One-pot multi-component process for the synthesis of 4-azaphenanthrene-3,10-dione, 1,8-dioxo-octahydroxanthene and tetrahydrobenzo[b]pyran derivatives catalyzed by the deep eutectic solvent choline chloride-oxalic acid

Article abstract of DOI:10.1515/znb-2019-0155

An effective method based on choline chloride (ChCl)-oxalic acid (Ox) deep eutectic solvent was proposed for the synthesis of 4-azaphenanthrene-3,10-dione, 1,8-dioxo-octahydroxanthene and tetrahydrobenzo[b]pyran derivatives. The eutectic mixture worked as

Full text of DOI:10.1515/znb-2019-0155

Z. Naturforsch. 2020; aop
Mohammad Hosein Sayahi, Maryam Gorjizadeh, Melan Meheiseni and Soheil Sayyahi*
One-pot multi-component process for the synthesis of
4-azaphenanthrene-3,10-dione, 1,8-dioxo-octahydroxanthene
and tetrahydrobenzo[b]pyran derivatives catalyzed by the deep
eutectic solvent choline chloride-oxalic acid
https://doi.org/10.1515/znb-2019-0155
A number of methods are available in literature for
the synthesis of these heterocycles. The acid-catalyzed
condensation of dimedone with aromatic aldehydes to
get 1,8-dioxo-octahydroxanthenes seems to be a highly
efficient reaction [4, 15]. It is worthy to mention that, with
the addition of malononitrile to the reaction mixture, the
preparation of tetrahydrobenzo[b]pyran scaffolds would
be possible [16, 17]. The conventional synthetic method
for the preparation of 4-azaphenanthrene-3,10-diones
involves a four-component condensation of Meldrum’s
acid, an aldehyde, primary amine or ammonium acetate
and different 1,3-dicarbonyl compounds under different
conditions [8, 9].
Received October 2, 2019; accepted December 8, 2019
Abstract: An effective method based on choline chloride
(ChCl)-oxalic acid (Ox) deep eutectic solvent was pro-
posed for the synthesis of 4-azaphenanthrene-3,10-dione,
1,8-dioxo-octahydroxanthene and tetrahydrobenzo[b]
pyran derivatives. The eutectic mixture worked as both
the solvent and acidic catalyst for conversion. The impacts
of different variables, including the composition and vol-
ume of ChCl-Ox, and temperature, on reaction yield were
studied for optimization. The crucial advantages of this
process are simplicity of the experimental procedure, high
yields, short reaction times, high recyclability, and the use
of safe and inexpensive components.
A deep eutectic solvent (DES) is a fluid generally com-
posed of two or three cheap and safe components that are
Keywords: 4-azaphenanthrene-3,10-dione; deep eutec- capable of associating with each other through hydrogen
tic solvent; dioxo-octahydroxanthene; multi-component bond interactions. DESs typically have freezing points
reactions; solvent-free synthesis; tetrahydrobenzo[b] lower than those of starting individual components. One
pyran.
of the most widespread components used for the forma-
tion of DES is choline chloride (ChCl), an inexpensive,
chemically and thermally stable, biodegradable, non-
toxic and recyclable quaternary ammonium salt [18–20].
ChCl is capable of rapidly forming a DES in combination
with hydrogen donors such as acids [21], alcohols [22],
amines [23] or amides [24]. DES based on ChCl and organic
Brønsted acid is a well-known system for synthesizing dif-
ferent heterocycles acting both as a solvent and a Brøn-
sted-acidic catalyst [25].
In continuation of our research work on the appli-
cations of green catalysts for organic reactions [26–29],
we have carried out the synthesis of tetrahydrobenzo[b]
pyrans (Scheme 1), dioxo-octahydroxanthenes (Scheme 2)
and 4-azaphenanthrene-3,10-diones (Scheme 3) using the
DESs ChCl and oxalic acid (ChCl-Ox), an ionic liquid, at
room temperature.
1 Introduction
A multi-component reaction (MCR) is a convergent reac-
tion with at least three components to form a single
product, which incorporates most or even all of the start-
ing materials. MCRs have an important role in the synthe-
sis of different types of organic compounds [1–3]. In recent
years, 4H-pyran and 2-pyridone derivatives have been
considered as remarkable compounds because of their
pharmaceutical activities [4–9]. They exhibit a wide range
of biological properties, including antifungal, antiviral,
antibiotic, anti-HIV and antitumor [10–14].
*Corresponding author: Soheil Sayyahi, Department of Chemistry,
Mahshahr Branch, Islamic Azad University, Mahshahr, I.R. Iran,
E-mail: sayyahi.soheil@gmail.com
Mohammad Hosein Sayahi: Department of Chemistry, Payame Noor
University, P.O. Box 19395-3697, Tehran, I.R. Iran
Maryam Gorjizadeh: Department of Chemistry, Shoushtar Branch,
Islamic Azad University, Shoushtar, I.R. Iran
Melan Meheiseni: Department of Chemistry, Mahshahr Branch,
Islamic Azad University, Mahshahr, I.R. Iran
2 Results and discussion
As stated before, DESs are cheap ionic liquid-like green
solvents. In this work the DES ChCl-Ox was selected
where Ox works not only as the hydrogen bond donor
but also as the catalyst for the MCR. In order to study the
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ꢀꢀꢀꢁ
2ꢀ ꢀM. H. Sayahi et al.: Synthesis of 4-azaphenanthrene-3,10-dione, 1,8-dioxo-octahydroxanthene
Scheme 1:ꢀSynthesis of tetrahydrobenzopyran derivatives 4a–h from aromatic aldehydes 1a–h, dimedone (2) and malononitrile (3) using
ChCl-Ox.
Scheme 2:ꢀSynthesis of 1,8-dioxo-octahydroxanthene derivatives 5a–h from aromatic aldehydes 1a–h and dimedone (2) using ChCl-Ox.
Scheme 3:ꢀSynthesis of 4-azaphenanthrene-3,10-dione derivatives 8a–g from aromatic aldehydes 1a–g with 4-hydroxycoumarin (6),
ammonia solution and dimedone (2) using ChCl-Ox.
catalytic efficiency of ChCl-Ox, we used 1 mmol of 4-chlo- catalyst amount (Table 1, entries 5–7). A further increase
robenzaldehyde (1, Arꢀ=ꢀ4-Cl–C6H4), 1 mmol of dimedone of the amount of catalyst had no pronounced effect on
(2) and 1 mmol of malononitrile (3) as a model reaction the yield, indicating that the acidity requirement is well
for the synthesis of 2-amino-3-cyano-4-(4-chlorophenyl)- fulfilled by this amount of catalyst (Table 1, entry 8). The
7,7-dimethyl-5-oxo-4H-5,6,7,8-tetrahydrobenzo[b]pyran effect of the reaction temperature was also studied by
(4c; Scheme 1, see Table 2 for formula). The reaction was performing the model reaction at different temperatures
carried out in different sets of conditions, and the effects varying from room temperature to 80°C, again using
of the ratio of ChCl to Ox, amount of catalyst, time and 0.5 mL of the DES. It was found that the condensation
temperature on the yield were studied. To investigate the reaction proceeded efficiently when the temperature was
effect of molar ratio, the ammonium salt ChCl was mixed increased to 60°C (Table 1, entries 9–13). Other ChCl-based
with Ox at different molar ratios (Table 1, entries 1–4). As DESs such as ChCl-malonic acid, ChCl-glycine, ChCl-cit-
is shown in Table 1, by increasing the molar ratio of ChCl ric acid and ChCl-urea were also examined. The results
to Ox to 1:2, the yield of the desired product increased to clearly show that ChCl-Ox is the optimal solvent and cata-
92%. Therefore, this molar ratio of ChCl to Ox was selected lyst for the reaction (Table 1, entries 13–17). It is worth to
as the best DES composition and was used for the follow- note that in a blank reaction without a catalyst (entry 18)
ing optimization experiments. To optimize the required only trace amounts of the corresponding product were
catalyst amount, the model reaction was carried out in the obtained even after prolonged reaction times (2 h).
presence of various amounts of the catalyst, and accord-
With these results in hand, we extended our studies to
ing to the obtained results, 0.5 mL was chosen as the best the reaction of dimedone and malononitrile with a variety
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ꢂ3
M. H. Sayahi et al.: Synthesis of 4-azaphenanthrene-3,10-dione, 1,8-dioxo-octahydroxantheneꢂ
Table 1:ꢀInvestigation of the DES in the synthesis of 2-amino-3-cyano-4-(4-chlorophenyl)-7,7-dimethyl-5-oxo-4H-5,6,7,8-tetrahydrobenzo[b]
pyran 4c under different conditions.
No. ꢁ
Catalyst (molar ratio)
ꢁ
Catalystꢁ
amount (mL)
Temp. (°C)ꢁ
Time (min)ꢁ
Yielda (%)
1
2
3
4
5
6
7
8
9
10 ꢃ
11 ꢃ
12 ꢃ
13 ꢃ
14 ꢃ
15 ꢃ
16 ꢃ
17 ꢃ
18 ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ChCl:oxalic acid (2:1)
ChCl:oxalic acid (1:1)
ꢃ
ꢃ
0.5ꢃ
0.5ꢃ
0.5ꢃ
0.5ꢃ
0.1ꢃ
0.3ꢃ
0.4ꢃ
0.6ꢃ
0.5ꢃ
0.5ꢃ
0.5ꢃ
0.5ꢃ
0.5ꢃ
0.5ꢃ
0.5ꢃ
0.5ꢃ
0.5ꢃ
–ꢃ
60
60
60
60
60
60
60
60
Rt
40
50
60
70
60
60
60
60
60
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
15ꢃ
15ꢃ
15ꢃ
15ꢃ
15ꢃ
15ꢃ
15ꢃ
15ꢃ
120ꢃ
15ꢃ
15ꢃ
15ꢃ
15ꢃ
15ꢃ
15ꢃ
15ꢃ
15ꢃ
120ꢃ
60
55
ChCl:oxalic acid (1:1.5) ꢃ
80
ChCl:oxalic acid (1:2)
ChCl:oxalic acid (1:2)
ChCl:oxalic acid (1:2)
ChCl:oxalic acid (1:2)
ChCl:oxalic acid (1:2)
ChCl:oxalic acid (1:2)
ChCl:oxalic acid (1:2)
ChCl:oxalic acid (1:2)
ChCl:oxalic acid (1:2)
ChCl:oxalic acid (1:2)
ChCl:citric acid (1:2)
ChCl:glycine (1:2)
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
92
35
68
81
93
Trace
65
81
92
92
65
50
ChCl:malonic acid (1:2)ꢃ
ChCl:urea (1:2)
None
82
ꢃ
ꢃ
45
Trace
aIsolated yields.
of electron-donating and electron-withdrawing aldehydes of catalytic amounts of ChCl-Ox (0.5 mL) produced the
to evaluate the scope of this methodology (Scheme 1). The corresponding 1-phenyl-1,4-dihydro-2H-9-oxa-4-aza-phen-
results are presented in Table 2. It is found that substitu- anthrene-3,10-diones in good to excellent yields in short
ents in the aromatic ring of the aldehydes have a minor reaction times.
effect on the reaction times. Aromatic aldehydes with
electron-withdrawing groups reacted faster than those cedures involves the Knoevenagel reaction, Michael
with electron-donating groups.
addition and intra-molecular cyclization. A proposed
In general, the mechanism of such synthetic pro-
The scope and generality of this catalytic system was mechanism to demonstrate the role of catalyst for the syn-
shown in the reaction of various types of aromatic alde- thesis of tetrahydrobenzo[b]pyran is shown in Scheme 4.
hydes with dimedone (Scheme 2). When the reaction The arylidenemalononitrile intermediate (I) was formed
was carried out using one equivalent of aromatic alde- initially by the Knoevenagel condensation between acti-
hyde and two equivalents of dimedone in the presence vated aldehyde and malononitrile in the presence of ChCl-
of 0.5 mL of ChCl-Ox under the same reaction conditions Ox. Subsequently, the Michael addition of the enolizable
used in the synthesis of the tetrahydrobenzopyran deriva- dimedone to the arylidenemalononitrile intermediate
tives 4a–h, 1,8-dioxo-octahydroxanthene derivatives (I), followed by intramolecular cyclization and final
5a–h were obtained in good to excellent yields (Table 3). tautomerization of intermediates, afforded the desired
The progress of the reaction was monitored by thin-layer product (Scheme 4). A similar mechanism may occur
chromatography (TLC) (EtOAc–hexane, 4:1, v/v). Work-up for the formation of 4-azaphenanthrene-3,10-dione and
of the reaction was very easy. After completion of the reac- 1,8-dioxo-octahydroxanthene derivatives.
tion, simple filtration of the reaction mixture provided the
In environmentally friendly methodologies, the recov-
crude product. Evaporation of the solvent under reduced ery of the prepared catalyst is highly preferable. For this
pressure and recrystallization gave the final pure product. purpose, the model reaction was selected again to investi-
To show the further applicability of this catalytic gate the reusability of the DES catalyst under the optimal
system, the synthesis of 4-azaphenanthrene-3,10-dione conditions. After completion of the reaction, the crude
derivatives 8a–g was investigated (Scheme 3, Table 4). product was separated by simple filtration. The DES cata-
The reaction of aromatic aldehydes with 4-hydroxycou- lyst was recovered by removing the aqueous layer under
marin, ammonia solution and dimedone in the presence vacuum from the filtrate. As is shown in Fig. 1, the DES
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ꢀꢀꢀꢁ
4ꢀ ꢀM. H. Sayahi et al.: Synthesis of 4-azaphenanthrene-3,10-dione, 1,8-dioxo-octahydroxanthene
Table 2:ꢀThree-component reaction of aromatic aldehydes 1a–h, dimedone (2) and malononitrile (3) to give tetrahydrobenzopyran
derivatives 4a–h.
No. ꢁ
Substrate
ꢁ
Product
ꢁ
Time
(min)
ꢁ Yielda
(%)
ꢁ M.p. (°C) [ref.]
ꢃ 229–231 [30]
1
ꢃ
ꢃ
ꢃ
20
ꢃ
87
2
ꢃ
ꢃ
ꢃ
15
ꢃ
92
ꢃ 201–203 [31]
3
4
5
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
15
15
25
ꢃ
ꢃ
ꢃ
92
88
90
ꢃ 211–213 [30]
ꢃ 118–120 [30]
ꢃ 218–220 [30]
6
ꢃ
ꢃ
ꢃ
20
ꢃ
85
ꢃ 210–212 [30]
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ꢂ5
M. H. Sayahi et al.: Synthesis of 4-azaphenanthrene-3,10-dione, 1,8-dioxo-octahydroxantheneꢂ
Table 2ꢀ(continued)
No. ꢁ Substrate
7 ꢃ
ꢁ
Product
ꢁ
Time
(min)
ꢁ Yielda
(%)
ꢁ M.p. (°C) [ref.]
ꢃ 178–180 [30]
ꢃ
ꢃ
15
ꢃ
87
8
ꢃ
ꢃ
ꢃ
30
ꢃ
85
ꢃ 205–207 [31]
aIsolated yields.
could be recycled and reused up to four times with only a The 1H and 13C NMR spectra of samples were recorded with
slight decrease in catalytic activity.
a Bruker Advanced DPX 400-MHz.
3 Conclusion
4.2 Preparation of a deep eutectic solvent
In summary, we have developed a novel multi-compo- In this study, the eutectic mixtures of ChCl and Ox were
nent approach for the one-pot synthesis of 4-azaphen- synthesized at molar ratios of 2:1, 1:1 and 1:2 and uti-
anthrene-3,10-dione, 1,8-dioxo-octahydroxanthene and lized as solvents and catalyst for the one-pot synthesis of
tetrahydrobenzo[b]pyran derivatives using a deep eutectic tetrahydrobenzo[b]pyran (4a–h), 1,8-dioxo-octahydrox-
mixture of ChCl and Ox in a molar ratio of 1:2 as a catalyst. anthene (5a–h) and 4-azaphenanthrene-3,10-dione deriv-
High yields, an environmentally benign solvent, the good atives (8a–h). To prepare these mixtures, ChCl and Ox
reusability of the catalyst and simple reaction conditions were mixed at Tꢀ=ꢀ60°C for approximately 15 min until a
are the noteworthy aspects of the protocol.
homogeneous, colorless liquid formed. The obtained DES
was used without any further purification.
4 Experimental section
4.3 General procedure for the synthesis of
tetrahydrobenzo[b]pyrans 4a–h
4.1 Materials and methods
Aldehyde (1 mol), dimedone (1 mol), malononitrile (1 mol)
All chemicals were commercial and were used as received. and DES (0.5 mL) as catalysts were mixed and heated
ThereactionsweremonitoredbyTLConsilicagelpolygram at 60°C for 15–30 min. After completion of the reaction
SILG/UV 254 plates. The yields of products refer to iso- monitored by TLC, water (5 mL) was added and the solid
lated compounds. Melting points were determined using product was filtered and washed with H2O. Then hot
Stuart scientific apparatus. FT-IR spectra were obtained as EtOH was poured on the precipitate until the product was
potassium bromide pellets in the range of 400–4000 cm−1 solved. Finally, products were recrystallized for more puri-
using a BOMEM MB-Series 1998 FT-IR spectrophotometer. fication (Table 2).
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6ꢀ ꢀM. H. Sayahi et al.: Synthesis of 4-azaphenanthrene-3,10-dione, 1,8-dioxo-octahydroxanthene
Table 3:ꢀThree-component reaction of aromatic aldehydes and dimedone to give 1,8-dioxo-octahydroxanthene derivatives 5a–h.
No. ꢁ
Substrate
ꢁ
Product
ꢁ
Timeꢁ
(min)
Yielda (%)ꢁ
ꢁ
M.p. (°C) [ref.]
200–202 [32]
1
ꢃ
ꢃ
ꢃ
ꢃ
15ꢃ
90ꢃ
ꢃ
2
ꢃ
ꢃ
20ꢃ
92ꢃ
ꢃ
232–234 [31]
3
ꢃ
ꢃ
ꢃ
15ꢃ
93ꢃ
ꢃ
225–227 [31]
4
ꢃ
ꢃ
ꢃ
10ꢃ
88ꢃ
ꢃ
240–243 [31]
5
ꢃ
ꢃ
ꢃ
20ꢃ
90ꢃ
ꢃ
210–212 [31]
6
ꢃ
ꢃ
ꢃ
20ꢃ
85ꢃ
ꢃ
219–222 [31]
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ꢂ7
M. H. Sayahi et al.: Synthesis of 4-azaphenanthrene-3,10-dione, 1,8-dioxo-octahydroxantheneꢂ
Table 3ꢀ(continued)
No. ꢁ Substrate
7 ꢃ
ꢁ
Product
ꢁ
Timeꢁ
(min)
Yielda (%)ꢁ
ꢁ
M.p. (°C) [ref.]
220–222 [31]
ꢃ
ꢃ
10ꢃ
90ꢃ
ꢃ
8
ꢃ
ꢃ
ꢃ
25ꢃ
85ꢃ
ꢃ
242–244 [31]
aIsolated yields.
4.4 General procedure for the synthesis of
1,8-dioxo-octahydroxanthene 5a–h
by recrystallization with EtOH to afford the corresponding
products in high yields.
Aromatic aldehydes (1 mmol), dimedone (2 mol) and
ChCl-Ox (0.5 mL) were added into a 5 mL round-bottom 4.6 Characterization data for compounds 8c,
flask and were stirred at 60°C for appropriate time accord-
8d, 8g and 4e
ing to Table 3. The progress of the reaction was monitored
by TLC. After completion of the reaction, water (5 mL) was 4.6.1 1-(4-Chloro-phenyl)-1,4-dihydro-2H-9-oxa-4-aza-
added and the solid was separated by filtration. The crude
products were obtained in high purity after purification
phenanthrene-3,10-dione (8c)
by recrystallization from ethanol. All the products were White powder; m.p. 218–220°C. – FT-IR (KBr, cm−1):
known compounds and were characterized by comparing νꢀ=ꢀ3185, 3139, 2923, 1690, 1637, 1605, 1571, 1515, 1464, 1407,
spectroscopic data and their melting points to the litera- 1368, 1318, 1240, 1195, 1012, 999, 829, 769, 739, 627, 547. –
ture values.
1H NMR (DMSO-d6, 500 MHz, ppm): δꢀ=ꢀ2.58 (dd, 1H), 3.32
(d, 1H), 4.37 (d, 1H), 7.20–8.24 (m, ArH, 8H), 11.01 (s, NH,
13
1H). – C NMR (DMSO-d6, 125 MHz, ppm): δꢀ=ꢀ171.6, 160.1,
4.5 General procedure for the preparation of 152.7, 147.2, 141.7, 134.0, 133.1, 130.2, 130.0, 125.7, 124.6, 118.4,
114.5, 104.4, 37.05, 36.4.
4-azaphenanthrene-3,10-diones 8a–g
To a mixture of 4-hydroxycoumarin (1 mmol), 28–30%
ammonia solution (5 mmol), dimedone (1 mmol) and aro- 4.6.2 1-(2,4-Dichloro-phenyl)-1,4-dihydro-2H-9-oxa-4-
matic aldehyde (1 mmol), ChCl-Ox (0.5 mL) was added. The
aza-phenanthrene-3,10-dione (8d)
mixture was stirred at 60°C for appropriate time according
to Table 4. After completion of the reaction, as indicated White powder; m.p. 185–187°C. – FT-IR (KBr, cm−1):
by TLC, H2O (5 mL) was added to the reaction mixture νꢀ=ꢀ3239, 3038, 2923, 1722, 1692, 1671, 1633, 1609, 1574, 1519,
and then the precipitate was filtered off and washed with 1463, 1363, 1324, 1200, 1165, 1049, 821, 766, 748, 630, 598,
1
EtOH and water. Finally, the crude product was purified 480. – H NMR (DMSO-d6, 500 MHz, ppm): δꢀ=ꢀ2.53 (dd,
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8ꢀ ꢀM. H. Sayahi et al.: Synthesis of 4-azaphenanthrene-3,10-dione, 1,8-dioxo-octahydroxanthene
Table 4:ꢀFour-component reaction of 4-hydroxycoumarin (6), ammonia solution, dimedone (2) and aromatic aldehydes 1a–g to give
1,8-dioxo-octahydroxanthene derivatives 8a–g.
No.
Substrate
Product
Time (min)
Yielda (%)
M.p. (°C) [ref.]
184–186 [33]
1
20
90
2
3
15
15
92
90
201–203 [33]
218–220
4
15
88
185–187
5
6
30
25
90
85
184–186 [33]
192–194 [33]
7
15
90
201–203
aIsolated yields.
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ꢂ9
M. H. Sayahi et al.: Synthesis of 4-azaphenanthrene-3,10-dione, 1,8-dioxo-octahydroxantheneꢂ
Scheme 4:ꢀPossible reaction pathway for the ChCl-Ox-catalyzed synthesis of tetrahydrobenzo[b]pyran derivatives 4a–h.
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10ꢀ ꢀM. H. Sayahi et al.: Synthesis of 4-azaphenanthrene-3,10-dione, 1,8-dioxo-octahydroxanthene
Acknowledgments: We gratefully acknowledge the
financial support of the Mahshahr Branch, Islamic Azad
University.
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1H), 3.33 (d, 1H), 4.65 (d, 1H), 7.20–8.24 (m, ArH, 7H), 11.13
(s, NH, 1H). – 13C NMR (DMSO-d6, 125 MHz, ppm): δꢀ=ꢀ170.9,
161.4, 154.3, 148.4, 138.3, 134.9, 134.2, 131.0, 130.2, 129.3,
125.8, 124.8, 118.4, 114.5, 103, 37.6, 34.4.
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4.6.3 1-(4-Nitro-phenyl)-1,4-dihydro-2H-9-oxa-4-aza-
phenanthrene-3,10-dione (8g)
White powder; m.p. 201–203°C. – FT-IR (KBr, cm−1):
νꢀ=ꢀ3265, 3078, 1723, 1690, 1684, 1625, 1511, 1459, 1411,
1348, 1277, 1231, 1196, 1155, 1112, 1070, 1004, 946, 906, 858,
1
758, 730, 632, 518. – H NMR (DMSO-d6, 500 MHz, ppm):
δꢀ=ꢀ2.89 (dd, 1H), 3.33 (d, 1H), 4.52 (d, 1H), 7.20–8.27 (m,
ArH, 8H), 11.10 (s, NH, 1H). – 13C NMR (DMSO-d6, 125 MHz,
ppm): δꢀ=ꢀ171.3, 161.6, 154.3, 150.6, 148.1, 147.6, 134.1, 129.6,
125.7, 125.4, 124.7, 118.4, 114.5, 103.6, 38.9, 36.9.
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dimethyl-5-oxo-4H-5,6,7,8-tetrahydrobenzo[b]
pyran (4e)
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White powder; m.p. 218–220°C. – FT-IR (KBr, cm−1):
νꢀ=ꢀ3425, 3321, 2995, 2187, 1672, 1638, 1598, 1484, 1365. – 1H
NMR (DMSO-d6, 500 MHz, ppm): δꢀ=ꢀ0.89 (s, 3H), 0.96 (s,
3H), 1.89 (d, 1H), 2.03 (d, 1H), 2.12 (s, 3H), 2.33 (s, 2H), 4.13
(s, 1H), 5.8 (s, NH, 2H), 6.90–9.96 (m, ArH, 4H). – 13C NMR
(DMSO-d6, 125 MHz, ppm): δꢀ=ꢀ196.0, 162.7, 158.8, 142.2,
136.0, 129.3, 127.5, 120.1, 113.2, 58.8, 50.4, 39.8, 35.5, 32.2,
28.8, 27.1, 21.0.
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5 Supplementary information
Characterization of the products 8c, 8d, 8g and 4e is given
as Supplementary information available online (http://
dx.doi.org/10.1515/znb-2019-0155).
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ꢁꢀꢀꢀ
M. H. Sayahi et al.: Synthesis of 4-azaphenanthrene-3,10-dione, 1,8-dioxo-octahydroxantheneꢂ
ꢂ11
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Supplementary Material:ꢀThe online version of this article offers
supplementary material (https://doi.org/10.1515/znb-2019-0155).
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Z. Naturforsch.ꢂ
ꢂ2020 | Volume x | Issue x(b)
Graphical synopsis
Mohammad Hosein Sayahi, Maryam
Gorjizadeh, Melan Meheiseni and Soheil
Sayyahi
One-pot multi-component process for
the synthesis of 4-azaphenanthrene-
3,10-dione, 1,8-dioxo-octahydroxanthene
and tetrahydrobenzo[b]pyran derivatives
catalyzed by the deep eutectic solvent
choline chloride-oxalic acid
https://doi.org/10.1515/znb-2019-0155
Z. Naturforsch. 2020; x(x)b: xxx–xxx
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