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991.
In 1959, Horner showed that metalated alkyldiphenylphosphane oxides react with aldehydes or ketones to give alkenes. With this reaction, the diphenylphosphoryl (Ph2PO) group made its entrance into synthetic organic chemistry. In the thirty-six years since that date, extensive research has shown that this olefination, the Horner–Wittig reaction, has unique properties that make it much more than simply the phosphane oxide cousin of the more famous phosphorus-based olefinations—the Wittig reaction (based on phosphonium salts) and the Wadsworth–Emmons reaction (based on phosphonate esters). Early work on the Horner–Wittig reaction concentrated on the reactivity of phosphane oxides and the regioselectivity of their reactions, but more recently the power of the Ph2PO group to control the stereochemistry of alkenes, and to produce “on demand” either stereoisomer in high stereochemical purity, has emerged. From the study of these stereocontrolled Horner–Wittig reactions arose the realization that the Ph2PO group is useful not only for the control of the two-dimensional stereochemistry of alkenes, but also of three-dimensional stereochemistry in general. After a brief introduction to phosphane oxide chemistry, this review will examine the Horner–Wittig reaction, in both its original and “stereocontrolled” varieties. From there, we will move on to an account of the stereoselective construction of molecules containing the Ph2PO group, concentrating on the stereochemical directing effects of the Ph2PO group and on the role of its unique combination of attributes—steric bulk, electronegativity, and Lewis basicity—in controlling these reactions. Finally, we will present what is intended as a practical guide to this chemistry, covering the type of functionalized alkenes that have been made with the help of the Ph2PO group and giving guidelines that we hope will help the organic chemist to make the most of the chemistry the Ph2PO group has to offer. 相似文献
992.
993.
Kazimierz?DarowickiEmail author Waldemar?Felisiak Artur?Zieliński 《Journal of mathematical chemistry》2005,38(4):701-711
Oscillations of species concentration are phenomena accompanying several types of electrochemical and purely chemical processes.
Importance of analyzing of such processes results from both scientific and practical reasons. In the paper the authors deal
with investigation of time dependent spectra of various stages of Belousov-Zhabotinsky type chemical oscillations. As the
analytical tool the discrete wavelet transform is proposed. 相似文献
994.
995.
Christelle Titier Jean-Pierre Pascault Mohamed Taha Boris Rozenberg 《Journal of polymer science. Part A, Polymer chemistry》1995,33(1):175-184
Epoxy-amine methacrylated prepolymers are prepared in a 1-step synthesis by the reaction of Bisphenol A diglycidyl ether, glycidyl methacrylate, and different diamines. The adaptation of these reactions to production processes with a reduced reaction time requires a kinetic control and the use of efficient catalysts. The comparative kinetic treatment of the epoxy-amine reaction in the frame of Horie's and Rozenberg's kinetic schemes have been made. Cases where an efficient acid catalyst is used are also examined. Structural studies of these reactions established the occurrence of a Michael amine/double bond addition, when some amines are used. © 1995 John Wiley & Sons, Inc. 相似文献
996.
The regioselectivity of the reactions of perimidine with cinnamic acids in polyphosphoric acid (PPA) depends on the P2O5 content. Procedures were developed for the synthesis of 4(9)- and 6(7)-cinnamoylperimidines. Cyclization of the latter under the action of an excess of AlBr3 was accompanied by dearylation to form 6-hydroxy-1,3-diazapyrene. 相似文献
997.
Ch. S. Becker G. I. Roshchupkina T. V. Rybalova Yu. V. Gatilov V. A. Reznikov 《Russian Chemical Bulletin》2007,56(6):1210-1215
In some cases, the reactions of enaminones of the imidazolidine 1-oxide series with the Vilsmeier reagent afford electrophilic
substitution products containing the dimethyl-aminomethylene group. In an acidic medium, these products undergo either hydrolytic
elimination of the dimethylaminomethylene moiety or hydrolysis of the latter to form the aldehyde group. The reaction of nitroenamine,
which is a derivative of imidazolidine 1-oxide, with the Vilsmeier reagent produces furoxane, viz., the nitroxyl biradical. Reduction of the latter affords the dioxime biradical.
Dedicated to the memory of Academician N. N. Vorozhtsov on the 100th anniversary of his birth.
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 6, pp. 1165–1170, June, 2007. 相似文献
998.
Hydrothermal Synthesis and Electrochemical Properties of Complex Cu(CH3C6H4COOH)2(2,2''-bipy)·(H2O) 总被引:1,自引:0,他引:1
The title complex has been synthesized by 4-methylbenzoic acid and 2,2'-bipyridine (bipy) in the mixed solvent of water and methanol. It crystallizes in the triclinic system, space group (P1-) with a = 0.7047(3), b = 1.1217(5), c = 1.6718(7) nm, α = 103.826(7), β = 90.772(6), γ = 104.195(6)°, C26H25CuN2O5.50, Mr = 517.02, V = 1.2404(9) nm3, Dc = 1.384 g/cm3, Z = 2, F(000) = 536, μ(MoKα= 0.921 mm-1, R = 0.0782 and wR = 0.2172. Structural analysis shows that the copper atom is coordinated with three oxygen atoms from two 4-methylbenzoic acids and one water molecule together with two nitrogen atoms from 2,2'-bipyridine, giving a distorted square-pyramid coordination geometry. The cyclic voltametric behavior of the complex has also been described. 相似文献
999.
本文是对旨在提高合成效率的化学反应选择性和金属有机化学关系的综述,按金属有机化合物的基元反应进行讨论。 相似文献
1000.
研究了真空条件下SnMe4在MCM-41分子筛表面的接枝反应,并用元素分析、ICP、GC-MS、XRD、FTIR、DRS、13C及119Sn MAS NMR、XPS、BET、TPD、TPR等方法对产物的组成、结构和性质进行了表征.结果表明, 两者可以定量地进行化学反应,将确定数目的甲基锡基团接枝在分子筛表面, 形成SnMe3/MCM-41物种;接枝反应发生在分子筛表面上, 不破坏MCM-41分子筛骨架结构;改性分子筛的BET比表面积有所降低,孔体积变小, 表面性质发生变化.四甲基锡在MCM-41上接枝反应的温度为343 K,比它与HY沸石的反应温度(193 K)高得多,并且产物SnMe3/MCM-41的热稳定性也高于SnMe3/HY. 相似文献