The Journal of Organic Chemistry
Page 28 of 56
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(CDCl
3
, 101 MHz): δ = 167.5, 155.5, 134.3, 133.0, 132.1, 131.7, 128.7, 128.3, 127.1, 112.2,
+
111.9, 56.4, 43.1. MS (ESI) m/z: [M+H] Calcd. for C15
H15BrNO
2
320.03, found 320.00. EA
–
1
(
%): Calcd.: C 56.27 H 4.41 N 4.37; found: C 56.08 H 4.39 N 4.25. IR (cm ): 3307 (w), 3240
(w), 3055 (w), 3008 (w), 2964 (w), 2926 (w), 2831 (w), 1626 (m), 1539 (s), 1493 (s), 1460
(
w), 1427 (w), 1402 (w), 1352 (w), 1261 (s), 1259 (s), 1180 (w), 1147 (w), 1061 (w), 1024
m), 1022 (m), 170 (w), 137 (w), 885 (w), 860 (w), 814 (m), 754 (m), 698 (s), 667 (w).
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(
f
R (hexane/ EtOAc 4:1) = 0.1.
N–(3–Iodo–4–methoxybenzyl)benzamide (10e) was synthesized according to TP 1 from
benzamide (242 mg, 2.0 mmol), paraformaldehyde (72 mg, 2.4 mmol), 2–iodoanisole
(0.78 mL, 6.0 mmol, 3.0 equiv.) and Bi(OTf)
3
(66 mg, 0.1 mmol) in nitromethane (4 mL) at
1
00 °C for 16 h. Purification by chromatography (hexane/EtOAc 4:1) yielded the product as
1
colorless solid (578 mg, 79%). m.p.: 106–107 °C. H–NMR (CDCl , 400 MHz): δ = 7.79 –
3
7.76 (m, 3H), 7.50 (t, J = 7.3 Hz, 1H), 7.43 (t, J =7.4 Hz, 2H), 7.31 (d, J = 8.4 Hz, 1H), 6.78
1
3
(
d, J = 8.4 Hz, 1H), 6.42 (bs, 1H), 4.54 (d, J = 5.7 Hz, 2H), 3.87 (s, 3H). C–NMR (CDCl
3
,
1
01 MHz): δ = 167.4, 157.8, 139.1, 134.4, 132.6, 131.8, 129.5, 128.8, 127.1, 111.1, 86.3,
+
56.6, 43.0. MS (ESI) m/z: [M+H] Calcd. for C15
Calcd.: C 49.07 H 3.84 N 3.81; found: C 49.03 H 3.88 N 3.66. IR (cm ): 3280 (w), 3030 (w),
927 (w), 2831 (w), 1626 (s), 1578 (w), 1527 (m), 1485 (m), 1460 (m), 1400 (w), 1363 (w),
1288 (m), 1250 (m), 1225 (m), 1178 (w), 1144 (w), 1074 (w), 1047 (m), 1018 (m), 978 (w),
22 (w), 887 (w), 841 (w), 798 (m), 692 (s), 667 (m). R (hexanes/ EtOAc 4:1) = 0.1.
2
H15INO 368.01, found 368.40. EA (%):
–1
2
9
f
N–(5–Chloro–2–methoxybenzyl)benzamide (10f) was synthesized according to TP 1 from
benzamide (242 mg, 2.0 mmol), paraformaldehyde (72 mg, 2.4 mmol), 4–chloroanisole
(
0.73 mL, 6.0 mmol, 3.0 equiv.) and Bi(OTf) (66 mg, 0.1 mmol) in nitromethane (4 mL) at
3
1
00 °C for 16 h. Purification by chromatography (hexane/EtOAc 4:1) yielded the product as
1
colorless solid (459 mg, 83%). m.p.: 138–139 °C. H–NMR (CDCl
3
, 400 MHz): δ = 7.77 (d, J
=
8.0 Hz, 2H), 7.48 (t, J = 7.0 Hz, 1H), 7.43 (t, J = 7.6 Hz, 2H), 7.31 (bd, J = 2.1 Hz, 1H),
7
.22 (dd, J = 8.7, 2.3 Hz, 1H), 6.81 (d, 1H, J = 8.7 Hz), 6.65 (bs, 1H), 4.60 (d, J = 6.0 Hz,
13
2H), 3.86 (s, 3H). C–NMR (CDCl
3
, 101 MHz): δ = 167.3, 156.3, 134.7, 131.6, 129.7, 128.7,
+
1
28.6, 128.2, 127.1, 125.8, 111.7, 55.9, 39.5. MS (ESI) m/z: [M+H] Calcd. for C H ClNO
15
15
2
2
76.08, found 275.90. EA (%): Calcd.: C 65.34 H 5.12 N 5.08; found: C 65.19 H 5.07 N 4.93.
–
1
IR (cm ): 3269 (m), 3055 (w), 1624 (m), 1576 (m), 1543 (m), 1487 (m), 1443 (w), 1423 (w),
1
352 (w), 1294 (w), 1254 (w), 1244 (m), 1176 (w), 1174 (w), 1126 (m), 1053 (w), 1049 (w),
1
f
026 (m), 989 (w), 930 (w), 877 (w), 806 (m), 692 (s), 667 (w). R (hexane/ EtOAc 4:1) = 0.1.
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