在阳离子型表面活性剂CTMAB 存在下1,4-双肼酞嗪与微量钴显色反应的研究

在PH 7～8的磷酸盐缓冲溶液中,Co(Ⅱ)与1,4-双肼酞嗪(DHPH)在表面活性剂CTMAB存在下生成紫红色配合物,其组成比为o:DHPH= 1:1,最大吸收在510nm,表观摩尔吸光系数为2.2×10~4L.mol-1·cm-1,不稳定常数为2.1×10~-5,5～45μg Co/25ml范围内符合比尔定律,用于某些药物中微量钴的测定,结果较为满意。     

环境水样中痕量肼的荧光分析

基于在硫酸介质中，肼与罗丹明6G反应，使其荧光增强，建立了一种荧光测定痕量肼的新方法。该方法线性范围2．0－14．0μg/L，检出限为0．62μg/L。可用于环境水样中肼含量的测定，并进行了回收实验，回收率为97％－107％。     

钒与新显色剂 1,4-双肼酞嗪显色反应的研究及应用

研究了钒与新显色剂 1,4-双肼酞嗪的显色反应.在 pH 5.8 的 HAc-NaAc 缓冲溶液中,加入溴化十六烷基三甲铵于 60℃加热 10 min,钒与 1,4-双肼酞嗪形成稳定的螯合物,λmax=422nm,ε422=1.32×104 L·mol-1·cm-1,钒的浓度在 0 μg/25 mL～20 μg/25 mL 范围内符合比耳定律,检出限为 15 ng/mL,已用于测定钢样中的微量钒.     

氯代十六烷基吡啶存在下钯与1,4—双肼酞嗪新显色反应的研究

本文研究了１，４－双肼酞嗪（ＤＨＰＨ）与钯的配合显色反应，在阳离子型表面活性剂氯代十六烷吡啶存在下，在０．１～０．２ｍｏｌ／ＬＨＣｌ溶液中，试剂与钯形成１：１的稳定的亲黄绿色配合物，最大吸收峰在４００ｎｍ处，表观摩尔吸光系数为２．６×１０＾４。钯量在０～５０μｇ／２５ｍＬ范围内股从比尔定律，方法简便快速，选择性好，已用于催化剂中钯的测定，结果满意。     

氯代十六烷基吡啶存在下钯与1，4－双肼酞嗪新显色反应的研究

本文研究了１，４－双肼酞嗪（ＤＨＰＨ）与钯的配合显色反应，在阳离子型表面活性剂氯代十六烷基吡啶存在下，在０．１～０．２ｍｏｌ／ＬＨＣｌ溶液中，试剂与钯形成１：１的稳定的黄绿色配合物，最大吸收峰在４００ｎｍ处，表观摩尔吸光系数为２．６×１０￣４，钯量在０～５０μｇ／２５ｍＬ范围内股从比尔定律，方法简便快速，选择性好，已用于催化剂中钯的测定，结果满意。     

反相高效液相色谱同时测定复方降压药中三组分

建立了一种反相高效液相色谱法 ,用于同时测定复方降压药中三组分。采用YWGC1 8柱 ,以甲醇 醋酸 醋酸钠缓冲液 水 ( 60∶2 0∶2 0 )为流动相 ,流速为 0 .8mL·min- 1 ,二极管阵列检测器于检测波长 2 60nm测定。硫酸双肼酞嗪、氢氯噻嗪和氨苯喋啶的线性范围分别为 0 .0 8～ 1 .1mg/mL ,0 .0 1～ 0 .30mg/mL ,0 0 3～ 0 .45mg/mL ,检测限分别为 0 0 0 6mg/mL ,0 0 0 1mg/mL ,0 0 0 1mg/mL ,已用于北京降压0号样品的测定     

流动注射-化学发光法测定阿莫西林

阿莫西林在硫酸溶液中的降解产物与Ce(Ⅳ)在罗丹明6G的增敏作用下可产生化学发光。据此建立了流动注射化学发光测定阿莫西林的新方法。该方法线性范围为0.01～20.0mg·L~(-1),检出限为0.008mg·L~(-1),相对标准偏差(n=11,C=1.0mg·L~(-1)为0.7％。方法用于药物中阿莫西林含量的测定,结果满意。     

用反相高效液相色谱法测定人体血浆中盐酸氟桂利嗪含量

采用反相高效液相色谱法以桂利嗪为内标测定人体血浆中盐酸氟桂利嗪的含量.以V甲醇:V乙腈:V缓冲液=58:20:22的体系为流动相,用hypersilBDSC8不锈钢色谱柱、紫外检测器(检测波长254nm),血浆样品经乙酸乙酯萃取处理后进样测定.血浆中盐酸氟桂利嗪的含量在5～300μg/L范围内与盐酸氟桂利嗪的峰面积和桂利嗪的峰面积之比呈线性关系(r=0.9997),方法对盐酸氟桂利嗪的平均回收率为83.3%～85.0%,检出限为3μg/L(S/N=3).用该法测定了12名单次口服30mg西比灵(盐酸氟桂利嗪)胶囊的健康志愿者血浆中盐酸氟桂利嗪含量.结果表明,该药在血浆中含量平均达峰时间为(2.67±0.91)h,平均峰质量浓度为(154.9±66.0)μg/L.该法适用于盐酸氟桂利嗪药代动力学的临床监测和研究.     

间接原子吸收光谱法测定甲基硫酸新斯的明

建立了原子吸收光谱法间接测定甲基硫酸新斯的明的方法。在pH5．0溶液中，当四苯硼钠过量时可完全沉淀甲基硫酸新斯的明，在滤液中加入过量的KCl沉淀剩余的四苯硼钠，再测定滤液中的过量的钾，可以计算得到甲基硫酸新斯的明的质量分数。方法回收率在97％～103％之间，相对标准偏差为1．5％。     

药物中水合肼残留量的气相色谱分析

建立了用气相色谱-氮磷检测器(GC-NPD)测定药物中水合肼的新方法。其萃取和衍生采用同一种试剂-丙酮,一步完成,可简单快速地定量检测药物中水合肼的残留量,其检出限为41.0μg/kg;相对标准偏差小于4.1%;回收率在101.5%~107.8%。已用于药物中水合肼的残留量分析。     

二氧化碳和丙烯直接合成甲基丙烯酸的NiPMo/TiO2催化剂的研究

用溶胶-凝胶法以磷钼酸(MPA)的镍盐溶液水解钛酸四丁酯制备了NiPMo/TiO2催化剂.使用ICP、 XRD、 TG-DTA、 IR、 TPD-MS和微反应技术研究了催化剂的化学组成、热稳定性、化学吸附性质和催化反应性能.杂多钼酸盐与TiO2通过O2-在TiO2表面发生了键合.在623 K下,杂多阴离子仍保持原有的Keggin结构.CO2在Lewis酸位Ni(Ⅱ)和Lewis碱位Ni-O-Mo的桥氧协同作用下生成CO2卧式吸附态Ni(Ⅱ)←O-(CO)←(O--Ni).丙烯有多种吸附态在催化剂上吸附.在563 K、 1 MPa和空速1500 h-1的反应条件下,丙烯的摩尔转化率为3.2%,产物MAA选择性为95%.     

Toward new camptothecins. Part 6: Synthesis of crucial ketones and their use in Friedländer reaction

In the context of the preparation of camptothecin and luotonin A analogs, the synthesis of some key keto-precursors and their use in Friedländer condensation are described. This paper also focuses on the stability of these keto intermediates and emphasizes the major differences between indolizinones and pyrroloquinazolinones series. Noteworthy is also the report of some original structures isolated as by-products of some experiments.     

α-Amino acid derived enaminones and their application in the synthesis of N-protected methyl 5-substituted-4-hydroxypyrrole-3-carboxylates and other heterocycles

A new and simple synthesis of novel N-protected methyl 5-substituted-4-hydroxypyrrole-3-carboxylates, which exist in equilibrium with their 4-oxo tautomers, has been developed in two steps starting from N-protected α-amino acids. The key intermediates are enaminones, which can also be isolated, characterized, and used for the construction of other functionalized heterocycles, before they spontaneously decompose to pyrrole products. 4-Hydroxypyrroles are prone to partial aerial oxidation but can be efficiently alkylated or reduced to stable polysubstituted pyrrolidine derivatives.     

Specific intramolecular aromatic CH insertion of diazosulfonamides

The chemoselectivity in the intramolecular CH insertion of various diazosulfonamides has been experimentally studied. The results reveal that the aliphatic 1,4-, 1,5-, or 1,6-C(sp³)?H insertions of diazosulfonamides are not accessible, while the aromatic 1,5-C(sp²)?H insertion can be realized specifically by adjusting the diazo-adjacent group. In addition, the general chemoselectivities in the intramolecular CH insertions of diazosulfonyl compounds are summarized. Generally, diazosulfones undergo both aromatic 1,5-C(sp²)?H and aliphatic 1,5- and 1,6-C(sp³)?H insertions, while diazosulfonates undergo aliphatic 1,5- and 1,6-C(sp³)?H insertions. However, diazosulfonamides only undergo aromatic 1,5-C(sp²)?H insertion.     

CoFe2O4自形成磁性液体场致结构化对磁化的影响

The Langevin paramagnetic theory can’t describe the relation between magnetization of ferrofluids and applied magnetic field. The structuralization of ferrofluids, which is considered the main influence factor of the magnetization, is regarded. The part of magnetization works is deposited when the structure is forming. This action influences the magnetization of ferrofluids directly or indirectly. On the base of the “compressing” model, the Langevin function that usually describes the magnetization of ferrofluid is modified, and a well-fitted curve is obtained. An equation of the relation between the equivalent volume fraction after being “compressed” and the intensity of magnetic field is discovered, which approximately describes the process of magnetization. The relation between the approximate initial susceptibility and the volume fraction can be obtained from modified formula.     

KMnO4-mediated oxidative CN bond cleavage of tertiary amines: Synthesis of amides and sulfonamides

KMnO₄-mediated oxidative CN bond cleavage of tertiary amines producing secondary amine was introduced, which was trapped by electrophiles (acyl chloride and sulfonyl chloride) to form amides and sulfonamides. The reaction could take place at mild condition, tolerating a wide range of function groups and affording products in moderate to excellent yields.     

Highly regioselective Buchwald–Hartwig amination at C-2 of 2,4-dichloropyridine enabling a novel approach to 2,4-bisanilinopyridine (BAPyd) libraries

The highly regioselective Buchwald–Hartwig amination at C-2 of the cheap and readily accessible reagent, 2,4-dichloropyridine with a range of anilines and heterocyclic amines is described. This new methodology is robust and provides a facile access to 4-chloro-N-phenylpyridin-2-amines on 0.25 mol scale. These intermediates undergo a further Buchwald–Hartwig amination at higher temperature to enable rapid exploration of the chemical space at C-4 and to provide a library of 2,4-bisaminopyridines.     

Chemistry of heterocyclic compounds at the A. E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences, over 50 years (Review)

The review contains a concise historical account and information on the most significant researches undertaken by the staff at the A. E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences on the Chemistry of Heterocyclic Compounds. Dedicated to Academician of the Russian Academy of Sciences B. A. Trofimov on his 70th jubilee. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1443–1502, October, 2008.     

N-Heterocyclic carbene-palladacyclic complexes: synthesis,characterization and their applications in the C-N coupling and α-arylation of ketones using aryl chlorides

N-Heterocyclic carbene-palladacyclic complexes 3 were successfully achieved in a one-pot procedure under mild conditions. The structure of 3a was unambiguously confirmed by X-ray single crystal diffraction and it was an active catalyst in the Buchwald-Hartwig amination and α-arylation of ketones even at very low catalyst loadings (0.01?mol%).     

Iodine-mediated oxidative Pictet-Spengler reaction using terminal alkyne as the 2-oxoaldehyde surrogate for the synthesis of 1-aroyl-β-carbolines and fused-nitrogen heterocycles

An efficient iodine-mediated oxidative Pictet-Spengler reaction in dimethyl sulphoxide (DMSO) using terminal alkynes as the 2-oxoaldehyde surrogate for the synthesis of aryl (9H-pyrido[3,4-b]indol-1-yl)methanones is described. The scope of the protocol includes the total synthesis of Fascaplysin, Eudistomins Y₁ and Y₂. The methodology is extended for preparing pyrrolo[1,2-a]-quinoxaline and indolo[1,5-a]quinoxaline derivatives. The utility of 1-aroyl-β-carbolines was demonstrated by performing palladium-catalyzed β-carboline directed ortho-C(sp2)-H functionalization of the phenyl ring with thiomethyl (SMe) group using DMSO as source and for accessing 4-aryl-canthin-6-ones.