新型荧光试剂N-9-吖啶-α-氨基酸的合成及表征

新型荧光试剂N-9-吖啶-α-氨基酸的合成及表征;荧光试剂; N-吖啶-α-氨基酸; 合成;表征     

N-(6-甲基-2-亚甲基吡啶)-( )-樟脑亚胺体系的不对称烷基化反应

目前,不对称合成光学活性化合物取得了较大进展,不对称合成α-氨基酸、β-氨基醇、α-取代苄胺的报道很多。但是,不对称合成生物碱类物质——α-取代氨甲基吡啶类化合物还未见文献报道,而此类化合物有潜在的应用前景。为此,我们以( )-樟脑为手性试剂     

β-氨基酸的合成: 等当体方法的应用

β-氨基酸是一类在药物开发和生物研究中有广泛应用的中间体. 由等当体合成β-氨基酸的方法具有结构定制、合成产物丰富、直观等特点, 是β-氨基酸合成领域中不可或缺的合成方法. 重点介绍近年来该领域具有代表性的工作.     

α-氟-β-氨基酸酯的合成

采用简易方法从取代苯乙酮出发制得α-氟-β-脱氢氨基酸酯;在N,N-二甲基甲酰胺存在下用三氯硅烷将其还原,高收率和非对映选择性地合成了α-氟-β-氨基酸酯,其结构经1H NMR,13C NMR和MS确证。     

固-液相转移催化合成 Ⅳ.α-甲基丝氨酸及其它氨基酸

利用活化了的氨基酸酯,通过烷基化反应合成α-氨基酸是近年来使用的简便方法。特别是以苯甲醛与简单的氨基酸酯反应生成的Schiff碱为底物,用固-液相转移催化烷基化反应合成a-氨基酸,不仅条件温和,而且操作简便,原料易得,选择性好。我们采用上述方法成功地合成了α-甲基     

基于手性18-冠-6-四羧酸络合作用的毛细管电泳分离β-氨基酸对映体

以D-(-)-酒石酸和一缩二乙二醇为原料,合成了(-)-18-冠-6-四羧酸(18C6H4),并将18C6H4作为手性添加剂,应用于β-氨基酸对映体的毛细管电泳分离。考察了背景电解质溶液(BGE)中18C6H4的浓度、BGE pH值、BGE组成、有机改性剂及运行电压等因素对分离的影响。在优化的分离条件下,即BGE的组成为10 mmol/L18C6H4,10 mmol/LTris,pH2.20,紫外检测波长为254 nm,所测试的5种β-氨基酸的出峰时间均在25 min内,分离因子1.04~1.08,分离度0.46~1.52。结果表明该方法简便快速,可方便地用于β-氨基酸对映体的分离和分析。     

3-(1′-烃氧亚氨基)乙基-4-羟基吡咯啉-2-酮类衍生物的合成与生物活性

以氨基酸乙酯为原料合成8种3-乙酰基-4-羟基吡咯啉-2-酮的类似物A, A与3种烃氧基胺盐酸盐反应合成了20个肟醚类衍生物3-(1'-烃氧亚氨基)乙基-4-羟基吡咯啉-2-酮(B), 其结构经 1H NMR, MS, IR和元素分析表征. 初步生物活性测定结果表明合成的化合物B具有一定的除草活性和抑制真菌活性.     

2-硫代-4-咪唑啉二酮的合成与表征

咪唑啉酮衍生物是一类线粒体呼吸抑制剂,对果树黑斑病及由卵菌引起的霜霉病、疫病等的活性很好。2-硫代-5-苯基亚甲基4-咪唑啉二酮衍生物不能用通法制取,其起始原料烯基氨基酸不稳定。本文用三组分串联aza-Wittig堍反应合成2-硫代-3-烷基-5-苯基亚甲基4-咪唑啉二酮类化合物。合成路线如下：     

从N-Fmoc-L-α-氨基酸合成对应的同系物N-Fmoc-L-β-氨基酸(Ⅰ)

描述了以重氮甲烷为重氮化试剂,以商品易得的N-Fmoc-L-α-氨基酸为原料,成功地运用Arndt-Eistert合成,仅通过两步反应,就高产率地合成了8个对应的同系物N-Fmoc-L-β-氨基酸的方法。     

一种合成α-硫代-β-氨基酸酯的新方法

以β-烯胺酯和N-硫代-丁二酰亚胺为原料,溴化铜为催化剂,经氧化偶联反应制得5个新型α-硫代-β-脱氢氨基酸酯(3a~3e);3经氢化硅烷化反应,合成了5个α-硫代-β-氨基酸衍生物(4a~4e),其结构由1H NMR表征。在最佳反应条件(3 0.1 mmol,三氯硅烷2.0 eq.,DCE 1 m L,于室温反应12 h)下,4a收率97%。     

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.     

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.     

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.