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21.
When heated with sodium ethoxide in ethanol 7-methylidenebicyclo[3.3.1]nonan-3-endo-ol (endo- 1 ) is converted into 1-methyl-2-oxa-adamantane ( 3 ). This reaction involves nucleophilic addition of a hydroxy group to an unactivated olefinic bond. Formation of the cyclic ether 3 also takes place when endo- 1 is heated in aqueous ethanol. This electrophilic addition is strongly catalysed by weak acids and suppressed by weak bases. These unusual reactions proceed more slowly with 7-methylbicyclo[3.3.1]non-6-en-3-endo-ol (endo- 2 ) and can be ascribed to a proximity effect. This follows from the IR . and NMR . spectra of endo- 1 and endo- 2 which show strong intramolecular hydrogen (OH-π) bonding. The unsaturated endo- and exo-alcohols 1 and 2 , respectively, undergo only exo-complexation with silver ion. 相似文献
22.
A microanalytical method for the determination of traces of natural brassinosteroids as their dansylaminophenylboronates by liquid chromatography with fluorimetric detection is described. The boronates are easily prepared by the reaction of brassinosteroids with dansylaminophenylboronic acid (DABA), which was newly synthesized as a precolumn fluorogenic reagent for brassinosteroids. The potential of the method is demonstrated by the separation of a standard brassinosteroid mixture and the analysis of a biologically active fraction sample obtained from an extract of Zea mays L. pollen. The detection limit of the DABA derivative was found to be 25 pg for brassinolide, which is superior to that of the phenanthreneboronate derivative. 相似文献
23.
Katayama H Ishihama Y Oda Y Asakawa N 《Rapid communications in mass spectrometry : RCM》2000,14(14):1167-1178
A novel method for electrophoretic mobility-assisted identifications of proteins, using capillary electrophoresis/mass spectrometry (CE/MS) under methanolic conditions, was developed. The number of functional groups of the enzymatic digest peptides was estimated from a single run CE/MS analysis and utilized as an additional tag for database searching in addition to the mass map of the peptides. The additional amino acid information thus obtained can improve the confidence level of the protein identification. The database searching software algorithm ProFound was modified to accept the tag, based on this new concept. In this study, optimization of the CE/MS conditions for the estimation of basic functional groups was performed as an example. An accurate value of the number of such functional groups was obtained from CE characteristics when methanolic buffer (methanol/formic acid/water = 60:20:20) was used, via an excellent correlation (r = 0.997) between the number of functional groups of the peptides and [MW((2/3))]. The mass spectrometry sensitivity was also improved when using the methanolic buffer in comparison with that obtained using aqueous 1% formic acid buffer. The identification of a protein of Saccharomyces cerevisiae, which was separated by two-dimensional electrophoresis, was performed using the methanolic buffer in combination with sheathless nanoelectrospray CE/MS. A protein spot that had not been identified by MALDI-TOFMS and LC/MS/MS was successfully identified using this new method. 相似文献
24.
Nagao M Asano K Umeda K Katayama H Ozawa F 《The Journal of organic chemistry》2005,70(25):10511-10514
[reaction: see text] Complex 1 bearing a diphosphinidenecyclobutene ligand (DPCB-OMe) catalyzes highly stereoselective hydrosilylation of diethynylarenes with HSiMe2Ph to afford (Z,Z)-bis(2-silylethenyl)arenes. Treatment of the hydrosilylation products with N-bromosuccinimide causes bromodesilylation in a stereospecific manner, giving (Z,Z)-bis(2-bromoethenyl)arenes in high geometrical purity (>98%). 相似文献
25.
A. Hamelin A. Katayama G. Picq P. Vennereau 《Journal of Electroanalytical Chemistry》1980,113(2):293-300
The kinetics of chelation of Pb(II), Zn(II) and Cd(II) with the ligand EDTA have been followed at the realistic trace concentration level 10?8–10?7M for both reactants in sea water and model solutions of its major salinity components by differential pulse stripping voltammetry. In this manner the specific influences of the salinity components on the formation rate constants [having in sea water for PbEDTA the order of 3×103 and for the EDTA chelates of Zn(II) and Cd(II) of 3×102 l M?1 s?1] could be determined. The measurements emphasize the pronounced specific influences of Ca(II) on the kinetics and course of the trace metal chelation in media where this alkaline earth ion is present in substantial excess to organic chelating agents. The experiments with EDTA are to be regarded as a close simulation of the chelation processes occurring for the trace metals studied by components with suitable chelation power of dissolved organic matter (DOM) in the sea and the resulting conclusions on the mechanism are thus of general significance. 相似文献
26.
Asymmetric hydrogenation of dehydrodipeptides, α-acylaminocinnamoyl-(S)-amino esters, catalyzed by rhodium complexes with chiral diphosphines gave either (R)-N-acylphenylalanyl-(S)-amino esters or (S)-N-acylphenylalanyl-(S)-amino esters with high diastereomeric purity up to 98–99% on using proper chiral ligands. 相似文献
27.
Journal of Algebraic Combinatorics - Motivated by the theory of correspondence functors, we introduce the notion of germ in a finite poset, and the notion of germ extension of a poset. We show that... 相似文献
28.
Balest R Cho K Ford WT Lohner M Park H Rankin P Smith JG Alexander JP Bebek C Berger BE Berkelman K Bloom K Browder TE Cassel DG Cho HA Coffman DM Crowcroft DS Dickson M Drell PS Dumas DJ Ehrlich R Elia R Gaidarev P Garcia-Sciveres M Gittelman B Gray SW Hartill DL Heltsley BK Henderson S Jones CD Jones SL Kandaswamy J Katayama N Kim PC Kreinick DL Lee T Liu Y Ludwig GS Masui J Mevissen J Mistry NB Ng CR Nordberg E Patterson JR Peterson D Riley D Soffer A Avery P Freyberger A Lingel K Prescott C 《Physical review letters》1995,75(21):3809-3813
29.
Barish B Chadha M Chan S Cowen DF Eigen G Miller JS O'Grady C Urheim J Weinstein AJ Acosta D Athanas M Masek G Paar HP Gronberg J Kutschke R Menary S Morrison RJ Nakanishi S Nelson HN Nelson TK Qiao C Richman JD Ryd A Tajima H Sperka D Witherell MS Procario M Balest R Cho K Daoudi M Ford WT Johnson DR Lingel K Lohner M Rankin P Smith JG Alexander JP Bebek C Berkelman K Bloom K Browder TE Cassel DG Cho HA Coffman DM Crowcroft DS Drell PS Ehrlich R Gaidarev P Galik RS Garcia-Sciveres M Geiser B 《Physical review D: Particles and fields》1995,51(3):1014-1033
30.
Balest R Cho K Daoudi M Ford WT Johnson DR Lingel K Lohner M Rankin P Smith JG Alexander JP Bebek C Berkelman K Bloom K Browder TE Cassel DG Cho HA Coffman DM Drell PS Ehrlich R Gaiderev P Garcia-Sciveres M Geiser B Gittelman B Gray SW Hartill DL Heltsley BK Jones CD Jones SL Kandaswamy J Katayama N Kim PC Kreinick DL Ludwig GS Masui J Mevissen J Mistry NB Ng CR Nordberg E Patterson JR Peterson D Riley D Salman S Sapper M Würthwein F Avery P Freyberger A Rodriguez J Stephens R Yang S Yelton J 《Physical review letters》1994,72(15):2328-2331