May-Jun 2005
A Convenient Synthesis of 2-Mercapto and 2-Chlorobenzothiazoles
729
6-Bromo-2-mercaptobenzothiazole (3a).
(DMSO-d ): δ 8.75 (s, 1H), 8.39 (d, J = 8.9 Hz, 1H), 8.33 (d, J =
13
6
9.0 Hz, 1H); C NMR (DMSO-d ): δ 157.83, 150.69, 147.42,
1
This compound has the following properties: H NMR
6
143.34, 124.62, 120.95, 118.16. EI-GCMS m/z (M ) 214.
Anal. Calcd. for C H ClN O S: C, 39.17; H, 1.41; N, 13.05.
+
(DMSO-d ): δ 13.82 (s, 1H), 7.95 (d, J = 1.9 Hz, 1H), 7.53 (d, J
13
6
= 8.5 Hz, 1H), 7.19 (d, J = 8.6 Hz, 1H); C NMR (DMSO-d ): δ
7
Found: C, 39.12; H, 1.65, N, 12.78.
3
2 2
6
190.34, 140.99, 131.96, 130.75, 124.73, 116.91, 114.50. ESI-
+
LCMS m/z (MH ) 248.
Anal. Calcd. for C H BrNS : C, 34.16; H, 1.64; N, 5.69.
5-(Trifluoromethyl)[1,3]thiazolo[5,4-b]pyridine-2-thiol (7a).
7
Found: C, 34.08; H, 1.61; N, 5.60.
4
2
1
This compound has the following properties: H NMR
(DMSO-d ): δ 14.00 (b, 1H), 8.18 (s, 1H), 7.72 (d, J = 8.0 Hz,
13
6
1H), 7.40 (d, J = 8.0 Hz, 1H); C NMR (DMSO-d ): δ 191.76,
2-Chloro-6-bromo-benzothiazole (3b).
6
144.51, 130.67, 125.02, 124.90, 124.77, 120.10, 113.42. EI-
1
This compound has the following properties: H NMR
(DMSO-d ): δ 8.38 (d, J = 1.7 Hz, 1H), 7.88 (d, J = 8.5 Hz, 1H),
13
+
GCMS m/z (M ) 235.
Anal . Calcd. for C H F NS : C, 40.84; H, 1.71; N, 5.95.
6
7.65 (d, J = 8.6 Hz, 1H); C NMR (DMSO-d ): δ 154.28,
8
Found: C, 41.06; H, 1.58, N, 5.82.
4
3
2
6
149.82, 138.04, 130.73, 125.57, 124.56, 119.32. EI-GCMS m/z
+
(M ) 249.
2-Chloro-5-(trifluoromethyl)[1,3]thiazolo[5,4-b]pyridine (7b).
A n a l. Calcd. for C H BrClNS: C, 33.83; H, 1.22; N, 5.64.
7
Found: C, 33.69; H, 1.10; N, 5.44.
3
1
This compound has the following properties: H NMR
(DMSO-d ): δ 8.66 (d, J = 8.5 Hz, 1H), 8.13 (d, J = 8.4 Hz, 1H);
13
6
C NMR (DMSO-d ): _ 161.76, 160.96, 150.36, 147.77, 135.98,
7-Chloro-2-mercaptobenzothiazole (4a).
6
125.43, 123.84; ESI-LCMS m/z (MH ) 239.
Anal. Calcd. for C H ClF N S: C, 35.23; H, 0.84; N, 11.74.
+
1
This compound has the following properties: H NMR
13
7
Found: C, 35.65; H, 0.75, N, 11.51.
2
3 2
(DMSO-d ): δ 7.35 (m, 2H), 7.20 (dd, J = 7.8, 1.1 Hz, 1H);
C
NMR (DMSO-d ): δ 188.66, 141.95, 128.61, 127.95, 124.51,
6
6
123.42, 111.07. ESI-LCMS m/z (MH ) 202.
Anal. Calcd. for C H ClNS : C, 41.69; H, 2.00; N, 6.94.
+
6-Isopropyl-2-mercaptobenzothiazole (8a).
7
Found: C, 41.56; H, 1.94, N, 6.81.
4
2
1
This compound has the following properties: H NMR
(DMSO-d ): δ 13.80 (s, 1H), 7.65 (s, 1H), 7.26 (d, J = 8.4 Hz,
6
1H), 7.20 (d, J = 8.0Hz, 1H), 2.92 (m, 1H), 1.20 (d, J = 6.7 Hz,
2,7-Dichloro-benzothiazole (4b).
13
6H); C NMR (DMSO-d ): δ 189.44, 145.50, 139.78, 129.85,
1
This compound has the following properties: H NMR
6
126.24, 119.62, 113.00, 34.45, 25.12; ESI-LCMS m/z (MH ) 210.
+
13
(DMSO-d ): δ 7.97 (dd, J = 7.8, 1.3 Hz, 1H), 7.62 (m, 2H);
C
NMR (DMSO-d ): δ 152.01, 150.13, 134.54, 127.86, 125.19,
6
Anal. Calcd. for C H NS : C, 57.38; H, 5.30; N, 6.69.
10 11 2
Found: C, 57.32; H, 5.22; N, 6.68.
6
124.41, 120.82. ESI-LCMS m/z (MH ) 204.
Anal. Calcd. for C H Cl NS: C, 41.20; H, 1.48; N, 6.86.
+
7
Found: C, 40.98; H, 1.24, N, 6.91.
3
2
2-Chloro-6-isopropyl-benzothiazole (8b).
1
This compound has the following properties: H NMR
6-Trifluoromethyl-2-mercaptobenzothiazole (5a).
(DMSO-d ): δ 7.96 (s, 1H), 7.85 (d, J = 8.4 Hz, 1H), 7.43 (d, J =
13
6
8.4Hz, 1H), 3.04 (m, 1H), 1.25 (d, J = 6.8 Hz, 6H); C NMR
1
This compound has the following properties: H NMR
(DMSO-d ): δ 152.04, 149.13, 147.17, 136.35, 126.61, 122.69,
+
(DMSO-d ): δ 14.00 (b, 1H), 8.18 (s, 1H), 7.72(d, J = 8.0 Hz,
13
6
119.96, 34.81, 25.25; ESI-LCMS m/z (MH ) 212.
6
1H), 7.40 (d, J = 8.0 Hz, 1H); C NMR (DMSO-d ): δ 191.76,
6
144.51, 130.67, 125.02, 124.90, 124.77, 120.10, 113.42. EI-
Anal. Calcd. for C
H ClNS: C, 56.73; H, 4.76; N, 6.62.
10 10
Found: C, 56.51; H, 4.55; N, 6.41.
+
GCMS m/z (M ) 235.
Anal. Calcd. for C H F NS : C, 40.84; H, 1.71; N, 5.95.
8
Found: C, 41.06; H, 1.58, N, 5.82.
4
3
2
6-Hydroxyl-2-mercaptobenzothiazole (9a).
1
This compound has the following properties: H NMR
2-Chloro-6-trifluoromethyl-benzothiazole (5b).
(DMSO-d ): δ 13.48 (s, 1H), 9.68 (s, 1H), 7.10 (d, J = 8.4 Hz,
13
6
1H), 7.03 (d, J = 2.5 Hz, 1H), 6.80 (dd, J = 8.7, 2.5 Hz, 1H);
1
This compound has the following properties: H NMR
C
NMR (DMSO-d ): δ 187.93, 155.13, 134.67, 131.36, 115.71,
(CDCl ): δ 8.09 (s, 1H), 8.05 (d, J = 8.5 Hz, 1H), 7.73 (d, J = 7.9
13
6
113.60, 108.18; ESI-LCMS m/z (MH ) 184.
Anal . Calcd. for C H NOS : C, 45.88; H, 2.75; N, 7.64.
3
Hz, 1H); C NMR (CDCl ): δ 156.30, 152.91, 136.24, 128.05,
+
3
124.00, 123.93, 123.46, 119.02; EI-GCMS m/z (M ) 237.
Anal. Calcd. for C H ClF NS: C, 40.43; H, 1.27; N, 5.89.
+
7
Found: C, 45.49; H, 2.52; N, 7.32.
5
2
8
Found: C, 40.71; H, 1.27, N, 5.83.
3
3
2,7-Di-chloro-6-hydroxy-benzothiazole (9b).
5-Nitro-2-mercaptobenzothiazole (6a).
1
This compound has the following properties: H NMR
1
This compound has the following properties: H NMR
(DMSO-d ): δ 10.87 (s, 1H), 7.76 (d, J = 8.7 Hz, 1H), 7.19 (d, J
13
6
= 8.7 Hz, 1H); C NMR (DMSO-d ): δ 151.98, 148.36, 143.34,
13
(DMSO-d ): δ 8.12 (d, J = 8.0 Hz, 1H), 7.90 (m, 2H); C NMR
6
136.97, 121.92, 116.87, 110.14. ESI-LCMS m/z (MH ) 220.
A n a l. Calcd. for C H Cl NOS: C, 38.20; H, 1.37; N, 6.36.
6
(DMSO-d ): δ 197.80, 152.08, 147.29, 124.87, 128.54, 124.59,
+
6
112.69. EI-GCMS m/z (M ) 213.
Anal. Calcd. for C H N O S : C, 39.61; H, 1.90; N, 13.20.
+
7
3
Found: C, 38.03; H, 1.52; N, 6.15.
2
7
Found: C, 40.01; H, 1.82, N, 13.07.
4 2 2 2
5-Amino-2-mercaptobenzothiazole (10a).
2-Chloro-5-nitro-benzothiazole (6b).
1
This compound has the following properties: H NMR
(DMSO-d ): δ 13.31 (b, 1H), 7.22 (d, J = 9.0 Hz, 1H), 6.53 (m,
6
1
This compound has the following properties: H NMR