ACCEPTED MANUSCRIPT
1
(
decomposition). H-NMR (600 MHz, DMSO-d ) δ 12.28 (br. s, 2H), 11.83 (br. s, 1H), 11.80 (br. s, 1H),
6
9
.10 (s, 1H), 8.89 (s, 1H), 8.46 (d, J = 8.7 Hz, 1H), 8.36 – 8.26 (m, 3H), 7.93 – 7.87 (m, 2H), 7.59 – 7.47
(
m, 8H), 7.43 (td, J = 8.0, 6.8 Hz, 2H), 7.25 (dd, J = 8.7, 2.0 Hz, 1H), 7.19 (dd, J = 8.7, 2.0 Hz, 1H), 6.98
dd, J = 7.8, 0.9 Hz, 1H), 6.91 (dd, J = 7.8, 0.9 Hz, 1H), 5.42 (s, 2H), 4.90 (s, 2H), 4.41 (q, J = 7.1 Hz, 4H),
(
13
1
.41 (t, J = 7.1 Hz, 6H). C NMR (151 MHz, DMSO-d ) δ 168.5 (C), 163.9 (C), 160.7 (C), 160.6 (C), 153.7
6
(
(
C), 153.5 (C), 143.5 (CH), 140.4 (CH), 136.93 (C), 136.87 (C), 134.1 (2xC), 130.3 (C), 130.2 (C), 127.6
C), 127.6 (C), 127.4 (2xCH), 126.6 (CH), 126. 4 (CH), 126.1 (CH), 126.1 (CH), 125.6 (CH), 125.34 (CH),
1
25.25 (CH), 125.2 (CH), 124.92 (C), 124.89 (C), 123.1 (C), 122.9 (C), 122.3 (CH), 122.2 (CH), 122.0
CH), 121.7 (CH), 120.7 (CH), 120.2 (CH), 116.0 (C), 115.5 (C), 112.1 (2xCH), 105.6 (CH), 105.3 (CH),
6.9 (CH ), 65.4 (CH ), 61.33 (CH ), 61.25 (CH ), 14.22 (CH ), 14.15 (CH ). HRMS (ESI+) calculated for
(
6
2
2
2
2
3
3
+
C H ClN O [M + H] 450.122, found 450.121.
24
21
3
4
Ethyl (E)-3-((2-(3-(tert-butyl)-1-(3-methylbenzyl)-1H-pyrazole-5-carbonyl)hydrazineylidene)methyl)-
-chloro-1H-indole-2-carboxylate (23) This compound was synthesized according to synthetic
procedure 2, starting with 3-(tert-butyl)-1-(3-methylbenzyl)-1H-pyrazole-5-carbohydrazide (26.7 mg,
.0932 mmol). The product was isolated as a mixture of Esyn and Eanti conformers (14:86) as white
6
0
1
solid (36.2 mg, 0.0696 mmol, 78%). M.p.: >237 °C (decomposition). H-NMR (600 MHz, DMSO-d ) δ
6
1
1
1
4
2.26 (br. s, 2H), 11.91 (br. s, 2H), 9.18 (s, 1H), 8.92 (s, 1H), 8.50 (d, J = 8.7 Hz, 1H), 8.07 (d, J = 8.7 Hz,
H), 7.51 (d, J = 1.9 Hz, 2H), 7.26 (dd, J = 8.7, 2.0 Hz, 2H), 7.18 (t, J = 7.6 Hz, 1H), 7.11 (t, J = 7.9 Hz,
H), 7.05 (d, J = 7.4 Hz, 2H), 6.98 (s, 2H), 6.96 (s, 2H), 6.88 (d, J = 7.7 Hz, 2H), 5.70 (s, 2H), 5.55 (s, 2H),
13
.43 (q, J = 7.1 Hz, 4H), 2.25 (s, 3H), 2.12 (s, 3H), 1.40 (t, J = 7.1 Hz, 6H), 1.31 (2s overlap, 18H). C
NMR (151 MHz, DMSO-d ) δ 160.6 (C), 159.6 (C), 155.7 (C), 143.6 (CH), 138.3 (C), 137.4 (C), 136.9 (C),
6
1
1
1
34.1 (C), 130.3 (C), 128.3 (CH), 127.8 (CH), 127.6 (C), 127.4 (CH), 125.7 (CH), 123.9 (CH), 123.1 (C),
22.2 (CH), 116.3 (C), 112.1 (CH), 104.4 (CH), 61.2 (CH ), 53.5 (CH ), 31.8 (C), 30.4 (3xCH ), 21.0 (CH ),
2
2
3
3
+
4.3 (CH ). HRMS (ESI+) calculated for C H ClN O [M + H] 520.211, found 520.211.
3
28 31
5
3
Ethyl (E)-6-chloro-3-((2-(4-(2,4-dichlorophenoxy)butanoyl)hydrazineylidene)methyl)-1H-indole-2-
carboxylate (24) This compound was synthesized according to synthetic procedure 2, starting with 4-
(
2,4-dichlorophenoxy)butanehydrazide (32.3 mg, 0.123 mmol). The product was isolated as a mixture
of Esyn and Eanti conformers (63:37) as white solid (49.2 mg, 0.0990 mmol, 85%). M.p.: >221 °C
1
(
decomposition). H-NMR (600 MHz, DMSO-d ) δ 12.22 (br. s, 2H), 11.50 (br. s, 1H), 11.42 (br. s, 1H),
6
8
.94 (s, 1H), 8.82 (s, 1H), 8.45 (d, J = 8.7 Hz, 1H), 8.26 (d, J = 8.7 Hz, 1H), 7.56 (d, J = 2.6 Hz, 1H), 7.55
d, J = 2.6 Hz, 1H), 7.49 (2d overlap, J = 1.9 Hz, 2H), 7.36 (dd, J = 8.9, 2.6 Hz, 1H), 7.34 (dd, J = 8.9, 2.6
Hz, 1H), 7.23 (dd, J = 8.7, 1.9 Hz, 1H), 7.20 (2d overlap, J = 8.9 Hz, 2H), 7.12 (dd, J = 8.7, 1.9 Hz, 1H),
(
4
=
1
1
.41 (q, J = 7.1 Hz, 4H), 4.18 (t, J = 6.3 Hz, 2H), 4.13 (t, J = 6.3 Hz, 2H), 2.90 (t, J = 7.2 Hz, 2H), 2.44 (t, J
13
7.2 Hz, 2H), 2.15 – 2.03 (m, 4H), 1.40 (t, J = 7.1 Hz, 6H). C NMR (151 MHz, DMSO-d ) δ 173.4 (C),
6
67.8 (C), 160.7 (2xC), 153.03 (C), 153.00 (C), 141.5 (CH), 139.3 (CH), 136.95 (C), 136.88 (C), 130.3 (C),
30.1 (C), 129.23 (CH), 129.20 (CH), 128.11 (CH), 128.09 (CH), 127.4 (C), 127.2 (C), 125.7 (CH), 124.9
(
(
(
CH), 124.4 (C), 124.3 (C), 123.1 (C), 122.9 (C), 122.44 (C), 122.41 (C), 122.0 (2xCH), 116.3 (C), 115.9
C), 115.2 (CH), 115.1 (CH), 112.2 (CH), 112.1 (CH), 68.5 (CH ), 68.4(CH ), 61.24(CH ), 61.17(CH ), 30.3
2
2
2
2
CH ), 28.5 (CH ), 24.3 (CH ), 23.6 (CH ), 14.2 (CH ), 14.1 (CH ). HRMS (ESI+) calculated for
2
2
2
2
3
3
+
C H Cl N O [M + H] 496.059, found 496.059.
22
21
3
3
4
Ethyl (E)-6-chloro-3-((2-((3-nitrophenyl)glycyl)hydrazineylidene)methyl)-1H-indole-2-carboxylate
25) This compound was synthesized according to synthetic procedure 2, starting with 2-((3-
(
1
6