Synthesis of new 3,3′-(1,4-phenylene)bis(1,5-diones) derivatives

Article abstract of DOI:10.1002/jhet.737

Several 3,3′-(1,4-phenylene)bis(1,5-diones) and their chalcone precursors have been prepared in good to excellent yield via aldol addition and Michael addition starting from 3-acetyl-2,5-dimethylfuran or 3-acetyl-2,5-dimethyl-thiophene with terephthalalde

Full text of DOI:10.1002/jhet.737

1434
Synthesis of New 3,30-(1,4-Phenylene)bis(1,5-Diones) Derivatives
Vol 48
Qiang Shao, Hui Liu, Ting-Ting Wang, and He-Ping Zeng*
Institute of Functional Molecule, School of Chemistry and Chemical Engineering, South China
University of Technology, Guangzhou 510641, People’s Republic of China
*E-mail: zenghp@scnu.edu.cn
Received July 25, 2010
DOI 10.1002/jhet.737
Published online 23 August 2011 in Wiley Online Library (wileyonlinelibrary.com).
Several 3,30-(1,4-phenylene)bis(1,5-diones) and their chalcone precursors have been prepared in good
to excellent yield via aldol addition and Michael addition starting from 3-acetyl-2,5-dimethylfuran or 3-
acetyl-2,5-dimethyl-thiophene with terephthalaldehyde in the presence of appropriate base NaOH or lith-
ium diisopropylamide. The kind and amount of alkali played a critical role in improving the reaction
rates and yields of the products.
J. Heterocyclic Chem., 48, 1434 (2011).
INTRODUCTION
acetyl-2,5-dimethyl thiophene and terephthalaldehyde, as
shown in Scheme 1. To improve the diversity of tetrake-
tones, the tandem addition and humdrum reactants [11],
which always lead to poor diversities, were avoided and a
new chalcone 2c was synthesized as precursor. Unsym-
metrical intermediates can reduce photochromic molecu-
lar symmetry and broaden the absorption spectrum, which
are very useful for multifrequency optical memories and
displays [17,18].
3,30-(1,4-Phenylene)bis(1,5-diones) as versatile syn-
thetic intermediates are important in the synthesis of pho-
toluminescence [1–3], biosensors [4], and photochromism
materials [5–8]. Li and Tian [9] synthesized hexatriene
compounds provided by the 1,2-dithienylethene structure,
which showed significant photochromic property. The tar-
get a, b-unsaturated compounds could also give rise to
other heterocyclic compounds such as pyridines. Higuchi
and coworkers [10] reported that Ru(II)-based metallo-
supramolecular coordination polymers were potential
photoluminescence device. The ligand terpyridines,
which had rich coordination chemistry and generally dis-
played a high binding affinity to many metal ions, were
obtained from the intermediate tetraketones. Thus, there
is significant interest in the development of new com-
pounds with tetraketones units. In the literature, we
noticed that arylene diketones were prepared from tereph-
thalaldehyde, isophthalaldehyde, 2,5-thiophenedicarbox-
aldehydes, and alkylphenyl ketones in the presence of al-
kali in ethanol [11–14]. Herein, we report the syntheses of
a series of 3,30-(1, 4-phenylene)bis(1,5-diones) deriva-
tives, which were well known to possess various biologi-
cal activities [15,16] from 3-acetyl-2,5-dimethylfuran/3-
RESULTS AND DISCUSSION
We envisioned the alkylation through the direct addi-
tion reactions of both 3-acetyl-2,5-dimethylfuran/3-ace-
tyl-2,5-dimethylthiophene with terephthalaldehyde fol-
lowing ref. 14. However, the reaction occurred in aque-
ous sodium hydroxide (aq.NaOH) gave low yields.
Maybe, it was attributed to poor activity and solubility
of the reagents in alcohols. Both reactions carried in tet-
rahydrofuran (THF) and N,N-dimethylformamide (DMF)
only gave byproducts. A flexible and diversified prepara-
tion of 3,30-(1,4-phenylene)bis(1,5-diones) derivatives
were carried out by convenient aldol addition and Mi-
chael addition.
C
V
2011 HeteroCorporation

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Synthesis of New 3,30-(1,4-Phenylene)bis(1,5-Diones) Derivatives
1435
Scheme 1
The requisite chalcones 2a, 2b, and 2c were prepared
from the corresponding commercially available 3-acetyl-
2,5-dimethylfuran or 3-acetyl-2,5-dimethylthiophene
and terephthalaldehyde. Directly using
a
catalytic
amount of 10% aq.NaOH, the desired chalcones 2a and
2b were obtained in 80 and 92% yields. Typically,
Table 1
Reaction conditions for the Michael addition of 3-acetyl-2,5-dimethylthiophene and 2ba.
.
Entries
Base
Solvent
T (ꢀC)
Time (h)
Yieldb
f
1
2
NaOH
aq.NaOHc
_
r.t.
r.t.
2
48
48
100
100
20
8
0
0
C2H5OH
C2H5OH
C2H5OH/CH2Cl2
C2H5OH/Toluenee
C2H5OH/THF
DMF
e
3
4
aq.NaOHa
0
0
aq.NaOHa
aq.NaOHa
aq.NaOH
r.t.
r.t.
r.t.
d
5
6
0
7
7
NaH(2.0 equiv)
NaH(2.0 equiv)
NaH(2.4 equiv)
NaH(2.0 equiv)
LDA(2.4 equiv)
LDA(2.4 equiv)
LDA(4.8 equiv)
LDA(4.8 equiv)
LDA(4.8 equiv)
LDA(6.0 equiv)
LDA(4.0 equiv)
r.t.
r.t.
r.t.
0
17
11
Trace
Trace
0
8
9
DMF
DMF
16
8
10
11
12
13
14
15
16
17
DMF
THF
24
6
ꢁ78 to ꢁ40
ꢁ78 to ꢁ40
ꢁ78 to ꢁ40
ꢁ25
THF
THF
20
20
2
0
Trace
68.5
60
60
62
THF
THF
THF
THF
ꢁ10
2
2
ꢁ25
ꢁ25
2
a All products were characterized by 1H, 13C NMR spectroscopy.
b Isolated yields.
c Reaction carried out under three different concentrations: 1, 10, and 50%.
d Using TBAI as the phase transfer catalyst.
e Reaction carried out under three different temperatures: r.t. (room temperature), 60ꢀC, and 80ꢀC.
f Without using any solvent.
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Q. Shao, H. Liu, T.-T. Wang, and H.-P. Zeng
Vol 48
Figure 1. The molecular structure and crystal packing of compound 3b.
terephthalaldehyde and 3-acetyl-2,5-dimethylthiophene
were stirred in the presence of 0.1mol/L NaOH in etha-
nol to obtain mono-additive intermediate 1, then treated
with 3-acetyl-2,5-dimethylfuran and sodium hydroxide
in ethanol to afford pale yellow powder 2c. These con-
ditions provided the expected products (1, 2c) in well-
pleasing NMR yields, 85 and 90%.
benzene C atom (C14) interacted with a carbonyl group
O atom (O1) of an adjacent molecule through CAHꢂꢂꢂO
˚
hydrogen bond [2.561(2) A], and one thiophene C atom
(C8) interacted with a carbonyl group O atom (O2) of
an adjacent molecule through CAHꢂꢂꢂO hydrogen bond
˚
[2.528 (3) A] to form a three-dimensional supramolecu-
lar array.
Table 1 showed the reaction conditions for the Mi-
chael addition of 3-acetyl-2,5-dimethylthiophene and 2b,
which was investigated by various parameters such as
base, solvent, and time. The reaction was initially per-
formed by dissolving and stirring the reactants in etha-
nol using aq.NaOH (1, 10, and 50%) without any cata-
lyst. But even after stirring for 48 h, the reaction was
incomplete and only byproducts were obtained (entries 2
and 3). Addition of the phase-transfer catalyst tetra-n-
butylammonium iodide (TBAI) had no improvement in
the occurrence of reaction (entries 4 and 5). Although
the products could be obtained by adding THF, in which
chalcones were well dissolved, the yield was only 7%
because of the self-reaction of chalcone in the presence
of NaOH (Table 1 entry 6). To improve the reaction
efficiency, the effect of organic base was then investi-
gated. It was found that lithium diisopropylamide
(LDA) gave the best result, whereas potassium tert-but-
oxide and NaH were less active or ineffective (entries
7–17).
A variety of 3,30-(1, 4-phenylene)bis(1,5-diones) have
been prepared from the corresponding chalcones under
optimized conditions described above. The results of
these tetraketones are summarized in Table 2. The new
chemistry provides the products in good to excellent
yields.
In conclusion, a convenient and efficient method for
preparing the important intermediate 3,30-(1, 4-phenyle-
ne)bis(1,5-diones) derivatives and their chalcones pre-
cursors with the proper use of NaOH or LDA has been
described. The kind and amount of alkali played a criti-
cal role in improving the reaction rates and yields of the
products. The main features of the present method are:
(1) the procedure is operationally simple using readily
available chemicals and can provide various symmetri-
cal 1,5-diketones in moderate to high yields of up to
70%; (2) employment of LDA as base is effective in
improving the chemical yield in some cases; (3) unsym-
metrical 1,5-diketones are also able to be prepared by
the present method. Transformation of tetraketones into
a new class of photoelectric compounds is in progress.
The reactions proceeded very smoothly and were
completed within 2 h (entries 14–17), showing one
major single spot on thin layer chromatography (TLC).
The products were isolated through chromatography af-
ter quenched with water. The yields of the products
were between 60 and 68%. The molecular structure of
compound 3b was also confirmed by X-ray diffraction
analysis, as shown in Figure 1.
EXPERIMENTAL
Terephthalaldehyde and NaH were purchased from Aladdin
Reagent Company. 3-Acetyl-2,5-dimethylfuran and 3-acetyl-
2,5-dimethylthiophene were purchased from Alfa Aesar, LDA
2M sol. in THF/n-heptane/ethylbenzene from Acros Organics.
In the crystal structure of compound 3b, C40H42O4S4,
the dihedral angles between the tolyl ring and thiophene
ring were 27.5(3) and 74.8(4)ꢀ, respectively. The two
thiophene rings in a ‘‘diagonal line’’ were parallel. One
˚
Toluene and DMF were dried over 4 A molecular sieves
before use. THF was freshly distilled from sodium/benzophe-
none under a nitrogen atmosphere before use. All other sol-
vents and reagents were purified by standard techniques or
Journal of Heterocyclic Chemistry
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November 2011
Synthesis of New 3,30-(1,4-Phenylene)bis(1,5-Diones) Derivatives
1437
Table 2
Synthesis of 3,30-(1,4-phenylene)bis(1,5-diones) (3a–3e)a.
Entries
1
Reagent
Product
Time (h)
1
Yield(%)b
70
2
2
68.5
3
1.5
59
4
2
65
5
2
61
a Reaction was conducted at ꢁ25ꢀC.
b Isolated yields.
used as supplied. TLC was carried out using commercially
prepared 100–400 mesh silica gel plates (GF254) that were
visualized by irradiation (254 nm) and column chromatography
was carried out using silica gel (200–300 mesh). Melting
points (m.p.) were determined with an X4 melting point
inspection instrument and the thermometer was uncorrected.
NMR spectra (1H and 13C, respectively) were measured in
deuterochloroform (CDCl3) on 400 MHz (operating frequen-
1
cies: H, 400.13 MHz; 13C, 100.61 MHz) FT spectrometers at
ambient temperature with tetramethylsilane (TMS) as an
Journal of Heterocyclic Chemistry
DOI 10.1002/jhet

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

November 2011
Synthesis of New 3,30-(1,4-Phenylene)bis(1,5-Diones) Derivatives
1439
3,30-(1,4-Phenylene)bis(1-(2,5-dimethylfuran-3-yl)-5-(2,5-dime-
thylthiophen-3-yl)pentane-1,5-dione) (3c). White crystal, yield
59%; m.p. 138––140ꢀC; IR (KBr) v: 2919, 1661, 1566, 1481,
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1364, 1226, 1136, 1003, 828, 665 cmꢁ1; H NMR (400 MHz,
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3.82–3.92 (m, 2H), 2.92–3.23 (m, 8H), 2.54 (s, 6H), 2.46 (s,
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3.22 (m, 8H), 2.54 (s, 3H), 2.46 (s, 9H), 2.39 (s, 3H), 2.23 (s,
9H); 13C NMR (101 MHz,CDCl3) d: 13.2, 14.3, 15.0, 15.9,
35.9, 36.1, 47.3, 47.4, 47.9, 105.6, 121.5, 126.0, 127.4, 127.5,
135.0, 135.5, 142.2, 147.3, 149.8, 157.0, 194.7, 195.0; APCI-
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1136, 820 cmꢁ1 1H NMR (400 MHz, CDCl3) d (ppm): 7.15
;
(s, 4H), 6.99 (s, 3H), 6.21 (s, 1H), 3.83–3.93 (m, 2H), 2.93–
3.23 (m, 8H), 2.55 (s, 9H), 2.46 (s, 3H), 2.39 (s, 9H), 2.23 (s,
3H); 13C NMR (101 MHz, CDCl3) d: 13.2, 14.3, 15.0, 15.9,
36.1, 36.3, 47.4, 47.8, 47.9, 105.6, 121.6, 126.0, 127.4, 127.5,
135.0, 135.5, 142.2, 147.3, 149.8, 157.0, 194.7, 195.0; APCI-
MS (m/z): 699.0. HRMS (FAB) calculated for C40H43O5S3
([MþHþ]): 699.2267. Found: 699.226.
Acknowledgments. Financial support from the National Natu-
ral Science Foundation of China (grant numbers 21071054,
2008B010800030, and 2009B091300045) is gratefully
acknowledged.
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Journal of Heterocyclic Chemistry
DOI 10.1002/jhet