Experimental Supporting Information Visible-Light, Iodine-Promoted Formation of N-Sulfonyl Imines and N-Alkylsulfonamides from Aldehydes and Hypervalent Iodine Reagents Megan D. Hopkins, Zachary C. Brandeburg, Andrew J. Hanson, and Angus A. Lamar* Department of Chemistry and Biochemistry, The University of Tulsa, 800 S. Tucker Dr., Tulsa, OK 74104, USA.
[email protected]
Index General information - LED chamber
S-1
Table of N-sulfonyl imine C-H peaks
S-2
Characterization of compounds
S-2
1
S-8
H and 13C NMR Spectra of N-alkylsulfonamides
On the left – A red LED strip (620 nm) light bath reaction vessel On the right – A white LED strip (cool white) light bath reaction vessel Photocatalytic reactions were set up in a light bath which was constructed in our laboratory as follows. Waterproof 5050 LED strips (12V with power adapter, 18 LEDs/foot, approximately 0.24 Watt per LED – 72 Watt per strip) are coiled around the interior of evaporating dish (170mm x 90mm) using the adhesive backing of the LED strip. A Petri dish (150 x 20 mm) is placed upside down at the bottom of the dish to serve as an elevated glass “floor” to ensure that a round-bottom flask receives maximum light exposure. The temperature inside the dish is monitored and is generally maintained (air-cooled) between 19-22 oC (the temperature has not been observed above 25 oC). 1
All values are reported in CDCl3
N-(4-methoxybenzyl)-4-methylbenzenesulfonamide (3aa)5 White solid (90 mg, 61% yield). M.p. 119-121 °C. Purification (hexanes:EtOAc, 60:40). Rf = 0.56. 1H NMR (400 MHz, CDCl3) δ = 7.75 (d, J = 8.0 Hz, 2H), 7.30 (d, J = 8.0 Hz, 2H), 7.10 (d, J = 8.0 Hz), 6.79 (d, J = 8.0 Hz, 2H), 4.72 (t, J = 4.0 Hz, MeO 1H), 4.04 (d, J = 4.0 Hz, 2H), 3.77 (s, 3H), 2.43 (s, 3H) ppm. 13C NMR (100 MHz, CDCl3) δ 159.3, 143.4, 136.8, 129.7, 129.2, 128.2, 127.2, 114.0, 55.3, 46.8, 21.5 ppm. IR (neat): ν = 3248, 2922, 1612, 1513, 1320, 1251, 1155, 1029, 815, 553 cm-1. HRMS (ESI): calculated for C15H18N1O3S1 [M + H]+ requires m/z 292.10074, found m/z 292.07983. Ts
NH
4-methyl-N-(4-methylbenzyl)benzenesulfonamide (smaller scale, 0.125 mmol) (3ba)5 Ts White solid (21 mg, 60%). M.p. 88-90 °C. Purification (hexanes:EtOAc, 70:30). Rf
= 0.50. 1H NMR (400 MHz, CDCl3) δ = 7.76 (d, J = 8.0 Hz, 2H), 7.31 (d, J = 8.0 Hz, 2H), 7.08 (s, 4H), 4.62 (t, J = 6.0 Hz, 1H), 4.07 (d, J = 6.0 Hz, 2H), 2.44 (s, 3H), 2.31 H3C (s, 3H) ppm. 13C NMR (100 MHz, CDCl3) δ 143.5, 137.7, 136.8, 133.1, 129.7, 129.3, 127.8, 127.2, 47.0, 21.5, 21.1 ppm. IR (neat): ν = 3261, 2921, 1597, 1323, 1151, 1093, 748, 665 cm-1. HRMS (ESI): calculated for C15H18N1O2S1 [M + H]+ requires m/z 276.10583, found m/z 276.10449. NH
2
N-benzyl-4-methylbenzenesulfonamide (3ca)5 White solid (66 mg, 50%). M.p. 114-116 °C. Purification (hexanes:EtOAc, 60:40). Rf = 0.71. 1H NMR (400 MHz, CDCl3) δ = 7.74 (d, J = 8.0 Hz, 2H), 7.29 (d, J = 8.0 Hz, NH 2H), 7.30-7.24 (m, 3H), 7.20-7.18 (m, 2H), 4.84 (t, J = 4.0 Hz, 1H), 4.11 (d, J = 4.0 Hz, 2H), 2.43 (s, 3H) ppm. 13C NMR (100 MHz, CDCl3) δ 143.5, 136.8, 136.2, 129.7, 128.7, 127.9, 127.8, 127.2, 47.2, 21.5 ppm. IR (neat): ν = 3268, 3064, 1598, 1453, 1321, 1160, 1058, 874, 805, 741 cm-1. HRMS (ESI): calculated for C14H16N1O2S1 [M + H]+ requires m/z 262.09018, found m/z 262.08948. Ts
N-(4-bromobenzyl)-4-methylbenzenesulfonamide (3da)6 Ts
White solid (78 mg, 45%). M.p. 113-115 °C. Purification (hexanes:EtOAc, 60:40). Rf = 0.69. 1H NMR (400 MHz, CDCl3) δ = 7.71 (d, J = 8.0 Hz, 2H), 7.36 (d, J = 8.0 Hz, 2H), 7.28 (d, J = 8.0 Hz, 2H), 7.07 (d, J = 8.0 Hz, 2H), 5.17 (t, J = 4.0 Hz, 1H), 4.06 Br (d, J = 4.0 Hz, 2H), 2.43 (s, 3H) ppm. 13C NMR (100 MHz, CDCl3) δ 143.7, 136.7, 135.4, 131.7, 129.7, 129.5, 127.1, 121.7, 46.5, 21.5 ppm. IR (neat): ν = 3269, 2920, 1597, 1317, 1155, 1072, 1013, 878, 802, 544 cm-1. HRMS (ESI): calculated for C14H15N1O2S1Br1 [M + H]+ requires m/z 342.00069, found m/z 341.99771. NH
N-(4-chlorobenzyl)-4-methylbenzenesulfonamide (smaller scale, 0.125 mmol) (3ea)5 Ts
White solid (27 mg, 74%). M.p. 105-107 °C. Purification (hexanes:EtOAc, 60:40). Rf = 0.68. 1H NMR (400 MHz, CDCl3) δ = 7.72 (d, J = 8.0 Hz, 2H), 7.29 (d, J = 8.0 Hz, 2H), 7.22 (d, J = 8.0 Hz, 2H), 7.13 (d, J = 8.0 Hz, 2H), 4.81 (t, J = 4.0 Hz, 1H), 4.08 Cl (d, J = 4.0 Hz, 2H), 2.43 (s, 3H) ppm. 13C NMR (100 MHz, CDCl3) δ 143.7, 136.7, 134.8, 133.7, 129.8, 129.2, 128.8, 127.1, 46.5, 21.5 ppm. IR (neat): ν = 3226, 2920, 1597, 1304, 1183, 816 cm-1. HRMS (ESI): calculated for C14H15N1O2S1Cl1 [M + H]+ requires m/z 296.05120, found m/z 296.05054. NH
4-methyl-N-(4-nitrobenzyl)benzenesulfonamide (3fa) NH
Ts Yellow solid (62 mg, 40%). M.p. 111-113 °C. Purification (hexanes:EtOAc, 60:40).
Rf = 0.47. 1H NMR (400 MHz, CDCl3) δ = 8.12 (d, J = 8.0 Hz, 2H), 7.74 (d, J = 8.0 Hz, 2H), 7.40 (d, J = 8.0 Hz, 2H), 7.30 (d, J = 8.0 Hz, 2H), 5.13 (t, J = 4.0 Hz, 1H), O 2N 4.24 (d, J = 4.0 Hz, 2H), 2.44 (s, 3H) ppm. 13C NMR (100 MHz, CDCl3) δ 144.0, 143.9, 136.6, 129.9, 128.4, 127.1, 123.8, 46.4, 27.5, 21.6 ppm. IR (neat): ν = 3252, 2855, 1516, 1309, 1150, 1109, 814 cm-1. HRMS (ESI): calculated for C14H15N2O4S1 [M + H]+ requires m/z 307.07525, found m/z 307.07452. N-(4-cyanobenzyl)-4-methylbenzenesulfonamide (3ga) Ts
White solid (63 mg, 44%). M.p. 120-126 °C. Purification (hexanes:EtOAc, 60:40). Rf = 0.38. 1H NMR (400 MHz, CDCl3) δ = 7.72 (d, J = 8.0 Hz, 2H), 7.53 (d, J = 8.0 Hz, 2H), 7.35 (d, J = 8.0 Hz, 2H), 7.29 (d, J = 8.0 Hz, 2H), 5.43 (t, J = 4.0 Hz, 1H), 4.17 NC (d, J = 4.0 Hz, 2H), 2.44 (s, 3H) ppm. 13C NMR (100 MHz, CDCl3) δ 143.9, 142.0, 136.6, 132.3, 129.8, 128.3, 127.0, 118.5, 111.5, 46.6, 21.5 ppm. IR (neat): ν = 3234, 2922, 2857, 2230, 1594, 1324, 1152, 1069, 842, 815, 548 cm-1. HRMS (ESI): calculated for C15H15N2O2S1 [M + H]+ requires m/z 287.08543, found m/z 287.08475. NH
3
4-methyl-N-(3-methylbenzyl)benzenesulfonamide (3ha)8 NH
Ts White solid (46 mg, 33%). M.p. 64-66 °C. Purification (hexanes:EtOAc, 60:40). Rf = 0.81.
H NMR (400 MHz, CDCl3) δ = 7.76 (d, J = 8.0 Hz, 2H), 7.31 (d, J = 8.0 Hz, 2H), 7.16 (t, J = 8.0 Hz, 1H), 7.06 (d, J = 8.0 Hz, 1H), 6.98 (m, 2H), 4.60 (t, J = 4.0 Hz, 1H), 4.09 (d, J = 4.0 Hz, 2H), 2.44 (s, 3H), 2.28 (s, 3H). 13C NMR (100 MHz, CDCl3) δ 143.5, 138.4, 136.8, 136.1, 129.7, 128.62, 128.59, 128.56, 127.2, 124.9, 47.3, 21.5, 21.2 ppm. IR (neat): CH3 ν = 3294, 3029, 2922, 1596, 1320, 1153, 1065, 908, 811, 664, 537 cm-1. HRMS (ESI): calculated for C15H18N1O2S1 [M + H]+ requires m/z 276.10583, found m/z 276.10513. 1
4-methyl-N-(2-methylbenzyl)benzenesulfonamide (smaller scale, 0.125 mmol) (3ia)7 CH3
White solid (23 mg, 33%). M.p. 113-117 °C. Purification (hexanes: EtOAc, 60:40). Rf = Ts 0.74. 1H NMR (400 MHz, CDCl3) δ = 7.77 (d, J = 8.0 Hz, 2H), 7.32 (d, J = 8.0 Hz, 2H), NH 7.21-7.10 (m, 4H), 4.46 (t, J = 4.0 Hz, 1H), 4.09 (d, J = 4.0 Hz, 2H), 2.44 (s, 3H), 2.24 (s, 3H) ppm. 13C NMR (100 MHz, CDCl3) δ 143.5, 136.7, 136.6, 133.8, 130.6, 129.7, 128.8, 128.2, 127.2, 126.2, 45.4, 21.5, 18.8 ppm. IR (neat): ν = 3260, 3023, 2925, 1597, 1489, 1423, 1318, 1152, 1091, 1041, 879, 806, 702, 654 cm-1. HRMS (ESI): calculated for C15H18N1O2S1 [M + H]+ requires m/z 276.10583, found m/z 276.10483. N-(3-methoxybenzyl)-4-methylbenzenesulfonamide (smaller scale, 0.125 mmol) (3ja)8 1 Ts Clear oil (15 mg, 40%). Purification (hexanes:EtOAc, 60:40). Rf = 0.15. H NMR
MeO
(400 MHz, CDCl3) δ = 7.76 (d, J = 8.0 Hz, 2H), 7.31 (d, J = 8.0 Hz, 2H), 7.19 (t, J = 8.0 Hz, 1H), 6.80-6.75 (m, 2H), 6.73 (s, 1H), 4.65 (m, 1H), 4.10 (d, J = 6.0 Hz, 2H), 3.75 (s, 3H), 2.44 (s, 3H) ppm. 13C NMR (100 MHz, CDCl3) δ 159.8, 143.6, 137.8, 136.8, 129.8, 129.7, 127.2, 120.0, 113.7, 113.1, 55.2, 47.3, 21.5 ppm. IR (neat): ν = 3279, 2922, 1597, 1586, 1490, 1455, 1436, 1320, 1288, 1262, 1152, 1091, 1040, 864, 812, 780, 660 cm-1. HRMS (ESI): calculated for C15H18N1O3S1 [M + H]+ requires m/z 292.10074, found m/z 292.09961. NH
N-[(2-Methoxyphenyl)methyl]-4-methylbenzenesulfonamide (3ka)8 Ts White solid (57 mg, 40%). M.p. 79-81 °C. Purification (hexanes:EtOAc, 70:30). Rf = 0.33.
H NMR (400 MHz, CDCl3) δ = 7.66 (d, J = 8.0 Hz, 2H), 7.21-7.16 (m, 3H), 7.06 (d, J = 8.0 Hz, 1H), 6.80 (t, J = 8.0 Hz, 1H), 6.73 (d, J = 8.0 Hz, 1H), 5.09 (t, J = 4.0 Hz, 1H), OMe 4.14 (d, J = 4.0 Hz, 2H), 3.73 (s, 3H), 2.38 (s, 3H) ppm. 13C NMR (100 MHz, CDCl3) δ 157.2, 143.0, 129.8, 129.4, 129.2, 127.03, 126.99, 124.3, 120.5, 110.1, 55.1, 44.0, 21.5 ppm. IR (neat): ν = 3304, 3254, 3014, 2949, 2837, 1602, 1404, 1325, 1148, 1024, 756, 663 cm-1. HRMS (ESI): calculated for C15H18N1O3S1 [M + H]+ requires m/z 292.10074, found m/z 292.09958. NH
1
N-(3-bromobenzyl)-4-methylbenzenesulfonamide (3la)6 NH
Ts White solid (36 mg, 22%). M.p. 78-80 °C. Purification (hexanes:EtOAc, 60:40). Rf = 0.57.
H NMR (400 MHz, CDCl3) δ =7.73 (d, J = 8.0 Hz, 2H), 7.37 (td, J = 4.0 Hz, 1H), 7.31 (d, J = 8.0 Hz, 2H), 7.27 (m, 1H), 7.15 (d, J = 4.0 Hz, 2H), 4.72 (t, J = 4.0 Hz, 1H), 4.11 (d, J = 4.0 Hz, 2H), 2.44 (s, 3H) ppm. 13C NMR (100 MHz, CDCl3) δ 143.8, 138.5, 136.7, 131.0, 130.8, 130.2, 129.8, 127.1, 126.4, 122.7, 46.6, 21.5 ppm. IR (neat): ν = 3259, 3067, Br 2918, 2852, 1570, 1435, 1316, 1149, 1052, 921, 814, 692, 529 cm-1. HRMS (ESI): calculated for C14H15N1O2S1Br1 [M + H]+ requires m/z 342.00069, found m/z 341.99731. 1
4
N-(2-bromobenzyl)-4-methylbenzenesulfonamide (3ma)6 NH
Ts Yellow oil (50 mg, 30%). Purification (hexanes:EtOAc, 80:20). Rf = 0.27. 1H NMR (400
MHz, CDCl3) δ = 7.71 (d, J = 8.0 Hz, 2H), 7.45 (d, J = 8.0 Hz, 1H), 7.30 (d, J = 8.0 Hz, 1H), 7.25 (d, J = 8.0 Hz, 2H), 7.21 (t, J = 8.0 Hz, 1H), 7.10 (t, J = 8.0 Hz, 1H), 5.03 (t, J Br = 6.0 Hz, 1H), 4.22 (d, J = 6.0 Hz, 2H), 2.41 (s, 3H) ppm. 13C NMR (100 MHz, CDCl3) δ 136.9, 135.5, 132.7, 130.5, 129.6, 129.5, 129.1, 127.7, 127.1, 123.4, 47.4, 21.5 ppm. IR (neat): ν = 3282, 2922, 1597, 1441, 1325, 1154, 1024, 811, 658 cm-1. HRMS (ESI): calculated for C14H15N1O2S1Br1 [M + H]+ requires m/z 342.00069, found m/z 341.99728. N-(4-methylbenzyl)benzenesulfonamide (3bb)11 NH
Bs White solid (52 mg, 40%). M.p. 76-79 °C. Purification (hexanes:EtOAc, 70:30). Rf
= 0.48. 1H NMR (400 MHz, CDCl3) δ = 7.87 (d, J = 8.0 Hz, 2H), 7.59 (tt, J = 8.0 Hz, 4.0 Hz, 1H), 7.51 (m, 2H), 7.06 (s, 4H), 4.75 (t, J = 4.0 Hz, 1H), 4.09 (d, J = 4.0 H3C Hz, 2H), 2.30 (s, 3H) ppm. 13C NMR (100 MHz, CDCl3) δ 139.9, 137.7, 133.1, 132.7, 129.3, 129.1, 127.8, 127.1, 47.1, 21.1 ppm. IR (neat): ν = 3264, 2920, 1615, 1445, 1318, 1156, 1038, 907, 805 cm-1. HRMS (ESI): calculated for C14H16N1O2S1 [M + H]+ requires m/z 262.09018, found m/z 262.08905. N-(4-chlorobenzyl)benzenesulfonamide (smaller scale, 0.125 mmol) (3eb)9 White solid (51 mg, 70%). M.p. 109-112 °C. Purification (hexanes:EtOAc, 70:30). Rf 1 H NMR (400 MHz, CDCl3) δ = 7.84 (d, J = 8.0 Hz, 2H), 7.61-7.57 (m, 1H), NH 7.51 (d, J = 8.0 Hz, 2H), 7.22 (d, J = 8.0 Hz, 2H), 7.12 (d, J = 8.0 Hz, 2H), 4.87 (t, J = 4.0 Hz, 1H), 4.11 (d, J = 4.0 Hz, 2H) ppm. 13C NMR (100 MHz, CDCl3) δ 139.8, 134.7, Cl 133.8, 132.8, 129.2, 128.8, 127.0, 46.6, 29.7 ppm. IR (neat): ν = 3255, 3059, 1598, 1490, 1320, 1181, 1091, 817 cm-1. HRMS (ESI): calculated for C13H13N1O2S1Cl1 [M + H]+ requires m/z 282.03555, found m/z 282.03458. Bs = 0.44.
N-(2-methylbenzyl)benzenesulfonamide (smaller scale, 0.125 mmol) (3hb)12 White solid (25 mg, 38%). M.p. 117-123 °C. Purification (hexanes:EtOAc, 60:40). Rf = 0.65. 1H NMR (400 MHz, CDCl3) δ = 7.88 (d, J = 8.0 Hz, 2H), 7.61-7.57 (m, 1H), Bs 7.53 (d, J = 8.0 Hz, 2H), 7.21-7.09 (m, 4H), 4.56 (t, J = 4.0 Hz, 1H), 4.12 (d, J = 4.0 Hz, NH 2H), 2.23 (s, 3H) ppm. 13C NMR (100 MHz, CDCl3) δ 139.6, 133.7, 132.7, 130.6, 129.3, 129.1, 128.9, 128.3, 127.1, 126.2, 45.4, 18.8 ppm. IR (neat): ν = 3274, 3068, 1448, 1323, 1159, 1092, 1036, 886, 722, 686 cm-1. HRMS (ESI): calculated for C14H16N1O2S1 [M + H]+ requires m/z 262.09018, found m/z 262.08923. CH3
4-chloro-N-(4-methylbenzyl)benzenesulfonamide (3bc) Cs White solid (59 mg, 40%). M.p. 120-122 °C. Purification (hexanes:EtOAc, 70:30).
Rf = 0.58. 1H NMR (400 MHz, CDCl3) δ = 7.77 (d, J = 8.0 Hz, 2H), 7.45 (d, J = 8.0 Hz, 2H), 7.06 (m, 4H), 4.86 (t, J = 4.0 Hz, 1H), 4.10 (d, J = 4.0Hz, 2H), 2.31 (s, 3H) H3C ppm. 13C NMR (100 MHz, CDCl3) δ 139.1, 138.5, 137.9, 132.8, 129.4, 129.3, 128.6, 127.8, 47.1, 21.1 ppm. IR (neat): ν = 3245, 2923, 1586, 1325, 1158, 1092, 1058, 757, 565 cm-1. HRMS (ESI): calculated for C14H15N1O2S1Cl1 [M + H]+ requires m/z 296.05120, found m/z 296.05029. NH
5
N-(4-bromobenzyl)-4-chlorobenzenesulfonamide (smaller scale, 0.125 mmol) (3dc) White solid (25 mg, 54%). M.p. 126-128 °C. Purification (hexanes:EtOAc, 70:30). Rf = 0.64. 1H NMR (400 MHz, CDCl3) δ = 7.77 (d, J = 8.0 Hz, 2H), 7.48 (d, J = 8.0 Hz, NH 2H), 7.41 (d, J = 8.0 Hz, 2H), 7.08 (d, J = 8.0 Hz, 2H), 4.82 (t, J = 4.0 Hz, 1H), 4.11 (d, J = 4.0 Hz, 2H) ppm. 13C NMR (100 MHz, CDCl3) δ 139.4, 138.3, 135.0, 131.8, Br 129.50, 129.45, 128.5, 122.0, 46.6 ppm. IR (neat): ν = 3246, 3087, 1573, 1320, 1153, -1 826 cm . HRMS (ESI): calculated for C13H12N1O2S1Cl1Br1 [M + H]+ requires m/z 361.94607, found m/z 361.94302. Cs
2-chloro-N-(4-methylbenzyl)benzenesulfonamide (3bd) O
Cl
White solid (25 mg, 17%). M.p. 64-66 °C. Purification (hexanes:EtOAc, 70:30). Rf = 0.53. 1H NMR (400 MHz, CDCl3) δ = 8.09 (d, J = 8.0 Hz, S NH 1H), 7.50-7.49 (m, 2H), 7.42-7.38 (m, 1H), 7.06 (s, 4H), 5.21 (t, J = 4.0 Hz, 1H), 4.07 (d, J = 4.0 Hz, 2H), 2.29 (s, 3H) ppm. 13C NMR (100 MHz, H3C CDCl3) δ 137.8, 137.1, 133.6, 132.6, 131.5, 131.4, 131.3, 129.3, 127.9, 127.2, 47.3, 21.1 ppm. IR (neat): ν = 3277, 3094, 2924, 1426, 1327, 1163, 1042, 760, 585 cm-1. HRMS (ESI): calculated for C14H15N1O2S1Cl1 [M + H]+ requires m/z 296.05120, found m/z 296.05140. O
N-(4-methoxybenzyl)-4-nitrobenzenesulfonamide (3ae)9 Tan solid (19 mg, 11%). M.p. 126-130 °C. Purification (hexanes:EtOAc, 60:40). Rf = 0.53. 1H NMR (400 MHz, CDCl3) δ = 8.31 (d, J = 8.0 Hz, 2H), 8.09 (d, J = 8.0 Hz, 2H), 7.08 (d, J = 8.0 Hz, 2H), 6.77 (d, J = 8.0 Hz, 2H), 4.82 (t, J = 4.0 Hz, 1H), MeO 4.16 (d, J = 4.0 Hz, 2H), 3.76 (s, 3H) ppm. 13C NMR (100 MHz, CDCl3) δ 146.1, 129.3, 128.6, 128.3, 127.4, 124.3, 121.0, 114.2, 55.3, 47.0 ppm. IR (neat): ν = 3269, 3110, 29`5, 2840, 1512, 1245, 1151, 1030, 817 cm-1. HRMS (ESI): calculated for C14H15N2O5S1 [M + H]+ requires m/z 323.07017, found m/z 323.22165. Ns
NH
N-(4-chlorobenzyl)-4-nitrobenzenesulfonamide (smaller scale, 0.125 mmol) (3ee)11 Oil (9 mg, 21%). Purification (hexanes:EtOAc, 60:40). Rf = 0.62. 1H NMR (400 MHz, Ns CDCl3) δ = 8.35 (d, J = 8.0 Hz, 2H), 8.02 (d, J = 8.0 Hz, 2H), 7.27 (d, J = 8.0 Hz, 2H), NH 7.15 (d, J = 8.0 Hz, 2H), 4.84 (t, J = 4.0 Hz, 1H), 4.21 (d, J = 4.0 Hz, 2H) ppm. 13C NMR (100 MHz, CDCl3) δ 145.9, 134.3, 134.0, 129.2, 129.0, 128.3, 124.4, 46.7, 29.7 Cl ppm. IR (neat): ν = 3265, 2921, 1606, 1341, 1156, 837 cm-1. HRMS (ESI): calculated for C13H12N2O4S1Cl1 [M + H]+ requires m/z 327.02063, found m/z 327.07776. N-(4-methylbenzyl)-3-nitrobenzenesulfonamide (3bf)10 O
White solid (12 mg, 8%). M.p. 110-113 °C. Purification (hexanes:EtOAc, 70:30). Rf = 0.36. 1H NMR (400 MHz, CDCl3) δ = 8.57 (t, J = 4.0 Hz, 1H), 8.38 (ddd, J = NH 4.0 Hz, 8.0 Hz, 1H), 8.13 (dt, J = 8.0 Hz, 1H), 7.67 (t, J = 8.0 Hz, 1H), 7.04 (s, 4H), H3C 4.93 (t, J = 4.0 Hz, 1H), 4.21 (d, J = 4.0 Hz, 2H), 2.28 (s, 3H) ppm. 13C NMR (100 + - N MHz, CDCl3) δ 142.6, 138.1, 132.5, 130.3, 129.4, 127.9, 127.1, 126.9, 122.4, 47.2, O O 21.0 ppm. IR (neat): ν = 3250, 3089, 2921, 1607, 1526, 1428, 1331, 1163 cm-1. HRMS (ESI): calculated for C14H15N2O4S1 [M + H]+ requires m/z 307.07525, found m/z 307.07416. O
S
6
References: 1. Hopkins, M. D.; Scott, K. A.; DeMier, B. C.; Morgan, H. R.; Macgruder, J. A.; Lamar, A. A., Formation of N-sulfonyl imines from iminoiodinanes by iodine-promoted, N-centered radical sulfonamidation of aldehydes. Organic & biomolecular chemistry 2017, 15 (43), 9209-9216. 2. Castellano, S.; Fiji, H. D. G.; Kinderman, S. S.; Watanabe, M.; de Leon, P.; Tamanoi, F.; Kwon, O., SmallMolecule Inhibitors of Protein Geranylgeranyltransferase Type I. Journal of the American Chemical Society 2007, 129 (18), 5843-5845. 3. Chen, D.; Chen, X.; Du, T.; Kong, L.; Zhen, R.; Zhen, S.; Wen, Y.; Zhu, G., Highly efficient and diastereoselective synthesis of 1,3-oxazolidines featuring a palladium-catalyzed cyclization reaction of 2butene-1,4-diol derivatives and imines. Tetrahedron Letters 2010, 51 (39), 5131-5133. 4. Kohler, M. C.; Yost, J. M.; Garnsey, M. R.; Coltart, D. M., Direct Carbon−Carbon Bond Formation via Soft Enolization: A Biomimetic Asymmetric Mannich Reaction of Phenylacetate Thioesters. Organic letters 2010, 12 (15), 3376-3379. 5. Gao, F.; Deng, M.; Qian, C., The effect of coordination on the reaction of N-tosyl imines with diethylzinc. Tetrahedron 2005, 61 (52), 12238-12243. 6. Zhu, M.; Fujita, K.-i.; Yamaguchi, R., Simple and Versatile Catalytic System for N-Alkylation of Sulfonamides with Various Alcohols. Organic letters 2010, 12 (6), 1336-1339. 7. Wallach, D. R.; Chisholm, J. D., Alkylation of Sulfonamides with Trichloroacetimidates under Thermal Conditions. The Journal of organic chemistry 2016, 81 (17), 8035-42. 8. Cui, X.; Shi, F.; Tse, M. K.; Gördes, D.; Thurow, K.; Beller, M.; Deng, Y., Copper-CatalyzedNAlkylation of Sulfonamides with Benzylic Alcohols: Catalysis and Mechanistic Studies. Advanced Synthesis & Catalysis 2009, 351 (17), 2949-2958. 9. Yrjölä, S.; Parkkari, T.; Navia-Paldanius, D.; Laitinen, T.; Kaczor, A. A.; Kokkola, T.; Adusei-Mensah, F.; Savinainen, J. R.; Laitinen, J. T.; Poso, A.; Alexander, A.; Penman, J.; Stott, L.; Anskat, M.; Irving, A. J.; Nevalainen, T. J., Potent and selective N-(4-sulfamoylphenyl)thiourea-based GPR55 agonists. European Journal of Medicinal Chemistry 2016, 107, 119-132. 10. Caddick, S.; Wilden, J. D.; Judd, D. B., Direct Synthesis of Sulfonamides and Activated Sulfonate Esters from Sulfonic Acids. Journal of the American Chemical Society 2004, 126 (4), 1024-1025. 11. Yu, X.; Liu, C.; Jiang, L.; Xu, Q., Manganese Dioxide Catalyzed N-Alkylation of Sulfonamides and Amines with Alcohols under Air. Organic letters 2011, 13 (23), 6184-6187. 12. Li, Z.-l.; Jin, L.-k.; Cai, C., Nickel-catalyzed product-controllable amidation and imidation of sp3 C-H bonds in substituted toluenes with sulfonamides. Organic & biomolecular chemistry 2017, 15 (6), 13171320.
7
Normalized Intensity
0
0.01
0.02
0.03
0.04
0.05
0.06
0.07
0.08
0.09
0.10
0.11
0.12
0.13
0.14
11.5
11.0
10.5
10.0
9.5
9.0
8.5
8.0
7.5
7.0
1.95 2.03 2.00 2.03 6.5 6.0 5.5 5.0 Chemical Shift (ppm)
4.5
1.03
4.0
2.123.06 3.5
3.0
2.5
2.99 2.0
1.5
1.0
This report was created by ACD/NMR Processor Academic Edition. For more information go to www.acdlabs.com/nmrproc/
KS-52-1Hreport
0.5
3aa 0
-0.5
Normalized Intensity
0
0.05
0.10
0.15
0.20
0.25
220
200
180
159.27 160
136.84
143.44 140
114.02 120 100 Chemical Shift (ppm)
80
77.32 77.00 76.68
0.30
60
40
20
21.52 46.76
55.26
129.24
This report was created by ACD/NMR Processor Academic Edition. For more information go to www.acdlabs.com/nmrproc/
KS-52-13Creport
0
3aa
127.16
129.70
-20
Normalized Intensity
0
0.05
0.10
0.15
0.20
0.25
0.30
11.5
11.0
10.5
10.0
9.5
9.0
8.5
8.0
1.95
7.5
7.0
2.003.86 6.5 6.0 5.5 5.0 Chemical Shift (ppm)
4.5
0.96
4.0
2.12 3.5
3.0
2.5
2.0
3.05 3.01 1.5
1.0
This report was created by ACD/NMR Processor Academic Edition. For more information go to www.acdlabs.com/nmrproc/
KS-44-F16-24-1H
0.5
3ba 0
-0.5
Normalized Intensity
0
0.05
0.10
0.15
0.20
0.25
220
200
180
160
143.47 140
137.70 136.79
129.33 129.71 133.14
0.30
120 100 Chemical Shift (ppm)
77.32 80
60
40
20
21.53
21.07
47.04
76.68
This report was created by ACD/NMR Processor Academic Edition. For more information go to www.acdlabs.com/nmrproc/
KS-44-F16-24-13C
0
3ba
127.18
-20
Normalized Intensity
0
0.05
0.10
0.15
0.20
0.25
0.30
11
10
9
8
7
2.00 2.33 2.94 2.01 6 5 Chemical Shift (ppm)
1.02
4
2.18 3
3.02 2
1
This report was created by ACD/NMR Processor Academic Edition. For more information go to www.acdlabs.com/nmrproc/
KS-54-1Hreport
3ca 0
Normalized Intensity
0
0.05
0.10
0.15
0.20
0.25
220
200
180
160
136.24
143.50 140
136.78
0.30
120 100 Chemical Shift (ppm)
77.33 80
60
40
20
21.53
47.23
76.70
127.85
This report was created by ACD/NMR Processor Academic Edition. For more information go to www.acdlabs.com/nmrproc/
KS-54-13Creport
0
3ca
127.16
129.72
-20
Normalized Intensity
0
0.05
0.10
0.15
0.20
0.25
0.30
11.5
11.0
10.5
10.0
9.5
9.0
8.5
8.0
7.5
7.0
2.01 1.98 2.08 1.95
6.5 6.0 5.5 5.0 Chemical Shift (ppm)
1.02 4.5
4.0
2.04 3.5
3.0
2.5
3.12 2.0
1.5
1.0
This report was created by ACD/NMR Processor Academic Edition. For more information go to www.acdlabs.com/nmrproc/
KS-55-1Hreport
0.5
3da 0
Normalized Intensity
0
0.05
0.10
0.15
0.20
0.25
220
200
180
160
135.40
143.65 140
136.69
129.74 127.09 131.66
0.30
121.72 120 100 Chemical Shift (ppm)
77.35 77.03 76.71 80
60
40
20
21.54
46.53
This report was created by ACD/NMR Processor Academic Edition. For more information go to www.acdlabs.com/nmrproc/
KS-55-13Creport
0
3da -20
Normalized Intensity
0
0.05
0.10
0.15
0.20
0.25
0.30
11.5
11.0
10.5
10.0
9.5
9.0
8.5
8.0
7.5
7.0
1.96 2.08 1.98 1.96
6.5 6.0 5.5 5.0 Chemical Shift (ppm)
0.95 4.5
4.0
2.06 3.5
3.0
2.5
3.11 2.0
1.5
1.0
This report was created by ACD/NMR Processor Academic Edition. For more information go to www.acdlabs.com/nmrproc/
KS-31-1H
0.5
3ea 0
Normalized Intensity
0
0.05
0.10
0.15
0.20
0.25
220
200
180
160
129.75 129.18 127.11 134.81
143.67 140
136.72 133.71
0.30
120 100 Chemical Shift (ppm)
77.32 77.00 80
60
40
20
21.53 46.53
76.68
This report was created by ACD/NMR Processor Academic Edition. For more information go to www.acdlabs.com/nmrproc/
KS-31-13C
3ea 0
-20
Normalized Intensity
0
0.05
0.10
0.15
0.20
0.25
0.30
11.5
11.0
10.5
10.0
9.5
9.0
8.5
8.0
7.5
7.0
1.71 2.01 1.81 2.00
6.5 6.0 5.5 5.0 Chemical Shift (ppm)
0.95 4.5
4.0
2.03 3.5
3.0
2.5
3.08 2.0
1.5
1.0
This report was created by ACD/NMR Processor Academic Edition. For more information go to www.acdlabs.com/nmrproc/
MH-n5-57-1Hreport
0.5
3fa 0
Normalized Intensity
0
0.05
0.10
0.15
0.20
0.25
220
200
180
160
136.59
144.02 143.94 140
120 100 Chemical Shift (ppm)
123.80
128.41 129.87 127.10
0.30
80
60
40
20
21.55 27.45
46.39
This report was created by ACD/NMR Processor Academic Edition. For more information go to www.acdlabs.com/nmrproc/
MH-n5-57-13Creport
0
3fa -20
Normalized Intensity
0
0.05
0.10
0.15
0.20
0.25
0.30
11.5
11.0
10.5
10.0
9.5
9.0
8.5
8.0
7.5
7.0
2.00 1.90 2.13 2.01
6.5 6.0 5.5 5.0 Chemical Shift (ppm)
0.99 4.5
4.0
2.06 3.5
3.0
2.5
3.11 2.0
1.5
1.0
This report was created by ACD/NMR Processor Academic Edition. For more information go to www.acdlabs.com/nmrproc/
MH-n5-79-1Hreport
0.5
3ga 0
Normalized Intensity
0
0.05
0.10
0.15
0.20
0.25
220
200
180
160
142.04 136.56 140
143.89
129.81 128.32 127.05 132.32
0.30
111.47 118.54 120 100 Chemical Shift (ppm)
77.36 77.04 76.72 80
60
40
20
21.53 46.55
This report was created by ACD/NMR Processor Academic Edition. For more information go to www.acdlabs.com/nmrproc/
MH-n5-79-13Creport
3ga 0
-20
Normalized Intensity
0
0.05
0.10
0.15
0.20
0.25
0.30
11.5
11.0
10.5
10.0
9.5
9.0
8.5
8.0
7.5
7.0
6.5 6.0 5.5 5.0 Chemical Shift (ppm)
2.022.10 1.03 0.98 2.00
4.5
0.97
4.0
2.16 3.5
3.0
2.5
2.0
3.27 3.09 1.5
This report was created by ACD/NMR Processor Academic Edition. For more information go to www.acdlabs.com/nmrproc/
MH-n5-64-1Hreport
1.0
3ha 0.5
0
-0.5
Normalized Intensity
0
0.01
0.02
0.03
0.04
0.05
0.06
0.07
0.08
0.09
0.10
0.11
0.12
0.13
0.14
0.15
220
200
180
160
143.48 140
127.18 128.56 129.70
0.16
120 100 Chemical Shift (ppm)
77.32 77.00 76.68 80
60
40
20
21.24
0.17
138.41 136.84 136.08
21.52
47.25
This report was created by ACD/NMR Processor Academic Edition. For more information go to www.acdlabs.com/nmrproc/
MH-n5-64-13Creport
0
3ha
124.86
-20
Normalized Intensity
0
0.05
0.10
0.15
0.20
0.25
0.30
11.5
11.0
10.5
10.0
9.5
9.0
8.5
8.0
7.5
7.0
2.02 2.12 0.99 2.99 6.5 6.0 5.5 5.0 Chemical Shift (ppm)
4.5
4.0
0.96 2.13 3.5
3.0
2.5
2.0
3.08 2.97 1.5
This report was created by ACD/NMR Processor Academic Edition. For more information go to www.acdlabs.com/nmrproc/
KS-34-1Hreport
1.0
0.5
3ia 0
-0.5
Normalized Intensity
0
0.05
0.10
0.15
0.20
0.25
220
200
180
160
133.84
143.53 140
136.71 136.55
127.18 128.84 130.59 129.71 120 100 Chemical Shift (ppm)
77.00 76.68 80
77.32
0.30
60
40
20
21.54 18.77
45.39
This report was created by ACD/NMR Processor Academic Edition. For more information go to www.acdlabs.com/nmrproc/
KS-34-13Creport
3ia
126.17
0
-20
Normalized Intensity
0
0.05
0.10
0.15
0.20
0.25
0.30
11
10
9
8
7
6 5 Chemical Shift (ppm)
2.012.17 0.95 1.99 0.92
1.05
4
2.13 3.14 3
3.06 2
1
This report was created by ACD/NMR Processor Academic Edition. For more information go to www.acdlabs.com/nmrproc/
MH-n4-78-1Hreport
3ja 0
Normalized Intensity
0
0.05
0.10
0.15
0.20
220
200
180
159.83 160
137.76 136.82
143.57 140
129.75 127.19
0.25
113.67 120.02 120 100 Chemical Shift (ppm)
113.12
0.30
77.33 77.01 80
60
40
20
21.54
47.26
55.20
This report was created by ACD/NMR Processor Academic Edition. For more information go to www.acdlabs.com/nmrproc/
MH-n4-78-13Creport
3ja
76.70
0
-20
Normalized Intensity
0
0.05
0.10
0.15
0.20
0.25
0.30
11
10
9
8
7
1.00 6 5 Chemical Shift (ppm)
1.803.03 0.94 0.92 0.95
4
2.11 3.54 3
3.02 2
1
This report was created by ACD/NMR Processor Academic Edition. For more information go to www.acdlabs.com/nmrproc/
MH-n5-83-1Hreport
3ka 0
Normalized Intensity
0
0.05
0.10
0.15
0.20
0.25
220
200
180
157.16 160
143.01 140
129.77 129.36 127.03 126.99
0.30
110.05
120.52 120 100 Chemical Shift (ppm)
77.32 77.00 80
60
40
20
21.45
43.99 55.14
This report was created by ACD/NMR Processor Academic Edition. For more information go to www.acdlabs.com/nmrproc/
MH-n5-83-13Creport
3ka
76.68
0
-20
Normalized Intensity
0
0.05
0.10
0.15
0.20
0.25
0.30
11.5
11.0
10.5
10.0
9.5
9.0
8.5
8.0
7.5
7.0
6.5 6.0 5.5 5.0 Chemical Shift (ppm)
1.97 0.99 1.98 0.97 1.89
4.5
0.98
4.0
2.03 3.5
3.0
2.5
3.08 2.0
1.5
1.0
This report was created by ACD/NMR Processor Academic Edition. For more information go to www.acdlabs.com/nmrproc/
MH-n5-80-1Hreport
0.5
3la 0
Normalized Intensity
0
0.01
0.02
0.03
0.04
0.05
0.06
0.07
0.08
0.09
0.10
0.11
0.12
220
200
180
160
143.75
138.53
140
130.82 130.96
0.13
129.79 127.11 126.38 120 100 Chemical Shift (ppm)
122.65
0.14
77.30 76.98 76.67 80
60
40
20
21.54
46.60
This report was created by ACD/NMR Processor Academic Edition. For more information go to www.acdlabs.com/nmrproc/
MH-n5-80-13Creport
0
3la -20
Normalized Intensity
0
0.05
0.10
0.15
0.20
0.25
0.30
11.5
11.0
10.5
10.0
9.5
9.0
8.5
8.0
7.5
7.0
0.97 6.5 6.0 5.5 5.0 Chemical Shift (ppm)
1.98 0.95 1.14 2.18 0.98
4.5
4.0
2.18 3.5
3.0
2.5
3.16 2.0
1.5
1.0
This report was created by ACD/NMR Processor Academic Edition. For more information go to www.acdlabs.com/nmrproc/
MH-n5-81-1Hreport
0.5
3ma 0
-0.5
Normalized Intensity
0
0.05
0.10
0.15
0.20
220
200
180
160
140
127.07 129.60 132.73 136.87 135.47
0.25
123.41 120 100 Chemical Shift (ppm)
80
77.33 77.01 76.69
0.30
60
40
20
21.50
47.42
This report was created by ACD/NMR Processor Academic Edition. For more information go to www.acdlabs.com/nmrproc/
MH-n5-81-13Creport
0
3ma -20
Normalized Intensity
0
0.05
0.10
0.15
0.20
0.25
0.30
11.5
11.0
10.5
10.0
9.5
9.0
8.5
8.0
7.5
7.0
2.00 1.01 2.11 4.00 6.5 6.0 5.5 5.0 Chemical Shift (ppm)
4.5
0.99
4.0
1.97 3.5
3.0
2.5
3.25 2.0
1.5
This report was created by ACD/NMR Processor Academic Edition. For more information go to www.acdlabs.com/nmrproc/
MH-n5-73-1Hreport
1.0
3bb 0.5
0
Normalized Intensity
0
0.05
0.10
0.15
0.20
0.25
220
200
180
160
140
132.65 133.07 139.85 137.72
127.10 129.34
0.30
120 100 Chemical Shift (ppm)
77.32 77.01 76.69 80
60
40
20
21.07
47.05
This report was created by ACD/NMR Processor Academic Edition. For more information go to www.acdlabs.com/nmrproc/
MH-n5-73-13Creport
3bb 0
-20
Normalized Intensity
0
0.005
0.010
0.015
0.020
0.025
0.030
0.035
0.040
14
13
12
11
10
9
8
7
0.98 6 5 Chemical Shift (ppm)
2.00 1.01 2.08 2.11 2.09
4
2.23 3
2
1
0
This report was created by ACD/NMR Processor Academic Edition. For more information go to www.acdlabs.com/nmrproc/
KS-33-1Hreport
-1
3eb -2
Normalized Intensity
-0.010
-0.005
0
0.005
0.010
0.015
0.020
0.025
0.030
0.035
0.040
0.045
0.050
0.055
0.060
0.065
0.070
0.075
0.080
220
200
180
160
139.78 140
132.80 134.71
0.085
129.16 128.81 127.04 120 100 Chemical Shift (ppm)
77.31 77.20 77.00 76.68 80
60
40
29.68
46.56
20
This report was created by ACD/NMR Processor Academic Edition. For more information go to www.acdlabs.com/nmrproc/
KS-33-13Creport
0
3eb -20
Normalized Intensity
0
0.05
0.10
0.15
0.20
0.25
0.30
11.5
11.0
10.5
10.0
9.5
9.0
8.5
8.0
7.5
7.0
1.95 1.04 2.01 4.03 6.5 6.0 5.5 5.0 Chemical Shift (ppm)
4.5
4.0
0.91 2.07 3.5
3.0
2.5
2.0
2.96 1.5
1.0
This report was created by ACD/NMR Processor Academic Edition. For more information go to www.acdlabs.com/nmrproc/
KS-36-1Hreport
0.5
0
3hb -0.5
Normalized Intensity
-0.01
0
0.01
0.02
0.03
0.04
0.05
0.06
0.07
0.08
0.09
0.10
0.11
0.12
0.13
0.14
0.15
0.16
220
200
180
160
129.11 127.10 130.62 140
139.57 133.70 132.74
0.17
120 100 Chemical Shift (ppm)
77.32 77.00 76.68 80
60
40
20
18.76 45.43
This report was created by ACD/NMR Processor Academic Edition. For more information go to www.acdlabs.com/nmrproc/
KS-36-13Creport
0
3hb
126.19
-20
Normalized Intensity
0
0.05
0.10
0.15
0.20
0.25
0.30
11.5
11.0
10.5
10.0
9.5
9.0
8.5
8.0
7.5
7.0
2.00 1.97 4.09
6.5 6.0 5.5 5.0 Chemical Shift (ppm)
1.01 4.5
4.0
2.15 3.5
3.0
2.5
3.20 2.0
1.5
1.0
This report was created by ACD/NMR Processor Academic Edition. For more information go to www.acdlabs.com/nmrproc/
MH-n5-75-1Hreport
0.5
3bc 0
-0.5
Normalized Intensity
0
0.05
0.10
0.15
0.20
0.25
220
200
180
160
139.10 138.47 137.86 140
129.33 129.38 132.79
128.56 127.83
0.30
120 100 Chemical Shift (ppm)
77.32 77.01 76.69 80
60
40
20
21.07
47.05
This report was created by ACD/NMR Processor Academic Edition. For more information go to www.acdlabs.com/nmrproc/
MH-n5-75-13Creport
0
3bc -20
Normalized Intensity
0
0.05
0.10
0.15
0.20
0.25
0.30
11.5
11.0
10.5
10.0
9.5
9.0
8.5
8.0
7.5
7.0
2.00 2.05 2.01 2.03
6.5 6.0 5.5 5.0 Chemical Shift (ppm)
1.00 4.5
4.0
2.10 3.5
3.0
2.5
2.0
1.5
1.0
This report was created by ACD/NMR Processor Academic Edition. For more information go to www.acdlabs.com/nmrproc/
MH-n4-76-1H
0.5
3dc 0
Normalized Intensity
-0.010
-0.005
0
0.005
0.010
0.015
0.020
0.025
0.030
0.035
0.040
0.045
0.050
0.055
0.060
0.065
0.070
0.075
0.080
0.085
0.090
0.095
220
200
180
160
140
129.50 129.45 128.49 134.95 131.84 138.33 139.37
0.100
122.04 120 100 Chemical Shift (ppm)
77.31 76.99 76.68 80
60
46.62 40
20
This report was created by ACD/NMR Processor Academic Edition. For more information go to www.acdlabs.com/nmrproc/
MH-n4-76-13C
0
3dc -20
Normalized Intensity
0
0.05
0.10
0.15
0.20
0.25
0.30
11.5
11.0
10.5
10.0
9.5
9.0
8.5
8.0
7.5
7.0
1.04 2.13 1.03 4.19
6.5 6.0 5.5 5.0 Chemical Shift (ppm)
1.04 4.5
4.0
2.10 3.5
3.0
2.5
3.24 2.0
1.5
1.0
This report was created by ACD/NMR Processor Academic Edition. For more information go to www.acdlabs.com/nmrproc/
ZB-33-1Hreport
0.5
3bd 0
-0.5
Normalized Intensity
0
0.05
0.10
0.15
0.20
220
200
180
160
140
133.61
0.25
137.80 137.13
127.91 129.31 131.40
0.30
120 100 Chemical Shift (ppm)
77.00 77.32 76.68 80
60
40
20
21.06
47.31
This report was created by ACD/NMR Processor Academic Edition. For more information go to www.acdlabs.com/nmrproc/
ZB-33-13Creport
3bd
127.19
0
-20
Normalized Intensity
0
0.01
0.02
0.03
0.04
0.05
0.06
0.07
0.08
0.09
0.10
0.11
0.12
0.13
0.14
11.5
11.0
10.5
10.0
9.5
9.0
8.5
8.0
1.29 0.61 2.00 7.5
7.0
1.97 2.02
6.5 6.0 5.5 5.0 Chemical Shift (ppm)
0.99 4.5
4.0
2.18 3.30 3.5
3.0
2.5
2.0
1.5
This report was created by ACD/NMR Processor Academic Edition. For more information go to www.acdlabs.com/nmrproc/
KS-61-1Hreport
1.0
3ae 0.5
0
Normalized Intensity
0
0.005
0.010
0.015
0.020
0.025
0.030
0.035
0.040
0.045
0.050
0.055
0.060
0.065
0.070
0.075
0.080
220
200
180
160
140
114.15 120 100 Chemical Shift (ppm)
121.04
129.31 128.29 124.27 127.36
0.085
77.30 76.98 76.67 80
60
46.95
55.29
146.08
40
20
This report was created by ACD/NMR Processor Academic Edition. For more information go to www.acdlabs.com/nmrproc/
KS-61-13Creport
0
3ae -20
Normalized Intensity
0
0.01
0.02
0.03
0.04
0.05
0.06
0.07
0.08
0.09
0.10
0.11
0.12
0.13
0.14
0.15
0.16
0.17
11
10
9
8
1.97 2.01
7
1.94 2.05
6 5 Chemical Shift (ppm)
0.98
2.19 4
3
2
1
This report was created by ACD/NMR Processor Academic Edition. For more information go to www.acdlabs.com/nmrproc/
MH-n4-77-1Hreport
3ee 0
Normalized Intensity
0
0.005
0.010
0.015
0.020
0.025
0.030
220
200
180
160
134.30 134.00 140
129.23 129.04 124.42 120 100 Chemical Shift (ppm)
77.33 77.01 76.69 80
60
40
29.70
46.74 145.89
20
This report was created by ACD/NMR Processor Academic Edition. For more information go to www.acdlabs.com/nmrproc/
MH-n4-77-13Creport1
0
3ee
128.30
-20
Normalized Intensity
0
0.005
0.010
0.015
0.020
0.025
0.030
0.035
0.040
0.045
0.050
0.055
0.060
0.065
0.070
0.075
0.080
0.085
0.090
0.095
0.100
11.5
11.0
10.5
10.0
9.5
9.0
8.5
8.0
7.5
0.97 1.08 1.11 1.19
7.0
4.17
6.5 6.0 5.5 5.0 Chemical Shift (ppm)
1.11 4.5
4.0
2.24 3.5
3.0
2.5
3.04 2.0
1.5
This report was created by ACD/NMR Processor Academic Edition. For more information go to www.acdlabs.com/nmrproc/
MH-n5-77-1Hreport
1.0
0.5
3bf 0
-0.5
Normalized Intensity
-0.01
0
0.01
0.02
0.03
0.04
0.05
0.06
0.07
0.08
0.09
0.10
0.11
220
200
180
160
142.57
138.06 140
127.91 129.42 132.49
0.12
126.86 122.38 120 100 Chemical Shift (ppm)
77.30 76.99 76.67 80
60
40
20
20.99
47.22
This report was created by ACD/NMR Processor Academic Edition. For more information go to www.acdlabs.com/nmrproc/
MH-n5-77-13Creport
0
3bf -20
Normalized Intensity
0
0.05
0.10
0.15
0.20
0.25
0.30
11.5
11.0
10.5
10.0
9.5
9.0
8.5
8.0
7.5
7.0
2.00 2.094.10 6.5 6.0 5.5 5.0 Chemical Shift (ppm)
4.5
1.02
4.0
0.97 3.5
3.0
2.5
2.0
3.19 3.15 1.5
1.0
This report was created by ACD/NMR Processor Academic Edition. For more information go to www.acdlabs.com/nmrproc/
KS-43-F12-20-1H
0.5
5 0
Normalized Intensity
0
0.01
0.02
0.03
0.04
0.05
0.06
0.07
0.08
0.09
0.10
0.11
0.12
0.13
0.14
0.15
0.16
220
200
180
160
137.70 143.48 140
120 100 Chemical Shift (ppm)
77.33 77.01 76.70 80
60
46.96 46.75 46.54 40
20
21.09
0.17
129.71 129.33 127.17 136.78 133.08
21.54
This report was created by ACD/NMR Processor Academic Edition. For more information go to www.acdlabs.com/nmrproc/
KS-43-F12-20-13C
0
5 -20
