 1H), 2.54-2.48 (m, 2H), 1.59-1.55 (m, 2H), 1.44-1.40 (m, 2H), 0.94 (t, J = 7.5 Hz, 3H) (The nitroarene is does not have a plane of symmetry according to 1H NMR analysis.); 13C NMR (125 MHz, CDCl3): δ 147.8, 145.3, 143.1, 139.5, 139.1, 138.2, 133.5, 132.2, 131.5, 130.3, 130.2, 129.6, 129.0, 127.5, 127.3, 124.0, 123.9, 120.6, 119.7, 30.7, 28.3, 22.4, 13.8 (The nitroarene appears to have a plane of symmetry by 13C NMR analysis; therefore, we assume that the unsymmetrical resonances must be coincidental.); IR (thin film) 3057, 2959, 2923, 2857, 1598, 1522, 1446, 1348, 1249, 769, 728 cm-1; HRMS (ESI) m/z calcd. for C25H23N2O3 (M+H)+ 399.1709, found 399.1705; mp 69-70 ºC.
Nitrone 3n: General procedure A: 9H-fluoren-9-one oxime 1 (0.059 g; 0.30 mmol), (Z)-1-(4fluorophenyl)hex-1-enylboronic acid 2n (0.200 g, 0.901 mmol), Cu(OAc)2 (0.108 g, 0.595 mmol), Na2SO4 (0.360 g, 2.53 mmol), and pyridine (0.240 mL, 2.97 mmol) afforded 3n as a yellow oil (0.069 g, 61%) after purification using medium pressure chromatography (1:10; ethyl acetate: hexanes). 1H NMR (500 MHz; CDCl3): δ 8.88 (d, J = 7.5 Hz, 1H), 7.70-7.67 (m, 3H), 7.57-7.55 (m, 2H), 7.48-7.45 (m, 1H), 7.40-7.37 (m, 1H), 7.35 (t, J = 7.5 Hz, 1H), 7.21-7.18 (m, 1H), 7.10 (t, J = 8.5 Hz, 2H), 6.12 (t, J = 7.5 Hz, 1H), 2.47-2.41 (m, 2H), 1.53-1.52 (m, 2H), 1.42-1.38 (m, 2H), 0.93 (t, J = 7.5 Hz, 3H); 13C NMR (125 MHz, CDCl3): δ 163.9 (d, J = 248 Hz), 144.7, 144.0, 139.4, 139.0, 132.4, 131.2, 130.7 (d, J = 9.0 Hz), 130.6, 130.2, 129.3, 128.9, 127.9, 127.4, 127.2, 124.2, 120.4, 119.6, 116.0 (d, J = 22 Hz), 30.9, 28.1, 22.5, 13.8; IR (thin film) 3061. 2955, 2926, 2857, 1602, 1529, 1508, 1249, 769, 728 cm-1; HRMS (ESI) m/z calcd. for C25H23FNO (M+H)+ 372.1764, found 372.1760.
Nitrone 3o: General procedure A was employed using the following reagents: 9H-fluoren-9-one oxime 1 (0.059 g; 0.30 mmol), (Z)-1-(4-(trifluoromethyl)phenyl)hex-1-enylboronic acid 2o (0.244 g, 0.897 mmol), Cu(OAc)2 (0.108 g, 0.595 mmol), Na2SO4 (0.360 g, 2.53 mmol), and pyridine (0.240 mL, 2.97 mmol). General procedure A afforded 3o as a yellow solid (0.069 g, 54%) after purification using medium pressure chromatography (1:10; ethyl acetate: hexanes). 1H NMR (500 MHz; CDCl3): δ 8.87 (d, J = 7.5 Hz, 1H), 7.71-7.65 (m, 7H), 7.50-7.47 (m, 1H), 7.41 (t, J = 7.5 Hz, 1H), 7.36 (t, J = 7.5 Hz, 1H), 7.20 (t, J = 7.5 Hz, 1H), 6.24 (t, J = 7.5 Hz, 1H), 2.52-2.48 (m, 2H), 1.58-1.54 (m, 2H), 1.43-1.39 (m, 2H), 0.94 (t, J = 7.5 Hz, 3H); 13C NMR (125 MHz, CDCl3): δ 145.1, 143.7, 139.5, 139.0, 135.4, 132.4 (d, J = 29 Hz), 132.0, 131.3, 130.5, 129.4, 129.1, 129.0, 128.6, 127.5, 127.3, 125.8 (q, J = 3.8 Hz), 124.9 (d, J = 270 Hz), 124.1, 120.5, 119.6, 30.8, 28.2, 22.5, 13.8; IR (thin film) 3057, 2959, 2926, 2864, 1606, 1529, 1321, 1245, 1129, 1067, 728 cm-1; HRMS (ESI) m/z calcd. for C26H23NOF3 (M+H)+ 422.1732, found 422.1723; mp 60-61 ºC.
III. Synthesis of Spiroisoxazolines 3 via Thermal Rearrangement of Fluorenone N-Vinyl Nitrones (Table 2).
General procedure B: A Teflon-sealed reaction flask was charged with a 0.1 M solution of 3 (1.0 equiv) in toluene. The reaction mixture was heated to 140 ºC for 12-36 h. Toluene was removed from the reaction mixture under vacuum and the crude reaction mixture was purified by medium pressure chromatography (1:10-1:3; ethyl acetate:hexanes) to give 5 as a yellow oil or white solid.
Spiroisoxazoline 5a: Spiroisoxazoline 5a was prepared using general procedure B. Nitrone 3a (0.083 g; 0.30 mmol) was dissolved in toluene (3 mL) and heated for 12 h. Solvent removal and purification by medium pressure chromatography (1:5; ethyl acetate: hexanes) afforded 5a as a colorless oil (0.067 g, 81%). 1H NMR (500 MHz; CDCl3): δ 7.63-7.59 (m, 2H), 7.56 (d, J = 7.5 Hz, 1H), 7.43 (d, J = 7.0 Hz, 1H), 7.38-7.36 (m, 2H), 7.32 (t, J = 7.5 Hz, 1H), 7.24 (t, J = 7.5 Hz, 1H), 3.63 (dd, J = 10.0 Hz, 5.0 Hz, 1H), 2.58-2.55 (m, 1H), 2.43-2.39 (m, 1H), 1.70-1.67 (m, 1H), 1.46-1.43 (m, 1H), 1.35 (t, J = 7.5 Hz, 3H), 0.42 (t, J = 7.5 Hz, 3H); 13C NMR (125 MHz, CDCl3): δ 164.0, 146.6, 142.9, 140.4, 140.3, 129.5, 129.4, 128.1, 127.5, 125.3, 123.7, 120.2, 120.0, 94.5, 58.5, 20.8, 20.7, 11.7, 10.8; IR (thin film) 2968, 2934, 2874, 1609, 1445, 1381, 1296, 1211, 863, 762, 730 cm-1; HRMS (ESI) m/z calcd. for C19H20NO (M+H)+ 278.1545, found 278.1537.
Spiroisoxazoline 5b: Spiroisoxazoline 5b was prepared using general procedure B. Nitrone 3b (0.055 g; 0.20 mmol) was dissolved in toluene (2 mL) and heated for 36 h. Solvent removal and purification by medium pressure chromatography (1:5; ethyl acetate: hexanes) afforded 5b as a colorless oil (0.038 g, 70%). 1H NMR (500 MHz; CDCl3): δ 7.62-7.59 (m, 2H), 7.51 (d, J = 7.0 Hz, 1H), 7.45 (d, J = 6.5 Hz, 1H), 7.37-7.35 (m, 2H), 7.32-7.30 (m, 1H), 7.25-7.24 (m, 1H), 3.53-3.50 (m, 1H), 2.99 (d, J = 14.5 Hz, 1H), 2.34-2.29 (m, 1H), 2.10-2.04 (m, 1H), 1.83 (d, J = 13.0 Hz, 1H), 1.51-1.44 (m, 3H), 1.34-1.2 (m, 1H); 13C NMR (125 MHz, CDCl3): δ 160.8, 147.3, 143.5, 140.2, 140.0, 129.3, 129.2, 128.2, 127.3, 126.0, 123.4, 120.2, 119.8, 93.5, 56.5, 28.0, 25.8, 25.4, 24.3; IR (thin film) 3057, 2938, 2860, 1635, 1453, 1303,
1206, 845, 757, 732 cm-1; HRMS (ESI) m/z calcd. for C19H18NO (M+H)+ 276.1388, found 276.1389; mp 176-177 ºC.
Spiroisoxazoline 5c: Spiroisoxazoline 5c was prepared using general procedure B. Nitrone 3c (0.050 g; 0.20 mmol) was dissolved in toluene (2 mL) and heated for 12 h. Solvent removal and purification by medium pressure chromatography (1:5; ethyl acetate: hexanes) afforded 5c as a colorless oil (0.034 g, 69%). 1H NMR (500 MHz; CDCl3): δ 7.62-7.59 (m, 2H), 7.53 (d, J = 8.0 Hz, 1H), 7.42-7.35 (m, 3H), 7.31 (t, J = 7.5 Hz, 1H), 7.25 (t, J = 7.5 Hz, 1H), 3.72 (q, J = 7.0 Hz, 1H), 2.12 (s, 3H), 0.95 (d, J = 7.5 Hz, 3H); 13C NMR (125 MHz, CDCl3): δ 160.5, 146.2, 142.9, 140.4, 140.2, 129.6, 129.5, 128.2, 127.5, 125.6, 123.5, 120.2, 119.9, 95.0, 52.9, 12.3, 12.0; IR (thin film) 3043, 2977, 2915, 1602, 1449, 1383, 1315, 1267, 858, 761, 728 cm-1; HRMS (ESI) m/z calcd. for C17H16NO (M+H)+ 250.1232, found 250.1240.
Spiroisoxazoline 5e: Spiroisoxazoline 5e was prepared using general procedure B. Nitrone 3e (0.043 g; 0.15 mmol) was dissolved in toluene (2 mL) and heated for 36 h. Solvent removal and purification by medium pressure chromatography (1:5; ethyl acetate: hexanes) afforded 5e as a colorless oil (0.032 g, 76%). 1H NMR (500 MHz; CDCl3): δ 7.61 (d, J = 7.5 Hz, 3H), 7.45 (d, J = 7.5 Hz, 1H), 7.40-7.30 (m, 3H), 7.24 (t, J = 7.5 Hz, 1H), 3.75 (d, J = 11.5 Hz, 1H), 3.05 (dd, J = 17 Hz, 5.0 Hz, 1H), 2.57-2.51 (m, 1H), 1.98-1.96 (m, 2H), 1.81-1.78 (m, 1H), 1.59-1.56 (m, 1H), 1.41-1.33 (m, 2H), 1.26-1.14 (m, 2H); 13C NMR (125 MHz, CDCl3): δ 165.4, 145.3, 143.3, 140.8, 140.0, 129.6, 129.5, 128.1, 127.5, 125.2, 123.8, 120.1, 119.9, 95.5, 60.0, 31.1, 29.7, 28.3, 27.3, 25.3; IR (thin film) 3061, 2925, 2852, 1606, 1445, 1312, 1214, 753, 730 cm-1; HRMS (ESI) m/z calcd. for C20H20NO (M+H)+ 290.1545, found 290.1544.
Spiroisoxazoline 5f: Spiroisoxazoline 5f was prepared using general procedure B. Nitrone 3f (0.055 g; 0.20 mmol) was dissolved in toluene (2 mL) and heated for 36 h. Solvent removal and purification by medium pressure chromatography (1:5; ethyl acetate: hexanes) afforded 5f as a white solid (0.041 g, 75%). 1H NMR (500 MHz; CDCl3): δ 7.63-7.60 (m, 2H), 7.54 (d, J = 7.5 Hz, 1H), 7.47 (d, J = 7.5 Hz, 1H), 7.41-7.37 (m, 2H), 7.34 (t, J = 7.5 Hz, 1H), 7.26-7.24 (m, 1H), 4.28 (dd, J = 11.0 Hz, 7.0 Hz, 1H),
3.78-3.70 (m, 2H), 3.56-3.52 (m, 1H), 3.47-3.45 (m, 1H), 2.91 (d, J = 14.0 Hz, 1H), 2.75-2.60 (m, 1H); 13 C NMR (125 MHz, CDCl3): δ 157.2, 146.4, 142.2, 140.1, 139.9, 129.8, 129.7, 128.5, 127.5, 125.6, 123.6, 120.5, 120.3, 91.9, 68.8, 67.0, 54.5, 27.0; IR (thin film) 3068, 2966, 2919, 2857, 1606, 1453, 1278, 1220, 1089, 845, 761, 732 cm-1; HRMS (ESI) m/z calcd. for C18H16NO2 (M+H)+ 278.1181, found 278.1188; mp 183-184 ºC.
Spiroisoxazoline 5g: Spiroisoxazoline 5g was prepared using general procedure B. Nitrone 3g (0.066 g; 0.20 mmol) was dissolved in toluene (2 mL) and heated for 36 h. Solvent removal and purification by medium pressure chromatography (1:3; ethyl acetate: hexanes) afforded 5g as a white solid (0.032 g, 49%). 1H NMR (500 MHz; CDCl3): δ 7.62-7.58 (m, 2H), 7.53 (d, J = 7.5 Hz, 1H), 7.43 (d, J = 7.5 Hz, 1H), 7.38-7.36 (m, 2H), 7.32 (t, J = 7.5 Hz, 1H), 7.25-7.21 (m, 1H), 4.05-3.81 (m, 5H), 2.98-2.94 (m, 1H), 2.69-2.63 (m, 1H), 1.99-1.97 (m, 1H), 1.86-1.81 (m, 2H), 1.49-1.45 (m, 1H); 13C NMR (125 MHz, CDCl3): δ 159.2, 146.8, 143.0, 140.1, 139.9, 129.6, 129.5, 128.3, 127.6, 125.7, 123.7, 120.3, 119.8, 108.3, 93.7, 64.7, 64.6, 54.3, 35.8, 33.4, 22.3; IR (thin film) 3051, 2963, 2884, 1442, 1274, 1116, 1072, 1044, 758, 730 cm-1; HRMS (ESI) m/z calcd. for C21H20NO3 (M+H)+ 334.1443, found 334.1442; mp 169-170 ºC.
Spiroisoxazoline 5l: Spiroisoxazoline 5l was prepared using general procedure B. Nitrone 3l (0.065 g; 0.20 mmol) was dissolved in toluene (2 mL) and heated for 12 h. Solvent removal and purification by medium pressure chromatography (1:5; ethyl acetate: hexanes) afforded 5l as a white solid (0.049 g, 78%). 1H NMR (500 MHz; CDCl3): δ 7.73-7.72 (m, 2H), 7.68 (d, J = 8.0 Hz, 1H), 7.64 (d, J = 7.0 Hz, 1H), 7.61 (d, J = 8.0 Hz, 1H), 7.53 (d, J = 7.5 Hz, 1H), 7.49-7.44 (m, 3H), 7.43-7.37 (m, 2H), 7.31-7.27 (m, 2H), 3.96 (dd, J = 10.0 Hz, 3.0 Hz, 1H), 1.88-1.81 (m, 1H), 1.80-1.73 (m, 1H), 0.46 (t, J = 7.5 Hz, 3H); 13C NMR (125 MHz, CDCl3): δ 161.8, 148.3, 141.7, 140.9, 139.2, 130.0, 129.8, 129.7, 129.5, 128.9, 128.5, 127.6, 127.4, 126.2, 123.3, 120.2, 120.0, 95.5, 56.9, 22.4, 12.1; IR (thin film) 3050, 2966, 2934, 2872, 1591, 1449, 1350, 1260, 874, 757, 696 cm-1; HRMS (ESI) m/z calcd. for C23H20NO (M+H)+ 326.1545, found 326.1540; mp 84-86 ºC.
Spiroisoxazoline 5m: Spiroisoxazoline 5m was prepared using general procedure B. Nitrone 3m (0.079 g; 0.20 mmol) was dissolved in toluene (2 mL) and heated for 12 h. Solvent removal and purification by medium pressure chromatography (1:5; ethyl acetate: hexanes) afforded 5m as a white solid (0.048 g, 61%). 1H NMR (500 MHz; CDCl3): δ 8.34 (d, J = 8.5 Hz, 2H), 7.90 (d, J = 8.5 Hz, 2H), 7.68 (d, J = 7.5 Hz, 1H), 7.65 (d, J = 7.5 Hz, 1H), 7.56 (d, J = 7.5 Hz, 1H), 7.46-7.39 (m, 3H), 7.31-7.29 (m, 2H), 4.04 (dd, J = 10.5 Hz, 3.0 Hz, 1H), 1.81-1.66 (m, 2H), 1.03-0.98 (m, 1H), 0.96-0.90 (m, 1H), 0.87-0.82 (m, 1H), 0.60-0.57 (m, 1H), 0.56 (t, J = 7.5 Hz, 3H); 13C NMR (125 MHz, CDCl3): δ 160.0, 148.4, 147.7, 141.2, 140.9, 139.2, 135.8, 130.1, 129.8, 128.6, 128.1, 127.6, 126.0, 124.2, 123.1, 120.4, 120.2, 96.5, 54.7, 29.2, 28.6, 22.1, 13.4; IR (thin film) 3053, 2952, 2923, 2864, 1602, 1522, 1446, 1245, 860, 769, 725 cm-1; HRMS (ESI) m/z calcd. for C25H23N2O3 (M+H)+ 399.1709, found 399.1711; mp 110-112 ºC.
Spiroisoxazoline 5n: Spiroisoxazoline 5n was prepared using general procedure B. Nitrone 3n (0.074 g; 0.20 mmol) was dissolved in toluene (2 mL) and heated for 12 h. Solvent removal and purification by medium pressure chromatography (1:5; ethyl acetate: hexanes) afforded 5n as a white solid (0.046 g, 62%). 1H NMR (500 MHz; CDCl3): δ 7.72-7.70 (m, 2H), 7.67 (d, J = 7.5 Hz, 1H), 7.64 (d, J = 7.0 Hz, 1H), 7.58 (d, J = 7.5 Hz, 1H), 7.49 (d, J = 7.5 Hz, 1H), 7.44-7.37 (m, 2H), 7.30-7.26 (m, 2H), 7.19-7.15 (m, 2H), 3.97 (dd, J = 10.0 Hz, 3.0 Hz, 1H), 1.77-1.71 (m, 2H), 1.03-0.98 (m, 1H), 0.96-0.89 (m, 1H), 0.86-0.81 (m, 1H), 0.60-0.59 (m, 1H), 0.56 (t, J = 7.0 Hz, 3H); 13C NMR (125 MHz, CDCl3): δ 164.7 (d, J = 250 Hz), 160.8, 148.2, 141.7, 140.9, 139.2, 134.7, 129.8, 129.5, 129.3 (d, J = 7.4 Hz), 128.5, 127.5, 126.1, 125.9 (d, J = 3.6 Hz), 123.2, 120.2, 116.2 (d, J = 22 Hz), 95.6, 55.3, 29.3, 28.7, 22.1, 13.4; IR (thin film) 3065, 2952, 2934, 2864, 1606, 1511, 1453, 1336, 1231, 1159, 835, 757, 728 cm-1; HRMS (ESI) m/z calcd. for C25H23NOF (M+H)+ 372.1764, found 372.1773; mp 83-84 ºC.
Spiroisoxazoline 5o: Spiroisoxazoline 5o was prepared using general procedure B. Nitrone 3o (0.084 g; 0.20 mmol) was dissolved in toluene (2 mL) and heated for 12 h. Solvent removal and purification by medium pressure chromatography (1:5; ethyl acetate: hexanes) afforded 5o as a white solid (0.057 g, 68%). 1H NMR (500 MHz; CDCl3): δ 7.85 (d, J = 7.0 Hz, 2H), 7.75 (d, J = 7.5 Hz, 2H), 7.68 (d, J = 7.0 Hz, 1H), 7.65 (d, J = 7.0 Hz, 1H), 7.57 (d, J = 7.0 Hz, 1H), 7.48-7.38 (m, 3H), 7.29-7.26 (m, 2H), 4.024.00 (d, J = 8.5 Hz, 1H), 1.78-1.72 (m, 2H), 1.01-0.99 (m, 1H), 0.94-0.90 (m, 1H), 0.84-0.81 (m, 1H), 0.62-0.59 (m, 1H), 0.56 (t, J = 7.0 Hz, 3H); 13C NMR (125 MHz, CDCl3): δ 160.6, 147.7, 141.5, 140.9, 139.2, 133.8, 131.8 (d, J = 33.0 Hz), 129.9, 129.7, 128.5, 127.6, 127.5, 126.1, 125.9 (q, J = 4.0 Hz), 124.9 (d, J = 264.0 Hz), 123.1, 120.3, 120.1, 96.0, 54.9, 29.3, 28.6, 22.1, 13.4; IR (thin film) 3057, 2959, 2930, 2864, 1446, 1321, 1165, 1122, 1071, 845, 757, 732 cm-1; HRMS (ESI) m/z calcd. for C26H23NOF3 (M+H)+422.1732, found 422.1743; mp 100-102 ºC.
IV. Additions and Rearrangements of N-Vinyl Nitrones: Preparation of Fluorene-Tethered Isoxazoles (Table 3).
General procedure C: A Teflon-sealed reaction flask was charged with a 0.1 M toluene solution of 3 (1.0 equiv) and an alkyne (3 equiv). The reaction mixture was heated to 140 ºC for 12-36 h. Toluene was removed from the reaction mixture under vacuum and the crude reaction mixture was purified by medium pressure chromatography (1:10-1:3; ethyl acetate:hexanes) to give 6-15 as oils or solids.
Isoxazole-tethered fluorene 6: Isoxazole-tethered fluorene 6 was prepared using general procedure C. Nitrone 3b (0.055 g; 0.20 mmol) and methyl propiolate (0.053 g, 0.63 mmol) were dissolved in toluene (2 mL) and heated for 36 h. Solvent removal and purification by medium pressure chromatography (1:201:3; ethyl acetate: hexanes) afforded 6b as a light yellow oil (0.043 g, 60%). 1H NMR (500 MHz; CDCl3): δ 8.14 (s, 1H), 7.82 (d, J = 7.5 Hz, 1H), 7.76 (d, J = 7.0 Hz, 1H), 7.70 (d, J = 7.0 Hz, 1H), 7.65 (d, J = 7.0 Hz, 1H), 7.38-7.32 (m, 1H), 7.31-7.28 (m, 3H), 6.71 (t, J = 7.0 Hz, 1H), 3.90 (s, 3H), 2.92-2.86 (m, 4H), 2.01-1.98 (m, 2H), 1.79-1.76 (m, 2H); 13C NMR (125 MHz, CDCl3): δ 165.8, 161.7, 143.7, 140.9, 139.2, 138.6, 137.4, 135.9, 133.2, 129.8, 127.9, 127.8, 127.6, 126.9, 124.9, 119.8, 119.7, 119.5, 52.1, 28.9, 28.8, 27.9, 26.7; IR (thin film) 3050, 2930, 2857, 1719, 1584, 1438, 1194, 1107, 769, 728 cm-1; HRMS (ESI) m/z calcd. for C23H22NO3 (M+H)+ 360.1600, found 360.1609.
Isoxazole-tethered fluorene 7: Isoxazole-tethered fluorene 7 was prepared using general procedure C. Nitrone 3b (0.055 g; 0.20 mmol) and ethyl but-2-ynoate (0.076 g, 0.68 mmol) were dissolved in toluene (2 mL) and heated for 12 h. Solvent removal and purification by medium pressure chromatography (1:20-1:3; ethyl acetate: hexanes) afforded 7b as an amorphous solid (0.039 g, 50%). 1H NMR (500 MHz; CDCl3): δ 7.82 (d, J = 7.5 Hz, 1H), 7.76 (d, J = 7.5 Hz, 1H), 7.70 (d, J = 7.5 Hz, 1H), 7.66 (d, J = 7.5 Hz, 1H), 7.36-7.28 (m, 4H), 6.70 (t, J = 7.5 Hz, 1H), 4.49 (q, J = 7.0 Hz, 2H), 2.88-2.82 (m, 4H), 2.56 (s, 3H), 1.97-1.94 (m, 2H), 1.78-1.76 (m, 2H), 1.39 (t, J = 7.0 Hz, 3H); 13C NMR (125 MHz, CDCl3): δ 162.6, 162.5, 156.0, 140.8, 139.2, 138.6, 137.4, 135.8, 130.0, 127.7, 127.5, 127.4, 127.0, 126.9, 124.9, 119.8,
119.7, 119.5, 60.8, 29.0, 28.8, 27.9, 26.8, 14.4, 11.9; IR (thin film) 3057, 2931, 2861, 1710, 1613, 1448, 1337, 1183, 1094, 736 cm-1; HRMS (ESI) m/z calcd. for C25H26NO3 (M+H)+ 388.1913, found 388.1902.
Isoxazole-tethered fluorene 8: Isoxazole-tethered fluorene 8 was prepared using general procedure C. Nitrone 3e (0.070 g; 0.24 mmol) and methyl propiolate (0.053 g, 0.63 mmol) were dissolved in toluene (2 mL) and heated for 36 h. Solvent removal and purification by medium pressure chromatography (1:201:3; ethyl acetate: hexanes) afforded 8 as a yellow oil (0.049 g, 54%). 1H NMR (500 MHz; CDCl3): δ 8.13 (s, 1H), 7.83 (d, J = 7.5 Hz, 1H), 7.64 (d, J = 7.5 Hz, 1H), 7.71 (d, J = 7.5 Hz, 1H), 7.66 (d, J = 7.5 Hz, 1H), 7.38-7.28 (m, 4H), 6.72 (t, J = 7.5 Hz, 1H), 3.90 (s, 3H), 2.86-2.84 (m, 4H), 1.90-1.85 (m, 2H), 1.75 (t, J = 7.5 Hz, 2H), 1.58-1.52 (m, 2H); 13C NMR (125 MHz, CDCl3): δ 165.8, 161.8, 143.7,140.8, 139.3, 138.5, 137.5, 135.6, 133.1, 130.5, 127.7, 127.4, 126.9, 126.8, 124.9, 119.8, 119.6, 119.4, 52.1, 29.2, 29.1, 28.9, 28.0, 26.7; IR (thin film) 3057, 2931, 2855, 1710, 1584, 1442, 1274, 1198, 1151, 1109, 730 cm-1; HRMS (ESI) m/z calcd. for C24H24NO3 (M+H)+ 374.1756, found 374.1761.
Isoxazole-tethered fluorene 10: Isoxazole-tethered fluorene 9 was prepared using general procedure C. Nitrone 3i (0.065 g; 0.20 mmol) and methyl propiolate (0.053 g, 0.63 mmol) were dissolved in toluene (2 mL) and heated for 36 h. Solvent removal and purification by medium pressure chromatography (1:201:3; ethyl acetate: hexanes) afforded 9 as a yellow oil (0.038 g, 47%). 1H NMR (500 MHz; CDCl3): δ 8.02 (s, 1H), 7.86 (d, J = 8.0 Hz, 1H), 7.77 (d, J = 7.0 Hz, 1H), 7.71 (d, J = 7.0 Hz, 1H), 7.65 (d, J = 7.5 Hz, 1H), 7.39-7.27 (m, 4H), 6.71 (t, J = 7.0 Hz, 1H), 3.87 (s, 3H), 3.05-3.00 (m, 1H), 2.94-2.90 (m, 1H), 2.89-2.77 (m, 2H), 2.14-2.11 (m, 1H), 1.79-1.75 (m, 1H), 1.53-1.52 (m, 1H), 1.00 (s, 9H); 13C NMR (125 MHz, CDCl3): δ 165.7, 161.7, 143.7, 140.9, 139.3, 138.5, 137.4, 135.2, 133.0, 131.1, 127.7, 127.4, 127.0, 126.9, 124.9, 119.9, 119.7, 119.5, 52.0, 49.2, 34.2, 30.8, 28.2, 28.1, 27.8; IR (thin film) 3054, 2953, 2864, 1720, 1584, 1445, 1321, 1195, 1113, 1005, 733 cm-1; HRMS (ESI) m/z calcd. for C27H30NO3 (M+H)+ 416.2226, found 416.2225.
Fluorene 11 and Isoxazole 12: Fluorene 10 and isoxazole 11 were prepared using general procedure C. Nitrone 3a (0.059 g; 0.21 mmol) and methyl propiolate (0.053 g, 0.63 mmol) were dissolved in toluene (2
mL) and heated for 12 h. Solvent removal and purification by medium pressure chromatography (1:201:3; ethyl acetate: hexanes) afforded 10 (0.027 g, 62%) as a white solid and 11 as a clear, colorless oil (0.020 g, 61%).
Fluorene 10:3,4 1H NMR (500 MHz; CDCl3): δ 7.87 (d, J = 7.0 Hz 1H), 7.77 (d, J = 7.5 Hz, 1H), 7.72 (d, J = 7.0 Hz, 1H), 7.68 (d, J = 7.5 Hz, 1H), 7.38-7.27 (m, 4H), 6.75 (t, J = 7.5 Hz, 1H), 2.89-2.85 (m, 2H), 1.32 (t, J = 7.5 Hz, 3H); 13C NMR (125 MHz, CDCl3): δ 140.8, 139.4, 138.6, 137.5, 135.0, 132.6, 127.6, 127.3, 126.9, 126.8, 124.9, 119.8, 119.6, 119.4, 22.7, 14.0; IR (thin film) 3053, 2966, 2930, 2868, 1645, 1442, 1165, 776, 728 cm-1; HRMS (EI) m/z calcd. for C16H14 (M+) 206.1096, found 206.1090; mp 46-48 ºC.
Isoxazole 11: 1H NMR (500 MHz; CDCl3): δ 8.15 (s, 1H), 3.90 (s, 3H), 2.85 (q, J = 7.5 Hz, 2H), 1.37 (t, J = 7.5 Hz, 3H); 13C NMR (125 MHz, CDCl3): δ 166.8, 161.8, 143.7, 133.1, 52.1, 21.7, 11.1; IR (thin film) 2950, 2877, 1724, 1584, 1438, 1198, 1109, 1002, 762 cm-1; HRMS (ESI) m/z calcd. for C7H10NO3 (M+H)+ 156.0661, found 156.0657.
Fluorene 10 and Isoxazole 12: Fluorene 10 and isoxazole 12 were prepared using general procedure C. Nitrone 3a (0.059 g; 0.21 mmol) and ethyl but-2-ynoate (0.076 g, 0.68 mmol) were dissolved in toluene (2 mL) and heated for 12 h. Solvent removal and purification by medium pressure chromatography (1:20-1:3; ethyl acetate: hexanes) afforded 10 (0.021 g, 48%) as a white solid and 12 as a clear, colorless oil (0.018 g, 46%).
Isoxazole 12:5 1H NMR (500 MHz; CDCl3): δ 4.38 (q, J = 7.0 Hz, 2H), 2.79 (q, J = 7.0 Hz, 2H), 2.58 (s, 3H), 1.39 (t, J = 7.0 Hz, 3H), 1.33 (t, J = 7.0 Hz, 3H); 13C NMR (125 MHz, CDCl3): δ 163.7, 162.6,
155.9, 127.3, 60.8, 21.5, 14.4, 11.9, 11.2; IR (thin film) 2975, 2934, 2874, 1710, 1622, 1448,1341, 1094, 736 cm-1; HRMS (ESI) m/z calcd. for C9H14NO3 (M+H)+ 184.0974, found 184.0972.
Fluorene 10 and Isoxazole 13: Fluorene 10 and isoxazole 13 were prepared using general procedure C. Nitrone 3a (0.059 g; 0.21 mmol) and ethyl 3-phenylpropiolate (0.100 g, 0.574 mmol) were dissolved in toluene (2 mL) and heated for 12 h. Solvent removal and purification by medium pressure chromatography (1:20-1:3; ethyl acetate: hexanes) afforded 10 (0.025 g, 58%) as a white solid and 13 as a clear, colorless oil (0.030 g, 59%).
Isoxazole 13:6 1H NMR (500 MHz; CDCl3): δ 8.03-8.02 (m, 2H), 7.46-7.42 (m, 3H), 4.42 (q, J = 7.0 Hz, 2H), 2.89 (q, J = 7.0 Hz, 2H), 1.41-1.38 (m, 6H); 13C NMR (125 MHz, CDCl3): δ 164.1, 162.3, 155.1, 130.0, 128.3, 127.2, 126.8, 126.5, 61.3, 21.6, 14.3, 11.2; IR (thin film) 3061, 2975, 2923, 1714, 1590, 1448, 1369, 1183, 1087, 765, 686 cm-1; HRMS (ESI) m/z calcd. for C14H16NO3 (M+H)+ 246.1130, found 246.1130.
Fluorene 10 and Isoxazole 14: Fluorene 10 and isoxazole 14 were prepared using general procedure C. Nitrone 3l (0.065 g; 0.20 mmol) and methyl propiolate (0.053 g, 0.63 mmol) were dissolved in toluene (2 mL) and heated for 12 h. Solvent removal and purification by medium pressure chromatography (1:201:3; ethyl acetate: hexanes) afforded 10 (0.026 g, 63%) as a white solid and 14 as a white solid (0.025 g, 62%).
Isoxazole 14:7 1H NMR (500 MHz; CDCl3): δ 8.28 (s, 1H), 8.11-8.10 (m, 2H), 7.47-7.46 (m, 3H), 3.94 (s, 3H); 13C NMR (125 MHz, CDCl3): δ 162.5, 161.8, 143.8, 134.4, 131.2, 128.8, 126.9, 126.4, 52.2; IR (thin film) 3065, 2955, 1722, 1559, 1453, 1321, 1249, 1147, 1114, 997, 776, 714, 693 cm-1; HRMS (ESI) m/z calcd. for C11H10NO3 (M+H)+ 204.0661, found 204.0669; mp 60-62 ºC.
V. Independent Synthesis of Nitrone 3b.
Compound S1:8 Diphenyl diselenide (2.34 g, 7.5 mmol) was suspended in EtOH (40 mL) in a roundbottom flask equipped with a septum and N2 inlet. A solution of NaBH4 (0.756 g, 20 mmol) in EtOH (40 mL) was added dropwise via syringe to the bright yellow reaction mixture over 20 min. The addition was halted (after 35 mL had been added) when all of the yellow color disappeared to give a colorless solution. The reaction mixture was then cooled to 0°C (ice/H2O bath) for 5 min and glacial acetic acid (2.28 mL, 40 mmol) was added dropwise via syringe. Next, 1-nitrocyclohexene (1.2 mL, 10 mmol) was added as a solution in EtOH (4 mL) via syringe and the reaction mixture was allowed to stir for 5 min at 0°C before the ice bath was removed and the reaction mixture was allowed to warm to 25 ºC and stir overnight. The reaction mixture was then poured into H2O (200 mL) and extracted with Et2O (100 mL). The organic layer was washed with H2O (100 mL) and the combined aqueous washes were back extracted with Et 2O (100 mL). The combined organic layers were then washed with brine (100 mL), dried with MgSO4, and concentrated to give the crude product which was purified by silica gel column chromatography (hexane to hexane/EA= 20/1) to give S-1 as a colorless liquid (1.30g, 46%). 1H NMR (500 MHz; CDCl3): δ 7.61 (d, J = 7.0 Hz, 2H), 7.38-7.37 (m, 1H), 7.32 (t, J = 7.0 Hz, 2H), 4.42 (dt, J = 11.0 Hz, 4.0 Hz, 1H), 3.40 (dt, J = 11.0 Hz, 4.0 Hz, 1H), 2.32-2.25 (m, 2H), 1.94-1.89 (m, 1H), 1.80-1.78 (m, 1H), 1.70-1.68 (m, 1H), 1.41-1.39 (m, 2H), 1.26-1.21 (m, 1H). 13C NMR (125 MHz, CDCl3): δ 137.1, 129.1, 128.8, 125.5, 89.5, 42.1, 32.5, 32.4, 25.8, 23.6. Compound S-2:9 Compound S-1 (0.200 g, 0.7 mmol) was dissolved in EtOH (7 mL) and dilute HCl (8 mL, 10%/wt) was added via syringe at 25 ºC. Zn dust (1.8 g, 28 mmol) was then added in small portions and the reaction mixture was stirred at 25 ºC overnight. When the reaction was completed, Na2CO3(aq) was added to the mixture until pH=9. The reaction mixture was extracted with ethylacetate (3 x 50 mL), dried with MgSO4, concentrated, and purified by silica gel column chromatography (hexane/EA/NEt3= 5/1/1) to give S-2 as a colorless liquid (0.091 g, 51%). 1H NMR (500 MHz; CDCl3): δ 7.58 (d, J = 7.0 Hz, 2H), 7.28-7.23 (m, 3H), 2.80-2.76 (m, 1H), 2.59 (dt, J = 10.5 Hz, 3.5 Hz, 1H), 2.14-2.12 (m, 1H), 1.99-
1.96 (m, 1H), 1.71-1.62 (m, 3H), 1.46-1.43 (m, 1H), 1.24-1.14 (m, 2H). 13C NMR (125 MHz, CDCl3): δ 135.8, 128.9, 127.8, 127.7, 54.4, 54.2, 35.8, 34.3, 27.2, 25.1. Compound 4: 9-Fluorenone (0.468 g, 2.6 mmol), amine S-2 (0.652 g, 2.6 mmol), TsOH (0.020 g), 4 Å molecular sieves (3.0 g) and toluene (5 mL) were placed into a three neck, round bottom flask connected to a condenser and an N2 inlet. The reaction mixture was then heated to 120°C for 24 h. The molecular sieves were then removed by filtration and the mixture was concentrated to give the crude imine. Recrystallization of the crude material from hexane gave 4 as a yellow solid (0.324 g, 29%). 1H NMR (500 MHz; CDCl3): δ 7.76 (d, J = 7.5 Hz, 1H), 7.68 (d, J = 7.0 Hz, 1H), 7.58-7.56 (m, 3H), 7.51-7.45 (m, 1H), 7.44-7.38 (m, 1H), 7.30-7.24 (m, 3H), 7.22-7.15 (m, 3H), 4.53-4.51 (m, 1H), 3.67-3.63 (m, 1H), 2.37-2.33 (m, 1H), 2.09-2.06 (m, 1H), 1.93-1.90 (m, 1H), 1.84-1.83 (m, 1H), 1.74-1.64 (m, 2H), 1.541.47 (m, 2H); 13C NMR (125 MHz, CDCl3): δ 161.2, 144.4, 143.8, 140.7, 138.6, 135.7, 134.7, 131.0, 130.7, 129.1, 128.7, 128.0, 127.3, 124.3, 123.0, 120.3, 119.1, 64.6, 50.4, 33.1, 33.0, 26.6, 24.4; IR (thin film) 3053, 2924, 2853, 1716, 1611, 1452, 1295, 1190, 918, 728 cm-1; HRMS (ESI) m/z calcd. for C25H24NSe (M+H)+ 418.1074, found 418.1077. Nitrone 3b: Imine 4 (0.208 g, 0.5 mmol) was dissolved in CH2Cl2 (4 mL) and the solution was cooled to -78 ºC for 10 min. A solution of m-CPBA (0.157 g, 0.6 mmol) in CH2Cl2 (4 mL) was added dropwise over 5 min. The reaction mixture was then stirred for 5 min at 25 ºC and then cooled to 0 ºC with an ice/water bath. A second portion of m-CPBA (0.157 mg, 0.6 mmol) was added to the reaction mixture as a CH2Cl2 (4 mL) solution and allowed to stir for 10 min. The reaction mixture was then cooled to -78 ºC, and i-Pr2NH (0.17 mL, 0.6 mmol) was added before warming to 25 ºC and stirring overnight. The reaction mixture was then poured into H2O (10 mL) and extracted with CH2Cl2 (3 x 10 mL). The combined organic layers were then washed with brine (100 mL), dried with MgSO4 and concentrated to give the crude product, which was purified by silica gel column chromatography (hexane/EA= 3/1) to give 3b as a yellow solid (0.015 g , 10%). 1H NMR (500 MHz; CDCl3): δ 8.85 (d, J = 8.0 Hz, 1H), 7.687.63 (m, 3H), 7.46-7.43 (m, 1H), 7.39 (t, J = 7.5 Hz, 1H), 7.34 (t, J = 7.5 Hz, 1H), 7.25-7.22 (m, 1H), 6.05-6.04 (m, 1H), 2.85-2.81 (m, 1H), 2.40-2.31 (m, 3H), 1.97-1.93 (m, 2H), 1.83-1.80 (m, 2H); 13C NMR (125 MHz, CDCl3): δ 145.3, 143.5, 139.2, 138.8, 132.4, 130.8, 130.6, 128.9, 128.8, 127.4, 127.0, 124.9, 123.9, 120.3, 119.4, 25.4, 24.2, 22.2, 21.2.
VI. Mechanistic Discussion. Proposed mechanisms for the conversion of N-vinyl nitrones to spiroisoxazolines and fluorene-tethered isoxazoles via nitrile oxide intermediates are illustrated below in Scheme S-1. Scheme S-1.
Although the intermediacy of a nitrile oxide is consistent with the final products observed for these transformations, two additional pieces of mechanistic data suggest that the conversion of N-vinyl nitrones to fluorene-tethered isoxazoles (or a mixture of substituted fluorenes and isoxazoles) in the presence of propiolates may not be proceeding via the same intermediates as spiroisoxazoline formation: 1) spiroisoxazolines do not form mixtures of substituted fluorenes and isoxazoles when heated in the presence of propiolates, and 2) spiroisoxazoline formation is not observed below 100 ºC, while mixtures of substituted fluorenes and isoxazoles can be isolated when N-vinyl nitrones are heated in the presence of propiolates at 80 ºC. The first experiment shows that spiroisoxazolines do not cyclorevert at elevated temperature to give nitrile oxides and do not function as intermediates on the reaction pathway to the formation of fluorene-tethered isoxazoles or mixtures of substituted fluorenes and isoxazoles. The reaction temperature data indicates that spiroisoxazoline formation requires a higher energy reactive intermediate than the formation of mixtures of substituted fluorenes and isoxazoles. Therefore, we have proposed an alternative mechanism for the preparation of tethered-isoxazoles or mixtures of fluorenes and isoxazoles which involves an initial interaction between the electron-deficient alkyne and the N-vinyl nitrone prior to cycloreversion (Scheme S-2). This reaction pathway could be further energetically favored by resonance stabilization of the build-up of partial positive charge at the quaternary carbon center of the tricyclic intermediate. Scheme S-2.
VII. Three-Dimensional Representations of 3g and 5m. Compound 3g
Compound 5m
Two inequivalent molecules are observed in the unit cell due to distortion of the n-Bu group.
VIII. References. 1. A. B. Pangborn, M. A. Giardello, R. H. Grubbs, R. K. Rosen, F. J. Timmers, Organometallics 1996, 15, 1518. 2. Patil, A. S., Mo, D.-L., Wang, H.-Y., Mueller, D. S. and Anderson, L. L. Angew. Chem. Int. Ed. 2012, 51, 7799. 3. Wawzonek, S.; Dufek, E. J. Am. Chem. Soc. 1956, 78, 3530. 4. Wolf, J.; Brandt, L.; Fries, A.; Werner, H. Angew. Chem. 1990, 102, 584. 5. McMurry, J. E. Org. Synth. 1973, 53, 59. 6. Ward, F. E.; Buckler, R. T. J. Org. Chem. 1980, 45, 4608. 7. Minakata, S.; Okumura, S.; Nagamachi, T.; Takeda, Y. Org. Lett. 2011, 13, 2966. 8. Hayama, T.; Tomoda, S.; Takeuchi, Y.; Nomura, Y. Tetrahedron Lett. 1982, 23, 4733. 9. Denis, J. N.; Vicens, J.; Krief, A. Tetrahedron Lett. 1979, 2697.
3a
5.86
2.93
0.98 1.05 1.00
9 8 1.94
1.00 1.06 0.90
7 6 0.90 0.95
5 4 3 2 1 PPM
1.189 1.174 1.159 1.147 1.131 1.117
2.878 2.863 2.848 2.833 2.603 2.589 2.574 2.559 2.335 2.321 2.310
7.699 7.685 7.473 7.458 7.444 7.405 7.390 7.376 7.343 7.329 7.314 7.261 7.219 7.203 7.189 5.788 5.773 5.759
8.883 8.868
3a
200 150 100 50 PPM
13.043 11.589
21.903 20.640
77.340 77.091 76.841
132.587 130.912 130.824 129.075 128.943 128.840 127.121 127.091 124.432 120.318 119.451
139.301 138.773
146.619 144.018
3a
200 150 100 50 PPM
13.043 11.603
21.903 20.654
130.824 129.090 128.943 128.840 127.136 127.091 124.447 120.318 119.451
3b
3.04
9 8 2.96
2.06
0.95 2.14
0.93 0.98
7 6 1.04
5 4 3 2.20
0.96
2 1 0PPM
1.971 1.960 1.835 1.823
2.383 2.335
2.861 2.828
7.690 7.661 7.646 7.477 7.463 7.449 7.406 7.391 7.375 7.366 7.351 7.337 7.260 7.247 7.231 6.071
8.849 8.834
3b
180 160 140 120 100 80 60 40 20 PPM
25.547 24.269 22.300 21.242
77.355 77.105 76.856
132.454 130.868 130.691 129.016 128.840 127.503 127.033 124.990 123.918 120.377 119.495
139.272 138.846
145.399 143.607
3b
200 150 100 50 0 PPM
25.562 24.269 22.300 21.242
130.882 129.016 128.840 127.503 127.033 124.990 123.918 120.377 119.495
3c
3.04
0.99
8 6 4 3.07
1.97
1.031.01 0.95
1.08 1.00 0.99
2 PPM
1.867 1.855
2.220
7.666 7.653 7.498 7.483 7.446 7.431 7.417 7.384 7.369 7.354 7.330 7.315 7.301 7.231 7.216 7.201 5.843 5.830
8.845 8.830
3c
160 140 120 100 80 60 40 20 PPM
13.984 12.955
77.414 77.164 76.900
132.410 130.882 130.647 129.046 128.811 127.562 127.003 123.859 123.080 120.377 119.524
143.254 142.960 139.243 138.875
3c
200 150 100 50 0PPM
13.984 12.955
130.882 129.046 128.811 127.562 127.003 123.859 123.080 120.377 119.524
3d
1.86
0.94
10 8 2.02
0.98
0.98 2.00
0.99
6 4 2.08
2.09
1.05
2 PPM
2.273 2.259 2.244 2.157
2.689
2.937
7.676 7.662 7.564 7.549 7.463 7.449 7.435 7.390 7.376 7.361 7.348 7.333 7.318 7.236 7.222 7.208 6.038
8.859 8.845
3d
200 150 100 50 PPM
22.403
31.601 31.145
77.355 77.105 76.856
147.588 144.811 139.360 138.875 132.293 131.088 130.456 129.251 128.869 127.562 127.473 127.136 123.668 120.421 119.554
3d
200 150 100 50 PPM
22.403
31.601 31.145
131.088 129.251 128.884 127.562 127.473 127.136 123.668 120.421 119.554
3e
2.00 2.09
0.97 1.02
9 8 1.03 0.97
0.981.02
7 6 5 4 3 1.94 1.98
1.00 1.05 1.92
1.06
2 1 PPM
2.828 2.818 2.796 2.787 2.683 2.665 2.633 2.361 1.966 1.950 1.888 1.871 1.813 1.791 1.770 1.757 1.726
7.734 7.718 7.681 7.666 7.458 7.444 7.429 7.391 7.376 7.362 7.343 7.329 7.314 7.260 7.250 7.235 7.220 6.150 6.139 6.129
8.840 8.826
3e
150 100 50 PPM
31.615 30.734 27.354 26.752 26.340
77.355 77.105 76.841
142.975 139.243 138.846 132.601 130.912 130.824 129.134 128.972 128.825 127.356 127.033 123.962 120.333 119.466
149.205
3e
200 150 100 50 PPM
31.615 30.748 27.354 26.752 26.340
130.824 129.134 128.972 128.825 127.356 127.033 123.977 120.333 119.466
3f
3.02 2.01 2.01
0.98
10 0.981.18
8 1.00
6 1.03
1.03
4 0.90 1.10
2 PPM
2.822 2.689
3.924
4.426 4.386 4.243
7.721 7.702 7.686 7.489 7.474 7.461 7.408 7.393 7.377 7.361 7.346 7.279 7.262 6.115
8.839 8.824
3f
180 160 140 120 100 80 60 40 20 PPM
25.723
64.352
77.326 77.076 76.811
132.205 131.264 130.397 129.384 128.913 127.841 127.106 124.153 123.389 120.480 119.613
144.415 142.211 139.419 139.081
3f
200 150 100 50 0PPM
25.723
64.366
131.264 129.398 128.913 127.841 127.106 124.153 123.389 120.480 119.613
3g
4.12
2.01 2.03
0.99
9 0.98 2.07
0.94
8 1.19 1.00
7 6 1.02
5 4 3 2.13
1.05
2 1 PPM
2.973 2.939 2.680 2.615 2.579 2.431 2.395 2.153 2.081 2.063 2.047
4.100 4.078 4.059 4.045 4.034
7.961 7.946 7.669 7.657 7.646 7.455 7.440 7.426 7.383 7.368 7.354 7.336 7.321 7.307 7.249 7.233 7.219 5.915
8.843 8.829
3g
150 100 50 PPM
24.563
30.778
34.789
64.881 64.646
77.370 77.120 76.870
139.110 132.337 131.015 130.618 129.090 128.766 127.811 127.062 124.785 122.272 120.156 119.510 106.962
144.518 144.341
3g
150 100 50 PPM
24.563
30.778
34.789
64.895 64.646
131.015 129.090 128.766 127.811 127.062 124.785 122.272 120.156 119.510
3h
6.00
1.94 1.04 2.06
9 8 1.45
0.98 0.98
0.480.50
7 6 5 4 3
1.58
1.27 0.76
0.51 1.02
2 1 PPM
2.642 2.607 2.554 2.512 2.472 2.313 2.275 2.238 2.171 2.151 2.139 2.128 2.048 1.262
3.078 2.990 2.956
7.784 7.770 7.723 7.710 7.697 7.629 7.614 7.490 7.476 7.461 7.420 7.405 7.387 7.373 7.348 7.334 7.310 7.294 7.279 7.261 6.159
8.883 8.870 8.856
3h
160 140 120 100 80 60 40 20 PPM
32.321 32.174 29.632 29.485 26.943 25.782
39.476 38.653
77.326 77.061 76.811
132.440 131.029 130.647 129.178 128.928 128.737 127.591 127.136 126.886 126.709 124.682 124.535 124.035 123.668 120.480 119.554
139.331 138.905
145.311 145.120
3h
150 100 50 PPM
32.335 32.174 29.646 29.485 26.943 25.797
39.476 38.653
131.015 129.178 128.928 128.737 127.591 127.106 126.886 126.709 124.696 124.535 124.035 123.668 120.494 119.569
3i 9.00
2.41
10 8 2.00
1.00
0.96 1.18 2.12 2.26
0.98
6 4 2
2.10
0.98
0.51
PPM
0.974
2.438 2.406 2.381 2.344 2.312 2.156 2.112 2.039 1.543
2.893 2.861
7.669 7.568 7.554 7.458 7.443 7.429 7.392 7.377 7.362 7.347 7.332 7.318 7.261 7.251 6.055 6.038
8.848
3i
160 140 120 100 80 60 40 20 PPM
32.423 32.203 27.428 27.281 26.267 25.944 23.857
43.634 42.782
77.370 77.120 76.856
145.370 145.179 143.974 143.386 139.316 139.199 138.875 138.802 132.469 130.897 130.853 130.706 128.987 128.840 127.547 127.062 127.018 125.225 125.123 124.094 123.639 120.377 119.495
3i
180 160 140 120 100 80 60 40 20 PPM
27.428 27.281 26.267 25.944 23.857
43.634 42.782
130.897 130.853 128.987 128.840 127.547 127.062 127.018 125.225 125.123 124.094 123.639 120.377 119.495
3j
7.05
2.80
0.92
10 0.97 1.00
8 1.87
6 4 2 PPM
2.171
7.900 7.874 7.726 7.711 7.686 7.672 7.661 7.609 7.595 7.470 7.456 7.443 7.431 7.416 7.406 7.391 7.383 7.369 7.339 7.324 7.309 7.261
8.305 8.278
8.909 8.894
3j
180 160 140 120 100 80 60 40 20 PPM
77.340 77.076 76.826
133.410 133.174 132.704 131.690 131.176 130.295 129.942 129.472 129.207 129.016 128.076 127.826 127.532 125.034 120.935 119.745
139.713 138.890
145.502
3j
200 150 100 50 PPM
132.704 131.690 131.176 129.942 129.472 129.222 129.016 128.076 127.826 127.532 125.034 120.935 119.745
3k
4.01 2.94
2.06
0.99
9 8 2.06
7 6 5 4 3 2.04
0.96
1.07 0.93 2.00
2 1 PPM
1.611 1.597 1.582 1.567 1.552 1.474 1.459 1.444 1.430 0.986 0.971 0.956
2.414 2.401 2.386 2.372
7.713 7.699 7.677 7.662 7.638 7.623 7.597 7.453 7.439 7.425 7.387 7.371 7.358 7.318 7.302 7.288 7.261 7.030 7.017 7.003
8.856 8.840
3k
200 150 100 50 PPM
13.895
22.344
30.748 29.353
77.326 77.076 76.811
139.551 138.758 134.688 134.276 133.101 130.897 130.309 129.207 128.913 127.606 127.327 124.932 120.759 119.613
144.121
3k
200 150 100 50 PPM
13.895
22.359
30.748 29.367
134.688 134.276 130.897 129.207 128.913 127.620 127.327 124.932 120.759 119.613
3l
5.05
2.87
1.95
0.90 0.98
8 3.00
2.09
1.06 0.97
6 4 2 PPM
1.193 1.179 1.164
2.550 2.537
7.741 7.726 7.706 7.696 7.583 7.569 7.488 7.474 7.459 7.416 7.402 7.388 7.376 7.361 7.348 7.333 7.318 7.260 7.208 7.192 7.178 6.105 6.090 6.075
8.918 8.903
3l
180 160 140 120 100 80 60 40 20 PPM
13.264
21.888
77.384 77.135 76.870
132.587 131.823 131.441 131.103 130.794 129.193 128.913 128.840 128.737 127.444 127.282 124.447 120.406 119.569
139.404 139.037
144.826
3l
180 160 140 120 100 80 60 40 20 PPM
13.264
21.888
131.455 131.103 129.222 129.193 128.913 128.840 128.737 127.444 127.282 124.447 120.406 119.569
3m
3.09
1.94
9 1.90
0.94
8 1.91
1.07 2.05 2.03
1.03
7 6 5 4 3 2.13
1.00 2.09
1.01
2 1 PPM
1.577 1.564 1.445 1.430 1.417 1.403 0.944 0.929 0.915
2.548 2.533 2.518 2.503 2.488
7.776 7.759 7.706 7.691 7.608 7.592 7.499 7.484 7.469 7.413 7.398 7.383 7.364 7.348 7.334 7.207 7.192 7.177 6.329 6.313 6.299
8.258 8.240
8.864 8.849
3m
180 160 140 120 100 80 60 40 20 PPM
13.822
22.506
30.807 28.353
77.355 77.105 76.856
147.882 145.326 143.166 139.610 139.125 138.244 133.512 132.308 131.543 130.324 129.692 129.060 127.576 127.327 124.035 123.947 120.700 119.760
3m
200 150 100 50 PPM
13.822
22.506
30.807 28.353
133.512 131.543 129.692 129.060 127.576 127.327 124.035 123.947 120.700 119.760
3n
2.92 2.99
2.03 2.27 2.17
0.91
9 1.04
8 1.13
7 2.10
6 5 4 3 2.05
1.00 2.03
2 1 PPM
1.538 1.426 1.412 1.398 1.385 0.932 0.918 0.904
2.165
2.469 2.417
7.705 7.691 7.677 7.562 7.551 7.485 7.472 7.458 7.407 7.392 7.378 7.354 7.340 7.325 7.210 7.195 7.181 7.105 7.088 7.072 6.126 6.112 6.097
8.883 8.869
3n
180 160 140 120 100 80 60 40 20 PPM
13.866
22.520
30.925 28.162
77.355 77.105 76.856
132.484 131.206 130.794 130.721 130.618 130.295 129.340 128.957 127.973 127.473 127.282 124.256 120.480 119.613 116.013 115.836
144.782 144.077 139.463 139.037
163.971 161.988
3n
180 160 140 120 100 80 60 40 20 PPM
13.866
22.535
30.939 28.162
131.206 130.794 130.721 130.295 129.354 128.957 127.473 127.282 124.256 120.480 119.613 116.013 115.851
3o 6.99
2.00
0.97
9 8 7 6 5 4 3 2.25 3.18
1.13 1.03
1.08 0.99 0.98 1.96
2 1 PPM
1.587 1.577 1.560 1.547 1.437 1.423 1.409 1.396 0.940 0.925 0.911
2.520 2.506 2.494 2.480
7.716 7.702 7.668 7.652 7.503 7.490 7.475 7.416 7.402 7.387 7.369 7.354 7.340 7.260 7.209 7.194 6.244 6.229 6.214
8.870 8.855
3o
140 120 100 80 60 40 20 PPM
13.822
22.506
30.851 28.207
77.296 77.047 76.797
132.410 132.087 131.367 130.897 130.677 130.515 129.501 129.148 129.016 128.693 127.503 127.327 125.828 124.902 124.109 120.568 119.657 118.320
139.566 139.081 135.452
145.120 143.753
3o
180 160 140 120 100 80 60 40 20 0 PPM
13.822
22.506
30.851 28.207
132.102 131.367 129.501 129.134 129.016 127.503 127.327 125.828 124.109 120.568 119.657
5a
3.11
1.01 1.12
8 1.00
7 6 5 4 1.03
1.02 1.05 1.04
3 2 3.11
1.92 1.99
1.06 1.10
1 PPM
2.599 2.584 2.568 2.553 2.437 2.422 2.406 2.390 1.704 1.691 1.677 1.666 1.556 1.479 1.464 1.459 1.451 1.444 1.436 1.431 1.417 1.351 1.336 1.321 0.424 0.409 0.395
3.633 3.624 3.614 3.604
7.632 7.614 7.597 7.562 7.547 7.434 7.420 7.389 7.376 7.366 7.324 7.309 7.294 7.261 7.247 7.232 7.217
5a
150 100 50 PPM
11.794 10.810
20.772 20.742
58.548
77.340 77.091 76.826
94.561
129.516 129.486 128.179 127.547 125.387 123.785 120.215 120.039
146.677 142.975 140.389 140.345
164.118
5b
3.19
1.96
8 1.98
1.01 0.92 1.00
7 6 5 4 1.00
3
1.02 1.24
2
1.01 1.15
0.97 1.02
1 PPM
1.548 1.516 1.490 1.474 1.447 1.418 1.347 1.321 1.295 1.260
1.839 1.813
2.343 2.317 2.294 2.044
2.995 2.966
3.539 3.524 3.505
7.628 7.611 7.591 7.516 7.502 7.455 7.442 7.370 7.318 7.304 7.258
5b
180 160 140 120 100 80 60 40 20 PPM
30.939 28.060 25.856 25.474 24.386
56.550
77.296 77.047 76.797
93.547
129.369 128.267 127.385 126.019 123.492 120.259 119.862
143.533 140.257 140.021
147.383
160.886
5b
180 160 140 120 100 80 60 40 20 PPM
28.060 25.856 25.474 24.372
56.550
129.369 128.267 127.385 126.019 123.506 120.274 119.877
5c
2.84
8 2.97
7 6 5 4 3 2
3.00
1.82 1.18
0.97 1.00 0.99
1 PPM
0.957 0.942
2.121
3.724 3.710 3.695 3.681
7.629 7.614 7.598 7.536 7.521 7.424 7.409 7.395 7.381 7.368 7.354 7.317 7.302 7.288 7.254 7.239 7.224
5c
150 100 50 PPM
12.309 12.044
52.979
77.340 77.091 76.841
95.031
129.575 129.501 128.238 127.503 125.666 123.580 120.259 119.936
146.251 142.931 140.403 140.212
160.592
5c
180 160 140 120 100 80 60 40 20 PPM
12.309 12.044
52.979
129.575 129.501 128.238 127.503 125.666 123.580 120.259 119.936
5e
3.00 3.18 2.12
1.03 0.96
8 1.00
7 6 5 4 1.02
3
1.00
2
2.13
1.15 2.29
1.13
1 PPM
1.983 1.963 1.811 1.787 1.592 1.568 1.410 1.386 1.362 1.337 1.260 1.238 1.213 1.179 1.167 1.145
3.052 3.042 3.018 3.008 2.576 2.550 2.518
3.758 3.735
7.615 7.600 7.459 7.444 7.406 7.391 7.376 7.362 7.346 7.337 7.322 7.307 7.260 7.247 7.232 7.217
5e
200 150 100 50 PPM
31.130 29.735 28.412 27.384 25.371
60.047
77.326 77.076 76.811
95.501
129.663 129.501 128.149 127.547 125.284 123.800 120.156 119.951
145.370 143.327 140.815 140.036
165.485
5e
200 150 100 50 0PPM
31.130 29.735 28.412 27.384 25.371
60.047
129.663 129.501 128.164 127.547 125.284 123.800 120.171 119.951
5f
1.96 2.01
8 1.97
1.01 1.25 1.00
7 6 5 1.04
1.04 1.01
4 1.03 1.01
0.99
3 2 1 PPM
1.258
3.786 3.772 3.750 3.738 3.716 3.703 3.567 3.546 3.524 3.471 3.467 3.448 3.424 3.419 2.917 2.889 2.750 2.737 2.724 2.710 2.697 2.683
4.287 4.273 4.265 4.251
7.639 7.623 7.617 7.602 7.543 7.528 7.470 7.455 7.414 7.400 7.387 7.373 7.348 7.333 7.318 7.260 7.242
5f
180 160 140 120 100 80 60 40 20 PPM
27.090
30.939
54.551
77.296 77.047 76.797 68.804 67.026
91.960
129.824 129.751 128.502 127.503 125.696 123.668 120.582 120.039
146.428 142.299 140.212 139.919
157.227
5f
200 150 100 50 PPM
27.090
54.537
68.804 67.026
129.824 129.751 128.502 127.503 125.696 123.668 120.582 120.039
5g
1.96 1.85 1.44 0.86
9 8 2.28 1.98
7 6 5 4
1.98
1.00
1.07 1.00
3
0.98
2
1.01
1.02
1 PPM
2.983 2.974 2.954 2.945 2.699 2.688 2.671 2.660 2.642 2.044 1.997 1.981 1.861 1.854 1.836 1.828 1.815 1.811 1.789 1.570 1.492 1.483 1.471 1.458
3.918 3.908 3.889 3.857 3.834 3.826 3.814
7.622 7.608 7.601 7.585 7.532 7.518 7.485 7.470 7.436 7.422 7.392 7.379 7.368 7.354 7.326 7.311 7.296 7.260 7.252 7.236
5g
200 150 100 50 0 PPM
22.388
35.876 33.481
54.302
64.690 64.601
77.311 77.061 76.811
93.767
146.868 143.034 140.183 139.992 129.619 129.516 128.355 127.664 125.754 123.712 120.377 119.877 108.314
159.240
5g
180 160 140 120 100 80 60 40 20 PPM
22.388
35.876 33.481
54.302
64.690 64.601
129.619 129.531 128.355 127.679 125.769 123.727 120.377 119.877
5l
3.03 2.14
8 3.00
1.05 1.04 1.88 1.90 2.04
0.96 0.86 0.98
7 6 5 4 3 2 1 PPM
0.468 0.453 0.438
1.871 1.857 1.850 1.842 1.835 1.800 1.785 1.781 1.771 1.766 1.758 1.751
3.963 3.957 3.944 3.937
7.733 7.726 7.682 7.666 7.645 7.631 7.613 7.598 7.532 7.517 7.473 7.445 7.430 7.415 7.406 7.390 7.376 7.313 7.297 7.285 7.272 7.260
5l
200 150 100 50 PPM
12.176
22.476
56.961
77.311 77.061 76.811
95.545
141.726 148.338 140.991 139.243 130.045 129.780 129.736 129.545 128.928 128.502 127.635 127.444 126.210 123.330 120.274 120.039
161.841
5l
150 100 50 0 PPM
12.176
22.476
56.946
130.045 129.780 129.560 128.928 128.502 127.635 127.444 126.210 123.330 120.274 120.039
5m
2.90
1.95 1.93
8 2.17 2.99
1.97
0.96 0.90 0.98 0.931.09
0.99 0.94
6 4 2 0.93
0 PPM
1.802 1.795 1.786 1.774 1.765 1.754 1.744 1.734 1.722 1.713 1.704 1.700 1.693 1.685 1.575 1.038 1.024 1.010 0.997 0.982 0.961 0.947 0.933 0.919 0.905 0.892 0.872 0.857 0.846
4.043 4.037 4.022 4.016
7.902 7.885 7.688 7.673 7.655 7.640 7.561 7.546 7.469 7.454 7.444 7.428 7.424 7.408 7.393 7.316 7.301 7.295 7.280 7.261
8.326
5m
200 150 100 50 PPM
13.455
22.124
29.279 28.647
54.728
77.326 77.076 76.811
96.530
141.270 140.947 139.287 135.834 130.104 129.883 128.605 128.120 127.694 126.092 124.226 123.168 120.450 120.230
148.499 147.721
160.092
5m
200 150 100 50 0 PPM
13.455
22.124
29.294 28.647
54.728
130.104 129.883 128.605 128.120 127.694 126.092 124.226 123.168 120.435 120.230
5n
1.86
8 2.02 1.91 2.96
1.01 0.91 2.27
7 1.96
0.97 0.97 1.06
1.001.05
6 5 4 1.13
3 2 1 0.88
PPM
1.776 1.767 1.756 1.747 1.727 1.719 1.710 1.036 1.024 1.010 0.997 0.982 0.965 0.951 0.936 0.923 0.909 0.861 0.835 0.827 0.605 0.595 0.567 0.553 0.539
3.979 3.973 3.959 3.953
7.729 7.714 7.703 7.676 7.661 7.642 7.628 7.586 7.571 7.499 7.484 7.441 7.426 7.410 7.405 7.389 7.375 7.305 7.291 7.284 7.269 7.261 7.190 7.174 7.157
5n
180 160 140 120 100 80 60 40 20 PPM
13.499
22.153
29.353 28.721
55.315
77.311 77.061 76.811
148.250 141.755 140.932 139.243 134.732 129.839 129.589 129.354 129.295 129.119 128.502 127.576 126.166 125.872 124.359 123.227 120.289 120.068 116.204 116.027 95.648
164.750 162.766 160.871
5n
150 100 50 PPM
13.499
22.168
29.353 28.721
55.315
129.839 129.589 129.369 129.295 128.502 127.591 126.166 123.227 120.289 120.083 116.204 116.027
5o
2.93
1.91 1.91
8 2.17 3.05 3.87
1.88 1.97
0.99 0.97
7 6 5 4 3 2 1 PPM
1.008 0.997 0.945 0.932 0.919 0.907 0.836 0.562 0.549 0.536
1.783 1.762 1.735 1.721
4.026 4.009
7.850 7.836 7.750 7.736 7.683 7.669 7.651 7.636 7.575 7.561 7.484 7.470 7.451 7.436 7.419 7.401 7.387 7.294 7.277 7.261
5o
180 160 140 120 100 80 60 40 20 PPM
13.455
22.124
29.308 28.618
54.963
77.296 77.047 76.782
96.074
141.505 147.956 140.932 139.272 133.160 131.896 131.632 129.957 129.736 128.546 127.650 126.122 125.916 124.917 123.198 122.801 120.362 120.142
160.665
5o
200 150 100 50 PPM
13.469
22.124
29.308 28.618
54.948
129.957 129.736 128.561 127.650 126.122 125.916 123.198 120.362 120.142
6
3.97 3.00 3.83
1.06 1.09 1.00
9 8 0.99 2.05 2.04
1.06 1.05
7 6 5 4 3 2 1 PPM
2.012 1.998 1.983 1.794 1.779 1.765
2.920 2.905 2.891 2.875 2.861
3.908
7.823 7.808 7.760 7.746 7.706 7.691 7.658 7.644 7.381 7.368 7.353 7.324 7.313 7.296 7.280 7.260 6.712 6.699 6.685
8.148
6
180 160 140 120 100 80 60 40 20 PPM
28.985 28.868 27.986 26.722
52.127
77.296 77.047 76.797
143.753 139.272 138.640 137.406 135.907 133.218 129.839 127.811 127.518 126.974 126.915 124.902 119.862 119.715 119.495
140.918
161.797
165.646
6
150 100 50 PPM
28.985 28.868 27.986 26.737
52.142
129.839 127.811 127.518 126.974 126.915 124.902 119.862 119.715 119.510
143.768
7
4.40
9 8 4.09
1.94 3.14
1.24 1.10
7 6 5 2.09
4 3 2.99
1.11 1.03
1.00 2.08
2 1 PPM
1.975 1.975 1.960 1.946 1.931 1.805 1.790 1.775 1.760 1.397 1.384 1.370
2.897 2.883 2.869 2.852 2.836 2.821 2.569
4.391 4.377 4.363 4.350
7.823 7.809 7.760 7.746 7.706 7.691 7.661 7.646 7.381 7.366 7.351 7.323 7.313 7.296 7.280 7.261 6.718 6.704 6.689
7
180 160 140 120 100 80 60 40 20 PPM
14.424 11.971
29.059 28.897 27.927 26.869
60.855
77.311 77.061 76.811
140.903 139.287 138.626 137.421 135.849 130.015 127.797 127.503 127.400 126.974 126.915 124.932 119.862 119.715 119.510
156.008
162.619 162.517
7
180 160 140 120 100 80 60 40 20 PPM
14.439 11.985
29.059 28.897 27.927 26.869
60.855
130.015 127.797 127.503 126.974 126.915 124.932 119.862 119.715 119.510
8
4.42
1.39 1.18
9 8 1.11
7 2.94 4.27
6 5 4
2.09
1.18 1.15 1.24
3 2 2.20
1.94
1 PPM
1.902 1.886 1.872 1.856 1.751 1.736 1.721 1.707 1.611 1.581 1.565 1.550 1.535 1.521
2.864 2.850 2.841
3.906
7.839 7.824 7.764 7.749 7.710 7.696 7.665 7.650 7.381 7.366 7.351 7.324 7.313 7.297 7.283 7.261 6.723 6.708 6.693
8.130
8
180 160 140 120 100 80 60 40 20 PPM
29.279 29.132 28.941 28.015 26.752
52.127
77.311 77.061 76.797
140.859 143.724 139.346 138.596 137.494 135.672 133.160 130.500 127.738 127.444 126.930 126.886 124.917 119.833 119.686 119.495
161.826
165.837
8
180 160 140 120 100 80 60 40 20 PPM
29.279 29.132 28.941 28.015 26.752
52.127
127.738 130.515 127.444 126.945 126.900 124.932 119.848 119.686 119.495
143.739
9
9.03
4.22
0.931.08 2.99
8 0.94
1.00 1.071.09
7 6 5 4 2.00
0.94
3
1.03
0.89
2
1.09
1.07
1 PPM
3.879 3.035 3.022 3.012 3.001 2.945 2.938 2.927 2.914 2.909 2.897 2.866 2.849 2.834 2.820 2.804 2.786 2.145 2.137 2.132 2.126 2.118 1.797 1.784 1.768 1.756 1.532 1.526 1.004
3.056 3.045
7.866 7.850 7.771 7.757 7.713 7.699 7.651 7.636 7.391 7.376 7.362 7.345 7.329 7.314 7.302 7.288 7.273 7.260 6.719 6.705 6.691
8.023
34.245 30.851 28.280 28.118 27.869
52.098 49.262
77.311 77.061 76.811
143.753 139.360 138.508 137.450 135.217 133.072 131.161 127.782 127.444 126.974 126.930 124.961 119.906 119.701 119.510
140.976
161.767
165.749
9
200
150
100
C13 standard parameters, BBO probe. F1: 125.900 F2: 1.000 EX: zgpg
SW1: 30303 PW: 2.7 us
OF1: 13850.7 NA: 274
PD: 2.0 sec
50
LB: 2.0
PPM
USER: root -- DATE: Wed May 02 18:17:26 2012 PTS1d: 16384 , 16384 Nuts - $mdl-3-58-p_2
9
200 150 100 50 PPM
30.851 28.280 28.133 27.869
52.098 49.262
131.161 127.782 127.444 126.974 126.930 124.961 119.906 119.701 119.510
143.753
10
4.02 3.22
0.981.02 2.05
1.04 0.93 0.99
9 8 7 6 5 4 3 2 1 PPM
1.531 1.327 1.312 1.298
2.897 2.882 2.867
7.872 7.858 7.775 7.760 7.721 7.707 7.686 7.671 7.388 7.373 7.359 7.341 7.328 7.314 7.307 7.291 7.277 7.261 6.756 6.742 6.727 5.300
10
180 160 140 120 100 80 60 40 20 PPM
14.057
22.741
77.296 77.047 76.797
140.815 139.448 138.640 137.553 135.070 132.616 127.650 127.371 126.915 126.871 124.990 119.804 119.671 119.495
11
3.00
8 7 6 5 4
3.00
1.96
0.91
3 2 1 PPM
1.370 1.356 1.340
2.856 2.842 2.827 2.812
3.901
7.260
8.145
11
180 160 140 120 100 80 60 40 20 PPM
11.060
21.668
52.112
77.311 77.047 76.797
133.116
143.709
161.870
166.822
11
200 150 100 50 0 PPM
11.060
21.668
52.127
143.709
12
3.07
1.96
8 7 6 5 4 3 3.22
1.82 2.99
2 1 PPM
1.395 1.382 1.367 1.336 1.321 1.307
2.790 2.776 2.761 2.746 2.584
4.388 4.374 4.361 4.347
7.259
12
200 150 100 50 PPM
14.410 11.956 11.221
21.565
60.825
77.296 77.032 76.782
127.297
155.905
163.795 162.590
12
150 100 50 PPM
14.410 11.956 11.221
21.565
60.825
13
5.85
3.21
2.01
9 8 2.00
7 6 5 1.75
4 3 2 1 PPM
1.410 1.402 1.395 1.389 1.380
2.906 2.891 2.876 2.861
4.429 4.415 4.400 4.386
5.282
7.468 7.455 7.441 7.425
8.036 8.021
13
200 150 100 50 0 PPM
14.351 11.280
21.697
61.310
77.340 77.076 76.826
130.089 128.355 127.253 126.827 126.563
155.111
164.177 162.340
13
180 160 140 120 100 80 60 40 20 PPM
14.351 11.280
21.697
61.325
130.089 128.355 126.563
14
3.10
10 8 3.00
1.88
0.94
6 4 2 PPM
3.949
7.478 7.466
8.285 8.114 8.103
14
150 100 50 PPM
52.274
77.326 77.061 76.811
134.467 131.250 128.869 126.930 126.430
143.842
162.561 161.811
14
200 150 100 50 PPM
52.274
131.250 128.869 126.930
143.842
4
3.32
8 3.32 2.98
1.48 1.52 0.88 1.25 2.25 1.31 1.07 1.11
0.98
7 6 5 0.96 0.93
4 2.34
3 2 1 PPM
2.378 2.364 2.332 2.096 2.069 1.920 1.849 1.838 1.830 1.747 1.722 1.697 1.670 1.647 1.540 1.517 1.498 1.477
3.672 3.654 3.638 3.631
7.767 7.752 7.712 7.697 7.683 7.669 7.588 7.573 7.559 7.512 7.497 7.488 7.473 7.458 7.440 7.425 7.417 7.411 7.402 7.387 7.305 7.291 7.276 7.261 7.244 7.224 7.207 7.185 7.170 7.157 4.539 4.533 4.522 4.514
4
150 100 50 PPM
26.649 24.445
33.011
50.496
64.616
77.399 77.135 76.885
144.488 143.871 140.785 138.670 135.760 134.732 131.059 130.706 129.119 128.708 128.296 128.002 127.312 124.359 123.036 120.377 119.172
161.180
4
200 150 100 50 PPM
26.664 24.460
33.026
50.511
64.616
135.760 134.732 131.059 130.706 129.119 128.708 128.296 128.002 127.312 124.359 123.036 120.391 119.172
S-1
1.95
8 1.94 2.26
0.92 1.00
7 6 5 4 3 2.09
1.00 1.10 1.10
2 1.17
1.13
1 PPM
2.320 2.310 2.299 2.294 2.271 2.251 1.950 1.943 1.925 1.919 1.901 1.895 1.877 1.870 1.808 1.781 1.695 1.685 1.415 1.392 1.264 1.258 1.240 1.216
3.401 3.387 3.379 3.365 3.357
4.422 4.414 4.400 4.393 4.379 4.371
5.287
7.614 7.600 7.385 7.370 7.357 7.326 7.312 7.298 7.280 7.261
S-1
200 150 100 50 0 PPM
25.841 23.666
32.541
42.136
77.414 77.149 76.900
89.521
129.163 128.884 125.534
137.142
S-1
200 150 100 50 0 PPM
25.841 23.666
32.541
42.121
89.521
129.163 128.869
137.142
S-2
3.34
9 8 3.08
2.08 1.00
7 6 5 4 3 0.97
1.03
2
2.68
1.22
1.10
1 0 PPM
2.806 2.787 2.769 2.762 2.597 2.590 2.576 2.570 2.557 2.550 2.148 2.121 1.993 1.968 1.715 1.682 1.630 1.621 1.460 1.455 1.436 1.242 1.222 1.203 1.186 1.163 1.140
7.282 7.264 7.250 7.236
7.582 7.568
S-2
200 150 100 50 PPM
27.251 25.165
35.862 34.363
54.419 54.287
77.370 77.120 76.870
128.928 127.885 127.767
135.849
S-2
200 150 100 50 0 PPM
27.251 25.165
35.862 34.378
54.419 54.287
128.928 127.767
135.849
