Month 2015
Evaluation of Novel Andrographolide-1,2,3-Triazole Derivatives
3
-(2-(3-(4-((1-(3-bromo-4-methylphenyl)-1H-1,2,3-triazol-4-
(
2H, m), 2.50–2.55 (m, 2H), 3.51–3.55 (d, 1H,
yl)methoxy)phenyl)-6a,10b-dimethyl-8-methylenedecahydro-1H-
naphtho[2,1-d][1,3]dioxin-7-yl)ethylidene)-4-hydroxydihydro
furan-2(3H)-one (3d). Yellow solid, yield 91%, mp 176–
77°C; IR (KBr): 3279 (C–H), 3058 (Ar–H), 2922 (C–H),
112 (C≡C), 1584 (C=N), 1466, 757 (C–N) cm ; H
NMR (CDCl , 300 MHz): δ 0.86 (s, 3H, H-20), 1.28–
J=11.11Hz), 3.58–3.64 (dd, 1H, J=4.52, 5.3Hz), 4.18–
4
1
(
Ar), 7.38–7.40 (d, 2H, J=8.5Hz, Ar), 7.44–7.5 (m, 1H,
Ar), 7.54–7.57 (d, 1H, J=7.7Hz, Ar), 7.70 (s, 1H,
triazole-H), 7.97–7.99 (d, 1H, J=7.9Hz, Ar); C NMR
.22 (d, 2H, J=11Hz), 4.37–4.43 (m, 1H), 4.58 (s, 1H, H-
7), 4.86 (s, 1H, H-17), 4.97–4.99 (d, 1H, J=5.1Hz), 5.28
1
2
s, 2H, CH -O), 5.68 (s, 1H, Ar-CH), 6.89–6.97 (m, 2H,
2
À1
1
3
1
1
(
1
(
5
7
.50 (m, 4H), 1.53 (s, 3H, H-18), 1.71–1.80 (bs, 2H),
.90–2.09 (bs, 2H), 2.07–2.25 (m, 3H), 2.56–2.61
13
(75MHz, CDCl ): δ 14.9 (CH , Ar), 15.7 (CH , C-20),
3 3 3
m, 2H), 4.21–4.24 (d, 1H, J= 10.5Hz), 4.33–4.37 (d,
H, J =12.24 Hz), 4.54–4.60 (m, 1H), 4.82 (s, 1H), 5.01
s, 1H), 5.08–5.13 (m, 1H), 5.39 (s, 2H), 5.93 (s, 1H),
.98–6.00 (d, 1H, J = 6.03Hz), 6.79–6.83 (m, 1H), 7.19–
.21 (d, 2H, J = 8.7 Hz, Ar), 7.50–7.53 (d, 2H, J = 8.7Hz,
2
2.2 (CH , C-6), 23.2 (CH , C-18), 25.2 (CH , C-11), 26.4
2 2 2
(CH , C-2), 36.5 (CH , C-1), 37.3 (CH , C-7), 37.9 (C, C-
2 2 2
1
0), 39.3 (C, C-4), 55.3 (CH, C-9), 56.4 (CH, C-5), 62.4
(CH , C-19), 66.6 (CH, C-14), 70.0 (CH , C-15), 74.7
2
2
(CH -O), 81.1 (CH, C-3), 95.3 (Ar-CO), 109.6 (CH , C-
2
2
Ar), 7.94–8.05 (dd, 4H, J= 8.8, 8.8 Hz, Ar), 8.41 (s, 1H),
.08 (s, 1H); ESI-MS: m/z 705 (M 1) observed for
1
1
7), 115.1 (CH, Ar), 125.0 (CH, Ar), 126.2 (CH, Ar),
27.7 (CH, Ar), 128.1 (CH, Ar), 128.5 (CH, Ar), 129.3
+
9
C H BrN O .
37
42
3 6
(CH, Ar), 130.1 (CH, Ar), 131.0 (C, C-13), 132.8 (C, Ar),
3-(2-(3-(4-((1-(2-chlorophenyl)-1H-1,2,3-triazol-4-yl)methoxy)
1
1
1
38.5 (C, Ar), 145.2, 146.9 (C, C-8), 149.1 (CH, C-12),
phenyl)-6a,10b-dimethyl-8-methylenedecahydro-1H-naphtho
[2,1-d][1,3]dioxin-7-yl)ethylidene)-4-hydroxydihydrofuran-2(3H)-
one (3e). Yellow solid, yield 92%, mp 92°C; IR (KBr):
279 (C–H), 3058 (Ar–H), 2922 (C–H), 2112 (C≡C),
1584 (C=N), 1466, 757 (C–N) cm ; H NMR (CDCl
300 MHz): δ 0.86 (s, 3H, H-20), 1.23–1.33 (m, 4H), 1.48
s, 3H, H-18), 1.75–1.92 (m, 3H), 1.97–2.09 (m, 1H), 2.18
+
58.8 (Ar-NO2), 176.5 (C, C-16); ESI-MS: m/z 671 (M
) observed for C H N O .
3
7 42 4 8
3
3
-(2-(3-(4-((1-(4-bromophenyl)-1H-1,2,3-triazol-4-yl)methoxy)
À1
1
phenyl)-6a,10b-dimethyl-8-methylenedecahydro-1H-naphtho
,
3
[
(
2,1-d][1,3]dioxin-7-yl)ethylidene)-4-hydroxydihydrofuran-2
3H)-one (3b). Yellow solid, yield 93%, mp 205–206°C;
(
(
IR (KBr): 3279 (C–H), 3058 (Ar–H), 2922 (C–H), 2112
s, 1H), 2.35–2.47 (m, 2H), 2.51–2.61 (m, 1H), 2.63
À1
1
(
(
C≡C), 1584 (C=N), 1466, 757 (C–N) cm ; H NMR
(s, 1H), 3.55–3.59 (d, 1H, J=12.5 Hz), 3.63–3.69 (dd, 1H,
J= 5.52, 5.52Hz), 4.23–4.27 (m, 2H), 4.43–4.48 (m,
1H), 4.62 (s, 1H, H-17), 4.91 (s, 1H, H-17), 5.04–3.05
(d, 1H, J=6.8Hz), 5.32 (s, 2H), 5.73 (s, 1H), 6.94–6.98
(m, 1H), 7.01–7.03 (d, 2H, J =9.03Hz, Ar), 7.43–7.49 (m,
4H, Ar), 7.57–7.64 (m, 2H); ESI-MS: m/z 646 (M 1)
observed for C36H40ClN O .
3-(2-(3-(4-((1-(4-chlorophenyl)-1H-1,2,3-triazol-4-yl)methoxy)
phenyl)-6a,10b-dimethyl-8-methylenedecahydro-1H-naphtho[2,1-
d][1,3]dioxin-7-yl)ethylidene)-4-hydroxydihydrofuran-2(3H)-
one (3f). Yellow solid, yield 85%, mp 200–202°C; IR
CDCl , 300MHz): δ 0.99 (s, 3H, H-20), 1.28–1.50 (m,
3
4
(
4
4
1
6
(
7
(
H), 1.53 (s, 3H, H-18), 1.71–1.80 (bs, 2H), 1.90–2.09
bs, 2H), 2.07–2.25 (m, 3H), 2.56–2.61 (m, 2H), 4.21–
.24 (d, 1H, J = 10.5Hz), 4.33–4.37 (d, 1H, J= 12.2Hz),
.54–4.60 (m, 1H), 4.82 (s, 1H, H-17), 5.01 (s, 1H, H-
7), 5.08–5.13 (m, 1H), 5.39 (s, 2H), 5.93 (s, 1H), 5.98–
.00 (d, 1H, J= 6.03 Hz), 6.79–6.83 (m, 1H), 7.19–7.21
+
3 6
d, 2H, J= 8.7Hz, Ar), 7.50–7.53 (d, 2H, J= 8.7 Hz, Ar),
.94–8.05 (dd, 4H, J = 8.8, 8.8Hz, Ar), 8.41 (s, 1H), 9.08
+
s, 1H triazole-H); ESI-MS: m/z 691 (M 1) observed for
(
(
(
4
(
KBr): 3279 (C–H), 3058 (Ar–H), 2922 (C–H), 2112
C≡C), 1584 (C=N), 1466, 757 (C–N) cm ; H NMR
CDCl , 300MHz): δ 0.87 (s, 3H, H-20), 1.25–1.30 (m,
C H N O .
À1
1
36 40 3 6
3
-(2-(3-(4-((1-(4-acetylphenyl)-1H-1,2,3-triazol-4-yl)methoxy)
3
phenyl)-6a,10b-dimethyl-8-methylenedecahydro-1H-naphtho
H), 1.48 (s, 3H, H-18), 1.56–1.66 (bs, 2H), 1.70–1.92
m, 3H), 1.99–2.05 (m, 2H), 2.38–2.49 (m, 2H), 2.53–
.61 (m, 2H), 3.56–3.59 (d, 1H, J= 11.8 Hz), 3.64–3.69
(dd, 1H, J= 5.02, 5.02Hz), 4.23–4.28 (m, 2H), 4.45–4.49
m, 1H), 4.62 (s, 1H, H-17), 4.92 (s, 1H, H-17), 5.03–
.07 (m, 1H), 5.30 (s, 2H), 5.73 (s, 1H), 6.95–7.01 (m,
H), 7.31–7.33 (d, 1H, J= 8.53 Hz, Ar), 7.43–7.45 (d,
H, J =9.03 Hz, Ar), 7.49–7.51 (d, 1H, J =9.03 Hz, Ar),
[
(
2,1-d][1,3]dioxin-7-yl)ethylidene)-4-hydroxydihydrofuran-2
3H)-one (3c). Yellow solid, yield 90%, mp 184–186°C;
2
IR (KBr): 3279 (C–H), 3058 (Ar–H), 2922 (C–H), 2112
À1
1
(
(
C≡C), 1584 (C=N), 1466, 757 (C–N) cm ; H NMR
(
CDCl , 300 MHz): δ 0.87 (s, 3H, H-20), 1.25 (s, 5H),
3
5
2
1
7
1
3
(
1
4
.29–1.36 (m, 2H), 1.48 (s, 3H, H-18), 1.78–1.94 (m,
H, AcO), 1.99–2.09 (m, 1H), 2.18 (s, 2H), 2.36–2.48
m, 2H), 2.53–2.61 (m, 1H), 2.64 (s, 1H), 3.56–3.6 (d,
H, J =11.3 Hz), 3.64–3.68 (dd, 1H, J= 6.02, 5.52Hz),
.23–4.28 (m, 2H), 4.44–4.48 (m, 1H), 4.63 (s, 1H,
.67–6.69 (d, 2H, J= 9.03 Hz, Ar), 8.01 (s, 1H, triazole-
H); ESI-MS: m/z 646 (M 1) observed for C H ClN O .
+
36
40
3 6
3
-(2-(6a,10b-dimethyl-8-methylene-3-(4-((1-(4-nitrobenzyl)-
H-17), 4.92 (s, 1H, H-17), 5.00–5.06 (d, 1H, J= 7.28Hz),
.32 (s, 2H), 5.73 (s, 1H), 6.95–6.98 (m, 1H), 7.00–7.03
d, 2H, J= 9.03 Hz, Ar), 7.43–7.49 (m, 4H, Ar),
.57–7.63 (m, 2H, Ar), 8.04 (s, 1H, triazole-H); ESI-MS:
1
1
H-1,2,3-triazol-4-yl)methoxy)phenyl)decahydro-1H-naphtho[2,
-d][1,3]dioxin-7-yl)ethylidene)-4-hydroxydihydrofuran-2(3H)-
one (3g). Yellow solid, yield 86%, mp 110–112°C; IR
(KBr): 3279 (C–H), 3058 (Ar–H), 2922 (C–H), 2112
(C≡C), 1584 (C=N), 1466, 757 (C–N) cm ; H NMR
5
(
7
+
À1
1
m/z 654 (M 1) observed for C H N O .
3
8 43 3 7
Journal of Heterocyclic Chemistry
DOI 10.1002/jhet