Recent Developments Towards Synthesis of (Het)arylbenzimidazoles

Benzimidazole is an important heterocycle that is widely researched and utilized by the pharmaceutical industry and is one of the five most commonly used five-membered aromatic heterocyclic compounds approved by the US Food and Drug Administration. In view of their wide-ranging bioactivities, systems containing benzimidazole as one of the moieties occupy a special place among other benzimidazole derivatives. Since 2010, many improved synthetic strategies have been developed for the construction of hetaryl- and arylbenzimidazole molecular scaffolds under environmentally benign conditions. This review emphasizes the recent trends and modifications frequently used in the synthesis of derivatives of benzimidazole such as the Phillips–Ladenburg and Weidenhagen reactions, as well as entirely new methods of synthesis, involving oxidative cyclization, cross-coupling, ring distortion strategy, and rearrangements carried out under environmentally benign conditions.1 Introduction2 From 1,2-Diaminobenzenes with Various One-Carbon Unit Suppliers2.1 Phillips–Ladenburg Reaction2.1.1 With (Het)arenecarboxylic Acids2.2.2 With (Het)arenecarboxylic Acid Derivatives2.2 Weidenhagen Reaction2.2.1 With (Het)arenecarbaldehydes or (Het)aryl Methyl Ketones2.2.2 With Primary Alcohols2.2.3 With Primary Alkylamines2.2.4 With 2-Methylazaarenes2.2.5 With Other One-Carbon Fragment Suppliers3 From 2-Haloacetanilides and Amines4 From Amidines5 From Tetrahydroquinazolines6 Mamedov Rearrangement7 Conclusions and Outlook

Influence of Compression Rings on the Dynamic Characteristics and Sealing Capacity of the Combustion Chamber in Diesel Engines

Internal combustion engines are widely implemented in several applications; however, they still face significant challenges due to the sealing capacity of the compression rings. Gas leakage through the crankcase, also known as blow-by, directly impacts power losses, overall efficiency, and global emissions. Therefore, the present study investigates the influence of parameters such as the ring gap, ring masses, and twist angle of the compression rings on the sealing capacity of the combustion chamber. A mathematical model is proposed to account for geometric, dynamic, and operational characteristics in a single-cylinder diesel engine. The results indicated that the greatest gas losses to the crankcase occur during the compression and combustion stages as a consequence of extreme pressure conditions. Specifically, at least 0.5% of the gases locked in the combustion chamber are released on each cycle, while increasing the mass of the compression rings boosts the gas leakage due to higher inertial forces in the rings. In contrast, a positive twist angle of the compression rings reduced the combustion gases leakage by . Additionally, a combined reduction in the gap of both compression rings minimized the leakage flows by 37%. In conclusion, the proposed model served as a robust tool to evaluate different parameters on the sealing capacity of the combustion chamber that contribute to minimizing global emissions. Secondary piston motion and ring distortion represent significant opportunities in future studies.

CtD Strategy to Construct Stereochemically Complex and Structu-ally Diverse Compounds from Griseofulvin

Complexity to Diversity (CtD) strategy, a strategy for the synthesis of stereochemically complex and structurally diverse small molecules from natural products using ring-distortion reactions, was applied in the synthesis of...

The Site Occupancy Assessment in Beryl Based on Bond-Length Constraints

The site preference for each cation and site in beryl based on bond-length calculations was determined and compared with analytical data. Tetrahedral SiO4 six-membered rings normally have no substitutions which results from very compact Si4+–O bonds in tetrahedra. Any substitution except Be would require significant tetrahedral ring distortion. The Be tetrahedron should also be negligibly substituted based on the bond-valence calculation; the tetrahedral Li–O bond length is almost 20% larger than Be2+–O. Similar or smaller bond lengths were calculated for Cr3+, V3+, Fe3+, Fe2+, Mn3+, Mg2+, and Al3+, which can substitute for Be but also can occupy a neighboring tetrahedrally coordinated site which is completely vacant in the full Be occupancy. The octahedral site is also very compressed due to dominant Al with short bond lengths; any substitution results in octahedron expansion. There are two channel sites in beryl: the smaller 2b site can be occupied by Na+, Ca2+, Li+, and REE3+ (Rare Earth Elements); Fe2+ and Fe3+ are too small; K+, Cs+, Rb+, and Ba2+ are too large. The channel 2a-site average bond length is 3.38 Å which allows the presence of simple molecules such as H2O, CO2, or NH4 and the large-sized cations-preferring Cs+.

Soft chromophore featured liquid porphyrins and their utilization toward liquid electret applications

Optoelectronically active viscous liquids are ideal for fabricating foldable/stretchable electronics owing to their excellent deformability and predictable π-unit–based optoelectronic functions, which are independent of the device shape and geometry. Here we show, unprecedented ‘liquid electret’ devices that exhibit mechanoelectrical and electroacoustic functions, as well as stretchability, have been prepared using solvent-free liquid porphyrins. The fluidic nature of the free-base alkylated-tetraphenylporphyrins was controlled by attaching flexible and bulky branched alkyl chains at different positions. Furthermore, a subtle porphyrin ring distortion that originated from the bulkiness of alkyl chains was observed. Its consequences on the electronic perturbation of the porphyrin-unit were precisely elucidated by spectroscopic techniques and theoretical modelling. This molecular design allows shielding of the porphyrin unit by insulating alkyl chains, which facilitates its corona-charged state for a long period under ambient conditions.