Experimental Supporting Information Visible-Light, Iodine ... - MDPI

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Visible-Light, Iodine-Promoted Formation of N-Sulfonyl Imines and ... Photocatalytic reactions were set up in a light bath which was constructed in our laboratory ..... of 1,3-oxazolidines featuring a palladium-catalyzed cyclization reaction of 2-.

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