N-(2-苦胺基乙基)单氮杂冠醚的合成

研究并比较了氮支套索型生色冠醚1a和1b两条不同的合成路线, 结果表明, 由N-苦基乙二胺(2)与1,11-二碘-3,6,9-三氧杂十一烷进行N-烷基化环化反应, 可方便地制备N-(2-苦胺基乙基)单氮杂-12-冠-4(1a), 但按此法未能获得更大环的-15-冠-5(1b);若从N-对甲苯磺酰基乙二胺(6)或N-(2-对甲苯磺酰胺基乙基)二乙醇胺(7)出发, 经环化, 脱除对甲苯磺酰基而制得的N-(2-氨基乙基)单氮杂冠醚5a和5b分别与苦基氯反应, 则可获得高产率的生色生色冠醚11a和1b.     

新的酚型开链冠醚及由其衍生的二苯并冠醚的合成

将水杨醛与碱和氯甲基甲基醚反应, 再经过NaBH4还原, 即制得邻(甲氧基甲氧基)苯甲醇, 然后将其在DMF中与NaH和二(或三)甘醇二对甲苯磺酸酯反应, 得开链冠醚1a和1b。1a和1b经稀酸水解, 即脱保护而分别生成新的酚型开链冠醚2a和2b。用2a与二甘醇二对甲苯磺酸酯和NaH在DMF溶液中反应, 合成顺型二苯并-20-冠-6(3); 而2a与环氧氯丙烷在NaOH水溶液中反应, 则合成了17-羟基二苯并-18-冠-5(4)。     

Synthesis and properties of novel thiaarenecyclynes

Novel thiaarenecyclynes 3 and 4 in which two thioether units and two benzene rings are alternately inserted into the single bonds of cyclooctatetrayne are synthesized. Their unique properties are described.     

基于联萘酚的手性冠醚的合成及其晶体结构

以R-或S-联萘酚、2,2′-联苯酚、间苯二酚、氯腈胺为原料合成了六个手性冠醚,所得冠醚的结构均经元素分析、质谱、红外光谱以及核磁共振氢谱和碳谱验证;并利用X射线衍射分析确定了单晶R-3的晶体结构.结果表明,合成产物属于单斜晶系,P2(1)/n空间群,晶胞参数为:a=1.181 8(2) nm,b=0.794 38(1...     

含萘并呋喃基团冠醚的合成及离子选择性研究

以2-羟基-1-萘甲醛和2-羟甲基冠醚为原料,合成3种新的含萘并呋喃基团冠醚(3a-3c),并经1 H NMR,13C NMR,MS及元素分析确证.碱金属和碱土金属离子的加入对体系的最大吸收波长影响不大.Li+使3b摩尔吸光度变大,Ca2+和Ba2+引起3a-3c最大发射波长λem发生相对较大红移,同时使其荧光强度降低.     

长链烷氧甲基冠醚的合成及表面活性

本文研究了通过长链烷氧甲基取代三甘醇(2)的环化反应合成一系列长链烷氧甲基-15-冠-5 (3) .在25℃, 35℃,45℃下测定了烷氧甲基冠醚化合物和(2)的表面张力,CMC及γ~C~M~C.结果显示,随着疏水链碳原子数的增加,CMC值减小,疏水链的碳原子数大于8的两亲分子在水溶液中可形成胶束.     

Synthesis and properties of naphthoquinonylamino-substituted benzocrown ethers

Naphthoquinonylaminobenzocrown ethers were synthesized by reactions of 4-aminobenzocrown ethers with 1,4-naphthoquinones. A hypsochromic shift of the long-wave absorption band was found to appear in the electron spectra when the compounds synthesized reacted with alkaline or alkaline-earth metal salts.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp. 452–454, March, 1994.     

Synthesis of novel crown ethers. Part 1. Coumestan and coumestan analog derivatives of crown ethers

The presented ethylenedioxy compounds5a,5d,6a and6c are examples of novel cyclic ethers, while macrocyclic polyethers represent new crown ether analogues. New coumestan-crowns5a-f, derivatives of 6,7-dihydroxy-3,4-dihydro-2H-dibenzofuran-1-one and 6,7-dihydroxy-3,3-dimethyl-3,4-dihydro-2H-dibenzofuran-1-one6a-e were synthesized from the correspondingo-dihydroxy compounds3a-b,4a-b and ditosylates or dichlorides of di- or triethylene glycol in the presence of K₂CO₃, in DMF/H₂O (15/1) solutions at 65–75 °C for 35 hours. The structure of the macrocyclic ethers obtained were confirmed by¹H-NMR,¹³C-NMR, IR spectra and elemental analyses.Presented at the Sixth International Seminar on Inclusion Compounds, Istanbul, Turkey, 27–31 August, 1995.     

Preparation and evaluation of novel chiral stationary phases covalently bound with chiral pseudo-18-crown-6 ethers

Novel chiral stationary phases consisting of silica gel covalently bound with chiral pseudo-18-crown-6 type hosts, which possess either an OH or OMe group as a binding functionality, were prepared for enantiomer-separation of lipophilic amines.     

含甲巯咪唑杂环为端基的非环冠醚的合成

本文以甲巯咪唑杂环为新的端基,在相转移催化条件合成了五个开链冠醚,这些化合物均通过元素分析、UV、IR 、^1H和^13CNMR波谱鉴定.     

Synthesis and characterization of monoazathiacrown ethers as ionophores for polymeric membrane silver-selective electrodes

Nine monoazathiacrown ethers have been synthesized and explored as ionophores for polymeric membrane Ag⁺-selective electrodes. Potentiometric responses reveal that the ion-selective electrodes (ISEs) based on 2,2′-thiodiethanethiol derivatives can exhibit excellent selectivities toward Ag⁺. The plasticized poly(vinyl chloride) membrane electrode using 22-membered N₂S₅-ligand as ionophore has been characterized and its logarithmic selectivity coefficients for Ag⁺ over most of the interfering cations have been determined as <−8.0. Under optimal conditions, a lower detection limit of 2.2 × 10⁻¹⁰ M can be obtained for the membrane Ag⁺-ISE.     

制备二氮杂冠醚和三氮杂冠醚的新方法

以糖精为原料合成二氮杂冠醚和三氮杂冠醚。使糖精与二甘醇或三甘醇二氯化物和N,N-二(β-氯乙基)丁胺的DMF溶液在少量碘化钾存在下烃化、氨解,再用二甘醇或三甘醇的二对甲苯磺酸酯烃化生成保护的冠醚环。后者与20％盐酸作用除去保护基生成游离的环体。此法合成路线短原料价廉易得。二氮杂18-冠-6总产率37％左右。     

The preparation of novel 1-propenyl ethers and their cationic photopolymerization

A series of nine difunctional 1-propenyl ether monomers bearing ether, ester, carbonate, and urethane groups were prepared based on trimethylolpropane diallyl ether as the starting material. The monomers were fully characterized and then subjected to photoinitiated cationic polymerization using diaryliodonium salts as photoinitiators. The course of the polymerizations was followed using Fourier transform real-time infrared spectroscopy and the relative reactivities of the various monomers were determined. It could be shown that the differences in reactivity could be related mainly to the basicity of the functional group introduced into the molecule. © 1996 John Wiley & Sons, Inc.     

二氨基二苯并-14-冠-4的合成与表征

二硝基二苯并冠醚;二氨基二苯并冠醚;二氨基二苯并-14-冠-4的合成与表征     

Synthesis,characterization, and electroluminescent performance of a novel copolyfluorene containing pendant crown ether groups

Copolyfluorene PFC containing pendant crown ether moieties was prepared by the palladium‐catalyzed Suzuki coupling reaction. The photo‐physical and electrochemical properties were investigated by absorption, photoluminescence (PL) spectroscopy, and cyclic voltammetry to elucidate the influence of the crown ether groups. In film state, its PL spectra (peaked at 430 and 452 nm) show noticeable red‐shift relative to 423 and 448 nm of poly(9,9‐dihexylfluorene) ( PF ). Thermal annealing leads to appearance of new emission at about 520 nm which has been attributed to formation of excimer. The highest occupied molecular orbital and lowest unoccupied molecular orbital levels of PFC were estimated to be ?5.68 and ?2.65 eV which contributed to balanced charges injection. Double‐layer electroluminescent device using PFC as emitting layer (ITO/PEDOT:PSS/ PFC /Ca/Al) revealed maximum luminance (7910 cd/m²) and maximum luminance efficiency (2.3 cd/A) superior to those of PF device (860 cd/m², 0.29 cd/A). Moreover, inserting a PFC layer between the PF emitting layer and calcium cathode led to reduced turn‐on voltage (4.1 V), much lower than 7.1 and 6.6 V of the double‐layer PFC and PF devices, respectively, and enhanced device performance (2800 cd/m² and 0.53 cd/A). © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 2985–2995, 2009     

单臂冠醚液晶LB膜的相变研究

研究了两种单臂冠醚液晶及配合物(1, 2及1.Eu^3^+)的LB膜的成膜特性,实验发出它们均可在气-液界面形成单分子膜, 但不易转移, 化合物1在压膜过程中出现一维相变。用CPK模型对成膜分子构型和面积进行估算, 其结果与实验相一致, 并讨论了冠醚液晶结构对LB膜相变的影响。     

Synthesis of novel macrocyclic crown ethers from D-glucose

A simple and efficient synthetic protocol for an easy access of carbohydrate-linked crown ethers from cheap and readily available D-glucose in good yields has been devised. The base-mediated cyclization of sugar-linked bis-iodo podands in CH₃CN with amines, including ethylamine and furfurylamine afforded the novel chiral monoaza-15-crown-5-type macrocyclic crown ethers anellated to 3-O-benzyl-1,2-O-isopropylidene-α-D-glucofuranose and 3-O-benzyl-1,2-O-isopropylidene-α-D-allofuranose. The glucose-based crown ethers have been characterized by spectroscopy techniques including IR, ¹H NMR, and ¹³C NMR.     

Synthesis of new indolyl crown ethers catalyzed with ferric hydrogensulfate

Efficient reaction of bis-indolyl podand with different aldehydes using Fe（HSO₄）₃ as catalyst to afford the corresponding new indolyl crown ethers is described.The structures of three distinct isomers have been optimized using HyperChem geometry optimizations.Also percentage of each isomer was obtained with ¹H NMR spectroscopy.     

From crown ethers to zeolites: Reaction of EtAlCl2 with crown ethers

In contrast to aluminum alkyls, alkyl aluminum halides such as EtAlCl₂ react with crown ethers to form cation-anion pairs which exhibit the liquid clathrate effect. Specifically, [12-C-4·AlCl₂][AlCl₃Et] and [18-C-6·AlCl₂][AlCl₃Et] have been isolated and characterized by X-ray diffraction techniques. The cations show aluminum in an octahedral environment made up of four of the oxygen atoms from the crown and two chlorine atoms. The 12-C-4 derivative crystallizes in the monoclinic space group P2₁/c with cell constants of a=7.497(4), b=22.121(8), c=12.339(5) Å, =94.99(3)^o, and Z=4 for =1.43 g cm^–3. Least-squares refinement based on 1413 observed reflections led to a final conventional R value of 0.093. The 18-C-6 complex belongs to the triclinic space group P1 with a=8.414(4), b=12.193(6), c=12.394(6) Å, =73.14(4), =86.07(4), =81.52(4)^o, and Z=2 for =1.45 g cm^–3. Refinement based on 2605 observed reflections led to R=0.063. The complex aluminum-containing species are related to a class of compounds called aluminoxanes.     

5-甲基-1,3,4-噻二唑-2-硫为端基的非环冠醚的合成

本文用2-巯基-5-甲基-1,3,4-噻二唑与二溴乙烷或低聚乙二醇溴化物合成了四种新的非环冠醚. 通过元素分析,UV,IR和^1H NMR波谱鉴定.