(S)-4-羟基吡咯烷-2-酮的简便合成

(S)-3-羟基-γ-丁内酯开环制得手性3,4-二羟基丁酸甲酯(2);对2的伯羟基进行对甲苯磺酰化、仲羟基进行苄基保护得4-对甲苯磺酰氧基-3-苄氧基丁酸甲酯(5);5在氨甲醇作用下合环、脱苄基保护合成了(S)-4-羟基吡咯烷-2-酮,总收率26%,其结构经1HNMR和HR-MS确认,比旋光值与文献值相符。     

(2R,4S)-4-甲基-2-哌啶甲酸乙酯的合成

以S-(-)-α-苯乙胺为原料,经一锅法制得1-(1-苄基)-6-乙氧羰基-4-甲基-3,4-二氢哌啶(3),收率58.7%。以10%Pd/C为催化剂,3经催化氢化脱苄合成了4-甲基-2-哌啶甲酸乙酯(4),收率96%;4通过减压分馏得(2R,4S)-4,含量95%,其结构经1H NMR,IR和MS确证。     

(3S,6S)-及(3S,6R)-3-苄氧甲基-6-甲基-吗啉-2,5-二酮的 制备及其晶体结构

以2-溴丙酸和N-叔丁氧羰基-O-苄基-L-丝氨酸为起始试剂首先制得N-(2-溴丙基)-O-苄基-L-丝氨酸(BPBS), 在N,N-二甲基甲酰胺(DMF)/三乙胺(Et3N)溶剂中80 ℃经9 h后BPBS发生分子内环化反应生成(3S,6S)-3-苄氧甲基-6-甲 基-吗啉-2,5-二酮[(3S,6S)-BMMD]及(3S,6R)-BMMD共存体, 产率70%. 将所制得的共存体以乙酸乙酯为重结晶溶剂, 采用微分重结晶法, 经4次“溶解-部分重结晶”操作循环制得两种纯光学构型的(3S,6S)-BMMD和(3S,6R)-BMMD. 将两种光学纯双手性中心的BMMD分别溶于乙酸乙酯, 室温下培养得(3S,6S)-BMMD和(3S,6R)-BMMD的单晶体, 以X射线衍射法测定上述两种BMMD的分子结构.     

(2S,3S)-1,2-环氧基-3-叔丁氧酰胺基-4-苯丁烷的合成

以(S)-苯丙氨酸为原料,经氨基保护、与对硝基苯酚成酯后与硫叶立德反应制得(S)-1-氯-3-叔丁氧酰胺基-4-苯基-2-丁酮(3);3经Meerwein-Poondrf-Verley还原、环合等反应合成了HIV-1蛋白酶抑制剂的关键中单体——(2S,3S)-1,2-环氧基-3-叔丁氧酰胺基-4-苯丁烷,总收率约45%,其结构经1H NMR和MS确证。     

(S)-(4-溴-2-甲苯)(3-甲基吗啉)甲酮的合成

以(S)-2-氨基丙醇和氯乙酰氯为起始原料,经酰化和环合反应制得(S)-5-甲基吗啉-3-酮（4）; 4经还原制得(S)-3-甲基吗啉(5); 5与4-溴-2-甲基苯甲酸酰化缩合合成了(S)-(4-溴2-甲基苯基)(3-甲基吗啉)-甲酮,总收率57%,其结构经¹H NMR 和 ¹³C NMR确证。     

（3S）-2,2-二甲基-3-苄氧基癸酸的合成

以(R)-pantolactone为原料，经还原、羟基保护、环合、开环、脱保护、氧化等8步反应，合成了(3S)-2，2-二甲基-3-苄氧基癸酸，总收率为40．0％．     

HIV-1 RT抑制剂研究I.1,3-二苄基-6-(3,4-环氧丁基)尿嘧啶的合成

报道了1,3-二苄基-6-(3,4-环氧丁基)尿嘧啶的合成新方法.以6-甲基尿嘧啶(1)为起始物,经1,3-二苄基-6-甲基尿嘧啶(2)及未见文献报道的1,3-二苄基-6-(3-丁烯基)尿嘧啶(3)和1,3-二苄基-6-(3-羟基-4-溴丁基)尿嘧啶(4),首次高收率合成了1,3-二苄基-6-(3,4-环氧丁基)尿嘧啶(5),并对其化学结构进行了表征.     

4-(4-吗啉)哌啶盐酸盐的合成

4-甲酸乙酯哌啶与溴苄反应,再经酰胺化和氨化反应制得关键中间体4-氨基-1-苄基哌啶(5);5与2,2-二溴二乙醚经环化反应制得N-苄基-4-(4-吗啉)哌啶,再经成盐,加氢合成了4-(4-吗啉)哌啶盐酸盐(1,总收率24.9%),1的结构经1HNMR,IR和GC-MS确认。     

5-[4-羟(氨)基苄基]-2-硫代-2,4-咪唑啉二酮磺酸酯(酰胺)的合成及其生物活性

以5-(4-羟基/氨基苄基)-2-硫代-2,4-咪唑啉二酮为原料,在三乙胺作傅酸剂的条件下与取代磺酰氯反应,得到28个新的5-(4-羟基/氨基苄基)-2-硫代-2,4-咪唑啉二酮苯磺酸酯/酰胺类化合物,它们的化学结构经1H NMR,MS和元素分析确证.初步生测结果表明:在100μg/mL浓度下,部分目标化合物均对供试植物病原菌和油菜显现出一定的抑制活性,如5-(4-氨基苄基)-2-硫代-2,4-咪唑啉二酮对碘苯磺酰胺(4d)对黄瓜灰霉病菌抑制率为80.7%,5-(4-羟基苄基)-2-硫代-2,4-咪唑啉二酮邻甲基苯磺酸酯(3n)和5-(4-氨基苄基)-2-硫代-2,4-咪唑啉二酮-2,4-二氯苯磺酰胺(4m)对油菜的生长抑制率分别为87.4%和81.5%.     

D-脯氨酸催化的(3S,4S)-4-氨基-3-羟基-5-苯基戊酸衍生物的合成

报道了一条合成(3S,4S)-4-氨基-3-羟基-5-苯基戊酸(Ahppa)衍生物的新路线。以氨基保护的L-苯丙氨酸为起始原料,依次经Weinreb胺缩合、还原、aldol缩合及溴仿4步反应合成了3个Ahppa衍生物,总收率5.8%~6.7%,其结构经¹H NMR, ¹³C NMR和ESI-MS确证。对反应条件进行了探讨,结果表明：催化剂D-脯氨酸用量对反应收率影响不大,对立体选择性影响较大;氨基上保护基体积较大有利于提高反应立体选择性。     

(4R,5S)-5-羟基-4-甲基-3-己酮的合成

农业害虫药材甲Stegobium panicem Linnae在我国各省区都有分布,主要危害谷类、食品、药材、图书、档案等.我国一般每年可以发2～3代,温度较高的地区可发生4代[1] .     

Multi-stage Ordered Mesoporous Carbon-graphene Aerogel-Ni3S2/Co4S3 for Supercapacitor Electrode

Transition metal sulfides have emerged as promising materials in supercapacitor. In this work, we firstly developed an interface-induced superassembly approach to fabricate NiS_x and CoS_x nanoparticles, which based on ordered mesoporous carbon-graphene aerogel composites for supercapacitor electrodes. The obtained multi-component superassembled nanoparticles-carbon matrix composites have controllable 3D porous structure of multi-stage composite. The two-dimensional graphene interlaced to form a 3D framework with large sponge-like pores, and then the graphene surface was loaded with mesoporous carbon with mesoporous pore size and vertical orientation. The composites display high specific capacitance of 958.1 F g⁻¹ at 0.1 A g⁻¹. The capacitance retains about 97.3 % after 3000 charging-discharging cycles at 2 A g⁻¹. These results indicate that the obtained OMC−GA−Ni₃S₂/Co₄S₃ is a promising material for electrochemical capacitors, which providing new technical methods and ideas for the research of new energy and analytical sensor materials in the fields of energy storage, photocatalysis, point-of-care testing devices and other fields.     

Ir2S3/ZnIn2S4催化下可见光诱导发生的烯烃/炔烃的高效硫氢化反应:Ir2S3的作用

C–S键的构建在化学中具有非常重要的意义.利用硫醇和烯烃/炔烃的硫氢化反应来构建C?S键是一种绿色、可持续和低成本的方法.本文以ZnCl₂,InCl₃,硫代乙酰胺为前驱体,在微量IrCl₃存在条件下,通过一步溶剂热法制备得到了含有不同Ir摩尔比(0.5 mol%,1 mol%和2 mol%)的Ir₂S₃/ZnIn₂S₄纳米复合材料,并考察了它在可见光下诱导烯烃/炔烃的硫氢化反应中的催化性能.以苄基硫醇和苯乙炔的硫氢化反应为模型反应,发现在ZnIn₂S₄中引入微量的Ir₂S₃可明显提升其性能,其中以0.5 mol%Ir₂S₃/ZnIn₂S₄为催化剂时反应性能最佳;反应15 h后苄基硫醇的转化率为97%,苄基苯乙烯基硫醚的产率为95%,明显高于以未修饰的ZnIn₂S₄为催化剂时的转化率和产率.在反应中加入自由基捕获剂TEMPO之后可淬灭该反应,表明与未修饰的ZnIn₂S₄相同,以Ir₂S₃/ZnIn₂S₄复合材料催化的硫氢化反应同样是由硫醇自由基诱发的反应.这种微量Ir₂S₃对ZnIn₂S₄上光诱导硫氢化反应的提升作用在所考察的多个系列底物的反应中都有不同程度的体现,尤其对于一些空间体积较大的底物,其提升作用尤为明显,表明微量Ir₂S₃的存在对ZnIn₂S₄上光诱导硫醇和烯烃/炔烃硫氢化反应的提升作用具有普适性.通过研究负载不同助催化剂(MoS₂,NiS和Pd)的ZnIn₂S₄纳米复合材料在烯烃/炔烃硫氢化反应中的性能及其电化学交流阻抗,我们发现,Ir₂S₃的存在可促进ZnIn₂S₄上光生电子空穴的分离,从而有利于巯基自由基的生成,同时还抑制了副物氢气的产生,因此,烯烃/炔烃的硫氢化反应性能显著提高.该文提出了一种在可见光下利用半导体光催化来构建C?S键的绿色途径,对于理解和设计新的光催化有机合成反应体系具有一定的指导意义.     

Ein neues Samariumnitridsulfid: Sm4N2S3

A New Samarium Nitride Sulfide: Sm₄N₂S₃ The oxidation of samarium with sulfur in the presence of SmCl₃ and NaN₃ as nitrogen source (molar ratio: 12:9:4:2, evacuated silica vessel, some NaCl as flux, 850°C, 7 d) yields Sm₄N₂S₃ as lath-shaped, dark red single crystals. The by-products (NaCl and NaSm₂Cl₆) are rinsed with water from the crude product. The crystal structure of Sm₄N₂S₃ (monoclinic, C2/m (no. 12), Z = 2, a = 1 318.04(12), b = 391.57(2), c = 1 031.76(9) pm, β = 130.874(6)°, R = 0.036, R_w = 0.031) contains two crystallographically different Sm³⁺, both in sixfold coordination of the anions. Besides distorted octahedra [(Sm1)N₃S₃] and [(Sm2)NS₅], tetrahedra [(N^3?)(Sm)] connected via two cis-oriented edges to form chains [N(Sm1)_3/3(Sm2)_1/1]³⁺ build up the Mayn structural feature. These are arranged in the fashion of a closest packing of rods and held together by two crystallographically different S^2? anions which take care for charge neutrality and three-dimensional interconnection.     

Synthesis of (3S,4R)-bengamide E

（3S,4R）-Bengamide E（2） was synthesized starting from D-glucono-δ-lactone（3） and the key deoxygenation step from 13 to 15 was achieved by the application of NaBH₃CN and ZnI₂.Compared with natural bengamide E（1）,the synthetic compound（35,4R）-bengamide E（2） was inactive against the cell growth of HUVEC and cancer cells.These data represent the significance of the stereochemistry at C-3 and C-4 of bengamides for structural recognition and binding with the target（s）.     

Enhanced Supercapacitor Performance Using a Co3O4@Co3S4 Nanocomposite on Reduced Graphene Oxide/Ni Foam Electrodes

To avoid an enormous energy crisis in the not-too-distant future, it be emergent to establish high-performance energy storage devices such as supercapacitors. For this purpose, a three-dimensional (3D) heterostructure of Co₃O₄ and Co₃S₄ on nickel foam (NF) that is covered by reduced graphene oxide (rGO) has been prepared by following a facile multistep method. At first, rGO nanosheets are deposited on NF under mild hydrothermal conditions to increase the surface area. Subsequently, nanowalls of cobalt oxide are electro-deposited on rGO/Ni foam by applying cyclic-voltammetry (CV) under optimized conditions. Finally, for the synthesis of Co₃O₄@Co₃S₄ nanocomposite, the nanostructure of Co₃S₄ was fabricated from Co₃O₄ nanowalls on rGO/NF by following an ordinary hydrothermal process through the sulfurization for the electrochemical application. The samples are characterized by using X-ray diffraction (XRD) and scanning electron microscopy (SEM). The obtained sample delivers a high capacitance of 13.34 F cm⁻² (5651.24 F g⁻¹) at a current density of 6 mA cm⁻² compared to the Co₃O₄/rGO/NF electrode with a capacitance of 3.06 F cm⁻² (1230.77 F g⁻¹) at the same current density. The proposed electrode illustrates the superior electrochemical performance such as excellent specific energy density of 85.68 W h Kg⁻¹, specific power density of 6048.03 W kg⁻¹ and a superior cycling performance (86% after 1000 charge/discharge cycles at a scan rate of 5 mV s⁻¹). Finally, by using Co₃O₄ @Co₃S₄/rGO/NF and the activated carbon-based electrode as positive and negative electrodes, respectively, an asymmetric supercapacitor (ASC) device was assembled. The fabricated ASC provides an appropriate specific capacitance of 79.15 mF cm⁻² at the applied current density of 1 mA cm⁻², and delivered an energy density of 0.143 Wh kg⁻¹ at the power density of 5.42 W kg⁻¹.     

Total synthesis of (3R, 4S)-4-hydroxylasiodiplodin

Abstract

An alternative and concise total synthesis of (3?R, 4S)-4-Hydroxylasiodiplodin has been reported from inexpensive and commercially available 6-heptenal and Orsellinic acid starting materials. The key steps involved in the synthesis are Wittig reaction, Sharpless epoxidation, Yamaguchi esterification and ring-closing metathesis (RCM).     

Association of （S）-Isoserine Derivatives and 2,2,4-Trimethyl-3-hydroxy-4- cyclohexenecarboxylate

IntroductionOptimization of leading structures is an importantsector in the study and exploitation of medicine, andthe association of 2,2,4-trimethyl-3-hydroxyl-cyclohex-4-enecarboxylic acid (1) and isoserine derivatives isone of the best methods for the …     

ZnIn2S4/g-C3N4复合材料的制备及可见光催化制氢性能

采用水热方法制备了ZnIn₂S₄/g-C₃N₄复合材料, 并通过X射线衍射(XRD)、 傅里叶变换红外光谱(FTIR)、 紫外-可见漫反射光谱(UV-Vis DRS)、 透射电子显微镜(TEM)和荧光光谱(PL)等手段对其结构和性能进行表征. 结果表明, 当ZnIn₂S₄的负载量为20%(质量分数)时, 复合材料表现出最佳的光催化制氢性能, 制氢速率可达到637.08 μmol·g^-1·h^-1, 分别为纯ZnIn₂S₄和纯g-C₃N₄的4倍和37倍. 其原因在于ZnIn₂S₄和g-C₃N₄之间具有紧密的异质结结构, 两者有效的结合改善了组分的能带匹配和界面电荷转移, 从而大幅增强了载流子的分离和迁移, 进而提高光催化的性能.