新型1,1′-双乙酰基二茂铁席夫碱的合成

通过1,1′-双乙酰基二茂铁双肼腙与芳醛(酮)的缩合反应,合成了6个新型1,1′-双乙酰基二茂铁席夫碱,其结构经1H NMR,IR和元素分析表征。     

钯(Ⅱ)-芳香氮碱-氨基酸三元配合物中的电子效应和芳环堆积作用

用pH-电位滴定法测定了Pd(L)(Aa)⁺三元配合物及相应的二元配合物,在25±0.5℃,30%的乙醇水溶液(体积分数),I=0.1(KNO₃)条件下的稳定常数及表征常数。其中L=邻菲罗啉(phen)、苯并咪唑邻菲罗啉(PIP)、邻菲罗啉-5,6-二酮(dophen)、2,9-二甲基邻菲罗啉(dmphen)和联吡啶3,3′-二羧酸(BDA);Aa为甘氨酸(gly)、苯丙氨酸(phe)、酪氨酸(tyr)、S-苄基-半胱氨酸(bcys)、谷氨酰胺(glu)和γ-谷氨酰-α-萘胺(gnapa)。从配合物配体间的电子效应和芳环堆积等观点对配合物的附加稳定性进行了讨论,并计算了电子效应和芳环堆积效应各自对三元配合物附加稳定性的贡献。     

Synthesis and Crystal Structure of 9-（ 4-M e tho xylphen yl ）-1,8-dioxo-3,4,5,6,7,9hexahydroxanthene under Microwave Irradiation

1INTRODUCTIONInthepastfewyears,potassiumchannelacti-vatorshavegainedincreasingattentionbecauseoftheirclinicalpotentialapplicationsinvariousdiseases.Oneofthemostpotentcompoundsamongthisnewclassofdrugsisthebenzopyranderivativecroma-kalim[1～4].Benzopyranaswellasitsderivativesex-hibitsextensivepharmacologicalandbiologicalacti-vities[5],suchasantibacterialactivities[6,,antitumor7]activity[8],hypotensiveeffect[9],antiproliferationef-fect[10],etc.Thetitlecompoundbearingabenzo-pyranstructuraluni…     

微波辐射下一步合成3-氨基-4-氰基-1-芳基-5,6,7,8-四氢异苯并吡喃

亚环己基马来腈与芳醛在哌啶催化下,经微波辐射一步合成3-氨基-4-氰基-1-芳基-5,6,7,8-四氢异苯并吡喃,反应7～11min,产率57%～94%.     

A novel vapor phase process for aromatic ketone synthesis

The vapor phase catalytic reaction between aromatic carboxylic acid and acetic acid was investigated. Many metal oxides catalyzed the reaction between 2methylbenzoic acid (OTA) and acetic acid (AA) to produce 2methylacetophenone (OMA), and weakly acidic oxides such as Th, U, Ce, and La oxide exhibited higher yield of OMA. The OMA yield depended on the catalyst support. SiO₂, Al₂O₃, TiO₂, and ZrO₂ with a surface area of less than 200 m² g^–1 appeared to be suitable as industrial catalyst supports. CeO₂ on Al₂O₃was chosen as an industrial catalyst for the synthesis of OMA because of higher productivity, longer catalyst life, and lifting of legal restrictions on catalyst handling. This catalyst system can also be applied to the syntheses of acetophenone, nitroacetophenone, and chloroacetophenone.     

Own N-layered integrated molecular orbital and molecular mechanics study of the reaction of OH<Superscript>−</Superscript> with polychlorinated hydrocarbons CH<Subscript>(4−n)</Subscript>Cl<Subscript>n</Subscript> (n=2–4)

The reliability of the two-layer own N-layered integrated molecular orbital and molecular mechanics (ONIOM) method was examined for the S_N2 reaction CH_(4–n)Cl_n+OH^–. In the ONIOM calculation, only the methyl chloride and OH^–were treated at a high level and the effect of polychlorination was taken into account only at a low level. The ONIOM results were compared with the target CCSD(T)/aug-cc-pVDZ//MP2/aug-cc-pVDZ results obtained by Borisov etal. [(2001) J. Phys. Chem. A 105:7724]. The ONIOM[MP2/aug-cc-pVDZ:B3LYP/6-31+G(d)] was found to reproduce well the target geometry and energy at the MP2/aug-cc-pVDZ level. The single-point improved energetics at the ONIOM[CCSD(T)/aug-cc-pVDZ:MP2/6-31+G(d)] is found to give results nearly as accurate as the target CCSD(T)/aug-cc-pVDZ//MP2/aug-cc-pVDZ results. The substantially reduced cost, 20% for optimization and 5% for single-point improved energy of the target cost for n=4, as well as small errors suggest that ONIOM is a powerful tool for accurate potential-energy surfaces of the reaction of large polyhalohydrocarbons.     

A new and versatile Ugi/SNAr synthesis of fused 4,5-dihydrotetrazolo[1,5-a]quinoxalines

A combinatorial synthetic route yielding fused tetrazolo[1,5-a]quinoxalines is described. The use of 2-fluorophenylisocyanide in the Ugi-tetrazole reaction (tetrazole-U-4CR) followed by a nucleophilic aromatic substitution (S_NAr) affords the tricylic tetrazolo[1,5-a]quinoxaline moiety in good yields and with high diversity.     

Fluidized-bed extraction of polycyclic aromatic hydrocarbons from contaminated soil samples

Summary Due to the carcinogenity and ubiquity of polycyclic aromatic hydrocarbons in the environment they are of ongoing interest to analytical chemistry. In this study, a comparison of the classic Soxhlet extraction and, fluidized-bed extraction, has been conducted. The extraction of polycyclic aromatic hydrocarbons by this technique has been optimized considering as experimental variables the variation of the number of extraction cycles and the holding time after reaching the heating temperature by means of a surface response design. The significance of the operational parameters of the fluidized-bed extraction on the performance characteristics has been investigated. For the determination of the analytes a selective clean-up of the extracts followed by a fast gas chromatography method with mass spectrometric detection was used, resulting in low limits of detection (0.2 pg μL⁻¹). The accuracy of the complete analytical method was established by extraction and analysis of reference materials.     

Elution of organic solutes from different polarity sorbents using subcritical water

The intermolecular interactions between organic solutes and sorbent matrices under subcritical water conditions have been investigated at a pressure of 50 bar and temperatures ranging from 50 to 250°C. Both polar and nonpolar organics (chlorophenols, amines, n-alkanes, and polycyclic aromatic hydrocarbons) and five different sorbent matrices (glass beads, alumina, Florisil, silica-bonded C₁₈, and polymeric XAD-4 resins) were used. From the same matrix, the polar solutes always eluted at lower temperatures, while the moderately polar and nonpolar solutes only eluted at higher temperatures. Similar to matrix effects previously observed using supercritical carbon dioxide, the sorbent type greatly influenced the elution efficiency under subcritical water conditions. Lower temperatures are sufficient to elute a particular solute from glass beads, alumina, and Florisil, but higher temperatures (less polar water) are needed to elute the same solute from silica-bonded C₁₈. The highest temperatures were required to elute aromatic organics from XAD-4. These matrix effects demonstrate that, while low temperature water can break inert or dipole interactions between solutes and glass beads, alumina, and Florisil, higher temperature water is required to interrupt the van der Waals attractions between solutes and silica-bonded C₁₈, and even higher temperatures needed to overcome the π-electron interactions between aromatic solutes and XAD-4.     

气相毛细管柱切割-反吹技术及归一化法分析汽油中的芳烃(英文)

 发展了一种采用毛细管气相柱切割 反吹技术分析汽油中芳烃的方法。利用强极性毛细管预柱将芳烃保留至n C10 的脂肪族化合物之后 ,并将其反吹到非极性毛细管柱中按沸点详细分离分析。该方法使预柱先流出的组分和分析柱流出的组分通过一个微型三通进入同一检测器中 ,因此可用归一化方法定量分析汽油中的芳烃。该方法可在 15min内完成汽油中苯至C10 芳烃的分析 ,结果的相对标准偏差 (RSD)≤ 3% ,切割误差为± 5s时分析结果的RSD≤ 4 %。