ACCEPTED MANUSCRIPT
-1
(
cm ): 3053, 2961, 2840, 2214, 1582, 1510, 1459, 1427, 1260, 1173, 1031, 839, 743,
+
+
6
73. .HRMS (ESI ): calcd for C H N O [M+H] :238.0975, found 238.0978.
14 11 3
[32]
(
Z)-4-methyl-N-(pyridin-2-yl)benzimidoyl cyanide (3f) : Yellow solid (42.4 mg, 96%);
o
1
mp: (88-90 C). H NMR (400 MHz, CDCl ) δ 8.58 (dd, J = 4.7, 0.9 Hz, 1H), 8.10 (d, J = 8.3
3
Hz, 2H ), 7.82 (td, J = 7.7, 1.8 Hz, 1H), 7.33 (d, J = 8.1 Hz, 2H ), 7.27-7.22 (m, 2H), 2.44 (s,
1
3
3
1
7
H). C NMR 100 MHz, CDCl δ 159.4, 148.9, 144.4, 141,0, 138.2, 131,1, 129.8, 128.7,
3
-1
22.7, 118.2, 111.6, 21,8. IR (cm ): 2919, 2214, 1576, 1558, 1458, 1428, 1297, 1212, 1001,
+
+
98, 722, 670. .HRMS (ESI ): calcd for C H N [M+H] : 222.1026, found 222.1027.
1
4
11
3
(
Z)-4-(methylsulfonyl)-N-(pyridin-2-yl)benzimidoyl cyanide (3g): Yellow solid (54.1 mg,
o
1
9
8
1
4
5%); mp: (155-157 C). H NMR (400 MHz, CDCl ) δ 8.65-8.63 (m, 1H), 8.45-8.43 (m, 2H),
3
1
3
.14-8.11 (m, 2H), 7.90 (td, J = 7.7, 1.8 Hz, 1H ), 7.39-7.35 (m, 2H), 3.13 (s, 3H). C NMR
00 MHz, CDCl δ 157.9, 148.9, 144.2, 138.5, 138.2, 129.5, 128.1, 128.0, 124.2, 119.9, 111.4,
3
-1
4.4. IR (cm ): 2920, 2203, 1573, 1546, 1427, 1395, 1294, 1143, 1005, 844, 781, 728. HRMS
+
+
(
ESI ): calcd for C H N O S [M+H] : 286.0645, found 286.0649.
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(
Z)-4-fluoro-N-(pyridin-2-yl)benzimidoyl cyanide (3h): Yellow solid (42.7 mg, 95%); mp
o
1
(
122-124 C). H NMR (400 MHz, CDCl ) δ 8.60-8.59 (m, 1H), 8.26-8.22 (m, 2H), 7.83 (td, J
3
1
3
=
7.7, 1.8 Hz, 1H), 7.30-7.19 (m, 4H). C NMR 100 MHz, CDCl δ 167.1, 164.6, 158.8,
3
1
48.9, 139.6, 138.3, 131.1 (d, J = 9.3 Hz), 130.0 (d, J = 3.0 Hz), 123.1, 118.6, 116.5, 116.3,
19
-1
111.5. F NMR (376 MHz, CDCl ) δ -104.3. IR (cm ): 2215, 1578, 1503, 1428, 1234, 1157,
3
+
+
8
42, 737, 663. HRMS (ESI ): calcd for C H N F [M+H] : 226.0775, found 226.0776.
13 8 3
[32]
(
Z)-4-chloro-N-(pyridin-2-yl)benzimidoyl cyanide (3i) : Yellow solid (40.5 mg, 84%);
o
1
mp (108-109 C). H NMR (400 MHz, CDCl ) δ 8.60 (d, J = 4.5 Hz, 1H), 8.17 (d, J = 8.6 Hz,
3
1
3
2
H), 7.85 (td, J = 7.7, 1.7 Hz, 1H), 7.52 (d, J = 8.7 Hz, 2H), 7.31-7.26 (m, 2H). C NMR 100
MHz, CDCl δ 158.7, 148.9, 139.8, 139.7, 138.4, 132.2, 129.9, 129.4, 123.3, 118.9, 111.4. IR
3
-
1
+
(
cm ): 2210, 1578, 1429, 1401, 1092, 1008, 836, 795, 736. HRMS (ESI ): calcd for
+
C H N Cl [M+H] 242.0480, found 242.0482.
13
8
3
(
Z)-4-bromo-N-(pyridin-2-yl)benzimidoyl cyanide (3j): Yellow solid (51.9 mg, 91%); mp
o
1
(
96-98 C). H NMR (400 MHz, CDCl ) δ 8.60 (dd, J = 4.8, 0.8 Hz, 1H), 8.10-8.07 (m, 2H),
3
1
3
7
.84 (td, J = 7.7, 1.8 Hz, 1H), 7.69-7.65 (m, 2H), 7.31-7.27 (m, 2H). C NMR 100 MHz,
CDCl δ 158.7, 148.9, 139.8, 138.3, 132.6, 132.3, 130.0, 128.5, 123.3, 118.9, 111.4. IR
3
-
1
+
(
cm ): 3052, 2209, 1576, 1549, 1474, 1426, 1069, 998, 831, 794, 742. HRMS (ESI ): calcd
+
for C H N Br [M+H] 285.9974, found 285.9979.
13
8
3
(
Z)-3-methoxy-N-(pyridin-2-yl)benzimidoyl cyanide (3k): Yellow liquid (43.1 mg, 91%);
1
H NMR (400 MHz, CDCl ) δ 8.60 (m, 1H), 7.85-7.78 (m, 2H), 7.75-7.74 (m, 1H), 7.44 (t, J
3
1
3
=
8.0 Hz, 1H), 7.29-7.25 (m, 2H), 7.17-7.14 (m, 1H), 3.88 (s, 3H). C NMR 100 MHz,
CDCl δ 160.0, 159.1, 148.9, 141.1, 138.3, 134.9, 130.0, 122.9, 122.0, 120.3, 118.3, 112.0,
3
-
1
1
1
2
11.5, 55.6. IR (cm ): 3057, 3004, 2940, 2838, 2216, 1583, 1485, 1460, 1429, 1288, 1227,
+
+
023, 876, 797, 743, 704. HRMS (ESI ): calcd for C H N O [M+H] 238.0975, found
1
4
11
3
38.0979.
(
Z)-3-fluoro-N-(5-methylpyridin-2-yl)benzimidoyl cyanide (3l): Yellow solid (45.9 mg,
o
1
9
7
6%); mp (67-69 C). H NMR (400 MHz, CDCl ) δ 8.43-8.42 (m, 1H), 8.01-7.98 (m, 1H),
3
.95-7.92 (m, 1H), 7.66-7.63 (m, 1H), 7.53-7.48 (m, 1H), 7.31-7.26 (m, 1H), 7.23 (d, J = 8.0
1
3
Hz, 1H), 2.40 (s, 3H). C NMR 100 MHz, CDCl δ 162.9,(d, J = 248.2 Hz), 156.1, 149.0,
3
1
38.8, 138.4 (d, J = 3.5 Hz), 136.1 (d, J = 7.7 Hz), 133.7, 130.6 (d, J = 8.0 Hz), 124.7 (d, J =
9