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Corresponding Derivatives (corresponding + derivative)
Selected AbstractsReactions of Polycyclic Ketones with Dimethoxycarbene; a Convenient Route for a ,One-Pot' Preparation of Some , -Hydroxycarboxylic Acid EstersHELVETICA CHIMICA ACTA, Issue 7 2007Jaros, aw Roma Abstract Polycyclic ,cage' ketones, such as pentacyclo[5.4.0.02,6.03,10.05,9]undecan-8-one (10), pentacyclo[5.4.0.02,6.03,10.05,9]undecane-8,11-dione (11), and adamantan-2-one (16) were treated with the nucleophilic dimethoxycarbene (DMC; 1), which was generated thermally from 2,5-dihydro-2,2-dimethoxy-5,5-dimethyl-1,3,4-oxadiazole (4a) in boiling toluene. In this ,one-pot' procedure, the , -hydroxycarboxylic acid ester 12 or a corresponding derivative 15 or 17 was obtained (Schemes,4,7). Additionally, ,cage' thione 21 was treated with DMC under the same conditions yielding dimethoxythiirane 22 (Scheme,8). Subsequent hydrolysis or desulfurization (followed by hydrolysis on silica gel) of 22 gave , -mercaptocarboxylate 25 and the corresponding desulfurized ester 24, respectively. In all cases, the addition of DMC occurred stereoselectively, and the addition from the exo -face is postulated to explain the structures of the isolated products. [source] Synthesis and Reactivity of Oxametallacyclic Niobium Compounds by Using ,,,-Unsaturated Carbonyl Ligands,EUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 14 2008Rocío A. Arteaga-Müller Abstract Reduction of mono(cyclopentadienyl)niobium complexes [NbCpRCl4] [CpR = C5Me4H (1), C5H4SiMe2Cl (2), C5H4SiMe3 (3)] with Na/Hg in the presence of methyl methacrylate [MMA, CH2=C(Me)C(O)OMe (a)], methyl acrylate [MA, CH2=CHC(O)OMe (b)] and mesityl oxide [MO, CMe2=CHC(O)Me (c)] afforded the corresponding derivatives [NbCpRCl2(LL)] [CpR = C5Me4H, LL = MMA (1a); CpR = C5H4SiMe2Cl, LL = MMA (2a), MA (2b), MO (2c); CpR = C5H4SiMe3, LL = MMA (3a), MA (3b)] in variable yields depending on both the cyclopentadienyl and the ,,,-unsaturated carbonyl compounds. The reactivity of these complexes was studied toward protic and Lewis acids. Addition of triflic acid TfOH (Tf = CF3SO2) to 3b gave the triflate complex [NbCpRCl2{(CH2)2C(O)OMe}(OTf)] [CpR = C5H4SiMe3 (4)]. The Lewis acids E(C6F5)3 (E = B, Al) reacted with complexes 2b and 3b to give the three-membered metallacyclic (or ,2 -enone) compounds [NbCpRCl2{,2 -CH2=CHC(OMe){O·E(C6F5)3}}] [CpR = C5H4SiMe2Cl, E = B (5), Al (6); CpR = C5H4SiMe3, E = B (7), Al (8)], which decomposed to the corresponding adducts MA·E(C6F5)3. The same reaction with the 2a and 3a derivatives only allowed the observation of the corresponding adducts MMA·E(C6F5)3. Complexes 2a,b and 3a,b reacted with CO with elimination of the acrylate compounds, MA and MMA, respectively, to give the carbonylniobium(III) compounds [NbCpRCl2(CO)2]2 [CpR = C5H4SiMe2Cl (9), C5H4SiMe3 (10)]. Analogous reactions with CNAr showed the elimination of the free MA and MMA compounds. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008) [source] Ionization potentials of heteroalkenes: a comparative studyAPPLIED ORGANOMETALLIC CHEMISTRY, Issue 12 2004Anna Chrostowska Abstract Methanimine, methylenephosphine and methylenearsine have been prepared in the gas phase and the gaseous flow has been analyzed by spectroscopy. Photoelectron spectra have been recorded and we report here a comparative study on these spectra. This comparison has been extended to the corresponding derivatives with a triple bond: hydrogen cyanide and methylidynephosphine. Estimation by theoretical calculations of the ionization potentials of the unknown methylidynearsine has been proposed. Copyright © 2004 John Wiley & Sons, Ltd. [source] Maximum likelihood estimation of a latent variable time-series modelAPPLIED STOCHASTIC MODELS IN BUSINESS AND INDUSTRY, Issue 1 2001Francesco Bartolucci Abstract Recently, Fridman and Harris proposed a method which allows one to approximate the likelihood of the basic stochastic volatility model. They also propose to estimate the parameters of such a model maximising the approximate likelihood by an algorithm which makes use of numerical derivatives. In this paper we propose an extension of their method which enables the computation of the first and second analytical derivatives of the approximate likelihood. As will be shown, these derivatives may be used to maximize the approximate likelihood through the Newton,Raphson algorithm, with a saving in the computational time. Moreover, these derivatives approximate the corresponding derivatives of the exact likelihood. In particular, the second derivative may be used to compute the standard error of the estimator and confidence intervals for the parameters. The paper presents also the results of a simulation study which allows one to compare our approach with other existing approaches. Copyright © 2001 John Wiley & Sons, Ltd. [source] Juvenile hormone,stimulated synthesis of acyl-glycerols and vitamin E in female accessory sexual glands of the fire bug, Pyrrhocoris apterus L.ARCHIVES OF INSECT BIOCHEMISTRY AND PHYSIOLOGY (ELECTRONIC), Issue 1 2009Pavel Jedli Abstract Secretory cells of the female accessory sexual glands (AG) of P. apterus grow and produce yellow oily exocrine secretion in response to stimulation by endogenous juvenile hormone (JH) or exogenous treatments by JH analogues. The secretion determines the property of future egg shells by coating the chorion surface of the oocytes that are passing individually through the common uterus during oviposition. Diapausing females with a physiologically inhibited endocrine system or females with artificially removed hormonal sources show inactive ovaries and empty AG without the secretory products. Ovary-ectomised females with the intact neuroendocrine system develop hypertrophic AG loaded with the oily secretion. This shows that there is no direct dependence between formation of the oily secretion in AG and ovarian growth. Chemical analysis of the secretory products revealed the presence of acetylated glycerols, with the most abundant stearoyl-diacetyl-glycerol, stearoyl-acetyl-propionyl-glycerol, and the corresponding derivatives of arachidonic acid. In addition to this, the JH-activated secretory cells of AG also produced , - and , -tocopherols. The possible antioxidant or antimutagenic action of these vitamin E compounds in insect reproduction has been emphasized. © 2009 Wiley Periodicals, Inc. [source] A robust bulk-solvent correction and anisotropic scaling procedureACTA CRYSTALLOGRAPHICA SECTION D, Issue 7 2005Pavel V. Afonine A reliable method for the determination of bulk-solvent model parameters and an overall anisotropic scale factor is of increasing importance as structure determination becomes more automated. Current protocols require the manual inspection of refinement results in order to detect errors in the calculation of these parameters. Here, a robust method for determining bulk-solvent and anisotropic scaling parameters in macromolecular refinement is described. The implementation of a maximum-likelihood target function for determining the same parameters is also discussed. The formulas and corresponding derivatives of the likelihood function with respect to the solvent parameters and the components of anisotropic scale matrix are presented. These algorithms are implemented in the CCTBX bulk-solvent correction and scaling module. [source] | ||||||||||