Reactivities of allenic and olefinic Michael acceptors towards phosphines

The kinetics of the reactions of tributylphosphine with allenic and olefinic Michael acceptors in dichloromethane at 20 °C was followed by photometric and NMR spectroscopic methods. Combination with DFT-calculated methyl anion affinities revealed the relevance of retroaddition barriers in phosphine-catalysed reactions when mixtures of allenic and olefinic substrates are used

A Predictive Model Towards Site‐Selective Metalations of Functionalized Heterocycles, Arenes, Olefins, and Alkanes using TMPZnCl⋅LiCl

The development of a predictive model towards site‐selective deprotometalation reactions using TMPZnCl⋅LiCl is reported (TMP=2,2,6,6‐tetramethylpiperidinyl). The pKa values of functionalized N‐, S‐, and O‐heterocycles, arenes, alkenes, or alkanes were calculated and compared to the experimental deprotonation sites. Large overlap (>80 %) between the calculated and empirical deprotonation sites was observed, showing that thermodynamic factors strongly govern the metalation regioselectivity. In the case of olefins, calculated frozen state energies of the deprotonated substrates allowed a more accurate prediction. Additionally, various new N‐heterocycles were analyzed and the metalation regioselectivities rationalized using the predictive model

A third generation of radical fluorinating agents based on N-fluoro-N-arylsulfonamides

Radical fluorination has been known for a long time, but synthetic applications were severely limited by the hazardous nature of the first generation of reagents such as F-2 and the strongly electrophilic nature of the second generation of reagents such as N-fluorobenzenesulfonimide (NFSI) and Selecfluor (R). Here, we report the preparation, use and properties of N-fluoro-N- arylsulfonamides (NFASs), a class of fluorinating reagents suitable for radical fluorination under mild conditions. Their N-F bond dissociation energies (BDE) are 30-45 kJ moI(-1) lower than the N-F BDE of the reagents of the second generation. This favors clean radical fluorination processes over undesired side reactions. The utility of NFASs is demonstrated by a metal-free radical hydrofluorination of alkenes including an efficient remote C-H fluorination via a 1,5-hydrogen atom transfer. NFASs have the potential to become the reagents of choice in many radical fluorination processes

Construction of α,α‐disubstituted α‐Amino Acid Derivatives via aza‐Morita‐Baylis‐Hillman Reactions of 2‐Aminoacrylates with Activated Olefins

A useful and convenient strategy for the synthesis of α,α‐disubstituted α‐amino acid (α‐AA) derivatives via aza‐Morita‐Baylis‐Hillman reaction of 2‐aminoacrylates with activated olefins has been developed. A variety of α‐AA derivatives containing an α‐amino tertiary center were synthesized in good to excellent yields. The kinetic profiles and calculated methyl anion affinity (MAA) values were employed to rationalize the reactivities of different Michael acceptors used in the reaction

Reliable Functionalization of 5,6-Fused Bicyclic N-Heterocycles Pyrazolopyrimidines and Imidazopyridazines via Zinc and Magnesium Organometallics

DFT-calculations allow prediction of the reactivity of uncommon N-heterocyclic scaffolds of pyrazolo[1,5-c]pyrimidines and imidazo[1,2-b]pyridazines and considerably facilitate their functionalization. The derivatization of these N-heterocycles was realized using Grignard reagents for nucleophilic additions to 5-chloropyrazolo[1,5-a]pyrimidines and TMP2Zn center dot 2MgCl(2)center dot 2LiCl allowed regioselective zincations. In the case of 6-chloroimidazo[1,2-b]pyridazine, bases such as TMP2Zn center dot MgCl2 center dot 2 LiCl, in the presence or absence of BF3 center dot OEt2, led to regioselective metalations at positions 3 or 8. Subsequent functionalizations were achieved with TMPMgCl center dot LiCl, producing various polysubstituted derivatives (up to penta-substitution). X-ray analysis confirmed the regioselectivity for key functional heterocycles

Ferrocenes with a Persulfurated Cyclopentadienyl Ring: Synthesis, Structural Studies, and Optoelectronic Properties

Persulfurated arenes are a fascinating class of functional molecules with a wide range of potential applications. Ferrocenes are also a multifaceted class of aromatic compounds that can easily be finetuned for an enormous variety of desired properties. A combination of both substance classes might yield an even wider field of applications. Herein, we describe the synthesis of two ferrocenes with one persulfurated cyclopentadienyl ring [C5(SR)5], with R=Me or Ph, together with their crystal structures, optical, and electrochemical properties. Both crystal structures show significant intramolecular sulfur‐iron interactions as well as weak intermolecular sulfur– contacts. Cyclovoltammetry of the [C5(SPh)5] compound shows a high oxidation potential of 651 mV vs. FcH/FcH+

Experimental Investigation on the Wear Performance of Nano-Additives on Degraded Gear Lubricant

This study investigates the degradation of a commercially available gear lubricant and the potential of nano-additives to mitigate such degradation. Initially, we performed an experimental study on the chemical degradation of commercially available API GL-4 EP90 gear lubricant by mixing the different concentrations of aqueous hydrochloric acid (aqueous HCl) varying from 0.0005% v/v up to 0.0025% v/v, while maintaining overall water content in the oil below the prescribed limits. The degradation was monitored using the pH value, total acid number (TAN) value, and attenuated total reflectance-Fourier transform infrared spectroscopy (ATR-FTIR) analysis. The experiments were performed on a developed gear test rig using conventional gear oil as well as chemically aged gear oil, and the corresponding results of pH value and wear debris were recorded. Based on the results, an empirical regression model between the concentration of aqueous HCl and lubricant aging time has been established. Under chemically aged lubricant, severe wear of gear was observed, which motivated us to explore suitable nano-additive to minimize the gear wear. Initially, three nano-additives—graphite, graphene, and “graphene oxide functionalized with silicon oxide (GO@SiO2)”—were chosen. A series of tests were conducted using the design of experiments method (L8 and L16 orthogonal array) to investigate the effect of nano-additives and to find the optimum additive for wear performance. Finally, experiments were conducted on gear setup using the degraded lubricant optimized with nano-additive. Overall results indicate a very significant contribution of nano-additives in decreasing gear wear

An Experimental Investigation of the Tribological Performance and Dispersibility of 2D Nanoparticles as Oil Additives

The present study aims to investigate the tribological performance of 2D nanoparticles such as graphene (G), molybdenum disulfide (MoS2), hexagonal boron nitride (hBN), and reduced graphene oxide (rGO) as gear lubricant additives. A new method of additive doping in gear lubricants was proposed and examined in terms of the degradation of lubricants. The additives were energized by ultrasonication, thermal agitation, and mechanical shearing to enhance the dispersibility and stability, which were confirmed using visual and rheological analysis. Further, the tribological performance of the nano-additives was studied by doping them in fresh lubricants, chemically degraded lubricants, and chemically degraded lubricants with surfactants. The results indicate that surface roughness and the method of mixing play a crucial role in reducing wear. The nano-additives exhibit an inverse relationship with the roughness, and their agglomeration results in a decline in performance. To mitigate agglomeration, oleic acid surfactant was employed, which diminished the effects of nano-additives and degraded the lubricant. The attenuated total reflectance-Fourier transform infrared spectroscopy (ATR-FTIR) analysis revealed that the oleic acid and deteriorating reagent work synergistically, leading to enhanced wear volume and reduced friction. The nano-additives were characterized using field emission scanning electron microscopy (FESEM) and transmission electron microscopy (TEM). Overall, the study presents a comprehensive plan for new method of additive mixing, stability, dispersibility and tribological performance of the selected 2D nanoparticles

Stereoselective and Stereospecific Triflate‐Mediated Intramolecular Schmidt Reaction: Ready Access to Alkaloid Skeletons

The stereoselectivity and stereospecificity of the triflate-mediated intramolecular Schmidt reaction of substituted 3-(1-azidocyclohexyl)propanol derivatives leading to octahydro-1H-pyrrolo[1,2-a]azepine, the structural skeleton of several important families of alkaloids such as the Stemona alkaloids, has been examined. The reaction involves an initial intramolecular SN2 reaction between the azide moiety and the triflate affording an intermediate spirocyclic aminodiazonoium salt that undergoes the expected 1,2-shift/N2-elimination followed by hydride-mediated iminium salt reduction. Remarkably, chiral alcohols are converted to the azabicyclic derivative with no or limited racemization. The initial asymmetric alcohol center controls the diastereoselectivity of the whole process, leading to the formation of one out of the four possible diastereoisomers of disubstituted octahydro-1H-pyrrolo[1,2-a]azepine. The origin of the stereoselectivity is rationalized based on theoretical calculations. The concise synthesis of (−)-(cis)-3-propylindolizidine and (−)-(cis)-3-butyllehmizidine, two alkaloids found in the venom of workers of the ant Myrmicaria melanogaster, is reported

Relative Eccentric Distance Sum/Product Indices for QSAR/QSPR: Development, Evaluation, and Application

In the present study, five detour/distance matrix based molecular descriptors (MDs) termed as relative eccentric distance sum/product indices (denoted by ^Rξ₁^SV, ^Rξ₂^SV, ^Rξ₃^SV, ^RPξ₁^SV, and ^RPξ₂^SV), as well as their topochemical versions denoted by (^Rξ₁^cSV, ^Rξ₂^cSV, ^Rξ₃^cSV, ^RPξ₁^cSV, and ^RPξ₂^cSV) have been conceptualized for exclusive use for molecules containing cyclic moieties. The said MDs exhibited exceptionally high discriminating power and high sensitivity toward branching/relative position of substituents in cyclic structures amalgamated with negligible degeneracy. Subsequently, the proposed MDs along with other MDs were successfully utilized for the development of models for the prediction of human glutaminyl cyclase (hQC) inhibitory activity using decision tree (DT), random forest (RF) and moving average analysis (MAA). A data set comprising of 45 analogues of substituted 3-(<i>1H</i>-imidazol-1-yl) propyl thiourea derivatives was used. DT identified proposed relative eccentric distance sum topochemical index-1 as the most important MD. High accuracy of prediction up to 96%, 93%, and 95% was observed in case of models derived from decision tree, random forest, and MAA, respectively. The statistical significance of proposed models was assessed through specificity, sensitivity, overall accuracy, Mathew’s correlation coefficient (MCC), and intercorrelation analysis