Various aldoximes and ketoximes synthesis of corresponding aldehydes and ketones in the presence of SiO2@FeSO4 nano composite as recoverable nano catalyst and NH2OH·HCl. The SiO2@FeSO4 nano composite system was carried out between 10 to 15 min in oil bath (70-80 °C) under solvent-free condition in excellent yields in addition this protocol can be used for industrial scales. This method offers some advantages in term of clean reaction conditions, easy work-up procedure, short reaction time, applied to convert α-diketones to α-diketoximes (as longer than other carbonyl compounds), α,β-unsaturated aldehydes and ketones to corresponding oximes and suppression of any side product. So we think that NH2OH•HCl/SiO2@FeSO4 nano composite system could be considered a new and useful addition to the present methodologies in this area. Structure of products and nano composite elucidation was carried out by 1H NMR, 13C NMR, FT-IR, scanning electron microscopy (SEM).
Involvement of Deep Eutectic Solvents in Extraction by Molecularly Imprinted ...Michal Jablonsky
Substantial research activity has been focused on new modes of extraction and refining
processes during the last decades. In this field, coverage of the recovery of bioactive compounds and
the role of green solvents such as deep eutectic solvents (DESs) also gradually increases. A specific
field of DESs involvement is represented by molecularly imprinted polymers (MIPs). The current state
and prospects of implementing DESs in MIPs chemistry are, based on the accumulated experimental
data so far, evaluated and discussed in this minireview.
Investigation of Total Phenolic Content and Antioxidant Activities of Spruce ...Michal Jablonsky
Extracts from spruce bark obtained using dierent deep eutectic solvents were screened for
their total phenolic content (TPC) and antioxidant activities. Water containing choline chloride-based
deep eutectic solvents (DESs) with lactic acid and 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, and
1,5-pentanediol, with dierent molar ratios, were used as extractants. Basic characteristics of the DESs
(density, viscosity, conductivity, and refractive index) were determined. All the DESs used behave
as Newtonian liquids. The extractions were performed for 2 h at 60 C under continuous stirring.
TPC was determined spectrophotometrically, using the Folin-Ciocalteu reagent, and expressed as
gallic acid equivalent (GAE). The antioxidant activity was determined spectrophotometrically by
2,2-diphenyl-1-picrylhydrazyl (DPPH) radical scavenging assay. The TPC varied from 233.6 to
596.2 mg GAE/100 g dry bark; radical scavenging activity (RSA) ranged between 81.4% and 95%.
This study demonstrated that deep eutectic solvents are suitable solvents for extracting phenolic
compounds from spruce bark.
Physico-chemical Properties in Relation of Drug actionPradnya Gondane
This is the presentation for B. Pharm. IV semester students. It includes all the physico-chemical properties which affect drug action like solubility, ionization, pH, pKa, Protein Binding, Chelation, Hydrogen Bonding, Partition Coefficient and steric factors which includes, optical, conformational and bio isosters. This is prepared according to the PCI syllabus for B. Pharm. IV Semester students for Subject Medicinal Chemistry-I
Involvement of Deep Eutectic Solvents in Extraction by Molecularly Imprinted ...Michal Jablonsky
Substantial research activity has been focused on new modes of extraction and refining
processes during the last decades. In this field, coverage of the recovery of bioactive compounds and
the role of green solvents such as deep eutectic solvents (DESs) also gradually increases. A specific
field of DESs involvement is represented by molecularly imprinted polymers (MIPs). The current state
and prospects of implementing DESs in MIPs chemistry are, based on the accumulated experimental
data so far, evaluated and discussed in this minireview.
Investigation of Total Phenolic Content and Antioxidant Activities of Spruce ...Michal Jablonsky
Extracts from spruce bark obtained using dierent deep eutectic solvents were screened for
their total phenolic content (TPC) and antioxidant activities. Water containing choline chloride-based
deep eutectic solvents (DESs) with lactic acid and 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, and
1,5-pentanediol, with dierent molar ratios, were used as extractants. Basic characteristics of the DESs
(density, viscosity, conductivity, and refractive index) were determined. All the DESs used behave
as Newtonian liquids. The extractions were performed for 2 h at 60 C under continuous stirring.
TPC was determined spectrophotometrically, using the Folin-Ciocalteu reagent, and expressed as
gallic acid equivalent (GAE). The antioxidant activity was determined spectrophotometrically by
2,2-diphenyl-1-picrylhydrazyl (DPPH) radical scavenging assay. The TPC varied from 233.6 to
596.2 mg GAE/100 g dry bark; radical scavenging activity (RSA) ranged between 81.4% and 95%.
This study demonstrated that deep eutectic solvents are suitable solvents for extracting phenolic
compounds from spruce bark.
Physico-chemical Properties in Relation of Drug actionPradnya Gondane
This is the presentation for B. Pharm. IV semester students. It includes all the physico-chemical properties which affect drug action like solubility, ionization, pH, pKa, Protein Binding, Chelation, Hydrogen Bonding, Partition Coefficient and steric factors which includes, optical, conformational and bio isosters. This is prepared according to the PCI syllabus for B. Pharm. IV Semester students for Subject Medicinal Chemistry-I
Applications of click chemistry in drug discoveryrita martin
his article focus mainly on click chemistry mechanisms and its applications, click chemistry is an easy way to generate substances quickly and reliably by joining small units together, with this ease of use mechanism, click chemistry as found its applications in various technologies especially in drug discovery ,medicinal chemistry, enzyme activity, chemistry natural products, material science, polymers, nanotechnology and bioconjugation
This Powerpoint describes what is Flow chemistry, what are its advantages over batch method, Continuous flow reactor and Applications of Continuous flow chemistry.
It is the presentation for Combinatorial Chemistry. this presentation should be helpful for B. Pharm students. It includes introduction, types, applications, advantages and disadvantages.
FEASIBILITY STUDY OF TREATMENT OF EFFLUENT FROM A BULK DRUG MANUFACTURING IND...Journal For Research
A study has been carried out on aerobic biological treatment of a bulk drug industrial effluent which is highly acidic in nature and shows high value of BOD5 (≈ 36000 mg/l), COD (≈ 84000 mg/l). Chemical treatment conducted for neutralizing the pH followed by biological treatment using a lab-scale reactor with acclimatized bacterial consortia isolated from natural soil has confirmed its feasibility for biological treatment. About 99% removal of COD from starting value of around 8000 mg/l has been achieved. The COD value in different hydraulic retention time (HRT) has been brought down to less than 100 mg/l in treated effluent, showing high removal of dissolved organics by aerobic biological treatment.
Combinatorial chemistry by Sunil Yadav SD Bihani College sri gangangar sunilkamal1045
The Combinatorial Chemistry is a scientific method in which a very large number of chemical entities are synthesized by condensing a small number of chemical compounds together in all combinations defined by a small set of chemical reactions.
IJRET : International Journal of Research in Engineering and Technology is an international peer reviewed, online journal published by eSAT Publishing House for the enhancement of research in various disciplines of Engineering and Technology. The aim and scope of the journal is to provide an academic medium and an important reference for the advancement and dissemination of research results that support high-level learning, teaching and research in the fields of Engineering and Technology. We bring together Scientists, Academician, Field Engineers, Scholars and Students of related fields of Engineering and Technology
Need for Vapour-Liquid Equilibrium Data Generation of Systems Involving Green...IJERA Editor
Much has been said and written over the years regarding green chemistry concept and use of green solvents. The green solvents can potentially replace the traditional or classical solvents in order to reduce the environment footprint or their harmful impact on human being and/or environment. Vapour-liquid equilibrium data is indispensable for the design of distillation columns for separation processes which account for a large percentage of total costs in a typical chemical plant. Though extensive approach has been made for the replacement of traditional solvents, but not enough consideration been given for vapour-liquid equilibrium data, required for designing separation processes in case of replacement with green solvents. So this paper aims at encouraging vapour-liquid equilibrium data generation for design of efficient separation for binary systems involving ethereal green solvents such as cyclopentyl methyl ether (CPME) and 2-methyl tetrahydrofuran (2-MeTHF). A brief review and outline of procedure for generating vapour-liquid equilibrium data is presented here.
Isolation and Screening of Hydrogen Producing Bacterial Strain from Sugarcane...Editor IJCATR
The aim of this study is to isolate a highly competent bacterium with potent cellulose degrading capability and a better
hydrogen producer. Soil sample from sugarcane bagasse yard was isolated, serially diluted and plated on cellulose specific nutrient
agar plate. Four colonies have been isolated in which a single colony has potent cellulose degrading ability and the highest hydrogen
productivity of 275.13 mL H2 L-1. The newly isolated bacterium was morphologically and biochemically characterized. The
molecular characterization of the bacterium was carried out using 16S rDNA sequencing and the organism was identified as
Bacilllus subtilis AuChE413. Proteomic analysis such as MALDI-TOF was carried out to differentiate the isolated Bacillus subtilis
from Bacillus thuringiensis and Bacillus amyloliquefaciens. Phylogenetic tree was constructed to analyze the evolutionary
relationship among different genus and species with the newly isolated strain.
A STUDY TO EVALUATE THE IN VITRO ANTIMICROBIAL ACTIVITY AND ANTIANDROGENIC E...Dr. Pradeep mitharwal
The present paper deals with synthesis and characterization
of some new chromium (III) Schiff base complexes using microwave irradiation
technique as well as conventional heating. The S∩N donor benzothiazolines, 1-
(2-furanyl) ethanone benzothiazoline (Bzt1N
∩
SH), 1-(2-thienyl) ethanone
benzothiazoline (Bzt2N
∩
SH) and 1-(2-pyridyl) ethanone benzothiazoline
(Bzt3N
∩
SH) were prepared by the condensation of ortho-aminothiophenol with
respective ketones in ethanol.
Applications of click chemistry in drug discoveryrita martin
his article focus mainly on click chemistry mechanisms and its applications, click chemistry is an easy way to generate substances quickly and reliably by joining small units together, with this ease of use mechanism, click chemistry as found its applications in various technologies especially in drug discovery ,medicinal chemistry, enzyme activity, chemistry natural products, material science, polymers, nanotechnology and bioconjugation
This Powerpoint describes what is Flow chemistry, what are its advantages over batch method, Continuous flow reactor and Applications of Continuous flow chemistry.
It is the presentation for Combinatorial Chemistry. this presentation should be helpful for B. Pharm students. It includes introduction, types, applications, advantages and disadvantages.
FEASIBILITY STUDY OF TREATMENT OF EFFLUENT FROM A BULK DRUG MANUFACTURING IND...Journal For Research
A study has been carried out on aerobic biological treatment of a bulk drug industrial effluent which is highly acidic in nature and shows high value of BOD5 (≈ 36000 mg/l), COD (≈ 84000 mg/l). Chemical treatment conducted for neutralizing the pH followed by biological treatment using a lab-scale reactor with acclimatized bacterial consortia isolated from natural soil has confirmed its feasibility for biological treatment. About 99% removal of COD from starting value of around 8000 mg/l has been achieved. The COD value in different hydraulic retention time (HRT) has been brought down to less than 100 mg/l in treated effluent, showing high removal of dissolved organics by aerobic biological treatment.
Combinatorial chemistry by Sunil Yadav SD Bihani College sri gangangar sunilkamal1045
The Combinatorial Chemistry is a scientific method in which a very large number of chemical entities are synthesized by condensing a small number of chemical compounds together in all combinations defined by a small set of chemical reactions.
IJRET : International Journal of Research in Engineering and Technology is an international peer reviewed, online journal published by eSAT Publishing House for the enhancement of research in various disciplines of Engineering and Technology. The aim and scope of the journal is to provide an academic medium and an important reference for the advancement and dissemination of research results that support high-level learning, teaching and research in the fields of Engineering and Technology. We bring together Scientists, Academician, Field Engineers, Scholars and Students of related fields of Engineering and Technology
Need for Vapour-Liquid Equilibrium Data Generation of Systems Involving Green...IJERA Editor
Much has been said and written over the years regarding green chemistry concept and use of green solvents. The green solvents can potentially replace the traditional or classical solvents in order to reduce the environment footprint or their harmful impact on human being and/or environment. Vapour-liquid equilibrium data is indispensable for the design of distillation columns for separation processes which account for a large percentage of total costs in a typical chemical plant. Though extensive approach has been made for the replacement of traditional solvents, but not enough consideration been given for vapour-liquid equilibrium data, required for designing separation processes in case of replacement with green solvents. So this paper aims at encouraging vapour-liquid equilibrium data generation for design of efficient separation for binary systems involving ethereal green solvents such as cyclopentyl methyl ether (CPME) and 2-methyl tetrahydrofuran (2-MeTHF). A brief review and outline of procedure for generating vapour-liquid equilibrium data is presented here.
Isolation and Screening of Hydrogen Producing Bacterial Strain from Sugarcane...Editor IJCATR
The aim of this study is to isolate a highly competent bacterium with potent cellulose degrading capability and a better
hydrogen producer. Soil sample from sugarcane bagasse yard was isolated, serially diluted and plated on cellulose specific nutrient
agar plate. Four colonies have been isolated in which a single colony has potent cellulose degrading ability and the highest hydrogen
productivity of 275.13 mL H2 L-1. The newly isolated bacterium was morphologically and biochemically characterized. The
molecular characterization of the bacterium was carried out using 16S rDNA sequencing and the organism was identified as
Bacilllus subtilis AuChE413. Proteomic analysis such as MALDI-TOF was carried out to differentiate the isolated Bacillus subtilis
from Bacillus thuringiensis and Bacillus amyloliquefaciens. Phylogenetic tree was constructed to analyze the evolutionary
relationship among different genus and species with the newly isolated strain.
A STUDY TO EVALUATE THE IN VITRO ANTIMICROBIAL ACTIVITY AND ANTIANDROGENIC E...Dr. Pradeep mitharwal
The present paper deals with synthesis and characterization
of some new chromium (III) Schiff base complexes using microwave irradiation
technique as well as conventional heating. The S∩N donor benzothiazolines, 1-
(2-furanyl) ethanone benzothiazoline (Bzt1N
∩
SH), 1-(2-thienyl) ethanone
benzothiazoline (Bzt2N
∩
SH) and 1-(2-pyridyl) ethanone benzothiazoline
(Bzt3N
∩
SH) were prepared by the condensation of ortho-aminothiophenol with
respective ketones in ethanol.
New Green Synthesis Approaches of Pharmacologically Active Heterocyclic Compo...ijtsrd
Green chemistry is a rapidly developing field providing a proactive avenue for the sustainable development of future science and technology. Green chemistry can be applied to the design of highly efficient, environmentally benign synthetic protocols to deliver life saving medicines, and to accelerate lead optimization processes in drug discovery, while minimizing environmental impact. It also offers enhanced chemical process economics, concomitant with a reduced environmental burden. There are relatively environmentally benign protocols for the synthesis of pharmaceutically active heterocycles that highlight the advantages of using green chemistry, for example, by proceeding under microwave irradiation or in aqueous reaction media. Chandra Prakash Gharu "New Green Synthesis Approaches of Pharmacologically Active Heterocyclic Compounds" Published in International Journal of Trend in Scientific Research and Development (ijtsrd), ISSN: 2456-6470, Volume-6 | Issue-5 , August 2022, URL: https://www.ijtsrd.com/papers/ijtsrd51793.pdf Paper URL: https://www.ijtsrd.com/chemistry/other/51793/new-green-synthesis-approaches-of-pharmacologically-active-heterocyclic-compounds/chandra-prakash-gharu
International Journal of Engineering Research and Applications (IJERA) is an open access online peer reviewed international journal that publishes research and review articles in the fields of Computer Science, Neural Networks, Electrical Engineering, Software Engineering, Information Technology, Mechanical Engineering, Chemical Engineering, Plastic Engineering, Food Technology, Textile Engineering, Nano Technology & science, Power Electronics, Electronics & Communication Engineering, Computational mathematics, Image processing, Civil Engineering, Structural Engineering, Environmental Engineering, VLSI Testing & Low Power VLSI Design etc.
IJERA (International journal of Engineering Research and Applications) is International online, ... peer reviewed journal. For more detail or submit your article, please visit www.ijera.com
Ecofriendly green biosynthesized of metallic nanoparticles: Bio-reduction mec...Al Baha University
Biomolecules of live plants, plant extracts and microorganisms such as bacteria, fungi, seaweeds, actinomycetes, algae and microalgae can be used to reduce metal
ions to nanoparticles. Biosynthesized nanoparticle effectively controlled oxidative stress, genotoxicity and apoptosis related changes. Green biosynthesized NPs
is alternative methods, which is hydrophilic, biocompatible, non-toxic, and used for coating many metal NPs with interesting morphologies and varied sizes. The
reducing agents involved include various water-soluble plant metabolites (e.g. alkaloids, phenolic compounds, terpenoids, flavonoids, saponins, steroids, tannins and
other nutritional compounds) and co-enzymes. The polysaccharides, proteins and lipids present in the algal membranes act as capping agents and thus limit using
of non-biodegradable commercial surfactants. Metallic NPs viz. cobalt, copper, silver, gold, platinum, zirconium, palladium, iron, cadmium and metal oxides such as
titanium oxide, zinc oxide, magnetite, etc. have been the particular focus of biosynthesis. Bio-reduction mechanisms, characterization, commercial, pharmacological
and biomedical applications of biosynthesized nanoparticles are reviewed.
Ecofriendly green biosynthesized of metallic nanoparticles:
Bio-reduction mechanism, characterization and
pharmaceutical applications in biotechnology industry
Copper catalyzed synthesis of N-Heterocycles containing one M-atomssusercbfc01
This presentation is based on my literature review on the topic Copper catalysed synthesis of N-Heterocycles containing one N-atom. I have prepared it using Mobile.A better presentation would have been prepared on laptop but option wasn't available for me
Au based nanomaterials (AuNMs) are known to possess many
attractive features such as unique electrical, optical and catalytic
properties as well as excellent biocompatibility. These outstanding
characteristics make them promising candidates as the signal reporters,
enhancement materials or others involved with bioassay, food safety
and environmental monitoring.
Biocompatibility of Poly (L-Lactic Acid) Synthesized In Polymerization Unit B...IJERA Editor
The absorbable polyacid is one of the most used and studied materials in tissue engineering. This work
synthesized a poly (L-lactic acid) (PLLA) through ring-opening polymerization and produced nanofibers by the
electrospinning process. The PLLA was analyzed by FTIR and the cytotoxicity was evaluated by the MTT assay
and Live/Dead®. The hemocompatibility was tested by platelet adhesion and hemolytic activity assay. The tests
were performed in contact with human mesenchymal cells at varying times. The high rates of cell viability and
proliferation shown by MTT and Live/Dead® tests demonstrate that this PLLA is a non-toxic material and the
hemocompatibility assay revealed that the biomaterial was also biocompatible. It was achieved as well the
successful production of electrospinning nanofibers, which can be converted for specific biomedical applications
in the future
Mass Transfer, Kinetic, Equilibrium, and Thermodynamic Study on Removal of Di...Ratnakaram Venkata Nadh
Three distinct agricultural waste materials, viz., casuarina fruit powder (CFP), sorghum stem powder
(SSP), and banana stem powder (BSP) were used as low-cost adsorbents for the removal of toxic lead(II)
from aqueous solutions. Acid treated adsorbents were characterized by scanning electron microscopy (SEM),
energy-dispersive X-ray spectroscopy (EDX), and Fourier transform infrared spectroscopy (FTIR). The
effects of parameters like adsorbent dose, pH, temperature, initial metal ion concentration, and time of
adsorption on the removal of Pb(II) were analyzed for each adsorbent individually and the efficiency order
was BSP > SSP > CFP. Based on the extent of compatibility to Freundlich/Langmuir/Dubinin–Radushkevich/
Temkin adsorption isotherms and different models (pseudo-first and second order, Boyd, Weber’s, and
Elovich), chemisorption primarily involved in the case of BSP and SSP, whereas simultaneous occurrence of
chemisorption and physisorption was proposed in the case of CFP correlating with the thermodynamic study
results conducted at different temperatures. Based on the observations, it was proposed that three kinetic
stages involve in the adsorption process, viz., diffusion of sorbate to sorbent, intra particle diffusion, and then
establishment of equilibrium. These adsorbents have a promising role towards the removal of Pb(II) from
industrial wastewater to contribute environmental protection
Nanoparticles Methods for Nanoparticles Synthesis Overviewijtsrd
Nanoparticles exist in several different morphologies such as spheres, cylinders, platelets, tubes etc. The word nanoparticles are used to describe a particle with size in the range of 1nm to 100nm, at least in one of the three possible dimensions. In this size range, the physical, chemical and biological properties of the nanoparticles changes in fundamental ways from the properties of both individual atoms molecules and of the corresponding bulk materials. The enormous diversity of the nanoparticles arising from their wide chemical nature, shape and morphologies, the medium in which the particles are present, the state of dispersion of the particles and most importantly, the numerous possible surface modifications the nanoparticles can be subjected to make this an important active field of science now a days. Dr. Ilamathi Jayaraman | Dr. Vijayakumari. S "Nanoparticles: Methods for Nanoparticles Synthesis: Overview" Published in International Journal of Trend in Scientific Research and Development (ijtsrd), ISSN: 2456-6470, Volume-5 | Issue-6 , October 2021, URL: https://www.ijtsrd.com/papers/ijtsrd46478.pdf Paper URL : https://www.ijtsrd.com/biological-science/biotechnology/46478/nanoparticles-methods-for-nanoparticles-synthesis-overview/dr-ilamathi-jayaraman
Physical and Structural Characterization of Biofield Treated Imidazole Deriva...albertdivis
The Aim of present study was to evaluate the impact of biofield treatment on two imidazole derivatives (i.e., imidazole and 2-methylimidazole) by various analytical methods.
SiO2@FeSO4 nano composite: A recoverable nano-catalyst for eco-friendly synth...Iranian Chemical Society
Various aldoximes and ketoximes synthesis of corresponding aldehydes and ketones in the presence of SiO2@FeSO4 nano composite as recoverable nano catalyst and NH2OH·HCl. The SiO2@FeSO4 nano composite system was carried out between 10 to 15 min in oil bath (70-80 °C) under solvent-free condition in excellent yields in addition this protocol can be used for industrial scales. This method offers some advantages in term of clean reaction conditions, easy work-up procedure, short reaction time, applied to convert α-diketones to α-diketoximes (as longer than other carbonyl compounds), α,β-unsaturated aldehydes and ketones to corresponding oximes and suppression of any side product. So we think that NH2OH•HCl/SiO2@FeSO4 nano composite system could be considered a new and useful addition to the present methodologies in this area. Structure of products and nano composite elucidation was carried out by 1H NMR, 13C NMR, FT-IR, scanning electron microscopy (SEM).
Photocatalytic degradation of some organic dyes under solar light irradiation...Iranian Chemical Society
Nanoparticles of the ZnO and TiO2 were synthesized and the physicochemical properties of the compounds were characterized by IR, X-ray diffraction (XRD), scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The XRD patterns of the ZnO and TiO2 nanoparticles could be indexed to hexagonal and rutile phase, respectively. Aggregated nanoparticles of ZnO and TiO2 with spherical-like shapes were observed with particle diameter in the range of 80-100 nm. These nanoparticles were used for photocatalytic degradation of various dyes, Rhodamine B (RhB), Methylene blue (MB) and Acridine orange (AO) under solar light irradiation at room temperature. Effect of the amount of catalyst on the rate of photodegradation was investigated. In general, because ZnO is unstable, due to incongruous dissolution to yield Zn(OH)2 on the ZnO particle surfaces and thus leading to catalyst inactivation,the catalytic activity of the system for photodegradation of dyes decreased dramatically when TiO2 was replaced by ZnO.
Modified magnetite nanoparticles with cetyltrimethylammonium bromide as super...Iranian Chemical Society
This paper reports application of cetyltrimethylammonium bromide (CTAB) coated magnetite nanoparticles (Fe3O4 NPs) as a novel adsorbent for removal of two types of disperse dyes, including disperse red 167, and disperse blue 183, from wastewater of textile companies. The effect of parameters including type of surfactant, pH of solution, surfactant concentration, and amount of salt, was investigated and optimized. The obtained results showed that the ratio of initial dye concentration to CTAB amounts has critical effect on removal processes so that removal efficiencies higher than 95% can be achieved even at high concentration of dyes as high as 500 mg l-1 when the ratio is optimum. Removal of dyes is very fast, and equilibrium is reached at times less than 10 min even for high concentration of the dyes. Very high adsorbent capacity (as high as 2000 mg g-1) was yielded for maximum tested concentration of the dyes (500 mg g-1). The obtained result was confirmed by thermogravimetric analysis data. This study showed that CTAB coated Fe3O4 NPs is a very efficient adsorbent for removal of dyes from wastewater of textile companies and has high capacity under optimum conditions.
Photocatalytic application of TiO2/SiO2-based magnetic nanocomposite (Fe3O4@S...Iranian Chemical Society
In this research we have developed a treatment method for textile wastewater by TiO2/SiO2-based magnetic nanocomposite. Textile wastewater includes a large variety of dyes and chemicals and needs treatments. This manuscript presents a facile method for removing dyes from the textile wastewater by using TiO2/SiO2-based nanocomposite (Fe3O4@SiO2/TiO2) under UV irradiation. This magnetic nanocomposite, as photocatalytically active composite, is synthesized via solution method in mild conditions. A large range of cationic, anionic and neutral dyes including: methyl orange, methylene blue, neutral red, bromocresol green and methyl red are used for treatment investigations. Neutral red and bromocresol green have good results in reusing treatment. The high surface area of nanocomposites improve the kinetic of wastewater treatment. In this method, by using the magnetic properties of Fe3O4 nanoparticles, TiO2-based photocatalyst could be separated and reused for 3 times. The efficiency of this method is respectively 100% and 65% for low concentration (10 ppm) and high concentration (50 ppm) of neutral red and bromocrosol green after 3 h treatment. The efficiency of treatment using the second used nanocomposite was 90% for 10 ppm of the same dyes.
Si-Imidazole-HSO4 Functionalized Magnetic Fe3O4 Nanoparticles as an Efficient...Iranian Chemical Society
An efficient and simple method for the preparation of Si-Imidazole-HSO4 functionalized magnetic Fe3O4 nanoparticles (Si-Im-HSO4 MNPs) and used as an efficient and reusable magnetic catalysts for the regioselective ring opening of epoxides under green conditions in water. This catalyst was used for the ring opening of epoxide corresponding to the thiocyanohydrins and azidohydrines. Compared to the classical ring opening of epoxides, this new method consistently has the advantage of excellent yields, short reaction times, and methodological simplicity.
Effect of the pillar ligand on preventing agglomeration of ZnO nanoparticles ...Iranian Chemical Society
Metal-Organic Frameworks (MOFs) represent a new class of highly porous materials. On this regard, two nano porous metal-organic frameworks of [Zn2(1,4-bdc)2(H2O)2∙(DMF)2]n (1) and [Zn2(1,4-bdc)2(dabco)]·4DMF·1⁄2H2O (2), (1,4-bdc = benzene-1,4-dicarboxylate, dabco = 1,4-diazabicyclo[2.2.2]octane and DMF = N,N-dimethylformamide) were synthesized and characterized. They were used for preparation of ZnO nanomaterials. With calcination of 1, agglomerated ZnO nanoparticles could be fabricated, but by the same process on 2, the tendency of ZnO nanoparticles to agglomeration was decreased. In addition, the ZnO nanoparticles prepared from compound 2 had smaller diameter than those obtained from compound 1. In fact, the role of organic dabco ligands in 2 is similar to the role of polymeric stabilizers in formation of nanoparticles. Finally, considering the various applications of ZnO nanomaterials such as light-emitting diodes, photodetectors, photodiodes, gas sensors and dye-sensitized solar cells (DSSCs), it seems that preparation of ZnO nanomaterials from their MOFs could be one of the simple and effective methods which may be applied for preparation of them.
Sulfonic-based precursors (SAPs) for silica mesostructures: Advances in synth...Iranian Chemical Society
Sulfonic acid-based precursors (SAP) play an important role in tailoring mesoporous silica’s and convert them to a solid acid catalyst with a Bronsted-type nature. These kinds of solid acids contribute to sustainable and green chemistry by their heterogeneous, recyclable, and high efficiency features. Therefore, knowing the properties and reactivity of SAPs can guide us to manufacture a sulfonated mesostructures compatible with reaction type and conditions. In the present review, some of the important SAPs, their reactivity and mechanism of functionalization are discussed.
Modification of mesoporous silica SBA-15 with different organic molecules to ...Iranian Chemical Society
The recognition of the biologically and environmentally important ions is of great interest in the field of chemical sensors in recent years. The fluorescent sensors as a powerful optical analytical technique for the detection of low level of various analytes such as anions and metal cations have been progressively developed due to the simplicity, cost effective, and selectivity for monitoring specific analytes in various systems. Organic-inorganic hybrid nanomaterials have important advantages as solid chemosensors and various innovative hybrid materials modified by fluorescence molecules were recently prepared. On the other hand, the homogeneous porosity and large surface area of mesoporous silica make it a promising inorganic support. SBA-15 as a two-dimensional hexagonal mesoporous silica material with stable structure, thick walls, tunable pore size, and high specific surface area is a valuable substrate for modification with different organic chelating groups. This review highlights the fluorescent chemosensors for ionic species based on modification of the mesoporous silica SBA-15 with different organic molecules, which have been recently developed from our laboratory.
Antibacterial ethylene propylene rubber impregnated with silver nanopowder: A...Iranian Chemical Society
Following our interest in reaching for a molded rubber article with possible detergent contact applications, durable silver nanopowder (AgNP) is synthesized by arc discharge, then mixed with varying ratios of ethylene propylene rubber (EPR), affording novel AgNP@EPR nanocomposites. X-ray diffraction (XRD) patterns of AgNP as well as AgNP@EPR show no trace of impurity, while scanning electron microscopy (SEM) indicates an average diameter of 50 nm for the former. Transmission electron microscopy (TEM) images while confirm the SEM results, show quite a few 5 nm AgNP particles lying beside some micro crumbs. Our DC arc discharge technique involves explosion of movable silver anode and static cathode by a current pulse between 5 to 10 A cm-2. A solution blending method is employed for preparation of AgNP@EPR nanocomposites. The AgNP is first dispersed in toluene using an ultrasonic homogenizer, and then thoroughly mixed with EPR in the same solvent whose removal gives nanocomposites of 2, 4, 6 and 8 vol% AgNP in EPR, showing strong antibacterial activity against both Escherichia coli and Staphylococcus aureus.
Photo-electrocatalytic activity of TiO2 nanotubes prepared with two-step anod...Iranian Chemical Society
To improve the photo-catalytic degradation of salicylic acid, we reported the fabrication of ordered TiO2 nanotube arrays by a simple and effective two-step anodization method and then these TiO2 nanotubes treated in a methanol solution under UV light irradiation. The TiO2 nanotubes prepared in the two-step anodization process showed better photo-catalytic activity than TiO2 nanotubes prepared in one-step anodization process. Also, compared with TiO2 nanotubes without the UV pretreatment, the TiO2 nanotubes pretreated in a methanol solution under UV light irradiation exhibited significant enhancements in both photocurrent and activity. The treated TiO2 nanotubes exhibited a 5-fold enhancement in photocurrent and a 2.5-fold increase in the photo-catalytic degradation of salicylic acid. Also the effect of addition of persulfate and periodate on the photo-catalytic degradation of salicylic acid were investigated. The results showed that the degradation efficiency of salicylic acid increased with increasing persulfate and periodate concentrations. These treated TiO2 nanotubes are promising candidates for practical photochemical reactors.
Oxidized multi walled carbon nanotubes for improving the electrocatalytic act...Iranian Chemical Society
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Selective Oxidation of Cyclohexene, Toluene and Ethyl Benzene Catalyzed by Bi...Iranian Chemical Society
Bis-(L-tyrosinato)copper(II) was reacted with 3-(chloropropyl)-trimethoxysilane functionalized silica that has infused magnetite to yield a magnetically separable catalyst in which the copper carboxylate is covalently linked to the silica matrix through the silane linkage. The immobilized catalyst has been characterized by spectroscopic studies (such as FT-IR, EPR, Magnetic Measurement, SEM) and chemical analyses. The immobilized catalytic system functions as an efficient heterogeneous catalyst for oxidation of cyclohexene, toluene and ethyl benzene in the presence of hydrogen peroxide (as an oxidant) and sodium bicarbonate (a co-catalyst). The reaction conditions have been optimized for solvent, temperature and amount of oxidant and catalyst. Comparison of the encapsulated catalyst with the corresponding homogeneous catalyst showed that the heterogeneous catalyst had higher activity and selectivity than the homogeneous catalyst. The immobilized catalyst could be readily recovered from the reaction mixture by using a simple magnet, and reused up to five times without any loss of activity.
A powerful and convenient reaction procedure for the C-N coupling reaction (the Buchwald-Hartwig reaction), yielding products of N-arylanilines and N-arylamines in both conventional heating and microwave irradiation has been reported. The protocol utilizes a stable and new supper ferromagnetic nanoparticle chelating N-heterocyclic dicarbene palladium(II) complex (Pd-NHC) as catalyst which helps/allows us to complete the reaction with only 0.002 mol% Pd producing high yield products. We also examined the reusability of the catalyst. It was found that the catalyst could be recovered by external magnetic field and reused for seven times without obvious loss in catalytic activity.
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1. Nano. Chem. Res., 1(1): 87-107, Winter and Spring 2016
DOI: 10.7508/ncr.2016.01.011
Perlite-SO3H nanoparticles as an efficient and reusable catalyst for one-pot three-
component synthesis of 1,2-dihydro-1-aryl-naphtho[1,2-e][1,3]oxazine-3-one
derivatives under both microwave-assisted and thermal solvent-free conditions:
single crystal X-ray structure analysis and theoretical study
A. Ramazania,
*, M. Rouhania,
*, E. Mirhadia
, M. Sheikhib
, K. Ślepokurac
and T. Lisc
a
Department of Chemistry, University of Zanjan, P.O. Box: 45195-313, Zanjan, Iran
b
Young Researchers and Elite Club, Gorgan Branch, Islamic Azad University, Gorgan, Iran
c
Faculty of Chemistry, University of Wrocław, 14 Joliot-Curie St., 50-383 Wrocław, Poland
(Received 9 October 2015, Accepted 18 October 2015)
ABSTRACT: A general synthetic route for the synthesis of 1,2-dihydro-1-aryl-naphtho[1,2-e][1,3]oxazine-3-one derivatives has been
developed using perlite-SO3H nanoparticles as efficient catalyst under both microwave-assisted and thermal solvent-free conditions. The
combination of 2-naphthol, aldehyde and urea enabled the synthesis of 1,2-dihydro-1-aryl-naphtho[1,2-e][1,3]oxazine-3-one derivatives in
the presence of perlite-SO3H nanoparticles in good to excellent yields. This method provides several advantages like simple work-up,
environmentally benign, and shorter reaction times along with high yields. In order to explore the recyclability of the catalyst, the perlite-
SO3H nanoparticles in solvent-free conditions were used as catalyst for the same reaction repeatedly and the change in their catalytic
activity was studied. It was found that perlite-SO3H nanoparticles could be reused for four cycles with negligible loss of their activity.
Single crystal X-ray structure analysis and theoretical studies also were investigated for 4i product. The electronic properties of the
compound have been analyzed using DFT calculations (B3LYP/6-311+G*). The FMO analysis suggests that charge transfer takes place
within the molecule and the HOMO is localized mainly on naphthalene and oxazinone rings whereas the LUMO resides on the naphthalene
ring.
Keywords: Perlite-SO3H nanoparticles; Oxazine-3-one; Microwave; Solvent-free conditions; Single crystal X-ray structure analysis
INTRODUCTION
The use of heterogeneous catalysts [1-3] has received
considerable importance in organic synthesis because of
their ease of handling, enhanced reaction rates, greater
selectivity, simple work-up, and recoverability of catalysts.
Among the various heterogeneous catalysts, particularly,
perlite nanoparticles has advantages of eco-friendly, low
cost, ease of preparation and catalyst recycling [4]. Perlite is
an amorphous volcanic glass that has relatively high water
content, typically formed by the hydration of obsidian.
Because of its low density and relatively low price, many
commercial applications for perlite have developed. In the
*Corresponding authors. E-mail: aliramazani@gmail.com;
rouhani.morteza@gmail.com
construction and manufacturing fields, it is used in
lightweight plasters and mortars, insulation and ceiling tiles,
however there are few reports about using perlite as suitable
support for catalytic applications [5-8].
Multicomponent reactions (MCRs) [9-13] can be
defined as convergent chemical processes where three or
more reagents are combined in such a way that the final
product retains significant portions of all starting materials.
Therefore, they lead to the connection of three or more
starting materials in a single synthetic operation with high
atom economy and bond-forming efficiency, thereby
increasing molecular diversity and complexity in a fast and
often experimentally simple fashion [14,15]. For this
reason, multicomponent reactions are particularly well
suited for diversity-oriented synthesis [16-18] and the
exploratory power arising from their conciseness makes
2. Ramazani et al./Nano. Chem. Res., Vol. 1, No. 1, 87-107, June 2016.
88
them also very powerful for library synthesis aimed at
carrying out structure-activity relationship (SAR) studies of
drug-like compounds, which are an essential part of the
research performed in pharmaceutical and agrochemical
companies [19,20]. For all these reasons, the development
of new multicomponent reactions is rapidly becoming one
of the frontiers of organic synthesis.
Aromatic condensed oxazinone derivatives have
received considerable attention due to the attractive
pharmacological properties associated with their
heterocyclic scaffold [21]. Since many of these heterocyclic
systems exhibit biological activities such as anti-
inflammatory, antiulcer, antipyretic, antihypertensive and
antifungal, these derivatives have become an integral part of
pharmacologically important heterocyclic compounds [22-
26]. Some of them also act as 5-HT ligands [27], DP
receptor antagonists [28], integrin antagonists [29], platelet
fibrinogen receptor antagonists [30], calmodulin antagonists
[31], inhibitors of the transforming growth factor b (TGF-b)
signaling pathway [32], soybean lipoxygenase [33], Janus
kinase (JAK) and other protein kinases [34]. Moreover,
benzo[1,4]oxazin-3-one analogs act as effective potassium
channel openers, immunomodulating reagents, and etc.
[35,36]. This class of heterocyclic compounds has been also
used as precursors in the synthesis of phosphinic ligands for
asymmetric catalysis [37]. Therefore, aromatic condensed
oxazinone derivatives scaffold can be viewed as a
‘privileged structure’ among pharmaceutical compounds
[38,39]. Inspite of their high potential, there are only few
reports which describe the synthesis of naphthalene-
condensed oxazinone derivatives [40-43]. In general, all
these methods require elevated temperature non recyclable
catalyst except those reported by Chaskar et al. [40].
Besides, a multi-step and cumbersome reaction involving
the use of harsh conditions is required for the synthesis of
starting materials such as amino alkylnaphthol. Therefore,
development of simple, robust and safer methodologies for
the synthesis of naphthoxazinone derivatives is of the prime
interest for obtaining these products under conditions
tolerated by sensitive functional groups from both synthetic
and environmental points of view [44].
Microwave chemistry and microwave-assisted organic
synthesis (MAOs) are nowadays undeniably effective tools
in medicinal chemistry [45]. The availability of safe, single-
mode dedicated microwave units has allowed the
incorporation of this new technology into accelerating drug-
discovery, hit-to-lead, and lead optimization programs. The
development of more economical synthetic routes can
ameliorate the overall process since drug discovery is a
costly exercise with a high attrition rate [45]. The use of
MAOs has been shown to dramatically reduce processing
times, increase product yields, and enhance the purity of the
product when compared to the conventionally processed
experiments [45]. Since there are several manufacturers of
professional-grade equipment and a plethora of adapted
methods, one can conclude that this interest continues to
grow [46].
Motivated by the afore-mentioned findings, and in a
continuation of our interest in synthesis of a wide range of
heterocyclic systems in our laboratory [47-54], we describe
here a facile one-pot three-component synthesis of 1,2-
dihydro-1-aryl-naphtho[1,2-e][1,3]oxazine-3-one
derivatives (4) from 2-naphthol (1), aldehyde (2) and urea
(3) in the presence of perlite-SO3H nanoparticles as efficient
catalyst under both microwave and thermal solvent-free
conditions (Scheme 1).
In recent years, computational chemistry has become an
important tool for chemists and a well-accepted partner for
experimental chemistry [55-58]. Density functional theory
(DFT) method has become a major tool in the
methodological arsenal of computational organic chemists.
In the present work, we investigate the energetic and
structural properties of crystal structures of 4i using DFT
calculations. The optimized geometry, frontier molecular
orbitals (FMO), detail of quantum molecular descriptors,
molecular electrostatic potential (MEP), chemical tensors,
natural charge and NBO analysis were calculated.
RESULTS AND DISCUSSION
Recently, it has been reported that multi-component
reactions of 2-naphthol (1) with benzaldehyde (2a) and urea
(3) in the presence of a number of catalysts and reagents
such as H2NSO3H [59], HClO4/SiO2 [60], 2,4,6-trichloro-
1,3,5-triazine [61], InCl3 [62] and CH3SO3H [63] afforded
uncyclized product (5a) in good yields, without any
formation of cycloadduct (4a) (Scheme 2).
To optimize the reaction conditions to give cycloadduct
3. Perlite-SO3H Nanoparticles as an Efficient and Reusable Catalyst/Nano. Chem. Res., Vol. 1, No. 1, 87-107, June 2016.
89
OH
CHO
H2N NH2
O
Perlite-SO3H NPs
MW or Thermal
conditions
O
H
N O
R
R
+ +
1 2 3 4i-j
Scheme 1. Synthesis of 1,2-dihydro-1-aryl-naphtho[1,2-e][1,3]oxazine-3-one derivatives (4a-j)
OH
CHO
H2N NH2
O
Catalyst
O
H
N O
+ +
1 2a 3
4a
OH
NH
O NH2
5a
Scheme 2. Possible cyclized and uncyclized products of the reaction
4. Ramazani et al./Nano. Chem. Res., Vol. 1, No. 1, 87-107, June 2016.
90
4a, the reaction of 2-naphthol (1) with benzaldehyde (2a)
and urea (3) in the presence of various types of perlite as
catalyst was used as a model reaction to oxazinone
derivatives synthesis. According to the obtained data, using
the perlite-SO3H nanoparticles (0.01 g) under solvent-free
conditions for the oxazinone formation represents the best
reaction conditions (Table 1).
Table 1 clearly demonstrates that perlite-SO3H
nanoparticles are an effective catalyst in terms of yield of
the obtained product. To find out the optimum quantity of
perlite-SO3H nanoparticles, the model reaction was carried
out at 110 °C using different quantities of perlite-SO3H
nanoparticles (Table 2). According to the obtained data,
0.01 g of perlite-SO3H nanoparticles gave the best yield in
45 min (Table 2, entry 3).
The above reaction was also examined in various
solvents (Table 3). The results indicated that different
solvents affect the efficiency of the reaction. These solvents
Table 1. Reaction between 2-Naphthol (1), Benzaldehyde (2a) and
Urea (3) in the Presence of Various Types of Perlite as
Catalyst under Thermal and Solvent-Free Conditionsa
Entry Catalyst Time
(min)
Yield
(%)
1 Perlite powder 90 10
2 Perlite nanoparticles 60 25
3 Perlite-SO3H nanoparticles 45 53
Table 2. Optimization Amount of perlite-SO3H nanoparticles on
the Reaction of 2-Naphthol (1), Benzaldehyde (2a) and
Urea (3) under Thermal and Solvent-Free Conditions
Entry Catalyst
(g)
Time
(min)
Yield
(%)
1 0.1 45 15
2 0.05 45 30
3 0.01 45 53
4 0.005 45 10
5. Perlite-SO3H Nanoparticles as an Efficient and Reusable Catalyst/Nano. Chem. Res., Vol. 1, No. 1, 87-107, June 2016.
91
required a longer time and gave low to moderate yields, and
the best results were obtained when solvent-free conditions
were used (Table 3, entry 5).
Encouraged by this success, we attempted the reaction
of 2-naphthol (1) with a range of other aromatic aldehydes
(2) and urea under similar conditions (using perlite-SO3H
nanoparticles), furnishing the respective 1,2-dihydro-1-aryl-
naphtho[1,2-e][1,3]oxazine-3-one derivatives in good
yields. The optimized results are summarized in Table 4.
The termal solvent-free conditions are well suited for either
Table 3. Solvent Effect on the Reaction Between 2-Naphthol (1), Benzaldehyde
(2a) and Urea (3) under Thermal and Solvent-Free Conditions (0.01 g)
Entry Solvent Time Yield
(%)a
1 H2O 24 (h) 20
2 MeOH 24 (h) 30
3 THF 24 (h) 50
4 DMF 24 (h) No reaction
5 Solvent-free 45 (min) 53
Table 4. Selected Interatomic Distances and Torsion Angles of 4i
Bond lengths (Å)
O(1)-C(1) 1.370(2) N(1)-C(1) 1.332(2)
O(1)-C(4) 1.3980(19) N(1)-C(2) 1.467(2)
O(2)-C(1) 1.2181(19) C(2)-C(3) 1.501(2)
Torsion angles (°)
C(2)-N(1)-C(1)-O(1) -18.4(2) C(13)-C(2)-C(3)-C(4) 101.27(17)
C(4)-O(1)-C(1)-N(1) -7.4(2) C(13)-C(2)-C(3)-C(12) -77.21(17)
C(1)-N(1)-C(2)-C(3) 32.44(19) C(1)-O(1)-C(4)-C(3) 15.3(2)
C(1)-N(1)-C(2)-C(13) -92.86(18) N(1)-C(2)-C(13)-C(18) -110.68(16)
N(1)-C(2)-C(3)-C(4) -22.52(18) C(3)-C(2)-C(13)-C(18) 127.03(16)
N(1)-C(2)-C(3)-C(12) 159.00(13) C(15)-C(16)-C(19)-C(20) -64.5(2)
C(15)-C(16)-C(19)-C(21) 171.36(17)
6. Ramazani et al./Nano. Chem. Res., Vol. 1, No. 1, 87-107, June 2016.
92
electron-donating or electron-withdrawing substituents on
the aromatic aldehydes.
Crystal Structure of 4i
Centrosymmetric crystals of 4i (space group P21/n)
contain racemic 4i compound. The molecular structure of
(S)-enantiomer is shown in Fig. 1. A summary of the
conditions for the data collection and the structure
refinement parameters are given in Experimental Part. The
selected geometrical parameters are given in Table 4.
In 4i molecule, the bond lengths and angles are within
normal ranges [64], and the overall conformation of 4i is
very similar to those observed in previously reported 1-
phenyl, 1-(4-fluorophenyl) and 1-(4-chlorophenyl)
derivatives [65-67]. The six-membered ring
O(1)/C(1)/N(1)/C(2)/C(3)/C(4) is slightly puckered (Cremer
& Pople [68] amplitude Q = 0.280(2) Å). The mutual
orientation of the planar regions, i.e. phenyl and
naphthalene moieties, is defined by the dihedral angle
between them, which is 77.6(1)°, and by the torsion angle
C(13)-C(2)-C(3)-C(12) amounting to -77.21(17)°.
In the crystal lattice of 4i, the adjacent molecules of the
same chirality, related by the action of the 21 screw axis, are
joined to each other viaN(1)-H(1N)···O(2)i
hydrogen
bondsand weak C(17)-H(17)···O(1)ii
interactions to form
homochiralchains running down the b-axis (Fig. 5;
geometry and symmetry codes therein). The inter-chain
contacts are provided by the weak π···π interactions
involving C(3)/C(4)/C(5)/C(6)/C(7)/C(12) rings of the
adjacent molecules related by the inversion
[centroid···centroidiii
distance of 3.652(2) Å,
centroid···plane perpendicular distance of 3.567(1)Å;
symmetry code (iii) -x,-y+1,-z+1)].
Also in order to decrease the reaction time, microwave
irradiation under solvent-free conditions was used. The
reaction time decreased from almost 1 h to a few minutes.
Moreover, the yields of products increased in all cases
examined (Table 5).
A plausible mechanism for the formation of 2-dihydro-
1-aryl-naphtho[1,2-e][1,3]oxazine-3-one derivatives in the
Fig. 1. (a) X-Ray crystal structure of (S)-enantiomer of 4i compound (displacement
ellipsoids at 50% probability level), (b) Geometrical structure of the 4i
compound (optimized at B3LYP/6-311+G* level).
7. Perlite-SO3H Nanoparticles as an Efficient and Reusable Catalyst/Nano. Chem. Res., Vol. 1, No. 1, 87-107, June 2016.
93
Fig. 2. Molecules of 4i joined to each other via N/C-H···O contacts (dashed lines) to form homochiralchains
running down the b-axis. [H···A, D···A, and D–H···A for N(1)-H(1N)···O(2)i
: 2.08(2), 2.807(2) Å
and 143(2)°; for C(17)–H(17)···O(1)ii
: 2.58, 3.187(2) Å and 122°. Symmetrycodes (i) -x+1/2, y+1/2,
-z+3/2; (ii) x, y+1, z].
Table 5. Reaction Between 2-Naphthol (1), Aromatic Aldehydes (2) and Urea (3) under Solvent-Free (I)
and Microwave-Assisteda
(II) Conditions Using 0.01 g Perlite-SO3H NPs as Catalyst
Entry Product Ar Time
(min)
Yield
(%)b
M.p.
(C)
I II I II Found Reported/Ref.
1 4a Ph 50 2 53 87 216-217 217-219/[44]
2 4b 4-ClC6H4 40 5 60 89 210-211 210-212/[63]
3 4c 3-ClC6H4 50 2 52 80 110 -
4 4d 2,3-Cl2C6H4 50 3 54 79 235-237 -
5 4e 4-BrC6H4 50 2 65 92 219-220 218-220/[44]
6 4f 3-BrC6H4 50 2 54 87 118 -
7 4g 4-MeC6H4 50 2 57 86 171-172 170-172/[64]
8 4h 4-MeOC6H4 50 3 52 83 187-188 186-188/[44]
9 4i 4-(CH3)2CHC6H4 50 2 53 75 205-207 -
10 4j 4-NO2C6H4 60 10 45 85 198-200 205-207/[44]
a
With a power of 900W. b
Isolated Yields.
8. Ramazani et al./Nano. Chem. Res., Vol. 1, No. 1, 87-107, June 2016.
94
presence of perlite-SO3H nanoparticles is shown in Scheme
3. It may be proposed that similar to several classical multi-
component condensations, the initial event in this reaction is
the condensation of aldehyde and urea to give reactive
acylimine intermediate. Subsequently, the resulting
acylimine intermediate undergoes a cyclization with 2-
naphthol affording the corresponding products and
ammonia [69,70].
In order to explore the recyclability of the catalyst, the
perlite-SO3H nanoparticles in solvent-free conditions were
used as a catalyst for the same reaction repeatedly and the
change in their catalytic activity was studied. The relation
between the number of cycles of the reaction and the
catalytic activity in terms of yield of the products is
presented in Fig. 3. It was found that perlite-SO3H
nanoparticles could be reused for four cycles with negligible
loss of their activity.
Electronic Properties and MEP Analysis
Quantum chemical methods are important to obtain
O
H
Perlite-SO3H NPs
O
H
H
NH2H2N
O
R R
OH
N
HR
NH2
O
Perlite-SO3H NPs
-H2O
H
N
R
NH2
O
H
-H+
OH
OH
NH
NH2O
O
H
N O
R
-NH3
R
Scheme 3. A proposed mechanism for the synthesis of 2-dihydro-1-aryl-naphtho[1,2-e][1,3]oxazine-3-
one derivatives in the presence of perlite-SO3H nanoparticles.
Fig. 3. Development of the yield after several recycling cycles of the catalyst.
9. Perlite-SO3H Nanoparticles as an Efficient and Reusable Catalyst/Nano. Chem. Res., Vol. 1, No. 1, 87-107, June 2016.
95
information about molecular structure and electrochemical
behavior. The Frontier Molecular Orbitals (FMO) analysis
was carried out for 4i compound at B3LYP/6-311+G* level
[71]. The results of FMO such as EHOMO, EHOMO-1, ELUMO,
ELUMO+1 and HOMO-LUMO energy gap (Eg) of the
molecule 4i are summarized in Table 6.
The energy values of the highest occupied molecular
orbital (EHOMO) can act as an electron donor and the lowest
unoccupied molecular orbital (ELUMO) can act as the electron
acceptor and their energy gaps reflect the chemical activity
of the molecule [72]. As shown in Fig. 4 and Table 6, EHOMO
and ELUMO of the title compound is -6.3 eV and -1.68 eV,
respectively. As seen in Fig. 4, charge transfer takes place
within the molecule. The graphic pictures of HOMO and
LUMO orbitals show that the HOMO of 4i molecule is
localized mainly on naphthalene and oxazinone rings,
Table 6. Calculated (B3LYP/6-311+G*) HOMO, LUMO, Energy Gaps
(HOMO-LUMO) and Related Molecular Properties of 4i Molecule
Property Value
Energy (Hatree-Fock) -1017.154
µD (Debye) 5.567
EHOMO (eV) -6.3
ELUMO (eV) -1.68
EHOMO-1 (eV) -6.89
ELUMO+1 (eV) -0.97
Energy gap (Eg) (eV) 4.62
Ionisation potential (I = - EHOMO) (eV) 6.3
Electron affinity (A = - ELUMO) (eV) 1.68
Chemical potential (µ =-(I + A)/2) (eV) -3.99
Global hardness (η = (I _
A)/2) (eV 2.31
Global electrophilicity (ω = µ2
/2 η) (eV) 3.44
Fig. 4. Calculated frontier molecular orbitals HOMO (a) and LUMO (b) of structure 4i.
10. Ramazani et al./Nano. Chem. Res., Vol. 1, No. 1, 87-107, June 2016.
96
whereas the LUMO is focused mainly on naphthalene ring.
The HOMO → LUMO transition implies an electron
density transfer from oxazinone to naphthalene ring.
Also in this work, electronic structure of the 4i
compound was studied using total densities of states (DOSs)
[73]. DOS plot shows population analysis per orbital and
demonstrates a simple view of the character of the
molecular orbitals in a certain energy range [74]. According
to Fig. 5, DOS analysis indicates that the calculated
HOMO-LUMO energy gap (Eg) of the 4i molecule is 4.62
eV.
A detail of quantum molecular descriptors of 4i structure
such as the ionization potential (I), electron affinity (A),
chemical hardness (η), electronic chemical potential (µ) and
electrophilicity (ω) are summarized in Table 6. Dipole
moment (µD) is a good measure for the asymmetric nature
of a structure [71]. The size of the dipole moment depends
on the composition and dimensionality of the 3D structures.
As shown in Table 6, dipole moment of the title structure is
5.567 Debye that the high value of dipole moment is due to
its asymmetric character that the atoms are irregularly
arranged which gives rise to the increased dipole moment.
In addition, the point group of structure is C1 (see Table 6).
The molecular electrostatic potential (MEP) was
checked out by theoretical calculations at B3LYP/6-311+G*
level. Molecular electrostatic potential shows the electronic
density and is useful in recognition sites for electrophilic
attack and nucleophilic reactions as well as hydrogen
bonding interactions [75,76]. The negative areas (red color)
of MEP are related to electrophilic reactivity and the
positive areas (blue color) to nucleophilic reactivity shown
in Fig. 6. Molecular electrostatic potential V(r) [77] value is
-8.930e-2
. According to the MEP maps in Fig. 6, negative
region of 4i compound is mainly focused over the oxygen in
C=O group (more color intensity), therefore it is useful
region for nucleophilic activity. In addition, the lowest
electron density with the highest intensity blue color is
observed for the hydrogen atom in N-H, therefore it is
suitable site for electrophilic attraction.
Atomic Charge
We calculated the charge distributions for the
equilibrium geometry of 4i molecule by Natural Bond
Orbital (NBO) analysis (natural charge) [71,78] at
B3LYP/6-311+G* level. The total charge of the
investigated molecule is equal to zero. According to Fig. 7,
the results of the NBO analysis reveal that the highest
positive charge belongs to C12 atom in the carbonyl group
(0.923e), while the highest value of negative charge is on
the N13 atom (-0.650e). In addition, oxygen atoms have
Fig. 5. Calculated DOS plots of 4i structure (usingB3LYP/6-311+G*).
11. Perlite-SO3H Nanoparticles as an Efficient and Reusable Catalyst/Nano. Chem. Res., Vol. 1, No. 1, 87-107, June 2016.
97
great negative charge (-0.603e and -0.539e). The carbon
atoms of the naphthalene ring bear negative charges except
C9 atom (close to oxygen atom) that bear positive charge
(0.333e), while the carbon atoms of the phenyl ring bear
negative charges. All hydrogen atoms have positive charge
and the H31 atom in N-H group has the highest positive
charge (0.403e).
The NMR parameters of 4i molecule are summarized in
Table 7. The C23 and C24 (methyl groups) have the highest
σiso value (158.160 ppm and 157.488 ppm, respectively),
Fig. 6. Molecular electrostatic potential (MEP) maps of 4i molecule calculated at B3LYP/6-311+G* level.
Fig. 7. Calculated (B3LYP/6-311+G*) natural charges (NBO) of the atoms of 4i molecule. (The Cartesian
coordinates of the optimized structure are available in the supplementary material.).
12. Ramazani et al./Nano. Chem. Res., Vol. 1, No. 1, 87-107, June 2016.
98
therefore they are shielder than other atoms due to
hyperconjugation effect. While O21 has the lowest σiso value
(15.809 ppm) and the highest σaniso value (368.673 ppm)
indicating that O21 is deshielder than other atoms.
According to Table 7, the σiso value of H31 in N-H group is
28.024 ppm that it is shielder than other hydrogen atoms.
The σiso value of C8, C9 and C10 in naphthalene ring is
61.439 ppm, 26.227 ppm and 63.745 ppm, respectively. It
shows the C9 atom is deshielder than the C8 and C10 atoms,
because the C9 atom is close to the oxygen atom (O11). The
Table 7. The NMR Parameter Values (ppm) of 4i at B3LYP/6-311+G* Level (Atom Labeling
Corresponds to Fig. 7)
Atoms isoσ anisoσ 11σ 22σ 33σ
C8 61.439 148.483 -29.251 53.110 160.428
C9 26.227 115.853 -59.743 34.962 103.462
C10 63.745 150.246 -11.722 39.048 163.909
O11 111.970 152.152 -6.869 129.374 213.404
C12 31.158 85.508 -62.895 68.205 88.163
N13 142.509 80.388 84.439 146.986 196.101
C14 120.416 18.273 110.190 118.460 132.598
C15 34.305 190.327 -57.467 -0.807 161.190
C16 51.738 156.924 -51.986 50.845 156.354
C17 49.950 152.875 -52.352 50.337 151.867
C18 26.033 208.813 -62.743 -24.399 165.242
O21 15.809 368.673 -142.092 -72.072 261.591
C23 158.160 35.295 143.106 149.685 181.690
C24 157.488 36.210 142.605 148.230 181.628
H30 24.835 5.801 20.434 25.368 28.703
H31 28.024 7.820 20.746 30.089 33.238
H32 26.316 6.502 22.692 25.605 30.651
H33 24.908 7.380 21.886 23.009 29.827
H34 24.956 6.927 21.294 23.999 29.574
H35 25.080 10.549 20.650 22.476 32.112
H36 25.070 11.936 20.097 22.086 33.028
13. Perlite-SO3H Nanoparticles as an Efficient and Reusable Catalyst/Nano. Chem. Res., Vol. 1, No. 1, 87-107, June 2016.
99
σiso values of C15, C16, C17 and C18 atoms in phenyl ring are
34.305 ppm, 51.738 ppm, 49.950 ppm and 26.033 ppm,
respectively. As shown, the C16 atom is shielder than other
and the C18 atom is deshielder than other carbon atoms of
phenyl ring.
NBO Analysis
Natural bond orbital (NBO) analysis is an important
method for studying interaction between bonds.79,80
The
results of NBO analysis such as the occupation numbers
with their energies for the interacting NBOs and the
polarization coefficient of atoms for 4i structure at
B3LYP/6-311+G* level are summarized in Table 8. The
size of polarization coefficients shows the importance of the
two hybrids in formation of the bond. In 4i structure, the
calculated bonding orbital for the C12-N13 bond is BD(1) =
0.6169sp1.82
+ 0.7870sp1.89
with high occupancy 1.98987 a.u.
and energy -0.85022 a.u.. The polarization coefficients of
C12 = 0.6169 and N13 = 0.7870 suggest that N13 is more
electron-rich than the C12 atom. The calculated natural
charge (NBO) of N13 atom is more negative (-0.650e) than
C12 atom (0.923e). Thus more the charge density resides on
the N13. The calculated bonding orbital for the C12-O21 is
BD(1) = 0.6002sp1.71
+ 0.7999sp1.53
with high occupancy
1.99197 a.u. and low energy -1.08004a.u.. The polarization
coefficient of O21(0.7999) is greater than C12(0.6002)
suggesting that O21 is more electron-rich (-0.603e) than C12
(0.923e). Also, in the bonding orbital of C9-O11 [BD(1)=
0.5642sp1.37
+ 0.8256sp2.05
] with high occupancy 1.98802
a.u. and energy -0.91039 a.u., the polarization coefficient of
C9(0.5642) is greater than O11(0.8256) indicating that O11 is
more electron-rich (-0.539e) than C9(0.333e). From the
natural hybrid orbitals C9-O11 and C12-O21, the BD(1)C9-O11
occupies a higher energy orbital (-0.91039 a.u.) with low
occupation number (1.98802 a.u.) and BD(1)C12-O21
occupies a lower energy orbital (-1.08004 a.u.) with high
polarization coefficient (1.99197 a.u.). According to the
calculated bondin orbital for the N13-H31, C14-H32 and C22-
H37 bonds, the polarization coefficients of N13, C14 and C22
are greater than that for H atoms indicative of the
Table 8. Calculated Natural Bond orbitals (NBOs) and Polarization Coefficient for Each Hybrid in Selected
Bonds of 4i Compound at B3LYP/6-311+G* Level (Atom Labeling Corresponds to Fig. 7)
Energy (a.u.) Bond (A-B)a
Occupancy (a.u.) A B
-0.70472 BD (1) C8-C9 1.96967 0.7016 sp1.97
0.7126 sp1.72
-0.91039 BD (1) C9-O11 1.98802 0.5642 sp3.46
d0.01
0.8256 sp1.97
-0.89961 BD (1) O11-C12 1.98798 0.8306 sp2.34
0.5568 sp2.62
d0.01
-0.85022 BD (1) C12-N13 1.98987 0.6169 sp1.82
0.7870 sp1.89
-1.08004 BD (1) C12-O21 1.99197 0.6002 sp1.71
0.7999 sp1.53
-0.75699 BD (1) N13-C14 1.97990 0.7848 sp1.83
0.6197 sp3.76
d0.01
-0.60087 BD (1) C22-C24 1.97659 0.7179 sp2.80
0.6161 sp2.36
-0.66460 BD (1) N13-H31 1.98062 0.8389 sp2.81
0.5442 s
-0.52141 BD (1) C14-H32 1.96904 0.7802 sp3.62
0.6256 s
-0.48408 BD (1) C22-H37 1.96907 0.7730 sp3.99
d0.01
0.6344 s
a
A-B is the bond between atoms A and B. (A: natural bond orbital and the polarization coefficient of atom;
A-B: natural bond orbital and the polarization coefficient of atom B).
14. Ramazani et al./Nano. Chem. Res., Vol. 1, No. 1, 87-107, June 2016.
100
importance of N13, C14 and C22 in formation of N13-H31, C14-
H32 and C22-H37 bonds compared to H atoms.
Electron donor orbital, acceptor orbital and the
interacting stabilization energy resulting from the second-
order micro disturbance theory [81] are reported in Table 9.
The electron delocalization from the filled NBOs (donors)
to the empty NBOs (acceptors) describes a conjugative
electron transfer process between them [82]. For each donor
(i) and acceptor (j), the stabilization energy E(2) associated
with the delocalization i→j is estimated. The resonance
energy (E(2)) detected the quantity of participation of
electrons in the resonance between atoms [71]. The results
of the NBO analysis, such as resonance energy (E(2)),
donor NBO (i) and acceptor NBO (j), for 4i compound at
B3LYP/6-311+G* level are listed in Table 9. According to
this table, the BD(1)N13-H31 orbital participates as donor
and the anti-bonding BD*(1)C10-O14 and BD*(1)O11-C12
orbitals act as acceptor and their resonance energies (E(2))
are 1.57 and 4.91, respectively. These values indicate large
charge transfer from the BD(1)N13-H31 to the anti-bonding
orbital of BD*(1)O11-C12 [BD(1)N13-H31→BD*(1)O11-C12].
Based on NBO analysis, the LP(1)N13 orbital participates as
donor and the anti-bonding BD*(1)C14-C15, BD*(1)C14-H32
and BD*(1)C15-C16 orbitals act as acceptor and their
resonance energies (E(2)) are 6.15, 93.29 and 1.54,
respectively. These values indicate large charge transfer
from the LP(1)N13 to anti-bonding orbital of BD*(1)C14-H32
[LP(1)N13→BD*(1)C14-H32]. Also, the resonance energies
(E(2)) for BD(2)C17-C18→BD*(2)C15-C16, BD(2)C17-
C18→BD*(1)C22-C23 and BD(2)C17-C18→BD*(1)C22-C24 are
Table 9. Significant Donor-Acceptor Interactions and Second Order Perturbation Energies of 4i Compound
Calculated at B3LYP/6-311+G* Level (Atom Labeling Corresponds to Fig. 7)
Donor NBO(i) Acceptor NBO(j) E(2)a
(kcal mol-1
) E(j)-E(i)b
(a.u.) F(i,j)c
(a.u.)
BD (1) N13-H31 BD* (1) C10-C14 1.57 1.06 0.039
BD* (1) O11-C12 4.91 0.99 0.064
BD (2) C17-C18 BD* (2) C15-C16 21.71 0.28 0.070
BD* (1) C22-C23 2.54 0.63 0.039
BD* (1) C22-C24 2.62 0.63 0.040
LP (1) O11 BD* (1) C8-C9 0.84 1.08 0.027
BD* (1) C9-C10 5.69 1.11 0.071
BD* (1) C12-N13 5.39 1.00 0.066
BD* (1) C12-O21 1.58 1.19 0.039
LP (1) N13 BD* (1) C14-C15 6.15 0.67 0.061
BD* (1) C14-H32 93.29 0.66 0.044
BD* (1) C15-C16 1.54 0.31 0.020
LP (2) O21 BD* (1) O11-C12 33.82 0.58 0.127
BD* (1) C12-N13 22.27 0.70 0.114
a
E(2) means energy of hyperconjucative interactions. b
Energy difference between donor and acceptor I and
j NBOs. c
F(i,j) is the Fock matrix element between i and j NBOs .
15. Perlite-SO3H Nanoparticles as an Efficient and Reusable Catalyst/Nano. Chem. Res., Vol. 1, No. 1, 87-107, June 2016.
101
21.71, 2.54 and 2.62 kcal mol-1
, respectively, showing large
charge transfer from BD(2)C17-C18 to the anti-bonding
orbital of BD*(2)C15-C16.
EXPERIMENTAL
General
All reagents were obtained from Merck (Germany) and
Fluka (Switzerland) and used without further purification.
Infrared spectra were recorded on a Jasco 6300 FTIR
spectrometer. Melting points were measured on an
Electrothermal 9100 apparatus and are uncorrected. The
microwave-assisted procedures were carried out in a
Milestone Microwave Oven operating at 1600 W. SEM
(Philips XL-30 SEM) with an acceleration voltage of 17 kV
was used to investigate the size of the nanoparticles.
Fig. 8. SEM image of the prepared perlite nanoparticles.
16. Ramazani et al./Nano. Chem. Res., Vol. 1, No. 1, 87-107, June 2016.
102
Preparation of the Perlite Nanoparticles
Perlite powder was first broken down to nano size using
the ball-milling technique at the frequency of 45 Hz for 20 h
under the dry grinding mode. The morphology and grain
size of the perlite nanoparticles was investigated by SEM
(12 nm) (Fig. 8). The results from X-ray diffraction (XRD)
showed that the sample was perlite nanoparticles as
indicated by broadened peaks around 2θ = 26◦
(Fig. 9).
Preparation of the Perlite-SO3H Nanoparticles
Perlite-SO3H nanoparticles, was easily prepared by a
simple mixing of the perlite nanoparticles and
chlorosulfonic acid at room temperature [83] (Scheme 4). A
250 ml suction flask was equipped with a constant pressure
dropping funnel containing chlorosulfonic acid (11.6 g, 0.1
mol) and a gas inlet tube for conducting HCl gas over an
adsorbing solution, i.e., H2O. Then, 30.0 g of the perlite
nanoparticles was charged into the flask. Chlorosulfonic
acid was added drop wise over a period of 30 min at room
temperature. After the addition was complete, the mixture
was shaken for 30 min. Perlite-SO3H was obtained as a
white solid. Surface morphology and particle size were
Fig. 9. X-ray diffraction pattern of the prepared perlite nanoparticles.
+ xClSO3H
-xHCl
OH
OH
OHHO
OSO3H
OSO3H
OSO3HHO3SO
PerliteNPs
PerliteNPs
r.t.
1 2 3
Scheme 4. Preparation of the perlite-SO3H NPs via surface modification of the perlite NPs by chlorosulfonic acid.
17. Perlite-SO3H Nanoparticles as an Efficient and Reusable Catalyst/Nano. Chem. Res., Vol. 1, No. 1, 87-107, June 2016.
103
obtained using SEM (28 nm) (Fig. 10).
One-Pot Synthesis of 1,2-Dihydro-1-aryl-
naphtho[1,2-e][1,3]oxazine-3-one derivatives (4a-j)
under Thermal Conditions
A mixture of β-naphthol (0.5 mmol), an aromatic
aldehyde (0.5 mmol) and urea (0.55 mmol) was heated at
110 °C in the presence of perlite-SO3H nanoparticles (0.01
g) for the indicated time (Table 1). After completion of the
reaction, boiling ethanol was added to the reaction mixture.
The catalyst was filtered off and the filtrate was then
concentrated and cooled to room temperature. The aqueous
ethanol 15% was added to the crude product, the precipitate
was separated and then recrystallized using aqueous ethanol
15% twice. The desired pure product(s) was characterized
by comparison of their spectroscopical data (FT-IR) and
Fig. 10. SEM image of the synthesized perlite-SO3H nanoparticles.
18. Ramazani et al./Nano. Chem. Res., Vol. 1, No. 1, 87-107, June 2016.
104
physical data with those of known oxazine-3-ones (Table 5).
One-Pot Synthesis of 1,2-Dihydro-1-aryl-
naphtho[1,2-e][1,3]oxazine-3-one Derivatives (4a-j)
under Microwave Irradiation
The mixture of β-naphthol (0.5 mmol), an aromatic
aldehyde (0.5 mmol) and urea (0.55 mmol) and perlite-
SO3H nanoparticles (0.01 g) was taken in a 50 ml Borosil
beaker. The reaction mixture was mixed properly with the
help of glass rod and then irradiated in a microwave oven
operating power (900 W) for 2-10 min. The progress of the
reaction was monitored by TLC, after completion of the
reaction; the hot ethanol was added to the reaction mixture
and the heterogeneous catalyst was isolated from the
mixture by a simple filtration. In continuation of work up,
the filtrate ethanol solution was concentrated. The aqueous
ethanol (15%) was added to the crude product, the
precipitate was separated and then recrystallized using
aqueous ethanol (15%) twice. The desired pure product(s)
was characterized by comparison of their spectroscopical
data (FT-IR) and physical data with those of known
oxazine-3-ones.
X-Ray Crystal-Structure Determination of 4i (Fig.
8)
The crystallographic measurement for 4i CCDC 966112
contains the supplementary crystallographic data for 4i
(These data can be obtained free of charge via
http://www.ccdc.cam.ac.uk.) was performed at 100(2) K on
a Kuma KM4-CCD κ-geometry four-circle diffractometer
with graphite-monochromatizedMoKα radiation. Data were
corrected for Lorentz and polarization effects. Data
collection, cell refinement, and data reduction and analysis
were carried out with the KM4-CCD software, CrysAlis
CCD and CrysAlis RED, respectively [84]. Empirical
(multi-scan) absorption correction was applied to the data
with the use of CrysAlis RED. The structure was solved by
direct methods with the SHELXS-2013 program [68], and
refined on F2
by a full-matrix least-squares technique using
SHELXL-2013 [68], with anisotropic thermal parameters for
the non-H atoms. The H atoms were found in difference
Fourier maps, and in the final refinement cycles the C-
bonded H atoms were repositioned in their calculated
positions and refined using a riding model, with C-H =
0.95-1.00 Å, and with Uiso(H) = 1.2Ueq(C) for CH, and
1.5Ueq(C) for CH3. The N-bonded H atom was refined
freely. The figures were made using DIAMOND program
[85].
Crystal Ddata for 4i
C21H19NO2, M = 317.37, yellow plate, crystal size 0.76
0.45 0.07 mm, monoclinic, space group P21/n (no. 14), a
= 11.919(3), b = 8.061(2), c = 17.437(4) Å, β = 102.89(3)°,
V = 1633.1(7) Å3
, T = 100(2) K, Z = 4, ρcalc = 1.291 g cm-3
,
μ = 0.08 mm-1
(for MoKα, λ = 0.71073 Å), Tmin = 0.943,
Tmax = 1.000, 7272 reflections measured, 3760 unique (Rint =
0.028), 2608 observed (I > 2σ(I)), θ range 3.1-28.7°,
parameters = 223, restraints = 0, R1 = 0.055, wR2 = 0.142
(observed refl.), GooF = S = 1.00, largest difference in peak
and hole, Δρmax and Δρmin = 0.30 and -0.25 e Å-3
.
COMPUTATIONAL DETAILS
In this work, to gain a further insight into the properties
of 4i, we have carried out quantum theoretical calculations
for this compound at B3LYP/6-311+G* level (DFT) [86-88]
by the Gaussian 03W program package [89] . At first, we
optimized structure using Gaussian 03W program (see Fig.
1). The electronic properties such as EHOMO, ELUMO, HOMO-
LUMO energy gap (Eg), EHOMO-1, ELUMO+1, natural charges,
molecular properties, dipole moment (μD) and point group
were detected [90]. The optimized molecular structure,
HOMO and LUMO surfaces were visualized using Gauss
View 03 program. We also calculated NMR parameters
such as chemical shift isotropic (CSI
) and chemical shift
anisotropic (CSA
) for title structure [79,91]. Also, the
electronic structure of 4i compound was studied by using
Natural Bond Orbital (NBO) analysis at the same level in
order to understand various second-order interactions
between the filled orbitals of one subsystem and vacant
orbitals of another subsystem, which is a measure of the
inter-molecular delocalization or hyper conjugation [71,92].
CONCLUSIONS
In conclusion, it can be said that a simple, eco-friendly,
green and efficient procedure for the synthesis of
19. Perlite-SO3H Nanoparticles as an Efficient and Reusable Catalyst/Nano. Chem. Res., Vol. 1, No. 1, 87-107, June 2016.
105
naphthalene condensed oxazinone derivatives from 2-
naphthol, aldehydes with urea is reported for the first time
by our research group using inexpensive, easily recyclable,
and efficient perlite-SO3H nanoparticles as catalysts in
economical and safe, solvent-free in both thermal and
microwave conditions. The method is very efficient, avoids
the use of expensive reagents, and leads to improved
product yields. To the best our knowledge, this is the first
report on perlite-SO3H nanoparticles catalyzed synthesis of
naphthaoxazinone derivatives and this new procedure opens
an important chapter in the efficient recyclability of perlite-
SO3H nanoparticles as an important catalyst. The ambient
conditions, high reaction rates, excellent product yields and
easy work-up procedures not only make this methodology
an alternative platform to the conventional acid/base
catalyzed thermal process but also bring it under the
umbrella of environmentally greener and safer synthetic
procedures. Additional applications of this technique are
currently under investigation. In the present study also, the
electronic properties of 4i compound have been analyzed
using DFT calculations (B3LYP/6-311+G*). The FMO
analysis suggests that charge transfer takes place within the
4i molecule and the HOMO is localized mainly on
naphthalene and oxazinone rings whereas the LUMO
resides on the naphthalene ring. According to the results of
NBO analysis, the highest positive and negative charge
values belong to carbon atom in carbonyl group (C12:
0.923e), and nitrogen atom (N13: -0.650e), respectvely.
NBO nalaysis also show that the polarization coefficients of
the electronegative atoms in calculated bonding orbital are
greater than electropositive atoms.
ACKNOWLEDGEMENTS
This work was supported by the “Iran National Science
Foundation: INSF”.
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