Ethoxide In Ethanol Research Articles

Optimization of the ETL titanium dioxide layer for inorganic perovskite solar cells

Titanium dioxide layers are the most popular electron transport layer (ETL) in perovskite solar cells. However most studies focuses on mesoporous structure and application with organic–inorganic hybrid perovskite. In this study, the topic of ETL in planar structure of inorganic CsPbBr3 perovskite solar cells was tackled, the presented approach will reduce production costs and improve cell stability, which is the greatest drawback of perovskite cells especially organic–inorganic perovskite. The potential application of these technology are greenhouses and building integrated PV sector. Here, the two TiO2 precursors titanium(IV) ethoxide in ethanol and titanium(IV) bis(acetylacetonate) diisopropoxide (Tiacac) were investigated, optimized and compared. TiO2 layers were deposited on high roughness FTO, without the use of a mesoporous layer, by spin coating method. The correlation between stock solution concentration and thickness of manufactured layers was tracked for both precursors as well as their difference in morphology of the final films and other properties. In particular, conformality and optical properties are better for Tiacac. Slightly lower refractive index of Tiacac-based titania reduced the reflective losses from 7.3 to 6.9% effectively. The obtained layers were used for inorganic solar cells of CsPbBr3 perovskite to finally settle the issue of optimal thickness and precursor. It is interesting that despite the supremacy in investigated properties of commonly used of the precursor Tiacac, the results of the cells pointed to the Tieth. The efficiency of the champion cell is 6.08% for Tieth, while 5.62% is noted for Tiacac. Trying to figure out this riddle, we shed a new light on the phenomena going on the ETL/inorganic perovskite interface investigating nanoroughness.

Synthesis and Molecular Docking Studies of Some Fluorinated 2-Aminopyrimidines, Pyrazoles and Isoxazoles as Possible Anti-cancer Agents

The reaction of a-fluoro-oxoketene dithioacetals (2) with guanidinium nitrate, hydrazine hydrate, and hydroxyl amine hydrochloride in the presence of sodium ethoxide in ethanol under reflux conditions produced new series of fluorinated 2-aminopyrimidines, pyrazoles, and isoxazoles. In silico study was carried out to explore the binding potential of all the synthesized compounds toward the cancer target receptors (EGFR and IGF1R). It is worth noting that 4-fluoro-5- (methylthio)-3-(naphthalen-4-yl)isoxazole (5h) had a higher affinity for both targets. In particular, the synthesized compound showed crucial interatomic interactions with IGF1R along with two hydrogen bond interactions (LYS1030 and ASP1150). Further, experimental investigation of this molecule will be an interesting direction to take to develop a new anti-cancer agent.. KEYWORDS :Anti-cancer activity, Fluorinated 2-aminopyrimidines, Isoxazoles and Pyrazoles, Molecular Docking Studies.

Asymmetric α-Cyanation of β-Keto Esters Catalyzed by Chiral Tin Alkoxides

AbstractA catalytic enantioselective α-cyanation reaction of β-keto esters with p-toluenesulfonyl cyanide (TsCN) as a cyanating reagent was achieved using an (R)-BINOL-derived chiral tin dibromide possessing 4-tert-butylphenyl groups at the 3- and 3′-positions as a chiral precatalyst in the presence of sodium ethoxide in ethanol. Optically active α-cyano-β-keto esters having a chiral quaternary carbon were obtained in good to high yields under the influence of the chiral tin diethoxide generated in situ.

Synthesis and Molecular Docking Studies of a Series of Amino-Pyrimidines as Possible Anti-Cancer Agents

The pyrimidine scaffold represents one of the privileged structures in chemistry, and there has been an increase in number of studies utilizing this scaffold and its derivatives. A series of 2-amino pyrimidines were synthesized by the reaction of ketene dimethyl thio-acetals with guanidinium nitrate in presence of sodium ethoxide in ethanol under reflux condition. Spectral analysis of the final compounds has been carried out using IR, 1H NMR, 13C NMR spectroscopy and HRMS. Further, the structure of one of the derivatives 4-ethoxy-6-(naphthalen-1-yl) pyrimidin-2-amine (2d) was confirmed by single crystal X-ray diffraction technique. X-ray diffraction analysis for 2d has been reported. The crystal structure of 2d is stabilized by intermolecular N–H…N, C–H…π and π…π weak interactions. To check whether pyrimidine could be ligands for two kinases involved in cancer, docking studies were performed. Few of the compounds showed strong binding affinity with IGF1R and EGFR.

Tetrasubstituted Phthalocyanines with Benzoic Acids Moieties

Phthalonitriles substituted with o-hydroxybenzoic, o-aminobenzoic, and o-mercaptobenzoic acids moieties were synthesized by nucleophilic substitution of bromine in 4-bromophthalonitrile and of nitro group in 4-nitrophthalonitrile. Template condensation of these phthalonitriles with metal acetates gave the corresponding phthalocyanines. Metal-free phthalocyanines were synthesized by dissociation of the magnesium complexes of the substituted phthalocyanines in a sulfuric acid medium. Treatment of the resultant phthalocyanines with sodium ethoxide in ethanol yielded sodium salts of the carboxylic acids. The spectral properties of the compounds synthesized were examined.

A useful ring transformation route to novel thiazepino[7,6-b]indoles from monochloro-β-lactam-fused 1,3-thiazino[6,5-b]indoles, analogues of cyclobrassinin

The Staudinger ketene-imine cycloaddition reactions of cyclobrassinin phytoalexin analogues 2-aryl-4,9-dihydro-1,3-thiazino[6,5-b]indoles with chloroacetyl chloride as a ketene source were investigated under different conditions. Both β-lactam ring formation and the N-chloroacetylation of the indole moiety took place. The indole N-chloroacetyl group can be easily removed by treatment in the presence of silica gel in methanol at reflux temperature. The selective β-lactam formation can be also achieved in certain cases under milder Staudinger conditions. The treatment of azeto[2,1-b]thiazino[6,5-b]indole-1-one derivatives with sodium ethoxide in ethanol provided the novel thiazepino[7,6-b]indole ring systems in a one-step ring transformation. The structures of the new ring systems were determined by means of IR and NMR spectroscopy.

Design, Synthesis, Characterization, and Antimicrobial Screening of Novel Indazole Bearing Oxadiazole Derivatives

Ethyl 2‐(2,6‐dioxocyclohexyl)‐2‐oxoacetate was prepared by reacting cyclohexane‐1,3‐dione (1) and diethyl oxalate (2) with the help of sodium ethoxide in ethanol at 0–5°C. Subsequent treatment of ethyl 2‐(2,6‐dioxocyclohexyl)‐2‐oxoacetate with hydrazine hydrate in ethanol resulted into ethyl 4‐oxo‐4,5,6,7‐tetrahydro‐2H‐indazole‐3‐carboxylate while without solvent in excess hydrazine hydrate on reflux resulted into 4‐oxo‐4,5,6,7‐tetrahydro‐2H‐indazole‐3‐carbohydrazide (3). The synthesis of novel indazole bearing oxadiazole derivatives (ODZ 01 to 16) has been achieved by the reaction of hydrazide of 2H‐indazole (3) with acid (4a, 4b, 4c, 4d, 4e, 4f, 4g, 4h, 4i, 4j, 4k, 4l, 4m, 4n, 4o, 4p) in the presence of POCl3, and the antimicrobial activity of synthesized novel compounds has been studied.

Novel organotin complexes derived from 2,2′-selenodiacetic acid: synthesis and biological evaluation

The reactions of 2,2′-selenodiacetic acid and the corresponding organotin(IV) chloride with sodium ethoxide in ethanol, or via a solvothermal synthetic route, have afforded four organotin polymers, namely, [(Me3Sn)2Se(CH2COO)2]n (1), [(Me2Sn)2Se(CH2COO)2(μ3-O)]n (2), [(Bu3Sn)2Se(CH2COO)2]n (3), and [(Bu2Sn)Se(CH2COO)2]n (4). All the complexes were fully characterized by elemental analysis, FT-IR, NMR (1H, 13C, and 119Sn) spectroscopy and single crystal X-ray diffraction analysis. The structural analysis reveals that complex 1 is a 2D-polymer containing interconnected 24-membered (Sn4O8C10Se2) macrocyclic rings. Unlike complex 1, the 2D polymer structure of complex 2 is made up of the typical ladder tetraorganodistannoxane unit containing 32-membered (Sn4O8C16Se4) macrocyclic rings. Complex 3 is a 3D corrugated polymeric structure in which the deprotonated dicarboxylic acid acts as a tetradentate ligand by four oxygen atoms. Complex 4 is a 1D zigzag coordination polymer and the tin coordination geometry is described as skewed-trapezoidal bipyramidal. In particular, preliminary cytotoxic assessments of the involvement of complex 4 in the apoptotic death of MDA cells were conducted, and the results revealed that the antiproliferative and proapoptotic effect of complex 4 in MDA cells prominently contributed to the overload of intracellular ROS levels and the dysfunctional depolarization of mitochondrial membranes.

Synthesis and Characterization of a Novel Two‐Dimensional Network Polymer Containing 18‐ and 26‐Membered Organotin Macrocycles

ABSTRACTThe reaction of 4‐mercaptophenylacetic acid with dimethyltin dichloride in the presence of sodium ethoxide in ethanol affords a novel two‐dimensional organotin network structure compound 1, which is an unusual network containing dinuclear 18‐membered and tetranuclear 26‐membered organotin macrocycles. The compound has been characterized by elemental analysis, IR, and 1H, 13C, and 119Sn NMR spectroscopy. Furthermore, we have also characterized the compound by X‐ray crystallography.

Mechanistic aspects of the lycopodine Michael-Claisen domino cyclization

The Michael-Claisen domino (MCD) cyclization used in the lycopodine synthesis by Stork, was evaluated mechanistically using DFT calculations. Calculations suggest that a dianion is not formed, which conforms to classical dianion formation normally requiring strong kinetic bases. Instead ethoxide in ethanol produces a monoanionic species driving the MCD cyclization. This endeavor has opened up potential to expand the scope of this unique reaction and provide educational clarity.

Continuous flow synthesis of tungsten oxide (WO3) nanoplates from tungsten (VI) ethoxide

Tungsten oxide (WO3) nanoplates with low reduction temperatures have been successfully synthesised using near- and super-critical water in a continuous flow system (CFS). A pipe in pipe reactor system was used to mix a cold flow of tungsten (VI) ethoxide in ethanol with a superheated flow of water containing 2.5% hydrogen peroxide. The addition of poly(ethylene glycol) (PEG) to the precursor solution was found to partially inhibit 2D growth. The WO3 crystals produced were all within the nanorange with aspect ratios of ca. 2.88, 2.61 and 4.24 depending on the conditions used. The effects of the heated water stream to precursor solution flow ratios as well as reaction temperature were studied. Our synthesis method has the advantage of being a continuous system that can rapidly produce WO3 with the ability to modify the size and shape of the nanoplates by adjusting the reaction conditions. This method has also been proven to be scalable at tonnes per year. The products here presented were characterised using High Resolution Transmission Electron Microscopy (HRTEM), Fourier Transform Infra-Red/Attenuated Total Reflectance Spectroscopy (FTIR/ATR), heated-stage X-ray Diffraction (XRD) with atmosphere control and Thermogravimetric Analysis (TGA) with H2 for reduction purposes.

Simple and scalable route for the ‘bottom-up’ synthesis of few-layer graphene platelets and thin films

Graphene has generated much interest owing to its exceptional electronic properties and high mechanical strength. This has enabled new types of electronic devices and composite materials to be envisaged. The main problem is the availability of the material and the difficulties associated with its synthesis. Here we have used a simple, convenient and scalable chemical vapour deposition method involving sodium ethoxide in ethanol to produce few-layer graphene sheets or platelets. The process has the advantage that it can be used to grow graphene films on non-metal containing substrates such as silicon wafer and quartz glass and that all non-carbon by-products are soluble in water.

C-Alkylation of α-acylamino ketones. A versatile synthesis of α-alkyl α-amino ketones

C-Alkylation of some α-acylamino ketones were achieved with alkyl halides by means of sodium ethoxide in ethanol. The present paper deals with the C-alkylation of N,N-diformylamino ketones and the difference in stability of the amide group.

Synthesis and structure of ethyl (Z)-α-formylamino-β-arylacrylates

Ethyl (Z)-α-formylamino-β-arylacrylates were obtained in good yields by the condensation of ethyl N, N-diformylamino acetate and aromatic aldehydes in the presence of sodium ethoxide in ethanol. The structure of ethyl α-formylaminocinnamate was characterized by single crystal X-ray diffraction measurement.

ChemInform Abstract: A Versatile New Method for Synthesis of Isoquinolines. 6,8- Dihydroxyisoquinoline Derivatives from 6-Methyl-1,3-oxazin-4-ones.

A versatile method for synthesis of isoquinolone derivatives (4a-h) from 2-substituted 6-methyl-4H-1,3-oxazin-4-ones (1a-h) is described. Transformation of 1a-h with diethyl acetonedicarboxylate (2) in the presence of potassium tert-butoxide afforded 6-substituted 3-acetyl-5-ethoxycarbonyl-4-ethoxycarbonylmethylene-2-pyridones (3a-h) in excellent yields. Dieckmann-type cyclization of 3a-h with sodium ethoxide in ethanol produced the corresponding isoquinolone derivatives (4a-h) in good yields, respectively

Synthetic transformations of higher terpenoids: XX. Synthesis and transformations of diterpene ureido esters

Lossen rearrangement of N-hydroxymaleopimaric acid amide p-toluenesulfonate in the presence of amines in methanol led to the formation of the corresponding diterpene ureido esters with high regio- and stereoselectivity. Treatment of the resulting ureides with phosphoryl chloride gave cyclic amidines via intramolecular ring closure. Substituted hydantoins were obtained by reactions of the ureido esters with glyoxal in acid medium, and their treatment with sodium ethoxide in ethanol afforded compounds of the naphtho[1,2-h]-quinazoline series.

Exceptional isolation of both imine and enamine desmotropes of 4,1-benzothiazepines

The desmotropy of differently substituted ( R∗)-3-ethoxycarbonyl-2-aryl-3,5-dihydro-4,1-benzothiazepines and 3-ethoxycarbonyl-2-aryl-1,5-dihydro-4,1-benzothiazepines was investigated. The target 4,1-benzothiazepines were obtained via the ring transformation of (2 R∗,2a S∗)-2-chloro-2a-aryl-2,2a-dihydro-2 H,4 H-azeto[1,2- a][3,1]benzothiazin-1-ones with sodium ethoxide in ethanol. The β-amino ester intermediate of the ring-enlargement reaction was isolated. Surprisingly, the desmotropes obtained could be separated by column chromatography and proved to be unexpectedly stable in solution. Further comparative studies revealed the existence of only the enamine forms of regioisomeric 2-ethoxycarbonyl-3-aryl-4,5-dihydro-7,8-dimethoxy-1,4-benzothiazepine derivatives; in this case, no desmotropy occurred. The structures were proved by means of NMR and IR spectroscopy.

Synthesis and Single Crystal X-Ray Structure of Bis[4-oxo-3- (2-ethoxycarbonylphenyl)-3,4-dihydroquinazolin-2-yl]disulfide

Diethyl 2,2´-thiocarbonyl-bis(azanediyl)dibenzoate was synthesized from the reaction of ethyl anthranilate with thiophosgene. Its treatment with sodium ethoxide in ethanol at room temperature gave ethyl 2-(4-oxo-2-thioxo-1,2-dihydroquinazolin-3(4H)-yl) benzoate, whereas in the presence of ethyl nitroacetate and under the same reaction conditions, the corresponding bis(quinazolin)disulfide was formed. Its structure was confirmed by IR, 1H and 13C NMR spectroscopy elemental analysis and single crystal X-ray structure determination.

Effect of solvent and temperature on the preparation of potassium niobate by hydrothermal-assisted sol–gel processing

In this study the preparation of potassium niobate powder, a material with high electro-optic and nonlinear optical coefficients, by hydrothermal-assisted sol–gel processing from potassium-niobium ethoxide [KNb(OC 2H 5) 6] have been performed. The development of potassium niobate phases by hydrothermal hydrolysis of potassium niobium ethoxide at 100 and 200 °C in ethanol, toluene, and a mixture of benzene and ethanol was pursued by X-ray diffraction. Selected powders obtained from hydrothermal-assisted sol–gel processing were characterized by X-ray powder diffraction, thermal analysis (TGA/DSC), and scanning electron microscopy (SEM). X-ray diffraction results showed that the hydrothermal hydrolysis of potassium-niobium ethoxide in ethanol at 100 and 200 °C results in the formation of cubic phase KNbO 3. Hydrolysis in a mixture of benzene/ethanol and toluene at 200 °C produces an orthorhombic phase KNbO 3, which is a mixture of the potassium deficient phase, K 4Nb 6O 17, and cubic and orthorhombic KNbO 3 phases. The potassium niobate powder prepared by the hydrothermal method had the advantage of low weight loss during calcination. SEM micrographs showed that the shape of particles prepared by hydrothermal-assisted sol–gel processing is more uniform when compared with the sample prepared by conventional sol–gel processing.

Synthesis and Spectroscopic Properties of Low-Symmetry Tribenzoporphyrazines with Annulated 6H-1,4-Diazepine Ring

Template co-condensation of 2,3-dicyano-5,7-diphenyl-6H-1,4-diazepine 1 with 10-fold molar excess of phthalodinitrile 2 in the presence of MgII propoxide or butoxide in the corresponding alcohol leads to a mixture of MgII-diazepinoporphyrazines 3–6 from which the low symmetry 3:1 species 3, which contains three annulated benzene and one 1,4-diazepine rings, is separated by column chromatography as the aquo complex, [2,4-diphenyltribenzo[b,g,l][1,4]diazepino[2,3-q]porphyrazinato(aquo)magnesium(ii)], [Bz3DzPzMg(H2O)]. The complex 3 can be demetalated in acetic or trifluoroacetic acids under mild conditions with formation of the corresponding free-base [Bz3DzPzH2] 3a. This latter is also formed by co-cyclotetramerization of the same precursors 1 and 2 in the presence of sodium ethoxide in ethanol or lithium butoxide in butanol followed by demetalation of the intermediate disodium or dilithium salts in acid medium. The constitution and structure of the obtained compounds were established on the basis of elemental analysis, mass spectrometry, and 1H NMR spectra. The variable temperature 1H NMR measurements provide evidence that in porphyrazines 3 and 3a the 1,4-diazepine ring exists predominantly in the 6H-form over a wide temperature range. The free energy of activation for the inversion of the 1,4-diazepine ring determined for 3 is 45.6 ± 1.7 kJ mol–1. Solution UV-visible spectra measurements in acidic media (CH2Cl2/CF3COOH) provide evidence that the MgII complex 3 is easily protonated on the meso-N atom of the porphyrazine macrocycle followed by slow demetallation with formation of the free base 3a in its neutral form or as a species protonated on the diazepine ring.