新型芳基修饰的藤黄酸衍生物的合成及其抗肿瘤活性

以取代酚或羟基吡啶为原料,在无水碳酸钾存在下,与溴代醇发生威廉姆森醚合反应制得中间体--芳（杂环）氧基醇(2a~2k); 2a~2k分别与藤黄酸通过光延反应合成了藤黄酸衍生物（3a~3k）。以DDC/HOSu为偶联剂,芳酸与3-氨基-1-丙醇经偶联反应制得中间体--芳酰氨基醇（5a~5h）; 5a~5h分别与藤黄酸通过光延反应合成了藤黄酸衍生物（6a~6h）。 2, 3, 5和6为新化合物,其结构经¹H NMR, ESI-MS和HR-MS表征。采用MTT法测定了3和6对肺腺癌细胞(A549)、肝癌细胞(HepG-2)和乳腺癌细胞(SK-BR-3)的体外抗肿瘤活性。结果表明：部分化合物对肿瘤细胞的抑制活性明显高于藤黄酸。     

介孔有机无机杂化材料的合成和表征及在Pinacol重排反应中的研究

以巯丙基-三乙氧基硅烷为有机硅源,采用接枝法合成了磺酸基功能化有机无机杂化材料(MCM-SO3H).XRD、FT-IR、BET的研究表明,磺酸基功能化介孔有机无机杂化材料具有非常高的比表面积和规整的六方孔道结构.酸性测定表明,MCM-SO3H含酸量为0.40mmolH /g.MCM-SO3H对pinacol重排反应具有很高的催化活性,在反应温度为383K时,pinacol的转化率接近100%,pinacolone的选择性达到90%左右.反应温度、反应时间、催化剂用量和溶剂对pinacol重排反应有很大的影响提高反应温度、延长反应时间和增加催化剂的用量,均可提高pinacol的转化率和pinacolone的选择性.中等极性溶剂有利于pinacol重排反应.     

新型含1,3,4-噻二唑的硫色满酮衍生物的合成及其抗真菌活性

以取代苯硫酚和顺丁烯二酸酐为原料,经迈克尔加成反应制得2-羧基-硫色满酮衍生物（2a~2d）; 2a~2d分别与氨基硫脲反应制得2-(5-氨基-1,3,4-噻二唑-2-基)硫色满-4-酮衍生物（3a~3d）; 3a~3d与酰氯经酰化反应合成了14个新型的含1,3,4-噻二唑的硫色满酮衍生物（5a~5n）,其结构经^1H NMR, ¹³C NMR和HR-ESI-MS表征。采用微量稀释法测定了5a~5n的抗真菌活性。结果表明：部分化合物对絮状表皮癣菌和总状毛霉菌有较好的抑制活性,优于阳性对照药氟康唑。     

Synthesis of 3-substituted-2-benzothiazolinone, 2-benzoxazolinone and benzothiazoline-2-thione

The reaction of 2-benzothiazolinone, 2-benzoxazolinone or benzothiazoline-2-thione under basic conditions with various electrophiles afforded the titled compounds 1-13, 29-31 and 40-48. The 3-(substituted-aminomethyl)-2-benzothiazolinone and related compounds 14-25 were prepared by the reaction of 3-(hydroxymethyl)-2-benzothiazolinone or the appropriate 2-benzothiazolinone and formaldehyde with the appropriate amine or substituted aniline. The reaction of 9, 13 or 25 with methyl iodide afforded the quaternary ammonium iodides 26-28. The reaction of the appropriate potassium salts of various phenol with 3-(chloromethyl)-2-benzothiazolinone afforded the 3-(substituted-phenoxymethyl)-2-benzothiazolinone and related compounds 32-39. The ethyl or isopropylxanthates 49-54 were synthesized by the reaction of 3-(chloromethyl)-2-benzo-thiazolinone and appropriate compounds with potassium ethyl or isopropyl xanthate. The reaction of 3-(chloromethyl)-2-benzothiazolinone with sodium sulfide afforded the sulfide 55.     

无添加剂条件下文石型碳酸钙晶须制备及影响因素研究

在不加任何结晶控制剂或模板条件下,以CaCl2和Na2CO3为原料,利用复分解反应法制备了具有较好形貌和高长径比,且分布均一的文石型碳酸钙晶须,并利用扫描电镜(SEM)、X-射线粉末衍射(PXRD)和傅里叶转换红外光谱图(FT-IR)等手段对其进行了表征。研究了浓度、滴加速度、反应温度、搅拌速度以及滴加方式等因素对碳酸钙晶须的影响。结果表明最佳制备工艺为:CaC12溶液与Na2CO3溶液的浓度为0.05 mol.L-1,溶液滴加速度为1 mL.min-1,反应体系温度为80℃,搅拌速度为250 r.min-1。     

Study of the carbon-13 and deuterium kinetic isotope effects in the Cl and OH reactions of CH4 and CH3Cl

Relative rate experiments have been carried out for three isotopologues of chloromethane and their reactions with Cl atoms and OH radicals. The OH and Cl reaction rates of CH2DCl and CHD2Cl were measured by long-path FTIR spectroscopy relative to CH3Cl at 298+/-2 K and 1013+/-10 hPa in purified air. The FTIR spectra were fitted using a nonlinear least squares spectral fitting method including measured high-resolution infrared spectra as references. The relative reaction rates defined by alpha=klight/kheavy were determined to be kOH+CH3Cl/kOH+CH2DCl=1.41+/-0.05, kOH+CH3Cl/kOH+CHD2Cl=2.03+/-0.05, kCl+CH3Cl/kCl+CH2DCl=1.42+/-0.04, and kCl+CH3Cl/kCl+CHD2Cl=2.27+/-0.04. The carbon-13 and deuterium kinetic isotope effects in the OH and Cl reactions of CH3Cl were investigated further using variational transition state theory, and the results were compared to similar calculations performed for the CH4+OH/Cl reaction systems. The calculations show that the order of magnitude difference for the carbon-13 kinetic isotope effect in the OH reaction of CH3Cl compared to CH4 reported by Gola et al. (Atmos. Chem. Phys. 2005, 5, 2395) can be explained by the lower barrier to internal rotation of the OH radical in the transition state of the CH4+OH reaction than in the CH3Cl+OH reaction. The deuterium kinetic isotope effects can be explained in terms of combined variational effects and tunneling.     

C_（60）的胺加成反应和电喷雾电离质谱（ESI－MS）检测

报道了Ｃ６０与１，３－丙二胺和Ｎ，Ｎ－二甲基－１，３－丙二胺的加合反应，反应产物未经预先离子化处理直接用ＥＳＬ－ＭＳ进行检测。由于反应产物从甲苯溶液中析出，避免了生成多胺基加合物，产物以单加成物为主。当加合反应在空气氛下进行时，有加合氧的产物Ｃ６０Ｏｎ（ＮＨ２—ＣＨ２ＣＨ２ＣＨ２ＮＲ２）ｍ（Ｒ＝Ｈ，ＣＨ３）存在。实验发现：Ｎ，Ｎ－二甲基－１，３－丙二胺比１，３－丙二胺更容易与Ｃ６０发生多胺基加成和氧加成反应。通过控制反应条件可制备Ｃ６０二胺的单加成产物。     

Formation and recyclization of heterocycles

Thiorhodanine is recyclized to 1,2,4-triazole-3-thione by reaction with hydrazine. The intermediate recyclization products were identified. 4-Iminothiazolidone is recyclized to 1,2,4-triazol-3-one by reaction with hydrazine, 1,3-oxazolid-4-one-2-thione forms 2-hydrazonooxazolid-4-one by reaction with hydrazine in neutral solvents. The intermediate transformation products were isolated and indicate that the reaction proceeds as a recyclization of the starting oxazolidone under the influence of hydrazine.See [1] for communication IV.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 1, pp. 39–41, January, 1971.     

异维A酸新木脂素酯的合成与表征

以香草醛(或对羟基苯甲醛)和丙二酸为原料,经Knoevenagel反应、酯化、氧化银为氧化剂的自由基仿生氧化偶联反应合成了新木脂素3a,3b。3a,3b分别与异维A酸酯化,合成了两种新型的异维A酸新木脂素酯4a和4b。用1H NMR,IR和MS对它们的结构进行了表征。研究了异维A酸酯的反应机理。     

新型-meso-四(4-十四氨基甲酰苯基)卟啉及其-金属（Co）配合物的合成与液晶性能

对羧基苯甲醛和吡咯经缩合反应制得meso-四(4-羧基苯基)卟啉(1); 1与氯化亚砜反应得meso-四(4-氯甲酰基苯基)卟啉(2); 2与n-十四胺反应制得meso-四(4-十四氨基甲酰苯基)卟啉(3); 3与CoC_l2经配位反应合成了meso-四(4-十四氨基甲酰苯基)卟啉钴(4)。 3和4为新化合物,其结构经U-Vis, ¹H NMR和IR表征。偏光显微镜和DSC检测结果表明： 3和4具有液晶性能。     

Theoretical study on the mechanism of reaction between 3-hydroxy-3-methyl-2-butanone and malononitrile catalyzed by lithium ethoxide

The The mechanism of reaction between 3-hydroxy-3-methyl-2-butanone and malononitrile for the synthesis of 2-dicyanomethylene-4, 5, 5-trimethyl-2,5-dihydrofuran-3-carbonitrile catalyzed by lithium ethoxide was investigated by density functional theory (DFT). The geometries and the frequencies of reactants, intermediates, transition states and products were calculated at the B3LYP/6-31G(d) level. The vibration analysis and the IRC analysis verified the authenticity of transition states. The reaction processes were confirmed by the changes of charge density at the bond-forming critical point. The results indicated that lithium ethoxide is an effective catalyst in the synthesis of 2-dicyanomethylene-4, 5, 5-trimethyl-2, 5-dihydrofuran-3-carbonitrile from malononi-trile and 3-hydroxy-3-methyl-2-butanone. The activation energy of the reaction with lithium ethoxide was 115.86 kJ·mol⁻¹ less than the uncatalyzed reaction. The mechanism of the lithium ethoxide catalyzed reaction differed from the mechanism of the uncatalyzed reaction.     

O原子与HNCO反应机理的量子化学及电子密度拓扑研究

采用MP2(Full),B3LYP,QCISD/MP2和CCSD(T)/MP2方法在6-311G(d,p)水平上对O原子与HNCO反应的微观机理进行了理论研究．采用MP2(Full)和B3LYP对反应位能面上的各驻点进行几何构型的全优化,振动分析和IRC计算证实了中间体和过渡态的真实性和相互连接关系．四种方法计算得到了四个反应通道的反应活化能．研究表明,O原子进攻HNCO中的H原子为反应的主要反应通道,该通道中形成了两个分子复合物,电子密度拓扑分析表明这两个分子复合物均为氢键复合物．     

C2H3自由基与O2反应的红外发射光谱及反应通道

不饱和多原子Ｃ２Ｈ３自由基在碳氢化合物燃烧过程中起着非常重要的作用,其各种基元反应影响整个燃烧过程的速率和形成的产物［１－３］．Ｇｕｔｍａｎ和合作者［６］测量了总包反应在室温的速率常数（（１． ０６±０． ２１） ×１０－１１ｃｍ３· ｍｏｌｅｃｕｌｅ－１· ｓ－１）,仅检测到ＨＣＯ和Ｈ２ＣＯ两个反应产物,Ｓｌａｇｌｅ和合作者［７］使用光电离质谱法研究了温度在２９９－１００５ Ｋ范围内,宏观反应的Ａｒｒｈｅｎ－ｎｉｕｓ表达式 ｋ＝（６． ９２±０． １７）×１０－１２ｅｘｐ（（１２０±１２）／ Ｔ） ｃｍ…     

氮杂环卡宾的合成及在氢转移反应中的应用

利用氯甲基吡啶与咪唑反应制备了一系列含吡啶取代咪唑L1～L5,考察了所得咪唑衍生物与钌化合物在碱性条件下原位形成的氮杂卡宾钌络合物对苯胺与醇氢转移反应的催化活性.研究了碱的种类、钌前体、温度等对反应的影响,结果表明RuCl3 H2O/1-(2-吡啶甲基)-3-甲基碘化咪唑(L3)/KOH催化体系在185℃时对苯胺与乙二醇反应的催化活性较高,选择性生成N-羟乙基苯胺,TON(单位活性转化的底物分数)可达2130.此外,还考察了RuCl3 H2O/L3/KOH催化体系对苯胺与丁醇、环己醇、异丙醇、苯甲醇反应的催化性能.在催化剂作用下,醇与苯胺可形成亚胺及仲胺,伯醇可以自氢转移反应形成酯,反应产物的结构及选择性取决于醇的结构及反应条件.     

Preparation of hexa-, penta- and tetraphenyl-2,6- and -2,7-naphthyridines

Di- and triphenyldibenzoylpyridines ( 1 ) were prepared by the condensation reaction of 3, 4-dibenzoyl-2, 5-diphenylthiophene ( 2 ) with methylamine derivatives 3 and by the subsequent oxidative ring cleavage of the resultant thieno[3, 4-c]pyridines 4 . The reaction of 1 with 3 afforded polyphenyl-2, 6- ( 5 ) and -2, 7-naphthyridines ( 6 ).     

Synthesis and structural characterization of a series of lanthanide(II) amides: steric effect of amido ligand

The synthesis and structures of a series of lanthanide(II) and lanthanide(III) complexes supported by the amido ligand N(SiMe3)Ar were described. Several lanthanide(III) amide chlorides were synthesized by a metathesis reaction of LnCl3 with lithium amide, including {[(C6H5)(Me3Si)N]2YbCl(THF)}2.PhCH3 (1), [(C6H3-iPr2-2,6)(SiMe3)N]2YbCl(mu-Cl)Li(THF)3.PhCH3 (4), [(C6H3-iPr2-2,6)(SiMe3)N]YbCl2(THF)3 (6), and [(C6H3-iPr2-2,6)(SiMe3)N]2SmCl3Li2(THF)4 (7). The reduction reaction of 1 with Na-K alloy afforded bisamide ytterbium(II) complex [(C6H5)(Me3Si)N]2Yb(DME)2 (2). The same reaction for Sm gave an insoluble black powder. An analogous samarium(II) complex [(C6H5)(Me3Si)N]2Sm(DME)2 (3) was prepared by the metathesis reaction of SmI2 with NaN(C6H5)(SiMe3). The reduction reaction of ytterbium chloride 4 with Na-K alloy afforded monoamide chloride {[(C6H3-iPr2-2,6)(SiMe3)N]Yb(mu-Cl)(THF)2}2 (5), which is the first example of ytterbium(II) amide chloride, formed via the cleavage of the Yb-N bond. The same reduction reaction of 7 gave a normal bisamide complex [(C6H3-iPr2-2,6)(SiMe3)N]2Sm(THF)2 (8) via Sm-Cl bond cleavage. This is the first example for the steric effect on the outcome of the reduction reaction in lanthanide(II) chemistry. 5 can also be synthesized by the Na/K alloy reduction reaction of 6. All of the complexes were fully characterized including X-ray diffraction for 1-7.     

Quantum chemical study on insertion and abstraction reaction of dichlorocarbene with methyl alcohol and methyl mercaptan

The insertion and abstraction reaction mechanisms of singlet and triplet CCl₂ with CH₃MH (M=O, S) have been studied by using the DFT, NBO and AIM methods. The geometries of reactions, the transition state and products were completely optimized by B3LYP/6–311G(d, p). All the energy of the species was obtained at the CCSD(T)/6–311G(d, p) level. The calculated results indicated that the major pathways of the reaction were obtained on the singlet potential energy surface. The singlet CCl₂ can not only trigger the insertion reaction with C-H and M-H in four pathways, by which the products P1 [CH₃OCHCl₂, reaction I(1)], P3[Cl₂HCCH₂OH, reaction I(2)], P5[CH₃SCHCl₂, reaction II(1)] and P7[Cl₂HCCH₂SH, reaction II(2)] are produced respectively, but also abstract M-H, resulting P4 [CH₂O+CH₂Cl₂, reaction I(3)] and P8[CH₂S+CH₂Cl₂, reaction II(3)]. In addition, the important geometries in domain pathways have been studied by AIM and NBO theories. Supported by the National Natural Science Foundation of China (Grant No. 20335030) and Foundation of Education Committee of Gansu Province (Grant No. 0708-11)     

Theoretical and Experimental Studies on the Reaction Mechanism of Cl2 ＋ I2- 2ICl

1 INTRODUCTION The reactions between halogen and halogen are basic reactions in chemistry. Especially, in the syn- thesis of iodo-substituted aromatic hydrocarbon, the reaction Cl2 I2 = 2ICl could heighten the usage of iodine atom to 100%. So far, to the best of our know- ledge, the studies about halogen-halogen reaction mechanisms are very few. In detail, only the struc- ture and stability studies of X2Y- (X, Y = Cl, Br and I) ions by calculating reaction potential energy sur- face…     

水热法合成Bi2S3纳米管及其生长机理

以硝酸铋[Bi(NO)3]和硫化钠(Na2S)为反应原料, 采用水热法在120 ℃下反应12 h, 制备出Bi2S3纳米管. 利用X射线粉末衍射(XRD)、扫描电子显微镜(SEM)、透射电子显微镜(TEM)、选区电子衍射(SAED)和高分辨透射电镜(HRTEM)对其结构和形貌进行了表征. 结果表明, 所制备的产物是结晶良好的正交相Bi2S3纳米管, 其外径为100~500 nm, 内径为50~200 nm, 长为1~5 μm. 根据实验结果讨论了Bi2S3纳米管的生长机理. 初步研究了反应温度和矿化剂种类对产物形貌和结构的影响.     

Derivatives of 3-(2-hydroxyethyl)2-benzothiazolinone and related compounds

The reaction of the appropriate 2-benzothiazolinone with 2-chloroethanol or 3-chloropropanol under basic conditions afforded 3-(2-hydroxyethyl or 3-hydroxypropyl)-2-benzothiazolinone and related compounds 1–7. The reaction of the alcohols 1,4, 5 or 7 with potassium hydroxide and excess carbon disulfide furnished the potassium salts of xanthic acid 8–11 which upon oxidation gave the disulfides 12–15. Esters of xanthic acid 16–23 were prepared by the reaction of 8 or 11 with various halogen compounds. Esters of acetic acid 24–28 were prepared by the reaction of the appropriate 2-benzothiazolinone with 2-bromoethyl acetate under basic conditions. Esterification of 1 with various acids afforded the esters 25, 29–32.