甲氧氯普胺与紫色素的荷移反应及其测定

研究了甲氧氯普胺与紫色素之间的荷移反应。确定了反应条件,建立了一种快速简便测定甲氧氯普胺的荷移分光光度法。实验表明,甲氧氯普胺与紫色素在乙醇介质中,室温条件下即可形成稳定的1∶1型荷移络合物,该络合物的λmax=540 nm,表观摩尔吸光系数为4.32×103L.mol-1.cm-1。测定结果的相对标准偏差为0.45%(n=6),回收率为98.3%~105.1%。     

阿替洛尔与紫色素的荷移反应研究

采用光度法研究了电子给予体阿替洛尔与电子接受体紫色素之间的荷移反应,据此建立了荷移光度法测定阿替洛尔含量的方法。实验表明,阿替洛尔与紫色素在乙醇介质中,室温条件下即可形成稳定的1∶1型荷移络合物,该络合物的最大吸收波长为542nm,表观摩尔吸光系数为6.17×103L.mo-l1.cm-1。阿替洛尔的质量浓度在0~35 mg.L-1范围内符合比尔定律,相关系数为0.9993。当阿替洛尔的质量浓度为20 mg.L-1时,测定结果的相对标准偏差(n=6)为0.78%。采用本法测定片剂中阿替洛尔的含量,平均回收率在98.9%~101.6%之间。     

紫色素荷移分光光度法测定阿奇霉素

提出了紫色素荷移分光光度法测定阿奇霉素。在乙醇介质中,阿奇霉素与紫色素生成的荷移络合物在546nm处产生一个强的吸收峰。在最佳反应条件下,吸光度与阿奇霉素的质量浓度在8.0~120mg·L-1范围内呈线性关系,检出限(3s/k)为2.6mg·L-1。该法用于分析市售阿奇霉素片剂,测定值与标示值相符。加标回收率在98.8%~101%之间,测定值的相对标准偏差(n=5)在1.7%~2.4%之间。     

克拉霉素与紫色素的荷移反应及其测定

建立了一种测定克拉霉素的荷移分光光度法。克拉霉素与紫色素在乙醇溶液中发生电荷转移反应,荷移络合物在548nm处有最大吸收,表观摩尔吸光系数是4.49×103L·mol-1·cm-1,该络合物的组成是1∶1;稳定常数是3.48×104;药物浓度在10~150mg/L范围内服从比耳定律。当克拉霉素浓度为100mg/L时,6次测定结果的相对标准偏差为1.2%。利用本法测定了克拉霉素制剂中有效成分的含量,并与文献法进行比较,二者结果基本吻合,回收率在97.0%以上。     

罗红霉素与紫色素的荷移反应及其测定

建立了一种测定罗红霉素的方便而快捷的荷移分光光度法。罗红霉素与紫色素在乙醇介质中发生电荷转移反应 ,荷移络合物在 5 4 4nm处有最大吸收 ;表观摩尔吸光系数是 6 .5 6× 10 3L·mol- 1 ·cm- 1 ,该络合物的组成是 1∶1,稳定常数是 3× 10 4 。药物浓度在 0～ 12 0mg L范围内服从比耳定律。当罗红霉素浓度为 5 0mg L时 ,5次测定结果的相对标准偏差为 1.3%。利用本法测定了罗红霉素胶囊中有效成分的含量 ,并与文献法进行比较 ,二者结果基本吻合 ,回收率在 96 %以上。     

琥乙红霉素与紫色素的荷移反应及其测定

建立了一种快速测定琥乙红霉素的荷移分光光度法。琥乙红霉素与紫色素在乙醇-水介质中发生电荷转移反应,荷移络合物在546 nm波长处有最大吸收,表观摩尔吸光系数为9.18×103L.mol-1.cm-1,络合物的组成为1∶1,稳定常数为1.9×105。药物质量浓度在0~90 mg.L-1范围内服从比耳定律,相关系数为0.999 7,当琥乙红霉素质量浓度为40 mg.L-1时,6次测定结果的相对标准偏差为1.24%。测定了琥乙红霉素片剂中有效成分的含量,并与药典方法进行比较,结果基本吻合。     

奥硝唑与氯醌酸的荷移反应研究

研究了奥硝唑与氯醌酸在正丙醇介质的荷移反应,建立了一种快速简便测定奥硝唑的荷移分光光度法.在室温下,荷移反应生成2∶1的荷移络合物,最大吸收波长为534nm,表观摩尔吸光系数为ε=1.08×104 L·mol-1·cm-1.奥硝唑的浓度在5.0~83mg/L范围内服从比尔定律,相关系数r=0.999 3,相对标准偏差为1.3%~2.1%,回收率为99.1%~101.7%.     

司帕沙星与茜素红荷移反应的研究

采用紫外分光光度法研究了π电子受体茜素红与电子给予体司帕沙星的荷移反应。确定了反应条件,建立了一种快速简便灵敏准确测定司帕沙星的荷移分光光度法。结果表明,司帕沙星与茜素红在(4+6)乙醇-水介质中,室温条件下即可形成1∶1稳定的荷移络合物,该络合物的最大吸收波长为530 nm,表观摩尔吸光系数为4.8×103L.mol-1.cm-1,司帕沙星药物质量浓度在6~160mg/L范围内服从比尔定律,r=0.9991。当该法用于片剂中司帕沙星的测定时,回收率为99.75%~100.00%,相对标准偏差为1.4%(n=10)。     

基于氯冉酸荷移分光光度法测定乙酰螺旋霉素含量

研究了乙酰螺旋霉素和氯冉酸在甲醇介质中发生的荷移络合反应,确定了最佳条件,从而建立了一种简便快速测定乙酰螺旋霉素的荷移分光光度法。荷移络合物的最大吸收波长为λ=531 nm,络合比为1∶1,该络合物的吸光度与乙酰螺旋霉素的浓度在1.2～20 mg/L范围内呈线性关系,线性相关系数r=0.9998,检出限为0.5 mg/L,相对标准偏差为1.2%,回收率为99.5%～101.2%。本方法用于对乙酰螺旋霉素片含量的测定,结果较为满意。     

阿替洛尔与醌茜素的荷移反应研究

研究了阿替洛尔与醌茜素之间的荷移反应。阿替洛尔作为电子给体,醌茜素作为电子受体,两者在乙醇-水介质中反应生成荷移络合物。该络合物的λmax=568nm,表观摩尔吸光系数为7.91×103L.mol-1.cm-1,阿替洛尔药物质量浓度在0～30mg/L范围内服从比耳定律,相对标准偏差为0.92%(n=6)。应用本法测定了片剂中阿替洛尔的含量,回收率为98.9%～101.6%。     

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%.     

Synthesis of 1-benzyloxypyrazin-2(1H)-one derivatives

Different approaches for the synthesis of 1-benzyloxypyrazin-2(1H)-one derivatives from simple amino acids have been investigated. A library of 33 precursors for the preparation of N-hydroxy pyrazinones was obtained in moderate to good yields.     

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.     

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.     

A general and convenient synthesis of 4-(tosylmethyl)semicarbazones and their use in amidoalkylation of hydrogen,heteroatom, and carbon nucleophiles

A general synthesis of previously unknown semicarbazone-based α-amidoalkylating reagents, 4-(tosylmethyl)semicarbazones, has been developed. The synthesis involved three-component condensation of semicarbazones of aliphatic or aromatic aldehydes with the same or other aldehydes and p-toluenesulfinic acid. The scope and limitations of this reaction were investigated. The compounds obtained were demonstrated to be an efficient α-(4-semicarbazono)alkylating agents. They were reacted with H- (sodium borohydride), O- (sodium methylate), S- (sodium phenylthiolate), N- (pyrrolidine, sodium succinimide), P- (trialkyl phosphites), and C-nucleophiles (sodium diethyl malonate) to give the corresponding products of the tosyl group substitution, 4-substituted semicarbazones, including analogues of nitrofurazone. Among the prepared compounds tested in vitro for antibacterial and antifungal activity, three nitrofuryl-containing semicarbazones exhibited high biological activities with minimum inhibitory concentration (MIC) values of 8–32 μg/mL.     

Sulfur-directed metal-free and regiospecific methyl C(sp3)–H imidation of thioanisoles

Regiospecific and direct imidation of the methyl C(sp³)–H bond of thioanisoles is realized under mild and metal-free conditions with N-fluorobis(benzenesulfonyl)imide as an oxidant and nitrogen source. Proposed mechanism suggests that thionium ion intermediates and a Pummerer-type reaction are involved. The imidation has advantages such as high step-economy, excellent functionality tolerance, and regiospecificity, giving structurally diverse imidation products.     

Synthesis of novel chiral bidentate hydroxyalkyl-N-heterocyclic carbene ligands and their application in palladium-catalyzed Mizoroki–Heck couplings and asymmetric addition of diethylzinc to benzaldehyde

A small library of new chiral bidentate hydroxyalkyl-imidazolium salts 1 is conveniently synthesized on multi-gram scale from inexpensive and commercially available chiral pool amino acids. The corresponding carbenes, generated by deprotonation of imidazolium salts 1, in combination with palladium(II) chloride were tested in the Mizoroki–Heck coupling reaction. The most significant results in terms of yields and reactivities were achieved with low catalyst loading. The catalytic activities of these imidazolium salts were also investigated in the asymmetric addition of diethylzinc to benzaldehyde. The use of MgO nanoparticles as an additive in conjunction with these ligands played a crucial role in increasing the efficiency of these reactions.