Chemical Papers
and were uncorrected. IR spectra were recorded on a JASCO
FT-IR 6100 using KBr disk (JASCO, Japan). NMR spectra
were measured with a Varian Mercury NMR 300 MHz spec-
trometer. 1H- and 13C NMR spectra were recorded with tri-
methylsilane as internal standard in DMSO. Chemical shifts
(δ) are given in ppm. The mass spectra were measured on a
Shimadzu GMMS-QP-1000 EX mass spectrometer at 70 eV.
Elemental analyses were carried out at the Microanalysis
Laboratory, Cairo University, Cairo, Egypt. The purity of all
new compounds was verifed by thin-layer chromatography
(TLC): Merck 0.2 mm silica gel 60 F254 analytic aluminum
plates, microchemical analysis (C/H/N) and spectroscopy.
The starting compound 2 was prepared according to the
reported procedures (Li et al. 2012).
142.9, 136.1, 130.4, 128.7, 128.3, 126.5, 126.5, 122.7 (C-
Ph & C-Ar), 143.8 (2CH = CHPh), 120.5 (2CH = CHPh),
9.7 (2CH3).
Synthesis of 1,1′‑(3,3′‑(1,1′‑(1,4‑phenylene)
bis(5‑methyl‑1H‑1,2,3‑triazole‑4,1‑diyl))bis(5‑phe‑
nyl‑1H‑pyrazole‑3,1(4H,5H)‑diyl))diethanone (5)
To a solution of bis-chalcone 4 (1 mmol, 0.5 g) in glacial
acetic acid 10 mL, hydrazine hydrate 80% (8 mmol, 0.26 g)
was added. The reaction mixture was refuxed for≈6 h, after
the completion of the reaction (TLC). The reaction mixture
was left to cool down, and the formed solid product was
fltered and washed with ethanol.
Yield 0.5 g (81%). light gray crystal, mp. 270–272 °C
Synthesis
1
(EtOH/DMF). IR: υmax/cm−1: 1694 (2C = O). H NMR
(DMSO) δH (ppm) (300 MHz): 2.31 (6H, s, 2H3C-acetyl),
2.70 (6H, s, 2 H3C), 3.18, 3.24 (2H, dd, J = 4.3, 18.2 Hz,
2pyr.H-4trans), 4.00, 4.06 (2H, dd, J = 11.8, 18.2 Hz,
2pyr.H-4cis), 5.54, 5.58 (2H, dd, J=4.3, 11.7 Hz, 2pyr.H-
5), 7.21–7.38 (10H, m, 2H-Ph), 7.94 (4H, s, H-Ar). Mass
spectrum (EI, 70 eV), m/z (%): 612 [M]+ (46).
Synthesis of 1,1′‑(1,1′‑(1,4‑Phenylene)
bis(5‑methyl‑1H‑1,2,3‑triazole‑4,1‑diyl))diethanone (3)
A mixture of potassium carbonate (50 mmol, 7 g), 1,4-diazi-
dobenzene (12.5 mmol, 2 g) and pentan-2,4-dione (27 mmol,
2.7 g) in absolute ethanol (50 mL) was heated in water bath
for 2 h (TLC). The product mixture was allowed to cool
down to room temperature; the reaction mixture was poured
on ice water. The solid product was fltered of and washed
with water.
Synthesis of 1,4‑bis(5‑methyl‑4‑(5‑phenyl‑4,5‑dihy‑
dro‑1H‑pyrazol‑3‑yl)‑1H‑1,2,3‑triazol‑1‑yl)benzene (6)
Yield 3.3 g (81%). Brown substance, mp. 262–264 °C
To a solution of bis-chalcone 4 (4 mmol, 2 g) in [ethanol
(10 mL), DMF (10 mL)] hydrazine hydrate 80% (32 mmol,
1 g) was added. The reaction mixture was refuxed for≈6 h
(TLC). The reaction mixture was left to cool down to r.t.,
and the formed solid product was fltered and washed with
ethanol.
(EtOH/DMF). IR: υmax/cm−1: 1688 (2C = O). H NMR
1
(DMSO) δH (ppm) (300 MHz): 2.60 (6H, s, 2H3C-acetyl),
2.65 (6H, s, 2H3C), 7.94 (4H, s, H-Ar). 13C NMR (DMSO)
δC (ppm) (75 MHz): 193.1 (2C = O), 142.9, 137.9, 135.9,
126.6 (C-Ar), 27.4 (2CH3-acetyl), 9.6 (2CH3). Mass spec-
trum (EI, 70 eV), m/z (%): 325 [M+1]+ (4), 324 [M] + (42).
Yield 1.7 g (80%). Pale yellow crystal, mp. 248–250 °C
1
(EtOH/DMF). IR: υmax/cm−1: 3425-3327 (br, 2NH). H
NMR (DMSO) δH (ppm) (300 MHz): 2.72 (6H, s, 2H3C),
3.31, 3.39 (2H, dd, J=6.4, J=19.5 Hz, 2pyr.H-4trans), 3.67,
3.74 (2H, dd, J=11.4, J=19.5 Hz, 2pyr.H-4cis), 4.95 (2H,
t, 2pyr.H-5), 5.41 (1H, s, HN), 7.27–7.39 (10H, m, 2H-Ph),
7.75 (4H, s, H-Ar), 10.03 (1H, s, NH). 13C NMR (DMSO-
TFA) δC (ppm) (75 MHz): 142.8, 137.9, 137.1, 136.1, 134.8,
128.6, 128.2, 127.2, 126.4 (C-Ph & C-Ar), 61.0 (2CH-Ph),
42.0 (2CH2-pyrazoline), 9.9 (2CH3). Mass spectrum (EI,
70 eV), m/z (%): 528 [M]+ (7), 104 (100).
Synthesis of 1,1′‑(1,1′‑(1,4‑phenylene)
bis(5‑methyl‑1H‑1,2,3‑triazole‑4,1‑diyl))bis(3‑phenyl‑
prop‑2‑en‑1‑one) (4)
To a stirred solution of bis-ketone 3 (9 mmol, 3 g) dis-
solved in dioxane (30 mL), a solution of sodium hydroxide
(20 mmol, 0.8 g) dissolved in water (10 mL) was added
in one portion. Benzaldehyde (18 mmol, 1.9 g) was added
slowly to the reaction mixture. The reaction mixture was
stirred at r.t. overnight. The residue product was fltrated of,
and washed with water to aford 4.
General synthesis of (7)
Yield 3.2 g (71%). Brown substance, mp. > 300 °C
(EtOH/DMF). IR: υmax/cm−1: 1665 (2C=O), 1599 (2C=C).
1H NMR (DMSO) δH (ppm) (300 MHz): 2.88 (6H, s, 2H3C),
7.48–7.50 (10H, m, 2H-Ph), 7.86 (2H, d, J=16.2 Hz, 2HC);
7.95 (4H, s, H-Ar), 8.05 (2H, d, J = 16.2 Hz, 2HC). 13C
NMR (DMSO-TFA) δC (ppm) (75 MHz): 183.2 (2C = S),
To a solution of compound 6 (1 mmol, 0.5 g) in DMF
(15 mL), appropriate isothiocyanate (2.1 mmol) [methyl-
(0.15 g) or benzyl isothiocyanate (0.3 g)] was added, the
reaction mixture was heated under refux for≈8–10 h (TLC).
1 3