Synthesis of substituted benzene derivatives by homo- and hetero-coupling of 2-bromobenzaldehyde and bromovinylaldehydes followed by McMurry coupling

A convenient synthetic approach to substituted benzene derivatives by modified Ullmann cross-coupling of 2-bromobenzaldehyde and bromovinylaldehydes followed by intramolecular McMurry coupling has been developed.     

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在常温常压下采用新型旋转电极等离子体反应器，对辉光等离子体作用下的甲烷偶联反应制C2烃进行了研究。结果表明，甲烷偶联反应的主要产物为C2H2，占C2烃的80%以上，能量效率在5.6%～11.2%之间；增加H2含量可以提高CH4转化率和C2烃收率；在500～2200kJ•mol−1的能量密度范围内，CH4转化率随能量密度的增大而线性增加，C2烃收率随着能量密度的增加呈峰形变化趋势。     

Angular momenta and eigenvectors of the weakly coupled T ⊗ t Jahn‐Teller system

The eigenvalues of the weakly coupled T ? t Jahn‐Teller problem are known for several decades, and the same holds also true for the eigenstates. These, however, are only given in the traditional position representation, which proves inconvenient if one attempts to extend the weak‐coupling treatment into the region of stronger coupling. Here the solution of the T ? t eigenvalue problem at weak coupling is derived in terms of creation and annihilation operators. This reformulation of the problem is nontrivial, since the algebraic form of the oscillator eigenvectors, being simultaneous angular‐momentum eigenstates, has been worked out only recently and is probably still widely unknown. The electronic and oscillator eigenstates are then coupled to form eigenvectors of the total angular momentum. Finally, in preparation for an extension of the weak‐coupling treatment, the action of the boson creation and annihilation operators on the oscillator eigenvectors is calculated, thus completing the algebraic approach to the weakly coupled T ? t system.     

Coupling Losses for Resonators with Unequal Apertures for Extended Fresnel Numbers

Coupling losses have been calculated for laser resonators with unequal apertures and extended Fresnel Numbers. This was done using both, diffraction theory and a simple linear model.A close form expression was derived to calculate coupling losses with reasonable accuracies for a limited range of paramters. This should help in the preliminary design of hole coupling laser resonators.     

Oxidative Coupling of Thiols to Disulfides with Ti(IV) in the Presence of NaI under Air Atmosphere

Ti(IV) as TiCl₃(O₃SCF₃) and TiO(O₂CCF₃)₂ are used as efficient catalysts for oxidative coupling of aliphatic, aromatic and heteroaromatic thiols to their disulfides in the presence of NaI under air atmosphere.     

Assignment of chemical shifts in benzohydroxamic acid and structure of its silylated derivatives by 15N enrichment

¹⁵N isotopic enrichment was necessary for the unequivocal assignment of the ¹H NMR lines to the protons in the NH–OH fragment of benzohydroxamic acid, BHXA, C₆H₅CONHOH, in dry dimethyl sulfoxide solutions. The assignment [δ(NH) = 11.21, δ(OH) = 9.01, ¹J(¹⁵N,¹H) = 102.2 Hz, ²J(¹⁵N,¹H) <1.5 Hz], which is opposite to that used by other authors, confirms the assignment extended to BHXA by Brown and co‐workers from the spectra of acetohydroxamic acid. The enrichment allowed also assignment of the ²⁹Si lines in the spectra of disilylated benzohydroxamic acid, (Z)‐tert‐butyldimethylsilyl N‐tert‐butyldimethylsilyloxybenzoimidate (2) and (Z)‐tert‐butyldiphenylsilyl N‐tert‐butyldiphenylsilyloxybenzoimidate (3), and confirmed structure of the monosilylated products, N‐tert‐butyldiphenylsilyloxybenzamide (4) and N‐tert‐butyldiphenylsilyloxy benzoimidic acid (5). Copyright © 2003 John Wiley & Sons, Ltd.     

Synthesis and absolute configuration of cordiaquinone K, antifungal and larvicidal meroterpenoid isolated from the Panamanian plant, Cordia curassavica

Total synthesis of cordiaquinone K, a new antifungal and larvicidal meroterpenoid, is reported. The absolute configuration of cordiaquinone K was confirmed by the synthesis.     

Rigid nitronyl-nitroxide-labelled anchoring molecules: syntheses, structural and magnetic investigations

The syntheses of two rigid organic molecular rods bearing a nitronyl-nitroxide radical and a terminal nitrogen-based functionality like a pyridine or a cyano group are reported. Both new paramagnetic molecules are fully characterized, including crystal structure analysis. Furthermore their magnetic behaviours in the crystalline state are investigated and their spin concentration corroborate their excellent purity. While the pyridine functionalized rod is synthesized by converting the corresponding benzaldehyde to the phenyl-nitronyl-nitroxide radical, the synthesis of the cyano functionalized rod demonstrates the accessibility of highly sophisticated spin-labelled molecules via cross-coupling reaction with a meta-iodo-phenyl-nitronyl-nitroxide moiety.