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61.
A new germacrenolide (1) and fourteen known terpenoids (2–15) were isolated from the barks of Magnolia maudiae (Dunn) Figlar (Magnoliaceae). The structure of (7αH,11βH)-2α,8α-dihydroxy-4α,5β-epoxy-germacr-1(10)-en-6α,12-olide (1) was elucidated by physical and spectroscopic data analysis, including 1D, 2D NMR and HR-ESI-MS. Lyratol F (9) was isolated from Magnolia for the first time. The structures of known compounds were established by comparing their spectroscopic data with those in literatures.  相似文献   
62.
Summary. N-Alkylation of certain angularly substituted heterocycles by C2- and C3-units provided appropriate precursors to construct stereoselectively the erythrinanone and several erythrinanone type analogues by intramolecular Friedel-Crafts acylation. The resulting aromatic ketones were catalytically reduced affording the corresponding parent frameworks including the hitherto unknown tetracyclus A-norschelhammerane. On the other hand, the stereoselective reduction of the carbonyl moiety offered a convenient approach to 11-hydroxylated erythrinanes with the natural occurring -configuration. The structures and the stereochemistry of the target compounds were proved by NMR spectroscopy.Part of PhD thesis, LMU München, D  相似文献   
63.
A tandem mass spectral database system consists of a library of reference spectra and a search program. State‐of‐the‐art search programs show a high tolerance for variability in compound‐specific fragmentation patterns produced by collision‐induced decomposition and enable sensitive and specific ‘identity search’. In this communication, performance characteristics of two search algorithms combined with the ‘Wiley Registry of Tandem Mass Spectral Data, MSforID’ (Wiley Registry MSMS, John Wiley and Sons, Hoboken, NJ, USA) were evaluated. The search algorithms tested were the MSMS search algorithm implemented in the NIST MS Search program 2.0g (NIST, Gaithersburg, MD, USA) and the MSforID algorithm (John Wiley and Sons, Hoboken, NJ, USA). Sample spectra were acquired on different instruments and, thus, covered a broad range of possible experimental conditions or were generated in silico. For each algorithm, more than 30 000 matches were performed. Statistical evaluation of the library search results revealed that principally both search algorithms can be combined with the Wiley Registry MSMS to create a reliable identification tool. It appears, however, that a higher degree of spectral similarity is necessary to obtain a correct match with the NIST MS Search program. This characteristic of the NIST MS Search program has a positive effect on specificity as it helps to avoid false positive matches (type I errors), but reduces sensitivity. Thus, particularly with sample spectra acquired on instruments differing in their setup from tandem‐in‐space type fragmentation, a comparably higher number of false negative matches (type II errors) were observed by searching the Wiley Registry MSMS. Copyright © 2013 John Wiley & Sons, Ltd.  相似文献   
64.
Preparation, 11B NMR, Vibrational Spectra, and Crystal Structure of [(C5H5N)2CH2][1-(O2N)B10H9] By reaction of [B10H10]2? in aqueous acetonitrile with a saturated solution of NO2 in dichloromethane [1-(O2N) · B10H9]2? and [B10H9(NO)B10H9]3? are formed which can be separated by ion exchange chromatography on diethylaminoethyl(DEAE) cellulose from the starting compound. The X-ray structure determination of [(C5H5N)2CH2][1-(O2N)B10H9] (triclinic, space group P1 , a = 7.1530(9), b = 8.3753(8), c = 15.198(2) Å, α = 96.00(1), β = 95.48(1), γ = 95.60(1)°, Z = 2) reveals the coordination of the NO2 group via N with a B1? N distance of 1.535(5) Å and an O2? N? O1 angle of 119.3(3)°. The 11B NMR spectrum exhibits the characteristic feature (1 : 1 : 4 : 4) of an apical monosubstituted B10 cluster with a strong downfield shift of the ipso-B atom at +13.4 ppm. The IR and Raman spectra show strong NO stretching vibrations at 1381 und 1420 cm?1.  相似文献   
65.
The stereochemistry of S N2 and S N2 substitutions of the allylic mesyloxy group in mesylates of prostaglandin allylic epimeric 13- and 15-alcohols under the action of various nucleophiles (H2O, MeOH, AcOH, LiBr) was studied. The substitution accompanied by rearrangement occurs with moderate (1.4–1.6 : 1) syn-stereoselectivity with respect to the configuration of the mesyloxy group, which increases with decreasing temperature and depends only slightly on the nature of the nucleophile.__________Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 2510–2518, November, 2004.  相似文献   
66.
The intramolecular Diels—Alder reaction of readily accessible 4-substituted 4-(N-furfuryl)aminobut-1-enes was studied and a new one-step method was developed for the synthesis of 6,8a-epoxy-1,2,3,4,4a,5,6,8a-octahydroisoquinoline (3-aza-11-oxatricyclo[6.2.1.01,6]undec-9-ene) derivatives. The [4+2]-cycloaddition proceeds stereoselectively to form exo-adducts. The influence of substituents at the nitrogen atom in 4-(N-furfuryl)aminobut-1-enes on the cycloaddition pathway was examined.  相似文献   
67.
The effects of the organic pigments C.I.P. RED 177 and C.I.P. Yellow 83 as nucleating agents on the crystallization of polypropylene were studied by DSC. The anthraquinone pigment exerted a significant effect, resulting in structural modifications with lower melting point, and particularly the -modification. The DSC curves exhibit four transition regions, with the following temperature intervals: I. 415–417 K, II. 423–425 K, III. 430–432 K and IV. 438–439 K. For evaluation of the -nucleation effect of pigments, the ratio (H 1+H 2)/(H 3+H 4) was suggested.  相似文献   
68.
11-Aminodrim-7-ene was synthesized from drimenol in four steps. Drimenol was oxidized into drimenal and its oxime was dehydrated by p-tosylchloride or acetic anhydride in pyridine to form 9-cyano-11-nordrim-7-ene, reduction of which by LiAlH4 in the presence of anhydrous AlCl3 produced 11-aminodrim-7-ene. The reaction of 9-cyano-11-nordrim-7-ene, NaBH4, and CoCl2·6H2O produced a mixture of drimenylamine and 7,8-dihydrodrimenylamine in a 2:1 ratio. Translated from Khimiya Prirodnykh Soedinenii, No. 3, pp. 311–314, May–June, 2009.  相似文献   
69.
This study aims to measure the oxidative status of LDL from human plasma (n=26) as assessed by biomarkers for lipid peroxidation, total hydroxyoctadecadienoic acid (tHODE), 7alpha- and 7beta-hydroxycholesterol (t7-OHCh), and 8-iso-prostaglandin F(2alpha) (t8-iso-PGF(2alpha)) after subfractionation of LDL with an anion-exchange HPLC (AE-HPLC). LDL was separated and quantified by AE-HPLC as LDL-1, LDL-2, and LDL-3 in the order of the anionic charge of the LDL particles. The concentrations of tHODE, t7-OHCh, and t8-iso-PGF(2alpha) in both plasma and LDL subfractions were assessed after reduction and saponification. In this method, the free and ester forms of hydroperoxides, ketones, and hydroxides of linoleic acid and cholesterol are measured as tHODE and t7-OHCh, respectively. It was found that tHODE significantly correlated with the proportion of LDL-2 and LDL-3 as well as with the concentration of malondialdehyde-modified LDL in plasma. Further, by the analyses of LDL subfractions, the concentrations of tHODE, t8-iso-PGF(2alpha), and t7-OHCh in LDL-3 were found to be significantly higher than those in LDL-1 and LDL-2. These results clearly indicate that the extent of oxidation increases in the order of LDL-1相似文献   
70.
A molecular dynamics study of the dark adapted visual pigment rhodopsin molecule was carried out. The interaction of the chromophore group, 11-cis-retinal, with the nearest amino acid residues in the chromophore center of the molecule, namely, in the region of the protonated Schiff base linkage, was analyzed. Most likely, the interaction of the CH=NH bond with the negatively charged amino acid residue Glu113 cannot be described as a simple electrostatic interaction of two oppositely charged groups. One can propose that not only Glu113 but also Glu181 and Ser186 are involved in stabilization of the protonated Schiff base linkage. Accord-ing to calculations, Glu181 interacts, as the counter-ion, with the Schiff base indirectly via Ser186. The intramolecular mechanisms of protonated Schiff base stabilization in rhodopsin are discussed. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 19–27, January, 2007.  相似文献   
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