March 2009
Synthesis, Characterization, and Reactions of Selected Multichalcone Derivatives
205
3,30-[1,3-Benzenediylbis(methyleneoxy-4,1-phenylene)]bis
{4,5-dihydro-5-[4-(dimethylamino)phenyl]-1-phenylpyrazol-3-yl}
(3a). This compound was obtained as orange solid (0.25 g,
63%), mp 172–174ꢁC; IR (potassium bromide): 1601, 1455,
(3C, central-Ph-C), 130.95 (6C, Ph-C), 161.90 (3C, Ph-C),
122.70 (3C, Ph-C), 143.70 (3C, Ph-C), 122.74 (3C, Ph-C),
114.55 (6C, Ph-C), 127.30 (6C, Ph-C), 142.10 (3C, Ph-C),
189.50 (3C, 3 ꢂ C¼¼O); ms: (5 kV, fd) m/z (%) 916 (100).
Anal. Calcd. for C60H57N3O6: C, 78.66; H, 6.27; N, 4.59.
Found: C, 78.43; H, 6.39; N, 4.45.
1
1382, 1219, 1076, 792 cmꢀ1; H NMR (deuteriochloroform): d
3.10 (s, 12H, CH3), 5.26 (s, 4H, 2 ꢂ OCH2), 7.09 (d, 4H, Ph-
H), 7.76 (m, 3H, central-Ph-H), 7.55 (s, 1H, central-Ph-H),
7.76 (d, 4H, Ph-H), 2.07 (dd, 4H, ACH2A), 4.12 (m, 2H,
ACHA), 6.70 (d, 4H, Ph-H), 6.99 (d, 4H, Ph-H), 7.10 (m,
10H, Phen-H); 13C NMR (deuteriochloroform): d 40.23 (4C,
CH3), 67.78 (2C, 5 ꢂ OCH2), 111.86 (4C, Ph-C), 125.09 (2C,
Ph-C), 140.48 (2C, central-Ph-C), 128.90 (2C, central-Ph-C),
130.14 (1C, central-Ph-C), 130.67 (4C, Ph-C), 128.35 (1C,
central-Ph-C), 162.09 (2C, Ph-C), 152.02 (2C, Ph-C), 40.23
(2C, ACH2A), 53.29 (2C, ACHA), 121.06 (2C, Ph-C), 114.40
(4C, Ph-C), 128.35 (4C, Ph-C), 143.52 (2C, Ph-C), 135.12
(2C, Ph-C), 113.57, 130.42, 132.08 (10C, Ph-C); ms: (5 kV,
fd) m/z (%) 817 (100). Anal. Calcd. For C54H52N6O2: C,
79.38; H, 6.42; N, 10.29. Found: C, 79.23; H, 6.29; N, 10.21.
3,30,300,3000-[1,2,4,5-Benzenetetrayltetrakis(methyleneoxy-4,1-
phenylene)]pentakis{4,5-dihydro-5-[4-(dimethylamino)phenyl]-
1-phenylpyrazol-3-yl} (3c). This compound was obtained as
brown solid (0.21 g, 55%), mp 106ꢁC (decomposition); IR (po-
(2E,20E,200E,2000E)-1,10,100,1000-[1,2,4,5-Benzenetetrayltetrakis
(methyleneoxy-4,1-phenylene)]tetrakis{3-[4-(dimethylamino)
phenyl]-2-propen-1-one} (2c). This compound was obtained as
pale-yellow powder (1.70 g, 75%), mp 240ꢁC (decomposition);
IR (potassium bromide): 1671, 1599, 1575, 1258, 1274, 827
cmꢀ1 1H NMR (deuteriochloroform): d 3.03 (s, 24H, CH3),
;
5.25 (s, 8H, 4 ꢂ OCH2), 6.99 (d, 8H, Ph-H), 7.42 (s, 2H, cen-
3
tral-Ph-H), 7.92 (d, 8H, Ph-H), 7.57 (d, 4H, J11–12 ¼ 16 Hz,
Ph-H), 7.94 (d, 4H, Ph-H), 7.00 (d, 8H, Ph-H), 6.71 (d, 8H, Ph-
H); 13C NMR (deuteriochloroform): d 40.00 (8C, CH3), 67.65
(4C, 4 ꢂ OCH2), 114.39 (8C, Ph-C), 130.90 (4C, Ph-C), 114.12
(2C, central-Ph-C), 129.82 (4C, central-Ph-C), 130.67 (8C, Ph-
C), 162.00 (4C, Ph-C), 124.20 (4C, Ph-C), 145.70 (4C, Ph-C),
124.20 (4C, Ph-C), 114.10 (8C, Ph-C), 127.10 (8C, Ph-C),
139.20 (4C, Ph-C), 189.01 (4C, 4 ꢂ C¼¼O); ms: (5 kV, fd) m/z
(%) 1195 (100). Anal. Calcd. for C78H74N4O8: C, 78.37; H,
6.24; N, 4.69. Found: C, 78.23; H, 6.12; N, 4.54.
tassium bromide): 1648, 1599, 1340, 1255, 1164, 812 cmꢀ1
;
(2E,20E,200E,2000E,20000E)-1,10,100,1000,10000-[1,2,3,4,5-Benzene-
pentaylpentakis(methyleneoxy-4,1-phenylene)]pentakis{3-[4-
(dimethylamino)phenyl]-2-propen-1-one} (2d). This compound
was obtained as red solid (0.35 g, 20%), mp 205ꢁC (decompo-
sition); IR (potassium bromide): 1661, 1598, 1505, 1371,
1H NMR (deuteriodimethylsulfoxide-d6): d 2.89 (s, 24H, CH3),
5.02 (s, 8H, 4 ꢂ OCH2), 6.84 (d, 8H, Ph-H), 7.34 (s, 2H, cen-
tral-Ph-H), 7.40 (d, 8H, Ph-H), 3.69 (dd, 8H, ACH2A), 5.04
(m, 4H, ACHA), 7.01 (d, 8H, Ph-H), 6.71 (d, 8H, Ph-H), 6.92
(m, 20H, Ph-H); 13C NMR (deuteriodimethylsulfoxide-d6): d
40.99 (8C, CH3), 69.10 (4C, 4 ꢂ OCH2), 112.90 (8C, Ph-C),
125.67 (4C, Ph-C), 114.12 (2C, central-Ph-C), 129.09 (4C,
central-Ph-C), 130.63 (8C, Ph-C), 164.12 (4C, Ph-C), 152.29
(4C, Ph-C), 42.28 (4C, ACH2A), 52.29 (4C, ACHA), 124.84
(4C, Ph-C), 114.40 (8C, Ph-C), 128.79 (8C, Ph-C), 139.74
(4C, Ph-C), 136.73 (4C, Ph-C), 113.60, 130.63, 130.84 (20C,
Ph-C); ms: (5 kV, fd) m/z (%) 1556 (100). Anal. Calcd. For
C102H98N12O4: C, 78.74; H, 6.35; N, 10.80. Found: C, 78.66;
H, 6.28; N, 10.69.
1
1231, 1165, 824 cmꢀ1; H NMR (deuteriochloroform): d 3.04
(s, 30H, CH3), 5.19 (s, 10H, 5 ꢂ OCH2), 6.87 (d, 10H, Ph-H),
7.40 (s, 1H, central-Ph-H), 7.83 (d, 10H, Ph-H), 7.66 (d, 5H,
3J11–12 ¼ 16 Hz, Ph-H), 7.72 (d, 5H, Ph-H), 6.82 (d, 10H, Ph-
H), 6.67 (d, 10H, Ph-H); 13C NMR (deuteriochloroform): d
40.00 (10C, CH3), 66.70 (5C, 5 ꢂ OCH2), 114.41 (10C, Ph-
C), 132.00 (5C, Ph-C), 114.19 (1C, central-Ph-C), 122.40–
125.14 (5C, central-Ph-C), 130.79 (10C, Ph-C), 161.70 (5C,
Ph-C), 122.30 (5C, Ph-C), 143.00 (5C, Ph-C), 121.20 (5C, Ph-
C), 114.10 (10C, Ph-C), 128.60 (10C, Ph-C), 143.00 (5C, Ph-
C), 190.76 (5C, 5 ꢂ C¼¼O); ms: (5 kV, fd) m/z (%) 1475
(100). Anal. Calcd. for C96H91N5O10: C, 78.18; H, 6.22; N,
4.75. Found: C, 78.06; H, 6.15; N, 4.68.
General procedure for the preparation of Multi arm pyr-
azolines (3a, c) and pyrazoles (4a, c). Phenylhydrazine (0.43
g, 4 mmol) in methanol (1.0 mL) was added dropwise at 0ꢁC
under nitrogen atmosphere to a solution of (0.31 g, 0.50
mmol) enone 2a or (0.30, 0.25 mmol) enone 2c respectively in
dry methanol (20 mL). The addition was completed within 5 h
after which the mixture was left stirring for about 30 h. The
reaction was followed by TLC in (40% toluene:60% ethyl ace-
tate) until completion. The solvent was evaporated under vac-
uum and the residual solid was purified by column chromatog-
raphy using (40% toluene:60% ethyl acetate) as eluant to yield
the pyrazolines 3a, c which already contains some autoxidation
product of pyrazoles 4a, c. The regular oxidation of pyrazo-
lines 3a, c to the corresponding pyrazoles 4a, c was achieved
by evaporating methanol and dissolving the residual solid in
boiling benzene (3.0 mL) then (0.09 g, 0.4 mmol) 2,3-
dichloro-5,6-dicyano-1,4-benzoquenone was added slowly with
stirring. After 1–2 h, the products were purified by column
chromatography using (50% toluene:50% ethyl acetate) as the
eluant for the compounds.
3,30-[1,3-Benzenediylbis(methyleneoxy-4,1-phenyl-ene)]bis
{5-[4-(dimethylamino)phenyl]-1-phenylpyrazol-3-yl} (4a). This
compound was obtained as dark brown solid (0.30 g, 75%),
mp 135–137ꢁC; IR (potassium bromide): 1669, 1599, 1255,
1213, 811 cmꢀ1 1H NMR (deuteriochloroform): d 2.92 (s,
;
12H, CH3), 5.11 (s, 4H, 2 ꢂ OCH2), 6.97 (d, 4H, 7-H), 7.40
(m, 3H, central-Ph-H), 7.27 (s, 1H, central-Ph-H), 7.54 (d, 4H,
Ph-H), 7.09 (s, 2H, Pyrazol-H), 7.38 (d, 4H, Ph-H), 6.97 (d,
4H, Ph-H), 7.14 (m, 10H, Ph-H); 13C NMR (deuteriochloro-
form): d 40.35 (4C, CH3), 63.14 (2C, 2 ꢂ OCH2), 114.98 (4C,
Ph-C), 130.30 (2C, Ph-C), 142.16 (2C, central-Ph-C), 129.58
(2C, central-Ph-C), 130.37 (1C, central-Ph-C), 130.63 (4C, Ph-
C), 127.10 (1C, central-Ph-C), 161.90 (2C, Ph-C), 159.40 (2C,
Ph-C), 105.35 (2C, Pyrazol-C), 142.16 (2C, Pyrazol-C), 125.34
(2C, Ph-C), 114.56 (4C, Ph-C), 128.82 (4C, Ph-C), 140.90
(2C, Ph-C), 139.83 (2C, Ph-C), 113.30, 127.19, 129.89 (10C,
Ph-C); ms: (5kV, fd) m/z (%) 813 (100). Anal. Calcd. For
C54H48N6O2: C, 79.78; H, 5.95; N, 10.34. Found: C, 79.64; H,
5.88; N, 10.31.
3,30,300,3000-[1,2,4,5-Benzenetetrayltetrakis(methyleneoxy-4,1-
phenyl-ene)]pentakis{5-[4-(dimethylamino)phenyl]-1-phenyl-
pyrazol-3-yl} (4c). This compound was obtained as dark
brown solid (0.17 g, 43%), mp 190ꢁC (decomposition); IR
Journal of Heterocyclic Chemistry
DOI 10.1002/jhet