690
Vol. 57, No. 7
137.8, 136.7, 135.7, 134.5, 131.9, 130.5, 128.6, 126.9, 125.0, 123.2, 117.1,
112.5, 64.0, 56.1, 42.0, 20.3. MS m/z: 822 (Mꢁ). Anal. Calcd for
C49H40F2N2O4S2: C, 71.51; H, 4.90; N, 3.40. Found: C, 71.46; H, 4.92; N,
3.34.
Jꢂ8.6 Hz, 4H, Ar-H), 7.36 (s, 2H, CH–S), 7.30—7.25 (m, 6H, Ar-H),
7.20—7.10 (m, 16H, Ar-H), 6.70—6.65 (m, 4H, Ar-H), 5.18 (d, Jꢂ1.7 Hz,
2H, CH–N), 4.21 (d, Jꢂ1.7 Hz, 2H, CH–S), 4.09 (s, 6H, OCH3), 3.41 (s, 2H,
CH2), 2.21 (s, 6H, CH3). 13C-NMR (DMSO-d6) d: 159.3, 154.0, 146.2,
142.7, 140.6, 136.4, 135.7, 134.5, 132.0, 130.1, 129.2, 128.9, 128.1, 127.4,
125.0, 123.5, 122.6, 117.6, 110.6, 71.1, 62.5, 56.5, 55.0, 42.0, 22.0. MS m/z:
1072 (Mꢁ). Anal. Calcd for C61H50Cl2F2N6O2S2: C, 68.34; H, 4.70; N, 7.84.
Found: C, 68.29; H, 4.77; N, 7.86.
Bis-[4-methoxy-3-[3-(4-fluorophenyl)-6-(4-methylphenyl)-2-benzyl-
3,3a,5,6-tetrahydro-2H-pyrazolo[3,4-d][1,3]thiazol-5-yl]phenyl]methane
(6d) This was obtained by reacting compound 5a (2.0 g) and p-benzylhy-
drazine (0.62 g) as described in the typical procedure and isolated as brown
solid. Yield 72%, mp 286—288 °C. IR (KBr) cmꢀ1: 3062, 2972, 1578, 1327,
1270. 1H-NMR (DMSO-d6) d: 7.38 (s, 2H, CH–S), 7.30—7.20 (m, 12H, Ar-
H), 7.15—7.10 (m, 16H, Ar-H), 6.70—6.65 (m, 4H, Ar-H), 4.95 (d,
Jꢂ1.8 Hz, 2H, CH–N), 4.20 (s, 4H, CH2), 4.09 (s, 6H, OCH3), 4.00 (d,
Jꢂ1.8 Hz, 2H, CH–S), 3.41 (s, 2H, CH2), 2.21 (s, 6H, CH3). 13C-NMR
(DMSO-d6) d: 166.2, 154.0, 146.3, 142.7, 136.7, 136.4, 135.6, 134.7, 133.1,
129.3, 128.7, 128.4,128.0, 127.5, 125.0, 122.6, 116.4, 110.5, 71.2, 63.1,
56.1, 55.5, 54.7, 41.9, 22.0. MS m/z: 1032 (Mꢁ). Anal. Calcd for
C63H56F2N6O2S2: C, 73.37; H, 5.47; N, 8.15. Found: C, 73.29; H, 5.41; N,
8.20.
Bis-[4-methoxy-3-[3-(4-fluorophenyl)-2-isopropyl-6-(4-methylphenyl)-
3,3a,5,6-tetrahydro-2H-pyrazolo[3,4-d][1,3]thiazol-5-yl]phenyl]methane
(6e) This was obtained by reacting compound 5a (2.0 g) and isopropylhy-
drazine (0.37 g) as described in the typical procedure and isolated as yellow
solid. Yield 76%, mp 249—251 °C. IR (KBr) cmꢀ1: 3065, 2980, 1572, 1327,
1270. 1H-NMR (DMSO-d6) d: 7.36 (s, 2H, CH-S), 7.21 (d, Jꢂ9.1 Hz, 2H,
Ar-H), 7.15—7.10 (m, 12H, Ar-H), 7.00 (d, Jꢂ8.6 Hz, 4H, Ar-H), 6.70—
6.65 (m, 4H, Ar-H), 4.89 (d, Jꢂ1.8 Hz, 2H, CH–N), 4.14 (s, 6H, OCH3),
4.09 (d, Jꢂ1.8 Hz, 2H, CH–S), 3.41 (s, 2H, CH2), 3.11 (m, 2H, CH–N), 2.21
(s, 6H, CH3), 0.98 (d, Jꢂ6.3 Hz, 12H, CH3). 13C-NMR (DMSO-d6) d: 164.7,
154.0, 147.8, 142.7, 136.4, 135.7, 134.7, 133.1, 129.1, 128.5, 128.2, 125.0,
122.6, 116.4, 110.5, 71.3, 59.2, 58.6, 54.7, 52.4, 42.0, 22.1, 20.2. MS m/z:
936 (Mꢁ). Anal. Calcd for C51H48F2N6O2S2: C, 69.68; H, 5.50; N, 9.56.
Found: C, 69.70; H, 5.45; N, 9.51.
Bis-[4-methoxy-3-[2-(Z)-5-(4-fluorophenyl)methylidene-3-(4-
chlorophenyl)-1,3-thiazolan-4-one]phenyl]methane (5b) This was ob-
tained by reacting compound 4b (3.26 g) and p-fluorobenzaldehyde (1.24 g)
as described in the typical procedure and isolated as brown solid. Yield 84%,
mp 237—239 °C. IR (KBr) cmꢀ1: 3035, 2989, 1719, 1535, 1182, 747, 686.
1H-NMR (DMSO-d6) d: 7.71, (s, 2H, CHꢂC), 7.63 (d, Jꢂ8.6 Hz, 4H, Ar-
H), 7.51 (d, Jꢂ8.3 Hz, 4H, Ar-H), 7.29—7.23 (m, 8H, Ar-H), 7.12 (d,
Jꢂ9.1 Hz, 2H, Ar-H), 6.92 (s, 2H, CH–S), 6.69 (s, 2H, Ar-H), 6.61 (d,
Jꢂ9.1 Hz, 2H, Ar-H), 4.12 (s, 6H, OCH3), 3.81 (s, 2H, CH2). 13C-NMR
(DMSO-d6) d: 165.7, 161.8, 154.0, 139.1, 137.9, 135.3, 134.5, 133.4, 131.7,
130.6, 128.9, 127.1, 126.6, 124.9, 122.7, 117.0, 112.9, 64.0, 56.1, 42.0. MS
m/z: 864 (Mꢁ). Anal. Calcd for C47H34Cl2F2N2O4S2: C, 65.36; H, 3.97; N,
3.24. Found: C, 65.37; H, 3.91; N, 3.19.
Bis-[4-methoxy-3-[2-(Z)-5-(4-fluorophenyl)methylidene-3-(4-nitro-
phenyl)-1,3-thiazolan-4-one]phenyl]methane (5c) This was obtained by
reacting compound 4c (3.37 g) and p-fluorobenzaldehyde (1.24 g) as de-
scribed in the typical procedure and isolated as brown solid. Yield 82%, mp
289—291 °C. IR (KBr) cmꢀ1: 3036, 2995, 1720, 1542, 1535, 1340, 1187,
684. 1H-NMR (DMSO-d6) d: 8.18 (d, Jꢂ8.7 Hz, 4H, Ar-H), 7.80—7.70 (m,
6H, Ar-HꢁCHꢂC), 7.47 (d, Jꢂ8.4 Hz, 4H, Ar-H), 7.32 (d, Jꢂ8.4 Hz, 4H,
Ar-H), 7.14 (d, Jꢂ9.1 Hz, 2H, Ar-H), 6.92 (s, 2H, CH–S), 6.60—6.57 (m,
4H, Ar-H), 4.19 (s, 6H, OCH3), 3.80 (s, 2H, CH2). 13C-NMR (DMSO-d6) d:
165.6, 161.7, 154.0, 146.3, 145.6, 137.8, 135.2, 134.5, 130.7, 129.3, 128.7,
128.0, 126.7, 125.1, 123.1, 117.1, 112.5, 64.0, 56.1, 42.0. MS m/z: 884
(Mꢁ). Anal. Calcd for C47H34F2N4O8S2: C, 63.79; H, 3.87; N, 6.33. Found:
C, 63.73; H, 3.89; N, 6.27.
Typical Procedure. Bis-[4-methoxy-3-[3-(4-fluorophenyl)-6-(4-
methylphenyl)-2-(aryl)-3,3a,5,6-tetrahydro-2H-pyrazolo[3,4-d][1,3]thia-
zol-5-yl]phenyl]methanes (6a—r) A mixture of compound 5 (5 mmol),
aryl/alkyl hydrazine (10 mmol) and anhydrous sodium acetate (5 mmol) in
glacial acetic acid (20 ml), was refluxed for 7 h. The reaction mixture was
concentrated and cooled to room temperature, the solid thus separated, was
filtered, washed thoroughly with water, the crude product thus obtained was
purified by column chromatography on silica gel with hexane–ethyl acetate
as eluent to afford pure compounds.
Bis-[4-methoxy-3-[3-(4-fluorophenyl)-6-(4-methylphenyl)-2-phenyl-
3,3a,5,6-tetrahydro-2H-pyrazolo[3,4-d][1,3]thiazol-5-yl]phenyl]methane
(6a) This was obtained by reacting compound 5a (2.0 g) and phenylhy-
drazine (0.54 g) as described in the typical procedure and isolated as brown
solid. Yield 69%, mp 256—258 °C. IR (KBr) cmꢀ1: 3078, 1598, 1328, 1256.
1H-NMR (DMSO-d6) d: 7.40 (s, 2H, CH–S), 7.29—7.24 (m, 6H, Ar-H),
7.18 (m, 8H, Ar-H), 7.14—7.05 (m, 14H, Ar-H), 6.70 (d, Jꢂ9.1 Hz, 2H, Ar-
H), 6.65 (s, 2H, Ar-H), 5.25 (d, Jꢂ1.8 Hz, 2H, CH–N), 4.20 (d, Jꢂ1.8 Hz,
2H, CH–S), 4.09 (s, 6H, OCH3), 3.42 (s, 2H, CH2), 2.21 (s, 6H, CH3). 13C-
NMR (DMSO-d6) d: 164.4, 154.1, 147.0, 146.3, 142.7, 136.4, 135.7, 134.6,
132.0, 129.7, 129.3, 128.0, 127.4, 124.9, 122.6, 119.0, 117.6, 114.8, 110.6,
71.1, 62.6, 56.5, 54.6, 42.0, 22.0. MS m/z: 1004 (Mꢁ). Anal. Calcd for
C61H52F2N6O2S2: C, 73.03; H, 5.22; N, 8.38. Found: C, 72.96; H, 5.27; N,
8.32.
Bis-[4-methoxy-3-[3-(4-fluorophenyl)-2-methyl-6-(4-methylphenyl)-
3,3a,5,6-tetrahydro-2H-pyrazolo[3,4-d][1,3]thiazol-5-yl]phenyl]methane
(6f) This was obtained by reacting compound 5a (2.0 g) and methylhy-
drazine (0.23 g) as described in the typical procedure and isolated as yellow
solid. Yield 66%, mp 229—231 °C. IR (KBr) cmꢀ1: 3062, 2969, 1571, 1327,
1
1266. H-NMR (DMSO-d6) d: 7.36 (s, 2H, CH–S), 7.21 (d, Jꢂ9.1 Hz, 2H,
Ar-H), 7.15—7.05 (m, 16H, Ar-H), 6.70—6.65 (m, 4H, Ar-H), 4.71 (d,
Jꢂ1.8 Hz, 2H, CH–N), 4.11 (s, 6H, OCH3), 4.00 (d, Jꢂ1.8 Hz, 2H, CH–S),
3.41 (s, 2H, CH2), 2.70 (s, 6H, N–CH3), 2.21 (s, 6H, CH3). 13C-NMR
(DMSO-d6) d: 164.7, 154.0, 142.7, 142.2, 136.4, 135.6, 134.7, 133.1, 129.1,
128.1, 128.4, 125.0, 122.6, 116.4, 110.6, 71.3, 62.5, 54.7, 52.5, 41.7, 35.7,
22.0. MS m/z: 880 (Mꢁ). Anal. Calcd for C51H48F2N6O2S2: C, 69.68; H,
5.50; N, 9.56. Found: C, 69.70; H, 5.45; N, 9.51.
Bis-[4-methoxy-3-[3-(4-fluorophenyl)-6-(4-chlorophenyl)-2-phenyl-
3,3a,5,6-tetrahydro-2H-pyrazolo[3,4-d][1,3]thiazol-5-yl]phenyl]methane
(6g) This was obtained by reacting compound 5b (2.1 g) and phenylhy-
drazine (0.54 g) as described in the typical procedure and isolated as brown
solid. Yield 68%, mp 249—251 °C. IR (KBr) cmꢀ1: 3078, 1598, 1572, 1327,
746. 1H-NMR (DMSO-d6) d: 7.42 (d, Jꢂ8.6 Hz, 4H, Ar-H), 7.36 (s, 2H,
CH–S), 7.30—7.20 (m, 18H, Ar-H), 7.10—7.05 (m, 6H, Ar-H), 6.70—6.65
(m, 4H, Ar-H), 5.18 (d, Jꢂ1.8 Hz, 2H, CH–N), 4.21 (d, Jꢂ1.8 Hz, 2H,
CH–S), 4.20 (s, 6H, OCH3), 3.41 (s, 2H, CH2). 13C-NMR (DMSO-d6) d:
166.0, 154.0, 147.8, 145.3, 142.6, 135.6, 134.7, 133.1, 132.4, 131.6, 128.9,
127.1, 126.6, 124.9, 122.6, 118.9, 117.4, 114.9, 110.6, 71.3, 62.5, 56.8,
54.7, 42.0. MS m/z: 1044 (Mꢁ). Anal. Calcd for C59H46Cl2F2N6O2S2: C,
67.87; H, 4.44; N, 8.05. Found: C, 67.85; H, 4.48; N, 8.00.
Bis-[4-methoxy-3-[3-(4-fluorophenyl)-6-(4-chlorophenyl)-2-(4-
methoxyphenyl)-3,3a,5,6-tetrahydro-2H-pyrazolo[3,4-d][1,3]thiazol-5-
yl]phenyl]methane (6h) This was obtained by reacting compound 5b
(2.1 g) and p-methoxyphenylhydrazine (0.69 g) as described in the typical
procedure and isolated as brown solid. Yield 70%, mp 274—276 °C. IR
(KBr) cmꢀ1: 3065, 1579, 1562, 1327, 747. 1H-NMR (DMSO-d6) d: 7.42 (d,
Jꢂ8.6 Hz, 4H, Ar-H), 7.36 (s, 2H, CH–S), 7.29 (d, Jꢂ8.6 Hz, 4H, Ar-H),
7.20—7.15 (m, 10H, Ar-H), 6.92 (d, Jꢂ8.8 Hz, 4H, Ar-H), 6.80—6.70 (m,
8H, Ar-H), 5.18 (d, Jꢂ1.8 Hz, 2H, CH–N), 4.21 (d, Jꢂ1.8 Hz, 2H, Ar-H),
4.11 (s, 6H, OCH3), 3.70 (s, 6H, OCH3), 3.41 (s, 2H, CH2). 13C-NMR
(DMSO-d6) d: 166.0, 155.9, 154.0, 146.2, 142.4, 140.5, 135.4, 134.7, 133.2,
131.6, 130.4, 127.1, 126.3, 124.9, 123.0, 122.6, 117.4, 113.7, 110.5, 71.2,
Bis-[4-methoxy-3-[3-(4-fluorophenyl)-6-(4-methylphenyl)-2-(4-
methoxyphenyl)-3,3a,5,6-tetrahydro-2H-pyrazolo[3,4-d][1,3]thiazol-5-
yl]phenyl]methane (6b) This was obtained by reacting compound 5a
(2.0 g) and p-methoxyphenylhydrazine (0.69 g) as described in the typical
procedure and isolated as dark yellow solid. Yield 70%, mp 281—283 °C.
1
IR (KBr) cmꢀ1: 3065, 1596, 1327, 1256. H-NMR (DMSO-d6) d: 7.38 (s,
2H, CH–S), 7.21 (d, Jꢂ9.1 Hz, 2H, Ar-H), 7.20—7.10 (m, 16H, Ar-H), 6.90
(d, Jꢂ8.9 Hz, 4H, Ar-H), 6.86 (d, Jꢂ8.9 Hz, 4H, Ar-H), 6.70—6.65 (m, 4H,
Ar-H), 5.18 (d, Jꢂ1.7 Hz, 2H, CH–N), 4.21 (d, Jꢂ1.7 Hz, 2H, CH–S), 4.09
(s, 6H, OCH3), 3.70 (s, 6H, OCH3), 3.41 (s, 2H, CH2), 2.21 (s, 6H, CH3).
13C-NMR (DMSO-d6) d: 159.3, 156.0, 154.0, 146.3, 142.7, 141.2, 136.4,
135.7, 134.7, 132.0, 129.3, 128.1, 127.4, 124.9, 122.6, 121.9, 117.6, 114.7,
110.5, 71.1, 62.6, 56.5, 55.9, 54.0, 42.1, 22.0. MS m/z: 1064 (Mꢁ). Anal.
Calcd for C63H56F2N6O3S2: C, 71.17; H, 5.31; N, 7.90. Found: C, 71.12; H,
5.27; N, 7.86.
Bis-[4-methoxy-3-[3-(4-fluorophenyl)-6-(4-methylphenyl)-2-(4-
chlorophenyl)-3,3a,5,6-tetrahydro-2H-pyrazolo[3,4-d][1,3]thiazol-5-
yl]phenyl]methane (6c) This was obtained by reacting compound 5a
(2.0 g) and p-chlorophenylhydrazine (0.71 g) as described in the typical pro-
cedure and isolated as brown solid. Yield 67%, mp 267—269 °C. IR (KBr)
1
cmꢀ1: 3064, 1580, 1327, 1260, 748. H-NMR (DMSO-d6) d: 7.50 (d,