以2-苯氧乙基为氮支链的[18]和[15]环系氮支套索冠醚的合成及其络合性能

以2-苯氧乙醇为起始剂, 合成了两种新型氮支套索冠醚: N-(2-苯氧乙基)单氮杂-18-冠-6 (18CE)与N-(2-苯氧乙基)单氮杂-15-冠-5 (15CE). 通过红外光谱、核磁共振氢谱和紫外光谱表征了新冠醚及其中间体的结构. 用电导滴定法研究了两冠醚与Na^＋, K^＋, Ag^＋, NH^4＋, Ni^2＋, Cu^2＋, Pb^2＋和Co^2＋在25 ℃的配位作用, 计算了1∶1配合物的稳定常数. 实验结果表明, 由于N-(2-苯氧乙基)引入氮杂冠醚环和参与配位, 18CE和15CE配合物的稳定常数分别比单氮杂-18-冠-6, N-(2-羟基乙基)单氮杂-18-冠-6, N-(2-甲氧基乙基)单氮杂-18-冠-6和单氮杂-15-冠-5, N-(2-甲氧乙基)单氮杂-15-冠-5, N-(2-甲氧乙基)单氮杂-15-冠-5的对应配合物明显提高. 配合物的稳定常数和紫外光谱皆提供了支链的苯氧基参与配位的信息.     

含松香骨架的手性氮杂冠醚的合成及其在不对称Michael 加成反应中的应用

以松香为原料, 合成了4个手性氮杂冠醚: N-脱氢松香基单氮杂-12-冠-4、N-脱氢松香基单氮杂-15-冠-5、N-脱氢松香基单氮杂-18-冠-6和N-降解脱氢松香基单氮杂-12-冠-4, 并用于催化不对称查尔酮Michael加成反应, 发现这些手性氮杂冠醚可以有效地催化2-硝基丙烷与查尔酮的不对称Michael加成, Michael加成产物ee最高达35%.     

Synthesis,Alkali Metal Picrate Extraction Properties,and X-Ray Crystal Structure of a Novel,Cage-Annulated Monoaza-18-Crown-6 Host

Compound 5, a cage-annulated monoaza-18-crown-6 macrocyclic polyether, has been synthesized, and its alkali metal picrate extraction capabilities have been assessed relative to those of the parent monoaza-18-crown-6 host system. It was observed that both 5 and monoaza-18-crown-6 are selective K⁺ picrate extractants; however, 5 appears generally to be a somewhat more efficient alkali metal picrate extractant than monoaza-18-crown-6. Interestingly, both the avidity and selectivity of 5 toward extraction of alkali metal picrates from aqueous solution into CHCl₃ appears to be pH dependent. In addition, the X-ray crystal structure of an unusual hydronium ion complex of 5 [i.e., 5(HCl)(H ₂ O)-(CHCl ₃ ) ₂] has been determined. The X-ray structure thus determined is compared with the corresponding structure of 5(HCl)(H ₂ O) that has been calculated via application of B3LYP Density Functional Theory.     

Phase-transfer catalytic activity of soluble polystyrenes containing crown ether moieties and hydroxyl groups adjacent to the macrorings

Soluble polystyrenes with crown ether structures and hydroxyl groups adjacent to the macrorings were prepared by the reaction of epoxide-containing polystyrenes with monoaza-15-crown-5 or monoaza-18-crown-6. Rate of formation of the polymer-bound alkali cation-crown alkoxide ion pair from the soluble polystyrenes and aqueous NaOH or KOH depended on the loading of crown ether and hydroxyl units and on the size of the macroring. The elimination of HCl from less reactive 2-chloroethylbenzene with aqueous NaOH or KOH in the presence of the soluble polystyrene catalysts under two-phase conditions was limited mainly by the intrinsic reaction rate. The elimination of HBr from more reactive 2-bromoethylbenzene in the presence of the less (11%) ring-substituted polymer catalyst with 18-crown unit was limited by the alkoxide formation rate. © 1994 John Wiley & Sons, Inc.     

Substituent dependent fluorescence response of diazacrown-based PET sensors

The sensing ability of three 1,10-diaza-18-crown-6 based sensors bearing a coumarin fluorophore was studied and compared with the analogous monoaza-18-crown-6 sensor. Coordination experiments between hosts and organic ammonium salts with varying steric demand were studied using fluorescence and ¹H NMR spectroscopy. We have found that the fluorescent signal generated on complexation was greatly influenced by the structure of the sensor. Surprisingly, in two cases, we observed the decrease of fluorescence on complexation, which was attributed to changes in the conformational dynamics of the sensors on complexation.     

Chromogenic benzo- and monoaza-12-crown-4, 13-crown-4 and 14-crown-4 lithium-selective crown ethers

Chromogenic benzo-12-crown-4, benzo-13-crown-4 and benzo-14-crown-4 ethers have been compared with monoaza-12-crown-4 and monoazal-13-crown-4 ethers. Of these compounds, monoaza-13-crown-4 exhibited the best analytical characteristics toward the selective determination of lithium. K(ex)Li/K(ex)Na was 525 for the monoaza-crown-4 compound.     

Cation-complexation-induced aggregation and specific ion conduction of lipophilic crowned azobenzenes

Lipophilic azobenzene derivatives incorporating a monoazacrown or oligooxyethylene moiety were employed as a component of ion-conducting composite films containing a polyester elastomer and an alkali metal (Li⁺, Na⁺, K^–) perchlorate. Composite films of monoaza-15-crown-5-containing azobenzene1 exhibited ionic conductivities following the order of Na > Li > K, reflecting the cation-binding selectivity of the 15-crown-5 ring. The ion-conducting behavior of composite films of1 is quite different from that of composite films containing a 1 : 1 mixture of an azobenzene derivative without any crown moiety andN-phenyl-monoaza-15-crown-5 (ionic conductivity order of Li > Na > K >). It was suggested that cation and anion migration is predominant in the LiClO₄ and NaClO₄ systems, respectively. The specific ion conduction can be attributed to ordered aggregation of1 induced by cation complex formation of its crown moiety. Azobenzene derivatives incorporating a monoaza-12-crown-4, monaza-18-crown-6, or oligooxyethylene moiety cannot afford such aggregate formation and specific ion-conduction as is seen in the1 system.     

EDTA冠醚衍生物——Ⅷ.两个长桥链双冠醚的合成

前文报道的由EDTA桥联的水溶性双冠醚,虽然对碱土金属离子的配位有其特点,但可能是由于桥键不够长和二个刚性苯环的存在,桥键上两个羧甲基不但不起配位协同作用,反而阻碍了两个冠醚环的靠近,从而未显示出预期的高络合特性。为此,我们按下式合成了两个更长桥键的双冠醚1和2:     

Complexation of Macrocyclic Compounds with Nicotinamide in Dimethylsulphoxideand its Water Mixture

The complexation behavior of nicotinamide with macrocyclic polyethers viz, 15-crown-5, benzo-15-crown-5, 18-crown-6, dicyclohexano-18-crown-6, dibenzo-18-crown-6, dibenzo-24-crown-8, 1,4,7,10,13,16-hexathiacyclooctadecane, monoaza-15-crown-5, 1,4,10-trioxa-7,13-diaza-cyclopentadecane, 5,6,14,15-dibenzo-1,4-dioxa-8,12-diazacyclopentadecane, 7,16-dibenzyl-1,4,10,13-tetraoxa-7,16-diazacyclooctadecane, 1,4,7-tritosyl-1,4,7-triazacyclononane, 1,4,7,10-tetratosyl-1,4,7,10-tetraazacyclododecane and 1,4,8,11-tetraazacyclooctadecane has been studied in dimethylsulphoxide (DMSO) and 90% DMSO + water using differential pulse polarography and complexation constants have been reported. Nicotinamide forms stable complexes with six-membered coronand rings of the crown ethers. The nature of the atoms (oxygen, sulfur and nitrogen) in the coronand ring is observed to affect the stability of the complex. The stoichiometry and stability constants of the complexes were determined by monitoring the shifts in peak potentials of the polarograms of nicotinamide against the ligand concentration. The Gibbs free energy change turns out to be negative at 25°C, which indicates the spontaneity of the binding of nicotinamide with crown ethers. The mole ratio of nicotinamide to the macrocyclic compound was also determined and it was found that the complexes were of 1:1 type with respect to crown ethers. The tendency of nicotinamide to form complexes with macrocycles is found to be greater in DMSO than in DMSO + water.     

Bis(crown ether)s as Na+-K+ ATPase model in a liquid membrane

A new type of bis(crown ether)s containing 15-crown-5 and monoaza-18-crown-6 actively transported Na⁺ and K⁺ in opposite directions across a dichloromethane membrane by pH control. The effect of the structure of the ion carriers on their transport abilities was examined. A key point for the molecular design of the carriers is how to give them complexing ability toward Na⁺ under acidic conditions. A proper choice of the transport conditions was found to be essential for the success of the double uphill transport.This paper is dedicated to the memory of the late Dr C. J. Pedersen.     

含有冠醚基团的有机硅化合物(Ⅱ)——烯基氮杂冠醚的硅氢化和固载化氮杂冠醚的一些性能

本文报道了N-烯丙基、N-(10-十一碳烯基)氮杂15-冠-5与氨杂18-冠-6的合成、硅氢化、固载化,以及所得气相法二氧化硅固载的氮杂冠醚对苦味酸钠、钾的络合容量和正溴己烷碘代反应的相转移催化活性。     

Crown bowl: metallocyclophane by self-assembly of 4'-pyridylmethyl-armed 12-crown-4 ethers with Ag+ ions

New 3'-pyridylmethyl- and 4'-pyridylmethyl-armed monoaza-12-crown-4 ethers were prepared by the reductive amination of monoaza-12-crown-4 with the appropriate pyridinecarbaldehyde in the presence of NaBH(OAc)3. X-ray crystallography, cold electrospray ionization mass spectrometry, and 1H NMR titration experiments show that Ag+ complexes with 3'-pyridylmethyl- and 4'-pyridylmethyl-armed monoaza-12-crown-4 ethers are dimetallo[3.3]metacyclophane and trimetallo[3.3.3]paracyclophane, respectively (crown bowl). The structure of the metallocyclophanes can be controlled by the positions of the N atoms in the pyridine side arms and the ring size of the crown moiety.     

Spectroscopic correlations between supermolecules and molecules. Anatomy of the ion-modulated electronic properties of the nitrogen donor in monoazacrown-derived intrinsic fluoroionophores

The synthesis, absorption and emission spectra, fluorescence quantum yields, and fluorescence lifetimes of three compound series of trans-4,4'-disubstituted aminostilbenes (1-3) are reported. The chromo-/fluoroionophoric behavior of the monoaza-15-crown-5- (A15C5) and monoaza-18-crown-6 (A18C6)-derived species (1A(5)()-3A(5)() and 1A(6)()-3A(6)()) in acetonitrile and dichloromethane are also investigated. Great similarities in electronic spectroscopic properties (chemical shifts, wavelength, intensity, and lifetime) between the metal ion-complexed supermolecules and the corresponding chloro-substituted molecules have been observed: namely, 1A(5)()/Ca(2+)-3A(5)()/Ca(2+) approximately 1A(6)()/Ba(2+)-3A(6)()/Ba(2+) approximately 1C-3C in acetonitrile and 1A(5)()/Na(+)-2A(5)()/Na(+) approximately 1A(6)()/K(+)-2A(6)()/K(+) approximately 1C-2C in dichloromethane. Such spectroscopic correlations allow us to define the metal ion-modulated electronic character of the azacrown nitrogen atom in the ground and excited states and, in turn, to gain insights into the observed fluoroionophoric behavior of these probes in terms of the size and direction of fluorescence shifts and intensity variations.     

Synthesis and Photochromism of Crowned Spirobenzothiapyran: Facilitated Photoisomerization by Cooperative Complexation of Crown Ether and Thiophenolate Moieties with Metal Ions

Spirobenzothiapyrans bearing monoaza-12-crown-4, -15-crown-5, -18-crown-6, and oligooxyethylene moieties were synthesized, and their photochromism was examined in the presence of cations in acetonitrile. The cation complexation by their crown ether moieties cannot induce thermal isomerization to their corresponding colored merocyanine form, unlike the corresponding spirobenzopyran derivatives. The UV-light-induced isomerization was, however, facilitated by the cation complexation of the crown ether moieties and the affinity of the merocyanine thiophenolate anion to metal ions, especially in the presence of Li(+) and Ag(+). The presence of Ag(+) brought about the most remarkable effect in the facilitation of photoisomerization of the spirobenzothiapyrans and the thermal stability of the colored merocyanine form mainly due to the powerful interaction of the thiophenolate anion with the soft metal ion.     

Synthesis and optical characterization of novel azacrown ethers containing an acridinone or an N-methylacridinone unit as potential fluorescent chemosensors

Four new achiral and four new chiral monoazacrown ethers containing an acridinone or an N-methylacridinone fluorescent signalling unit were prepared by reacting chloromethyl-substituted acridinone derivatives with achiral monoazacrown ethers with different cavity sizes and enantiopure monoaza-18-crown-6 ethers having two methyl and two isobutyl groups on their chiral centres, respectively. The operation of these chemosensors is based on the photoinduced electron transfer (PET) process, thus they show fluorescence enhancement in the presence of cationic guests. Their fluorescent behaviour as well as their complexation properties towards selected metal ions and the enantiomers of α-(1-naphthyl)ethylammonium perchlorate and potassium mandelate were examined.     

Chiral and phase transfer agents

Starting from 1,32,4-di-O-ethylidene-D-glucitol (1), two regioisomeric monoaza-18-crown-6 ethers withC ₂ symmetry were synthesized. A simple route was suggested for the preparation of a diol that is a convenient intermediate for the synthesis of chiral aza-crown ethers from diol1.For Part 7, see ref. 1.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 4, pp. 782–785, April, 1993.     

Inclusion compounds: The products of the interaction of silicon,germanium and boron fluorides with crown ethers

This review deals with the problem of the interaction of Si(IV), Ge(IV) and B(III) fluorides with crown ethers and their aza analogues. The crystallographic structures have been determined of the stable products obtained by the interaction of H₂SiF₆ solution with the following crown ethers: 18-crown-6 (18C6), monoaza-18C6 (MA18C6), 1,10-diaza-18C6 (DA18C6) and 1,7-diaza-15C5 (DA 15C5). The complexes obtained are stabilized by a system of H-bonds of the O-H... O, N-H. ... O, N-H...F and O-H ... F types. For H₂GeF₆ the adducts obtained are similar to those obtained using H₂SiF₆. The crystal structures of three new boron fluoride-containing complexes with 18-membered crown ethers are also described. During macrocycle complexation the guest entities undergo chemical transformations which are stabilized by creation of the H- bond system. The results of vibrational and NMR spectra are also discussed.Presented at the Sixth International Seminar on Inclusion Compounds, Istanbul, Turkey, 27–31 August, 1995.     

Synthesis and rare earth metal ion-sensing properties of aza-crown derivative incorporating with diaryl-1,3,4-oxadiazole

A new fluorescent chemosensor (A18C6-Ox) in which a monoaza-18-crown-6 is linked to a diaryl-1,3,4-oxadiazole fluorophore by a methylene spacer has been synthesized to evaluate binding interaction with the rare earth ions by means of absorption and emission spectrophotometry. Absorption spectra of A18C6-Ox showed a broad band at 289nm and there was no significant change in the presence of Sc3+, La3+, Pr3+, Sm3+, Gd3+, Tb3+, Yb3+ and Lu3+ except for Ce3+ and Eu3+. From the emission spectral change of A18C6-Ox, interaction of the rare earth ions with A18C6-Ox is very strong. The formation of A18C6-Ox complexing with Sc3+, La3+, Pr3+, Sm3+, Gd3+, Tb3+, Yb3+ and Lu3+ leads to an increase in fluorescence intensity of A18C6-Ox, while Ce3+ and Eu3+ ions interact strongly causing fluorescence quenching of A18C6-Ox. In addition, the optimal complexation stoichiometry of the rare earth ions with A18C6-Ox was investigated by the fluorescent titration.     

Synthesis and fluorescence studies of novel bis(azacrown ether) type chemosensors containing an acridinone unit

Three new bis(azacrown ether)s containing an acridinone fluorescent signalling unit were prepared by reacting 9-chloro-4,5-bis(chloromethyl)acridine with monoazacrown ethers with different cavity sizes followed by a hydrolysis step. Their fluorescent characteristics and the complexation properties of the one containing two monoaza-18-crown-6 ether receptors towards selected metal ions were studied. The operation of the latter ligand is based on the photoinduced electron transfer (PET) process, thus it shows fluorescence enhancement in the presence of metal ions. Since the sensor molecule contains two receptor moieties, it is able to form two types of complex with 1:1 and 1:2 ligand to metal ion ratios, which have different emission spectra. The reason for this spectral difference may be that the 1:1 complex is a sandwich type one in which the acridinone unit can undergo structural changes.     

Synthesis, Extraction Ability and Application in an Asymmetric Synthesis of Azacrown Ethers Derived from D-Mannitol

New chiral monoaza-15-crown-5 ethers have been synthesised from 1,2:5,6-di-O-isopropylidene-D-mannitol. The substituent at the nitrogen atom has a major influence on the cation extraction ability of the azacrown. These sugar-based crown ethers show asymmetric induction as chiral phase transfer catalysts in the Michael addition of 2-nitropropane to chalcone (67% ee).