Synthesis of calcium silicate nanoparticles and its catalytic application in Friedlander reaction

Article abstract of DOI:10.1080/24701556.2016.1241274

This work describes the nitric acid catalysed synthesis of wollastonite (CaSiO3) nanoparticles (NP) from tetraethyl orthosilicate and calcium nitrate tetrahydrate. The formed calcium silicate nanoparticles were characterized by Fourier transform infrared

Full text of DOI:10.1080/24701556.2016.1241274

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Synthesis of Calcium silicate nanoparticles and its catalytic application in Friedlander
reaction
Jeyakannu Palanirajaa, Prabhakarn Arunachalamb, U. Vijayalakshmic,*, Mohamed A.
Ghanemb, Selvaraj Mohana Roopana,*
aChemistryof Heterocycles & Natural Product Research Laboratory, Department of Chemistry,
School of Advanced Sciences; VIT University, Vellore 632 014, India.
bElectrochemistry Research Group, Chemistry Department, College of Science, King Saud
University, Riyadh 11451, Saudi Arabia.
cDepartment of Chemistry, School of Advanced Sciences; VIT University, Vellore 632 014,
India.
Corresponding Author: * Email: mohanaroopan.s@gmail.com; mohanaroopan.s@vit.ac.in;
Abstract
This work describes the nitric acid catalysed synthesis of wollastonite (CaSiO3) nanoparticles
(NP) from tetra ethyl ortho silicate and calcium nitrate tetra hydrate. The formed calcium
silicate nanoparticles were characterized by Fourier transforms infra-red spectroscopy (FT-IR),
Powder X-ray Diffraction (PXRD) and scanning electron microscopy (SEM) equipped with X-
ray micro analysis. The CaSiO3 NPs showed an excellent yield (93%) towards the synthesis of
quinolines via Friedlander reaction. The synthesised compound 3-dimethyl-7-nitro-9-phenyl-
3,4-dihydroacridin-1(2H)-one was characterized by various spectroscopic techniques.
Keywords
Calcium silicate, Particles, nanosized, Friedlander reaction, Spectroscopy
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1. Introduction
Ceramic processing is the developing of chemical route for blending the powder
materials [1]. The Wollastonite (CaSiO3) is a significant material in ceramics, tile and cement
manufacturing industries. A congregation of favourable properties such as low shrinkage,
whiteness, lack of volatile constituents, good strength, fluxing characteristics, body permeability,
and acicular shape render wollastonite useful in several ceramic and other applications [2].
Recently, the novel techniques such as spray pyrolysis sol–gel [3-6], hydrothermal [7], polymer
pyrolysis [8], etc. has been successfully employed for synthesis of silicate-based phosphor. The
ceramics of calcium silicates (CaSiO3) are identifying as a hopeful bioactive materials for bone
tissue engineering [9].
Heterocyclic compounds have considered as one of the important molecules in
pharmaceutical applications. Today’s severe environmental problem is to reduce the formation of
inorganic wastes, solvent waste, and side products [10-13]. The chemistry field is moving
towards the eco-friendly synthesis [14, 15]. Important research and development frontier in
modern science is Nanoscience [16]. By reducing the catalyst’s size, there will be a more
surfaces has been exposed to the reactants for good yield [17-19]. In continuation of our earlier
work, we have utilized CaSiO3 as nanocatalysts for the formation of quinolines. We have
developed inexpensive, economic and novel route for the synthesis of calcium silicate (CaSiO3)
NPs. The produced CaSiO3 NPs then was used as a catalyst towards the synthesis of quinolines
via Friedlander reaction.
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2. Methodology
2.1. General procedure for synthesis of CaSiO3 NPs
The following compounds were added to double distilled water in the sequential order:
1.0 M HNO3, Tetra Ethyl Ortho Silicate (TEOS 99% purity) and soluble calcium nitrate tetra
hydrate (Ca (NO3)2.4H2O 99% purity). 16.67g of TEOS was added to double distilled water
under vigorous stirring. Then added 4.72g of [Ca (NO3)2. 4H2O] that was dissolved in 12 ml of
1.0 M HNO3 under stirring. After 30 min of hydrolysis, a homogeneous solution was obtained.
Nitric acid was used to catalyse the TEOS hydrolysis using H2O/TEOS molar ratio of 12:1 and
H2O/ HNO3 volume ratio of 6:1. The round bottom (RB) flask containing solution was
hermetically sealed and placed in an oil bath at different ageing temperature at 50 C to 90 C for
5 h. Finally, the gel was dried in an oven at 110 C for 16 h. The dried gels were recovered from
the oven and transferred into an alumina crucible and sintered at 900 C for 2 h to obtain the
CaSiO3 catalyst.
As shown in scheme 1, an equimolar amount of (2-amino-5-nitrophenyl)
(phenyl)methanone, 1 and 5,5-dimethylcyclohexane-1,3-dione, 2 were taken in an clean round
bottom flask and 10 mol % CaSiO3 NPs were added to the flask and the mixture was heated at
120 C for 30 min. The movement of the reaction was supervised by thin layer chromatography
test. The reaction mixture was allowed to room temperature and EtOAc (2*30 mL) was added.
Then the reaction mixture was filtered and evaporated the filtrate followed by washing with
hexane to afford the product as off-white solid with yield of 93 %. The used CaSiO3 NPs was
separated and dried for further utilized for the same reaction. The CaSiO3 NPs has been reused
five times without significant variation in the isolated yield and it was clearly stated in Figure 2.
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We have carried out five replications, provided the isolated yields 93, 93, 91, 91 and 90 %
respectively.
Characterization of 3, 3-dimethyl-7-nitro-9-phenyl-3,4-dihydroacridin-1(2H)-one, 3

1
The off-white solid; Yield 93 %; mp: 195-197 C; H NMR (400 MHz, CDCl3) δ 1.20 (s, 6H, -
CH3), 2.64 (s, 2H, -CH2), 3.34 (s, 2H, -CH2),7.20 – 7.22 (m, 2H, ArH), 7.57-7.59 (m, 3H, ArH),
8.19 – 8.22 (d, 1H, ArH), 8.45 – 8.46 (m, 1H, ArH), 8.51-8.54 (m,1H, ArH).; 13C NMR (100
MHz, CDCl3) δ 28.3, 32.2, 48.6, 54.1, 124.1, 124.8, 125.0, 126.7, 128.0, 128.5, 128.5, 130.4,
135.7, 145.5, 150.8, 152.8, 165.1, 197.1. HRMS: m/z calcd. for C21H18N2O3 346.1317 found
346.1142.
3. Results & discussion
Fig. 1 shows the FTIR, Powder XRD and SEM – EDAX characterisation of CaSiO3 NPs.
The XRD displays more noticeable development of 320, –432 and –921 hkl crystal planes of
calcium silicate (JCPDS Card No. 27-0088) and it confirms the presence of crystalline nature of
CaSiO3 nanoparticles (Fig. 1a). In application point of view, we have optimized the Friedlander
reaction conditions using CaSiO3 NPs (10 mol %). In Fig. 1b the FTIR spectra shows the H-O-H
deformation band observed at 1631cm-1 indicates the presence of incorporated water in the SiO2
network. The hydroxyl band at 3450cm-1 was attributed to OH- groups on the surface of silicone
which could be due to the formation of silica gel through hydrolysis and condensation of TEOS
(387). The bands at 470 and 810 cm-1 are attributed to the ring structure of the SiO4 tetrahedral.
The absorption sharp peak at 1086 cm-1 suggested the cross-linking of Si-O-Si bands that
occurred via hydrolysis and condensation (385). This observation was further confirmed by the
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fact that the intensity of the band at 950 cm-1, related to Si-OH stretching vibration is also found
to be developed (Fig. 1b). From the SEM analysis (Fig. 1c), the particles are found to be
spherically agglomerated, and the size of the particles are in the range of 200 nm. The elemental
composition of calcium silicate powder was further evidenced by EDAX analysis in Fig. 1d. All
the corresponding elements such as Ca and Si are confirmed from the spectra, and the Au peak
has arisen from the gold substrate used for the analysis.
The spectroscopic assignment of the acridone, 3 was done and shown in (Fig. S1). In 1H NMR
of the compound, 3 there are three singlets, and it has 12 protons which include 6 methyl and 6
methylene protons. A singlet peak at δ 0.91 assigned to 6 methyl protons (2* -CH3), another
two singlets are appeared at δ 2.35 and δ 3.13 corresponding to the 6 methylene protons ( 3 * -
CH2). In the case of compound 1, there are 10 protons which include 8 aromatic protons and one
–NH2 protons. The –NH2 proton appears at δ 6.06, and aromatic protons appear in the range of δ
6.67-7.61 (Fig. S2). The product 3 has 18 protons which include 6 methyl, 4 methylene and 8
aromatic protons. The 6 methyl protons (H-20 and H-21) shown at δ 1.21 (2 * -CH3) and 4
methylene protons (2 * -CH2) shown at δ 2.64 (H-4) and δ 3.34 (H-2). Then the remaining eight
Ar-H were resonating in the range of δ 7.50 – 8.54 (8 ArH)
In 13C NMR, there are 4 signals at δ 28.3, 32.2, 48.6, and 54.1 are corresponds to C-20, C-21,
C-3, C-4 and C-2 respectively. The C-20 and C-21 appear at single signal due to their same
environment and we are getting a peak at δ 197.1 is assigned for C-1 (-C=O carbon). The
remaining protonated and non-protonated carbons resonate in their respective aromatic region.
The compound 3 has two methyl carbons (C-20, C-21), two methylene carbons (C-2, C-4), one
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aliphatic methine carbon (C-3), seven aromatic non-protonated carbons, eight aromatic methine
carbons and one carbonyl carbon (Fig S3). The assignment of aromatic carbon by using 13C
NMR alone is quite difficult. The assignment of carbon peaks is simplifying by recording DEPT
-45, DEPT-90 and DEPT-135. The DEPT – 45 NMR of the compound 3 shows only protonated
carbons. It shows 11 protonated carbon signals which is matching with the required product. The
DEPT -90 NMR also recorded for compound 3, there are eight methine carbons complies with
product’s structure. We are getting 6 signals from DEPT -90 NMR, the C-14 and C-18 appears at
δ 128.0 and C-15 and C-17 appears at 128.5 due to their same environment (Fig. S3). We also
record the DEPT -135 NMR for compound 3 which provides the information about methyl,
methylene and methine carbons attached to the compound. We are getting, one upward signal at
δ 28.3 corresponds to C-20and C-21. Then two inverted signals at δ 48.8 and δ 54.1 are an
assignment for C-3 and C-4 respectively. Usually, the methine carbons are not shown in DEPT-
135 NMR.
4. Conclusions
We developed an easy and economic method to synthesize calcium silicate NPs. The calcium
silicate NPs provide promising result towards the synthesis of quinolones via Friedlander
reaction and 93 % of yield was achieved.
Supplementary Material
Supplemental data for this article can be accessed at the publisher’s website.
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Acknowledgements
We acknowledge the support by VIT-SIF for NMR and GC-MS analysis. The authors would
like to extend their sincere appreciation to the Deanship of Scientific Research at King Saud
University for funding this Research group NO: RG-1437-015. Dr. S. Mohana Roopan thanks
DST and DBT for providing research fund.
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(a)
(b)
Si-O-Si stretch
Si-O-Si bending
750 500
Wavenumber(cm-1)
1500
1250
1000
20
30
40
2theta()
50
60
70
(c)
(d)
Fig. 1 XRD (a), FT-IR (b), SEM (c) and EDAX (d) analysis of calcium silicate
nanoparticles `
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Fig. 2 Reusability of CaSiO3 NPs towards a Friedlander reaction
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Scheme. 1 Synthesis of 3,3-dimethyl-7-nitro-9-phenyl-3,4-dihydroacridin-1(2H)-one, 3
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