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1.
《Tetrahedron letters》1988,29(46):5957-5960
The facile synthesis of [n](2,4)pyridinophane ring system (n = 9–6) was accomplished by the reaction of N-(1-phenylvinyl)iminophosphorane with cyclic α, β-unsaturated ketones. The chain flipping was studied by 1H NMR spectra at various temperatures. 相似文献
2.
Masahiko Shibahara Motonori Watanabe Masahiko Suenaga Taisuke Matsumoto 《Tetrahedron letters》2009,50(12):1340-5015
A variable temperature 1H NMR study of the [3.3](3,5)pyridinophane indicated that the syn(chair/chair) is more stable than syn(chair/boat) by 0.2 kcal/mol in solution, whereas the trimethylene bridges show disorder even at −150 °C in the solid state. A transition state search by ab initio MO calculations suggested two competitive conformational changes for syn(chair/chair)-syn(chair/boat) conversion via a bridge wobble or a ring inversion in the [3.3](3,5)pyridinophane. 相似文献
3.
Two methods utilized in the synthesis of [9](2,4)pyrrolophanes are reported. The first, an application of the Paal-Knorr cyclization, involved the condensation of ammonia with 3-formylcyclododecanone. The second method employed the condensation of 3-chlorocyclododec-2-en-1-one with diethyl aminomalonate. 相似文献
4.
Oxacalix[n]arenes, reassessed members of the calixarene family in which the traditional methylene bridges are replaced by oxygen atoms, have emerged as a promising class of macrocycles in recent years. This tutorial review summarizes the synthetic progress made in the field during the last few years and aims to stimulate its current evolution from a merely synthetic to a more applied branch of macro- and supramolecular chemistry. 相似文献
5.
The conformational behavior of a series of crown-fused dithia[n.3.3](1,2,6)cyclophanes (126-CPs) and dithia[n.3.3](1,3,5)cyclophanes (135-CPs) was investigated by variable-temperature 1H and 13C NMR spectroscopy, X-ray crystallography and density functional theory (DFT) calculations. Single crystal X-ray structure analysis showed that two thia-bridges in 126-CPs adopted a pseudochair-pseudochair (cc) conformation and the cyclophane decks underwent a ring-tilting motion in the case of [10.3.3](1,2,6)cyclophane (1a). In contrast, the thia-bridges in 135-CPs took both cc and pseudoboat-pseudochair (bc) conformations, and the ring-tilting process was also found in [10.3.3](1,3,5)cyclophane (2a). Variable temperature 1H NMR study revealed that there was no wobbling-motion for two thia-bridges in 126-CPs while thia-bridges in 135-CPs experienced a wobbling-process with a conformational barrier of 9.21 and 8.80 kcal mol−1, respectively, for 2a and [13.3.3](1,3,5)cyclophane (2b). DFT calculations for the two cyclophanes series revealed that 126-CPs preferred a cc conformation which was consistent with the experimental observation; similarly, 135-CPs took a preferential cc conformation, agreeing with 2a having a predominant cc conformer (cc:bc ratio=70:30), but not 2b having a predominant bc conformer (cc:bc ratio=15:85) in the solid state. 相似文献
6.
7.
Synthesis of the titled tropolonophones has been attempted. Though the [7]-compound was obtained, the lower homolog was failed to be synthesized probably because of the strain imposed on the desired compound. The former tropolonophane was shown to exist in the enolone form. PMR and electronic spectra of [7] and [8]-homologs and their methylethers revealed some nonplanarity in the 7-membered rings. PMR spectrum also established the conformation of the bridge in the former compound. 相似文献
8.
Syntheses of [2.2](2,6,2′,7′)naphthalenophane and its corresponding diene have been accomplished by standard procedures from 2,13-dithia[3.3](2,6,2′,7′)naphthalenophane. The transition state for conformational flipping of [2/2](2,6,2′,7′)naphthalenophane requires the two naphthalene rings to become perpendicular to each other with insertion of the 1- and 8-hydrogens of one naphthalene ring into the cavity of the π-electron cloud of the other naphthalene ring. The kinetic parameters for the conformational flipping process have been measured by a selective pulse Fourier transform NMR technique. 相似文献
9.
The highly strained [5](2,4)quinolinophane system can be generated as an intermediate (2b), which is extremely susceptible towards the attack of both nucleophilic and electrophilic species. Addition of water at the carbon bridgehead C2 occurs rapidly and is followed by rearrangements to give a strain free product 10. An unusual carbene addition at the N1C2 bond of 2b is proposed to explain the formation of the strained ‘anti-Bredt’ type olefin 11. 相似文献
10.
Two cyclophanes, [2.2](2,6)biphenylenophane and [2](2,6)biphenyleno[2](2,6)naphthalenophane, were prepared. 相似文献
11.
12.
Dr. Kiran Sagar Unikela Dr. Parisa Ghods Ghasemabadi Dr. Václav Houska Dr. Louise N. Dawe Dr. Yuming Zhao Dr. Graham J. Bodwell 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(1):390-400
A gram-scale synthesis of a series of 1,1,n,n-tetramethyl[n](2,11)teropyrenophanes (n=7–9) has been accomplished as well as the first synthesis of the next higher homologue 1,1,10,10-tetramethyl[10](2,11)teropyrenophane. The scale-up of the original small-scale synthesis required the development of several heavily modified synthetic methods, including a chlorination/Friedel–Crafts alkylation protocol and an iodination/Wurtz coupling protocol, which were performed on 25–30 g and 30–60 g scales, respectively. Two separate sets of conditions for the key teropyrene-forming cyclodehydrogenation reaction at the end of the synthetic pathway were developed, an acid-promoted one for the two less strained congeners and an acid-free method for the two more strained homologues. 相似文献
13.
Inokuma S Ide H Yonekura T Funaki T Kondo S Shiobara S Yoshihara T Tobita S Nishimura J 《The Journal of organic chemistry》2005,70(5):1698-1703
[2.n](2,6)Pyridinocrownophanes (3a-e) were efficiently prepared by intramolecular [2 + 2] photocycloaddition of vinylpyridine derivatives under irradiation using a 400-W high-pressure mercury lamp through a Pyrex filter. They were of cis-configuration with respect to the cyclobutane ring, which was proven by the specific methine proton NMR resonances at delta 3.98-4.08. From ESI-MS analysis 3a-e were found to form 1:1 complexes with Ag+ cation. In a liquid-liquid extraction, 3 showed the highest affinity toward Ag+ cation among several heavy metal nitrates. In this series, 3c possessing four ethereal oxygen atoms was found to show the highest Ag+ affinity, according to the liquid-liquid extraction and determination of stability constant with the cation. The photoreactivity of precursor vinylpyridines is discussed by the predictor gamma(r(c)) proposed by Caldwell. 相似文献
14.
Shigeru Nishiyama Yoshikazu Shizuri Daizo Imai Shosuke Yamamura Yukimasa Terada Masatake Niwa Kazuaki Kawai Hideyuki Furukawa 《Tetrahedron letters》1985,26(27):3243-3246
Isocitreoviridinol has been newly isolated from the mycelium of B. (IFO 6050) together with citreoviridinol, and their stereostructures have also been elucidated by means of chemical method: the 2,6-dioxabicyclo[3.2.1]octanes have been made, one of which is regarded as a promising synthetic intermediate of citreoviridinol. In addition, isocitreoviridinol diacetate has been derived from citreoviridin in 3 steps. 相似文献
15.
The [5.7](n)cyclacenes represent a novel class of all sp(2)-hybridized carbon structures. In contrast to the isomeric [n]cyclacenes, [5.7](n)cyclacenes are predicted at the B3LYP/6-31G* level of theory to have stable, closed-shell singlet ground state configurations. Predicted geometries, electronic structures, band gaps, nucleus-independent chemical shift (NICS) values, and strain energies for this new family of cyclic conjugated molecules are presented. 相似文献
16.
The synthesis of [2.2](2,6,2',7')naphthalenophane -1,11 - diene 4 has been effected by pyrolysis of the bis-sulphoxide 10, in turn prepared by a ring-contraction procedure of the [3.3]dithiacyclophane 7. The diene 4 has been fully characterized by spectroscopic and chemical methods. The variable-temperature 1H NMR spectra of the diene 4 indicated that the compound undergoes conformational flipping in solution and has a conformational energy barrier ΔG≠25°. 14.9 kcal mol-1 and a coalescence temperature Tc 38° for the internal protons Hc and Hc' (at 100 MHz). These results differ from those previously recorded. A complete assignment of the pmr spectrum of the cyclophane diene 4 at 270 MHz is presented together with the spectrum of the corresponding saturated [2.2]cyclophane 3. 相似文献
17.
A novel synthesis of 5-cyano[n](2,4)pyridinophane-6-ones 12a-d (n= 9, 8, 7, and 6) consists of allowing cyanoacetatoamide to react with cycloalk-2-enones. Their static and dynamic properties as well as structural characteristics are studied on the basis of their spectroscopic properties, cyclic voltammetry, and theoretical calculations. The (1)H and (13)C NMR spectra at various temperatures have clarified the dynamic behavior of the methylene chains for [7](2,4)- and [6](2,4)pyridinophane-6-one derivatives 12c and 12d. The energy barrier (Delta G(++)) of the bridge flipping of 12c is estimated to be 12.0 kcal mol(-1)(T(c)= 0 degree C). On the other hand, compound 12d undergoes pseudorotation (conformational change of the methylene chain) at room temperature, and does not undergo bridge flipping even at 150 degree C in DMSO-d(6). The energy barrier (Delta G(++)) of the pseudorotation of the methylene chain 12d of is found to be 10.5 kcal mol(-1)(T(c)=-25 degree C), and thus, two stable conformers of the hexamethylene bridge of 12d are determined as predicted by theoretical calculations. Deformation of the pyridone ring of 12d is also determined by X-ray crystallographic analysis. Furthermore, chemical transformations of 12a-c leading to 5-carbamoyl[n](2,4)pyridinophanes 15a-c are also accomplished successfully in moderate to good yields. 相似文献
18.
对叔丁基杯芳烃与稀土配合物的合成表征及抑菌活性 总被引:1,自引:0,他引:1
合成了对叔丁基杯[6]芳烃(H6L)及对叔丁基杯[8]芳烃(H8L′)与稀土RE(La,Sm和Tb)的配合物,通过元素分析、红外光谱进行表征,研究了这些配合物对高山红景天立枯丝核菌(Rhizoctonia solai Kuhn)和尖孢镰刀菌(Fusarium oxyporumSchlecht)的抑菌活性.结果表明,其配合物组成分别为[RE(H4L)(DMF)4(OH)].H6L和[RE(H6L′)(NO3)(DMF)4].2DMF(RE=La,Sm,Tb;H4L为电离出两个H 的H6L;H6L′为电离出两个H 的H8L′).配合物对这两种真菌均有较好的抑菌效果,浓度高则抑菌能力强,杯[8]芳烃稀土配合物的抑菌能力较杯[6]芳烃稀土配合物强. 相似文献
19.