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21.
Uroš Grošelj Dieter Seebach D. Michael Badine W. Bernd Schweizer Albert K. Beck Ingo Krossing Petra Klose Yujiro Hayashi Tadafumi Uchimaru 《Helvetica chimica acta》2009,92(7):1225-1259
Structures of the reactive intermediates (enamines and iminium ions) of organocatalysis with diarylprolinol derivatives have been determined. To this end, diarylprolinol methyl and silyl ethers, 1 , and aldehydes, Ph? CH2? CHO, tBu? CH2? CHO, Ph? CH=CH? CHO, are condensed to the corresponding enamines, A and 3 (Scheme 2), and cinnamoylidene iminium salts, B and 4 (Scheme 3). These are isolated and fully characterized by melting/decomposition points, [α]D, elemental analysis, IR and NMR spectroscopy, and high‐resolution mass spectrometry (HR‐MS). Salts with BF4, PF6, SbF6, and the weakly coordinating Al[OC(CF3)3]4 anion were prepared. X‐Ray crystal structures of an enamine and of six iminium salts have been obtained and are described herein (Figs. 2 and 4–8, and Tables 2 and 7) and in a previous preliminary communication (Helv. Chim. Acta 2008 , 91, 1999). According to the NMR spectra (in CDCl3, (D6)DMSO, (D6)acetone, or CD3OD; Table 1), the major isomers 4 of the iminium salts have (E)‐configuration of the exocyclic N?C(1′) bond, but there are up to 11% of the (Z)‐isomer present in these solutions (Fig. 1). In all crystal structures, the iminium ions have (E)‐configuration, and the conformation around the exocyclic N‐C? C‐O bond is synclinal‐exo (cf. C and L ), with one of the phenyl groups over the pyrrolidine ring, and the RO group over the π‐system. One of the meta‐substituents (Me in 4b , CF3 in 4c and 4e ) on a 3,5‐disubstituted phenyl group is also located in the space above the π‐system. DFT Calculations at various levels of theory (Tables 3–6) confirm that the experimentally determined structures (cf. Fig. 10) are by far (up to 8.3 kcal/mol) the most stable ones. Implications of the results with respect to the mechanism of organocatalysis by diarylprolinol derivatives are discussed. 相似文献
22.
Biswanath Das Kongara Ravinder Reddy Bommena Ravikanth Akella Venkata Subrahmanya Sarma Balasubramanian Sridhar 《Helvetica chimica acta》2008,91(6):1137-1143
Chemical investigation on two samples of the flowers of Parthenium hysterophorus afforded two new pseudoguaianolides (one from each sample) together with several known constituents. The structures of the new compounds were established by extensive spectroscopic (1D‐ and 2D‐NMR) studies. The X‐ray crystallographic analysis of one of these compounds was also accomplished. 相似文献
23.
Michal Korenko Marián Kucharík Jozef Vincenc Oboňa Dušan Janičkovič Rosa Córdoba José María De Teresa Blanka Kubíková 《Helvetica chimica acta》2008,91(7):1389-1399
The rapid‐solidification processing (by a cooling rate of 105–106 K/s) was used for the preparation of deeply undercooled cryolite/alumina (Na3AlF6/Al2O3) melts. We found a mass of nanotubes on the surface of these undercooled melts. The nanotubes were preferentially located on the defect places of the surface with the following approximate dimensions: base≈100×100 nm, length≈1000 nm. The solidified samples with the nanotubes on the surface were analyzed by scanning electron microscopy (SEM), energy‐dispersive X‐ray spectroscopy (EDX), X‐ray diffraction (XRD), and infrared spectroscopy (IR). 相似文献
24.
An anatomically accurate eye model with a shell-structure lens 总被引:1,自引:0,他引:1
A human eye model based on anatomically accurate eye model previously proposed by Liou, has been transformed into a new eye model, in which laminated structure of the lens is considered. The crystalline lens is presented in the form of hundreds of shells with rotational symmetry, and with constant index within each shell. The refractive index increases from the cortical shell to the inner one, according to the equation proposed by Smith G. et al. The anterior surface of the lens is prolate, whereas the posterior surface of the lens is oblate which is consistent with the anatomical data. A ray tracing procedure has been applied to study the refractive structure of the eye. The optical characters of the model have been studied. The reason that the wings occur on the spherical aberration curve has been given. And we found that the lens with gradient refractive index and lens with shell structure can give same longitudinal spherical aberration results. 相似文献
25.
Igor V. Zatovsky Nikolay S. Slobodyanik V. I. Ivanenko Yu. S. Oseledchik V. Yu. Letsenko Tetiana I. Ushchapivska 《Crystal Research and Technology》2016,51(2):178-182
Solid solutions KTi1‐XHfXOPO4 (х = 0.008 – 0.107) possessing the KTiOPO4 structure, have been synthesized in molten system K2O‐P2O5‐TiO2‐HfF4. The crystal growth experiment of Hf‐doped KTP crystal has been reported. The X‐ray powder diffraction data and chemical analysis are also presented. It has been shown that KTiOPO4 crystal structure slightly changes when Hf incorporates into the framework. Transmission/absorption spectra of KTi0.974Hf0.026OPO4 crystals have been recorded. The incorporation of Hf ions shifts the optical absorption edge in the UV‐visible spectrum towards the long‐wavelength region with absorption near 387 nm. 相似文献
26.
《Helvetica chimica acta》2017,100(4)
[K(crypt‐222)]+ ( 1 ) and [K(crypt‐222)]+ ( 3 ) are isostructural, displaying nearly identical unit cell parameters. The two structures are similar to the extent that the previously reported [K(crypt‐222)]+ model can be refined against the new data for [K(crypt‐222)]+ , with extra electron density being observed from the fourth fluorine atom of the . In agreement with experimental observations, theoretical calculations suggest that deprotonated [K(crypt‐222)]+ is highly unstable even at as low as 195 K. The previously considered 1:1 CHF 3 clathrate of deprotonated [K(crypt‐222)]+ (crystallographically indistinguishable from 1 ) is ruled out on the basis of all available data. 相似文献
27.
Morteza Bararjanian Saeed Balalaie Frank Rominger Sanaz Barouti 《Helvetica chimica acta》2010,93(4):777-784
A three‐component reaction of benzaldehyde derivatives, methyl cyanoacetate, and guanidinium carbonate affords 2‐amino‐4‐aryl‐1,6‐dihydro‐6‐oxopyrimidine‐5‐carbonitriles and the four‐component reaction of benzaldehyde derivatives, methyl cyanoacetate, and guanidinium hydrochloride in the presence of piperidine leads to piperidinium salts of pyrimidinones. X‐ray crystallography data confirm self‐assembly and H‐bonding in these compounds. 相似文献
28.
Yang Yu Hao Gao Yi Dai Ying Wang He‐Ru Chen Xin‐Sheng Yao 《Helvetica chimica acta》2010,93(4):763-771
Eight new monoterpenoids, jasminoside J ( 1 ), jasminoside K ( 2 ), 6′‐O‐trans‐sinapoyljasminoside B ( 3 ), 6′‐O‐trans‐sinapoyljasminoside L ( 4 ), jasminosides M–P ( 5 – 8 ), together with three known analogues, jasminoside C ( 9 ), jasminol E ( 10 ), and sacranoside B ( 11 ), were isolated from the fruit of Gardenia jasminoides Ellis (Rubiaceae). Their structures were elucidated by spectral and chemical methods. 相似文献
29.
The thermal reactions of the 2,2,3‐trisubstituted N‐phthalimidoaziridine 1a with dimethyl acetylenedicarboxylate (DMAD), thioketones 4a – 4d , and dimethyl azodicarboxylate ( 5 ) proceed even at room temperature leading to the five‐membered cycloadducts 2a, 6 – 8 , and 12 , respectively, with retention of the spatial arrangement of the aziridine substituents, in contrast to the expectation based on the conservation of orbital symmetry in concerted reactions. The analogous reactions of the tetrasubstituted phthalimidoaziridine 1b with thioketones at 40° lead to the 1,3‐thiazolidine derivatives 10 and 11 as mixtures of diastereoisomers. These unexpected results may be explained by either the isomerization of the intermediate azomethine ylides or a non‐concerted stepwise cycloaddition reaction of these ylides with the dipolarophiles. The structures of some adducts have been determined by X‐ray crystallography. 相似文献
30.
A facile, convenient, and one‐pot multi‐step synthesis of substituted piperidin‐2‐ones from the Baylis–Hillman alcohols derived from various aldehydes and acrylonitrile, involving Johnson–Claisen rearrangement, reduction of an α,β‐unsaturated nitrile moiety into the saturated amine‐skeleton, followed by cyclization, in an operationally simple procedure, is described. 相似文献