手性溶剂萃取分离顺式二氯菊酸对映体

研究了顺式二氯菊酸(cis-PA)对映体在含有酒石酸酯手性选择体的水-1-2-二氯乙烷两相溶液中的萃取分配行为,考察了有机相种类、L-酒石酸酯浓度、水相pH、L-酒石酸酯烷基链长度和萃取温度等因素对萃取分离效果的影响.结果表明,L-酒石酸酯与II对映体形成的复合物稳定性比与I对映体形成的复合物要好;1.2-二氯乙烷作为有机相效果较好;随着L-酒石酸酯浓度的增大,分配系数K逐渐增大,而分离因子α先增大然后开始减小;随着pH的增大,K和α都降低;L-酒石酸酯烷基链长度及萃取温度对K和α有较大影响.     

反式第一菊酸对映体的手性选择剂立体选择性分离

研究反式第一菊酸(trans-CA)对映体在含有手性选择剂酒石酸酯的水-有机相双相体系中的萃取分配行为,考察有机相的种类、酒石酸酯烷基链长度、水相的pH值和酒石酸酯的浓度对分配系数K和分配因子α的影响.研究结果表明:1,2-二氯乙烷作为有机相效果较好,D-酒石酸酯与( )-反式第一菊酸对映体形成的复合物稳定性比与(-)-反式第一菊酸对映体形成的复合物稳定性要大,而L-酒石酸酯的萃取性能与此相反,它与(-)-反式第一菊酸对映体形成的复合物稳定性比与( )-反式第一菊酸对映体形成的复合物稳定性要大.酒石酸酯取代烷基链长对分配系数K和分离因子α有很大影响;分配系数K和分离因子α均随pH的升高而降低;分配系数K随着酒石酸酯浓度的增大而增大,分离因子α先随浓度增大而稳定上升,后随浓度增大而缓慢下降.     

疏水性L-酒石酸酯立体选择性萃取分离氯噻酮对映体

研究了氯噻酮对映体在含有疏水性L-酒石酸酯手性选择体的水-1,2-二氯乙烷两相系统萃取分配行为,考察了pH、L-酒石酸酯烷基链长度、L-酒石酸酯浓度和磷酸盐浓度对分配系数和分离因子的影响。实验表明：L-酒石酸酯与氯噻酮I( )-对映体比与Ⅱ(-)-对映体形成更稳定的非对映体复合物;随着L-酒石酸酯取代烷基链长的增长,分配系数和分离因子增大;随着pH增大,分配系数增大,而分离因子降低;同时,L-酒石酸酯和磷酸盐浓度影响也比较大。     

酒石酸酯立体选择性萃取分离功夫菊酸对映体

研究了功夫菊酸对映体在含有手性选择剂酒石酸酯的水-有机相双相体系中的萃取分配行为,考察了水相的pH、酒石酸酯的浓度、磷酸盐浓度、温度和酒石酸酯烷基链长度对分配系数(K)和分离因子(α)的影响.研究结果表明:分配系数(K)随pH的升高而降低,随着酒石酸酯浓度的增大而增大,分离因子(α)随pH的升高和酒石酸酯浓度的增大先增加后降低,pH和酒石酸酯浓度分别为5.50和0.30 mol/L时取得较好的分离效果;分配系数(K)和分离因子(α)都随磷酸盐浓度增大而减小;温度、取代烷基链长对分配系数(K)和分离因子(α)亦有较大影响.     

立体选择性萃取分离反式DV菊酸对映体

研究了反式DV菊酸对映体在含有手性选择体酒石酸酯的水-有机相双相体系中的萃取分配行为,考察了有机稀释剂种类、酒石酸酯的浓度、温度、水相的pH值、酒石酸酯烷基链长度对分配系数(D)和分配因子(α)的影响.研究表明:三氯甲烷作稀释剂时萃取分离效果较好;温度升高使分配系数增大,分离因子减小;分配系数随pH的升高而降低,随着酒石酸酯浓度的增大而增大,分离因子随pH的升高和酒石酸酯浓度的增大先增加后降低,pH和酒石酸酯浓度分别为4.50和0.40mol/L时取得较好的分离效果;取代烷基链长对分配系数(D)和分离因子(α)亦有较大影响.     

双相(O/W)识别手性萃取分离α-环己基扁桃酸对映体

提出一种新的手性分离技术双相(O/W)识别手性萃取. 研究了α-环己基扁桃酸对映体在D(L)-酒石酸异丁酯1,2-二氯乙烷有机相和β-环糊精衍生物水相萃取体系中的分配行为; 考察了β-环糊精衍生物种类和浓度、酒石酸酯构型和浓度、水相pH 值等因素对萃取性能的影响. 实验结果表明, 双相(O/W)识别手性萃取具有很强的手性分离能力, 羟丙基β-环糊精、羟乙基β-环糊精、甲基β-环糊精均对S-α-环己基扁桃酸对映体的识别能力大于对R-α-环己基扁桃酸对映体的识别能力, 其中以羟丙基β-环糊精的识别能力最强; 而D-酒石酸异丁酯的识别能力刚好相反; 在羟丙基β-环糊精和D-酒石酸异丁酯萃取体系中, α-环己基扁桃酸外消旋体一次萃取分离后, 水相中S-对映体e.e.%达到27.6%, R-和S-对映体的分配系数(k_R和k_S)分别为2.44和0.98, 分离因子(α)达2.49; 同时pH值和萃取剂浓度对手性分离能力有显著影响. 双相(O/W)识别手性萃取对外消旋体化合物的制备性分离有着十分重要的意义.     

二(2-乙基己基)磷酸与酒石酸衍生物复合萃取拆分扁桃酸外消旋体

本文研究了扁桃酸对映体在含二(2-乙基己基)磷酸(D2EHPA)与酒石酸衍生物复合手性选择剂的正辛醇-水两相体系中的萃取分配行为,考察了酒石酸衍生物的种类和初始浓度、D2EHPA的初始浓度、扁桃酸的初始浓度、萃取温度对分配系数和分离因子的影响.结果显示,复合手性选择剂能提高分配系数和分离因子,D2EHPA与D-酒石酸衍生物的复合手性选择剂与L-扁桃酸对映体比与D-扁桃酸对映体形成更稳定的非对映体复合物;且D2EHPA与二对甲基苯甲酰酒石酸(DTTA)的复合手性选择剂的手性选择性大于D2EHPA与二苯甲酰酒石酸(DBTA)的复合手性选择剂;同时,扁桃酸的初始浓度、萃取温度对分配系数和分离因子的影响较大.     

手性酯类萃取剂萃取拆分α-环己基扁桃酸外消旋体

研究了α-环己基扁桃酸对映体在含有疏水性D酒石酸酯手性选择体的1,2-二氯乙烷和水两相系统萃取分配行为,考察了酒石酸酯烷基链长度、pH值和D酒石酸酯浓度对分配比和分离因子的影响。实验表明：D酒石酸酯与R-α-环己基扁桃酸对映体比与S—α-环己基扁桃酸对映体形成更稳定的非对映体复合物;随着pH值增大,分配比减小,分离因子也随之降低;同时,D酒石酸酯浓度的影响也比较大。     

疏水性L-酒石酸酯萃取分离特非那丁对映体

研究了特非那丁对映体在含有疏水性L-酒石酸酯的1,2二氯乙烷溶液及甲醇水溶液两相中的萃取分配行为,考察了不同烷基链长的L-酒石酸酯,L-酒石酸酯的浓度,有机溶剂的种类,及其溶解特非那丁的甲醇水溶液浓度对分配系数K和分离因子α的影响。实验表明:L-酒石酸酯与特非那丁Ⅱ对映体形成的复合物稳定性比与特非那丁Ⅰ对映体形成的复合物稳定性要大,三类有机溶剂的萃取性能为醇>1,2二氯乙烷>烷烃;甲醇的浓度在50%~90%时,随着溶解特非那丁的甲醇水溶液中的甲醇浓度的增加,分配系数和分离因子均降低;当甲醇的浓度为50%时,可以得到最佳的K和α;随着L-酒石酸酯的浓度的提高,分配系数K和α分离因子先增加然后减小;当L-酒石酸酯的浓度约为0.25 mol/L时,K和α达到最大值;L-酒石酸酯的碳链长度对分配系数K和分离因子α也有很大的影响。     

酮洛芬对映体的双相识别手性萃取分离

研究了酮洛芬在溶有酒石酸酯的有机相和β-环糊精衍生物水相萃取体系中的分配行为;考察了有机溶剂、酒石酸酯、环糊精衍生物的种类、萃取剂浓度和pH等因素对分离效果的影响。结果表明,β-环糊精衍生物优先识别S-对映体而不是R-对映体,但L-酒石酸酯的识别能力刚好相反;1,2-二氯乙烷作为有机溶剂,三甲基-β-环糊精和L-酒石酸异丁酯做手性萃取剂是最好的选择;萃取剂的浓度和pH对分离效果有明显影响;当三甲基-β-环糊精和L-酒石酸异丁酯的浓度分别为0.1mol/L和0.2mol/L、水相pH=2.5时,分离效果最好。     

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.