首页 | 本学科首页   官方微博 | 高级检索  
相似文献
 共查询到20条相似文献,搜索用时 343 毫秒
1.
The syntheses of monotetrathiafulvalene-calix[4]pyrrole 5 and bistetrathiafulvalene-calix[4]pyrrole 6, prepared from the acid-catalyzed condensation of monopyrrolo[3,4-d]tetrathiafulvalene (MPTTF, 7) with acetone in the presence of tripyrrane 8 and dipyrromethane 9, respectively, are described. Compound 5 and the previously reported tetrathiafulvalene-calix[4]pyrrole 4 both adopt a 1,3-alternative conformation in the solid state, as determined from X-ray crystallographic analysis. The anion binding properties of the tetrathiafulvalene-calix[4]pyrroles 5 and 6, as well as those of the parent meso-octamethylcalix[4]pyrrole (1), were investigated in acetone using (1)H NMR spectroscopic and isothermal titration calorimetry (ITC) techniques and, within the error limits of the methods, were generally found to give concordant results. On the basis of the results of the ITC studies carried out in 1,2-dichloroethane, increasing the number of tetrathiafulvalene units annulated to the calix[4]pyrrole system serves to enhance the anion binding affinities substantially but at the price of lowered selectivity. Cyclic voltammetry (CV) studies, carried out in 1,2-dichloroethane, provided evidence of an anion-dependent electrochemical response with Cl(-) and Br(-) ions. This response was particularly dramatic in the case of the monotetrathiafulvalene-calix[4]pyrrole 5, with a DeltaE(max) of -145 mV being seen after the addition of approximately 1 equiv of Cl(-) ion.  相似文献   

2.
The first synthesis of 1,4,9,10-tetrahydro-4,9-methanobenzo[4,5]cyclohepta[1,2-b]pyrrole (11) was achieved by the photochemical intramolecular [2 + 2] cycloaddition of N-phenoxycarbonyl- (5a) and N-ethoxycarbonyl-2-[2-(2-vinylphenyl)]pyrrole (6a), respectively, followed by basic hydrolysis of the isolated N-substituted 1,4,9,10-tetrahydro-4,9-methanobenzo[4,5]cyclohepta[1,2-b]pyrroles (10a, 10b). Some competitively formed products were also isolated.  相似文献   

3.
3-[2-[p-(Un)substituted phenyl]imidazo [2,1-b]benzothiazol-3- yl]propionic acid derivatives (2a--e) were prepared via the interaction of the corresponding 2-[p-(un)substituted phenyl]imidazo[2,1-b]benzothiazoles (1a--e) with acrylic acid in the presence of acetic anhydride and acetic acid. Esterification of 2a--e produced methyl esters (3a--e). Upon the interaction of 3a with m-chloroperbenzoic acid, the S-dioxide (4a) was obtained. Compound 5a was prepared from 4a by alkaline hydrolysis. Vilsmeier formylation for 1a--e produced novel [2-[p-(un)substituted phenyl]imidazo[2,1-b]benzothiazol-3- yl]formaldehyde derivatives (6a--e). Derivatives 6a--e reacted with ethyl bromoacetate to give ethyl 3-hydroxy-3-[2-[p-(un)substituted phenyl]imidazo[2,1-b]benzothiazol- 3-yl]propionate esters (7a--e). Compound dl-7a was resolved with l-(+)-tartaric acid. Compounds 2a--e showed weak or no activity in the carrageein-induced paw edema assay. Compound 4a significantly inhibited the leakage of pontamine-sky blue dye into the peritoneal cavity of mice, in the capillary permeability inhibition assay. Compound 5a inhibited the writhing by 62% in the acetic acid-induced writhing assay.  相似文献   

4.
In this study, seven new compounds p-(4-butyl-phenylazo)calix[6]arene(1), p-(4-(phenylazo)phenylazo)calix[6]arene (2),p-(4-hydroxyphenylazo)calix[6]arene (3),p-{4-[N-(thiazol-2-yl)sulfamoyl]phenylazo\}calix[6]arene(4), p-(4-acetamidophenylazo)calix[6]arene (5),p-(thiazol-2-ylazo)calix[6]arene (6) andp-(2-sulfanylphenylazo)calix[6]arene (7) have been synthesizedfrom calix[6]arene by diazo coupling with the corresponding aromaticamines. UV-Vis, IR, 1H and 13C NMR spectral data have been used to elucidate the structures of the compounds elemental analyses  相似文献   

5.
In the search for organic ferromagnets polymers with a conjugated backbone and pendant persistent radicals are one route of interest. The synthesis of poly[4-(4-ethynylphenyl)-2′,4′,6′-trinitro-2,6-diphenyldiphenylamine] (p-3) and poly[4-(3-ethynylphenyl)-2′,4′,6′-trinitro-2,6-diphenyldiphenylamine] (m-3) as precursors of polyradicals are described. A dinuclear rhodium cyclooctadiene chloride complex as polymerization catalyst was used to yield polymers with molecular weights (gel-permeation chromatography) of 100 000 for m-3 and 210 000 for p-3 .  相似文献   

6.
l-(2-Aminophenyl)pyrrole (I) and l-[2-(aminomethyl)]phenylpyrrole hydrochloride (III) undergo cyclization reactions with aldehydes and ketones to form 4,5-dihydropyrrolo[l,2-a]- quinoxalines and 5,6-dihydropyrrolo[l,2-a][l,4]benzodiazepines, respectively. It was also found that the use of the free base of compounds corresponding to III do not cyclize directly but lead instead to the intermediate Schiff bases which are subsequently cyclized to the desired benzodiazepines by treatment with hydrochloric acid.  相似文献   

7.
In order to develop analgesic compounds possessing a sulfur atom in the alicyclic ring, novel cis-fused heterocycles, [1]benzothiopyrano[3,4-b]pyrrole derivatives (II) were synthesized via a unique cyclization reaction starting from 4-(4-methoxyphenylthio)-2-butanone (1) or 6-methoxy-3,4-dihydro-2H-1-benzothiopyran-4-one (7). The analgesic effects of benzothiopyranopyrroles (16, 18) were measured by means of the writhing test. The phenolic derivative 18 completely inhibited the appearance of writhing at the dose of 50 mg/kg, but the methoxy derivative 16 had no analgesic effect.  相似文献   

8.
Calix[6]pyrrole 2 and the "hybrid systems" calix[3]furan[3]pyrrole 12, calix[2]furan[4]pyrrole 13, and calix[1]furan[5]pyrrole 14, have been synthesized by increasing conversion of the furan units present in the readily accessible calix[6]furan 3 to pyrroles. The host-guest chemistry of these novel macrocycles towards a number of anions, including halogen ions, dihydrogen phosphate, hydrogen sulfate, nitrate, and cyanide has been investigated in solution by (1)H NMR titration techniques and/or phase transfer experiments. The solid-state structures of the free receptors 2, 12, and 13, the 1:1 complexes of calix[6]pyrrole 2 with chloride and bromide, and the 1:1 complex of 14 with chloride are also reported.  相似文献   

9.
Calixpyrrole-based oligomeric compounds were synthesized by "click chemistry" from the corresponding alkyne- and azide-functionalized calix[4]pyrroles. Calix[4]pyrrole 3, possessing an alkyne functional group, was prepared through a mixed condensation of pyrrole with acetone and but-3-ynyl 4-oxopentanoate. Another alkyne-group-containing calix[4]pyrrole 5 was obtained by treatment of 4'-hydroxyphenyl-functionalized calixpyrrole 4 with propargyl bromide. Tetrakis(azidopentyl)-functionalized calix[4]pyrrole 7 was synthesized by reacting NaN(3) with tetrabromopentyltetraethylcalix[4]pyrrole 6, which was prepared through a condensation reaction of pyrrole and 7-bromohept-2-one. Oligomeric calixpyrrole compounds were found to be capable of extracting tetrabutylammonium chloride and fluoride salts from aqueous media. Extraction abilities of the oligomeric compounds were monitored by NMR and UV/Vis spectroscopy and thermogravimetric analysis.  相似文献   

10.
The conformational preference of calix[4]pyrrole and its fluoride and chloride anion-binding properties have been investigated by density functional theory calculations. Geometries were optimized by the BLYP/3-21G and BLYP/6-31G methods, and energies were evaluated with the BLYP/6-31+G method. To model the effect of medium, the SCIPCM solvent model was also employed. Four typical conformations of the parent substituent-free calix[4]pyrrole were studied. Both in the gas phase and in CH(2)Cl(2) solution, the stability sequence is predicted to be 1,3-alternate > partial cone > 1,2-alternate > cone. The cone conformation is predicted to be about 16.0 and 11.4 kcal/mol less stable in the gas phase and CH(2)Cl(2) solution, respectively. This is mainly due to electrostatic repulsions arising from the all-syn pyrrole/pyrrole/pyrrole/pyrrole arrangement present in this conformer. The existence of possible 1:1 and 1:2 anion-binding modes were explored in the case of fluoride anion, and the factors favoring the 1:1 binding mode are discussed. The calculated binding energy for fluoride anion is about 15 kcal/mol larger than that for chloride anion. The calculated binding energy for chloride anion agrees with the experimental value very well. The presence of meso-alkyl substituents destabilizes the cone conformer with respect to the 1,3-alternate conformer and, therefore, reduces the anion-binding affinity by 3-4 kcal/mol. The strength of N-H- - -anion hydrogen bonds in the various structures subject to study were estimated on the basis of the calculated anion-binding energies and the predicted structural deformation energies of substituent-free calix[4]pyrrole.  相似文献   

11.
The recent discovery of calix[3]pyrrole, a porphyrinogen-like tripyrrolic macrocycle, has provided an unprecedented strain-induced ring expansion reaction into calix[6]pyrrole. Here, we synthesized calix[n]furan[3-n]pyrrole (n=1∼3) macrocycles to investigate the reaction scope and mechanism of the ring expansion. Single crystal X-ray analysis and theoretical calculations revealed that macrocyclic ring strain increases as the number of inner NH sites increases. While calix[1]furan[2]pyrrole exhibited almost quantitative conversion into calix[2]furan[4]pyrrole within 5 minutes, less-strained calix[2]furan[1]pyrrole and calix[3]furan were inert. However, N-methylation of calix[2]furan[1]pyrrole induced a ring-expansion reaction that enabled the isolation of a linear reaction intermediate. The mechanism analysis revealed that the ring expansion consists of regioselective ring cleavage and subsequent cyclodimerization. This reaction was further utilized for synthesis of calix[6]-type macrocycles.  相似文献   

12.
It is shown that 2-methyl-3-carbethoxy-4H,8H,5,6-dihydrothieno[2,3-d]thia[1]pyrano [4,3-b]pyrrole and 8-methyl-9-carbethoxy-10H,5,6-dihydrothieno[2,3-d]thia[1]chromeno[4,3-b]pyrrole and their S,S-dioxides, respectively, are obtained in the reaction of 2-methyl-3-carbethoxy-4-thienylhydrazine with tetrahydro-4-thiopyrone, tetrahydro-4-thiopyrone S, S-dioxide, 4-thiochromanone, and 4-thiochromanone S,S-dioxide in the presence of an acid catalyst.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 2, pp. 195–196, February, 1979.  相似文献   

13.
杯[4]芳烃在毛细管电泳中的应用研究   总被引:5,自引:0,他引:5  
最近,杯芳烃在分离科学中的应用研究激起了人们的很大兴趣.在液相色谱中,固载化的杯芳烃被用作固定相,对金属离子和氨基酸酯的盐酸盐进行了分离[1].在气相色谱中,钟振林等[2]评价了主链含杯芳烃的聚硅氧烷作为毛细管固定相的性能.杯芳烃在毛细管电泳中的应用仅见1篇应用杯「6]芳烃的报道[3].本文首次报道杯卜[4]芳烃在毛细管电泳中的应用.鉴于毛细管电泳一般在水介质中进行,本文合成了水溶性的磺化杯卜[4]芳烃,并将其作为毛细管电泳添加剂来分离硝基苯酚异构体,获得满意的结果.1仪器和试剂Spectra-Phoresis1000型毛细管电泳…  相似文献   

14.
Thermolysis of a benzene solution of N-[4-(p-(methoxybenzyl)seleno)cyclohexanoyl]-N,S-dimethyldithiocarbonate affords the hitherto unknown 7-selenabicyclo[2.2.1]heptane in 48% conversion and in 20% yield after chromatography. G3(MP2)-RAD calculations predict a rate constant of 5 × 10(4) s(-1) at 80 °C (3.8 × 10(6) s(-1) at 200 °C) for the intramolecular homolytic substitution process involved in this cyclization.  相似文献   

15.
Rare examples of heteroditopic scorpionate ligands [m-(pz(HO)BtBu)(pz2BtBu)C6H4]2- ([m]2-) and [p-(pz(HO)BtBu)(pz2BtBu)C6H4]2- ([p]2-) are reported. As a unique feature, both ligands possess a chiral boron centre. Treatment of [m]2- and [p]2- with FeII and CoII ions, respectively, gives the dinuclear metallomacrocycles [FeII2(micro-m)2] and [CoII2(micro-p)2]. The molecular structures of the colourless complex [FeII2(micro-m)2] and the red-purple complex [CoII2(micro-p)2] have been determined by X-ray crystallography. To meet the geometric requirements of macrocycle formation, the two asymmetric boron centres have opposite absolute configurations in the case of [FeII2(micro-m)2] and the same configuration in [CoII2(micro-p)2].  相似文献   

16.
The hybrid calix[2]phenol[2]pyrrole 4 and the fused pyrrolidine-containing macrocycle 9 were synthesized from two different isomeric starting materials, namely dimethyl 2-hydroxyisophthalate and 5-hydroxyisophthalate, respectively. The fused species 9 is devoid of obvious substrate binding properties. In contrast, the heterocalix system 4 displays the fluoride-induced conformational changes characteristic of the parent system.  相似文献   

17.
A new type of alkalide compound, Li+(calix[4]pyrrole)M- (M = Li, Na, and K), is presented in theory, which may be stable at room temperature. It has been shown by our calculations that the first hyperpolarizability (beta) is considerably large by means of the density functional theory method. The beta values are determined at the B3LYP/6-311++G level (for the alkali atoms the 6-311++G(3df) basis set is employed) as 8.9 x 103, 1.0 x 104, and 2.4 x 104 au for M = Li, Na, and K, respectively. These beta values are much larger than that of electride Li+(calix[4]pyrrole)e- (beta = 7.3 x 103 au) by a factor of 1.2 to 3.4. Comparing to the cryptand calix[4]pyrrole, the beta values of Li+(calix[4]pyrrole)M- are enhanced by 20-60 times. It is revealed, for the first time, that the beta value of alkalide compounds depends on the atomic number of the alkali anion, and it can be enhanced by choosing the akali anions with larger atomic numbers. The alkali anion in the alkalide compound decreases the transition energy and also increases the oscillator strength of the main transition, consequently the beta value is enhanced. This study proposes such a novel way to synthesize and design new NLO materials by using the alkali atom with a larger atomic number to create an anion in alkalide compounds.  相似文献   

18.
采用密度泛函理论的M06-2X/6-31G(d, p)方法对杯[4]吡咯(CP)与卤素离子(X-=F-, Cl-, Br-)及卤素-铵根离子对的各种可能组装体系进行了系统研究. 详细讨论了各体系的结构、结合能、自然键轨道分析(NBO)和Multiwfn波函数分析的情况. 结果显示杯[4]吡咯与卤素阴离子的相互作用主要是氢键, 波函数分析显示在CPCl-和CP-Br-复合物中长程范德华力和空间位阻作用也明显存在. 杯[4]吡咯能与卤素-铵根离子形成稳定的复合物, 主要通过氢键作用、阴-阳离子的静电作用以及阳离子-π相互作用.从理论上探讨了杯[4]吡咯与离子或离子对的2:1组装体系,但相对于1:1组装体系来讲, 2:1体系并不占优势.本文结果进一步表明, 杯[4]吡咯不仅是一种阴离子受体,而且也是一种良好的离子对受体,尤其是对涉及氟离子的客体,更是如此.  相似文献   

19.
Bioconjugates of the neuropeptide Enkephalin (Enk = -Tyr-Gly-Gly-Phe-Leu-) labeled with organotransition metal tris-pyrazolylborate (Tp) complexes are reported. p-[Enk-OH]COC6H4TpPtMe3 and p-[Enk-OH]COC6H4Tp(Me)Re(CO)3 have been synthesized by solid-phase peptide synthesis (SPPS), purified by RP-HPLC, and characterized by ESI-mass spectrometry and 1H NMR and IR spectroscopies. p-[Enk-OH]COC6H4TpPtMe3 and p-[Enk-OH]COC6H4Tp(Me)Re(CO)3 constitute the first examples of Tp complexes employed in SPPS.  相似文献   

20.
The synthesis, spectroscopic characterization and preliminary complexation properties of functionalized calix[4]pyrroles are described. To date, two generalized preparative approaches have been pursued (i) modifying the basic pyrrole-plus-ketone synthesis of calix[4]pyrrole by using microwave irradiation protocol, (ii) the basic meso-tetra(methyl) meso-tetra(p-nitrophenyl) calix[4]pyrrole skeleton was functionalized to give hydroxamic acids, especially in the meso-position of the macrocycles. The structures of novel calix[4]pyrrole hydroxamic acid derivatives were confirmed on the basis of various physico-chemical techniques such as elemental analysis, FT-IR, 1H NMR and FAB-Mass. The results of preliminary studies on the extraction of vanadium (V) with the host calix[4]pyrrole hydroxamic acids were elucidated by significant examination of UV–Vis spectroscopy and ICP-AES. Single crystal structure of basic meso-tetra(methyl) meso-tetra (p-nitro phenyl) calix[4]pyrrole moiety has also been reported.  相似文献   

设为首页 | 免责声明 | 关于勤云 | 加入收藏

Copyright©北京勤云科技发展有限公司  京ICP备09084417号