A Modified Synthesis of Some Novel Polycyclic Aromatic Phenazines and Quinoxalines by Using the Tungstate Sulfuric Acid (TSA) as a Reusable Catalyst under Solvent‐free Conditions

Considering the synthesis of new compounds, we developed heterocyclic chemistry. We also helped to improve the classical synthetic route for the synthesis of quinoxalines and phenazines through implement in terms of solvent‐free reaction. For the condensation of 1,2‐dicarbonyls and o‐phenylenediamines under solvent‐free conditions at room temperature, tungstate sulfuric acid (TSA) was found to be an efficient and reusable reagent. The high yield of the pure products and simple preparation of the catalyst have allowed the synthesis of several phenazines and quinoxalines using this methodology.     

涂布2,4-二硝基苯肼的环形溶蚀器/滤膜系统和高效液相色谱法检测大气中二羰基化合物

建立了环形溶蚀器/滤膜系统(Annular denuder/filter pack system)和2,4-二硝基苯肼(DNPH)-高效液相色谱法(HPLC)采集和检测大气中气相和颗粒相二羰基化合物的方法。DNPH作为吸附剂分别涂布在环形溶蚀器的内壁和3层滤膜上,当大气样品经过环形溶蚀器时,含有气相二羰基化合物的气体吸附到环形溶蚀管内壁上与DN-PH发生反应,而颗粒相部分穿过环形溶蚀管,采集到滤膜上。样品经乙腈洗脱、浓缩后,采用HPLC进行分析。根据不同的采样流速、采样时间和DNPH的涂布量采集到的二羰基化合物的浓度,确定的最佳采样条件为:采样流速4 L/min,采样时间4~5 h,DNPH浓度0.47 g/L。使用Tedlar bag验证环形溶蚀器乙二醛和甲基乙二醛的采集效率(分别为82%和85%)。利用此方法对实际大气中的二羰基化合物进行了检测。     

Nickel‐catalyzed oxidative esterification of formamides with 1,3‐dicarbonyl compounds under mild reaction conditions

Synthesis of enol carbamates was achieved via nickel‐catalyzed oxidative coupling of formamides with 1,3‐dicarbonyl compounds in the presence of tert ‐butyl hydroperoxide at 40 °C. Various derivatives of enol carbamates were synthesized by this method in good to excellent yields.     

Molecular structure of mono- and dicarbonyls of rhodium and palladium

Summary Density Functional Theory has been applied to the study of the molecular structure of neutral and positively charged mono- and dicarbonyls of rhodium and palladium. The calculated optimized geometries, dissociation energies and normal frequencies are reported for the MCO, MCO⁺, M(CO)₂ and M(CO) ₂ ⁺ systems (where M=Rh and Pd), and the trends are discussed in detail. For neutral carbonyls, we interpret the M–C bond strength in terms of repulsion, which must be avoided, and attraction. These are related to the metal atom properties, such as the atomic splittings and the atomic ionization energies. In ionic carbonyls, the bonding is characterized by electrostatic attraction and repulsion. The rhodium carbonyls are generally found to be more stable than the corresponding palladium carbonyls. The palladium dicarbonyls are found to be linear, while both linear and bent structures are stable for rhodium dicarbonyls. An interpretation of these trends is made.