Biogenic synthesis of ZnO nanoparticles from Parthenium histerophorus extract and its catalytic activity for building bioactive polyhydroquinolines

Article abstract of DOI:10.1007/s11164-020-04365-8

Abstract: In the present protocol, biogenic synthesis of ZnO nanoparticles using an aqueous extract of weed, i.e. Parthenium is efficiently carried out. The proficient and operationally simple catalytic application of biogenic ZnO nanoparticle is explored towards a synthesis of pharmaceutically relevant and densely functionalized polyhydroquinolines by condensation of four components viz. aromatic aldehyde, dimedone, ethyl acetoacetate, and ammonium acetate. The synthesized polyhydroquinolines were screened for their antimicrobial activity against bacteria and fungi; some of them exhibit better to excellent activity. The developed protocol is enriched with captivating advantages such as excellent yields, shorter reaction time, recyclable catalyst and constructive use of an aqueous extract of Parthenium for the synthesis of ZnO nanoparticle. Graphical abstract: [Figure not available: see fulltext.]

Full text of DOI:10.1007/s11164-020-04365-8

Research on Chemical Intermediates (2021) 47:1743–1758
https://doi.org/10.1007/s11164-020-04365-8
Biogenic synthesis of ZnO nanoparticles from Parthenium
histerophorus extract and its catalytic activity for building
bioactive polyhydroquinolines
Prasad Mane1,2 · Bipin Shinde · Pankaj Mundada · Bhausaheb Karale ·
2
3
4
Arvind Burungale1
,5
Received: 25 April 2020 / Accepted: 11 December 2020 / Published online: 5 January 2021
©
The Author(s), under exclusive licence to Springer Nature B.V. part of Springer Nature 2021
Abstract
In the present protocol, biogenic synthesis of ZnO nanoparticles using an aque-
ous extract of weed, i.e. Parthenium is eꢀciently carried out. The proꢁcient and
operationally simple catalytic application of biogenic ZnO nanoparticle is explored
towards a synthesis of pharmaceutically relevant and densely functionalized poly-
hydroquinolines by condensation of four components viz. aromatic aldehyde, dime-
done, ethyl acetoacetate, and ammonium acetate. The synthesized polyhydroquino-
lines were screened for their antimicrobial activity against bacteria and fungi; some
of them exhibit better to excellent activity. The developed protocol is enriched with
captivating advantages such as excellent yields, shorter reaction time, recyclable cat-
alyst and constructive use of an aqueous extract of Parthenium for the synthesis of
ZnO nanoparticle.
Supplementary information The online version of this article (https://doi.org/10.1007/s11164-020-
0
4365-8)
*
Arvind Burungale
asburungale@gmail.com
1
2
3
4
5
Department of Chemistry, Yashavantrao Chavan Institute of Science, Satara,
Maharashtra 415001, India
Department of Chemistry, Karmaveer Bhaurao Patil College, Vashi, Navi Mumbai,
Maharashtra 400703, India
Department of Biotechnology, Yashavantrao Chavan Institute of Science, Satara,
Maharashtra 415001, India
Department of Chemistry, Radhabai Kale Mahila Mahavidyalaya, Ahmednagar,
Maharashtra 414001, India
Yashwantrao Chavan Mahavidyalaya, Pachwad, Satara, Maharashtra 415513, India
Vol.:(012
1
3456789)
3

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P. Mane et al.
Graphical abstract
Keywords Biogenic synthesis · Heterocycles · Heterogeneous catalysis ·
Polyhydroquinoline
Introduction
The intention of scientiꢁc community is changed towards conservation of the
environment, thus catalyst recovery and reusability have great signiꢁcance in
catalysis. New catalytic synthetic methods in organic chemistry that satisfy
environmental constraint are largely accepted by the pharmaceutical and chemi-
cal industries [1–5]. Nanotechnology is emerging as a brand new discipline of
research coping with the synthesis of nanoparticles and nanomaterials for their
applications in numerous ꢁelds such as electrochemistry, catalysis, sensors,
and biomedicines. [6, 7]. Many chemical strategies are used for the synthesis
of nanoparticles; but, due to several barriers to those methods such as the use
of toxic compounds, requirement of very high temperature and time consump-
tion, research focus has recently shifted towards the improvement of easy and
eco-friendly synthesis protocols [8]. The synthesis of diꢂerent types of nanopar-
ticles from various weeds like parthenium has attracted considerable attention
[
9, 10]. Biogenic synthesis of nanoparticle fulꢁls the need for an eco-friendly
and environmentally clean synthetic method of a nanoparticles [11]. In recent
years, biogenic synthesis of nanoparticles and exploring their catalytic applica-
tion in organic transformation create a centre of attention in the ꢁeld of catalysis
[
12–14]. Zinc oxide nanoparticles (ZnO NPs) have a great ability to be used as
a catalyst for a variety of organic and inorganic reactions. Also, without diꢀ-
culty, retrievable ZnO NPs make them a promising, safe and reusable catalyst.
Hence, the cheaper and particularly eꢀcient ZnO NPs are used inside the natural
1
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Biogenic synthesis of ZnO nanoparticles from Parthenium…
1745
transformation [15, 16]. The synthesis of new chemical structures has always
been a major challenge in the ꢁeld of organic transformation. Multicomponent
reactions (MCRs) fascinated the research community because they address both
diversity and complexity in organic synthesis in the context of green chemistry
[
17, 18]. In MCRs, the nature of the catalyst plays a noteworthy role in determin-
ing yield, selectivity, and general applicability. Therefore, the development of an
inexpensive, retrievable, and heterogeneous catalyst for MCRs become an area of
remarkable attention. [19–23]
Nitrogen-containing heterocyclic compounds are present in several natural and
pharmaceutical products due to their vital role in human life. It has been reported
that polyhydroquinoline (PHQ) scaꢂolds are bioactive molecules and used in dif-
ferent kinds of pharmaceuticals (Fig. 1). Therefore, the synthesis of PHQ has
produced a great interest in organic and medicinal ꢁelds. These derivatives have
broad spectra of biological activities such as antihypertensive, vasodilator, anti-
mutagenic, antitumor, anticonvulsant, antidiabetic, antianxiety, antidepressive,
analgesic, seditative, bronchodilator, hypnotic, and anti-inꢃammatory activities.
Furthermore, these compounds are also used as calcium channel blockers for the
treatment of cardiovascular diseases like hypertension [24–31]. Literature survey
reveals that several protocols are used for the synthesis of PHQ using various
catalysts such as Sc(OTf) [32], CuO [33], t-BuOK [34], HClO4–SiO2 [35], mor-
3
pholine [36], Yb(OTf)3 [37], Mn(III) complex [38], magnetic Fe3O4 nanoparti-
cles [39], [Msim]Cl [40].
However, most of these methods suꢂer from some drawbacks such as low
yields, extended reaction times, harsh reaction conditions, tedious work-up pro-
cedures, toxic solvents and application of expensive catalysts. Therefore, a great
deal of eꢂort is directed to develop an eꢀcient catalytic system for the synthesis
of polyhydroquinoline to overcome the drawbacks. Here, we impart biogenic-syn-
thesized ZnO nanoparticle as an eꢀcient catalytic system for synthesis of poly-
hydroquinoline and more ever this is the ꢁrst time report on constructive use of
an aqueous extract of Parthenium for the preparation of ZnO nanoparticle and
its catalytic activity in the synthesis of bioactive polyhydroquinoline. Thus, the
synthesis of such bioactive molecules using modern-day catalytic tools such as
nanoparticles is an essential task in organic chemistry.
NO
2
Cl
CO
NO
CO
2
O
MeO
2
C
2
Et
MeO
2
C
2
Me
MeO
2
C
N
O
O
N
H
NH
2
N
H
N
H
Amlodipine
Fig. 1 Quinoline-based bioactive scaꢂolds
Nifedipine
Nicardipine
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P. Mane et al.
Experimental
General
All solvents, chemicals and reagents were purchased from Sigma-Aldrich and
used as received; 3-formyl chromone was prepared by Vilsmeier–Haack reaction
of 2-hydroxy acetophenone with DMF and POCl3. Melting points were recorded
by the open-glass capillary method and are uncorrected. The progress of the
reaction was monitored by thin-layer chromatography (TLC). The IR spectrum
(
υmax, cm-1) was recorded on lambda FTIR-7600 spectrophotometer using KBr
pellets. 1 H and 13 C spectra of pure products were recorded by using CDCl sol-
3
vent on Brucker 400 MHz and 100 MHz spectrometer, respectively, with TMS as
an internal standard.
Preparation of Parthenium leaves extract
To prepare the Parthenium leaves extract, around 5 mg of Parthenium leaves
were washed thoroughly with distilled water. Then, the leaves were deveined and
crushed in 10 ml of distilled water using mortar and pestle. The extract was col-
lected by passing through a double-layered muslin cloth.
Synthesis of ZnO nanoparticles
In a 250-ml conical ꢃask, 35 ml of 0.02 M of zinc acetate solution was taken. In
this, 2 ml of plant extract was added drop-wise. After this, the reaction was kept
under continuous vigorous stirring at room temperature for 4–5 h. Then, 2.0 M
NaOH solution was added drop-wise with continuous stirring to get a pale yellow
coloured solution and kept at room temperature overnight. The white precipitate
of Zn(OH) settles down at the bottom of the conical ꢃask. This white precipitate
2
is washed with distilled water for 2–3 times and then again washed with methanol
for 3–4 times and air-dried and then calcined at 400 °C for 3 h to get ZnO.
Typical procedure for the synthesis of polyhydroquinoline derivatives
A mixture of aromatic aldehyde (1 mmol), dimedone (1 mmol), ethyl acetoac-
etate (1 mmol) and ammonium acetate (1 mmol) in ethanol (10 ml) was stirred
at room temperature on a magnetic stirrer with ZnO nanoparticles (10 mol %) for
an appropriate time, as shown in Table 2. The TLC technique (ethyl acetate: hex-
ane—1:9, v/v) was used to monitor the said reaction. After the successful com-
pletion of the reaction, the product was isolated by extracting with ethyl acetate.
Then, catalyst recovery is done by the centrifugation method and is reused for
the next reaction after washing with distilled water and ethyl acetate. Finally, the
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Biogenic synthesis of ZnO nanoparticles from Parthenium…
1747
O
Ar
O
O
O
O
O
ZnO
O
+
+
+
NH OAc
Ar
H
4
O
Water:Ethanol
7:3
O
N
H
1
2
3
4
5
Scheme 1 Reaction between aldehyde, dimedone, ethylacetoacetate and ammonium acetate in the pres-
ence ZnO nanocatalyst
product was dried, recrystallized from hot ethanol and characterized by FTIR,
1
H-NMR and 13 C-NMR techniques (Scheme 1).
Results and discussion
Herein, we have synthesized ZnO NPs via two various paths: chemogenic
(
NaOH) and Parthenium leaf extract transformation from zinc acetate. We also
investigated the catalytic application of biogenic ZnO NPs for the synthesis of
polyhydroquinoline at room temperature. The characterization of ZnO NPs is
described below:
Fig. 2 XRD patterns, FTIR spectrum of ZnO NPs (simple co-precipitation method) (a, b) the XRD pat-
terns FTIR spectrum of Parthenium transformed ZnO NPs (c, d)
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1748
P. Mane et al.
Structural study of biogenic ZnO NPs
The structural study is conducted using the XRD technique. The XRD patterns
of chemogenic ZnO NPs (co-precipitation method) and Parthenium transformed
ZnO NPs is illustrated in Fig. 2a–d. It shows the polycrystalline nature of both
chemogenic and Parthenium transformed ZnO NPs. Bragg’s reꢃection peaks at
2
θ value of 31.72, 34.88, 36.72, 47.99, 56.56, 63.68, 67.90 and 69.36° correspond
to (100), (002), (101), (102), (110), (103), (112), and (201) lattice planes, respec-
tively. It also shows the maximum intense hkl plane (101) at 2θ 36.72°. These
peaks were in good agreement with the reported literature and well-consistent
with the JCPDS ꢁle No. 75–0576. The crystallite size (D) of ZnO was determined
by Debye–Scherrer’s formula, as shown in Eq. (1) [41].
kλ
D =
(1)
ꢀ
cos ꢁ
This shows that the synthesized NPs are identical to the hexagonal phase of zinc
oxide. The crystallite size (D) of ZnO NPs for the most intense plane (101) is
1
5.30 nm for biogenic ZnO NPs.
The Fourier transform infrared (FT-IR) spectra of ZnO NPs are shown in
Fig. 2b. IR band at 3430 shows the presence of (N–H) stretching of amines on
surface of ZnO NPs. IR bands at 2921, 1546, 1386 cm-1 indicate (C–H), (C=C),
(
–NO2) stretching of aromatic and nitrocompounds on the surface of ZnO NPs.
This shows that amino, various aromatic, nitrogroups of Parthenium leaf extract
are involved in the synthesis of ZnO NPs. These groups are incorporated on the
surface of ZnO NPs. The strong IR band at 422 cm-1 conꢁrms the presence of
Zn–O stretching vibration, which is consistent with the reported IR spectra for
ZnO NPs.
The eꢂect of Parthenium leaf extract is determined by comparing lattice strain
(
Table 1), calculated by using formula
ꢀav = ꢁ∕ tan ꢂ
(2)
The average lattice strain of parthenium transformed ZnO NPs is increased
than chemo genic ZnO (Table 1) due to the decrease in particle size. This shows
that various bio-groups of parthenium were directly involved and aꢂects the syn-
thesis of ZnO NPs. The agglomeration ZnO NPs is avoided due to presence of
phenolic, amino, various aromatic, nitrogroups in parthenium leaf extract.
Table 1 Eꢂect of parthenium leaf extract on FWHM, crystallite size and lattice strain of ZnO NPs
Nanoparticles
Source
2θ
FWHM
Crystallite
Size (nm)
Lattice
(
Degree)
(β)
Strain (%)
ZnO
ZnO
NaOH
36.30
0.008275
0.008290
20.25
15.30
0.6405
0.6880
Parthenium leaf 36.40
extract
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Biogenic synthesis of ZnO nanoparticles from Parthenium…
1749
2
Fig. 3 a UV–Visible absorption spectrum b (αhυ) versus hυ plot of ZnO parthenium transformed green
ZnO NPs
Fig. 4 FE-SEM (a, b) and EDS (c) images of Parthenium transformed green ZnO NPs
Optical measurement
Optical properties of parthenium transformed green ZnO NPs were conducted by
using the UV–visible spectrophotometer. The study has been carried within the
wavelength range of 200–800 nm (Fig. 3). Absorption edge was observed at 370 nm.
The band gap is premeditated by using formula
n
(αhυ) = A(Eg − hυ)
(3)
where, ‘n’ determines electronic transition causing absorption which is 3/2 for direct
forbidden, 1/2 for direct allowed, 2 for indirect allowed and 3 for indirect forbidden
transitions.‘α’ absorption coeꢀcient, ‘hν’ is incident photon energy, ‘A’ is constant.
2
The plot of (αhυ) verses hυ is conspired to get band gap for synthesized ZnO NPs
which is 3.24. It is nearly same as reported [41]
Morphological analysis
Parthenium transformed green ZnO NPs were studied by the FE-SEM technique.
Figure 4 depicts lower and higher magniꢁcation images of biogenic ZnO NPs. ZnO
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1750
P. Mane et al.
NPs display with a grain-like morphology (Fig. 4a and b). The average particle size
of ZnO NPs is 90 nm. This shows an eꢀcient surface available for nanocatalysis
in polyhydroquinoline synthesis. EDS technique is used for elemental analysis. The
peak values at 0.420, 1.266 keV approve the presence of O and Zn elements in syn-
thesized ZnO NPs (Fig. 4c). The weights (%) and atomic (%) conꢁrms the formation
of ZnO NPs via Parthenium leaf extracts.
Optimization of reaction conditions
To ꢁnd out the optimal reaction condition, we ꢁrst select the model reaction of
4
-chlorobenzaldehyde, dimedone, ethylacetoacetate, and ammonium acetate for the
synthesis of compound 5d (Entry 4, Table 3). In the absence of catalyst, the desired
product was obtained in very low yield after 8 h. On the other hand, good results
are obtained in the presence of ZnO catalyst (Table 2, Entries 2–8). Encouraged by
these good results in hand, we decided to optimize the reaction conditions (Table 3).
Thus, the use of a prepared catalyst in the synthesis of polyhydroquinoline deriva-
tives was investigated under diꢂerent reaction conditions. We optimized the reaction
conditions such as catalyst amount, solvent selection and reaction time. The solvent
eꢂect was checked by taking water, ethanol and diꢂerent combination of water and
ethanol mixtures. We found that 7:3 water/ethanol was the best combination which
was conꢁrmed by the yield of the product (Table 2). Quantity of catalyst required for
the reaction is also checked by varying the mol% of ZnO catalyst using the model
reaction of 4-chlorobenzaldehyde, dimedone, ethylacetoacetate and ammonium ace-
tate. It was found that 10 mol% catalyst loading is enough for the completion of
reaction with an excellent yield of the product.
Also, it was found that the reaction can tolerate a wide range of aliphatic, hetero-
cyclic, and aromatic aldehydes carrying either electron-donating or electron-with-
drawing substituents in the ortho-, meta-, and para-positions (Table 3).
The catalysis of ZnO NPs (Co-precipitation and Parthenium transformed ZnO)
depicts excellent eꢀciency than reported literature (Table 4). It is also observed that
the catalysis of Parthenium transformed ZnO NPs is excellent with respect to yield
and time of reaction than ZnO NPs (Co-precipitation) catalysis. It is due to smaller
Table 2 Optimization of diꢂerent reaction conditions for the synthesis of polyhydroquinoline
Entry
Catalyst
mol %)
Solvent
Temperature
(°C)
Time
Yield
(%)
(
(min.)
1
2
3
4
5
6
7
8
No catalyst
Water
Water
Ethanol
Water: ethanol (9:1)
Water: ethanol (8:2)
Water: ethanol (8:2)
Water: ethanol (7:3)
Water: ethanol (7:3)
80
25
80
100
80
120
90
480
300
180
150
120
120
25
35
48
65
70
75
78
95
90
ZnO (5 mol%)
ZnO (5 mol%)
ZnO (10 mol%)
ZnO (10 mol%)
ZnO (15 mol%)
ZnO (10 mol%)
ZnO (15 mol%)
120
45
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3

Biogenic synthesis of ZnO nanoparticles from Parthenium…
1751
Table 3 Synthesis of various polyhydroquinolines using ZnO as a catalyst
Entry
Aromatic Aldehyde
Time (min.)
Yield
Melting Point (°C)
Found
Literature
5
a
30
90
201–204
202–204 [42]
O
O
O
N
H
5
b
Me
35
90
259–262
260–261 [42]
O
O
O
N
H
5
5
5
c
d
e
OMe
35
25
25
91
95
94
257–260
245–246
241–243
257–259 [42]
245–248 [43]
242–244 [44]
O
O
O
O
O
O
O
O
O
N
H
Cl
N
H
NO
2
N
H
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3

1752
P. Mane et al.
Table 3 (continued)
Entry Aromatic Aldehyde
Time (min.)
25
Yield
92
Melting Point (°C)
Found
Literature
5
f
Cl
240–242
241–243 [45]
Cl
O
O
O
N
H
5
5
5
5
g
h
i
Br
30
25
40
45
90
94
85
88
253–254
183–185
210–212
251–253
253–255 [44]
184–186 [45]
209–211 [45]
New Report
O
O
O
N
H
F
O
O
O
N
H
OH
MeO
O
O
O
N
H
j
O
O
O
O
O
N
H
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3

Biogenic synthesis of ZnO nanoparticles from Parthenium…
Table 3 (continued)
1753
Entry
Aromatic Aldehyde
Time (min.)
Yield
86
Melting Point (°C)
Found
Literature
New Report
5
k
Me
45
255–257
O
O
O
O
O
N
H
5
l
Br
45
90
258–261
New Report
O
O
O
O
O
N
H
5
5
m
n
35
35
87
85
245–247
237–239
246–248 [42]
238–240 [42]
O
O
O
O
N
H
S
O
O
O
N
H
particle size of biogenic ZnO. This directly shows the involvement of parthenium
leaf extract for in situ synthesis of ZnO.
Minimum inhibition concentration (MIC) evaluation
The agar cub method [46] was imparted for assessment of the minimum inhibi-
tory concentration (10–100 μg) for antimicrobial testing of various polyhydro-
quinoline derivatives. The two bacterial strains E. coli (gram-negative) and B.
subtilis (gram-positive bacteria) were used for the determination of MIC values
using ampicillin as positive and 1% DMSO as negative control. Similarly, two
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P. Mane et al.
Table 4 Comparison of results of ZnO nanoparticles with and without leaf extract for synthesis of poly-
hydroquinoline with literature reported catalysts
Entry Catalyst
Conditions
Time
Yield (%) References
1
2
3
4
5
6
Nano-CuO
Yb(OTf)3
(Bzacen)MnCl
[Msim]Cl
No catalyst
Solvent free 25 °C
Ethanol
Ethanol, reꢃux
Ethanol, reꢃux
Ethanol
35 min 90
5 h 90
30 min 92
[31]
[35]
[36]
[38]
3 h
6 h
90
89
85
[40]
ZnO (simple co-precip-
Water: Ethanol (7:3) 1 h
Present work (First report)
itation)
6
Parthenium transformed Water: Ethanol (7:3) 25 min 95
ZnO
Present work (First report)
Table 5 Minimum inhibitory concentration (MIC) evaluation of synthesized various polyhydroquino-
lines
Entry
Antibacterial activity
Antifungal activity
E. coli
B. subtilis
A. niger
S. cereviase
5
5
5
5
5
5
5
5
5
5
5
5
5
5
a
b
c
d
e
f
g
h
i
j
k
l
m
n
32.67± 1.15
26.33± 1.53
29.00± 1.00
22.33± 0.58
21.67± 1.53
22.33± 0.58
20.33± 1.53
19.67± 1.53
25.33± 1.15
26.67± 0.58
28.67± 1.53
20.67± 0.58
23.67± 1.15
24.33± 1.53
23.00± 1.00
–
29.00± 1.00
20.67± 1.53
31.33± 1.53
25.67± 1.15
20.00± 1.00
21.67± 1.53
19.67± 0.58
20.33± 0.58
27.00± 1.00
21.00± 1.00
27.00± 1.00
20.67± 1.15
22.67± 0.58
25.00± 1.00
21.67± 0.58
–
29.67± 1.15
26.33± 0.58
24.33± 0.58
23.67± 1.53
15.67± 0.58
16.00± 1.00
13.33± 0.58
16.67± 0.58
28.67± 1.15
33.33± 0.58
23.33± 1.15
16.33± 0.58
16.67± 0.58
18.33± 0.58
–
28.33± 0.58
29.33± 1.15
28.33± 0.58
25.33± 0.58
16.67± 0.58
16.33± 1.53
15.33± 0.58
17.67± 0.58
32.67± 0.58
29.67± 1.53
22.00± 1.00
17.33± 0.58
21.33± 0.58
19.67± 0.58
–
Ampicillin
Miconazole
16.67± 0.58
19.67± 0.58
fungal stains A. niger and S. cereviase using miconazole as the standard drug
were used for the evaluation of the minimum inhibitory concentration. The above
data represent the mean ± standard error of three replicates (Table 5). MIC is the
lowest concentration of a drug that inhibits the growth of a particular organism
under a speciꢁc condition. Among them, 5e, 5f, 5 g, 5 h, 5 l exhibit excellent
results. Analysis of structure–activity relationship suggested that the substituted
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3

Biogenic synthesis of ZnO nanoparticles from Parthenium…
1755
functional group nitro, chloro, bromo and ꢃuoro plays a signiꢁcant role in micro-
bial inhibitory activity.
Reusability of catalyst
Recovering and recycling are major advantages of heterogeneous catalysts com-
pared to homogeneous catalysts. The recyclability of the catalyst was studied using
a model reaction between 4-chlorobenzaldehyde, dimedone, ethyl acetoacetate and
ammonium acetate in the presence of the catalyst under the optimization conditions.
After completion of the reaction, the product was extracted by using ethyl acetate
and the catalyst was separated by the centrifugation method. Finally, the pure prod-
uct was obtained by recrystallizing it from hot ethanol. The recycled catalyst was
washed, dried and reused for further runs without a noticeable decrease in catalytic
activity even after ꢁve consecutive runs (Fig. 5).
Spectroscopic data of some synthesized polyhydroquinoline derivatives
Ethyl 1, 4, 5, 6, 7, 8‑hexahydro‑2, 7,
7‑trimethyl‑5‑oxo‑4‑phenylquinoline‑3‑carboxylate (Entry 5a, Table 2)
−
1
IR (υ , cm , KBr): 3310.25 (N–H), 1720.36 (ester C=O), 1632.19 (ketone C=O);
max
1
H NMR (400 MHz, CDCl , δ ppm): 0.84 (s, 3H), 1.01 (s, 3H), 1.13 (t, J=7.1 Hz,
3
3
H), 2.12–2.45 (m, 4H), 2.41 (s, 3H), 3.96 (q, J=7.1, 2H), 4.84 (s, 1H), 7.22–7.06
1
3
(
m, 5H), 9.07 (s, 1H); C NMR (100 MHz, CDCl , δ ppm): 19.54, 21.65, 27.24,
3
2
1
7
9.42, 32.76, 35.77, 41.22, 50.71, 51.03, 105.91, 112.50, 127.66, 128.73, 135.45,
43.49, 143.89, 147.65, 167.91, 195.45. Anal. Calcd. for C H NO : C, 74.31; H,
2
1
25
3
.42; N, 4.13. Found: C, 74.35; H, 7.46; N, 4.17. These spectroscopic values are
shown in electronic supplementary data (ESM 1).
Ethyl 4‑(4‑chlorophenyl)‑1, 4, 5, 6, 7, 8‑hexahydro‑2, 7, 7‑trimethyl‑5‑oxoquinoline
‑3‑carboxylate (Entry 5d, Table 2)
−
1
IR (υ , cm , KBr): 3413.38 (N–H), 1724.04 (ester C=O), 1631.41 (ketone C=O);
max
1
H NMR (400 MHz, CDCl , δ ppm): 0.81 (s, 3H), 1.08 (s, 3H), 1.11 (t, J=6.5 Hz,
3
3
H), 1.94–2.44 (m, 4H), 2.44 (s, 3H), 3.94 (q, J=6.5 Hz, 2H), 4.84 (s, 1H), 7.40
Fig. 5 Reusability of catalyst for
100
95
synthesis of polyhydroquinoline
94
9
3
9
2
9
9
8
8
5
0
5
0
89
1
2
3
4
5
Runs
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3

1756
P. Mane et al.
(
d, J=8.8 Hz, 2H), 7.05 (d, J=8.8 Hz, 2H), 9.14 (s, 1H); 13C NMR (100 MHz,
CDCl , δ ppm): 19.46, 27.10, 29.42, 32.71, 36.07, 41.09, 50.67, 50.07, 105.36,
3
1
11.87, 119.86, 129.66, 131.05, 143.94, 145.87, 148.10, 167.63, 195.44. Anal Calcd
for C H ClNO : C, 67.46; H, 6.47; Cl, 9.48; N, 3.75. Found: C, 67.49; H, 6.51; Cl,
2
1
24
3
9
.52; N, 3.79. These spectroscopic values are shown in electronic supplementary
data (ESM 2).
Ethyl 4‑(4‑nitrophenyl)‑1, 4, 5, 6, 7, 8‑hexahydro‑2, 7, 7‑trimethyl‑5‑oxoquinoline
‑3‑carboxylate (Entry 5e, Table 2)
−
1
IR (υ , cm , KBr): 3381.80 (N–H), 1720.06 (ester C=O), 1639.19 (ketone C=O),
max
1
1
1
521.77, 1345.25 (NO group); H NMR (400 MHz, CDCl , δ ppm): 0.89 (s, 3H),
2
3
.10 (s, 3H), 1.14 (t, J=6.8 Hz, 3H), 2.12–2.30 (m, 4H), 2.35 (s, 3H), 3.89 (q,
J=6.8 Hz, 2H), 4.96 (s, 1H), 7.80 (d, J=7.2 Hz, 2H), 8.05 (d, J=7.2 Hz, 2H), 9.16
1
3
(
s, 1H); C NMR (100 MHz, CDCl , δ ppm): 14.17, 19.32, 27.04, 29.37, 32.73,
3
3
1
6
6.98, 40.77, 50.57, 60.07, 104.95, 111.02, 121.27, 122.87, 128.62, 134.77, 144.72,
48.18, 149.29, 149.41,167.00, 195.71. Anal Calcd for C H N O : C, 65.61; H,
2
1
24
2
5
.29; N, 7.29. Found: C, 65.67; H, 6.31; N, 7.32. These spectroscopic values are
shown in electronic supplementary data (ESM 3).
Ethyl 1, 4, 5, 6, 7, 8‑hexahydro‑2, 7, 7‑trimethyl‑5‑oxo‑4‑(4‑oxo‑4H‑chromen‑3‑yl)
quinoline‑3‑carboxylate (Entry 5j, Table 2)
−
1
IR (υ , cm , KBr): 3315.05 (N–H), 1727.06 (ester C=O), 1624.41 (ketone C=O);
max
1
H NMR (400 MHz, CDCl , δ ppm): 0.91 (s, 3H), 1.05 (s, 3H), 1.08 (t, J=7.4 Hz,
3
3
H), 2.12–2.30 (m, 4H), 2.39 (s, 3H), 4.05 (q, J=7.4 Hz, 2H), 4.90 (s, 1H),
1
3
7
.13–7.31 (m, 1H), 7.43–7.63 (m, 4H), 9.20 (s, 1H); C NMR (100 MHz, CDCl ,
3
δ ppm): 24.74, 26.92, 27.47, 31.97, 35.78, 42.22, 51.13, 115.36, 116.18, 123.08,
1
24.28, 126.48, 128.86, 134.12, 149.39, 154.26, 164.28, 191.18, 197.48. Anal Calcd
for C H NO : C, 70.74; H, 6.18; N, 3.44. Found: C, 70.79; H, 6.21; N, 3.48. These
2
4
25
5
spectroscopic values are shown in electronic supplementary data (ESM 4).
Conclusion
We have fabricated a simple, proꢁcient, and greener protocol for the synthesis of
pharmaceutically privileged scaꢂolds polyhydroquinoline via Hantzsch multi-
component condensation of aromatic aldehydes, dimedone, ethyl acetoacetate and
ammonium acetate employing biogenic ZnO nanoparticles from Parthenium extract
as a green and reusable catalyst. This nanocatalyst ZnO was characterized by XRD,
FTIR, UV, FE-SEM techniques and can be reused several times with little loss of
its catalytic activity. Some polyhydroquinoline derivatives (Entry 5e, 5f, 5 g, 5 h,
5
l) show better to excellent antimicrobial activity against fungi and bacteria which
proves their biological signiꢁcance. From an environment—economical point of
view, this method oꢂers several noteworthy advantages such as shorter reaction
time, simple workup procedure, environmentally benign reaction conditions, use of
1
3

Biogenic synthesis of ZnO nanoparticles from Parthenium…
1757
retrievable catalyst, non-toxic and low catalyst loading to furnish excellent yield of
the product.
Acknowledgements Authors are thankful to the Department of Chemistry, Yashavantrao Chavan Insti-
tute of Science, Satara for providing laboratory facilities and also thankful to the research advisory com-
mittee, for providing seed money.
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