1438
Q. Shao, H. Liu, T.-T. Wang, and H.-P. Zeng
Vol 48
internal standard. Infrared (IR) spectra were obtained on a
Bruke Tensor 27 spectrometer. Low-resolution mass spectra
(MS) were recorded on an Esquire HCT plus. The mode of
ionization used was atmospheric pressure chemical ionization
(APCI) with methanol or THF as solvent. High resolution
mass spectrometer [HRMS (FAB)] was recorded on MAT
95XP, Thermo.
(400 MHz, CDCl3) d(ppm): 7.69 (d, J ¼ 15.7Hz, 2H), 7.63 (s,
4H), 7.29 (d, J ¼15.7Hz, 2H), 7.08 (s, 2H), 2.72 (s, 6H), 2.45
(s, 6H); 13C NMR (101 MHz, CDCl3) d:15.0, 16.0, 125.8,
125.9, 128.8, 135.4, 136.5, 136.8, 142.3, 147.6, 186.0; APCI-
MS (m/z): 406.5.
1-(2,5-Dimethylfuran-3-yl)-3-(4-((E)-3-(2,5-dimethylthiophen-
3-yl)-3-oxoprop-1-enyl phenyl)prop-2-en-1-one) (2c). Light yel-
low solid, yield 3.4 g, 86%; m.p. 163–165ꢀC; IR (KBr) v:
2915, 1653, 1587, 1473, 1401, 1223, 1133, 972, 816, 709
X-ray diffraction analysis. All diffraction data were col-
lected on a Bruker Smart 1000 CCD diffractometer with
1
graphite-monochromated Mo Ka radiation (k ¼ 0.71073 A) at
cmꢁ1; H NMR (400 MHz, CDCl3) d(ppm): 7.70 (d, J ¼ 15.7
˚
room temperature using the program SMART and processed
by SAINTþ. Space groups of these compounds were deter-
mined from systematic absences and further justified by the
refinement results. In all cases, the structures were solved by
direct methods and refined using full-matrix least-squares/dif-
ference Fourier techniques using SHELX. All nonhydrogen
atoms were refined with anisotropic displacement parameters.
All hydrogen atoms of the ligands were placed at idealized
positions and refined as riding atoms with the relative isotropic
parameters of the heavy atoms to which they are attached. The
H atoms of water located from the difference Fourier map in
the final stage of refinement.
Hz, 1 H), 7.69 (d, J ¼ 15.7 Hz, 1 H), 7.63 (s, 4 H), 7.31 (d, J
¼ 15.8 Hz, 1H), 7.21 (d, J ¼ 15.8 Hz, 1H), 7.09 (s, 1H), 6.34
(s, 1 H), 2.72 (s, 3 H), 2.62 (s, 3H), 2.45 (s, 3H), 2.30 (s, 3H);
13C NMR (400 MHz, CDCl3) d: 13.3, 14.5, 15.1, 16.0, 105.6,
125.0, 125.7, 125.8, 128.8, 135.4, 136.7, 141.6, 142.3, 150.1,
158.2, 185.6, 186.0; APCI-MS (m/z): 391.0.
General procedure for 3a–3e. After cooled to ꢁ25ꢀC, to
a round-bottom flask, 3-acetyl-2,5-dimethylfuran or 3-ace-
tyl-2,5-dimethylthiophene (0.6 mmol) and 0.3 mL of LDA
(2M) were added to 2.5 mL of dry THF. The yellow solu-
tion was stirred for 10 min and compounds 2a, 2b, and 2c
(0.12 mmol) were dissolved in dry THF (2 mL), and then
added dropwise to the flask under Argon. After kept for 15
min at the temperature below ꢁ25ꢀC, the reaction mixture
was stirred at room temperature for 0.5–2 h. When the reac-
tion was completed (monitored by TLC), the mixture was
quenched with water, and pH was adjusted to 5–6 with 1M
HCl. The solvent was removed by rotary evaporation.
Dichloromethane (3 ꢃ 20 mL) was added to the residue to
give a solid/liquid mixture. The mixture was filtered and the
solid was thoroughly washed with dichloromethane (3 ꢃ 10
mL). The combined filtrates were concentrated in vacuum
and the residue was purified by flash column chromatogra-
phy and recrystallization. With this method, compounds 3a–
3e were prepared.
4-(3-(2,5-Dimethylthiophen-3-yl)-3-oxoprop-1-enyl) benz-
aldehyde (1). A mixture of terephthalaldehyde (1.34 g, 10
mmol), 0.1mol/L NaOH (20 mL), and 3-acetyl-2,5-di-methyl-
thiophene (1.8 g, 12 mmol) was refluxed for 12 h. Water was
added (10 mL) and pH was adjusted to 5–6 with 1M HCl. The
yellow mixture was filtered, washed with water and cold etha-
nol and then crystallized from a mixture of CH2Cl2 and etha-
nol. A light yellow powder was obtained in 85% yield; m.p.
137–139ꢀC; IR (KBr) v: 2915, 1692, 1656, 1600, 1564, 1474,
1228, 1210, 1164, 1136, 988, 818, 732 cmꢁ1 1H NMR (400
;
MHz, CDCl3) d(ppm): 10.04 (s, 1H), 7.92 (d, J ¼ 8.2Hz, 2H),
7.76 (d, J ¼ 8.3Hz, 2H), 7.72 (d, J ¼15.8Hz, 1H), 7.39 (d, J
¼15.7Hz, 1H), 7.10 (s, 1H), 2.73 (s, 3H), 2.46 (s, 3H); 13C
NMR (101 MHz, CDCl3) d: 15.0, 16.0, 112.5, 125.7, 127.6,
128.7, 130.2, 135.6, 136.2, 137.0, 140.8, 141.5, 148.3, 185.5,
191.5; APCI-MS (m/z): 270.3.
3,30-(1,4-Phenylene)bis(1,5-bis(2,5-dimethylfuran-3-yl)pen-
tane-1,5-dione) (3a). White crystal, yield 70%; m.p. 144–
146ꢀC; IR (KBr) v: 2922, 1676, 1566, 1005, 948, 844 cmꢁ1
;
General procedure for 2a–2c. Terephthalaldehyde or 1
(10 mmol) and 3-acetyl-2,5-dimethylfuran (22 mmol) were
mixed together in a round-bottom flask with 30 mL ethanol,
followed by the addition of 10% aq.NaOH (3 mL). The
mixture was stirred for the appropriate time (0.5–1 h) at
room temperature. After completion of the reaction indicated
by TLC, water was added (10 mL), and the pH adjusted to
3–4 with 1M HCl; the yellow mixture was filtered, washed
with water and cold ethanol, and crystallized from a mixture
of CH2Cl2 and ethanol.
1H NMR (400 MHz, CDCl3) d (ppm): 7.16 (s, 4H), 6.22 (s,
4H), 3.82–3.92 (m, 2H), 2.91–3.11 (m, 8H), 2.46 (s, 12H),
2.23 (s, 12H); 13C NMR (101 MHz, CDCl3) d: 13.2, 14.3,
36.0, 47.3, 105.6, 121.6, 127.5, 127.7, 149.8, 147.0, 157.0,
195.0; APCI-MS (m/z): 651.1. HRMS (FAB) calculated for
C40H43O8 ([MþHþ]): 651.2952. Found: 651.2951.
3,30-(1,4-Phenylene)bis(1,5-bis(2,5-dimethylthiophen-3-yl)pen-
tane-1,5-dione) (3b). Colorless crystal, yield 68.5%; m.p. 180–
182ꢀC; IR (KBr) v: 2916, 1660, 1546, 1476, 1365, 1216, 1130,
826 cmꢁ1 1H NMR (400 MHz, CDCl3) d (ppm): 2.38 (s,
;
3,30-(1,4-Phenylene)bis(1-(2,5-dimethylfuran-3-yl)prop-2-en-
1-one) (2a). Yellow crystal, yield 3.0 g, 80%; m.p. 182–
183ꢀC; IR (KBr) v : 2912, 1656, 1581, 1397, 1226, 1178,
12H), 2.55 (s, 12H), 3.04–3.21 (m, 8H), 3.84–3.92 (m, 2H),
6.99 (s, 4H), 7.15 (s, 4H); 13C NMR (101 MHz, CDCl3) d:
15.0, 16.0, 36.3, 47.9, 126.0, 127.5, 135.0, 135.5, 142.2, 147.0,
194.7; APCI-MS (m/z): 714.7.
1011, 973, 822, 711,506 cmꢁ1 1H NMR (400 MHz, CDCl3)
;
d(ppm): 7.70 (d, J ¼ 15.8 Hz, 2H), 7.62 (s, 4H), 7.21 (d, J ¼
15.7 Hz, 2H), 6.34 (s, 2H), 2.62 (s, 6H), 2.30 (s, 6H); 13C
NMR (101 MHz, CDCl3) d: 13.3, 14.5, 105.6, 122.4, 125.0,
128.8, 136.7, 141.6, 150.1, 158.2, 185.6; APCI-MS (m/z):
374.0.
The single crystal of 3b was obtained in dichloromethane
and ethyl acetate solution (1:2). The crystal structure has been
registered at the Cambridge Crystallographic Data Centre and
allocated the deposition number CCDC 768841. C40H42O4S4,
˚
Mr
¼
715.02, space group Pbca,
a
¼15.640(3) A,
b
3,30-(1,4-Phenylene)bis(1-(2,5-dimethylthiophen-3-yl)prop-
2-en-1-one) (2b). Light yellow solid, yield 2.94 g, 92%; m.p.
185–186ꢀC; IR (KBr) v: 2915, 1653, 1592, 1479, 1358, 1331,
¼10.139(2) A, c ¼ 23.730(5) A, V ¼ 3763.0(13) A ꢁ3. Z ¼ 4,
Dx ¼ 1.262 g/cmꢁ3, F (000) ¼1512, T ¼ 293 K, R (reflec-
tions) ¼ 0.0415(2493), wR2 (reflections) ¼ 0.1157(3385), and
ymax ¼ 25.200.
˚
˚
˚
1224, 1196, 1138, 977, 815, 719, 679, 490 cmꢁ1 1H NMR
;
Journal of Heterocyclic Chemistry
DOI 10.1002/jhet