The separation of n-butane (n-C4H10) and isobutane (isoC(4)H(10)) is industrially critical but remains challenging due to their highly similar structures and physicochemical properties. Herein, we report a microporous heterometallic pillared-layer metal-organic framework (NXU-2-Tb) featuring one-dimensional hourglass-shaped pore channels with periodic narrow apertures. Its unique pore geometry facilitates rapid diffusion and efficient adsorption of n-C4H10, while narrow apertures effectively restrict isoC(4)H(10) access. Kinetic adsorption experiments confirm that the shrinkage pore apertures are key to hindering the diffusion of branched isoC(4)H(10), resulting in a kinetic selectivity of 24.2, while maintaining an n-C4H10 uptake capacity of 41.2 cm(3) g(-1). Density functional theory (DFT) calculations confirm the kinetic separation mechanism, revealing diffusion energy barriers of 47.54 kJ mol(-1) and 77.55 kJ mol(-1) for n-C4H10 and isoC(4)H(10), respectively. Breakthrough experiments demonstrate that NXU-2-Tb achieves efficient separation of n-C4H10/isoC(4)H(10) mixtures over a wide range of flow rates and temperatures, yielding high-purity isoC(4)H(10) (>99.99%). Remarkably, NXU-2-Tb exhibits excellent skeleton stability and reusability after multiple breakthrough cycles, establishing its potential as a highly promising adsorbent for industrial n-C4H10/isoC(4)H(10) separation. This work highlights the critical role of precise pore geometry in discriminating structurally similar molecules and provides a promising strategy for energy-efficient alkane isomer separation.
Reported herein is the aromatization-driven and TfOH-promoted 1,5-intramolecular hydride transfer reductive amination for the synthesis of N-benzyl-2-(pyrrolo[1,2-a]quinoxalin-4-yl)aniline. This system is efficient and green because it is metal-free, requires no external hydrides, and reaches completion under room temperature conditions in a short time (15 min). The extraordinary reactivity is attributed to the "bifunctional reagent" 2-(4,5-dihydropyrrolo[1,2-alpha]quinolin-4-yl)aniline, which facilitates proton transfer during the condensation process and acts as an intrinsic hydride source to reduce the imine, and is rationalized by theoretical and experimental studies.
A concise method for the synthesis of ( E )‐(2‐bromovinyl)arylselenoxides using calcium carbide as a solid alkyne source, tetrabutylammonium tribromide as a solid bromine source, benzoyl peroxide as an oxidant and an initiator, and 1,2‐diaryldiselenides as starting materials through a one‐pot procedure is described. The target products were obtained via cascade reactions involving the simultaneous formation of SeC, SeO, and CBr bonds. The salient features for this protocol are the use of inexpensive and easy‐to‐handle solid alkyne source instead of flammable and explosive gaseous acetylene, the use of safe and convenient solid bromine source instead of toxic and corrosive liquid bromine, high stereoselectivity, transition metal‐free conditions, wide functional tolerance, satisfactory yield, and simple workup procedures. The reactions can also be carried out on a gram scale.
A [3 + 1 + 2] annulation strategy for the modular synthesis of polysubstituted pyridines, such as 2,6-diarylnicotinic acid esters and nicotinonitriles, is described. Multicomponent reactions employ β-enamine esters/β-enamine nitriles and aromatic aldehydes as starting materials, and calcium carbide as a source of alkyne. The key advantages of this method include the use of an inexpensive and easy-to-handle solid alkyne source instead of flammable and explosive gaseous acetylene, a broad substrate scope with good functional group tolerance, high yield, operational simplicity, and scalability to the gram scale.
Lightweight and highly conductive carbon nanotube fibers (CNTFs) are attractive for flexible electronics, yet their performance remains constrained by inefficient charge transport. Here we report a synergistic doping strategy that integrates in-plane nitrogen doping with endohedral molybdenum pentachloride (MoCl5) incorporation to produce CNTFs with exceptional electrical properties and environmental durability. Nitrogen doping creates sidewall defect sites that promote MoCl5 encapsulation, yielding a strong charge-transfer effect and markedly increased carrier density. The resulting fibers achieve a high specific electrical conductivity of 14166 S m2 kg-1 and a current carrying capacity of 1241 A mm-2, surpassing copper by 115% and 28%, respectively. The CNTFs also exhibit high flexibility and environmental stability, retaining performance under thermal, mechanical, and solvent stresses. When woven into textiles, they deliver an electromagnetic shielding effectiveness of 92.7 dB (8.2-12.4 GHz). This work establishes a scalable doping approach for fabricating ultrahigh-conductivity CNTFs for advanced flexible electronics.
A variety of multifunctionalized 1,2-dihydropyridines are efficiently constructed through copper(I)-catalyzed one-pot three-component reactions using readily available 2-[(amino)methylene]malononitriles and sulfonyl azides, as well as inexpensive and easy-to-handle solid calcium carbide instead of flammable and explosive gaseous acetylene. This concise protocol enables the direct formation of important 1,2-dihydropyridines bearing amino, cyano, and sulfonylimino groups in one step by installing two C-N bonds and one C-C bond. This strategy has salient features of broad substrate scope, a low-cost catalyst, mild reaction conditions, high efficiency, simple workup procedures, and gram-scale applicability.
To address the challenges associated with phenolic wastewater purification, including high operational difficulty, elevated cost, and prolonged processing time, this study synthesized a magnetic biochar (FKBC) from pre-carbonized tomato pomace via sequential KOH impregnation-pyrolysis activation and iron salt impregnation-pyrolysis magnetization. The resulting material exhibited a high specific surface area (1225.2 m2 & sdot;g- 1), a hierarchical pore structure, and abundant oxygen-containing functional groups. Under the optimal conditions (pH 6, 25 degrees C), FKBC removed 95.2% of phenol from mixed phenolic wastewater within 5 min, achieving a maximum adsorption capacity of 171.4 mg & sdot;g- 1. The strong magnetic properties imparted by Fe0/Fe3O4 incorporation facilitated material recovery, and after five consecutive cycles, the recovery rate remained at 95.7%, while the phenol removal rate exceeded 80%, indicating excellent cycling stability and reusability. Adsorption kinetics and isotherm analyses showed that the process followed pseudo-first-order kinetics and the Temkin model. A series of characterizations further revealed that the adsorption mechanism primarily involved pore filling, it-it interactions, and hydrogen bonding. In real wastewater treatment, FKBC attained efficient removal (99.8%) of phenolic compounds, demonstrating strong application potential. This work offers a viable route for valorizing tomato pomace while providing an efficient, renewable adsorbent for phenolic wastewater treatment.
C-(Hetero)aryl glycosides are privileged in pharmaceutical chemistry, yet their stereoselective synthesis remains challenging. We report an iodide-anion-enabled cobalt-catalyzed reductive cross-electrophile coupling of glycosyl chlorides with (hetero)aryl bromides, affording C-(hetero)aryl glycosides with high efficiency and stereoselectivity. Mechanistic studies reveal that iodide modulates halide coordination at cobalt, preventing Co-Cl deactivation and enabling the formation of the active L9-CoI2(II) species. This work establishes iodide as a multifunctional promoter in cobalt-catalyzed C-glycosylation.
A concise method for the construction of 1-aroyl-2-methylbenzimidazoles using solid calcium carbide as a C2 source, N-(2-aminophenyl)benzamides as substrates, tosyl azides as a mediator, through a one-step procedure is described. The target products were effectively obtained through cascade annulations, involving the one-step formation of two C-N bonds. The salient features for this protocol are the use of inexpensive, abundant, and easy-to-handle solid C2 source, easily synthesized reactants, low-cost catalyst, wide functional tolerance, satisfactory yield, and simple workup procedure. The reactions can also be carried out on a gram scale.
A novel, facile synthesis of substituted and functionalized aryl amides has been developed. This one-pot procedure involves an Et3N/H2O-promoted cascade C-Cl bond activation and amidation of trichloromethyl aromatic compounds with amines, using water as a solvent and oxygen source. Moreover, both water and triethylamine used in the reaction can be recovered and reused. This method represents a sustainable and eco-friendly alternative to traditional methodologies, offering advantages such as a wide substrate range, metal-free conditions, and scalability to gram-scale synthesis. Notably, this method effectively addresses the low-yield limitations associated with earlier aromatic amine-based substrate systems.
A concise method for the construction of 2-aryl-3-benzylbenzo[4,5]imidazo[1,2-a]pyrimidines using solid calcium carbide as an alkyne source, 2-aminobenzimidazoles, and (hetero)aromatic aldehydes as substrates through one-pot three-component procedure is described. The target products were effectively obtained through A3 coupling, 6-endo-dig cyclization, isomerization, and dehydration cascade processes. The salient features of this protocol are the use of an inexpensive, abundant and easy-to-handle solid alkyne source instead of flammable and explosive gaseous acetylene, low-cost catalyst, wide functional tolerance, satisfactory yield, and simple workup procedure. The reactions can also be carried out on a gram scale.
N-Sulfonyl acetamidine moieties are widely present in many biologically active compounds and organometallic complexes, and are particularly used as intermediates in organic synthesis. Herein, a novel and practical method for the synthesis of N-sulfonyl acetamidines through one-pot three-component reactions of sulfonyl azides, amines, and calcium carbide is described. This method is suitable for different amines including secondary amines, primary amines, aliphatic amines, aromatic amines, and alicyclic amines as raw materials, and various aromatic and aliphatic azides as starting materials. The notable features of this protocol include the use of inexpensive, abundant, and easy-to-handle solid calcium carbide instead of flammable and explosive gaseous acetylene as an alkyne source, the use of a low-cost catalyst, mild reaction conditions, satisfactory yield, and simple workup procedures. The method can also be extended to synthesis on a gram scale.
A novel method for the one-step construction of spirocarbocyclic scaffolds by dearomatizing annulation is described. A number of spiro[indene-1,1'-naphthalen]-2'-ones are efficiently synthesized by reactions of 1-arylnaphthalen-2-ols with aryl iodides and calcium carbide through Csp2-H activation and simultaneous formation of four C-C bonds. Meanwhile, a series of spiro[cyclopentane-1,1'-naphthalene]-2,4-dien-2'-ones are effectively obtained by reactions of 1-bromonaphthalen-2-ols with aryl iodides and calcium carbide through cross-coupling and simultaneous formation of seven C-C bonds. The salient feature of this protocol is the use of an inexpensive and easy-to-handle solid alkyne source as a substitute for flammable and explosive gaseous acetylene. In addition, satisfactory yields and a simple workup procedure are also advantages of this method. The corresponding products can also be synthesized on a gram scale.
This metal-free, one-pot method synthesizes aryl amides via Et 3 N/H 2 O-promoted C–Cl activation. Using recyclable water as solvent, it features broad scope, gram-scale synthesis, and overcomes prior low-yield limits.
Vinyl thianthrenium salts, generated from one-pot addition of alkynes and thianthrene, undergo cascade cyclization with aryl- or alkyl-nitriles to afford 2,4,6-trisubstituted pyrimidine derivatives in good yields without acid, additive and base.
A complementary strategy employing nucleophilic addition reactions was demonstrated, using calcium carbide as the acetylene source, 2-bromophenylthiophenol as substrate, and copper as catalyst. This approach is distinguished by its reliance on stable, easy-to-handle acetylene surrogates, broad substrate applicability, tolerance to open-air aqueous conditions, and facile scalability to gram-level synthesis.
This study proposes an effective method for direct hydroxylation/carbonylation of benzyl C─H bonds. The key feature of this synthesis method is the use of electrochemical conditions that eliminate the need for metal‐free catalyst or oxidants. Water serves as a direct oxygen source to achieve direct hydroxylation/carbonylation of benzyl C─H bonds. The reaction exhibits good selectivity and a broad application range. By controlling the reaction conditions, various types of hydroxylation and carbonylation products can be synthesized, and the feasibility of gram‐scale reactions can be verified.
Triphenylphosphine, iodide and N-chloro-arylsulfonamides could generate amidyl radicals via EDA (Electron Donor-Acceptor) complexes under visible light irradiation, and this strategy enables the synthesis of valuable δ-chloro-arylsulfonamide and N-arylsulfonylpyrrolidine motifs in moderate yields. This blue LED-induced method utilizes more readily available reagents, providing advantages in terms of cost efficiency, broad substrate scope, and functional-group compatibility.
Herein, we explore a visible light‐enabled radical addition for the construction of N‐sulfonyl and N‐acyliminophosphorane using triarylphosphine and N‐sulfonyl and N‐acylaminopyridinium salts in the absence of transition metal, photocatalyst, oxidant or base. This method employs PAr3 as both the reaction catalyst to promote the generation of amidyl radical via N−N bond cleavage of N‐sulfonyl and N‐acylaminopyridinium salts, and materials for the preparation of N‐sulfonyl and N‐acyliminophosphorane products. This transformation exhibits abroad substrate scope and good functional group compatibility.