10.1002/cssc.201100649
The research focuses on the synthesis of functional acetylene derivatives from calcium carbide, exploring its potential as a sustainable feedstock for the chemical industry. The study addresses the challenges of calcium carbide's low solubility and difficulty in controlling mono-substitution reactions by developing efficient catalytic protocols for the synthesis of various functional acetylene derivatives. The experiments involve the use of calcium carbide as a nucleophilic carbon source in AAA (aldehyde, alkyne, amine) and AHA (alkyne, haloalkane, amine) coupling reactions, utilizing copper catalysts such as CuCl and CuI. Reactants include calcium carbide, various aldehydes or ketones, amines, and copper catalysts, with solvents like dichloromethane and acetonitrile. The analyses used to monitor the reactions and characterize the products encompass thin-layer chromatography, gas chromatography–mass spectrometry (GC–MS), and nuclear magnetic resonance (NMR) spectroscopy, providing detailed information on the chemical shifts, multiplicity, coupling constants, and integration of the synthesized products.
10.1246/bcsj.81.1028
The research focuses on the synthesis and solid-state polymerization of triyne and enediyne derivatives with similar π-conjugated structures. The main content involves the synthesis of three diacetylene monomer model compounds: 10-phenyl-5,7,9-decatriynyl N-phenylcarbamate (1), (E)-10-phenyldec-9-en-5,7-diynyl N-phenylcarbamate (2), and (E)-10-phenyldec-5-en-7,9-diynyl N-phenylcarbamate (3). The properties and solid-state polymerization of these compounds were investigated, with a particular emphasis on how the conjugation effect of double and triple bonds influences the polymerization process. The experiments utilized various reactants, including copper(I) chloride, isopropylamine, ethanol, and phenyl isocyanate, among others, to synthesize the monomers through coupling reactions and subsequent transformations. The analyses used to characterize the monomers and polymers included UV-visible spectroscopy, IR spectroscopy, NMR spectroscopy, powder X-ray diffraction, and elemental analysis. These techniques provided insights into the monomer structures, conjugation systems, crystallographic features, and the polymerization sites within the conjugated multiple bonds. The study revealed that only certain crystal forms of the monomers were polymerizable, and the polymerization sites could be controlled by the introduction of a double bond next to the polymerizable butadiyne moieties.
10.1107/S0108270107054960
The study focuses on the synthesis and crystal structure analysis of a copper(I) complex with an unconjugated dimine ligand, specifically the 1:1 adduct of N,N-bis(2-chlorobenzylidene)ethylenediamine (cbzen) with copper(I) chloride, resulting in the ionic compound [Cu(C16H14Cl2N2)]2][CuCl2]-CH3CN. The purpose of the study is to examine the nature of the complex formed and its coordination chemistry, which is of interest due to the potential applications of such complexes in catalytic processes, photosensitization reactions, light-harvesting studies, and the design of supramolecular arrays. The chemicals used in the study include copper(I) chloride (CuCl) as the metal halide, and N,N-bis(2-chlorobenzylidene)ethylenediamine (cbzen) as the nitrogen-based ligand. These chemicals serve to form the bis(ligand)copper(I) cation and a dichloridocuprate(I) anion, along with a molecule of acetonitrile solvent, which together constitute the crystal structure of the compound under investigation.
10.1021/ic020369k
The study investigates the chemistry of Cu(I) and Cu(II) complexes of various ?-diketiminate ligands (L-). The researchers prepared and characterized a series of these complexes, focusing on their structural properties, magnetic behavior, and reactivity with oxygen. Key chemicals involved include ?-diketiminate ligands with different substitution patterns, copper(I) chloride (CuCl), and copper(I) acetonitrile complexes (LCu(MeCN)). The study reveals that the ligands' structural features significantly influence the formation of monomeric or dimeric copper complexes, as well as their reactivity with oxygen, leading to the formation of rare examples of neutral bis(μ-oxo)dicopper complexes. The findings provide insights into the role of ligand substituents in modulating the stability and reactivity of copper complexes, which has implications for understanding metallobiochemistry and catalysis.
10.1039/c4ob02208d
The research focuses on the development of a mild and efficient method for the conversion of arylboronic acids into arylthiocyanates using a copper-catalyzed aerobic oxidative process. The study employs trimethylsilylisothiocyanate (TMSNCS) as a thiocyantion reagent and utilizes NaF as a promoter under an oxygen atmosphere, with CuCl serving as the catalyst. The cross-coupling reaction is conducted at ambient temperature and is found to be effective for a broad range of functional groups, including strong electron-withdrawing groups. The experiments involve the optimization of reaction conditions, including the evaluation of various catalysts, ligands, additives, and solvents, ultimately leading to the identification of an optimal condition that involves the use of 20 mol% CuCl, 20 mol% TMEDA as a ligand, 1 equiv. of NaF, and 4 equiv. of K2CO3 in acetonitrile at room temperature for 12 hours, with 3? molecular sieves. The substrate scope was also investigated, demonstrating the versatility of the method with both electron-donating and electron-withdrawing arylboronic acids. The reaction mechanism is proposed based on the formation and reactivity of CuSCN as an intermediate, with both TMEDA and O2 being essential for the transformation. The study concludes that the developed protocol offers a milder and more efficient approach for aromatic oxidative thiocyanation, with potential applications in the synthesis of a variety of aryl thiocyanates.
10.1016/j.jorganchem.2006.12.023
The research focuses on the synthesis of monophosphine and diphosphine ligands for diplatinum polyynediyl complexes, with the aim of creating new functionality-containing systems and model compounds. The study involves a series of chemical reactions using various reactants, such as Br(CH2)4Br, NaO(CH2)2CH@CH2, KPPh2, CH3CH2OC(O)CH@C(CH3)2, and BrMg(CH2)3CH@CH2, among others. These reactants are subjected to different conditions and catalysts, like CuCl and Grubbs’ catalyst, to yield a variety of monophosphines and diphosphines. The synthesized compounds are then used to form platinum complexes, which are crucial for the study of 'insulated molecular wires'. The research also explores the introduction of Lewis basic functionality into the sp3 chains of the complexes. The experiments are confirmed through techniques like NMR spectroscopy, IR spectrometry, and mass spectrometry, which are used to characterize the new compounds and analyze their structures and purities. The study provides efficient syntheses of functionalized monophosphines and diphosphines, some of which are novel contributions to the field, with potential applications in areas such as fluorous chemistry and the formation of crown-ether-like metal complexes.
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