Supporting Information Ruthenium-catalyzed Decarboxylative and Dehydrogenative Formation of Highly Substituted Pyridines from Alkene-tethered Isoxazol-5(4H)-ones Kazuhiro kamoto,* Kohei Sasakura, Takuya Shimbayashi, and Kouichi he* Department of Energy and Hydrocarbon Chemistry, Graduate School of Engineering, Kyoto University, Katsura, Nishikyo-ku, Kyoto 615-8510 (Received May 13, 2016; CL-160480; E-mail: kokamoto@scl.kyoto-u.ac.jp, ohe@scl.kyoto-u.ac.jp) Copyright The Chemical Society of Japan
Ruthenium-catalyzed Decarboxylative and Dehydrogenative Formation of Highly Substituted Pyridines from Alkene-Tethered Isoxazol-5(4H)-ones Kazuhiro kamoto,* Kohei Sasakura, Takuya Shimbayashi and Kouichi he* Department of Energy and Hydrocarbon Chemistry, Graduate School of Engineering, Kyoto University, Katsura, Nishikyo-ku, Kyoto 615-8510, Japan e-mail: kokamoto@scl.kyoto-u.ac.jp; ohe@scl.kyoto-u.ac.jp 1. General. NMR spectra were recorded on JEL EX-400 spectrometer (400 MHz for 1 H NMR and 100 MHz for 13 C NMR) or Bruker AVANCE-500 spectrometer (500 MHz for 1 H NMR and 126 MHz for 13 C NMR). Chemical shifts are reported in δ ppm referenced to CDCl 3 (δ 7.26 for 1 H NMR and δ 77.00 for 13 C NMR). High-resolution mass spectra (HRMS) were measured with JEL JMX-SX 102A spectrometer (FAB) or ThermoFisher Scientific EXACTIVE (ESI). Dry toluene and THF were purified by passed through a neutral alumina column under nitrogen atmosphere. All other materials were purchased and used without further purification. 2. Preparation of substrates. The yields have not been optimised. The following isoxazol-5(4h)-ones were made according to the literature procedures 1,2 : 1a, 1c, 1e, 1o, 1p. 3-(4-methoxyphenyl)-4-methyl-4-(2-methylallyl)isoxazol-5(4H)-one (1b) Et Cl (1.2 equiv) K 2 C 3 (1.5 equiv) NaI (0.25 equiv) acetone, reflux, 24 h Et NH 2 H HCl (3.0 equiv) NaAc (1.0 equiv) EtH/H 2 reflux, 3 days N To a 50 ml round-bottle flask was added ethyl 3-(4-methoxyphenyl)-2-methyl-3-oxopropanoate (1.00 g, 4.25 mmol), acetone (8 ml), 3-chloro-2-methylprop-1-ene (0.50 ml, 5.1 mmol), K 2 C 3 (0.880 g, 6.4 mmol) and NaI (0.156 g, 1.1 mmol). The reaction mixture was refluxed for 24 h, then filtered and evaporated. H 2 (10 ml) was added and the mixture was extracted with AcEt (20 ml x 3). The combined organic layer was washed with brine (15 ml), the dried over MgS 4, filtered and evaporated. The residue was subjected to silica gel column chromatography (hexane/acet = 10:1) to afford ethyl 2-(4-methoxybenzoyl)-2,4-dimethylpent-4-enoate as pale yellow oil (0.795 g, 2.74 mmol) in 64% yield. S1
To a 50 ml round-bottle flask was added ethyl 2-(4-methoxybenzoyl)-2,4-dimethylpent-4-enoate (0.795 g, 2.74 mmol), NH 2 H HCl (0.571 g, 8.22 mmol), NaAc (0.227 g, 2.74 mmol), EtH (4.5 ml) and H 2 (0.9 ml). The reaction mixture was refluxed for 3 days, then 12 N HClaq (0.91 ml) was added to the mixture and refluxed for more 30 minutes. After cooling to rt, H 2 (5 ml) was added and the reaction mixture was extracted with AcEt (20 ml x 3). The combined organic layer was washed with brine (15 ml), the dried over MgS 4, filtered and evaporated. The residue was subjected to silica gel column chromatography (hexane/acet = 8:1) to afford 3-(4-methoxyphenyl)-4-methyl-4-(2-methylallyl)isoxazol-5(4H)-one as an orange solid (0.426 g, 1.64 mmol) in 60 % yield. mp. 33.8-36.0 ºC. 1 H NMR (500 MHz, CDCl 3, 25 ºC): δ 1.63 (s, 3H), 2.75 (s, 2H), 3.87 (s, 3H), 4.59 (s, 1H), 4.75 (s, 1H), 6.98 (d, J = 8.9 Hz, 2H), 7.75 (d, J = 9.2 Hz, 2H). 13 C NMR (75.5 MHz, CDCl 3, 25 ºC): δ 22.9, 23.7, 44.8, 50.6, 55.4, 114.5, 115.7, 120.4, 128.5, 139.1, 162.1, 167.9, 181.4. HRMS (ESI) calcd for C 15 H 17 N 3 Na (M+Na) + 282.1101, found 282.1093. 3-(4-bromophenyl)-4-methyl-4-(2-methylallyl)isoxazol-5(4H)-one (1d) Br Et Cl (1.2 equiv) K 2 C 3 (1.5 equiv) NaI (0.25 equiv) Br acetone, reflux, 24 h H Et 1) NaH (1.2 equiv) 2) I (1.3 equiv) THF, 0 C to rt, 20 h Br Et NH 2 H HCl (3.0 equiv) NaAc (1.0 equiv) EtH/H 2 reflux, 3 days Br N To a 200 ml round-bottle flask was added ethyl 3-(4-bromophenyl)-3-oxopropanoate (4.55 g, 16.8 mmol), acetone (30 ml), 3-chloro-2-methylprop-1-ene (1.97 ml, 20.2 mmol), K 2 C 3 (3.48 g, 25.2 mmol) and NaI (0.629 g, 4.2 mmol). The reaction mixture was refluxed for 24 h, then filtered and evaporated. H 2 (40 ml) was added and the mixture was extracted with AcEt (30 ml x 3). The combined organic layer was washed with brine (40 ml), the dried over MgS 4, filtered and evaporated. The residue was subjected to silica gel column chromatography (hexane/acet = 20:1) to afford ethyl 2-(4-bromobenzoyl)-4-methylpent-4-enoate as a white solid (2.83 g, 8.71 mmol) in 52% yield. To a flamed-dried 100 ml two-necked round-bottle flask was added NaH (60% in mineral oil, 0.384 mg, 9.6 mmol) and THF (20 ml). Ethyl 2-(4-bromobenzoyl)-4-methylpent-4-enoate (2.60 g, 8.0 mmol) was added to the reaction mixture at 0 C and the mixture was stirred for 30 min at the S2
same temperature. Then I (0.65 ml, 10.4 mmol) was added. After stirred at rt for 20 h, the mixture was quenched by H 2 (20 ml), then extracted with AcEt (10 ml 4). The combined organic layer was washed with brine (15 ml), then dried over MgS 4, filtered and evaporated. The residue was subjected to silica gel column chromatography (hexane/acet = 30:1) to afford ethyl 2-(4-bromobenzoyl)-2,4-dimethylpent-4-enoate as colorless oil (1.61 g, 4.75 mmol) in 59% yield. Isoxazolone 1d was prepared from ethyl 2-(4-bromobenzoyl)-2,4-dimethylpent-4-enoate according to similar procedure to isoxazolone 1b. 0.580 g, 1.88 mmol, 42%. A pale red solid. mp. 62.0-62.8 ºC. 1 H NMR (400 MHz, CDCl 3, 25 ºC): δ 1.57 (s, 3H), 1.63 (s, 3H), 2.72 (d, J = 14.6 Hz, 1H), 2.78 (d, J = 14.7 Hz, 1H), 4.56 (s, 1H), 4.76 (t, J = 1.4 Hz, 1H), 7.62 (d, J = 9.2 Hz, 2H), 7.67 (d, J = 8.7 Hz, 2H). 13 C NMR (100 MHz, CDCl 3, 25 ºC): δ 22.9, 23.6, 44.8, 50.3, 115.9, 126.3, 127.0, 128.2, 132.4, 138.8, 167.6, 180.9. HRMS (FAB) calcd for C 14 H 15 N 2 Br (M+H) + 308.0286, found 308.0287. 4-methyl-4-(2-methylallyl)-3-(thiophen-2-yl)isoxazol-5(4H)-one (1f) S Et Cl (1.2 equiv) K 2 C 3 (1.5 equiv) NaI (0.25 equiv) acetone, reflux, 24 h S H Et 1) NaH (1.2 equiv) 2) I (1.3 equiv) THF, 0 C to rt, 20 h S Et 1) NH 2 H HCl (3.0 equiv) NaAc (1.0 equiv) 2) NaH (4.0 equiv) S N EtH/H 2, reflux, 4 days Isoxazolone 1f was prepared according to similar procedure to isoxazolone 1d except the final step. To a 50 ml round-bottle flask was added ethyl 2,4-dimethyl-2-(thiophene-2-carbonyl)pent-4-enoate (2.66 g, 10 mmol), NH 2 H HCl (2.08 g, 30.0 mmol), NaAc (0.828 g, 10.0 mmol), EtH (15 ml) and H 2 (3 ml). The reaction mixture was refluxed for 3 days, then NaH (1.60 g, 40.0 mmol) was added to the mixture and refluxed for more 1 day. After cooling to rt, H 2 (5 ml) was added and the reaction mixture was extracted with AcEt (30 ml x 3). The combined organic layer was washed with brine (40 ml), the dried over MgS 4, filtered and evaporated. The residue was subjected to silica gel column chromatography (hexane/acet = 20:1) to afford 4-methyl-4-(2-methylallyl)-3-(thiophen-2-yl)isoxazol-5(4H)-one as colorless oil (0.613 g, 2.61 mmol) in 26% yield. 1 H NMR (400 MHz, CDCl 3, 25 C): δ 1.59 (s, 3H), 1.64 (s, 3H), 2.75 (s, 2H), 4.62 (s, 1H), 4.78 (quin, J = 2.3 Hz, 1H), 7.16 (dd, J = 4.0, 5.0 Hz, 1H), 7.54-7.56 (m, 2H). NMR (126 MHz, CDCl 3, 25 ºC): δ 22.9, 23.6, 44.8, 50.8, 116.1, 127.8, 129.0, 129.8, 129.9, 138.8, 13 C S3
164.6, 180.6. HRMS (ESI) calcd for C 12 H 13 N 2 SNa (M+Na) + 258.0559, found 258.0554. 4-methyl-3-phenyl-4-(2-phenylallyl)isoxazol-5(4H)-one (1g) Et 1) NaH (1.2 equiv) 2) Br (1.4 equiv) Et THF, 0 C to rt, 20 h NH 2 H HCl (3.0 equiv) NaAc (1.0 equiv) EtH/H 2 reflux, 3 days N To a flamed-dried 50 ml two-necked round-bottle flask was added NaH (60% in mineral oil, 0.242 g, 6.0 mmol) and THF (10 ml). Ethyl 2-methyl-3-oxo-3-phenylpropanoate (1.03 g, 5.0 mmol) was added to the reaction mixture at 0 C and the mixture was stirred for 30 min at the same temperature. Then (3-bromoprop-1-en-2-yl)benzene (1.38 g, 7.0 mmol) was added. After stirred at rt for 20 h, the mixture was quenched by saturated NH 4 Cl aq (7 ml), then extracted with AcEt (7 ml 4). The combined organic layer was washed with brine (15 ml), then dried over MgS 4, filtered and evaporated. The residue was subjected to silica gel column chromatography (hexane/acet = 25:1) to afford ethyl 2-benzoyl-2-methyl-4-phenylpent-4-enoate as pale yellow oil (1.17 g, 3.65 mmol) in 73% yield. Isoxazolone 1g was prepared from ethyl 2-benzoyl-2-methyl-4-phenylpent-4-enoate according to similar procedure to isoxazolone 1b. 0.431 g, 1.48 mmol, 40%. Colorless oil. 1 H NMR (500 MHz, CDCl 3, 25 ºC): δ 1.70 (s, 3H), 3.19 (s, 2H), 5.02 (s, 1H), 5.14 (s, 1H), 7.05-7.13 (m, 5H), 7.32 (t, J = 7.7 Hz, 2H), 7.42 (t, J = 7.7 Hz, 2H), 7.52 (d, J = 7.4 Hz, 1H). 13 C NMR (75.5 MHz, CDCl 3, 25 ºC): δ 23.6, 42.3, 51.2, 118.4, 126.5, 126.8, 127.8, 127.95, 128.04, 128.7, 131.2, 139.7, 143.3, 167.8, 180.7. HRMS (ESI) calcd for C 19 H 17 N 2 Na (M+Na) + 314.1152, found 314.1142. 3-(4-bromophenyl)-4-methyl-4-(2-phenylallyl)isoxazol-5(4H)-one (1h) Br Et 1) NaH (1.2 equiv) 2) Br (1.4 equiv) THF, 0 C to rt, 20 h Br Et NH 2 H HCl (3.0 equiv) NaAc (1.0 equiv) EtH/H 2 reflux, 3 days Br N Isoxazolone 1h was prepared according to similar procedure to isoxazolone 1g. 1.41 g, 3.80 mmol, 38% (for 2 steps). A white solid. mp. 119.0-120.8 ºC. 1 H NMR (400 MHz, CDCl 3, 25 ºC): δ 1.68 (s, 3H), 3.13 (d, J = 14.2 Hz, 2H), 3.18 (d, J = 14.2 Hz, 2H), 5.04 (s, 1H), 5.15 (s, 1H), 7.03 (d, J = 6.8 Hz, 2H), 7.09 (t, J = 8.3 Hz, 2H), 7.14 (t, J = 6.8 Hz, 1H), 7.34 (d, J = 8.3 Hz, 2H), 7.44 (d, J = 8.3 Hz, 2H). 13 C NMR (75.5 MHz, CDCl 3, 25 ºC): δ 23.4, 42.3, 51.1, 118.6, 125.8, 126.8, 126.9, S4
127.86, 127.93, 128.0, 132.0, 139.6, 143.1, 167.0, 180.3. HRMS (FAB) calcd for C 19 H 17 N 2 Br (M+H) + 370.0443, found 370.0450. 4-cinnamyl-4-methyl-3-phenylisoxazol-5(4H)-one (1i) Et H (1.3 equiv) Pd(P 3 ) 4 (2 mol%) AcH (10 mol%) 100 C, neat, 8 h Et NH 2 H HCl (3.0 equiv) NaAc (1.0 equiv) EtH/H 2 reflux, 3 days N Ethyl (E)-2-benzoyl-2-methyl-5-phenylpent-4-enoate was made according to the literature procedures. 3 Isoxazolone 1i was prepared according to similar procedure to isoxazolone 1b. 2.37 g, 8.13 mmol, 54% (for 2 steps). An orange solid. mp. 54.5-55.5 C. 1 H NMR (500 MHz, CDCl 3, 25 ºC): 1.68 (3, 3H), 2.86 (d, J = 7.7 Hz, 2H), 5.84 (td, J = 7.7, 15.6 Hz, 1H), 6.36 (d, J = 15.6 Hz, 1H), 7.19-7.26 (m, 5H), 7.50 (t, J = 7.5 Hz, 2H), 7.55 (t, J = 7.5 Hz, 1H), 7.78 (d, J = 6.7 Hz, 2H). 13 C NMR (126 MHz, CDCl 3, 25 ºC): δ 21.9, 40.4, 51.3, 121.0, 126.5, 126.9, 127.9, 128.0, 128.5, 129.3, 131.7, 135.8, 136.2, 168.2, 180.9. HRMS (ESI) calcd for C 19 H 17 N 2 Na (M+Na) + 314.1152, found 314.1145. (E)-4-methyl-4-(2-methyl-3-phenylallyl)-3-phenylisoxazol-5(4H)-one (1j) 1) NaH (1.2 equiv) NH 2 H HCl Br (1.1 equiv) N 2) (1.3 equiv) pyridine Et Et (1.1 equiv) THF, 0 C to rt, 20 h EtH reflux, 3 days Isoxazolone 1j was prepared according to similar procedure to isoxazolone 1g except the final step. To a 50 ml round-bottle flask was added ethyl (E)-2-benzoyl-2,4-dimethyl-5-phenylpent-4-enoate (1.65 g, 4.88 mmol), NH 2 H HCl (0.372 g, 5.36 mmol), pyridine (0.44 ml, 5.36 mmol), EtH (10 ml). The reaction mixture was refluxed for 3 days. After cooling to rt, H 2 (5 ml) was added and the reaction mixture was extracted with AcEt (20 ml x 3). The combined organic layer was washed with brine (15 ml), the dried over MgS 4, filtered and evaporated. The residue was subjected to silica gel column chromatography (hexane/acet = 15:1) to afford (E)-4-methyl-4-(2-methyl-3-phenylallyl)-3-phenylisoxazol-5(4H)-one as an yellow solid (0.748 g, 2.45 mmol) in 50 % yield. mp. 45.5-46.5 ºC. 1 H NMR (500 MHz, CDCl 3, 25 ºC): δ 1.67 (d, J = 1.2 Hz, 3H), 1.73 (s, 3H), 2.91 (s, 2H), 6.10 (s, 1H), 7.00 (d, J = 7.4 Hz, 2H), 7.16 (t, J = 7.4 Hz, 1H), 7.24 (t, J = 7.4 Hz, 2H), 7.46-7.54 (m, 3H), 7.83 (d, J = 8.6 Hz, 2H). 13 C NMR (126 MHz, CDCl 3, S5
25 ºC): δ 18.3, 23.4, 47.8, 51.0, 126.6, 126.9, 128.0, 128.3, 128.8, 129.1, 130.7, 131.6, 131.7, 137.1, 168.4, 181.3. HRMS (ESI) calcd for C 20 H 19 N 2 Na (M+Na) + 328.1308, found 328.1306. (E)-4-methyl-4-(2-methylbut-2-en-1-yl)-3-phenylisoxazol-5(4H)-one (1k) Et 1) K 2 C 3 (2.0 equiv) Br 2) (1.1 equiv) acetone, reflux, 36 h Et NH 2 H HCl (3.0 equiv) NaAc (1.0 equiv) EtH/H 2 reflux, 3 days N Isoxazolone 1k was prepared according to similar procedure to isoxazolone 1b. 1.23 g, 5.04 mmol, 52% (for 2 steps). Pale yellow oil. 1 H NMR (500 MHz, CDCl 3, 25 ºC): δ 1.42 (d, J = 6.7 Hz, 3H), 1.43 (s, 3H), 1.64 (s, 3H), 2.73 (s, 2H), 5.11 (q, J = 6.7 Hz, 1H), 7,46-7.54 (m, 3H), 7.79 (d, J = 7.1 Hz, 2H). 13 C NMR (126 MHz, CDCl 3, 25 ºC): δ 13.4, 16.3, 23.3, 47.2, 51.0, 125.2, 126.9, 128.4, 129.0, 129.2, 131.5, 168.6, 181.4. HRMS (ESI) calcd for C 15 H 17 N 2 Na (M+Na) + 266.1152, found 266.1151. 4-(cyclohex-1-en-1-ylmethyl)-4-methyl-3-phenylisoxazol-5(4H)-one (1l) Et 1) NaH (1.2 equiv) 2) Br (1.4 equiv) Et THF, 0 C to rt, 20 h 1) NH 2 H HCl (3.0 equiv) NaAc (1.0 equiv) 2) NaH (4.0 equiv) EtH/H 2, reflux, 4 days N Isoxazolone 1l was prepared according to similar procedure to isoxazolone 1f. 0.252 g, 0.934 mmol, 47% (for 2 steps). Colorless oil. 1 H NMR (500 MHz, CDCl 3, 25 ºC): δ 1.37-1.49 (m, 4H), 1.63 (s, 3H), 1.68-1.74 (m, 2H), 1.74-1.87 (m, 2H), 2.68 (s, 2H), 5.29 (s, 1H), 7.46-7.54 (m, 3H), 7.79 (d, J = 7.7 Hz, 2H). 13 C NMR (126 MHz, CDCl 3, 25 ºC): δ 21.6, 22.5, 23.2, 25.0, 28.8, 45.5, 50.8, 126.8, 127.1, 128.2, 128.9, 131.36, 131.39, 168.6, 181.4. HRMS (ESI) calcd for C 17 H 19 2 NNa (M+Na) + 292.1308, found 292.1303. 4,4-Diallyl-3-phenyl-4H-isoxazol-5-one (1m) S6
Et Br (5.0 equiv) K 2 C 3 (3.0 equiv) acetone, reflux, 24 h Et NH 2 H HCl (3.0 equiv) NaAc (1.0 equiv) EtH/H 2 reflux, 36 h N To a 300 ml round-bottle flask was added ethyl 3-oxo-3-phenylpropanoate (5.19 ml, 30.0 mmol), acetone (120 ml), 3-bromoprop-1-ene (13.0 ml, 150 mmol) and K 2 C 3 (12.4 g, 90.0 mmol). The reaction mixture was refluxed for 24 h, then filtered and evaporated. H 2 (10 ml) was added and the mixture was extracted with AcEt (20 ml x 3). The combined organic layer was washed with brine (15 ml), the dried over MgS 4, filtered and evaporated. The residue was subjected to silica gel column chromatography (hexane/acet = 10:1) to afford ethyl 2-allyl-2-benzoylpent-4-enoate as pale yellow oil (8.101 g, 29.7 mmol) in 99% yield. Isoxazolone 1m was prepared from ethyl 2-allyl-2-benzoylpent-4-enoate according to similar procedure to isoxazolone 1b. 571 mg, 2.37 mmol, 8%. Pale yellow oil. 1 H NMR (CDCl 3 ): δ 2.73 (dd, J = 14.2, 7.3 Hz, 2H), 2.78 (dd, J = 14.2, 7.3 Hz, 2H), 5.06 (dd, J = 16.8, 1.5 Hz, 1H), 5.08 (d, J = 10.7 Hz, 1H), 5.49 (ddt, J = 16.1, 11.2, 7.3 Hz, 1H), 7.45 7.58 (m, 3H), 7.78 (d, J = 6.8 Hz, 2H). 13 C NMR (CDCl 3 ): δ 40.0, 56.5, 121.0, 126.7, 128.0, 129.2, 129.6, 131.7, 166.4, 179.8. HRMS (ESI) calcd for C 15 H 15 2 NNa (M+Na) + 264.0995, found 264.0995. (E)-4-methyl-4-(2-methylpenta-2,4-dien-1-yl)-3-phenylisoxazol-5(4H)-one (1n) Et K 2 C 1) 3 (2.0 equiv) Br 2) (1.1 equiv) acetone, reflux, 58 h Et NH 2 H HCl (3.0 equiv) NaAc (1.0 equiv) EtH/H 2 reflux, 3 days N Isoxazolone 1n was prepared according to similar procedure to isoxazolone 1b. 1.42 g, 5.56 mmol, 44% (for 2 steps). Yellow oil. 1 H NMR (500 MHz, CDCl 3, 25 ºC): δ 1.59 (s, 3H), 1.68 (s, 3H), 2.78 (s, 2H), 4.96 (d, J = 16.8 Hz, 1H), 4.99 (d, J = 10.6 Hz, 1H), 5.60 (d, J = 10.6 Hz, 1H), 6.36 (dt, J = 16.8, 10.6 Hz, 1H), 7.47-7.54 (m, 3H), 7,78 (d, J = 8.6 Hz, 2H). 13 C NMR (126 MHz, CDCl 3, 25 ºC): δ 17.1, 23.4, 47.1, 50.9, 117.6, 126.9, 128.2, 129.1, 130.8, 131.3, 131.6, 132.1, 168.4, 181.2. HRMS (ESI) calcd for C 16 H 17 2 NNa (M+Na) + 278.1152, found 278.1151. S7
3. Decarboxylative cycloaddition of isoxazol-5(4h)-ones. N [RuCl 2 (p-cymene)] 2 (2.5 mol%) 5,5'-dimethyl-2,2'-bipyridyl (5 mol%) toluene, 100 C, 19 h N 1a 4a Typical procedure: To a flame-dried Schlenk tube were added toluene (2.0 ml), [RuCl 2 (p-cymene)] 2 (3.1 mg, 0.005 mmol) and 5,5 -dimethyl-2,2 -bipyridyl (1.8 mg, 0.01 mmol). After stirring for 15 min, 4-methyl-4-(2-methylallyl)-3-phenylisoxazol-5(4H)-one 1a (45.9 mg, 0.2 mmol) was added and stirred at 100 ºC for 19 h. The reaction mixture was filtered through a pad of Florisil and the filtrate was concentrated under vacuum. The residue was chromatographed on Silica Gel 60N (hexane/acet = 8/1) to give 3,5-dimethyl-2-phenylpyridine 4a as pale pink oil (25.2 mg, 0.138 mmol) in 69% yield. CAS: [27063-86-1]. 1 H NMR (500 MHz, CDCl 3, 25 C): δ 2.32 (s, 3H), 2.34 (s, 3H), 7.37 (t, J = 7.6 Hz, 1H), 7.39 (s, 1H), 7.43 (t, J = 7.6 Hz, 2H), 7.50 (d, J = 7.6 Hz, 2H), 8.35 (s, 1H). 13 C NMR (126 MHz, CDCl 3, 25 C): δ 17.9, 19.9, 127.6, 128.1, 128.9, 130.1, 131.4, 139.1, 140.6, 147.4, 155.9. HRMS (ESI) calcd for C 13 H 14 N (M+H) + 184.1121, found 184.1118. 2-(4-methoxyphenyl)-3,5-dimethylpyridine (4b) CAS: [90713-93-2] N Pale red oil (25.4 mg, 0.119 mmol, 60% yield). 1 H NMR (500 MHz, CDCl 3, 25 C): δ 2.33 (s, 6H), 3.85 (s, 3H), 6.96 (ddd, J = 1.8, 3.1, 8.6 Hz, 2H), 7.37 (s, 1H), 7.46 (ddd, J = 1.8, 3.1, 8.6 Hz, 2H), 8.33 (s, 1H). 13 C NMR (126 MHz, CDCl 3, 25 C): δ 18.1, 20.3, 55.5, 113.7, 130.2, 130.5, 131.3, 133.4, 139.4, 147.6, 155.8, 159.4. HRMS (ESI) calcd for C 14 H 16 N (M+H) + 214.1226, found 214.1222. 3,5-dimethyl-2-(4-(trifluoromethyl)phenyl)pyridine (4c) F 3 C N S8
Yellow oil (29.0 mg, 0.115 mmol, 58% yield). 1 H NMR (500 MHz, CDCl 3, 25 C): δ 2.32 (s, 3H), 2.36 (s, 3H), 7.42 (s, 1H), 7.63 (d, J = 8.3 Hz, 2H), 7.69 (d, J = 8.3 Hz, 2H), 8.39 (s, 1H). 13 C NMR (126 MHz, CDCl 3, 25 C): δ 17.9, 19.7, 124.2 (q, J = 271.8 Hz), 125.1 (q, J = 2.9 Hz), 129.4, 129.8 (q, J = 31.5 Hz), 130.2, 132.3, 139.3, 144.1, 147.7, 154.4. HRMS (ESI) calcd for C 14 H 13 NF 3 (M+H) + 252.0995, found 252.0990. 2-(4-bromophenyl)-3,5-dimethylpyridine (4d) Br N Colorless oil (33.4 mg, 0.127 mmol, 64% yield). 1 H NMR (500 MHz, CDCl 3, 25 C): δ 2.30 (s, 3H), 2.33 (s, 3H), 7.38 (s, 1H), 7.39 (d, J = 8.3 Hz, 2H), 7.55 (d, J = 8.3 Hz, 2H), 8.34 (s, 1H). 13 C NMR (126 MHz, CDCl 3, 25 C): δ 17.9, 19.8, 121.9, 130.0, 130.7, 131.2, 131.8, 139.2, 139.5, 147.5, 154.6. HRMS (ESI) calcd for C 13 H 13 NBr (M+H) + 262.0226, found 262.0220. 3,5-dimethyl-2-(naphthalen-2-yl)pyridine (4e) N A white solid (32.0 mg, 0.133 mmol, 66% yield). mp. 92.5-93.5 ºC. 1 H NMR (500 MHz, CDCl 3, 25 C): δ 2.37 (s, 3H), 2.38 (s, 3H), 7.43 (s, 1H), 7.48 (m, 2H), 7.66 (dd, J = 1.5, 8.3 Hz, 1H), 7.88 (m, 2H), 7.91 (d, J = 8.3 Hz, 1H), 7.97 (s, 1H), 8.40 (s, 1H). 13 C NMR (126 MHz, CDCl 3, 25 C): δ 18.0, 20.0, 126.0, 126.1, 127.1, 127.6, 127.7, 128.1, 128.3, 130.4, 131.6, 132.8, 133.1, 138.1, 139.2, 147.5, 155.8. HRMS (ESI) calcd for C 17 H 16 N (M+H) + 234.1277, found 234.1273. 3,5-dimethyl-2-(thiophen-2-yl)pyridine (4f) S N Yellow oil (16.4 mg, 0.087 mmol, 43% yield). 1 H NMR (500 MHz, CDCl 3, 25 C): δ 2.31 (s, 3H), 2.52 (s, 3H), 7.10 (dd, J = 3.7, 4.9 Hz, 1H), 7.34 (s, 1H), 7.38 (d, J = 4.9 Hz, 1H), 7.41 (d, J = 3.7 Hz, 1H), 8.29 (s, 1H). 13 C NMR (126 MHz, CDCl 3, 25 C): δ 17.9, 21.2, 126.3, 126.7, 127.5, 129.1, 131.2, 139.8, 145.2, 147.3, 148.8. HRMS (ESI) calcd for C 11 H 12 NS (M+H) + 190.0685, found 190.0681. S9
3-methyl-2,5-diphenylpyridine (4g) CAS: [90554-53-3] N A white solid (32.2 mg, 0.131 mmol, 66% yield). mp. 112.2-112.3 ºC. 1 H NMR (500 MHz, CDCl 3, 25 C): δ 2.44 (s, 3H), 7.41 (t, J = 7.3 Hz, 2H), 7.47 (t, J = 7.3 Hz, 2H), 7.49 (t, J = 7.7 Hz, 2H), 7.57 (d, J = 7.3 Hz, 2H), 7.63 (d, J = 7.7 Hz, 2H), 7.77 (d, J = 1.7 Hz, 1H), 8.77 (d, J = 1.7 Hz, 1H). 13 C NMR (126 MHz, CDCl 3, 25 C): δ 20.2, 127.1, 127.9, 128.2, 128.99, 129.03, 130.6, 135.0, 136.9, 137.7, 140.3, 145.4, 157.5. HRMS (ESI) calcd for C 18 H 16 N (M+H) + 246.1277, found 246.1273. 2-(4-bromophenyl)-3-methyl-5-phenylpyridine (4h) Br N A white solid (42.1 mg, 0.130 mmol, 65% yield). mp. 158.9-159.9 ºC. 1 H NMR (500 MHz, CDCl 3, 25 C): δ 2.43 (s, 3H), 7.42 (t, J = 7.6 Hz, 1H), 7.48 (t, J = 8.6 Hz, 2H), 7.49 (t, J = 7.6 Hz, 2H), 7.60 (d, J = 8.6 Hz, 2H), 7.62 (d, J = 7.6 Hz, 2H), 7.78 (s, 1H), 8.75 (s, 1H). 13 C NMR (126 MHz, CDCl 3, 25 C): δ 20.4, 122.6, 127.3, 128.3, 129.3, 130.9, 131.0, 131.6, 135.5, 137.3, 137.8, 139.4, 145.8, 156.4. HRMS (ESI) calcd for C 18 H 15 NBr (M+H) + 324.0382, found 324.0377. 3-methyl-2,6-diphenylpyridine (4i) N Pink oil (24.3 mg, 0.0991 mmol, 50% yield). 1 H NMR (500 MHz, CDCl 3, 25 C): δ 2.39 (s, 3H), 7.35-7.47 (m, 6H), 7.61 (m, 4H), 8.05 (d, J = 7.0 Hz, 2H). 13 C NMR (126 MHz, CDCl 3, 25 C): δ 19.9, 118.6, 126.8, 127.8, 128.0, 128.5, 128.6, 129.1, 129.2, 139.3, 139.4, 140.9, 154.5, 158.1. HRMS (ESI) calcd for C 18 H 16 N (M+H) + 246.1277, found 246.1274. 3,5-dimethyl-2,6-diphenylpyridine (4j) CAS: [14435-89-3] S10
N A white solid (32.0 mg, 0.123 mmol, 62% yield). mp. 129.5-130.1 ºC. 1 H NMR (500 MHz, CDCl 3, 25 C): δ 2.37 (s, 6H), 7.35 (t, J = 7.3 Hz, 2H), 7.42 (dd, J = 7.3, 7.6 Hz, 4H), 7.47 (s, 1H), 7.58 (d, J = 7.6 Hz, 4H). 13 C NMR (126 MHz, CDCl 3, 25 C): δ 19.6, 127.6, 128.0, 129.1, 129.2, 140.7, 141.1, 155.8. HRMS (ESI) calcd for C 19 H 18 N (M+H) + 260.1434, found 260.1431. 2,3,5-trimethyl-6-phenylpyridine (4k) CAS: [1350770-03-4] N Colorless oil (27.1 mg, 0.137 mmol, 69% yield). 1 H NMR (500 MHz, CDCl 3, 25 C): δ 2.26 (s, 3H), 2.29 (s, 3H), 2.51 (s, 3H), 7.29 (s, 1H), 7.34 (t, J = 7.3 Hz, 1H),7.42 (t, J = 8.0 Hz, 2H), 7.49 (d, J = 7.1 Hz, 2H). 13 C NMR (126 MHz, CDCl 3, 25 C): δ 18.9, 19.6, 22.4, 127.7, 128.0, 128.3, 129.3, 129.9, 139.9, 141.1, 154.3, 155.6. HRMS (ESI) calcd for C 14 H 16 N (M+H) + 198.1277, found 198.1275. 3-methyl-2-phenyl-5,6,7,8-tetrahydroquinoline (4l) N Colorless oil (23.8 mg, 0.107 mmol, 53% yield). 1 H NMR (500 MHz, CDCl 3, 25 C): δ 1.80-1.84 (m, 2H), 1.88-1.93 (m, 2H), 2.25 (s, 3H), 2.77 (t, J = 6.5 Hz, 2H), 2.93 (t, J = 6.4 Hz, 2H), 7.24 (s, 1H), 7.34 (t, J = 7.3 Hz, 1H), 7.41 (t, J = 7.3 Hz, 2H), 7.47 (d, J = 7.3 Hz, 2H). 13 C NMR (126 MHz, CDCl 3, 25 C): δ 19.7, 23.1, 23.6, 28.6, 32.5, 127.7, 127.8, 128.3, 129.2, 130.8, 139.3, 141.2, 154.6, 156.1. HRMS (ESI) calcd for C 16 H 18 N (M+H) + 224.1434, found 224.1429. 3-allyl-2-phenylpyridine (4m) N Pale pink oil (28.8 mg, 0.147 mmol, 74% yield). 1 H NMR (500 MHz, CDCl 3, 25 C): δ 3.41 (d, J = 6.4 Hz, 2H), 4.98 (dd, J = 3.2, 17.1 Hz, 1H), 5.10 (dd, J = 3.2, 10.4 Hz, 1H), 5.91 (ddt, J = 17.1, 10.4, 6.4 Hz, 1H), 7.23 (dd, J = 4.6, 8.0 Hz, 1H), 7.38-7.45 (m, 3H), 7.49-7.51 (m, 2H), 7.62 (dd, J = S11
1.5, 7.6 Hz, 1H), 8.56 (dd, J = 1.5, 4.6 Hz, 1H). 13 C NMR (126 MHz, CDCl 3, 25 C): δ 36.8, 116.7, 122.2, 127.8, 128.1, 128.9, 132.7, 136.7, 137.9, 140.3, 147.3, 158.9. HRMS (ESI) calcd for C 14 H 14 N (M+H) + 196.1121, found 196.1119. 2-ethyl-3,5-dimethyl-6-phenylpyridine (4n ) N Et Pale red oil (27.4 mg, 0.130 mmol, 65% yield). 1 H NMR (500 MHz, CDCl 3, 25 C): δ 1.27 (t, J = 7.6 Hz, 3H), 2.83 (q, J = 7.6 Hz, 2H), 2.27 (s, 3H), 2.33 (s, 3H), 7.29 (s, 1H), 7.34 (t, J = 7.3 Hz, 1H), 7.42 (t, J = 7.3 Hz, 2H), 7.51 (d, J = 7.3 Hz, 2H). 13 C NMR (126 MHz, CDCl 3, 25 C): δ 13.5, 18.3, 19.7, 28.7, 127.7, 127.9, 128.3, 129.1, 129.4, 140.4, 141.3, 155.6, 159.0. HRMS (ESI) calcd for C 15 H 18 N (M+H) + 212.1434, found 212.1432. 5-methyl-2,3-diphenylpyridine (4o) N A white solid (9.2 mg, 0.038 mmol, 19% yield). mp. 119.5-120.5 ºC. 1 H NMR (500 MHz, CDCl 3, 25 C): δ 2.42 (s, 3H), 7.16-7.18 (m, 2H), 7.21-7.22 (m, 3H), 7.25-7.27 (m, 3H), 7.32-7.34 (m, 2H), 7.53 (d, J = 1.5 Hz, 1H), 8.52 (d, J = 1.5 Hz, 1H). 13 C NMR (126 MHz, CDCl 3, 25 C): δ 18.0, 127.1, 127.4, 127.8, 128.2, 129.5, 129.8, 131.6, 135.5, 139.1, 140.0, 140.1, 148.8, 154.5. HRMS (ESI) calcd for C 18 H 16 N (M+H) + 246.1277, found 246.1272. 3-(2-methylallyl)-2-phenyl-1H-indole (5o) H N A pale orange solid (36.4 mg, 0.147 mmol, 74% yield). mp. 58.5-59.5 ºC. 1 H NMR (500 MHz, CDCl 3, 25 C): δ 1.83 (s, 3H), 3.54 (s, 2H), 4.67 (s, 1H), 4.83 (s, 1H), 7.12 (t, J = 7.5 Hz, 1H), 7.20 (t, J = 7.5 Hz, 1H), 7.34-7.38 (m, 2H), 7.45 (t, J = 7.5 Hz, 2H), 7.54-7.59 (m, 3H), 8.04 (br, 1H). 13 C NMR (126 MHz, CDCl 3, 25 C): δ 23.0, 33.0, 110.7, 110.8, 111.0, 119.56, 119.6, 122.2, 127.6, 127.8, 128.8, 129.7, 133.1, 135.2, 135.9, 144.8. HRMS (ESI) calcd for C 18 H 18 N (M+H) + 248.1434, S12
found 248.1429. 3-methyl-2-phenyl-1H-indole (5p) CAS: [10257-92-8] H N A pale pink solid (28.9 mg, 0.139 mmol, 70% yield). mp. 86.5-87.5 ºC. 1 H NMR (500 MHz, CDCl 3, 25 C): δ 2.46 (s, 3H), 7.14 (t, J = 7.3 Hz, 1H), 7.20 (t, J = 7.3 Hz, 1H), 7.34 (d, J = 8.0 Hz, 2H), 7.46 (t, J = 7.6 Hz, 2H), 7.56-7.61 (m, 3H), 7.96 (br, 1H). 13 C NMR (126 MHz, CDCl 3, 25 C): δ 9.88, 108.9, 110.9, 119.2, 119.8, 122.5, 127.5, 128.0, 129.0, 130.3, 133.6, 134.2, 136.1. HRMS (ESI) calcd for C 15 H 14 N (M+H) + 208.1121, found 208.1121. 4. X-ray crystallographic data Table S1. Crystallographic data of 4h Empirical Formula C 18 H 14 BrN Formula Weight 324.22 Crystal Color, Habit colorless, chip Crystal System monoclinic Lattice Parameters a (Å) 9.940(5) b (Å) 9.771(4) c (Å) 14.831(8) β ( ) 102.388(6) V (Å 3 ) 1406.8(12) Space Group P2 1 /c (#14) Z value 4 D calc (g cm 3 ) 1.531 F 000 656.00 µ (MoKα) (cm 1 ) 29.187 Radiation MoKα (λ = 0.71075 Å) graphite monochromatographyd Temperature ( C) 129.8 Max 2θ ( ) 55.0 No. of Reflections asured Total: 11078 Structure Solution Direct thods (SIR2011) Refinement Full-matrix least-squares on F 2 No. bservations (All reflections) 3208 No. Variables 181 Reflection/Parameter Ratio 17.72 Residuals: R 1 ; wr 2 0.0730; 0.1561 Goodness of Fit Indicator 1.136 Max Shift/Error in Final Cycle 0.000 Maximum peak in Final Diff. Map (e Å 3 ) 0.54 Minimum peak in Final Diff. Map (e Å 3 ) 0.69 S13
Figure S1. RTEP drawing of pyridine 4h with 50% probability level. 5. References 1) kamoto, K.; da, T.; Kohigashi, S.; he, K. Angew. Chem. Int. Ed. 2011, 50, 11470. 2) kamoto, K.; Shimbayashi, T.; Tamura, E.; he, K. Chem. Eur. J. 2014, 20, 1490. 3) Patil, N. T.; Yamamoto, Y. Tetrahedron Lett. 2004, 45, 3101. S14
C:\Users\ohe20\Documents\nmrdata_ohe\nanya\Intramolecular cyclization of isoxazolones\- isoxazolone.als DFILE - isoxazolone.als CMNT DATIM 2015-09-03 11:01:39 BNUC 1H EXMD zg30 BFRQ 500.03 MHz BSET 3.08 KHz BFIN 7.89 Hz PINT 32768 FREQU 10000.00 Hz SCANS 16 ACQTM 3.2768 sec PD 1.0000 sec PW1 15.00 usec CTEMP -273.1 c EXREF 16.15 ppm BF 0.30 Hz RGAIN 156 2.00 2.01 0.99 1.00 2.05 3.13 3.10 10 8 6 4 2 0 7.7604 7.7561 7.7463 7.7421 7.2630 6.9859 6.9682 4.7503 4.7472 4.5910 3.8714 2.7539 1.6291 1.5718 0.0002 S15
C:\Users\ohe20\Documents\nmrdata_ohe\nanya\Intramolecular cyclization of isoxazolones\- isoxazolone 13C.als DFILE - isoxazolone 13C.als CMNT DATIM Thu Sep 03 21:45:57 2015 BNUC 13C EXMD BCM BFRQ 75.45 MHz BSET 124.00 KHz BFIN 1840.00 Hz PINT 32768 FREQU 20356.23 Hz SCANS 2028 ACQTM 1.6097 sec PD 1.3900 sec PW1 4.50 usec 1H CTEMP 22.9 c SLVNT CDCL3 EXREF 77.00 ppm BF 0.00 Hz RGAIN 28 200 150 100 50 0 181.4110 167.8551 162.1088 139.0744 128.4862 120.3888 115.7359 114.5028 77.4275 77.0000 76.5807 55.4125 50.6034 44.8242 23.7382 22.9408 S16
C:\Users\ohe20\Documents\nmrdata_ohe\nanya\Intramolecular cyclization of isoxazolones\br- isoxazolone.als DFILE Br- isoxazolone.als CMNT DATIM 2015-09-28 13:08:52 BNUC 1H EXMD single_pulse.ex2 BFRQ 395.88 MHz BSET 6.28 KHz BFIN 0.87 Hz PINT 13107 FREQU 5938.15 Hz SCANS 8 ACQTM 2.2073 sec PD 5.0000 sec PW1 3.50 usec 1H CTEMP 22.8 c SLVNT CDCL3 EXREF 0.00 ppm BF 0.10 Hz RGAIN 48 2.17 2.00 1.04 1.04 1.09 1.00 3.25 3.28 4.08 10 8 6 4 2 0 7.6835 7.6778 7.6732 7.6618 7.6561 7.6515 7.6332 7.6275 7.6160 7.6103 7.6057 7.2624 4.7596 4.7561 4.7527 4.5627 2.7992 2.7626 2.7351 2.6985 1.6296 1.5690 1.5633 1.5358 0.0000 S17
C:\Users\ohe20\Documents\nmrdata_ohe\nanya\Intramolecular cyclization of isoxazolones\br-- zolone 13C.als DFILE Br-- zolone 13C.als CMNT DATIM Fri Jan 29 15:19:01 2016 BNUC 13C EXMD BCM BFRQ 100.40 MHz BSET 125.00 KHz BFIN 10500.00 Hz PINT 32768 FREQU 27118.64 Hz SCANS 80 ACQTM 1.2083 sec PD 1.7920 sec PW1 4.80 usec 1H CTEMP 27.4 c SLVNT CDCL3 EXREF 77.00 ppm BF 0.10 Hz RGAIN 31 200 150 100 50 0 180.8720 167.6173 138.8193 132.4308 128.2156 126.9643 126.3139 115.9242 77.3211 77.0000 76.6872 50.2767 44.7196 23.5780 22.8865 S18
\\Landisk-ohe\nmr\Sasakura\NMR\pyridine _ \sasaex489.pure.1h.als DFILE sasaex489.pure.1h.als CMNT DATIM 2016-04-13 21:36:56 BNUC 1H EXMD zg30 BFRQ 500.03 MHz BSET 3.08 KHz BFIN 7.89 Hz PINT 32768 FREQU 10000.00 Hz SCANS 16 ACQTM 3.2768 sec PD 1.0000 sec PW1 15.00 usec CTEMP 24.8 c EXREF 0.00 ppm BF 0.30 Hz RGAIN 119 1.88 0.94 1.07 1.00 2.04 3.15 3.02 10 8 6 4 2 0 7.5588 7.5569 7.5502 7.5484 7.5465 7.5423 7.5404 7.2634 7.1761 7.1681 7.1657 7.1584 4.7873 4.7843 4.7812 4.6244 2.7568 1.6424 1.5923 0.0000 S19
\\Landisk-ohe\nmr\Sasakura\NMR\pyridine _ \sasaex489.pure.13c.als DFILE sasaex489.pure.13c.als CMNT DATIM 2016-04-13 22:15:38 BNUC 13C EXMD zgpg30 BFRQ 125.74 MHz BSET 5.21 KHz BFIN 6.77 Hz PINT 32768 FREQU 31250.00 Hz SCANS 720 ACQTM 1.0486 sec PD 2.0000 sec PW1 10.00 usec CTEMP 25.7 c EXREF 77.00 ppm BF 1.00 Hz RGAIN 198 200 150 100 50 0 180.5799 164.5529 138.7717 129.9429 129.7836 128.9796 127.8343 116.1155 77.2503 77.0000 76.7421 50.7940 44.8399 23.5641 22.9346 S20
C:\Users\ohe20\Documents\nmrdata_ohe\nanya\Intramolecular cyclization of isoxazolones\- isoxazolone.als DFILE - isoxazolone.als CMNT DATIM 2015-09-03 11:05:48 BNUC 1H EXMD zg30 BFRQ 500.03 MHz BSET 3.08 KHz BFIN 7.89 Hz PINT 32768 FREQU 10000.00 Hz SCANS 16 ACQTM 3.2768 sec PD 1.0000 sec PW1 15.00 usec CTEMP -273.1 c EXREF 16.15 ppm BF 0.30 Hz RGAIN 198 1.95 1.00 2.06 4.91 1.02 1.01 2.00 3.15 10 8 6 4 2 0 7.5277 7.5130 7.5106 7.4337 7.4184 7.4038 7.3696 7.3360 7.3202 7.3049 7.2610 7.1285 7.1194 7.1151 7.1114 7.1053 7.0901 7.0773 7.0742 7.0706 7.0577 7.0535 5.1383 5.0150 3.1853 1.7041 1.5600 0.0001 S21
C:\Users\ohe20\Documents\nmrdata_ohe\nanya\Intramolecular cyclization of isoxazolones\- isoxazolone 13C.als DFILE - isoxazolone 13C.als CMNT DATIM Thu Sep 03 14:27:04 2015 BNUC 13C EXMD BCM BFRQ 75.45 MHz BSET 124.00 KHz BFIN 1840.00 Hz PINT 32768 FREQU 20356.23 Hz SCANS 4200 ACQTM 1.6097 sec PD 1.3900 sec PW1 4.50 usec 1H CTEMP 22.9 c SLVNT CDCL3 EXREF 77.00 ppm BF 0.00 Hz RGAIN 28 200 150 100 50 0 180.6629 167.7975 143.2670 139.7485 131.2072 128.7328 128.0423 127.9518 127.8450 126.8338 126.5296 118.3501 77.4193 77.0000 76.5725 51.1542 42.2676 23.5573 S22
C:\Users\ohe20\Documents\nmrdata_ohe\nanya\Intramolecular cyclization of isoxazolones\br- isoxazolone.als DFILE Br- isoxazolone.als CMNT DATIM Thu Sep 24 14:49:54 2015 BNUC 1H EXMD NN BFRQ 399.65 MHz BSET 124.00 KHz BFIN 10500.00 Hz PINT 16384 FREQU 7992.01 Hz SCANS 16 ACQTM 2.0501 sec PD 2.9500 sec PW1 7.00 usec 1H CTEMP 28.2 c SLVNT CDCL3 EXREF 0.00 ppm BF 0.12 Hz RGAIN 25 1.86 1.94 0.92 1.95 1.94 1.00 1.00 2.01 3.04 10 8 6 4 2 0 7.4478 7.4270 7.3526 7.3319 7.2587 7.1635 7.1452 7.1281 7.1098 7.0891 7.0732 7.0402 7.0232 5.1454 5.0368 3.1968 3.1614 3.1480 3.1126 1.6814 1.5362 0.0000-0.0085 S23
C:\Users\ohe20\Documents\nmrdata_ohe\nanya\Intramolecular cyclization of isoxazolones\br- isoxazolone 13C.als DFILE Br- isoxazolone 13C.als CMNT DATIM Thu Sep 24 19:19:18 2015 BNUC 13C EXMD BCM BFRQ 75.45 MHz BSET 124.00 KHz BFIN 1840.00 Hz PINT 32768 FREQU 20356.23 Hz SCANS 1352 ACQTM 1.6097 sec PD 1.3900 sec PW1 4.50 usec 1H CTEMP 23.1 c SLVNT CDCL3 EXREF 77.00 ppm BF 0.12 Hz RGAIN 28 200 150 100 50 0 180.3258 166.9754 143.1108 139.6334 131.9882 128.0094 127.9272 127.8614 126.9325 126.8420 125.7980 118.6296 77.4193 77.0000 76.5725 51.0637 42.3416 23.3764 S24
\\Landisk-ohe\nmr\Sasakura\NMR\sample NMR\sasaex1i.1H.als DFILE sasaex1i.1h.als CMNT DATIM 2016-04-21 12:44:46 BNUC 1H EXMD zg30 BFRQ 500.03 MHz BSET 3.08 KHz BFIN 7.89 Hz PINT 32768 FREQU 10000.00 Hz SCANS 16 ACQTM 3.2768 sec PD 1.0000 sec PW1 15.00 usec CTEMP 24.8 c EXREF 16.14 ppm BF 0.30 Hz RGAIN 69 1.94 0.99 1.95 0.97 0.97 2.00 3.01 5.06 10 8 6 4 2 0 7.7876 7.7742 7.5691 7.5539 7.5399 7.5167 7.5020 7.4874 7.2646 7.2536 7.2487 7.2353 7.2091 7.1938 6.3772 6.3461 5.8676 5.8523 5.8371 5.8212 5.8059 5.2884 2.8716 2.8563 1.6814 1.6100 0.0000 S25
E:\NMR\sasakura\sasaex1i.13C\10\fid DFILE fid CMNT DATIM 2016-04-21 13:23:30 BNUC 13C EXMD zgpg30 BFRQ 125.74 MHz BSET 5.21 KHz BFIN 6.77 Hz PINT 32768 FREQU 31250.00 Hz SCANS 720 ACQTM 1.0486 sec PD 2.0000 sec PW1 10.00 usec CTEMP 25.8 c EXREF 77.00 ppm BF 1.00 Hz RGAIN 198 200 150 100 50 0 180.8606 168.2013 136.1853 135.7226 131.7026 129.2375 128.4790 127.9329 127.8722 126.9013 126.4159 120.9244 77.2503 77.0000 76.7421 51.2491 40.3496 21.8272 S26
\\Landisk-ohe\nmr\Sasakura\NMR\sample NMR\sasaex1k.1H.als DFILE sasaex1k.1h.als CMNT DATIM 2016-04-15 12:47:14 BNUC 1H EXMD zg30 BFRQ 500.03 MHz BSET 3.08 KHz BFIN 7.89 Hz PINT 32768 FREQU 10000.00 Hz SCANS 16 ACQTM 3.2768 sec PD 1.0000 sec PW1 15.00 usec CTEMP 24.5 c EXREF 0.00 ppm BF 0.30 Hz RGAIN 119 1.94 2.95 0.80 1.68 0.99 1.93 0.96 2.00 3.03 2.96 10 8 6 4 2 0 7.8389 7.8248 7.8218 7.5374 7.5221 7.5081 7.4934 7.4788 7.4648 7.2573 7.2444 7.2292 7.1743 7.1596 7.1450 7.0064 6.9918 6.0964 2.9100 1.7290 1.6686 1.6662 1.5526 0.0000 S27
E:\NMR\sasakura\sasaex.1k.13C\10\fid DFILE fid CMNT DATIM 2016-04-15 13:19:43 BNUC 13C EXMD zgpg30 BFRQ 125.74 MHz BSET 5.21 KHz BFIN 6.77 Hz PINT 32768 FREQU 31250.00 Hz SCANS 600 ACQTM 1.0486 sec PD 2.0000 sec PW1 10.00 usec CTEMP 25.8 c EXREF 77.00 ppm BF 1.00 Hz RGAIN 198 200 150 100 50 0 181.3232 168.4061 137.0575 131.7481 131.6495 130.6938 129.1389 128.7824 128.3197 127.9860 126.9013 126.5827 77.2503 77.0000 76.7421 51.0140 47.8056 23.4428 18.2622 S28
E:\NMR\sasakura\sasaex.1l.1H\10\fid DFILE fid CMNT DATIM 2016-04-15 13:24:18 BNUC 1H EXMD zg30 BFRQ 500.03 MHz BSET 3.08 KHz BFIN 7.89 Hz PINT 32768 FREQU 10000.00 Hz SCANS 16 ACQTM 3.2768 sec PD 1.0000 sec PW1 15.00 usec CTEMP 24.7 c EXREF 0.00 ppm BF 0.30 Hz RGAIN 99 10 8 6 4 2 0 7.7968 7.7827 7.5362 7.5215 7.5166 7.5099 7.5069 7.5038 7.4898 7.4776 7.4745 7.4605 7.4574 7.2627 5.1279 5.1144 5.1028 5.0900 2.7293 1.6356 1.5685 1.4373 1.4349 1.4172 0.0000 S29
\\Landisk-ohe\nmr\Sasakura\NMR\sample NMR\sasaex1l.13C.als DFILE sasaex1l.13c.als CMNT DATIM 2016-04-15 13:56:45 BNUC 13C EXMD zgpg30 BFRQ 125.74 MHz BSET 5.21 KHz BFIN 6.77 Hz PINT 32768 FREQU 31250.00 Hz SCANS 600 ACQTM 1.0486 sec PD 2.0000 sec PW1 10.00 usec CTEMP 25.9 c EXREF 77.00 ppm BF 1.00 Hz RGAIN 198 200 150 100 50 0 181.4143 168.5805 131.4978 129.2375 129.0251 128.3880 126.8786 125.1644 77.2503 77.0000 76.7421 51.0140 47.2064 23.2531 16.2598 13.4382 S30
\\Landisk-ohe\nmr\Sasakura\NMR\sasaNMR501-600\sasaex532.pure.1H.als DFILE sasaex532.pure.1h.als CMNT DATIM 2016-01-18 17:10:08 BNUC 1H EXMD zg30 BFRQ 500.03 MHz BSET 3.08 KHz BFIN 7.89 Hz PINT 32768 FREQU 10000.00 Hz SCANS 16 ACQTM 3.2768 sec PD 1.0000 sec PW1 15.00 usec CTEMP -273.1 c EXREF 0.00 ppm BF 0.30 Hz RGAIN 13 2.00 3.00 1.00 2.07 2.22 2.08 3.12 4.22 10 8 6 4 2 0 7.7986 7.7833 7.5203 7.5069 7.4910 7.4764 7.4611 5.2908 2.6829 1.8383 1.7992 1.7687 1.7156 1.6259 1.4501 1.4233 1.4098 S31
\\Landisk-ohe\nmr\Sasakura\NMR\sasaNMR501-600\sasaex532.pure.13C.als DFILE sasaex532.pure.13c.als CMNT DATIM 2016-01-18 17:38:17 BNUC 13C EXMD zgpg30 BFRQ 125.74 MHz BSET 5.21 KHz BFIN 6.77 Hz PINT 32768 FREQU 31250.00 Hz SCANS 512 ACQTM 1.0486 sec PD 2.0000 sec PW1 10.00 usec CTEMP -273.1 c EXREF 77.00 ppm BF 1.00 Hz RGAIN 198 200 150 100 50 0 181.3763 168.6260 131.3992 131.3612 128.9341 128.2438 127.0682 126.7875 77.2579 77.0000 76.7421 50.7789 45.4922 28.7901 25.0128 23.2152 22.5098 21.6148 S32
S33
S34
\\Landisk-ohe\nmr\Sasakura\NMR\sample NMR\sasaex1n.1H.als DFILE sasaex1n.1h.als CMNT DATIM 2016-04-15 15:02:20 BNUC 1H EXMD zg30 BFRQ 500.03 MHz BSET 3.08 KHz BFIN 7.89 Hz PINT 32768 FREQU 10000.00 Hz SCANS 16 ACQTM 3.2768 sec PD 1.0000 sec PW1 15.00 usec CTEMP 24.9 c EXREF 0.00 ppm BF 0.30 Hz RGAIN 69 3.36 5.25 0.92 0.91 1.97 2.00 2.97 3.26 10 8 6 4 2 0 7.7858 7.7718 7.7687 7.7559 7.7376 7.5282 7.5136 7.4953 7.4806 7.4666 7.2627 6.3943 6.3735 6.3607 6.3522 6.3400 6.3186 5.6161 5.5948 5.0009 4.9814 4.9478 2.7782 1.7266 1.6961 1.6802 1.6448 1.6137 1.6021 1.5868 0.0000 S35
\\Landisk-ohe\nmr\Sasakura\NMR\sample NMR\sasaex1n.13C.als DFILE sasaex1n.13c.als CMNT DATIM 2016-04-15 15:00:19 BNUC 13C EXMD zgpg30 BFRQ 125.74 MHz BSET 5.21 KHz BFIN 6.77 Hz PINT 32768 FREQU 31250.00 Hz SCANS 720 ACQTM 1.0486 sec PD 2.0000 sec PW1 10.00 usec CTEMP 25.6 c EXREF 77.00 ppm BF 1.00 Hz RGAIN 198 200 150 100 50 0 181.1791 168.4213 132.0742 131.5812 131.3157 130.8379 129.0706 128.2438 126.9165 117.5794 77.2503 77.0000 76.7421 50.8851 47.1002 23.3745 17.0942 S36
\\Landisk-ohe\nmr\Sasakura\NMR\sasaNMR501-600\sasaex547.pure.1H.als DFILE sasaex547.pure.1h.als CMNT DATIM 2016-01-26 18:06:06 BNUC 1H EXMD zg30 BFRQ 500.03 MHz BSET 3.08 KHz BFIN 7.89 Hz PINT 32768 FREQU 10000.00 Hz SCANS 16 ACQTM 3.2768 sec PD 1.0000 sec PW1 15.00 usec CTEMP -273.1 c EXREF 16.14 ppm BF 0.30 Hz RGAIN 99 0.93 0.27 2.01 2.00 2.08 6.21 10 8 6 4 2 0 8.3531 7.5102 7.4950 7.4468 7.4315 7.4162 7.3906 7.3674 7.2588 2.3433 2.3219-0.0003 S37
\\Landisk-ohe\nmr\Sasakura\NMR\sasaNMR501-600\sasaex547.pure.13C.als DFILE sasaex547.pure.13c.als CMNT DATIM 2016-01-26 18:51:45 BNUC 13C EXMD zgpg30 BFRQ 125.74 MHz BSET 5.21 KHz BFIN 6.77 Hz PINT 32768 FREQU 31250.00 Hz SCANS 720 ACQTM 1.0486 sec PD 2.0000 sec PW1 10.00 usec CTEMP -273.1 c EXREF 77.00 ppm BF 1.00 Hz RGAIN 198 200 150 100 50 0 155.9289 147.3806 140.6149 139.0903 131.4371 130.1022 128.9492 128.0694 127.6446 77.2579 77.0000 76.7497 19.8702 17.9285 S38
\\Landisk-ohe\nmr\Sasakura\NMR\sasaNMR501-600\sasaex559.pure.1H.als DFILE sasaex559.pure.1h.als CMNT DATIM 2016-02-08 19:38:18 BNUC 1H EXMD zg30 BFRQ 500.03 MHz BSET 3.08 KHz BFIN 7.89 Hz PINT 32768 FREQU 10000.00 Hz SCANS 16 ACQTM 3.2768 sec PD 1.0000 sec PW1 15.00 usec CTEMP -273.1 c EXREF 16.15 ppm BF 0.30 Hz RGAIN 99 1.00 2.08 1.03 2.15 3.27 6.46 10 8 6 4 2 0 8.3339 7.4703 7.4532 7.3684 7.2604 6.9748 6.9577 3.8512 2.3303 0.0001 S39
\\Landisk-ohe\nmr\Sasakura\NMR\sasaNMR501-600\sasaex559.pure.13C.als DFILE sasaex559.pure.13c.als CMNT DATIM 2016-02-08 20:17:01 BNUC 13C EXMD zgpg30 BFRQ 125.74 MHz BSET 5.21 KHz BFIN 6.77 Hz PINT 32768 FREQU 31250.00 Hz SCANS 720 ACQTM 1.0486 sec PD 2.0000 sec PW1 10.00 usec CTEMP -273.1 c EXREF 77.00 ppm BF 1.00 Hz RGAIN 198 200 150 100 50 0 159.4407 155.8227 147.5930 139.3634 133.4471 131.2778 130.4814 130.2084 113.7339 77.5082 77.2579 77.0000 55.5422 20.3102 18.1485 S40
\\Landisk-ohe\nmr\Sasakura\NMR\sasaNMR501-600\sasaex591.pure.1H.als DFILE sasaex591.pure.1h.als CMNT DATIM 2016-03-01 17:39:51 BNUC 1H EXMD zg30 BFRQ 500.03 MHz BSET 3.08 KHz BFIN 7.89 Hz PINT 32768 FREQU 10000.00 Hz SCANS 16 ACQTM 3.2768 sec PD 1.0000 sec PW1 15.00 usec CTEMP -273.1 c EXREF 0.00 ppm BF 0.30 Hz RGAIN 89 1.00 2.22 2.09 1.07 3.42 3.19 10 8 6 4 2 0 8.3686 7.7046 7.6881 7.6393 7.6228 7.4214 7.2609 2.3601 2.3216 0.0000 S41
E:\NMR\sasakura\sasaex591.fr3.13C\10\fid DFILE fid CMNT DATIM 2016-03-01 18:18:50 BNUC 13C EXMD zgpg30 BFRQ 125.74 MHz BSET 5.21 KHz BFIN 6.77 Hz PINT 32768 FREQU 31250.00 Hz SCANS 720 ACQTM 1.0486 sec PD 2.0000 sec PW1 10.00 usec CTEMP -273.1 c EXREF 77.00 ppm BF 1.00 Hz RGAIN 198 200 150 100 50 0 154.4043 147.6613 144.1495 139.3027 132.2639 130.2235 129.8822 129.6243 129.3892 127.4702 125.3085 125.1037 125.0733 125.0430 125.0202 123.1468 120.9926 77.2503 77.0000 76.7421 19.7110 17.9437 S42
\\Landisk-ohe\nmr\Sasakura\NMR\sasaNMR501-600\sasaex598.pure.1H.als DFILE sasaex598.pure.1h.als CMNT DATIM 2016-03-04 19:22:09 BNUC 1H EXMD zg30 BFRQ 500.03 MHz BSET 3.08 KHz BFIN 7.89 Hz PINT 32768 FREQU 10000.00 Hz SCANS 16 ACQTM 3.2768 sec PD 1.0000 sec PW1 15.00 usec CTEMP -273.1 c EXREF 0.00 ppm BF 0.30 Hz RGAIN 50 1.00 2.17 3.23 3.41 3.23 10 8 6 4 2 0 8.3400 7.5655 7.5490 7.3970 7.3836 7.3805 2.3345 2.3033 S43
\\Landisk-ohe\nmr\Sasakura\NMR\sasaNMR501-600\sasaex598.pure.13C.als DFILE sasaex598.pure.13c.als CMNT DATIM 2016-03-04 20:00:55 BNUC 13C EXMD zgpg30 BFRQ 125.74 MHz BSET 5.21 KHz BFIN 6.77 Hz PINT 32768 FREQU 31250.00 Hz SCANS 720 ACQTM 1.0486 sec PD 2.0000 sec PW1 10.00 usec CTEMP -273.1 c EXREF 77.00 ppm BF 1.00 Hz RGAIN 198 200 150 100 50 0 154.6015 147.5096 139.4544 139.2192 131.8088 131.1792 130.6634 130.0263 121.9028 77.2579 77.0000 76.7497 19.7944 17.8982 S44
\\Landisk-ohe\nmr\Sasakura\NMR\sasaNMR601-700\sasaex615.fr3.1H.als DFILE sasaex615.fr3.1h.als CMNT DATIM 2016-03-11 18:28:45 BNUC 1H EXMD zg30 BFRQ 500.03 MHz BSET 3.08 KHz BFIN 7.89 Hz PINT 32768 FREQU 10000.00 Hz SCANS 16 ACQTM 3.2768 sec PD 1.0000 sec PW1 15.00 usec CTEMP 24.7 c EXREF 0.00 ppm BF 0.30 Hz RGAIN 119 1.00 1.06 1.12 2.12 1.06 2.15 1.05 3.27 3.32 10 8 6 4 2 0 8.4028 7.9738 7.9188 7.9017 7.8792 7.6692 7.6527 7.5081 7.5014 7.4959 7.4886 7.4330 7.2554 2.3808 2.3711 1.6576 0.0000 S45
\\Landisk-ohe\nmr\Sasakura\NMR\sasaNMR601-700\sasaex615.fr3.13C.als DFILE sasaex615.fr3.13c.als CMNT DATIM 2016-03-11 19:03:19 BNUC 13C EXMD zgpg30 BFRQ 125.74 MHz BSET 5.21 KHz BFIN 6.77 Hz PINT 32768 FREQU 31250.00 Hz SCANS 640 ACQTM 1.0486 sec PD 2.0000 sec PW1 10.00 usec CTEMP 25.9 c EXREF 77.00 ppm BF 1.00 Hz RGAIN 198 200 150 100 50 0 155.8151 147.5248 139.2041 138.0588 133.1437 132.7948 131.5509 130.4055 128.2969 128.1377 127.6901 127.6446 127.0606 126.1049 126.0594 77.2579 77.0000 76.7497 20.0068 17.9816 S46
\\Landisk-ohe\nmr\Sasakura\NMR\sasaNMR501-600\sasaex575.pure.1H.als DFILE sasaex575.pure.1h.als CMNT DATIM 2016-02-16 15:28:00 BNUC 1H EXMD zg30 BFRQ 500.03 MHz BSET 3.08 KHz BFIN 7.89 Hz PINT 32768 FREQU 10000.00 Hz SCANS 16 ACQTM 3.2768 sec PD 1.0000 sec PW1 15.00 usec CTEMP -273.1 c EXREF 0.00 ppm BF 0.30 Hz RGAIN 69 1.00 1.02 1.10 1.06 1.08 3.41 3.40 10 8 6 4 2 0 8.2881 7.4147 7.4074 7.3811 7.3714 7.3396 7.2560 7.1163 7.1083 7.0992 2.5212 2.3070 S47
\\Landisk-ohe\nmr\Sasakura\NMR\sasaNMR501-600\sasaex575.pure.13C.als DFILE sasaex575.pure.13c.als CMNT DATIM 2016-02-16 16:07:00 BNUC 13C EXMD zgpg30 BFRQ 125.74 MHz BSET 5.21 KHz BFIN 6.77 Hz PINT 32768 FREQU 31250.00 Hz SCANS 720 ACQTM 1.0486 sec PD 2.0000 sec PW1 10.00 usec CTEMP -273.1 c EXREF 77.00 ppm BF 1.00 Hz RGAIN 198 200 150 100 50 0 148.7990 147.2744 145.2038 139.8185 131.2096 129.0554 127.4626 126.6586 126.2718 77.2579 77.0000 76.7497 21.2280 17.8754 S48
\\Landisk-ohe\nmr\Sasakura\NMR\sasaNMR501-600\sasaex580.pure.1H.als DFILE sasaex580.pure.1h.als CMNT DATIM 2016-02-18 16:15:13 BNUC 1H EXMD zg30 BFRQ 500.03 MHz BSET 3.08 KHz BFIN 7.89 Hz PINT 32768 FREQU 10000.00 Hz SCANS 16 ACQTM 3.2768 sec PD 1.0000 sec PW1 15.00 usec CTEMP -273.1 c EXREF 0.00 ppm BF 0.30 Hz RGAIN 112 0.89 1.04 2.17 2.06 3.99 1.99 3.00 10 8 6 4 2 0 8.7666 7.7791 7.6418 7.6265 7.5868 7.5722 7.5063 7.4910 7.4703 7.4550 7.4214 7.4068 7.3921 7.2536 2.4400 0.0000 S49
\\Landisk-ohe\nmr\Sasakura\NMR\sasaNMR501-600\sasaex580.pure.13C.als DFILE sasaex580.pure.13c.als CMNT DATIM 2016-02-18 16:54:10 BNUC 13C EXMD zgpg30 BFRQ 125.74 MHz BSET 5.21 KHz BFIN 6.77 Hz PINT 32768 FREQU 31250.00 Hz SCANS 720 ACQTM 1.0486 sec PD 2.0000 sec PW1 10.00 usec CTEMP -273.1 c EXREF 77.00 ppm BF 1.00 Hz RGAIN 198 200 150 100 50 0 157.4534 145.3934 140.3342 137.7250 136.8983 134.9565 130.6407 129.0327 128.9872 128.1680 127.9480 127.0909 77.2579 77.0000 76.7497 20.1736 S50
\\Landisk-ohe\nmr\Sasakura\NMR\sasaNMR501-600\sasaex548.fr2.1H.als DFILE sasaex548.fr2.1h.als CMNT DATIM 2016-01-27 19:04:49 BNUC 1H EXMD zg30 BFRQ 500.03 MHz BSET 3.08 KHz BFIN 7.89 Hz PINT 32768 FREQU 10000.00 Hz SCANS 16 ACQTM 3.2768 sec PD 1.0000 sec PW1 15.00 usec CTEMP -273.1 c EXREF 16.14 ppm BF 0.30 Hz RGAIN 119 1.00 1.11 1.14 0.47 4.47 4.36 3.24 10 8 6 4 2 0 8.7522 7.7776 7.6329 7.6176 7.6128 7.5957 7.5090 7.4938 7.4773 7.4602 7.4303 7.4156 7.4004 7.2570 2.4281 S51
\\Landisk-ohe\nmr\Sasakura\NMR\sasaNMR501-600\sasaex548.fr2.13C.als DFILE sasaex548.fr2.13c.als CMNT DATIM 2016-01-27 19:45:50 BNUC 13C EXMD zgpg30 BFRQ 125.74 MHz BSET 5.21 KHz BFIN 6.77 Hz PINT 32768 FREQU 31250.00 Hz SCANS 720 ACQTM 1.0486 sec PD 2.0000 sec PW1 10.00 usec CTEMP -273.1 c EXREF 77.00 ppm BF 1.00 Hz RGAIN 198 200 150 100 50 0 156.3992 145.7802 139.4392 137.7630 137.3154 135.5482 131.5964 130.9820 130.8682 129.3285 128.3349 127.3337 122.5703 77.5082 77.2503 77.0000 20.3936 S52
\\Landisk-ohe\nmr\Sasakura\NMR\sasaNMR501-600\sasaex592.pure.1H.als DFILE sasaex592.pure.1h.als CMNT DATIM 2016-03-02 10:16:40 BNUC 1H EXMD zg30 BFRQ 500.03 MHz BSET 3.08 KHz BFIN 7.89 Hz PINT 32768 FREQU 10000.00 Hz SCANS 16 ACQTM 3.2768 sec PD 1.0000 sec PW1 15.00 usec CTEMP -273.1 c EXREF 0.00 ppm BF 0.30 Hz RGAIN 56 1.94 3.82 3.00 6.36 10 8 6 4 2 0 8.0610 8.0470 7.6430 7.6289 7.6125 7.4733 7.4587 7.4434 7.4367 7.4208 7.4068 7.3915 7.3787 7.3641 7.2243 2.3869 S53
\\Landisk-ohe\nmr\Sasakura\NMR\sasaNMR501-600\sasaex592.pure.13C.als DFILE sasaex592.pure.13c.als CMNT DATIM 2016-03-02 10:44:35 BNUC 13C EXMD zgpg30 BFRQ 125.74 MHz BSET 5.21 KHz BFIN 6.77 Hz PINT 32768 FREQU 31250.00 Hz SCANS 512 ACQTM 1.0486 sec PD 2.0000 sec PW1 10.00 usec CTEMP -273.1 c EXREF 77.00 ppm BF 1.00 Hz RGAIN 198 200 150 100 50 0 158.1057 154.4877 140.9107 139.3937 139.3027 129.2299 129.1464 128.5700 128.5321 128.0163 127.8418 126.7875 118.5958 77.2503 77.0000 76.7421 19.8551 S54
\\Landisk-ohe\nmr\Sasakura\NMR\sasaNMR501-600\sasaex552.pure.1H.als DFILE sasaex552.pure.1h.als CMNT DATIM 2016-01-28 20:31:03 BNUC 1H EXMD zg30 BFRQ 500.03 MHz BSET 3.08 KHz BFIN 7.89 Hz PINT 32768 FREQU 10000.00 Hz SCANS 16 ACQTM 3.2768 sec PD 1.0000 sec PW1 15.00 usec CTEMP -273.1 c EXREF 16.14 ppm BF 0.30 Hz RGAIN 119 1.15 2.10 3.85 4.00 6.00 10 8 6 4 2 0 7.5880 7.5728 7.4690 7.4342 7.4190 7.4043 7.3628 7.3482 7.2517 2.3729 0.0000 S55
\\Landisk-ohe\nmr\Sasakura\NMR\sasaNMR501-600\sasaex552.pure.13C.als DFILE sasaex552.pure.13c.als CMNT DATIM 2016-01-28 21:10:01 BNUC 13C EXMD zgpg30 BFRQ 125.74 MHz BSET 5.21 KHz BFIN 6.77 Hz PINT 32768 FREQU 31250.00 Hz SCANS 720 ACQTM 1.0486 sec PD 2.0000 sec PW1 10.00 usec CTEMP -273.1 c EXREF 77.00 ppm BF 1.00 Hz RGAIN 198 200 150 100 50 0 155.7696 141.0927 140.7135 129.2071 129.0706 128.0315 127.6143 77.2579 77.0000 76.7497 19.6048 S56
\\Landisk-ohe\nmr\Sasakura\NMR\sasaNMR501-600\sasaex595.pure.1H.als DFILE sasaex595.pure.1h.als CMNT DATIM 2016-03-02 19:02:56 BNUC 1H EXMD zg30 BFRQ 500.03 MHz BSET 3.08 KHz BFIN 7.89 Hz PINT 32768 FREQU 10000.00 Hz SCANS 16 ACQTM 3.2768 sec PD 1.0000 sec PW1 15.00 usec CTEMP -273.1 c EXREF 0.00 ppm BF 0.30 Hz RGAIN 99 1.97 2.02 0.99 1.02 0.27 3.00 2.99 3.14 10 8 6 4 2 0 7.4941 7.4800 7.4306 7.4159 7.4001 7.3580 7.3433 7.3287 7.2908 7.2554 2.5090 2.2869 2.2624 0.0000 S57
\\Landisk-ohe\nmr\Sasakura\NMR\sasaNMR501-600\sasaex595.pure.13C.als DFILE sasaex595.pure.13c.als CMNT DATIM 2016-03-02 19:41:37 BNUC 13C EXMD zgpg30 BFRQ 125.74 MHz BSET 5.21 KHz BFIN 6.77 Hz PINT 32768 FREQU 31250.00 Hz SCANS 720 ACQTM 1.0486 sec PD 2.0000 sec PW1 10.00 usec CTEMP -273.1 c EXREF 77.00 ppm BF 1.00 Hz RGAIN 198 200 150 100 50 0 155.6179 154.2830 141.1762 139.9398 129.9353 129.2678 128.3425 128.0087 127.7205 77.5082 77.2579 77.0000 22.4491 19.5668 18.9069 S58
\\Landisk-ohe\nmr\Sasakura\NMR\sasaNMR501-600\sasaex554.pure.1H.als DFILE sasaex554.pure.1h.als CMNT DATIM 2016-02-01 17:33:10 BNUC 1H EXMD zg30 BFRQ 500.03 MHz BSET 3.08 KHz BFIN 7.89 Hz PINT 32768 FREQU 10000.00 Hz SCANS 16 ACQTM 3.2768 sec PD 1.0000 sec PW1 15.00 usec CTEMP -273.1 c EXREF 16.14 ppm BF 0.30 Hz RGAIN 56 1.94 1.97 0.99 1.11 2.04 2.02 3.00 2.15 2.05 10 8 6 4 2 0 7.4818 7.4672 7.4232 7.4086 7.3939 7.3530 7.3384 7.3244 7.2401 2.9466 2.9344 2.9216 2.7861 2.7732 2.7616 2.2508 1.9273 1.9164 1.9072 1.8956 1.8828 1.8419 1.8297 1.8181 1.8077 1.7961 S59
\\Landisk-ohe\nmr\Sasakura\NMR\sasaNMR501-600\sasaex554.pure.13C.als DFILE sasaex554.pure.13c.als CMNT DATIM 2016-02-01 18:14:07 BNUC 13C EXMD zgpg30 BFRQ 125.74 MHz BSET 5.21 KHz BFIN 6.77 Hz PINT 32768 FREQU 31250.00 Hz SCANS 720 ACQTM 1.0486 sec PD 2.0000 sec PW1 10.00 usec CTEMP -273.1 c EXREF 77.00 ppm BF 1.00 Hz RGAIN 198 200 150 100 50 0 156.0882 154.5939 141.2217 139.2875 130.8076 129.1920 128.3273 127.8419 127.7129 77.5082 77.2579 77.0000 32.5067 28.6233 23.5717 23.0559 19.6882 S60
\\Landisk-ohe\nmr\Sasakura\NMR\sasaNMR501-600\sasaex578.pure.1H.als DFILE sasaex578.pure.1h.als CMNT DATIM 2016-02-17 21:07:09 BNUC 1H EXMD zg30 BFRQ 500.03 MHz BSET 3.08 KHz BFIN 7.89 Hz PINT 32768 FREQU 10000.00 Hz SCANS 16 ACQTM 3.2768 sec PD 1.0000 sec PW1 15.00 usec CTEMP -273.1 c EXREF 16.15 ppm BF 0.30 Hz RGAIN 99 0.94 1.03 1.99 2.05 1.00 0.31 0.98 0.95 1.00 1.00 2.06 10 8 6 4 2 0 8.5656 8.5626 8.5565 8.5528 7.6300 7.6148 7.5147 7.5116 7.4982 7.4506 7.4372 7.4335 7.4219 7.4060 7.3920 7.3773 7.2589 7.2455 7.2358 7.2296 7.2205 5.9468 5.9346 5.9266 5.9217 5.9138 5.9004 5.8924 5.8876 5.8802 5.8674 5.1167 5.1137 5.0960 5.0929 4.9941 4.9904 4.9599 4.9562 3.4207 3.4079 S61
\\Landisk-ohe\nmr\Sasakura\NMR\sasaNMR501-600\sasaex578.pure.13C.als DFILE sasaex578.pure.13c.als CMNT DATIM 2016-02-17 21:45:58 BNUC 13C EXMD zgpg30 BFRQ 125.74 MHz BSET 5.21 KHz BFIN 6.77 Hz PINT 32768 FREQU 31250.00 Hz SCANS 720 ACQTM 1.0486 sec PD 2.0000 sec PW1 10.00 usec CTEMP -273.1 c EXREF 77.00 ppm BF 1.00 Hz RGAIN 198 200 150 100 50 0 158.8794 147.3200 140.3115 137.9374 136.6783 132.6507 128.8582 128.1149 127.9708 122.1683 116.7223 77.2503 77.0000 76.7421 36.7771 S62
\\Landisk-ohe\nmr\Sasakura\NMR\sasaNMR501-600\sasaex590.pure.1H.als DFILE sasaex590.pure.1h.als CMNT DATIM 2016-02-26 17:30:16 BNUC 1H EXMD zg30 BFRQ 500.03 MHz BSET 3.08 KHz BFIN 7.89 Hz PINT 32768 FREQU 10000.00 Hz SCANS 16 ACQTM 3.2768 sec PD 1.0000 sec PW1 15.00 usec CTEMP -273.1 c EXREF 0.00 ppm BF 0.30 Hz RGAIN 99 1.93 1.99 0.98 0.96 2.00 3.01 2.97 3.29 10 8 6 4 2 0 7.5240 7.5209 7.5075 7.4324 7.4178 7.4025 7.3580 7.3433 7.2884 7.2536 2.8532 2.8380 2.8227 2.8074 2.3259 2.2698 1.2890 1.2743 1.2591 0.0000 S63
\\Landisk-ohe\nmr\Sasakura\NMR\sasaNMR501-600\sasaex590.pure.13C.als DFILE sasaex590.pure.13c.als CMNT DATIM 2016-02-26 18:09:24 BNUC 13C EXMD zgpg30 BFRQ 125.74 MHz BSET 5.21 KHz BFIN 6.77 Hz PINT 32768 FREQU 31250.00 Hz SCANS 720 ACQTM 1.0486 sec PD 2.0000 sec PW1 10.00 usec CTEMP -273.1 c EXREF 77.00 ppm BF 1.00 Hz RGAIN 198 200 150 100 50 0 159.0008 155.6331 141.2975 140.4253 129.3513 129.1010 128.2969 127.8798 127.6826 77.5082 77.2503 77.0000 28.6612 19.6503 18.3457 13.5141 S64