Arch. Pharm. Chem. Life Sci. 2016, 349, 1–13
I. Chaaban et al.
ARC HH PHARM
Archiv der Pharmazie
8
.42–8.45 (m, 1H, naphthalenyl-C
5
-H); 12.22 (s, 1H, OH);
): 14.4, 54.5, 99.3, 101.6, 121.4, 123.5,
26.0, 126.2, 126.8, 127.3, 128.0, 130.3, 130.5, 134.7, 147.2,
49.7, 153.5, 154.2. Anal. calcd. for C20 S: C, 66.10;
3.33 (s, 3H, OCH
3
); 6.17 (s, 1H); 7.41–7.48 (m, 4H); 7.54–7.57
13
C NMR (75 MHz, CDCl
3
(m, 2H); 7.96–8.00 (m, 1H); 8.21–8.25 (m, 1H); 11.78 (s, 1H, OH);
1
3
1
1
C NMR (75 MHz, DMSO-d
121.7, 123.3, 125.7, 126.4, 126.9, 127.9, 128.2, 131.0, 131.9,
140.9, 147.1, 148.3, 153.4, 154.1. Anal. calcd. for C21 S:
6
): 14.7, 21.1, 55.0, 101.2, 103.5,
17 3 2
H N O
H, 4.71; N, 11.56. Found: C, 66.38; H, 4.68; N, 11.65. HRMS (ESI):
m/z calcd. for
19 3 2
H N O
þ
C
H N
20 18 3
O
2
S: 364.1120 [MþH] ; found:
C, 66.82; H, 5.07; N, 11.13. Found: C, 66.78; H, 4.82; N, 11.24.
HRMS (ESI): m/z calcd. for C21
found: 378.1276.
þ
3
64.1120.
H
N
20 3
O
2
S: 378.1276 [MþH] ;
2
-[5-(Ethylsulfanyl)-4-phenyl-4H-1,2,4-triazol-3-yl]-4-
methoxynaphthalen-1-ol (13b)
Yield 75%; mp: 163–164°C; IR (ATR, y cm ): 3155 (OH), 1632
2-[5-(Ethylsulfanyl)-4-(4-tolyl)-4H-1,2,4-triazol-3-yl]-4-
ꢁ
1
methoxynaphthalen-1-ol (13f)
1
ꢁ1
(
(
C–N), 1256, 1161 (C–S–C), 1236, 1026 (C–O–C); H NMR
300 MHz, CDCl CH ); 3.29 (q, 2H,
): 1.47 (t, 3H, J ¼ 7.2 Hz, SCH
CH ); 3.25 (s, 3H, OCH ); 5.98 (s, 1H); 7.40–7.43
m, 2H); 7.51–7.54 (m, 2H); 7.60–7.64 (m, 3H); 8.02–8.05 (m,
Yield 75%; mp: 149–150°C; IR (ATR, y cm ): 3134 (OH), 1637
(C–N), 1252, 1167 (C–S–C), 1229, 1024 (C–O–C); 1H NMR
3
2
3
J ¼ 7.2 Hz, SCH
2
3
3
(300 MHz, DMSO-d
3H, C -CH
); 3.18 (q, 2H, J ¼ 7.3 Hz, SCH
OCH ); 6.18 (s, 1H); 7.40–7.50 (m, 4H); 7.54–7.58 (m, 2H); 7.98–
8.00 (m, 1H); 8.23–8.26 (m, 1H); 11.81 (s, 1H, OH); C NMR
(75 MHz, DMSO-d ): 15.2, 21.1, 26.9, 55.0, 101.2, 103.5, 121.6,
123.3, 125.7, 126.4, 126.9, 127.9, 128.3, 131.0, 132.0, 140.8,
147.1, 148.3, 152.4, 154.0. Anal. calcd. for C22 S: C,
6
): 1.35 (t, 3H, J ¼ 7.3 Hz, SCH
2 3
CH ); 2.40 (s,
CH ); 3.34 (s, 3H,
(
6
H
4
3
2
3
13
1
H); 8.41–8.45 (m, 1H); 12.20 (s, 1H, OH); C NMR (75 MHz,
): 14.6, 26.8, 54.5, 99.4, 101.6, 121.4, 123.5, 126.0, 126.2,
26.8, 127.3, 128.1, 130.3, 130.4, 134.8, 147.2, 149.8, 152.6,
54.1. Anal. calcd. for C21 S: C, 66.82; H, 5.07; N, 11.13.
3
13
CDCl
3
1
1
6
19 3 2
H N O
Found: C, 66.52; H, 5.05; N, 11.12. HRMS (ESI): m/z calcd. for
21 3 2
H N O
þ
C
H N
21 20 3
O
2
S: 378.1276 [MþH] ; found: 378.1276.
67.50; H, 5.41; N, 10.73. Found: C, 67.42; H, 5.38; N, 10.72.
2
3
-[4-(4-Chlorophenyl)-5-(methylsulfanyl)-4H-1,2,4-triazol-
General method for the synthesis of compounds 14a–f
A cold solution of ceric ammonium nitrate (1.64 g, 2.99 mmol)
in water (3 mL) was added gradually to a stirred ice-cool
suspension of sulfanyltriazolyl-methoxynaphthalenols 13a–f
(1.0 mmol) in acetonitrile (20 mL). The reaction mixture was
stirred in an ice bath for 5 min, then treated with crushed ice.
The yellow precipitates were filtered, washed with water, air
dried, and recrystallized from cyclohexane.
-yl]-4-methoxynaphthalen-1-ol (13c)
ꢁ
1
Yield 87%; mp: 185–186°C; IR (ATR, y cm ): 3109 (OH), 1639
1
(
(
C–N), 1252, 1169 (C–S–C), 1227, 1024 (C–O–C); H NMR
300 MHz, CDCl ): 2.66 (s, 3H, SCH ); 3.46 (s, 3H, OCH ); 6.25 (s,
H); 7.55–7.58 (m, 2H); 7.61–7.63 (m, 2H); 7.67–7.70 (m, 2H);
.99–8.02 (m, 1H); 8.20–8.23 (m, 1H); 11.35 (s, 1H, OH);
3
3
3
1
7
1
3
C NMR (75 MHz, CDCl
26.0, 126.3, 126.9, 127.5, 129.3, 130.5, 133.1, 140.4, 147.3,
49.8, 153.2, 154.2. Anal. calcd. for C20 16ClN S: C, 60.37; H,
3
): 14.4, 54.5, 99.1, 101.2, 121.5, 123.5,
1
1
4
H
3
O
2
2-[5-(Methylsulfanyl)-4-phenyl-4H-1,2,4-triazol-3-yl]-
naphthalene-1,4-dione (14a)
Yield 76%; mp: 177–178°C with decomposition; IR (ATR,
.05; N, 10.56. Found: C, 60.10; H, 4.02; N, 10.83. HRMS (ESI):
þ
m/z calcd. for C20
H17ClN
3
O
2
S: 398.0730 [MþH] ; found:
ꢁ
1
1
3
98.0730.
y cm ): 1666 (C–O), 1622 (C–N), 1254, 1128 (C–S–C); H NMR
300 MHz, CDCl ): 2.76 (s, 3H, SCH ); 7.27–7.29 (m, 2H); 7.40–
7.42 (m, 4H); 7.66–7.76 (m, 2H); 7.85 (d, 1H, J ¼ 7.8 Hz); 8.07
(
3
3
2
-[4-(4-Chlorophenyl)-5-(ethylsulfanyl)-4H-1,2,4-triazol-3-
1
3
yl]-4-methoxynaphthalen-1-ol (13d)
Yield 84%; mp: 154–155°C; IR (ATR, y cm ): 3097 (OH), 1636
(d, 1H, J ¼ 6.9 Hz); C NMR (75 MHz, CDCl
126.7, 129.7, 129.8, 131.4, 131.7, 133.6, 134.1, 134.2, 136.7,
139.6, 150.2, 155.2, 181.3, 183.9. Anal. calcd. for C19 S:
3
): 14.6, 126.3, 126.4,
ꢁ
1
1
(
(
C–N), 1254, 1161 (C–S–C), 1227, 1022 (C–O–C); H NMR
300 MHz, CDCl CH ); 3.32 (q, 2H,
): 1.47 (t, 3H, J ¼ 7.5 Hz, SCH
CH ); 3.34 (s, 3H, OCH ); 5.92 (s, 1H); 7.35 (d,
H, J ¼ 8.4 Hz); 7.51–7.54 (m, 2H); 7.60 (d, 2H, J ¼ 8.4 Hz); 8.04–
13 3 2
H N O
3
2
3
C, 65.69; H, 3.77; N, 12.10. Found: 65.52; H, 3.79; N, 12.00.
þ
J ¼ 7.5 Hz, SCH
2
3
3
HRMS (ESI): m/z calcd. for C19
found: 348.0807.
H
N
14 3
O
2
S: 348.0807 [MþH] ;
2
8
(
1
3
.06 (m, 1H); 8.41–8.44 (m, 1H); 11.99 (s, 1H, OH); C NMR
): 14.6, 26.9, 54.6, 99.2, 101.2, 121.4, 123.5,
26.0, 126.3, 126.9, 127.5, 129.4, 130.5, 133.2, 136.7, 147.3,
49.8, 152.4, 154.0. Anal. calcd. for C21 18ClN S: C, 61.23;
75 MHz, CDCl
1
1
3
2-[5-(Ethylsulfanyl)-4-phenyl-4H-1,2,4-triazol-3-yl]-
naphthalene-1,4-dione (14b)
Yield 86%; mp: 186–187°C with decomposition; IR (ATR,
H
3
O
2
ꢁ
1
1
H, 4.40; N, 10.20. Found: C, 61.36; H, 4.27; N, 9.97. HRMS (ESI):
m/z calcd. for C21
y cm ): 1664 (C –– O), 1620 (C –– N), 1254, 1124 (C–S–C); H NMR
(300 MHz, CDCl CH ); 3.33 (q, 2H,
): 1.46 (t, 3H, J ¼ 7.2 Hz, SCH
J ¼ 7.2 Hz, SCH CH ); 7.26–7.29 (m, 2H); 7.41–7.42 (m, 4H); 7.65–
.76 (m, 2H); 7.84 (d, 1H, J ¼ 6.9 Hz); 8.07 (d, 1H, J ¼ 6.9 Hz);
þ
H19ClN
3
O
2
S: 412.0887 [MþH] ; found:
3
2
3
4
12.0887.
2
3
7
1
3
4
-Methoxy-2-[5-(methylsulfanyl)-4-(4-tolyl)-4H-1,2,4-
C NMR (75 MHz, CDCl
129.6, 131.4, 131.7, 133.7, 134.1, 134.1, 136.8, 139.5, 150.0,
154.5, 181.2, 183.8. Anal. calcd. for C20 S: C, 66.46; H,
3
): 14.6, 26.9, 126.3, 126.4, 126.7, 129.6,
triazol-3-yl]naphthalen-1-ol (13e)
Yield 58%; mp: 195–196°C; IR (ATR, y cm ): 3138 (OH), 1634
ꢁ
1
15 3 2
H N O
1
(
(
C–N), 1250, 1163 (C–S–C), 1225, 1024 (C–O–C); H NMR
300 MHz, DMSO-d ): 2.39 (s, 3H, C -CH ); 2.65 (s, 3H, SCH );
4.18; N, 11.63. Found: C, 66.71; H, 4.27; N, 11.38. HRMS (ESI): m/z
þ
6
6
H
4
3
3
calcd. for C20
H
16
N
3
O
2
S: 362.0963 [MþH] ; found: 362.0963.
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10