¨
Ozlen G u¨ zel, A. Salman / Bioorg. Med. Chem. 14 (2006) 7804–7815
7812
1
.85–1.91 (m, 2H, pip. C –H), 2.14 (s, 2H, C –H), 2.32–
3
(morph. C ), 55.40 (morph. C ), 70.30 (morph. C
3 5 2
5
2
.48 (m, 3H, N–CH ), 3.95 (br s, 4H, pip. C2,6–H), 5.61
3
and C ), 45.00 (N–CH –S), 122.25 (bzi. C ), 126.00
6 2 4
(
s, 2H, N–CH –S), 7.67–7.77 (m, 3H, bzi. C5,6,7–H),
2
(bzi. C ), 126.24 (bzi. C ), 136.18 (bzi. C ), 137.00
7 3a 6
+
.86–7.89 (m, 1H, bzi. C –H); EIMS: m/z 371 (M ).
7
Anal. Calcd for C H N O S (371.50): C, 45.26; H,
(bzi. C ), 137.60 (bzi. C ), 150.90 (C@O), 190.30
4
5
7a
(C@S). Anal. Calcd for C H N O S (386.51): C,
1
4
17
3
3
3
15 18
2
4 3
4
1
.61; N, 11.31; S, 25.89. Found: C, 45.51; H, 4.62; N,
1.16; S, 25.67.
46.61; H, 4.69; N, 7.25; S, 24.89. Found: C, 46.93;
H, 4.36; N, 7.06; S, 24.80.
4.13. (1,1-Dioxido-3-oxo-1,2-benzisothiazol-2(3H)-
yl)methyl 4-phenylpiperazin-1-carbodithioate (11)
4.17. (1,1-Dioxido-3-oxo-1,2-benzisothiazol-2(3H)-
yl)methyl N-methyl-N-[3-(dibenzo[b,e]-bicyclo[2.2.
2
]octadienyl)propyl]dithiocarbamate (15)
Yellow powder (62%): mp 172–177 ꢁC; IR(KBr): t
1
1
2
4
6
2
733 (C@O), 1243 (C@S);
H
NMR (CDCl /
White powder (10%): mp 90–125 ꢁC; IR(KBr): t 1734
3
1
00 MHz): d 3.15 (t, 4H, J = 5.15 Hz, pip. C3,5–H),
(C@O), 1182 (C@S); H NMR (CDCl /200 MHz): d
3
.13 (br s, 4H, pip. C2,6–H), 5.70 (s, 2H, N–CH –S),
.69–6.77 (m, 3H, phenyl C3,4,5–H), 7.06–7.14 (m,
1.56 (s, 3 H, N–CH ), 1.78–1.82 (m, 2H, C –H ), 2.17–
2
3
2
2
2.27 (m, 2H, C2
(s, 1H, C3 –H), 3.63 (s, 1H, C3
J = 7.70 Hz, C4 –H), 4.25–4.38 (m, 2H, C –H ), 5.85,
0
–H ), 2.42–2.53 (m, 2H, C –H ), 3.42
2 3 2
H, phenyl C2,6–H), 7.71–7.81 (m, 3H, bzi. C5,6,7
–
0
0
–H), 4.02 (t, 1H,
H), 7.91–7.95 (m, 1H, bzi. C –H); EIMS: m/z 433
4
0
1
2
+
M ). Anal. Calcd for C H N O S (433.57): C,
(
5.91 (2s, 2H, N–CH –S), 7.01–7.28 (m, 8H, Ar–H),
2
1
9
19
3
3
3
52.63; H, 4.42; N, 9.69; S, 22.19. Found: C, 53.01;
H, 4.32; N, 9.57; S, 22.15.
7.78–7.95 (m, 3H, bzi. C5,6,7–H), 8.05-8.09 (m, 1H, bzi.
C –H); Anal. Calcd for C H N O S Æ2.5 H O
4
29 28
2
3
3
2
(593.77): C, 58.65; H, 5.51; N, 4.71; S, 16.19. Found:
C, 58.34; H, 5.10; N, 4.53; S, 16.18.
4.14. (1,1-Dioxido-3-oxo-1,2-benzisothiazol-2(3H)-
yl)methyl pyrrolidin-1-carbodithioate (12)
4.18. General method for the synthesis of (1,1-dioxido-3-
oxo-1,2-benzisothiazol-2(3H)-yl)methyl O-alkyl dithio-
carbonates (16–20)
White needles (47%); mp 138–139 ꢁC; IR(KBr): t 1724
1
(
C@O), 1238 (C@S); H NMR (CDCl /200 MHz): d
3
1
J = 6.59 Hz, pyr. C2,5–H), 5.87 (s, 2H, N–CH –S),
.94–2.09 (m, 4H, pyr. C3,4–H), 3.64, 3.95 (2t, 4H,
The ethanolic solution of 3 (5 mmol) and b (5 mmol)
were refluxed for 1 h. After evaporation of the solvent
in vacuo, products were washed with water and purified
by recrystallization from ethanol.
2
7
bzi. C –H); EIMS: m/z 342 (M ). Anal. Calcd for
.82–7.93 (m, 3H, bzi. C5,6,7–H), 8.05–8.09 (m, 1H,
+
4
C H N O S (342.46): C, 45.59; H, 4.12; N, 8.18; S,
1
3
14
2
3 3
2
8.09. Found: C, 45.90; H, 4.54; N, 8.07; S, 28.11.
4.19. (1,1-Dioxido-3-oxo-1,2-benzisothiazol-2(3H)-
yl)methyl O-ethyl dithiocarbonate (16)
4.15. (1,1-Dioxido-3-oxo-1,2-benzisothiazol-2(3H)-
yl)methyl morpholin-1-carbodithioate (13)
White powder (37%): mp 60–64 ꢁC; IR(KBr): t 1743
1
White powder (32%): mp 170–181 ꢁC; IR(KBr): t 1732
(C@O), 1256 (C@S);
H
NMR (DMSO-d /
6
1
(
C@O), 1222 (C@S); H NMR (CDCl /200 MHz): d
400 MHz): d 1.44 (t, 3H, J = 7.01 Hz, ethyl CH3),
3
3
morph. C2,6–H), 5.87 (s, 2H, N–CH –S), 7.80–7.97 (m,
.75 (s, 4H, morph. C3,5–H), 3.91, 4.34 (2br s, 4H,
4.69 (q, 2H, J = 6.99Hz, O–CH ), 5.50 (s, 2H, N–
CH –S), 7.99–8.14 (m, 3H, bzi. C5,6,7–H), 8.32 (d,
2
2
2
1
3
13
3
H, bzi. C5,6,7–H), 8.03–8.10 (m, 1H, bzi. C –H);
4
C
1H, J = 7.32 Hz, bzi. C –H);
4
C NMR (proton
NMR (APT, DMSO-d /125 MHz): d 52.40 (morph.
decoupled, DEPT-135
14.14 (ethyl CH ), 42.43 (N–CH –S), 71.89 (ethyl
/
DMSO-d /125 MHz):
d
6
6
C ), 55.00 (morph. C ), 66.26 (morph. C and C6),
3
5
2
3
2
4
1
1
4.98 (N–CH –S), 122.45 (bzi. C ), 126.07 (bzi. C ),
2
O–CH ), 122.44 (bzi. C ), 126.11 (bzi. C ), 126.39
2 4 7
(bzi. C ), 136.16 (bzi. C ), 137.02 (bzi. C ), 137.57
3a 6 5
4
7
26.42 (bzi. C ), 136.14 (bzi. C ), 137.00 (bzi. C ),
3
a
6
5
37.68 (bzi. C ), 158.98 (C@O), 192.76 (C@S). Anal.
(bzi. C ), 158.81 (C@O), 210.13 (C@S); EIMS: m/z
7
a
7a
+
317 (M ). Anal. Calcd for C H NO S (317.41):
Calcd for C H N O S (358.46): C, 43.56; H, 3.94;
N, 7.81; S, 26.84. Found: C, 43.94; H, 4.00; N, 7.68; S,
1
3
14
2
4
3
11 11
4 3
C, 41.62; H, 3.49; N, 4.41; S, 30.31. Found: C,
41.69; H, 3.13; N, 4.36; S, 30.73.
2
6.78.
4.16. (1,1-Dioxido-3-oxo-1,2-benzisothiazol-2(3H)-
yl)methyl 2,6-dimethylmorpholin-1-carbodithioate (14)
4.20. (1,1-Dioxido-3-oxo-1,2-benzisothiazol-2(3H)-
yl)methyl O-propyl dithiocarbonate (17)
Light green crystals (35%): mp 118–120 ꢁC; IR(KBr):
Light yellow flakes (40%): mp 45–50 ꢁC; IR(KBr): t 1745
1
1
t 1732 (C@O), 1236 (C@S); H NMR (CDCl /
(C@O), 1246 (C@S); H NMR (DMSO-d /400MHz): d
3
6
2
morph. C –H ), 3.63 (s, 2H, morph. C –H), 4.4
00 MHz): d 1.21 (s, 6H, 2· CH ), 2.82 (s, 2H,
0.98 (t, 3H, J = 7.31 Hz, propyl CH ), 1.84–1.89
(m, 2H, propyl–CH –), 4.61 (t, 2H, J = 6.58 Hz, propyl
3
3
3
,5
ax.
2,6
2
(
C –H
br s, 1H, morph. C –Hequiv), 5.40 (br s, 1H, morph.
3
O–CH ), 5.50 (s, 2H, N–CH –S), 7.99–8.14 (m, 3H,
2
2
), 5.85 (s, 2H, N–CH –S), 7.77–7.92 (m,
2
bzi. C5,6,7–H), 8.32 (d, 1H, J = 7.32 Hz, bzi. C –H);
4
5
equiv
+
EIMS: m/z 331 (M ). Anal. Calcd for C H NO S
3
H, bzi. C5,6,7–H), 8.00–8.07 (m, 1H, bzi. C –H);
4
C NMR (HSQC, DMSO-d /125 MHz): d 19.75
12 13
4
3
1
3
(331.43): C, 43.49; H, 3.95; N, 4.23; S, 29.02. Found:
C, 43.50; H, 3.92; N, 4.19; S, 28.75.
6
(
morph. C –CH ), 19.85 (morph. C –CH ), 55.18
2 3 6 3