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831.
AntnioF.DeC. Alcntara MariaG.F. Vaz HumbertoO. Stumpf Dorila Pil‐Veloso WagnerB. DeAlmeida 《Helvetica chimica acta》2004,87(2):425-438
Conformational studies of 1,3‐dihydroxy‐4,4,5,5‐tetramethyl‐2‐(pyridin‐1‐yl)imidazolidine ( 1a ) and 1,3‐dihydroxy‐4,4,5,5‐tetramethyl‐2‐(pyridin‐3‐yl)imidazolidine ( 1b ), carried out by using 1D 1H‐ and 13C‐NMR and 2D HMQC, HMBC, and NOESY experiments and with the aid of theoretical calculations, indicate that the OH groups are trans to the pyridinyl substituent. Because the two 1H‐NMR signals of the Me groups are distinguishable and do not change between 290 and 380 K, it is proposed that 1a and 1b have each only one conformation in this temperature range. This behavior was not found with 1,3‐dihydroxy‐4,4,5,5‐tetramethyl‐2‐(pyridin‐2‐yl)imidazolidine ( 1c ) because its Me 1H‐NMR signals cross over at 300 K. Hence, more than one conformation must be present, beyond those produced by simple inversions. Theoretical calculations including temperature and solvent effects were performed to provide further information on the conformational analysis and to help to assign the NMR data. The combination of NMR measurements and quantum‐chemical calculations is shown to be a very promising strategy for conformational analysis studies in solution. 相似文献
832.
Grald Lelais Peter Micuch Delphine Josien‐Lefebvre Francesco Rossi Dieter Seebach 《Helvetica chimica acta》2004,87(12):3131-3159
The Ser, Cys, and His side chains play decisive roles in the syntheses, structures, and functions of proteins and enzymes. For our structural and biomedical investigations of β‐peptides consisting of amino acids with proteinogenic side chains, we needed to have reliable preparative access to the title compounds. The two β3‐homoamino acid derivatives were obtained by Arndt–Eistert methodology from Boc‐His(Ts)‐OH and Fmoc‐Cys(PMB)‐OH (Schemes 2–4), with the side‐chain functional groups' reactivities requiring special precautions. The β2‐homoamino acids were prepared with the help of the chiral oxazolidinone auxiliary DIOZ by diastereoselective aldol additions of suitable Ti‐enolates to formaldehyde (generated in situ from trioxane) and subsequent functional‐group manipulations. These include OH→OtBu etherification (for β2hSer; Schemes 5 and 6), OH→STrt replacement (for β2hCys; Scheme 7), and CH2OH→CH2N3→CH2NH2 transformations (for β2hHis; Schemes 9–11). Including protection/deprotection/re‐protection reactions, it takes up to ten steps to obtain the enantiomerically pure target compounds from commercial precursors. Unsuccessful approaches, pitfalls, and optimization procedures are also discussed. The final products and the intermediate compounds are fully characterized by retention times (tR), melting points, optical rotations, HPLC on chiral columns, IR, 1H‐ and 13C‐NMR spectroscopy, mass spectrometry, elemental analyses, and (in some cases) by X‐ray crystal‐structure analysis. 相似文献
833.
A series of phenyl modified polydimethylsiloxane (PDMS) / polyhydrogenmethylsiloxane (PHMS) random copolymers containing both internal Si‐H and terminal SiH2 and T (MeSiO3/2) units was synthesized in one step through n‐BuLi‐catalyzed ring‐opening polymerization of cyclic comonomers and characterized by GPC, IR and 1H and 29Si NMR. Sequential microstructures of these copolymers were determined by 29Si‐NMR spectroscopy. Epoxy‐modified polysiloxanes were prepared and used as comparable standards for the assignment of the NMR spectra. A hydride‐transfer mechanism has been proposed to account for the formation of terminal Si‐H and T group. Detailed sequential analyses and chemical shifts of 29Si‐NMR for various siloxane units are reported for the first time. 相似文献
834.
The synthesis and basic photophysical characteristics of a novel green fluorescent polyvinylcarbazole polymer containing 4‐N,N‐dimethylaminoethyleneamino‐1,8‐naphthalimide side chains has been described. The ability to sense metal cations has been monitored by fluorescence emission spectroscopy. It is shown that the fluorescent intensity is very sensitive to the Fe2+ cations and the copolymer can be used as an homogeneous and heterogeneous fluorescent sensor for Fe2+ cations. Copyright © 2004 John Wiley & Sons, Ltd. 相似文献
835.
Meiyappan Muthuraman Jean‐Franois Nicoud Muriel Bagieu‐Beucher 《Acta Crystallographica. Section C, Structural Chemistry》2000,56(9):1077-1078
The title compound, alternatively sodium pyridin‐2‐olate trihydrate, Na+·C5H3N2O3?·3H2O, crystallizes in the P space group. It is made up of edge‐shared chains of NaO6 octahedra with five water molecules and one 5‐nitro‐2‐pyridonate anion. Four of these water molecules are bicoordinating, involved in connecting the adjacent octahedra, and the fifth is coordinated to only one octahedron. The crystal structure is stabilized by a network of strong O—H?O and O—H?N interactions. The organic moieties occupy the space between the chains with an antiparallel alignment. 相似文献
836.
Manuel Cano Beatriz Palenzuela J. Luis Ávila Rafael Rodríguez‐Amaro 《Electroanalysis》2007,19(9):973-977
A PVC/TTF‐TCNQ composite electrode has been employed as detector in a flow injection system. The proposed method allows the simultaneous detection of ascorbic acid (AA) and uric acid (UA) in mixtures by using a FIA system in a simple manner, without pre‐treatment or modified electrode. This method is based on the amperometric determination of (a) ascorbic acid at 0.15 V and (b) both analytes at 0.35 V, being the response linear in the range 1×10?2–4×10?4 M for both analytes with detection limits (S/N=3) of 1.2×10?4 M and 8.1×10?5 M for AA and UA, respectively. 相似文献
837.
Two new uncommon nitrogenous sesquiterpenes, 11‐ethoxy‐3‐formamidotheonellin ( 1 ) and 7‐ethoxy‐3‐formamidobisabolane‐8,10‐diene ( 2 ), together with two known related sesquiterpenes, 3‐formamidotheonellin (=theonellin formamide; 3 ) and theonellin isothiocyanate ( 4 ), were isolated from the Hainan sponge Axinyssa aff. variabilis. Their structures were determined on the basis of extensive spectroscopic analysis and by comparison of their NMR data with those of known compounds. 相似文献
838.
Zhan‐Xin Zhang Wei‐Dong Xie Ping‐Lin Li Yan‐Ping Shi Zhong‐Jian Jia 《Helvetica chimica acta》2006,89(12):2927-2933
Six new compounds were isolated from the whole plant of Sonchus uliginosus, including three eudesmane‐type sesquiterpenoids (1β,6α)‐1,6,14‐trihydroxyeudesm‐3‐en‐12‐oic acid γ‐lactone ( 1 ), (1β,6α)‐1,6,14‐trihydroxyeudesma‐3,11(13)‐dien‐12‐oic acid γ‐lactone ( 2 ), and (1β,6α)‐1,6‐dihydroxy‐14‐O‐[(4‐hydroxyphenyl)acetyl]eudesma‐3,11(13)‐dien‐12‐oic acid γ‐lactone ( 3 ), and three phenylpropane derivatives, 4‐hydroxy‐γ,3,5‐trimethoxybenzenepropanol ( 6 ), γ,3,4,5‐tetramethoxybenzenepropanol ( 7 ), and γ,3,4,5‐tetramethoxybenzenepropanol acetate ( 8 ), together with the two known compounds 4 and 5 . The new structures were elucidated by means of spectroscopic methods, such as IR, EI‐MS, HR‐ESI‐MS, 1D‐ and 2D‐NMR, and by comparison of the spectroscopic data with those reported for structurally related compounds. 相似文献
839.
The isolation and identification of twenty‐one components (including four new triterpenoid saponins and one new triterpenoid acid) from the root of Rhaponticum uniflorum (L.) DC. (Compositae) are described. Their structures were determined on the basis of spectral analysis and chemical trans formation. The new compounds were identified as 3‐O‐α‐L‐arabinopyranosyl‐urs‐12,18(19)‐dien‐28‐oic acid β‐D‐glucopyranosyl ester, 3β‐ hydroxyurs‐12,18(19)‐dien‐28‐oic acid β‐D‐glucopyranosyl ester, 3β‐hydroxyurs‐12,19(29)‐dien‐28‐oic acid β‐D‐glucopyranosylester, 3‐O‐α‐L‐arabinopyranosyl‐urs‐9(11),12‐dien‐28‐oic acid β‐D‐glucopyranosyl ester and 2 α,3 α, 19α,25‐tetrahydroxyurs‐12‐en‐23,28‐dioic acid. 相似文献
840.
Ju‐Yeon Lee Eun‐Ju Park 《Journal of polymer science. Part A, Polymer chemistry》2002,40(11):1742-1748
Methyl 3,4‐di‐(2′‐hydroxyethoxy)benzylidenecyanoacetate ( 3 ) was prepared by hydrolysis of methyl 3,4‐di‐(2′‐vinyloxyethoxy)benzylidenecyanoacetate ( 2 ). Diol 3 was condensed with 2,4‐toluenediisocyanate, 3,3′‐dimethoxy‐4,4′‐biphenylenediisocyanate, and 1,6‐hexamethylenediisocyanate to yield polyurethanes 4 – 6 containing the nonlinear optical chromophore 3,4‐dioxybenzylidenecyanoacetate. The resulting polyurethanes 4 – 6 were soluble in common organic solvents such as acetone and dimethylformamide. Polymers 4 – 6 indicated thermal stability up to 300 °C in thermogravimetric thermograms with glass‐transition temperature values obtained from differential scanning calorimetric thermograms in the range of 78–102 °C. The second‐harmonic generation coefficients (d33) of the poled polymer films were around 6.9 × 10?9 esu. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 1742–1748, 2002 相似文献