DOI: 10.1002/slct.

201900907 Communications

1
2 z Sustainable Chemistry
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Citric Acid/MCM-48 Catalyzed Multicomponent Reaction:
6 An Efficient Method for the Novel Synthesis of Quinoline
7
8 Derivatives
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10 Samson O. Akpotu,[a, b] Brenda Moodley,[a] Boddu Vamsi,[c] Augustine Ofomaja,[b]
11 Suresh Maddila,*[a, c] and Sreekantha B Jonnalagadda[a]
12
13
A facile, efficient and suitable green approach has been molecules and the application of green chemistry principles,
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designated for the one-pot synthesis of quinoline derivatives in which are relevant in the framework of the present study.
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the presence of citric acid doped MCM-48 (CAMCM-48) as a Mobil catalytic material (MCM-48) is a distinctive class of
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heterogeneous catalyst. The prepared material was character- material which possesses narrow pore size distribution, uniform
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ized by using various techniques like P-XRD, SEM, TEM, TGA, pores, high surface area and thermal stability.[8–10] These proper-
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FTIR and structural properties was determined by BET analysis. ties displays the appropriateness of MCM-48 as a catalyst,
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The reaction progressed efficiently under ethanol solvent catalyst support and sorbent for carbon-based materials.[8,11]
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system at room temperature condition to afford the corre- The hydroxyl (OH) functional groups present on the silica (SiO2)
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sponding products. This protocol offers many advantages such surface can be exploited for specific adsorption and
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as simple synthesis, easy work-up, short reaction times catalysts.[12,13] MCM-48 surface alteration by citric acid (CA) will
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(15 min), good stability, reusability and no chromatographic noticeably increase its activity sites in the direction of cationic
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separation techniques plus excellent yields (91-98%). surfaces.
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Heterocyclic molecules have attracted significant attention
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in the fields of medicinal, agro chemical and computational
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studies.[14,15] A review of simple and facile approaches for the
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improvement of heterocyclic compounds is of utmost signifi-
29 Introduction
cance in organic chemistry[16,17] Quinolines are important
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Heterogeneous catalyst (HC) materials plays a significant building blocks in recent heterocyclic chemistry protocols due
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starring role in manufacturing chemical processes and most of to their huge biological and pharmaceutical possessions.[18–20]
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these procedures requires the use of solid catalysts in one or These quinoline derivatives are well-known for their various
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more stages.[1,2] HCs possesses unique physical and chemical biological activity such as anti-microbial,[21] anti-oxidant,[22] anti-
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properties such as low volatility, controlled miscibility and infective,[23] anti-cancer,[24] anti-viral,[25] Alzheimer’s,[26] and anti-
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thermal stability which are determinants to their simple malarial activities.[27] Also few quinolines are used as agro-
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recovery and recyclability.[3] Generally, HCs are valuable due to chemical agents.[28,29] Recently, these moiety protocols have
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simple synthetic approaches, cost-effectiveness, higher yields been described using different catalysts such as K2CO3,[30]
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and better selectivity.[3–5] In recent times, HCs have been proven AcOH,[31] ZrO2-SO3H,[32] nano-Fe3O4[33] and ZnO/ultrasound.[34]
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to play a significant role in multicomponent reactions (MCRs), Some of these protocols have shortcomings such as use of
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which contains one-pot preparation of different reactants. This toxic reagents, harsh reaction conditions, expensive reagents
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has led to vast investigation with the occurrence of scientific and catalysts, lengthy reaction times, lower yields and/or non-
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enhancements in biological and agrochemical fields.[6,7] Further, recyclability, which limits their scope in practical applications.
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MCRs are applied for relatively simple synthesis of organic Therefore, the development of an environmentally benign and
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high yielding protocol for the novel synthesis of quinoline
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derivatives will be highly advantageous.
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Therefore, we continue our investigation for improving the
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[a] Dr. S. O. Akpotu, Dr. B. Moodley, Dr. S. Maddila, Prof. S. B Jonnalagadda efficiency, eco-friendliness and green approach for the syn-
48 School of Chemistry & Physics, University of KwaZulu-Natal, Westville thesis of various heterocycles.[35–38] In recent past, we have
49 Campus, Chilten Hills, Private Bag 54001, Durban-4000, South Africa.
stated few methodologies for the synthesis of different
50 [b] Dr. S. O. Akpotu, Prof. A. Ofomaja
Department of Chemistry, Vaal University of Techology, P.Bag X021, medicinal stimulating molecules.[39–44] The current investigation
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Vanderbijlpak 1900, South Africa. lays emphasis on the synthesis of novel citric acid doped MCM-
52 [c] B. Vamsi, Dr. S. Maddila 48 solid material which was applied as a catalyst for the first
53 Department of Chemistry, GITAM Institute of Sciences, GITAM University,
time, and also its use in the synthesis of novel quinolines by
54 Visakhapatnam, Andhra Pradesh, India
E-mail: sureshmskt@gmail.com the reaction of aromatic aldehydes, malononitrile, 5,5-dimethyl-
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Supporting information for this article is available on the WWW under cyclohexane-1,3-dione and ammonium acetate at room tem-
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https://doi.org/10.1002/slct.201900907 perature with EtOH as green solvent in excellent yields.
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 Communications
Results and discussion
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Synthesis of functionalized 1,4-dihydropyridine-2,3-dicarboxy-
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lates were prepared by the reaction of aromatic aldehyde
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(1 mmol), 1,3-dicarbonyl compound (1 mmol), malononitrile
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(1 mmol), NH4OAc (1.1 mmol) and 1.0%CAMCM-48 (50 mg) in
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10 mL ethanol was added to a reaction flask and stirred at
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room temperature (R.T). The progress and the completion of
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reaction was monitored by TLC (Scheme 1). After completion of
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11 Figure 1. (a) Low angle scans of samples and (b) Wide angle scans of
12 samples
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Scheme 1. Synthesis of novel quinoline derivatives
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the reaction, catalyst was recovered by simple filtration.
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Subsequently, the ethanol solvent was evaporated and the
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separated solid was filtered and washed with ethanol to purify
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the products obtained. The resulting products were established
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on the basis of their physical properties and spectral data. The
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instrumentation details and physical characterization data are
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provided in supporting information (S1).
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Figure (1b) represents the XRD diffraction patterns for
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prepared un-modified MCM-48 and CA doped MCM-48 catalyst
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materials. 2.5CAMCM-48 exhibited crystalline peaks which was
33 Figure 2. FTIR spectra of samples
attributed to the presence of huge quantities of CA being
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loaded on the MCM-48 support. The large amorphous peaks
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observed (at 20 and 30(Θ)) characterizes siliceous material is an
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indication of the amorphous nature of the siliceous materials in Besides, absorption peaks observed at 1050 cm 1 and
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the samples.[12] Figure (1a) showed the low angle XRD scan 805 cm 1 corresponds to Si-O Si group due to asymmetric
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profiles for all catalyst materials acquired (from 0 to 6(Θ)). It stretching vibrations, respectively.[13] The band in the region of
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showed four intense reflection peaks at 200, 210, 400 and 420 1425 cm 1 may be ascribed to C O from the -COOH group
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for MCM-48 material with a distinctive cubic Ia3d symmetry.11 from citric acid which was non-existent in the unmodified
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The peak intensity was decreased by increasing CA concen- material. CA grafting resulted in vibrations around 1715–
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tration. The variances in CA concentration led to deviation in 1730 cm 1, which was due to the esterification of CA with
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spectra peaks signifying that the CA absorption showed a MCM-48 forming a C=O bond from the COOH group in CA.
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significance part in the silica phase. However, for 2.5CAMCM-48 This image represents the thermal profile of MCM-48 and
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with a higher CA concentration, the two diffraction peaks (400 CAMCM-48 catalyst materials. For MCM-48 degradation, firstly
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and 420) disappeared signifying partial reduction in orderliness there was the removal of adsorbed water which occurred with
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of mesoporous structure. a weight loss of 4.5% at 150 °C. The next phase had a
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FTIR spectra of pure MCM-48 and CA doped MCM-48 degradation loss in mass of about 0.5% at 350 °C, it had a
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catalyst material was presented in Figure 2. The broad vibration minor loss in mass owing to the decomposition of residual
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bands at 3400 cm 1 for both materials are attributed to the carbon, loss of H2O from silanol, dehydroxylation and removal
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presence of water and –OH stretch functional groups. For of CTAB organic groups. Beyond 650 °C MCM-48 became
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MCM-48, the main bands present at 960 and 1630 cm 1, thermally stable, with no noticeable change in mass. For the
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conforms to the stretching and bending vibrations of Si-OH CA-doped MCM-48 degradation, initially, there was the removal
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group. Further, the band at 1630 cm 1 in CAMCM-48 is due the of physisorbed water in CA and CTAB at 150–350 °C. There
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inter-molecular hydrogen bond from the carboxyl groups. were further mass losses as carbon present in surfactant and
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CA decomposed. Further degradation occurred which can be
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ChemistrySelect 2019, 4, 7003 – 7009 7004 © 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
 Communications
ascribed to loss of water on condensation of adjacent silanol obtained from XRD analysis which revealed the hexagonal
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groups and removal of the CTAB template and residual carbon order of the MCM-48 mesopores. The morphology revealed a
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in CA at between 150–650 °C. The TGA data are provided in hexagonal shape with visible monomodal pore sizes of (2.3 nm)
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supporting information (S2). on the (100) crystal face and an even wall of parallel channels
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Figure 3 demonstrates the N2 adsorption-desorption iso- on 110 crystal face. The pore size of (2.3 nm) was similar to the
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therms and pore size distribution profiles for MCM-48 and values of (2.0 nm) obtained from the BET analysis. 2.5CAMCM-
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48 shown reduction to its ordered nature due to effect of
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which was also confirmed by P-XRD analysis.
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The stoichiometric quantities of the four reactants, 2-
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methoxybenzaldehyde 1 a (1.0 mmol), cyclohexane-1,3-dione 2
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(1.0 mmol), malonitrile 3 (1.0 mmol), and ammonium acetate 4
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(1.1 mmol) were used in the pilot reaction to examine the
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influence of various strictures on the scope of reaction and
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yields thereof, with the aim of an enhancing reaction
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conditions. Initially, in the absence of catalyst and solvent
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conditions, no reaction was noticed even after 10 h of stirring
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neither at R.T. nor reflux (Table 2, entries 1 & 2). Next,
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19 Figure 3. (a) N2 adsorption-desorption isotherms and (b) Pore size distribu- Table 2. Optimal condition for the synthesis of 5a by 1.0CAMCM-48
20 tion of samples catalysta
21 Entry Catalyst Solvent Condition Time (h) Yield (%)b
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1 – – R.T. 10 –
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CAMCM-48 catalyst materials. All the isotherms are of type-IV 2 – – Reflux 10 –
24 3 K2CO3 EtOH R.T. 8 17
with an H2 type hysteresis loop. It indicates that the pores
25 4 NaOH EtOH R.T. 7.5 15
inside the materials are typically of a mesoporous nature. The 5 pyridine EtOH R.T. 8.0 09
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catalyst materials have pore size in the range (2 - 4 nm) which 6 EMB EtOH R.T. 7.0 20
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characterizes mesoporous material according to IUPAC classi- 7 L-proline EtOH R.T. 6.5 24
28 8 AcOH EtOH R.T. 5.0 39
fication. MCM-48 had a mono modal narrow pore distribution
29 9 TFA EtOH R.T. 4.5 43
of 2 nm very close to the micro pore region. However, there 10 CA EtOH R.T. 2.5 51
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was a small pocket of pores between (6 - 10 nm) for 11 MCM EtOH R.T. 2.0 72
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2.5CAMCM-48. The results indicated that citric acid presents on 12 SiO2 EtOH R.T. 2.5 66
32 13 Fe3O4 EtOH R.T. 3.0 59
MCM-48 reduces surface area and pore volume (Table 1).
33 14 1.0CA/SiO2 EtOH R.T. 1.0 89
34 15 1.0CA/Fe3O4 EtOH R.T. 0.75 85
16 1.0CAMCM-48 EtOH R.T. 0.25 98
35 Table 1. Surface area, pore diameter and pore volume measurements for
a
36 MCM-48 and CAMCM-48 samples All products were characterised by IR, 1H NMR, 13C NMR, 15N NMR & HR-MS
37 spectral analysis. b Isolated yields.
Sample] SBET(m2/g) Pore diameter (nm) Pore volume (cm3/g)
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MCM-48 1048 2.64 0.91
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0.5CAMCM-41 792 2.91 0.60
40 1.0CAMCM-41 716 2.58 0.48 introducing of different catalysts to the synthetic ideal was
41 2.5CAMCM-41 472 2.87 0.35
examined at R.T. in EtOH solvent conditions. Basic inorganic
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and organic catalysts like K2CO3, NaOH and pyridine were
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examined to determine trace product at R.T. after 7 h (Table 2,
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SEM morphology (Figure 4) of MCM-48 contained a mixture entries 3–5). The ionic liquids 1-ethyl-3-methylimidazolium
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of circles and rods with a mean size of (95 nm) and an average bromide (EMB) and L-proline were tested to obtain lower
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diameter size of 2.8 nm. It appeared as an even aggregation desired product after 6 h of stirring (Table 2, entries 6 & 7).
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with visible void reflecting porosity of the materials. At near Furthermore, only moderate amount of product was produced
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observation of the SEM micrograph showed by CA as it is in the presence of acidic catalysts such as AcOH, trifluoroacetic
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noticeable on slight particle similar to circles of MCM-48. The acid (TFA) and citric acid (CA) at R.T. in ethanol solvent
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micrograph analysis of 2.5CAMCM-48 showed that it had condition (Table 2, entries 8–10). Interestingly, when the
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reduced pore volume and a condensed structure which reactions were also conducted, heterogeneous acidic catalysts
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indicated a higher concentration of CA loaded on MCM-48. like SiO2, Fe3O4, and MCM48 was ideal owing to their excess.
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HRTEM micrographs of all the materials are presented The product yields were good in short reaction time (Table 2,
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(Figures 5). They appeared as unique dimensional, vastly well- entries 11–13). Among the chosen acidic catalysts, citric acid
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arranged hexagonal-honey-comb structure of silicate material gave relatively higher yield (Table 2, entries 13). Therefore,
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which is typical of MCM-48. This corroborates the results using citric acid as support mixed oxide catalysts 1.0CASiO2,
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ChemistrySelect 2019, 4, 7003 – 7009 7005 © 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
 Communications

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33 Figure 4. SEM images of (a) MCM-48 (b) 0.5CAMCM-48 (c) 1.0CAMCM-48 (d) 2.5CAMCM-48

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Table 3. Optimization of various solvent conditions for 1.0CAMCM-48
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1.0CAFe3O4 and 1.0CAMCM-48, were prepared and their catalysta
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efficiency was tested to enhance catalytic activity. Extraordinary Entry Solvent Time (minutes) Yield* (%)
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yields (90-98%) were obtained with the mixed catalysts in
39 1 No solvent 120 –
15 min reaction time in ethanol and at R.T. (Table 2, entry 14–
40 2 n-hexane 120 –
16). Among the three catalysts investigated, 1.0CAMCM-48 3 1,4-dioxane 120 –
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gave the best results, which resulted into the target functional- 4 THF 90 21
42 5 DMF 90 29
ized quinolone in 98% yield selectively in 15 min reaction time
43 6 MeOH 45 88
under R.T.
44 7 EtOH 15 98
The pilot reaction was observed in the absence of solvent 8 isopropanol 60 70
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and also using various solvents to explore their influence in the a
46 Reaction conditions: catalyst (50 mg) and solvent (10 mL) were stirred at
preparation of quinolines. Initially, the reaction did not proceed room temperature. * = Isolated yields. – = No Reaction observed.
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under solvent free conditions (Table 3, entry 1). Subsequently,
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the reaction was conducted in non-polar solvents such as n-
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hexane and 1,4-dioxane, however, no product was formed in
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more reaction time (Table 3, entries 2 & 3). Then, polar aprotic Based on the progressive significances, 1.0CAMCM-48
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solvents like THF and DMF were used and low yields were catalyst was chosen to obtain excellent yields in EtOH solvent
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recorded. When polar protic solvents like isopropanol, EtOH conditions. When the amount of 1.0CAMCM-48 catalyst was
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and MeOH were used and yield were good (Table 3, entries 6– reduced from 50 mg to 20 mg, the reaction time increased
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8), with ethanol exhibiting the best result (Table 3, entry 7). It (from 15 to 60 min) and product yield decreased (from 98 to
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can therefore be concluded that polar solvents gave higher 62%) (Table 4). However, when the amount of catalyst was
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yields in a shorter reaction period. increased from 50 mg to 100 mg, yield did not improve with
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ChemistrySelect 2019, 4, 7003 – 7009 7006 © 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
 Communications

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30 Figure 5. HRTEM images of (a) MCM-48 (b) 0.5CAMCM-48 (c) 1.0CAMCM-48 (d) 2.5CAMCM-48
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33 Table 4. Optimization of various weight % for 1.0CAMCM-48catalysta Table 5. Synthesis of quinoline derivatives with 1.0CAMCM-48 catalysta
34 Entry Catalyst (mg) Time (min) Yield (%) Entry R Product Yield Mp °C Turnover frequency
35 (%) (min 1)
1 20 60 62
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2 40 60 80 1 4-Br 5a 98 212- 6.30
37 3 50 15 98 214
38 4 60 15 98 2 2-Cl 5b 97 197- 8.08
39 5 80 15 98 198
6 100 20 96 3 2,3- 5c 92 200- 7.15
40
a
(OCH3)2 201
41 Reaction conditions: catalyst and solvent (10 mL) were stirred at R.T. 4 2-Br 5d 94 219- 7.84
42 * = Isolated yields 221
43 5 4-OCH3 5e 92 282- 7.07
284
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6 2,5- 5f 95 212- 8.12
45 (OCH3)2 213
no benefit in reaction time (Table 4). Therefore, 50 mg of
46 7 3,4- 5g 93 240- 9.15
1.0CAMCM-48 at R.T. with EtOH as solvent was considered (OCH3)2 242
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optimized amount of catalyst for ideal reaction which gave 8 2,4,6- 5h 94 219- 7.81
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98% yield in short reaction time (15 min). (OCH3)3 221
49 9 H 5i 98 262- 6.30
– No reaction
50 263
After obtaining optimum reaction conditions, the simplifica- 10 Furan 5j 96 239- 8.08
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tion of this catalytic scheme was proven by a series of various 241
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aromatic aldehydes, cyclohexane-1,3-dione, malonitrile and 11 2-NO2 5k 92 208- 7.15
53 210
ammonium acetate to produce the anticipated products under
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the enhanced conditions. As presented in Table 5, we explored a
New compounds/no literature available
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the reaction with various aromatic aldehydes such as electron
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donating and/or electron withdrawing groups at ortho, meta
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ChemistrySelect 2019, 4, 7003 – 7009 7007 © 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
 Communications
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(NRF) of South Africa, and University of KwaZulu-Natal, Durban,
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Chem. 2016, 40, 770–780.
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50 Keywords: Green synthesis · Heterogeneous catalyst · MCM- 3413–3423
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 Communications
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4
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Maddila, Y. Kotaiah, S. Moganavelli, S. B. Jonnalagadda, Med. Chem. Res. Submitted: March 11, 2019
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2016, 25, 283–291. Accepted: June 4, 2019
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