Organophosphites: An Addition to the Arsenal of Organocatalysts

Organophosphites are nucleophilic in nature and can act as a good leaving group owing to the stability of the phosphite anion. This dual reactivity makes them good candidates for nucleophilic organocatalysis. However, phosphites were introduced only in 2004 as the umpolung catalyst for acylsilane substrates utilizing sequential Brook rearrangements. Very recently, phosphites have been reported to catalyze aza-rearrangements and radical reactions. In this review, we discuss the reactivity parameters to understand its lack of use, as well as the potential for catalysis.     

Characterizations of Null Holomorphic Sectional Curvature of G C R-Lightlike Submanifolds of Indefinite Nearly K ¨ahler Manifolds

We obtain the expressions for sectional curvature, holomorphic sectional curvature and holomorphic bisectional curvature of a GCR-lightlike submanifold of an indefinite nearly K ¨ahler manifold and obtain characterization theorems for holo-morphic sectional and holomorphic bisectional curvature. We also establish a condi-tion for a GCR-lightlike submanifold of an indefinite complex space form to be a null holomorphically flat.     

Investigation of biosourced carboxymethyl cellulose-ionic liquid polymer electrolytes for potential application in electrochemical devices

Biosourced carboxymethyl cellulose polymer electrolytes have been studied for potential application in electrochemical devices. The carboxymethyl cellulose was obtained by reacting cellulose derived from kenaf fibre with monochloroacetic acid. Films of the biosourced polymer electrolytes were prepared by solution-casting technique using ammonium acetate salt and (1-butyl)trimethyl ammonium bis(trifluoromethylsulfonyl)imide ionic liquid as charge carrier contributor and plasticizer, respectively. The shift of peak of carboxyl stretching in the Fourier transform infrared spectra confirmed the interactions between the host biosourced polymer with the ionic liquid. Scanning electron microscopy indicated that the incorporation of ionic liquid changed the morphology of the electrolyte films. The room temperature conductivity determined using impedance spectroscopic technique for the film without ionic liquid was 6.31 × 10^?4 S cm^?1 while the highest conductivity of 2.18 × 10^?3 S cm^?1 was achieved by the film integrated with 20 wt% (1-butyl)trimethylammonium bis(trifluoromethanesulfonyl) imide. This proved that the incorporation of ionic liquid into the salted system improved the conductivity. The improvement in conductivity was due to an increase in ion mobility. The results of linear sweep voltammetry showed that the electrolyte was electrochemically stable up to 3.07 V.     

Iodine assisted palladium catalyzed ring opening of bicyclic hydrazines with organoboronic acids: stereoselective synthesis of functionalized cyclopentenes and alkylidene cyclopentenes

A novel reactivity of organoboronic acids with bicyclic hydrazines leading to the stereoselective formation of trans-vicinal disubstituted cyclopentenes in good to excellent yield is discussed. The reaction of cyclopentadiene and fulvene derived azabicyclic alkenes with organoboronic acids afforded the trans-3,4-disubstituted cyclopentenes and alkylidene cyclopentenes in good to excellent yields. The products, having a broad range of substituents, are important intermediates in the synthesis of a number of pharmaceutically important molecules.     

Anilinolysis of O‐butyl phenyl phosphonochloridothioate in acetonitrile: Synthesis,characterization, kinetic study,and reaction mechanism

This paper describes a simple optimized method for the synthesis of O‐butyl phenyl phosphonochloridothioate ( 4 ) under mild conditions. The target compounds were characterized by ¹H‐nuclear magnetic resonance (NMR), ¹³C‐NMR, and ³¹P‐NMR spectroscopy, as well as mass spectroscopy. The apparent structure of 4 was confirmed by optimization using the B3LYP/6‐311 + G(d,p) level in the Gaussian 09 program in acetonitrile. The nucleophilic substitution reactions of 4 with X‐anilines (XC₆H₄NH₂) and deuterated X‐anilines (XC₆H₄ND₂) were investigated kinetically in acetonitrile at 55.0°C. The free energy relationship with X in the anilines looked biphasic concave upwards with a break region between X = H and X = 3‐MeO, giving large negative ρ_X and small positive β_X values. The deuterium kinetic isotope effects were secondary inverse (k_H/k_D < 1: 0.789‐0.995) and the magnitudes, (k_H/k_D), increased when the nucleophiles were changed from weakly basic to strongly basic anilines. A concerted S_N2 mechanism is proposed on the basis of the selectivity parameters and the variation trend of the deuterium kinetic isotope effects with X.     

Application of Euler Neural Networks with Soft Computing Paradigm to Solve Nonlinear Problems Arising in Heat Transfer

In this study, a novel application of neurocomputing technique is presented for solving nonlinear heat transfer and natural convection porous fin problems arising in almost all areas of engineering and technology, especially in mechanical engineering. The mathematical models of the problems are exploited by the intelligent strength of Euler polynomials based Euler neural networks (ENN’s), optimized with a generalized normal distribution optimization (GNDO) algorithm and Interior point algorithm (IPA). In this scheme, ENN’s based differential equation models are constructed in an unsupervised manner, in which the neurons are trained by GNDO as an effective global search technique and IPA, which enhances the local search convergence. Moreover, a temperature distribution of heat transfer and natural convection porous fin are investigated by using an ENN-GNDO-IPA algorithm under the influence of variations in specific heat, thermal conductivity, internal heat generation, and heat transfer rate, respectively. A large number of executions are performed on the proposed technique for different cases to determine the reliability and effectiveness through various performance indicators including Nash–Sutcliffe efficiency (NSE), error in Nash–Sutcliffe efficiency (ENSE), mean absolute error (MAE), and Thiel’s inequality coefficient (TIC). Extensive graphical and statistical analysis shows the dominance of the proposed algorithm with state-of-the-art algorithms and numerical solver RK-4.     

3-Phenyl-4-benzoyl-5-isoxazolonate complex of Eu3+ with tri-n-octylphosphine oxide as a promising light-conversion molecular device

Three new europium complexes, [Eu(PBI)3.3H2O] (1), [Eu(PBI)3.2TOPO] (2), and [Eu(PBI)3.2TPPO.H2O] (3) (where HPBI, TOPO, and TPPO stand for 3-phenyl-4-benzoyl-5-isoxazolone, tri-n-octylphosphine oxide, and triphenylphosphine oxide, respectively), with different neutral ligands were synthesized and characterized by elemental analysis, Fourier transform infrared, (1)H NMR, thermogravimetric analysis, and photoluminescence (PL) spectroscopy. The coordination geometries of the complexes were calculated using the Sparkle/AM1 (Sparkle Model for the Calculation of Lanthanide Complexes within the Austin Model 1) model. The ligand-Eu3+ energy-transfer rates were calculated in terms of a model of the intramolecular energy-transfer process in lanthanide coordination compounds reported in the literature. The room-temperature PL spectra of the europium(III) complexes are composed of the typical Eu3+ red emission, assigned to transitions between the first excited state (5D0) and the multiplet (7F(0-4)). On the basis of emission spectra and lifetimes of the 5D0-emitting level, the emission quantum efficiency (eta) was determined. The results clearly show that the substitution of water molecules by TOPO leads to greatly enhanced quantum efficiency (i.e., 26% vs 92%) and longer 5D0 lifetimes (250 vs 1160 micros). This can be ascribed to a more efficient ligand-to-metal energy transfer and a less nonradiative 5D0 relaxation process. Judd-Ofelt intensity parameters (Omega2 and Omega4) were determined from the emission spectra for the Eu3+ ion based on the 5D0 --> 7F2 and 5D0 --> 7F4 electronic transitions, respectively, and the 5D0 --> 7F1 magnetic-dipole-allowed transition was taken as the reference. A point to be noted in these results is the relatively high value of the Omega2 intensity parameter for all of the complexes. This may be interpreted as being a consequence of the hypersensitive behavior of the 5D0 --> 7F2 transition. The dynamic coupling mechanism is, therefore, dominant, indicating that the Eu3+ ion is in a highly polarizable chemical environment.     

Iodobenzene diacetate on alumina: Efficient synthesis of 1,3,4‐oxadiazolyl‐1,8‐naphthyridines in solventless system using microwaves

1‐(5‐Aryl‐[1,3,4]oxadiazol‐2‐ylmethyl)‐3‐(p‐methoxyphenyl)‐1H‐[1,8]naphthyridin‐2‐ones ( 5 ) were synthesized by the oxidative cyclization of [2‐oxo‐3‐(p‐methoxyphenyl)‐2H‐[1,8]naphthyridin‐1‐yl]acetic acid arylidene‐hydrazides ( 4 ) with alumina‐supported iodobenzene diacetate (IBD) in solvent‐free conditions under microwave irradiation. The products are obtained in good yields and in a state of high purity.     

Impact of generalized dissipative coefficient on warm inflationary dynamics in the light of latest Planck data

The warm inflation scenario in view of the modified Chaplygin gas is studied. We consider the inflationary expansion to be driven by a standard scalar field whose decay ratio \(\Gamma \) has a generic power-law dependence with the scalar field \(\phi \) and the temperature of the thermal bath T. By assuming an exponential power-law dependence in the cosmic time for the scale factor a(t), corresponding to the intermediate inflation model, we solve the background and perturbative dynamics considering our model to evolve according to (1) weak dissipative regime and (2) strong dissipative regime. Specifically, we find explicit expressions for the dissipative coefficient, scalar potential, and the relevant inflationary observables like the scalar power spectrum, scalar spectral index, and tensor-to-scalar ratio. The free parameters characterizing our model are constrained by considering the essential condition for warm inflation, the conditions for the model evolves according to weak or strong dissipative regime, and the 2015 Planck results through the \(n_s\)–r plane.     

Influence of plasticizer on ionic conductivity of PVC-PBMA polymer electrolytes

Plasticized polymer electrolytes comprising of ethylene carbonate as the plasticizing agent in poly (vinyl chloride) [PVC]–poly (butyl methacrylate) [PBMA] blended polymer electrolytes were prepared by solution casting technique. Complex formation, structural elucidation, conductivity, dielectric parameters (?′, ?″, M′, and M″), thermal stability, and surface morphology are brought out from FTIR, XRD, ac impedance analysis, dielectric studies, thermogravimetry/differential thermal analysis, and scanning electron microscopic studies, respectively. Polymer electrolytes are found to exhibit higher ionic conductivity at higher concentration of plasticizer at the cost of their mechanical stability. Conductivity of 1.879 × 10^?4 S cm^?1 is exhibited by the polymer electrolyte consisting of 69% of plasticizer with appreciable thermal stability up to 523 K. Temperature and frequency dependence of conductivity is found to follow Vogel Tammann Fulcher relation and Jonscher power law, respectively. Real and imaginary parts of dielectric constants are found to decrease with increase in frequency which could be due to the electrode polarization effect.