2-(4-氯苯基)-3-甲基丁酸的消旋

以酸酐及有机惰性溶剂作混合溶剂，少量叔胺等作催化剂，2-(4-氯苯基)-3-甲基丁酸能在比较温和的条件下基本完全消旋，收率接近90％。     

海绵Spongia sp.化学成分的研究（I）

应用气相色谱－质谱联用技术从海绵Ｓｐｏｎｇｉａ ｓｐ．中分离鉴定出４个化学成分：１．－氯－２,２－二对氯苯基乙烯（ＤＤＭＵ,Ｉ）、１,１－二氯－２,２－二对氯苯基乙烯（ＤＤＥ,Ⅱ）、１,１－二氯－２,２－二对氯苯乙烷（ＤＤＤ,Ⅲ）和角鲨烯（Ⅳ）。前３个化合物是首次从Ｓｐｏｎｇｉａ属海绵中分离得到。     

Application of ketenes to well‐defined polyester synthesis. II. Synthesis of reactive polyester by living anionic polymerization of (4‐halophenyl)ethylketene

Novel ketenes, (4‐chlorophenyl)ethylketene and (4‐bromophenyl)ethylketene, were synthesized by dehydrochlorination of 2‐(4‐halophenyl)butanoyl chlorides, and their anionic polymerizations by lithium (4‐methoxyphenoxide) in tetrahydrofuran at ?20 °C were carried out to afford the corresponding polyesters with narrow molecular weight distributions (weight‐average molecular weight/number‐average molecular weight < 1.3) quantitatively. Polymerizations with various feed ratios afforded the corresponding polyesters with predictable molecular weights and narrow molecular weight distributions. Kinetic studies of the polymerizations at ?78 °C revealed that the polymerization rates were apparently larger than that of ethylphenylketene, which is considered to be responsible for the enhanced electrophilicities of the monomers via the introduction of electron‐negative halogen atoms. Monomer conversion agreed with the first‐order kinetic equation. These results strongly support the living mechanism of this polymerization. The obtained polyesters were modified by a palladium‐catalyzed coupling reaction of the side‐chain 4‐halophenyl group with 4‐methoxyphenylboronic acid, demonstrating their potential as reactive polymers. © 2001 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 39: 2093–2102, 2001     

Die ersten nicht-fluorierten Arylxenon-Kationen: Reaktionen von Xenondifluorid mit Chlorphenylbor-, -lithium-, -silicium- und -zinn-Derivaten

The First Non-fluorinated Arylxenon Cations: Reactions of Xenon Difluoride with Chlorophenylboron, -lithium, -silicon, and -tin Derivatives Tris(chlorophenyl)boranes BAr₃ (Ar = 2,6-Cl₂C₆H₃, 2,4,6-Cl₃C₆H₂) could be prepared from the reactions of ArMgI with BF₃ · O(CH₃)₂ in about 25% yield. The reactions of these boranes and of B(4-ClC₆H₄)₃ with XeF₂ in the presence of BF₃ · O(CH₃)₂ led to the formation of [XeAr][BF₄]. The compound [Xe(4-ClC₆H₄)][BF₄] was isolated in 34% yield as a colourless solid with a decomposition point of ?4 ± 2°C. The derivatives with the substituents 2,6-Cl₂C₆H₃ and 2,4,6-Cl₃C₆H₂ could only be obtained as a product mixture. Reactions of XeF₂ with Li(2,6-Cl₂C₆H₃), (CH₃)₃Si(2,6-Cl₂C₆H₃) and the hitherto unknown (CH₃)₃Sn(2,4,6-Cl₃C₆H₂) did not give evidence for the formation of an arylxenon derivative.     

海绵Spongia sp.化学成分的研究（Ⅰ）

应用气相色谱－质谱联用技术从海绵Spongia sp. 中分离鉴定出4个化学成分： 1－氯－2,2－二对氯苯基乙烯(DDMU,Ⅰ)、 1,1－二氯－2,2－二对氯苯基乙烯(DDE,Ⅱ)、 1,1－二氯－2,2－二对氯苯乙烷(DDD, Ⅲ)和角鲨烯（Ⅳ）。前3个化合物是首次从Spongia属海绵中分离得到。     

Syntheses of 1,5-Benzothiazepines: Part XXXVI—Syntheses and Antimicrobial Evaluation of 2-(2-Chlorophenyl)-4-(4-chlorophenyl/2-thienyl)-2,5-dihydro-8-substituted-1,5-benzothiazepines

Six 5-substituted-2-aminobenzenethiols have been reacted with 3-(2-chlorophenyl)-1-(4-chlorophenyl)-2-propenone and 3-(2-chlorophenyl)-1-(2-thienyl)-2-propenone in dry ethanol saturated with dry HCl gas, to obtain twelve new compounds, 8-substituted-2-(2-chlorophenyl)-4-(4-chlorophenyl/2-thienyl)-2,5-dihydro-1,5-benzothiazepines in satisfactory yields. The structures of the final products have been assigned by elemental microanalyses data for elements, C, H, and N and by IR, ¹ H NMR, and mass spectroscopies. The synthesized compounds have been evaluated for their relative antimicrobial activity against the gram-positive bacteria, Staphylococcus aureus, gram-negative bacteria, Pseudomonas aeruginosa and the fungus, Candida albicans. The compounds have been found to show little antibacterial activity, but interestingly, showed significant antifungal activity.     

2-[4-氨基-5-(2,4-二氯苯基)-4H-1,2,4-三唑-3-硫亚甲基酰胺]-3-甲基苯甲酰正丙胺的合成

以2,4-二氯苯甲酸为原料,经酯化、胺化、取代和环合4步反应合成了中间体3-巯基-4-氨基-5-(2,4-二氯)苯基-1,2,4-三唑(4)。以乙腈为溶剂,K2CO3为催化剂,4与2-(2-氯乙酰氨基)-3-甲基-N-丙基苯甲酰胺于室温反应3 h合成了2-[4-氨基-5-(2,4-二氯苯基)-4H-1,2,4-三唑-3-硫亚甲基酰胺]-3-甲基苯甲酰正丙胺,收率78%,其结构经1H NMR,IR,ESI-MS和元素分析确证。     

Application of Alkali Metal Hydroxides for the Preparation of gem‐Chlorophenylcyclopropanes

gem‐Chlorophenylcyclopropanes 3 are conveniently prepared by reaction of benzal chloride (1) with alkenes 2, carried out either in the presence of solid potassium hydroxide and 18‐crown‐6 as a catalyst or cesium hydroxide monohydrate, without solvent.     

Quantum‐chemical,IR, NMR,and X‐ray diffraction studies on 2‐(4‐chlorophenyl)‐1‐methyl‐ 1H‐benzo[d]imidazole

The title molecule, 2‐(4‐chlorophenyl)‐1‐methyl‐1H‐benzo[d]imidazole (C₁₄H₁₁ClN₂), was prepared and characterized by ¹H NMR, ¹³C NMR, IR, and single‐crystal X‐ray diffraction. The molecular geometry, vibrational frequencies, and gauge including atomic orbital (GIAO) ¹H and ¹³C NMR chemical shift values of the title compound in the ground state have been calculated by using the Hartree‐Fock (HF) and density functional theory (DFT/B3LYP) method with 6‐31G(d) basis sets, and compared with the experimental data. The calculated results show that the optimized geometries can well reproduce the crystal structural parameters, and the theoretical vibrational frequencies and GIAO ¹H and ¹³C NMR chemical shifts show good agreement with experimental values. The energetic behavior of the title compound in solvent media has been examined using B3LYP method with the 6‐31G(d) basis set by applying the Onsager and the polarizable continuum model (PCM). Besides, molecular electrostatic potential (MEP), frontier molecular orbitals (FMO) analysis, and nonlinear optical (NLO) properties of the title compound were investigated by theoretical calculations. © 2010 Wiley Periodicals, Inc. Int J Quantum Chem, 2011     

氟哌啶醇的示差脉冲吸附伏安法测定

氟哌啶醇,化学名4-[4-基-4-(4-氯苯)-4-羟基派啶]-4’-氟丁酰苯,是一种重要的抗精神病药。该药物的测定主要采用紫外光度法,其他尚有气相和薄层色谱法,荧光法等。但灵敏度都不够高,难以用于微量和痕量分析,特别是病人体液中含量的监测。 Bishop等发现,氟哌啶醇在金和铂电极上既不还原也不氧化,认为这种药物在上述电极上不具有电活性。本文发现氟哌啶醇能吸附于玻碳电极,并发生氧化反应。据此拟定了吸附伏安法测定该药物的方案,并研究了药物在玻碳表面的吸附行为。