1,5-苯并硫氮杂-α-丁烯二酰亚氨基-β-内酰胺衍生物的合成、晶体结构及其抑菌活性

丁烯二酰亚氨基乙酰氯与1,5-苯并硫氮杂反应, 合成了8个1,5-苯并硫氮杂-α-丁烯二酰亚氨基-β-内酰胺衍生物, 用IR, MS, 1H NMR和元素分析表征了产物的结构, 用单晶X射线衍射法确证了产物的立体结构. 生物活性研究表明, 此类化合物有一定的抑菌作用, 其中对金黄色葡萄球菌和白色葡萄球菌的抑菌效果相对较好.     

无催化剂条件下的全氟烷基取代的1H-苯并[b][1,4]二氮-2(3H)-酮的简易合成

1,5-苯并二氮-2-酮作为一个独特的骨架广泛存在于很多具有生理活性的化合物中,而全氟烷基的引入影响到有机化合物的理化性质以及生理活性的改变.因此将全氟代烷基引入1,5-苯并二氮-2-酮的方法的研究正变得日趋重要.发展了一个制备全氟代烷基取代的1,5-苯并二氮-2-酮的简易方法.采用全氟代炔酸甲酯为含氟砌块,与邻芳基二胺,以无水甲苯为溶剂,在无催化剂存在条件下,80℃反应24 h,以较好的收率顺利得到4-全氟烷基-1,3-二氢-1,5-苯并二氮-2-酮类化合物.     

2-甲基-1,5-苯并硫氮杂的基态和激发态反应的研究 II:2-甲基-1,5-苯并硫氮杂的光异构化和Fries重排

2-甲基-1,5-苯并硫氮杂(2a-2d)在苯溶液中光照生成相应的2,4-异构化产物3a-3d,其中2a和2d同时还生成双键位移产物4a和4d.4a经碱性醇解生成一对2, 4-异构体2b和3b.2-甲基-4-芳酰氧基-1,5-苯并硫氮杂(2e-2g)在苯中光照主要经Fries重排生成2-甲基-3-芳酰基-1,5-苯并硫氮杂-4(5H)-酮(5e-5g).同时还生成少量2,4-异构化产物2-芳酰氧基-4-甲基-1,5-苯并硫氮杂(3e-3g).但2-甲基-4-烷基酰氧基-1,5-苯并硫氮杂(2i,2j)在相同条件下光照只生成2,4-异构化产物-2-烷基酰氧基-4-甲基-1,5-苯并硫氮杂(3i,3j).2-甲基-4-对硝基苯甲酰氧基-1,5-苯并硫氮杂(2h)可发生热Fries重排,生成2-甲基-3-对硝基苯甲酰基-1,5-苯并硫氮杂-4(5H)-酮(5h).化学和光谱数据证明5e-5h和6e-6h为互变异构体.     

新型含2-苯基-1,2,3-三唑基的1,5-苯并硫氮杂革及其β-内酰胺衍生物的合成

α,β-不饱和酮(1a～1e)与邻氨基苯硫酚反应,得到含2-苯基-1,2,3-三唑基的1,5-苯并硫氮杂革(2a～2e),然后以其为原料与烯酮"现场"进行[2+2]环加成,合成出一系列含2-苯基-1,2,3-三唑基的β-内酰胺并合的1,5-苯并硫氮杂革衍生物(3a～3j).产物经1H NMR,IR,元素分析及MS加以确证.     

2-甲基-1,5-苯并硫氮杂的基态和激发态反应的研究 I: 2-甲基-1,5-苯并硫氮杂-4(5H)-酮的卤化和亲核取代反应

2-甲基-1,5-苯并硫氮杂-4(5H)-酮(1a)与不同的氯化试剂-五氯化磷、三氯氧磷和氯化砜在不同的条件下氯化,可分别生成:2-甲基-4-氯-1,5-苯并硫氮杂(2a)、2-氯-4-甲基-1,5-苯并硫氮杂(3a)、2-二氯甲基苯并噻唑(5)、2-三氯甲基苯并噻唑(6)和2-甲基-1,5-苯并硫氮杂-4(5H)-酮盐酸盐(4).2-甲基-4-氯-1,5-苯并硫氮杂与醇钠反应生成相应的2-甲基-4-烷氧基-1,5-苯并硫氮杂外,还可以分离到它的2,4-异构体,2-烷氧基-4-甲基-1,5-苯并硫氮杂.产物的结构均经元素分析、红外光谱、^1H和^1^3C核磁共振谱和质谱鉴定.     

2-甲基-6-(3-甲基-2-丁烯基)对苯二醌的合成

以邻甲基苯酚为原料,与1-氯-2-甲基-2-丁烯反应生成2-甲基-6-(3-甲基-2-丁烯基)苯酚,然后催化氧化得到目标产物2-甲基-6-(3-甲基-2-丁烯基)对苯二醌。该合成路线简单,易于操作,最终收率51%。     

无外加催化剂条件下邻取代芳香醛与5,5-二甲基-1,3-环己二酮的反应研究

在DMF溶剂中,不外加催化剂使邻取代芳香醛(1)与5,5-二甲基-1,3-环己三酮(2)发生缩合和加成反应生成3,3,6,6-四甲基-4a-羟基-9-芳基-1,8二氧化-2,3,4,4a,5,6,7,8,9a-十氢化-1H氧杂蒽(3a～3d)。在同样条件下,邻羟基芳香醛与5,5-二甲基-1,3-环己三酮则发生缩合,加成和脱水反应生成3,3-二甲基-9-(5,5-二甲基-3-羟基-2-环己烯-1-酮-2-基)-1-氧代-2,3,4,9-四氢化-1 氧杂蒽(4a～4b)。用单晶X-射线分析法确定了产物3a和4a的晶体结构。     

2-烷氧羰基烷基/正丁基-4-芳基-1,5-苯并硫氮杂类化合物的合成及抑菌活性的研究

设计、合成了三类2位取代-1,5-苯并硫氮杂衍生物:2-烷氧羰基甲基-4-芳基-1,5-苯并硫氮杂、2-烷氧羰基乙基-4-芳基-1,5-苯并硫氮杂和2-正丙基-4-芳基-1,5-苯并硫氮杂.所有目标化合物结构经过元素分析,IR,MS,HRMS及1H NMR确证.研究了2-烷氧羰基烷基/正丁基-4-芳基-1,5-苯并硫氮杂的合成反应条件,测定了目标化合物的抑真菌活性.通过对该类化合物抑真菌活性的评价,进一步明确乙酯基在1,5-苯并硫氮杂1的生物活性中所起的作用.     

2-甲基-1,5-苯并硫氮杂(艹卓)的基态和激发态反应的研究 Ⅲ.2-甲基-1,5-苯并硫氮杂(艹卓)-4(5H)-酮与4-甲基-1,5-苯并硫氮杂(艹卓)-2(3H)-酮间的互变异构

Ried和Marx曾报道邻氨基硫代苯酚与乙酰乙酸乙酯或二烯酮反应分别合成了2-甲基-1,5-苯并硫氮杂(艹卓)-4(5H)-酮(la)和4-甲基-1,5-苯并硫氮杂(艹卓)-2(3H)-酮(lb)。但有关这两个化合物的结构鉴定除可查到la的红外光谱数据外,它们的~1HNMR和~13CNMR数据均未见报道     

1,3-偶极环加成合成新型含2-苯基-1,2,3-三唑基-1,5-苯并硫氮杂(艹/卓)噁二唑并合衍生物

α,β-不饱和酮(1a～1e)与邻氨基苯硫酚反应, 得到含2-苯基-1,2,3-三唑基1,5-苯并硫氮杂(艹/卓)(2a～2e), 然后以此化合物为原料同1,3-偶极子氧化腈"现场"发生1,3-偶极环加成, 合成出一系列含2-苯基-1,2,3-三唑基的1,2,4-(口恶)二唑并合的1,5-苯并硫氮杂衍生物(3a～3j). 产物经元素分析、 IR、 1H NMR及MS加以确证.     

HEPT类化合物的QSAR研究

为定量结构／活性相关性研究提取了量子化学参数,拓扑指数Am,分子连接性指数^mxt及疏水性常数,同时应用正交变换和最佳变量子集算法（Leaps-and-Bonds)进行了变量压缩和选择,进而实施了多元回归分析,并由此结果进行了HEPT类化合物（1－[(2-hydroxyethoxy)methyl]-6-(phenylthio)-thymine derivatives)的结构／活性关系的理论解释,进行了人工神经网络法对于该类化合物的活性预测,其结构明显好于多元回归法。     

Effect of the pH of the medium on the chemical shifts in the PMR spectra and on the distribution of the π-electron density

The dependence of the chemical shifts of the ring protons on the pH of the medium for a number of 4-hydroxyquinoline derivatives was studied by means of PMR spectroscopy. The dipolar and uncharged hydroxy forms exist in equilibrium in aqueous solutions. The effect of intramolecular hydrogen bonding on the character of the dependence of the chemical shift on the pH of the medium in the case of 3-piperidinomethyl-4-hydroxyisoquinoline was investigated. The possibility of the separate protonation of the ring nitrogen and the side-chain nitrogen in 3-piperidinomethyl-4-hydroxyisoquinoline was established. The distribution of the -electron density in 4-hydroxyisoquinoline is in good agreement with its chemical behavior.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 11, pp. 1546–1549, November, 1971     

Effect of the pH of the medium on the chemical shifts in the PMR spectra and on the distribution of the π-electron density

The dependence of the chemical shift of the ring protons on the pH of the medium for a number of 3-hydroxyquinoline derivatives was studied by PMR spectroscopy. The regions of ionization of the molecules, which correspond to the ranges of acidic, neutral, and alkaline media, were found. In D₂O, 3-hydroxyquinoline is present only in the uncharged hydroxy form. The presence of intramolecular hydrogen bonding in 4-dimethylaminomethyl-3-hydroxyquinoline has a substantial effect on the character of the dependence of the chemical shift on the pH of the medium; the existence of separate protonation of the nitrogen atoms of the ring and the side chain of 4-dimethylaminomethyl-3-hydroxyquinoline was established. The distribution of the -electron density in the 3-hydroxyquinoline molecule is in good agreement with its chemical behavior during electrophilic substitution.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 11, pp. 1540–1545, November, 1971.     

On the theory underlying the Car-Parrinello method and the role of the fictitious mass parameter

The theory underlying the Car-Parrinello extended-Lagrangian approach to ab initio molecular dynamics (CPMD) is reviewed and reexamined using "heavy" ice as a test system. It is emphasized that the adiabatic decoupling in CPMD is not a decoupling of electronic orbitals from the ions but only a decoupling of a subset of the orbital vibrational modes from the rest of the necessarily coupled system of orbitals and ions. Recent work [J. Chem. Phys. 116, 14 (2002)] has pointed out that, due to the orbital-ion coupling that remains once adiabatic decoupling has been achieved, a large value of the fictitious mass mu can lead to systematic errors in the computed forces in CPMD. These errors are further investigated in the present work with a focus on those parts of these errors that are not corrected simply by rescaling the masses of the ions. It is suggested that any comparison of the efficiencies of Born-Oppenheimer molecular dynamics (BOMD) and CPMD should be performed at a similar level of accuracy. If accuracy is judged according to the average magnitude of the systematic errors in the computed forces, the efficiency of BOMD compares more favorably to that of CPMD than previous comparisons have suggested.     

液滴荧光传感与计算机联用技术在微量分析中的应用

通过在LS55型荧光-磷光-发光分光光度计上加装液滴产生及调节附件,采用计算机采集与分析处理数据,成功地研制了双通道液滴光化学传感装置.利用葡聚糖凝胶对复合维生素B中不同组分的选择性吸附来达到分离与同时检测的目的,并将其用于复合维生素B药片的分析,取得了满意的结果.     

On the volume-dependence of the index of refraction from the viewpoint of the complex dielectric function and the Kramers-Kronig relation

How indices of refraction n(omega) of insulating solids are affected by the volume dilution of an optical entity and the mixing of different, noninteracting simple solid components was examined on the basis of the dielectric function epsilon(1)(omega) + iepsilon(2)(omega). For closely related insulating solids with an identical composition and the formula unit volume V, the relation [epsilon(1)(omega) - 1]V = constant was found by combining the relation epsilon(2)(omega)V = constant with the Kramers-Kronig relation. This relation becomes [n(2)(omega) - 1]V = constant for the index of refraction n(omega) determined for the incident light with energy less than the band gap (i.e., h omega < E(g)). For a narrow range of change in the formula unit volume, the latter relation is well approximated by a linear relation between n and 1/V.