新型螺吡喃化合物的合成及应用研究

设计合成了几种新型螺吡喃化合物(SP), 采用¹H NMR, IR 和MS 对其结构进行表征. 研究了目标产物的光致变色性能及其影响因素, 并对SP1 在高分子材料领域的应用作了初步研究. 结果表明: 苯并吡喃环连有强吸电子基时, 最大吸收峰红移; 1 位N原子上连有柔性长链基团时, 热褪色速率较慢; 采用紫外光照射目标产物不同时间, SP1 表现出较好的抗光疲劳性. 分别以SP1 为接枝组分和共混组分制备两种高分子材料SP-g-hPMMA 和SP-m-PMMA, 通过紫外光辐照动力学研究表明, SP-g-hPMMA 和SP-m-PMMA 均表现出比SP1 优异的光致变色性能, 且不影响PMMA 的机械性能. SP1 有望用于高分子光致变色材料领域.     

Synthesis and Fluorescence Properties of Novel Pyrazolo-Isoquinoline Compounds

Russian Journal of General Chemistry - In this study, a series of pyrazoloisoquinoline compounds with novel structures were synthesized by 1,3-dipolar cycloaddition method. The products demonstrate...     

新型席夫碱化合物的合成及其荧光性质

以对硝基氯苯为起始原料,经取代和还原反应制得4-氨基-N,N-二羟乙基苯胺(3);3与芳香醛经缩合反应合成了4个新型的席夫碱衍生物(5a~5d),其结构经1H NMR,13C NMR,IR,MALDI-TOF MS,元素分析和X-射线单晶衍射(5a)表征。利用FL研究了5a~5c的荧光性能。实验结果表明:5a在210 nm波长激发下,在232 nm,283 nm和338 nm出现发射峰;在230 nm波长激发下,5b和5c的发射峰分别位于253 nm和324 nm,258 nm和323 nm。     

快速检测巯基化合物的新方法

本文利用巯基化合物对异硫氰酸荧光素(FITC)的荧光猝灭作用,建立了一种快速检测巯基化合物的新方法。实验中发现,巯基化合物能够猝灭FITC的荧光,据此发展了检测巯基化合物的新方法。本方法的用时非常短,在优化了pH、反应时间等条件后能在5min之内完成对巯基化合物的检测。在最佳条件下对实际样品的测试取得了很好的效果,且具有良好的选择性。对谷胱甘肽(GSH)、高半胱氨酸(Hcy)、半胱氨酸(Cys)、二硫苏糖醇(DTT)的检测限分别达到3.08、2.66、1.28和1.92μmol/L。     

新型1,4-二苯并二氮杂酮类衍生物的合成及其抗癌活性

以取代邻硝基苯甲酸为起始原料,与二氯亚砜反应制得邻硝基苯甲酰氯,再与苯胺在碱性条件下反应制得酰胺衍生物(6a~6d);以醋酸钯为催化剂,6a~6d经NBS溴代制得溴代衍生物(7a~7d); 7a~7d依次经N-烷基化反应,还原反应和分子内C-N键环合反应合成了10个新型的1,4-二苯并二氮杂酮类化合物(10a~10j),产率61%~78%,其结构经¹H NMR, ¹³C NMR和HR-MS(ESI)表征。初步体外活性测试结果表明:10a~10j对非小细胞肺癌细胞（A549）,人乳腺癌细胞（MDA-MB-231）和宫颈癌细胞(HeLa)均有抑制作用。其中,10g和10i对A549, 10g对MDA-MB-231, 10h和10i对HeLa的抑制率大于50%。     

新型苄基氨基甲酸酯类化合物的合成及其抗菌活性

以邻氯苄胺为原料,经6步反应制得中间体2-氯-5-［1-(氧丙炔基亚氨基)乙基］苄基氨基甲酸甲酯（7）;取代芳基肟经氯化后再分别与7经环合反应合成了一系列新型的苄基氨基甲酸酯类化合物（10a~10l）,其结构经¹H NMR表征。初步的抗菌活性测试表明：在用药量为200 mg·L^-1时,大部分化合物对水稻纹枯病显示出较好的抗菌活性,其中10f的抑菌活性最高,抑制率95%。     

具有复合性能的新型三脚架型多苯并咪唑季铵盐类化合物的合成、表征和应用

合成了15种新型三脚架结构苯并咪唑季铵盐类化合物(3a~3o)。 通过IR、NMR和HRMS等技术手段对目标产物(3a~3o)进行了结构表征。 并对目标化合物调节植物生长活性进行了评价。 结果表明, 目标化合物浓度为10 mg/L时, 化合物3a、3c、3f、3g、3h、3i和3j均具有优良的促细胞分裂活性, 最高达88.3%, 比参照物三唑酮(50.2%)的促细胞分裂活性更高, 但生长素活性不明显;目标化合物均具有优异的除草活性, 其中化合物3i效果最明显, 可以达到95.6%。 同时利用荧光光谱, 探究了4种代表性目标分子对人体中常见的6种阴离子的荧光识别, 结果发现目标化合物能较好的识别I^- , 可作为I^-荧光识别探针。     

Synthesis of Novel Indole Schiff Base Compounds and Their Antifungal Activities

A series of novel indole Schiff base derivatives (2a–2t) containing a 1,3,4-thiadiazole scaffold modified with a thioether group were synthesized, and their structures were confirmed using FT-IR, ¹H NMR, ¹³C NMR, and HR-MS. In addition, the antifungal activity of synthesized indole derivatives was investigated against Fusarium graminearum (F. graminearum), Fusarium oxysporum (F. oxysporum), Fusarium moniliforme (F. moniliforme), Curvularia lunata (C. lunata), and Phytophthora parasitica var. nicotiana (P. p. var. nicotianae) using the mycelium growth rate method. Among the synthesized indole derivatives, compound 2j showed the highest inhibition rates of 100%, 95.7%, 89%, and 76.5% at a concentration of 500 μg/mL against F. graminearum, F. oxysporum, F. moniliforme, and P. p. var. nicotianae, respectively. Similarly, compounds 2j and 2q exhibited higher inhibition rates of 81.9% and 83.7% at a concentration of 500 μg/mL against C. lunata. In addition, compound 2j has been recognized as a potential compound for further investigation in the field of fungicides.     

新荧光试剂1-甲酰基苯并三唑缩邻氨基苯酚的合成及其在蛋白质测定中的应用

蛋白质的定量测定对解释蛋白质结构及其作用机制具有重要意义。文献报道的测定方法很多,其中荧光光度法由于灵敏度高、线性范围宽,备受关注。本实验用苯并三唑甲醛、邻氨基苯酚为原料,合成了1-甲酰基苯并三唑缩邻氨基苯酚(FBTP)。以之为荧光探针,用于蛋白质的测定,结果满意。     

High-Energy Phosphonium Compounds and Their Application to Polymer Synthesis

High-energy phosphonium compounds, the N-phosphonium salts of pyridines, were prepared by the oxidation of phosphorous acid and its esters with mercuric salts or halogens in pyridines, or by a hydrolysis-dehydration reaction of diphenyl and triaryl phosphites or phosphonites. These salts are very reactive to nucleophiles, activating carboxyl, amino, or hydroxyl compounds via the corresponding N-phosphonium salts to yield carboxylic amides and esters in high yields on further aminolysis, alcoholysis, and acidolysis. These reactions, especially the hydrolysis-dehydration reactions with phosphites, were successfully extended to the direct polycondensation reaction of dicarboxylic acids with diamines, of free α-amino acids or dipeptides, and of carbon dioxide and disulfide with diamines under mild conditions, yielding linear polymers of high molecular weight (polyamides, polypeptides, polyureas, and polythioureas).     

新型含醚结构噻唑类化合物的合成及其抑菌活性

根据活性基团拼接原理,以对羟基硫代苯甲酰胺和4,4,4-三氟-2-氯乙酰乙酸乙酯为原料,经环化反应制得中间体2-(4'-羟基)苯基-4-三氟甲基-5-噻唑甲酸乙酯(3);3与取代苄基氯或氯乙酸反应合成了5个新型的含醚结构噻唑类化合物(5a~5e),其结构经1H NMR,ESI-MS和元素分析表征。用离体平皿法考察了5a~5e对小麦赤霉病和纹枯病细菌的抑菌活性。结果表明,5a~5e均有一定的抑制活性。其中2-(4'-间氟苄氧基苯基)-4-三氟甲基噻唑-5-甲酸乙酯5c抑菌活性最好,对小麦赤霉病和纹枯病细菌的抑菌活性分别为37.8%和53.3%。     

Synthesis,Fluorescence and Dielectric Properties of Two Novel Compounds Based on Triethylenediamine Derivatives

Two compounds C_8H_(18)N_2Br_3Mn_(0.5)(1) and C_(12)H_(26)N_2Cl_4Mn(2) based on triethylenediamine derivatives were synthesized by solution method and were characterized by elemental analysis, infrared spectroscopy, single-crystal X-ray structure analysis, fluorescence test, circular dichroism(CD) analysis and dielectric measurement, respectively. According to single-crystal X-ray determination, compound 1 crystallizes in the cubic system, space group Pa3 with a = b = c = 13.7246(5) ?, Z = 24, V = 2585.2(3) ?~3; and compound 2 crystallizes in the orthorhombic system, space group P212121 with a = 7.9716(13), b = 15.309(3), c = 15.804(3) ?, Z = 4 and V = 1928.7(6) ?3. Fluorescent analysis of compound 1 showed an intense emission band at 670 nm when the exciting radiation was set at 378 nm and fluorescent analysis of compound 2 showed an intense emission band at 515 nm when the exciting radiation was set at 363 nm. Dielectric constants of compounds 1 and 2 were measured at different frequencies with temperature variation.     

新型硫醇硫组合电极研制及性能测试

把玻璃参比电极、环状的银-硫化银指示电极、以及铂丝屏蔽电极组合形成新型硫醇硫组合电极,研究了在含有0.2 mol/L硫离子的醇-水-氨介质中,在表面活性剂存在下,以环状银电极为阳极,恒定微电流电沉积的方式制备硫化银敏感层的条件。由此法制得的新型硫醇硫组合电极在Ag 浓度为1.0×10-1~1.0×10-5mol/L范围内斜率为59.0±0.5 mV/pC,测量下限为2.2×10-6mol/L,与同类商品电极相比,响应速度快、记忆效应小、重复性好、电位稳定,易于批量生产,具有较强的适应性和应用价值。     

新型1,4-二氢吡啶基尾式卟啉的合成及其抗菌活性研究

以乙酰乙酸乙酯、4-羟基苯甲醛、碳酸氢铵和二溴烷烃为原料,经两步反应合成溴烷氧基1,4-二氢吡啶;再将其与5-对羟基苯基-10,15,20-三苯基卟啉缩合,得到了12种新型的卟啉-二氢吡啶及其金属锌配合物,结构通过NMR,IR和HRMS进行详细表征.研究中测试了这些复杂的卟啉-二氢吡啶化合物对金黄色葡萄球菌(Staphylococcus aureus,ATCC 25923)和大肠杆菌(Escherichia coli,ATCC 25922)的抑菌活性,实验结果显示这12种化合物都有很好的抑菌活性,其中对金黄色葡萄球菌抑菌效果较好,且卟啉-二氢吡啶二元化合物的抑菌效果优于两种单体.     

新型苯并二氮卓类化合物的合成

分别以2-氯-3-硝基吡啶和4,6-二氯-5-硝基嘧啶为起始原料,经取代、还原、Bischler-Napieralski关环和氧化反应合成了新型含酮羰基的吡啶并苯并二氮卓类化合物(6a~6c)和嘧啶并苯并二氮卓类化合物(6d),其结构经1H NMR,13C NMR和ESI-MS表征。并重点考察了氧化反应条件,实验结果表明,合成6a~6c时,用乙腈作溶剂,硅藻土作载体,氧化效果较好;合成6d时,以THF为溶剂、活性炭为载体,效果较好。     

Synthesis of Novel Benzocyclobutene Compounds

Novel benzocyclobutene derivatives, 3-mercaptobicyclo[4.2.0]octa-1,3,5-triene (2), and 3-chlorosulfonylbicyclo[4.2.0]octa-1,3,5-triene (3), have been synthesized in good yields from easily accessible bromobenzocyclobutene 5.     

上转换荧光化合物DMSSB与CSSB的合成、结构与光物理性质

以苯并噻唑为电子受体,以双苯乙烯基为共轭桥链,分别以二甲基胺和咔唑为电子给体合成了2个新的有机化合物DMSSB(反式,反式-2-{4-[(4-N,N-二甲基胺)苯乙烯基]苯乙烯基}-1,3-苯并噻唑)和CSSB(反式,反式-2-{4-[(4-N-咔唑)苯乙烯基]苯乙烯基}-1,3-苯并噻唑).用X射线衍射方法测定了CSSB的晶体结构.用波长为800nm的激光激发时,DMSSB与CSSB在THF中分别发出强的上转换橙色(λ_max=589nm)和蓝绿色荧光(λ_max=488nm).2个化合物在不同溶剂中的光物理数据和理论计算结果表明,苯并噻唑基是一个很好的电子受体.     

Novel Approach to the Synthesis of Phosphorus Sulfur Organic Compounds and Their Metal Complexes

Abstract

The reaction of elemental phosphorus (P_{ti 4}) and sulfur with protonodonor reagents (alcohols, phenols, and thiols) has been studied in the presence of amines and complexes based on trialkyltrithiophosphites and transition metal halides. A novel approach to the synthesis of phosphorus sulfur organic compounds has been proposed on the basis of these reactions.     

各种烯基锆化合物的合成及其在立体选择性合成二(三)取代的烯烃中的应用

烯基锆化合物及硒基烯基锆化合物、锡基烯基锆化合物、磺酰基烯基锆化合物、亚磺酰基烯基锆化合物、硅基烯基锆化合物等金属或杂原子取代的烯基锆化合物 ,可通过锆氢化反应高产率和高选择性地制得 .这些试剂可与各种亲电试剂反应立体选择性地合成二取代或三取代的烯烃化合物