A highly efficient CuI nanoparticles-catalyzed synthesis of tetrahydrochromenediones and dihydropyrano[c]chromenediones under grinding

Article abstract of DOI:10.1515/znb-2015-0195

A concise and CuI nanoparticle-catalyzed synthesis of tetrahydrochromenediones and dihydropyrano[c]chromenediones under solvent-free grinding conditions via the three-component condensation reaction of Meldrum's acid, an aromatic aldehyde, and an active m

Full text of DOI:10.1515/znb-2015-0195

Z. Naturforsch. 2016; aop
Shahrzad Abdolmohammadi*, Reza Ghiasi and Sam Ahmadzadeh-Vatani
A highly efficient CuI nanoparticles-catalyzed
synthesis of tetrahydrochromenediones and
dihydropyrano[c]chromenediones under grinding
DOI 10.1515/znb-2015-0195
enhancers [25, 26], for the treatment of neurodegenerative
diseases, including Alzheimer’s disease [27] and schizo-
phrenia disorder [28].
Received November 26, 2015; accepted February 18, 2016
Abstract:AconciseandCuInanoparticle-catalyzedsynthe-
sis of tetrahydrochromenediones and dihydropyrano[c]-
chromenediones under solvent-free grinding conditions
via the three-component condensation reaction of
Meldrum’s acid, an aromatic aldehyde, and an active
methylene compound, including dimedone or 4-hydroxy-
coumarin, was developed. This new method gives desir-
able advantages such as simple reaction setup, very mild
reaction conditions, production of the desired products in
high yields without by-products, recyclability of the cata-
lyst, and environmentally benign procedure.
We have recently developed a series of heterocy-
clic syntheses using nanostructured catalysts [29–31].
Herein, we report a highly efficient and practical method
for the synthesis of 4-aryl-7,7-dimethyl-4,6,7,8-tetrahydro-
2H-chromene-2,5(3H)-diones (4a–g) and 4-aryl-3,4-dihy-
dro-2H,5H-pyrano[3,2-c]chromene-2,5-diones (6a–g) via a
condensation reaction of Meldrum’s acid, aromatic alde-
hydes, and active methylene compounds, including dime-
done or 4-hydroxycoumarin, catalyzed by CuI nanoparticles
(CuI NPs) under solvent-free grinding (Scheme 1). In view
of the above-mentioned useful properties of chromenes,
Keywords: CuI nanoparticles; dihydropyrano[c]chromen- various synthetic methods have been developed for the
ediones; environmentally benign procedure; solvent-free preparation of these compounds [32–36]. To the best of our
grinding; tetrahydrochromenediones.
knowledge, a synthesis of tetrahydrochromenediones and
dihydropyrano[c]chromenediones catalyzed by CuI NPs
has not been reported in the literature as yet.
1 Introduction
The utility of nanostructured metal salts as catalysts in
organic synthesis lies in their better properties compared
to the bulk size [1, 2]. Nanosized copper iodide is one reus-
able Lewis acid catalyst, which has revealed several cata-
lytic activities for the synthesis of organic compounds and
others [3–12].
Chromene is a prominent structural motif found in
various natural and nonnatural products, which have
been reported to show a wide spectrum of useful bio-
logical properties such as antioxidant [13, 14], anticancer
[15–18], antimicrobial [19–22], hypotensive [23], and local
anesthetic [24]. In addition, they can be used as cognitive
2 Results and discussion
To optimize the reaction condition, benzaldehyde (2a) was
chosen as the representative starting material in a typical
reaction with Meldrum’s acid (1) and dimedone (3) in the
presence of CuI NPs under grinding to synthesize the cor-
responding chromenedione 4a (Scheme 2 and Table 1).
Different amounts of catalyst were examined first.
After 15 min with 5, 10 and 15 mol% of CuI NPs, yields
of 38%, 92%, and 90%, respectively, were obtained. It is
important to note that in the absence of CuI NPs, only a
trace amount of product was found after 30 min (Table 1,
entries 1–4).
When the grinding time was increased from 10 to
15 min, the yield of product 4a was increased. However,
further increase of the grinding time to 20 min failed to
improve the yield of product 4a (Table 1, entries 3 and
5–6).
After the completion of the model reaction, the catalyst
was recovered from the reaction mixture by a procedure
*Corresponding author: Shahrzad Abdolmohammadi, Faculty of
Science, Department of Chemistry, Islamic Azad University, East
Tehran Branch, PO Box 33955-163, Tehran, Iran,
Tel.: +98-21-3359 4950, Fax: +98-21-3359 4332,
E-mail: s.abdolmohamadi@yahoo.com; s.abdolmohamadi@iauet.ac.ir
Reza Ghiasi and Sam Ahmadzadeh-Vatani: Faculty of Science,
Department of Chemistry, Islamic Azad University, East Tehran
Branch, PO Box 33955-163, Tehran, Iran
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ꢀꢀꢀꢁ
2ꢀ
ꢀS. Abdolmohammadi et al.: Synthesis of tetrahydrochromenediones and dihydropyrano[c]chromenediones
O
Ar
O
O
O
3
O
4
O
O
O
CuI NPs (10 mol%)
Grinding, r. t.
O
+
O
Ar
H
O
O
HO
1
2
O
Ar
O
5
O
O
6
Scheme 1:ꢀSynthetic routes to chromenediones 4a–g and pyrano[3,2-c]chromene-2,5-diones 6a–g.
Tavakoli et al. [37]. The X-ray powder diffraction (XRD)
pattern and the scanning electron microscope (SEM)
image of the synthesized CuI NPs have been presented
in a previously published article [38]. The XRD pattern
showed sharp peaks for CuI NPs matching with the
standard cubic structure of crystalline CuI (cubic space
H
O
2a
+
O
O
O
Grinding, r. t.
O
̅
group F43m, aꢀꢁ=ꢁꢀ6.0545 Å: JCPDS 82-2111). The SEM result
O
O
O
O
O
also showed that the CuI NPs were triangle-shaped with
a size range of 30–40 nm (see Abdolmohammadi and
Karimpour [38] for an SEM image of the thus prepared
CuI NPs).
1
3
4a
Scheme 2:ꢀOptimization of reaction conditions in the synthesis of
chromenedione 4a.
Different types of aromatic aldehydes carrying either
electron donating or withdrawing substituents and
dimedone or 4-hydroxycoumarin as active methylene
compounds with Meldrum’s acid as a model substrate
were then explored under the optimized reaction condi-
tions (Table 2), and high yields of desired products were
obtained.
According to the proposed mechanism (Scheme 3),
this catalytic protocol can be explained by a Knoevenagel-
Michael sequence reaction. CuI NP is an effective catalyst
for the formation of alkene 9, readily prepared in situ
from the Knoevenagel condensation of Meldrum’s acid 1
and aromatic aldehyde 2, which proceed via carbocation
7 and then intermediate 8. The enol form of dimedone 3
Table 1:ꢀEffect of different amounts of CuI NPs and grinding time on
the synthesis of chromenedione 4a.
Entry
CuI NPs (mol%)
Grinding time (min)
Yield (%)a
1
2
3
4
5
6
0
5
10
15
10
10
30
15
15
15
10
20
Trace
38
91
90
79
91
aIsolated yield.
described in the Experimental section and reused up to then adds to alkene 9 in a Michael-type addition to gen-
four times without significant loss of catalytic potential erate intermediate 10. The cyclization of 10 followed by
(product yields: 91%, 90%, 88%, and 85%, respectively).
the elimination of acetone gives product 4 after the decar-
The CuI NPs that were used as catalyst in this work boxylation of intermediate 11. The formation of pyrano-
were prepared by a literature procedure developed by chromenediones 6 can be explained analogously.
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ꢁꢀꢀꢀ
ꢂ3
S. Abdolmohammadi et al.: Synthesis of tetrahydrochromenediones and dihydropyrano[c]chromenedionesꢂ
Table 2:ꢀSynthesis of chromene-2,5(3H)-diones 4a–g and pyrano[3,2-c]chromene-2,5-diones 6a–g catalyzed by CuI NPs.
Productꢁ
Ar
ꢁ
Active methyleneꢁ
compound
Yield (%)a,b
ꢁ
ꢁ
M.p. (°C)
Observedꢁ
Literature
4a
4b
4c
4d
4e
4f
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
C6H5
2-Cl-C6H4
4-Cl-C6H4
ꢃ
ꢃ
ꢃ
3ꢃ
3ꢃ
3ꢃ
3ꢃ
3ꢃ
3ꢃ
3ꢃ
5ꢃ
5ꢃ
5ꢃ
5ꢃ
5ꢃ
5ꢃ
5ꢃ
91ꢃ
94ꢃ
95ꢃ
89ꢃ
94ꢃ
93ꢃ
96ꢃ
97ꢃ
98ꢃ
93ꢃ
96ꢃ
94ꢃ
93ꢃ
97ꢃ
101–103ꢃ
131–133ꢃ
156–158ꢃ
141–143ꢃ
182–184ꢃ
127–129ꢃ
163–165ꢃ
168–170ꢃ
210–212ꢃ
196–197ꢃ
196–198ꢃ
184–186ꢃ
146–147ꢃ
181–183ꢃ
99–101 [34]
134–135 [34]
160–161 [34]
4-(CH3)2N-C6H4ꢃ
138–140 [34]
3-HO-C6H4
4-CH3O-C6H4
3-O2N-C6H4
C6H5
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
–
126–127 [34]
4g
6a
6b
6c
6d
6e
6f
–
169–171 [35, 36]
2-Cl-C6H4
4-Cl-C6H4
4-(CH3)2N-C6H4ꢃ
3-HO-C6H4
4-CH3O-C6H4
3-O2N-C6H4
212–214 [35, 36]
197–199 [35, 36]
–
ꢃ
ꢃ
ꢃ
–
143–145 [35, 36]
–
6g
aYields refer to those of pure isolated products characterized by IR, 1H NMR and 13C NMR spectroscopy, and elemental analyses.
bIn all cases, the reaction time was 15 min under solvent-free grinding.
O
O
O
O
1
O
Ar
+O Cu
H
OH
O
O
O
Ar
H
+
O
O
7
Cu
8
O
O
H
2
O
Ar
Ar
CuI NPs
H
O
H2O
+
HO
O
O
3
9
Ar
O
Ar
O
Ar
O
O
O
CO2
acetone
HOOC
O
O
O
O
O
O
HO
4
11
10
Scheme 3:ꢀThe possible reaction mechanism.
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ꢀꢀꢀꢁ
4ꢀ ꢀS. Abdolmohammadi et al.: Synthesis of tetrahydrochromenediones and dihydropyrano[c]chromenediones
The structures of the compounds were confirmed by D-(+)-glucose solution was added dropwise into the solution
their satisfactory elemental analyses, infrared (IR), and 1H of copper nitrate for the reduction of the Cu to Cu under
and 13C NMR spectroscopy. Selected spectroscopic data are vigorous stirring, and then the LiI solution was added into
given in the Experimental section. The synthesized cata- the previously mentioned solution. The mixture was stirred
+2
+
lyst was fully characterized by XRD and SEM techniques.
for approximately 30 min at room temperature. After the
completion of the reaction, a gray precipitate was obtained.
The solid product was filtered and washed with deionized
water and absolute EtOH, respectively, and finally dried in
vacuo for several hours to give the pure catalyst [37].
3 Conclusion
We have reported a simple route for the synthesis of tet-
rahydrochromenediones and dihydropyrano[c]chromen-
ediones under solvent-free conditions using a grinding 4.3 General procedure for the synthesis of
technique promoted by CuI NPs. Compared with known
compounds 4a–g and 6a–g
methods [34–36], this new protocol is endowed with high
yields of products, short reaction time, reusability of cata- Meldrum’s acid (1, 1 mmol), aromatic aldehydes 2(1 mmol),
lyst, mild reaction conditions, and very simple operation. active methylene compounds 3 or 5 (1 mmol), and CuI NPs
(1.9 mg, 10 mol%) were placed in a mortar. The mixture
was ground with a mortar and pestle at room temperature
for 15 min. After the completion of the reaction indicated
4 Experimental section
by TLC, the resulting mixture was diluted with dimethyl-
formadide (DMF) (5 mL) and then centrifuged for 5 min
at 2000 rpm to recover the catalyst. The organic solution
was then poured into ice-cold water (10 mL) to give a solid
4.1 Materials and methods
All chemicals used in this work were purchased from Merck precipitate, which was filtered off and recrystallized from
and Fluka in high purity (Kimiaexir Chemical Company, EtOH (95%) to afford the pure product.
Tehran, Iran). Melting points were determined with an Elec-
trothermal 9100 apparatus and are uncorrected (Islamic
Azad University, East Tehran Branch, Tehran, Iran). Fourier 4.4 Selected spectroscopic and physical
transform infrared spectra were obtained using a Bruker
Equinox 55 Golden Gate Micro-ATR spectrometer (Chemistry
data
and Chemical Engineering Research Center of Iran, Tehran, 4.4.1 4-Phenyl-7,7-dimethyl-4,6,7,8-tetrahydro-2H-
1
Iran). H NMR and 13C NMR spectra were recorded on a
chromene-2,5(3H)-dione (4a)
Bruker DRX-500 AVANCE at 500 and 125 MHz, respectively,
using tetramethylsilane (TMS) as internal standard and White solid, yield 0.246 g (91%), m. p. 101–103°C (lit: 99–
[D6] dimethylsulfoxide (DMSO) as a solvent (Sharif Univer- 101°C [34]). – IR (KBr, cm−1): νmaxꢀꢁ=ꢁꢀ3034, 1768, 1660, 1511,
sity of Technology, Tehran, Iran). Elemental analyses were 1120. – 1H NMR: δꢀꢁ=ꢁꢀ1.09 (s, 3H, CH3), 1.13 (s, 3H, CH3), 2.29
conducted using a Foss-Heraeus CHN-O-Rapid analyzer (d, 1H, H-8, 2JHHꢀꢁ=ꢁꢀ16.0 Hz) 2.42 (d, 1H, H-8, 2JHHꢀꢁ=ꢁꢀ16.0 Hz),
2
(Polymer and Petrochemical Institute, Tehran, Iran). The 2.52 (s, 2H, H-6), 2.96 (d, 1H, H-3, JHHꢀꢁ=ꢁꢀ12.0 Hz,), 3.02 (d,
microscopic morphology of the catalyst was visualized by 1H, H-3, 2JHHꢀꢁ=ꢁꢀ12.0 Hz), 4.30 (m, 1H, H-4), 7.22 (m, 5H, H-Ar)
an SEM LEO 1455VP (Chemistry and Chemical Engineering ppm. – 13C NMR: δꢀꢁ=ꢁꢀ26.1 (CH3), 29.3 (CH3), 32.0 (CH2), 32.8
Research Center of Iran, Tehran, Iran). Powder X-ray diffrac- (CH2), 35.7 (CH2), 40.8 (CH), 51.0 (C), 106.6 (C), 122.5 (CH),
tion data were determined on a Philips X’Pert diffractometer 125.8 (2CH), 129.8 (2CH), 143.1 (C), 161.6 (Cꢁ=ꢁO), 163.7 (C),
using CuKα radiation (λꢀꢁ=ꢁꢀ1.54 Å) (Chemistry and Chemical 196.3 (Cꢁ=ꢁO) ppm. – Analysis for C17H18O3 (270.33): calcd. C
Engineering Research Center of Iran, Tehran, Iran).
75.53, H 6.71; found C 75.81, H 6.55%.
4.2 General procedure for the preparation of 4.4.2 4-(2-Chlorophenyl)-7,7-dimethyl-4,6,7,8-
tetrahydro-2H-chromene-2,5(3H)-dione (4b)
CuI NPs
Cu(NO3)2·3H2O was used as the Cu source for the prepara- Lemon solid, yield 0.286 g (94%), m. p. 131–133°C (lit:
tion of the catalyst by a precipitation approach. Initially, the 134–135 [34]). – IR (KBr, cm–1): νmaxꢀꢁ=ꢁꢀ3046, 1755, 1697, 1534,
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ꢁꢀꢀꢀ
S. Abdolmohammadi et al.: Synthesis of tetrahydrochromenediones and dihydropyrano[c]chromenedionesꢂ ꢂ5
3
13
1083. – 1H NMR: δꢀꢁ=ꢁꢀ1.14 (s, 3H, CH3), 1.16 (s, 3H, CH3), 2.41 (d, 1H, H-Ar, JHHꢀꢁ=ꢁꢀ7.4 Hz) ppm. – C NMR: δꢀꢁ=ꢁꢀ36.8 (CH2),
2
(s, 2H, H-8), 2. 58 (d, 1H, H-6, JHHꢀꢁ=ꢁꢀ17.4 Hz), 2.62 (d, 1H, 37.1 (CH), 105.6 (C), 113.2 (C), 116.9 (CH), 122.8 (CH), 126.3
H-6, 2JHHꢀꢁ=ꢁꢀ17.4 Hz), 2.95 (m, 2H, H-3), 4.73 (s, 1H, H-4), 7.24 (CH), 128.1 (2CH), 128.8 (CH), 130.3 (2CH), 133.2 (CH), 141.2
13
(m, 4H, H-Ar) ppm. – C NMR: δꢀꢁ=ꢁꢀ26.8 (CH3), 28.7 (CH3), (C), 154.1 (C), 156.7 (C), 160.1 (Cꢁ=ꢁO), 163.9 (Cꢁ=ꢁO) ppm. –
32.5 (CH2), 33.1 (CH2), 36.0 (CH2), 41.2 (CH), 50.4 (C), 107.3 Analysis for C18H12O4 (299.29): calcd. C 72.24, H 4.04; found
(C), 126.6 (CH), 128.3 (CH), 129.0 (CH), 130.1 (CH), 133.6 (C), C 72.19, H 4.12%.
137.1 (C), 160.4 (Cꢁ=ꢁO), 164.1 (C), 198.0 (Cꢁ=ꢁO) ppm. – Anal-
ysis for C17H17ClO3 (304.77): calcd. C 67.0, H 5.62; found C
66.83, H 5.48%.
4.4.6 4-(Dimethylaminophenyl)-3,4-dihydro-2H,5H-
pyrano[3,2-c]chromene-2,5-dione (6d)
4.4.3 4-(3-Hydroxyphenyl)-7,7-dimethyl-4,6,7,8-
tetrahydro-2H-chromene-2,5(3H)-dione (4e)
White powder, yield 0.322 g (96%), m. p. 196–198°C. – IR
(KBr, cm–1): νmaxꢀꢁ=ꢁꢀ1769, 1694, 1667, 1082. – 1H NMR: δꢀꢁ=ꢁꢀ3.04
(s, 6H, 2NCH3), 3.09 (d, 1H, H-3, 2JHHꢀꢁ=ꢁꢀ15.8 Hz), 3.17 (d, 1H,
2
Yellow solid, yield 0.269 g (94%), m. p. 182–184°C. – IR H-3, JHHꢀꢁ=ꢁꢀ15.8 Hz), 4.48 (s, 1H, H-4), 6.87 (d, 2H, H-Ar,
(KBr, cm–1): νmaxꢀꢁ=ꢁꢀ3395, 3052, 1764, 1709, 1558, 1096. – H JHHꢀꢁ=ꢁꢀ8.0 Hz), 7.26 (d, 2H, H-Ar, JHHꢀꢁ=ꢁꢀ8.3 Hz), 7.35 (m, 2H,
1
3
3
3
NMR: δꢀꢁ=ꢁꢀ0.94 (s, 3H, CH3), 1.04 (s, 3H, CH3), 2.19 (s, 2H, H-Ar), 7.48 (t, 1H, H-Ar, JHHꢀꢁ=ꢁꢀ8.2 Hz), 7.80 (d, 1H, H-Ar,
H-8), 2.41 (s, 2H, H-6), 2.63 (m, 2H, H-3), 4.64 (m, 1H, H-4), JHHꢀꢁ=ꢁꢀ8.6 Hz) ppm. – 13C NMR: δꢀꢁ=ꢁꢀ35.7 (CH2), 36.8 (CH),
3
7.19 (m, 2H, H-Ar), 7.32 (m, 2H, H-Ar), 9.05 (s, 1H, OH) 45.4 (NCH3), 104.7 (C), 112.9 (C), 114.5 (2CH), 115.9 (CH),
13
ppm. – C NMR: δꢀꢁ=ꢁꢀ27.0 (CH3), 29.2 (CH3), 31.9 (CH2), 32.2 123.2 (CH), 124.7 (CH), 127.4 (2CH), 129.3 (C), 132.3 (CH),
(CH2), 37.1 (CH2), 41.7 (CH), 50.7 (C), 105.7 (C), 114.2 (CH), 149.8 (C), 152.5 (C), 159.2 (C), 161.2 (Cꢁ=ꢁO), 164.4 (Cꢁ=ꢁO) ppm.
115.9 (CH), 117.0 (CH), 121.7 (CH), 140.2 (C), 146.3 (C), 160.5 – Analysis for C20H17NO4 (335.36): calcd. C 71.63, H 5.11, N
(Cꢁ=ꢁO), 164.5 (C), 198.2 (Cꢁ=ꢁO) ppm. – Analysis for C17H18O4 4.18; found C 71.59, H 5.28, N 4.27%.
(286.33): calcd. C 71.31, H 6.34; found C 71.10, H 6.17%.
4.4.7 4-(3-Hydroxyphenyl)-3,4-dihydro-2H,5H-
4.4.4 4-(3-Nitrophenyl)-7,7-dimethyl-4,6,7,8-tetrahydro-
2H-chromene-2,5(3H)-dione (4g)
pyrano[3,2-c]chromene-2,5-dione (6e)
White powder, yield 0.290 g (94%), m. p. 184–186°C. –
Pale yellow solid, yield 0.303 g (96%), m. p. 163–165°C. – IR IR (KBr, cm–1): νmaxꢀꢁ=ꢁꢀ3324, 1753, 1714, 1642, 1113. – H
1
1
2
(KBr, cm–1): νmaxꢀꢁ=ꢁꢀ3085, 1691, 1666, 1623, 1131. – H NMR: NMR: δꢀꢁ=ꢁꢀ3.12 (d, 1H, H-3, JHHꢀꢁ=ꢁꢀ16.0 Hz), 3.23 (d, 1H, H-3,
2
δꢀꢁ=ꢁꢀ1.02 (s, 3H, CH3), 1.16 (s, 3H, CH3), 2.07 (d, 1H, H-8, JHHꢀꢁ=ꢁꢀ16.0 Hz), 4.45 (s, 1H, H-4), 7. 19 (m, 2H, H-Ar), 7. 32 (m,
2JHHꢀꢁ=ꢁꢀ15.8 Hz), 2.12 (d, 1H, H-8, JHHꢀꢁ=ꢁꢀ15.8 Hz), 2.38 (s, 2H, H-Ar), 7.36 (m, 2H, H-Ar), 7.64 (t, 1H, H-Ar, 3JHHꢀꢁ=ꢁꢀ7.8 Hz),
2
3
13
2H, H-6), 2.62 (m, 2H, H-3), 4.54 (m, 1H, H-4), 7.33 (m, 1H, 7.78 (d, 1H, H-Ar, JHHꢀꢁ=ꢁꢀ7.8 Hz), 9.45 (s, 1H, OH) ppm. – C
13
H-Ar), 8.92 (m, 3H, H-Ar) ppm. – C NMR: δꢀꢁ=ꢁꢀ27.2 (CH3), NMR: δꢀꢁ=ꢁꢀ35.3 (CH2), 36.2 (CH), 106.1 (C), 112.5 (CH), 113.3
28.9 (CH3), 32.2 (CH2), 33.0 (CH2), 36.4 (CH2), 42.4 (CH), (C), 114.6 (CH), 115.4 (CH), 120.1 (CH), 122.3 (CH), 123.5 (CH),
51.2 (C), 106.2 (C), 121.0 (CH), 125.2 (CH), 130.7 (CH), 129.6 125.6 (CH), 133.2 (CH), 139.1 (C), 154.1 (C), 155.6 (C), 158.7
(CH), 141.7 (C), 145.1 (C), 162.3 (Cꢁ=ꢁO), 164.2 (C), 196.7 (Cꢁ=ꢁO) (C), 160.8 (Cꢁ=ꢁO), 163.9 (Cꢁ=ꢁO) ppm. – Analysis for C18H12O5
ppm. – Analysis for C17H17NO5 (315.32): calcd. C 64.75, H (308.29): calcd. C 70.13, H 3.92; found C 69.97, H 4.01%.
5.43, N 4.44; found C 64.53, H 5.55, N 4.27%.
4.4.8 4-(4-Methoxyphenyl)-3,4-dihydro-2H,5H-
4.4.5 4-Phenyl-3,4-dihydro-2H,5H-pyrano[3,2-c]
chromene-2,5-dione (6a)
pyrano[3,2-c]chromene-2,5-dione (6f)
White powder, yield 0.30 g (93%), m. p. 146–147°C (lit:
White powder, yield 0.290 g (97%), m. p. 168–170°C (lit: 143–145 [35, 36]). – IR (KBr, cm–1): νmaxꢀꢁ=ꢁꢀ1774, 1705, 1668,
169–171 [35, 36]). – IR (KBr, cm–1): νmaxꢀꢁ=ꢁꢀ1784, 1702, 1659, 1102. – 1H NMR: δꢀꢁ=ꢁꢀ3.10 (d, 1H, H-3, 2JHHꢀꢁ=ꢁꢀ16.0 Hz), 3.19 (d,
1087. – 1H NMR: δꢀꢁ=ꢁꢀ3.13 (d, 1H, H-3, 2JHHꢀꢁ=ꢁꢀ16.1 Hz), 3.20 (d, 1H, H-3, 2JHHꢀꢁ=ꢁꢀ16.0 Hz), 3.71 (s, 3H, OCH3), 4.50 (s, 1H, H-4),
1H, H-3, 2JHHꢀꢁ=ꢁꢀ16.1 Hz), 4.52 (s, 1H, H-4), 7.28 (m, 3H, H-Ar), 6.79 (d, 2H, H-Ar, 3JHHꢀꢁ=ꢁꢀ8.4 Hz), 7.17 (d, 2H, H-Ar, 3JHHꢀꢁ=ꢁꢀ8.4
7.29 (d, 1H, H-Ar, JHHꢀꢁ=ꢁꢀ7.0 Hz), 7.34 (d, 1H, H-Ar, JHHꢀꢁ=ꢁꢀ7.0 Hz), 7.37 (m, 2H, H-Ar), 7.69 (t, 1H, H-Ar, 3JHHꢀꢁ=ꢁꢀ8.0 Hz), 7.88
3
3
3
3
13
Hz), 7.39 (m, 2H, H-Ar), 7.61 (t, 1H, H-Ar, JHHꢀꢁ=ꢁꢀ7.2 Hz), 7.91 (d, 1H,H-Ar, JHHꢀꢁ=ꢁꢀ8.1 Hz) ppm. – C NMR: δꢀꢁ=ꢁꢀ34.8 (CH2),
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ꢀꢀꢀꢁ
6ꢀ ꢀS. Abdolmohammadi et al.: Synthesis of tetrahydrochromenediones and dihydropyrano[c]chromenediones
[11] J. Safaei-Ghomi, A. Ziarati, R. Teymuri, Bull. Korean. Chem. Soc.
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36.7 (CH), 56.1 (OCH3), 105.9 (C), 114.1 (C), 116.6 (CH), 117.5
(2CH), 125.8 (CH), 127.8 (CH), 130.7 (2CH), 132.8 (CH), 152.3
(C), 156.2 (C), 158.5 (C), 159.1 (C), 160.9 (Cꢁ=ꢁO), 164.1 (Cꢁ=ꢁO)
ppm. – Analysis for C19H14O5 (322.32): calcd. C 70.80, H
4.38; found C 70.65, H 4.16%.
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4.4.9 4-(3-Nitrophenyl)-3,4-dihydro-2H,5H-pyrano[3,2-c]
chromene-2,5-dione (6g)
[16] F. Cheng, A. Ishikawa, Y. Ono, T. Arrheniusa, A. Nadzana,
Bioorg. Med. Chem. Lett. 2003, 13, 3647.
White powder, yield 0.327 g (97%), m. p. 181–183°C. – IR
1
(KBr, cm–1): νmaxꢀꢁ=ꢁꢀ1780, 1713, 1654, 1567, 1382, 1110. – H
[17] D. Grée, S. Vorin, L. Manthati, F. Caijo, G. Viault, F. Manero,
P. Juin, R. Grée, Tetrahedron. Lett. 2008, 49, 3276.
[18] W. Kemnitzer, S. Jiang, H. Zhang, S. Kasibhatla, C. Crogan-Grundy,
C. Blais, G. Attardo, R. Denis, S. Lamoth, H. Gourdeau, B. Tseng,
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Farmaco 2002, 57, 715.
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2
NMR: δꢀꢁ=ꢁꢀ3.12 (d, 1H, H-3, JHHꢀꢁ=ꢁꢀ16.0 Hz), 3.20 (d, 1H, H-3,
2JHHꢀꢁ=ꢁꢀ16.0 Hz), 4.47 (s, 1H, H-4), 7.33 (m, 2H, H-Ar), 7.54
3
(t, 1H, H-Ar, JHHꢀꢁ=ꢁꢀ7.4 Hz), 7.62 (m, 2H, H-Ar), 7.75 (m, 2H,
3
H-Ar), 7.87 (d, 1H, H-Ar, JHHꢀꢁ=ꢁꢀ7.6 Hz) ppm. – 13C NMR:
δꢀꢁ=ꢁꢀ36.5 (CH2), 37.7 (CH), 104.8 (C), 113.7 (C), 116.2 (CH),
120.3 (CH), 121.5 (CH), 123.8 (CH), 125.6 (CH), 130.5 (CH),
131.6 (CH), 132.4 (CH), 142.3 (C), 145.4 (C), 154.1 (C), 158.7
(C), 160.8 (Cꢁ=ꢁO), 163.9 (Cꢁ=ꢁO) ppm. – Analysis for C18H11NO6
(337.29): calcd. C 64.01, H 3.29, N 4.15; found C 63.89, H 3.14,
N 4.23%.
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Acknowledgments: S.A. is grateful to the Islamic Azad
University, East Tehran Branch, for financial support of
this work.
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Z. Naturforsch.ꢂ
ꢂ2016 | Volume x | Issue x(b)
Graphical synopsis
O
Shahrzad Abdolmohammadi, Reza
Ghiasi and Sam Ahmadzadeh-Vatani
A highly efficient CuI nanoparticles-
catalyzed synthesis of tetrahydro-
chromenediones and dihydropyrano[c]
chromenediones under grinding
Ar
O
O
O
O
O
O
O
O
CuI NPs (10 mol%)
H Grinding, r.t.
+
O
Ar
O
O
HO
O
Ar
O
O
DOI 10.1515/znb-2015-0195
Z. Naturforsch. 2016; x(x)b: xxx–xxx
O
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