N-Boc-氨基噻吩的相转移催化N-烷基化

N-Boc-氨基噻吩的相转移催化N-烷基化;N-Boc-氨基;噻吩;N-烷基化;相转移催化     

N-Boc-氨基噻吩的相转移催化N-烷基化

N-Boc-氨基噻吩的相转移催化N-烷基化;N-Boc-氨基;噻吩;N-烷基化;相转移催化     

相转移法制备金属纳米粒子研究进展

相转移法是可控合成纳米金属粒子的一种简便、有效而重要的方法。通过相转移试剂的作用,水相中制备得到的大量金属纳米粒子在稳定剂的包裹下能够几乎完全转移到有机相当中。所得到的金属纳米粒子尺度均匀,形貌独特,结构稳定。本文综述了相转移方法制备金属纳米粒子的发展、动向以及相转移剂和稳定剂的应用情况。     

微波辐射相转移催化制备高取代N-烷基化壳聚糖

微波辐射相转移催化制备高取代N-烷基化壳聚糖;壳聚糖;烷基化;微波辐射;相转移催化     

相转移催化法合成对位和间位苯二甲酰基硫脲衍生物

酰基硫脲化合物;相转移催化合成;相转移催化法合成对位和间位苯二甲酰基硫脲衍生物     

新型相转移催化剂的合成及其催化水解反应研究

相转移催化(PTC)技术是70年代初发展起来的应用在有机合成中的新技术。由于相转移催化剂能使反应速度加快,产率明显提高,反反化学通报1,2年第,期此,近年来相转移催化这一技术发展很快。高分子相转移催化剂,由于它具有在反应完毕后容易分离     

季鏻盐型三相相转移催化剂的制备及其化学结构与相转移催化活性的关系

 使用两种 ω-氯代酰氯 (氯乙酰氯与氯丁酰氯) 对交联聚苯乙烯微球 (CPS) 进行 Friedel-Crafts 酰基化反应,使用 1,4-二氯甲氧基丁烷对 CPS 微球进行氯甲基化反应, 分别将可交换的氯引入 CPS 微球表面, 制备了化学改性的 CPS 微球. 然后使用三苯基膦对改性微球进行季鏻化反应, 制备了间隔臂 (spacer arm) 长度不同的三种季鏻 (QP) 盐型三相相转移催化剂 QP-CPS. 考察了主要反应条件对制备过程的影响, 并以氯化苄与乙酸钠合成乙酸苄酯的反应体系作为三相相转移催化的模型体系, 初步考察了 QP-CPS 的相转移催化活性,探索了催化剂结构与相转移催化活性的关系. 结果表明, 季鏻盐的化学稳定性较差,在制备过程中需控制反应时间与温度, 且宜选用极性较高的溶剂. 季鏻盐型三相相转移催化剂 QP-CPS 对乙酸苄酯的合成具有较高的催化活性, 在液-固-液之间可有效地实现反应物种乙酸根的转移. 与季铵盐 (QN) 型三相相转移催化剂 QN-CPS 相比, 季鏻盐型三相相转移催化剂 QP-CPS 具有更高的相转移催化活性. 间隔臂越长, QP-CPS 的相转移催化活性越高, QP-CPS 的亲水和亲油性能对相转移催化活性也有很大的影响.     

逆向相转移催化在有机合成中的应用

系统地总结了逆向相转移催化在有机合成中的应用,逆向相转移催化的作用在于逆向相转移催化剂能将底物分子从有机相转移至水相中发生反应,着重介绍了几种典型的逆向相转移催化剂如吡啶及其衍生物;杯芳烃;环糊精及其衍生物,水溶性过渡金属配合物在有机合成中的应用。     

杂多阴离子的相转移化学（Ⅳ）：杂多阴离子与NO的配位反应

杂多阴离子的相转移化学（Ⅳ）──杂多阴离子与ＮＯ的配位反应王恩波，刘霞，王作屏，许林，高丽娟（东北师范大学化学系，长春，１３００２４）关键词杂多阴离子，相转移，ＮＯ配位Ｐｏｐｅ等［１］发现表面含有配位水分子的杂多阴离子可以在相转移作用下转移到非极性溶...     

聚合物生物碱相转移催化剂的合成及其对多类化学反应的催化性能

聚合物生物碱相转移催化剂的合成及其对多类化学反应的催化性能黄锦霞，陈家威，蒋济隆，卢军（湖北大学化学系，武汉４３００６２）（广西师范大学化学系，南宁５３０００１）关键词相转移催化剂，聚合物，生物碱，三相催化，不对称反应相转移催化反应是有机合成中较为活...     

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.     

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.     

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.     

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.     

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.     

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.     

Selective syntheses of 2H-1,3-oxazines and 1H-pyrrol-3(2H)-ones via temperature-dependent Rh(II)-carbenoid-mediated 2H-azirine-ring expansion

The Rh(II)-catalyzed reaction of 2-carbonyl-substituted 2H-azirines with ethyl 2-cyano-2-diazoacetate or 2-diazo-3,3,3-trifluoropropionate provides an easy access to 2H-1,3-oxazines and 1H-pyrrol-3(2H)-ones. These compounds can be selectively prepared from the same starting material using temperature as the only varied parameter. The 2-azabuta-1,3-diene intermediate, a common precursor for both heterocyclic products, isomerizes into 2H-1,3-oxazine under kinetic control, while 1H-pyrrol-3(2H)-one is the sole product of the reaction at elevated temperatures. According to DFT-calculations a one-atom oxazine ring contraction involving ring-opening to a 2-azabuta-1,3-diene intermediate, followed by a 1,5- and 1,2-prototropic shift leads to the consecutive formation of imidoylketene and azomethine ylide, which then further undergo cyclization to the pyrrole derivative.     

Copper catalyzed/mediated synthetic methodology for ebselen and related isoselenazolones

Scope of the copper catalyzed/mediated selenium-nitrogen coupling reaction has been studied for the synthesis of isoselenazolones. It is noticed that the 2-chloro, 2-bromo-, and 2-iodo-aryl amides substrates can be exploited in the selenium-nitrogen coupling reaction by employing 25-100 mol % of CuI/1,10-phenanthroline (L) and potassium carbonate as a base in DMF. Furthermore, electron rich 2-chloro-arylamides also underwent selenium-nitrogen coupling reaction to give biologically important selenium-nitrogen heterocycles. Also, copper-catalyzed selenium-nitrogen coupling reaction has been meticulously applied for the synthesis of diaryl diselenides having methoxy, amine, and amide functionality from respective aryl iodides in the presence of stoichiometric amount of succinimide as an external Se-N coupling partner.