基于分子内旋转受限原理的线性共轭小分子的AIE性能研究

研究了6个线性共轭化合物4-丁基联苯(L1)、4,4’-二异丙基联苯(L2)、5,5’-二甲基-2,2’-联吡啶(L3)、2-([1,1’-联苯]-4-)噻吩(L4)、1,1’-联萘(L5)和5-苯基-2,2’-联噻吩(L6)的紫外-可见光谱和荧光发射光谱。结果表明,化合物L1、L2和L3均具有聚集诱导发光(AIE)性能,化合物L4、L5和L6则不具有AIE性能。该研究结果表明,二联苯(或两个简单芳杂环相连)系列化合物具有AIE性能,分子内旋转受限(RIR)是该系化合物产生AIE现象的机理。但是在二联苯的结构基础上继续增加链的长度,或者引入体积更大的芳环(萘环),化合物不再具有AIE性能。     

1,1,1-三氯-2-取代肼基-3-硝基丙烷及其衍生物的合成

叙述了以1,1,1-三氯-2-乙酰氧基-3-硝基丙烷和1,1,1-三氯-2-肼基-3-硝基丙烷为原料,合成脂肪和芳香肼类、酰肼类、偶氮类以及腙类等四十三个新化合物的方法,将N-芳基-N'-[2-(1,1,1-三氯-3-硝基)丙基]肼用N-溴代丁二酰亚胺氧化成1,1-二氯-2-芳偶氮基-3-硝基丙烯后,不经分离直接加入过量的醇和定量的水继续反应,可方便地获得β-硝基丙酮酸酯腙类化合物,收率达60%以上。初步抑菌活性测定结果表明,大多数化合物呈现不同程度的抑菌活性,其中以肼类和偶氮类化合物的活性最高,丙酮酸酯腙类化合物次之。     

2-芳基-3-N-乙酰基-5-(4-甲氧苯基)-1,3,4-噁唑啉类化合物的合成

4-甲氧基苯甲酰肼与芳醛反应得到相应的酰腙(2),2与乙酸酐脱水环化合成了标题化合物,其结构经1H NMR,IR,MS和元素分析表征。     

2-芳基-3-N-丙酰基-5-(4-硝基苯基)-1,3,4-噁唑啉类化合物的合成与表征

4-硝基苯甲酰肼与芳醛反应得到相应的酰腙(2),2与丙酸酐脱水环化合成了标题化合物,其结构经1H NMR,IR,MS和元素分析表征。     

对甲苯磺酰胺基乙酰腙类化合物的生物活性及其量子化学计算

以对甲苯磺酰氯为原料, 通过与氨基乙酸反应得到中间体对甲苯磺酰氨基乙酸, 再经酯化、肼解得到对甲苯磺酰氨基乙酰肼, 然后与相应的醛缩合得一系列对甲苯磺酰胺基乙酰腙类化合物. 其结构经元素分析, IR, 1H NMR和13C NMR确证. 采用量子化学方法, 在DFT-B3LYP/6-31G*水平上计算了标题化合物4a～4g的反应热、电荷分布和前线轨道能级. 初步生物活性试验结果表明该系列部分化合物在不同浓度下对植物的生长调节表现出一定的规律性.     

芳基磺酰和亚磺酸类化合物参与的偶联反应研究进展

芳基磺酰和亚磺酸类化合物参与的偶联反应是近年来发展起来的一类高效的合成方法.芳基磺酰氯、芳基亚磺酸(钠),芳基磺酰肼等可以作为脱硫性芳基化、芳磺酰化和还原性芳硫化的试剂合成各种联芳烃、芳基砜类化合物和芳基硫醚化合物.综述了近几年芳基磺酰类化合物参与的偶联反应研究发展,结合本课题组的工作,探讨了该类化合物在C—C键、C—SO2键和C—S键的构筑方面的新应用和新进展.     

3-N-丙酰基-2-芳基-5-(2-碘苯基)-1,3,4-噁唑啉类化合物的合成

2-碘苯甲酰肼与芳醛反应得到相应的酰腙(1),1再与丙酸酐脱水环化合成了3-N-丙酰基-2-芳基-5-(2-碘苯基)-1,3,4-噁唑啉类化合物,其结构经1H NMR,IR,MS和元素分析表征。     

三桥联杯[6]酰腙衍生物和相关化合物的合成

以杯[6]芳烃和杯[6]-1,4-冠-4为起始原料,经过醚化引入酯基,接着用水合肼肼解得到杯[6]酰肼衍生物2和6,然后再与水杨醛进行缩合反应,高产率合成了两例杯[6]酰腙衍生物3和7.化合物6与2倍的二水杨醛乙二醚进行"1+2"缩合反应,得到了一例新型结构的杯[6]-1,4-2,6-3,5-三桥联酰腙衍生物8,产率73%.新化合物2,3,6,7和8的结构经元素分析、红外光谱、质谱、核磁共振谱等证实.     

苯甲酰丙酮苯甲酰腙锰配合物的合成

以氧、氮为配位原子的锰配合物特别是多核配合物由于可作为多种锰蛋白活性部位的模型配合物研究,因此日益受到人们的关注。以β-二酮和芳酰肼形成的腙类化合物(H_2L)可作为三齿配体(ONO)以HL~-和L~(2-)的形式和过渡金属离子配位,但至今未见有关锰配合物的研究报导。本文利用由苯甲酰丙酮和苯甲酰肼缩合而形成的苯甲酰丙酮苯甲酰腙C_(17)H_(16)O_2N_2(H_2L)合成了锰(Ⅲ)配合物Mn(HL)L、Mn(HL)L·H_2O和Mn_2L_2(OCH_3)_2·2H_2O。     

酚酞聚芳醚酮酮环状齐聚物的合成及开环聚合

从4,4’-二氟三苯二酮(DFTBDK)和酚酞出发,利用"拟高稀(pseudo high dillution)"技术,一步法制备酚酞聚芳醚酮酮环状齐聚物(c-PEKK-C),成环率78%。基质辅助激光解吸电离飞行时间质谱MALDI-TOF MS数据表明,聚合产物系聚合度为n=2~8的环状低聚物,其中以二、三聚体为主要成分(占环化产物的85%)。运用J-S高分子环化理论证实4,4’-二氟三苯二酮的单体结构有利于形成环状化合物。以4,4’-联苯二酚钾盐为催化剂,在300~350℃范围内,N2气保护下,环状齐聚物进行熔融开环聚合反应得到相应的线性高相对分子质量酚酞聚芳醚酮酮(ROP-PEKK-C),GPC测得其Mw为1.2×105。     

A new type of calixarene: octahydroxypyridin

A new type of calixarene has been synthesised. Like resorcinol and a number of resorcinol derivatives, 2,6-dihydroxypyridine has been proven to form cyclic tetramers in moderate yields with a number of aliphatic and two aromatic aldehydes in acidic media. The problem of the formation of configurational isomers can be reduced by increasing the reaction temperature and time. With electron-rich aromatic aldehydes, 2,6-dihydroxypyridine unexpectedly yields deep-coloured acyclic quinoid systems. The octahydroxypyridine[4]arenes may have a high potential as receptors for molecular recognition and self organisation.     

Microwave irradiation assisted synthesis, alkylation reaction, and configuration analysis of aryl pyrogallol[4]arenes

A series of aryl pyrogallol[4]arenes were efficiently synthesized in excellent yields by cyclocondensation of pyrogallol with aromatic aldehydes under microwave irradiation. The structures of aryl pyrogallol[4]arenes were confirmed by characterization of their acylated derivatives. Under microwave irradiation, alkylation reactions of aryl pyrogallol[4]arenes with some alkylating reagents such as n-butyl iodide, benzyl chloride, and ethyl α-chloroacetate were also finished quickly to yield fully O-alkylated products. The ¹H NMR spectra and crystal structures showed that the acylated and alkylated aryl pyrogallol[4]arenes existed mainly in rctt (cis-trans-trans) configuration.     

芳香寡聚磺酸酯桥联大环化合物的合成和紫外光谱

以芳香二磺酰氯和芳香二酚为原料,三乙胺作缚酸剂,二氯甲烷作溶剂,采取一步成环法合成了一系列新型的、芳环单元不同的芳香寡聚磺酸酯桥联大环化合物。 合成产物的结构用IR、¹H NMR、¹³C NMR和MALDI-TOF等技术手段进行了确认。 并对合成方法、紫外光谱和变温核磁结构研究进行了有价值的探讨。 化合物3~5的DMF溶液的最大紫外吸收峰在266 nm处,化合物6在267 nm处,摩尔吸光系数分别是4.65×10⁴、5.61×10⁴、5.09×10⁴和9.98×10⁴ L/(mol·cm);检出限分别是2.15×10^-7、1.78×10^-7、1.96×10^-7和1.00×10^-7 mol/L。 变温核磁数据证明,苯环上连有支链有利于固定构象,可以通过这种方法合成结构固定的杯芳烃。     

Encapsulated guest molecules in the dimer of octahydroxypyridine[4]arene

Recently a new type of calix[4]arenes has been synthesized via condensation of 2,6-dihydroxypyridine and a number of aldehydes. This type of pyridine[4]arenes forms capsules consisting of two single pyridine[4]arenes. These capsules can incorporate different guest molecules, like carboxylic acids and amides in this case. We proved that the guest acids really are incorporated inside the cavity of the capsules by electrospray mass spectrometry, NMR spectroscopy, and theoretical calculations.     

A Remote ‘Imidazole’‐Based Ruthenium(II) Para‐Cymene Pre‐catalyst for the Selective Oxidation Reaction of Alkyl Arenes and Alcohols

Herein we disclosed the use of a remote ‘imidazole’‐based precatalyst [(para‐cymene)Ru^II(L)Cl]⁺, C‐1 where L=2‐(4‐substituted‐phenyl)‐1H‐imidazo[4,5‐f]^[1,10] phenanthroline) for the selective oxidation of a variety of alkyl arenes/heteroarenes and alcohols to their corresponding aldehydes or ketones in presence of tert‐butyl hydroperoxide (TBHP). The remote ‘imidazole’ moiety present in the complex facilitates the activation of oxidant and subsequent generation of active species via the release of para‐cymene from C‐1 , which in‐turn was less effective without the ‘imidazole’ moiety. The mechanistic features of C‐1 promoted oxidation of alkyl arenes were also assessed from spectroscopic, kinetic, and few control experiments. The substrate scope for C‐1 promoted oxidation reaction was assessed based on the selective oxidation of 27‐different alkyl arenes/heteroarenes and 25 different alcohols to their corresponding aldehydes/ketones in moderate to good yields.     

Three-Component Reaction of 5,5-Dimethylcyclohexan-1,3-dione,Aromatic Aldehydes,and Acetonitrile in the Presence of Chlorosulfonic Acid Forming N-[(2-Hydroxy-4,4-dimethyl-6-oxocyclohexene-1-yl)-aryl-methyl]-acetamides

A three-component reaction between 5,5-dimethylcyclohexan-1,3-dione (dimedone), aromatic aldehydes, and acetonitrile in the presence of chlorosulfonic acid afforded N-[(2-hydroxy-4,4-dimethyl-6-oxocyclohexene-1-yl)-aryl-methyl]-acetamides in good yields. The temperature-dependent ¹H NMR of one of the products has been investigated.     

Iodine-catalyzed Friedel-Crafts alkylation of electron-rich arenes with aldehydes: efficient synthesis of triarylmethanes and diarylalkanes

Iodine is shown to be an efficient catalyst for the Friedel-Crafts alkylation of arenes with a wide variety of aldehydes in toluene under ‘open-flask’ and mild conditions. In the presence of 10 mol % of iodine, the reaction of arenes with aromatic aldehydes gives the corresponding triarylmethane derivatives (TRAMs), regioselectively, in good to excellent yields. On the other hand, a series of diarylalkane derivatives is synthesized smoothly by the reaction with aliphatic aldehydes.     

含磺胺嘧啶结构单元β-氨基酮的合成及其生物活性

通过原子经济的Mannich反应实现了磺胺嘧啶、1-萘乙酮与芳香醛三组分的连接,直接合成了16个含有磺胺嘧啶结构单元的未见报道的β-氨基酮;所得化合物经¹H NMR、¹³C NMR、HRMS和MS等技术手段确证其结构。 生物活性测试结果显示,在17.04~19.69 nmol/L浓度范围内,所有目标分子的α-葡萄糖苷酶抑制活性很弱,但部分目标分子的过氧化物酶体增殖物激活受体反应元件(PPRE)激动活性较好,最高达到了52%。     

氨基甲酸酯功能化离子液体高效液相色谱固定相的制备与初步评价

合成一种了氨基酸衍生物：4,4′-二苯亚甲基桥联-二[2-(1-咪唑基)-3-苯基丙醇氨基甲酸酯](ImPh-Carb),并将其键合到硅胶上制备了一种新的氨基甲酸酯功能化的离子液体HPLC固定相（ImPh-Carb-Silica）。 利用1H NMR、13C NMR、MS和FTIR对ImPh-Carb进行了表征;通过FTIR和元素分析对ImPh-Carb-Silica固定相进行了表征,根据N含量计算得到ImPh-Carb-Silica的键合量为0.19 mmol/g。 以5种芳烃、5种酚类化合物和4种有机磷农药为分析物,分别在正相和反相色谱模式下对固定相的色谱分离性能进行了评价,同时考察了流动相的变化与溶质保留因子lg k之间的关系。 结果表明,该固定相与溶质分子间存在多重作用力,如疏水、氢键、π-π和偶极-诱导偶极作用等,使其能同时在正相和反相色谱模式下使用;在正相色谱条件下固定相对酚类化合物和有机磷农药表现出较好的分离选择性。     

N‐Trifluoromethylthiosaccharin: An Easily Accessible,Shelf‐Stable,Broadly Applicable Trifluoromethylthiolating Reagent

A new, electrophilic trifluoromethylthiolating reagent, N‐trifluoromethylthiosaccharin, was developed and can be synthesized in two steps from saccharin within 30 minutes. N‐trifluoromethylthiosaccharin is a powerful trifluoromethylthiolating reagent and allows the trifluoromethylthiolation of a variety of nucleophiles such as alcohols, amines, thiols, electron‐rich arenes, aldehydes, ketones, acyclic β‐ketoesters, and alkynes under mild reaction conditions.