July 2014
Synthesis of New Bis[4,5-dihydro-1-phenyl-5-thienyl-3-(phenyl-4-alkoxy)-
1H-pyrazole]derivatives
1169
Hz, OCH2CH2CH2CH2), 1.41 (4H, m, OCH2CH2CH2CH2); 13C
NMR (100 MHz, CDCl3): d 160.50 (C-4000), 155.78 (C-3), 147.71
(C-200), 145.90 (C-10), 144.80 (C-1000), 128.56 (C-500), 127.11
(C-300), 126.60 (C-400), 126.48 (C-2000, 6000), 124.59 (C-30,50),
118.99 (C-40), 114.69 (C-3000,5000), 113.50 (C-20, 60), 67.45
(OCH2CH2CH2CH2), 59.74 (C-5), 43.62 (C-4), 28.49
(OCH2CH2CH2CH2), 25.79 (OCH2CH2CH2CH2), 25.19
(OCH2CH2CH2CH2); MS (ESI): m/z (M)+ 718. Anal. Calcd for
C46O2N4H46S2: C, 73.60%; H, 6.13%; N, 7.46%; S, 8.53%; found:
C, 73.89%; H, 6.15%; N, 7.43%; S, 8.49%.
Synthesis of 1,5-bis[3-(4-phenyl)-4,5-dihydro-1-phenyl-5-
(thiophen-2-yl)-1H-pyrazole]pentane 4c. The compound 4c
was prepared from the reaction of bischalcone 3c (1.0 g,
0.00189 mol) with phenyl hydrazine (0.40824 g, 0.00378 mol)
under similar conditions as described earlier for 4a.
4c: brown solid; yield 65%; mp: 125–127ꢁC, IR (KBr) cmꢀ1
1592 (C═N), 2930 and 2869 (methylene C–H), 1234 and 1026
1
(C–O); H NMR (400 MHz, CDCl3): d 7.68 (4H, d, Jp,o =8.6Hz,
00
H-2000,6000), 7.32 (2H, d, J3 ,4 =3.7Hz, H-3 ), 7.19 (2H, d, J5 ,4
=
00 00
00
0
5.0 Hz, H-500), 7.02 (6H, m, H-30,40,50), 6.92 (4H, d,
Jo =8.6Hz, H-3000,5000), 6.90 (2H, dd, J= 3.7, 5.0 Hz, H-400), 6.79
(4H, t, J=7.2Hz, H-20,60), 5.62 (2H, dd, JXA =6.2Hz, JXM =11.8
Hz, HX), 4.03 (4H, t, Jvic =6.0Hz, OCH2CH2CH2), 3.81 (2H, dd,
Synthesis of 1,10-bis[3-(4-phenyl)-4,5-dihydro-1-phenyl-5-
(thiophen-2-yl)-1H-pyrazole]decane 4f.
The compound 4c
was obtained from the reaction of bischalcone 3f (1.0 g,
0.00167 mol) with phenyl hydrazine (0.3607 g, 0.00334 mol)
under similar conditions as used earlier for 4a.
J= 11.8 Hz, JMA = 17.2 Hz, HM), 3.24 (2H, dd, JAX =6.2Hz, JAM
=
17.2 Hz, HA), 2.32 (4H, quintet, Jvic =6.0Hz, OCH2CH2CH2),
1.58 (2H, m, OCH2CH2CH2); 13C NMR (100 MHz, CDCl3): d
160.19 (C-4000), 155.50 (C-3), 147.67 (C-200), 145.80 (C-10), 144.70
(C-1000), 128.59 (C-500), 127.19 (C-300), 126.67 (C-2000, 6000), 126.60
(C-400), 124.03 (C-30,50), 118.79 (C-40), 114.48 (C-3000,5000), 113.45
(C-20, 60), 67.10 (OCH2CH2CH2), 59.49 (C-5), 43.47 (C-4), 28.39
(OCH2CH2CH2), 25.67 (OCH2CH2CH2); MS (ESI): m/z (M + H)+
677. Anal. Calcd for C43O2N4H40S2: C, 72.88%; H, 5.64%; N,
7.90%; S, 9.03%; found: C, 72.59%; H, 5.62%; N, 7.93%; S, 9.06%.
Synthesis of 1,6-bis[3-(4-phenyl)-4,5-dihydro-1-phenyl-5-
4f: yellow solid; yield 60%; mp: 126–128ꢁC, IR (KBr) cmꢀ1
1593 (C═N), 2929 and 2857 (methylene C–H), 1230 and 1021
1
(C–O); H NMR (400 MHz, CDCl3): d 7.64 (40H0 , d, Jo = 8.7 Hz,
H-2000, 6000), 7.34 (2H, d, J3 ,4 = 3.6 Hz, H-3 ), 7.19 (2H, d,
00 00
J5”,4” = 5.2 Hz, H-500), 7.10 (6H, m, H-30, 40, 50), 6.94 (2H, dd,
J = 3.6, 5.2 Hz, H-400), 6.92 (4H, d, Jo = 8.7 Hz, H-3000,5000), 6.75
(4H, t, J = 7.0 Hz, H-20, 60), 5.56 (2H, dd, JXA = 6.9Hz, JXM = 11.5
Hz, HX), 3.98 (4H, t, Jvic = 6.3 Hz, OCH2CH2CH2CH2CH2), 3.82
(2H, dd, JMX = 11.8 Hz, JMA =17.0 Hz, HM), 3.20 (2H, dd, JAX
=
(thiophen-2-yl)-1H-pyrazole]hexane 4d.
The compound 4c
6.9 Hz, JAM = 17.0Hz, HA), 1.79 (4H, quintet, Jvic = 6.3Hz,
OCH2CH2CH2CH2CH2), 1.46 (4H, quintet, Jvic = 6.3Hz,
OCH2CH2CH2CH2CH2), 1.35 (8H, m, OCH2CH2CH2CH2CH2);
13C NMR (100 MHz, CDCl3): d 159.35 (C-4000), 156.23 (C-3),
145.79 (C-10), 145.62 (C-200), 144.88 (C-1000), 128.38 (C-500),
126.90 (C-300), 126.43 (C-400), 125.97 (C-2000, 6000), 124.46 (C-
30,50), 118.74 (C-40), 114.15 (C-20, 60), 113.19 (C-3000,5000), 67.47
(OCH2CH2CH2CH2CH2), 59.73 (C-5), 43.54 (C-4), 28.84
(OCH2CH2CH2CH2CH2), 28.72 (OCH2CH2CH2CH2CH2), 28.61
(OCH2CH2CH2CH2CH2), 25.42 (OCH2CH2CH2CH2CH2); MS (ESI): m/
z (M + 1)+ 747. Anal. Calcd for C48O2N4H50S2: C, 74.03%; H, 6.42%; N,
7.20%; S, 8.22%; found: C, 74.32%; H, 6.39%; N, 7.22%; S, 8.25%.
Synthesis of 1,12-bis[3-(4-phenyl)-4,5-dihydro-1-phenyl-5-
(thiophen-2-yl)-1H-pyrazole]dodecane 4g. The compound 4c
was synthesized from the reaction of bischalcone 3g (1.0 g,
0.0016 mol) with phenyl hydrazine (0.3456 g, 0.0032mol) under
similar conditions as described earlier for 4a.
was obtained by treating bischalcone 3d (1.0 g, 0.00185 mol) with
phenyl hydrazine (0.3996g, 0.00370 mol) under similar conditions
as described earlier for 4a.
4d: yellow solid; yield 61%; mp: 166–168ꢁC, IR (KBr) cmꢀ1 1599
(C═N), 2937 and 2876 (methylene C–H), 1240 and 1018 (C–O);
1H NMR (400 MHz, CDCl3): d 7.66 (4H, d, Jo =8.8Hz, H-2000,600000),
00
00 00
00 00
7.40 (2H, d, J3 ,4 =3.8Hz, H-3 ), 7.24 (2H, d, J5 ,4 =5.2Hz, H-5 ),
7.10 (6H, m, H-30, 40, 50), 6.93 (2H, dd, J=3.8, 5.2Hz, H-400), 6.88
(2H, d, Jo =8.8Hz, H-3000, 5000), 6.73 (4H, t, J=8.7Hz, H-20, 60), 5.59
(2H, dd, JXA =6.7Hz, JXM = 12.2 Hz, HX), 4.00 (4H, t,
Jvic =6.0Hz, OCH2CH2CH2), 3.85 (2H, dd, JMX = 12.2 Hz, JMA
=
17.4 Hz, HM), 3.23 (2H, dd, JAX =6.6Hz, JAM = 17.4 Hz, HA), 1.56
(4H, quintet, Jvic =6.0Hz, OCH2CH2CH2), 1.51 (4H, quintet, Jvic =6.0
Hz, OCH2CH2CH2); 13C NMR (100 MHz, CDCl3): d 160.39 (C-4000),
155.58 (C-3), 147.73 (C-200), 145.95 (C-10), 144.86 (C-1000), 128.78
(C-500), 127.14 (C-300), 126.69 (C-400), 126.43 (C-2000, 6000), 124.60
(C-30, 50), 118.91 (C-40), 114.62 (C-3000,5000), 113.48 (C-20, 60), 67.23
(OCH2CH2CH2), 59.59 (C-5), 43.50 (C-4), 28.43 (OCH2CH2CH2),
25.70 (OCH2CH2CH2); MS (ESI): m/z (M + Na)+ 713. Anal. Calcd
for C44O2N4H42S2: C, 73.13%; H, 5.82%; N, 7.76%; S, 8.86%; found:
C, 72.83%; H, 5.84%; N, 7.73%; S, 8.89%.
4g: orange solid; yield 63%; mp: 110–112ꢁC, IR (KBr) cmꢀ1 1596
(C═N), 2923 and 2875 (methylene C–H), 1238 and 1029 (C–O); 1H
NMR (400 MHz, CDCl3): d 7.66 (4H, d, Jo =8.8Hz, H-2000,6000), 7.0204
(2H, dd, J= 3.7, 0.8 Hz, H-300), 7.16 (2H, d, J5 ,4 =5.2Hz, H-5 ),
00 00
7.04 (6H, m, H-30,40, 50), 6.98 (4H, d, Jo =8.8Hz, H-3000, 5000), 6.90
(2H, dd, J= 3.7, 5.5 Hz, H-400), 6.74 (4H, t, J=7.2Hz, H-20, 60),
5.60 (2H, dd, JXA =6.6Hz, JXM = 11.8 Hz, HX), 3.98 (4H, t, Jvic =6.4
Hz, OCH2CH2CH2CH2CH2CH2), 3.84 (2H, dd, JMX = 11.8 Hz,
JMA = 17.2 Hz, HM), 3.21 (2H, dd, JAX =6.6Hz, JAM = 17.2 Hz, HA),
1.78 (4H, quintet, Jvic =6.4Hz, OCH2CH2CH2CH2CH2CH2), 1.45
(4H, quintet, Jvic = 6.4 Hz, OCH2CH2CH2CH2CH2CH2), 1.30
(12H, m, OCH2CH2CH2CH2CH2CH2); 13C NMR (100 MHz,
CDCl3): d 160.45 (C-4000), 155.42 (C-3), 145.53 (C-200), 145.78
Synthesis of 1,8-bis[3-(4-phenyl)-4,5-dihydro-1-phenyl-5-
(thiophen-2-yl)-1H-pyrazole]octane 4e.
The compound 4c
was prepared from the reaction of bischalcone 3e (1.0 g,
0.00175mol) with phenyl hydrazine (0.378g, 0.0035 mol) under
similar conditions as used earlier for 4a.
4e: yellow solid; yield 70%; mp: 152–154ꢁC, IR (KBr) cmꢀ1 1595
(C═N), 2920 and 2858 (methylene C–H), 1241 and 1034 (C–O); 1H
NMR (400 MHz, CDCl3): d 7.60 (4H, d, Jo =8.2Hz, H-2000,600000),
00
000
(C-10), 144.79 (C-1 ), 128.43 (C-500), 126.98 (C-300), 126.58 (C-
00 00
00 00
7.38 (2H, d, J3 ,4 =3.8Hz, H-3 ), 7.23 (2H, d, J5 ,4 =4.9Hz, H-5 ),
7.10 (6H, m, H-30,40, 50), 6.92 (2H, dd, J= 3.8, 4.9 Hz, H-400), 6.86
(4H, d, Jo =8.2Hz, H-3000,5000), 6.74 (4H, t, J=7.0Hz, H-20, 60), 5.58
(2H, dd, JXA =6.8Hz, JXM = 12.2 Hz, HX), 3.99 (4H, t, Jvic =6.1Hz,
OCH2CH2CH2CH2), 3.83 (2H, dd, JMX = 12.2 Hz, JMA =16.5Hz,
HM), 3.22 (2H, dd, JAX =6.8Hz, JAM =16.5Hz, HA), 1.78 (4H,
quintet, Jvic =6.1Hz, OCH2CH2CH2CH2), 1.48 (4H, quintet, Jvic =6.1
000
000
0
0
0
0
400), 124.61 (C-2 , 0600 ), 124.16 (C-3 , 5 ), 118.70 (C-4 ), 114.22 (C-2 ,
0
000
6 ), 113.21 (C-3 ,5 ), 67.38 (OCH2CH2CH2CH2CH2CH2), 59.62 (C-
5), 43.25 (C-4), 28.94 (OCH2CH2CH2 CH2CH2CH2), 28.77
(OCH2CH2CH2CH2CH2CH2), 28.42 (OCH2CH2CH2CH2CH2CH2),
28.02 (OCH2CH2CH2CH2CH2CH2), 25.45 (OCH2CH2CH2CH2CH2CH2);
MS (ESI): m/z (M + Na)+ 797. Anal. Calcd for C50O2N4H54S2:
Journal of Heterocyclic Chemistry
DOI 10.1002/jhet