芳基吡唑腙及其双杂环化合物的合成与抗菌活性

通过1-苯基-3-(4-甲基苯基)-4-甲酰基吡唑与芳氧乙酰肼的加成反应,合成了5个新型的吡唑腙类化合物(3a～3e);3在酸性条件下环合,合成了5个新型的吡唑双杂环化合物(4a～4e). 3和4的结构经1H NMR,IR,MS和元素分析表征.对3和4分别进行了棉花枯萎病菌(A),棉花黄萎病菌(B),棉花立枯病菌(C),瓜果腐霉病菌(D),番茄早疫病菌(E)及向日葵菌核病菌(F)等初步的抑菌活性测试.结果表明,4的抑菌效果明显高于3;其中4d和4e对A,C和D的抑制率大于90%,对E和F的抑制率大于80%.     

Synthesis and characterization of zinc AP-MOCVD precursors and their utility in the growth of ZnO

A novel beta-ketoimine, 4-N-(n-butylamino)-3-penten-2-one (1), and beta-enaminoester, Ethyl 3-N-(isopropylamino)-2-butenoate (2), were synthesized by the reaction of the 2,4-pentanedione or ethyl 3-oxo butanoate with the n-butyl and isopropyl amine, respectively. The isolated free ligands 1 and 2 were reacted with diethylzinc to afford Zn(CH3C(NCH2CH2CH2CH3)CHCOCH3)2 (3) and Zn(CH3C(NCH(CH3)2)CHC(O)OCH2CH3)2 (4) respectively. The isolated zinc complexes, 3 and 4, were characterized by elemental analysis, NMR, and MALDI-TOFMS. The molecular structure of 3 and 4 were determined via single crystal X-ray diffraction which revealed both compounds to be four coordinate, monomeric and homoleptic in the solid state. TG analysis showed the air stable compounds to be thermally robust as they both sublimed in a one-step process at atmospheric pressure. The compounds were utilized in the growth of ZnO via AP-MOCVD in the absence of additional oxidant. The carbon content of the film grown from 3 as determined by XPS was 26.2% while that of the film grown by 4 was 8.71%.     

Phloretamide及其衍生物的合成与抗氧化活性

以3-(4-羟基苯基)丙烯酰胺（Phloretamide）为先导化合物,取代苯丙烯酸为原料,经取代反应和酰胺化反应制得苯丙烯酰胺类化合物(2a~2d); 2经氢化还原反应合成了4个Phloretamide衍生物(3a~3d); 1, 2和3经去甲基化反应分别制得〖WTHZ〗〖STHZ〗1e, 2e~2f和3e~3f〖STBZ〗〖WTBZ〗。其中,3-(3,4,5-三羟基苯基)丙烯酰胺(2f), 3-(2,3,4-三羟基苯基)丙酰胺(3e)和3-(3,4,5-三羟基苯基)丙酰胺(3f)为新化合物,其结构经¹H NMR, ¹³C NMR和ESI-MS表征。初步抗氧化活性测定结果表明：c为10 μmol·L^-1时,2b, 2f和3f具有较好的自由基清除活性,其清除率分别为66.8%, 59.8%和69.4%,均优于阳性对照咖啡酸,咖啡酸苯乙酯和Vc。     

Theoretical investigation of the mechanisms and stereoselectivities of reductions of acyclic phosphine oxides and sulfides by chlorosilanes

Computational studies were performed to explain the highly varied stereoselectivities obtained in the reductions of acyclic phosphine oxides and sulfides by different chlorosilanes. The reductions of phosphine oxides by HSiCl(3), HSiCl(3)/Et(3)N, and Si(2)Cl(6) and the reductions of phosphine sulfides by Si(2)Cl(6) (all in benzene) were explored by means of B3LYP, B3LYP-D, and SCS-MP2 calculations. For the reductions of phosphine oxides by HSiCl(3), the calculations support the mechanism proposed by Horner in which a hydride is transferred from silicon to phosphorus through a four-centered, frontside transition state. This mechanism leads to retention of stereochemistry at phosphorus. For the other three reductions, two classes of mechanisms were explored. Phosphorane-based mechanisms that were previously proposed by Mislow and involve SiCl(3)(-) were compared with novel alternative mechanisms that involve nonionic rearrangement processes. In one of these, donor-stabilized SiCl(2) is formed as an intermediate. The calculations support a phosphorane-based mechanism for the reductions of phosphine oxides by HSiCl(3)/Et(3)N and Si(2)Cl(6) (which proceed with inversion) but favor the rearrangement pathways for the reductions of phosphine sulfides by Si(2)Cl(6) (which proceed with retention).     

Kinetics and mechanisms of the allyl + allyl and allyl + propargyl recombination reactions

The kinetics and mechanisms of the self-reaction of allyl radicals and the cross-reaction between allyl and propargyl radicals were studied both experimentally and theoretically. The experiments were carried out over the temperature range 295-800 K and the pressure range 20-200 Torr (maintained by He or N(2)). The allyl and propargyl radicals were generated by the pulsed laser photolysis of respective precursors, 1,5-hexadiene and propargyl chloride, and were probed by using a cavity ring-down spectroscopy technique. The temperature-dependent absorption cross sections of the radicals were measured relative to that of the HCO radical. The rate constants have been determined to be k(C(3)H(5) + C(3)H(5)) = 1.40 × 10(-8)T(-0.933) exp(-225/T) cm(3) molecule(-1) s(-1) (Δ log(10)k = ± 0.088) and k(C(3)H(5) + C(3)H(3)) = 1.71 × 10(-7)T(-1.182) exp(-255/T) cm(3) molecule(-1) s(-1) (Δ log(10)k = ± 0.069) with 2σ uncertainty limits. The potential energy surfaces for both reactions were calculated with the CBS-QB3 and CASPT2 quantum chemical methods, and the product channels have been investigated by the steady-state master equation analyses based on the Rice-Ramsperger-Kassel-Marcus theory. The results indicated that the reaction between allyl and propargyl radicals produces five-membered ring compounds in combustion conditions, while the formations of the cyclic species are unlikely in the self-reaction of allyl radicals. The temperature- and pressure-dependent rate constant expressions for the important reaction pathways are presented for kinetic modeling.     

静电纺丝技术制备LaCrO4和LaCrO3纳米带及其光催化性质

采用溶胶-凝胶法结合静电纺丝技术制备了PVP/[La(NO3)3|Cr(NO3)3]复合纳米带, 经热处理后得到LaCrO4纳米带和LaCrO3纳米带. 采用TG-DTA, XRD, SEM和EDS等测试手段对样品进行了表征. 结果表明, PVP/[La(NO3)3-Cr(NO3)3]复合纳米带表面光滑, 宽度为(9.1±1.9) μm, 厚度约385 nm; 经600 ℃焙烧后得到单斜独居石型LaCrO4纳米带, 宽度为(2.5±0.5) μm, 厚度约100 nm; 当焙烧温度为650~800 ℃时得到LaCrO3多孔纳米带, 属正交晶系, Pbnm空间群, 经650 ℃焙烧后得到的LaCrO3纳米带呈多孔结构, 带宽为(2.4±0.5) μm, 厚度约90 nm; 经800 ℃焙烧后得到的LaCrO3纳米带部分破碎形成LaCrO3纳米粒子, LaCrO3纳米带宽度约(1.3±0.4) μm, 厚度约90 nm, LaCrO3纳米粒子粒径约80 nm. 以罗丹明B为目标降解物, 研究了不同焙烧温度下产物的光催化性能, 其中800 ℃焙烧后得到的样品在紫外光照射下对罗丹明B的降解效果最好, 光照200 min后罗丹明B的降解率为94.6%.     

稀土酰基吡唑啉酮邻菲咯啉配合物的合成、表征及其生物活性

以稀土、邻菲咯啉、1-苯基-3-甲基-4-苯甲酰基-5-吡唑酮为原料在无水乙醇溶液中反应，制备了一类新型稀土三元配合物，通过元素分析、摩尔电导、基质辅助激光解析/电离质谱、 ¹H核磁共振谱、红外光谱、拉曼光谱、紫外光谱、热重-差热分析及电子显微镜等手段对其进行了表征，确定了该配合物的化学组成:RE(PMBP)₃Phen(RE=Sm³⁺，Eu³⁺，Y³⁺，Er³⁺，Gd³⁺)，抗菌实验结果表明，稀土三元配合物对大肠杆菌、金黄色葡萄球菌和白色念珠菌有较强的抑制作用，抗菌谱广。通过MTT比色法对配合物诱导癌细胞凋亡能力做了初步研究，结果表明其具有较强的抑杀癌细胞的作用。     

三氯环硼氮烷和聚硼氮烷的合成与表征

以三氯化硼和氯化铵为原料,甲苯为溶剂,高产率(98%)地合成了具有硼和氮的六元环结构的三氯环硼氮烷(1);1分别与正丙胺(Ⅰ)和异丙胺(Ⅱ)反应制得正丙胺基环硼氮烷(1~Ⅰ)和异丙胺基环硼氮烷(1~Ⅱ);1~Ⅰ和1~Ⅱ经过脱胺和热聚合反应制得聚硼氮烷先驱体(2和3).用IR,NMR和XRD等对2和3的组成与结构进行了分析,探讨了聚硼氮烷的胺基取代基对聚硼氮烷聚合反应性及产物结构的影响.研究结果表明,3具有更强的热聚合特性.     

First structural characterization of binary AsIII and SbIII azides

The highly explosive molecules As(N(3))(3) and Sb(N(3))(3) were obtained in pure form by the reactions of the corresponding fluorides with (CH(3))(3)SiN(3) in SO(2) and purification by sublimation. The crystal structures and (14)N NMR, infrared, and Raman spectra were determined, and the results compared to ab initio second-order perturbation theory calculations. Whereas Sb(N(3))(3) possesses a propeller-shaped, pyramidal structure with perfect C(3) symmetry, the As(N(3))(3) molecule is significantly distorted from C(3) symmetry due to crystal packing effects.     

Synthesis and characterization of two new cyclobutyl and aryl hydroxyethyl methacrylate monomers and their polymers

Two new hydroxyethyl methacrylates having aryl and cyclobutane rings were synthesized by addition to 1-(epoxyethyl)-3-aryl-3-methylcyclobutane to methacrylic acid. The monomers prepared are 2-(3-methyl-3-phenylcyclobutyl)-2-hydroxyethyl methacrylate (PCHEMA) and 2-(3-methyl-3-mesitylcyclobutyl)-2-hydroxyethyl methacrylate (MCHEMA). Both monomers were polymerized at 60°C in 1,4-dioxane solution using benzoyl peroxide as initiator. Poly(PCHEMA) and poly(MCHEMA) and their monomers were characterized by FT-IR and ¹H- and ¹³C-NMR techniques. Weight average molecular weights of the polymers were determined for poly(PCHEMA) poly(MCHEMA) by gel permation chromatography. Thermal stabilities of the polymers were essentially the same. Glass transition temperatures for poly(PCHEMA) and poly(MCHEMA) were determined as 105 and 137°C, respectively. No changes of the polymers by irradiation with UV light at 254 nm were observed. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35 : 2123–2128, 1997     

含咪唑功能基的手性羧酸酯和脂肪醇的合成

含咪唑功能基的手性羧酸酯和脂肪醇的合成;天然氨基酸;手性咪唑羧酸酯;手性咪唑脂肪醇;合成     

苯丙烯类葡萄糖氧苷的合成及其抗缺氧活性

以取代苯甲醛(1a~1t)为原料,通过Knoevenagel缩合、酯化和LiAlH₄还原等反应制得苯丙烯醇衍生物(3a~3t);以取代肉桂醛(1u~1x)为原料,经NaBH₄还原制得苯丙烯醇衍生物(3u~3x); 3a~3x与全乙酰化溴代葡萄糖经Koenigs-Knorr偶联反应及MeONa/MeOH体系脱除乙酰保护基反应,合成了24个苯丙烯类葡萄糖氧苷(5a~5x),其中5c,5f ~ 5x为新化合物,其结构经¹H NMR和ESI-MS表征。采用MTT法测定了5对缺氧损伤的内皮细胞(EA.hy926)的抗缺氧活性。实验结果表明： 5b, 5e, 5g, 5p, 5q, 5s, 5t和5y对EA.hy926的抗缺氧活性均高于经景天苷。     

氮杂环丁烷衍生物的合成及其抗肿瘤活性

以3-羟基氮杂环丁烷盐酸盐为原料,经取代、官能团转化制得3-氨基氮杂环丁烷化合物（3）; 3经衍生化合成了10个3-氨基氮杂环丁烷衍生物(4a~4j),其中4f~4j为新化合物,其结构经¹H NMR, ¹³C NMR和HR-MS（ESI-TOF)表征。采用MTT法初步测试了化合物的体外抗肿瘤活性。结果表明：4h对A549表现出较强的细胞毒活性（IC₅₀=8.06 μmol·L^-1）。     

铈酸钡和钇掺杂的铈酸钡复合氧化物的制备及其在钌基氨合成催化剂中的应用

 采用柠檬酸法合成了 BaCeO3 和掺杂 Y3+的 BaCe0.9Y0.1O3-δ 复合氧化物, 以 Ru3(CO)12 为前体, 利用浸渍法制备了 Ru/BaCeO3 和 Ru/BaCe0.9Y0.1O3-δ 催化剂. 通过 X 射线衍射、扫描电镜和透射电镜技术对样品进行了表征, 并在固定床反应器中考察了催化剂的氨合成反应活性. 结果表明, 载体 BaCeO3 的稳定性优于 BaCe0.9Y0.1O3-δ, 但 Ru/BaCe0.9Y0.1O3-δ 催化剂的氨合成活性明显高于 Ru/BaCeO3, 在 3.0 MPa, 15 000 h1, 425 oC 反应时, Ru/BaCe0.9Y0.1O3-δ 催化剂上氨合成反应速率达到 432.5 ml/(g•h), 是 Ru/BaCeO3 催化剂的 1.6 倍. 这种活性和稳定性的显著差异来自载体中 Ce4+ 与 Ru 纳米粒子间的电子作用.     

新型苯并咪唑衍生物的合成及其抗凝血活性

以3-［(3-氨基-4-甲基氨基苯甲酰)吡啶-2-基氨基］丙酸乙酯为原料,与4-氰基-3-氟苯取代基乙酸经环化反应制得3-【【2-｛［(4-氰基-3-氟苯取代基）甲基］-1-甲基-1-H-苯并咪唑-5-基｝羰基】吡啶-2-基】氨基丙酸乙酯（3a, 3e）; 3经水解和酰胺化反应制得3-【【【2-｛［(4-氰基-3-氟苯基)取代基］甲基｝-1-甲基-1H-苯并咪唑-5-基】羰基】吡啶-2-基氨基】丙酰取代胺基（6a~6h）;6与乙酰氧肟酸经环合反应合成了8个新型的苯并咪唑衍生物（7a~7h）,其结构经1H NMR和HR-ESI-MS表征。抗凝血活性结果表明： 7a和7c的抗凝血活性最好,其aPTT值分别为(83.1±4.2) s和(80.7±2.9) s,优于阳性对照药达比加群酯(75.3±2.1)s。     

The OsO4F-, OsO4F2(2)-, and OsO3F3- anions, their study by vibrational and NMR spectroscopy and density functional theory calculations, and the X-ray crystal structures of [N(CH3)4][OsO4F] and [N(CH3)4][OsO3F3

The fluoride ion acceptor properties of OsO4 and OsO3F2 were investigated. The salts [N(CH3)4][OsO4F] and [N(CH3)4]2[OsO4F2] were prepared by the reactions of OsO4 with stoichiometric amounts of [N(CH3)4][F] in CH3CN solvent. The salts [N(CH3)4][OsO3F3] and [NO][OsO3F3] were prepared by the reactions of OsO3F2 with a stoichiometric amount of [N(CH3)4][F] in CH3CN solvent and with excess NOF, respectively. The OsO4F- anion was fully structurally characterized in the solid state by vibrational spectroscopy and by a single-crystal X-ray diffraction study of [N(CH3)4][OsO4F]: Abm2, a = 7.017(1) A, b = 11.401(2) A, c = 10.925(2) A, V = 874.1(3) A3, Z = 4, and R = 0.0282 at -50 degrees C. The cis-OsO4F2(2-) anion was characterized in the solid state by vibrational spectroscopy, and previous claims regarding the cis-OsO4F2(2-) anion are shown to be erroneous. The fac-OsO3F3- anion was fully structurally characterized in CH3CN solution by 19F NMR spectroscopy and in the solid state by vibrational spectroscopy of its N(CH3)4+ and NO+ salts and by a single-crystal X-ray diffraction study of [N(CH3)4][OsO3F3]: C2/c, a = 16.347(4) A, b = 13.475(3) A, c = 11.436(3) A, beta = 134.128(4) degrees, V = 1808.1(7) A3, Z = 8, and R = 0.0614 at -117 degrees C. The geometrical parameters and vibrational frequencies of OsO4F-, cis-OsO4F2(2-), monomeric OsO3F2, and fac-OsO3F3- and the fluoride affinities of OsO4 and monomeric OsO3F2 were calculated using density functional theory methods.     

Linkage and redox isomerism in ruthenium complexes of catecholate, semiquinone, and o-acylphenolate ligands derived from 1,2-dihydroxy-9,10-anthracenedione (alizarin) and related species: syntheses, characterizations, and photophysics

The complexes Ru(CO)2L2(AL-2H) (AL = alizarin; L = PPh3, PCyc3, PBu3, P(m-NaSO3C6H4)3), Ru(CO)(dppe)(PBu3)(AL-2H), and RuH(CO)L2(AL-H) (L = PPh3, PCyc3), and Ru(CO)2L2(AR-2H) (AR = anthrarobin; L = PBu3) were prepared by reactions of Ru3(CO)12, L, and AL, and the complexes RuH(CO)(PPh3)2(AL-H), RuH(CO)(PPh3)2(QN-H) (QN = quinizarin), and RuH(CO)(PPh3)2(LQN-H) (LQN = leucoquinizarin) are prepared by reactions of RuH2(CO)(PPh3)3 with AL or QN. The AL-2H and AR-2H ligands act as 1,2-catecholates, whereas the AL-H, QN-H, LQN-H ligands are 1,9-o-acylphenolate ligands. RuH(CO)(PPh3)2(AL-H) is characterized by X-ray crystallography. The electrochemistry of these complexes is examined, and the semiquinone complexes [Ru(CO)2L2(AL-2H)]+ (L = PPh3, PCyc3, PBu3) and [Ru(CO)(dppe)(PBu3)(AL-2H)]+ are generated by chemical oxidation and were characterized by EPR and IR spectroscopy. The photophysical properties are also reported.     

酚羟基桥八胺穴醚及其镧系配合物的合成与表征(英)

通过将相应的席夫碱穴醚还原的方法合成了三个具有不同取代基（R=溴，4；苯基，5；甲基，6）的新的酚羟基桥的八胺穴醚，并对其进行了表征。将这些新穴醚与镧系元素的高氯酸盐反应制备了它们的镧系元素配合物(7～12)。核磁、质谱、红外、紫外和元素分析等表征结果表明这些镧系元素配合物为单核配合物并可能具有N₃O₃N₃型的对称配位结构。讨论了铕(Ⅲ)配合物8在乙腈溶液中的荧光性质。     

Synthesis of new cyclotriphosphazene derivatives bearing Schiff bases and their thermal and absorbance properties

In this study, a series of cyclotriphosphazene derivatives containing a Schiff base (3a–3d) were synthesized by the reactions of hexachlorocyclotriphosphazene (1) with bis-aryl Schiff bases ( 2a – 2d ) having different terminal groups (H, F, Cl, and Br). The products ( 3a – 3d ) were characterized by elemental and mass analyses, FT-IR, and ¹ H, ¹³ C, and ³¹ P NMR spectroscopies. Furthermore, the structure of compound 3a was also determined by X-ray crystallography. The thermal behaviors and the spectral properties of the new cyclotriphosphazene compounds ( 3a – 3d ) were investigated and the results were compared in the series.     

新型烷氧基嘧啶拼接3-吡咯螺环氧化吲哚类化合物的合成及其抗肿瘤活性

以取代烷氧基嘧啶3-烯键氧化吲哚衍生物为原料,与肌氨酸及多聚甲醛在甲苯中回流经1,3-偶极子3+2环加成反应,合成了8个新型烷氧基嘧啶拼接3-吡咯螺环氧化吲哚类化合物(3a~3h),产率67%~82%,d/r值6/1~20/1,其结构经~1H NMR,~(13)C NMR和HR-MS(ESI-TOF)表征。采用MTT法研究了3a~3h对人肺癌细胞(A549)、人前列腺癌细胞(PC-3)和人白血病细胞(K562)的体外抗肿瘤活性。结果表明:3d和3g对人白血病细胞K562具有明显的活性,IC50分别为24.1 mol·L~(-1)和32.4μmol·L~(-1),接近阳性对照药顺铂。