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151.
Jorge Castellanos-Soriano Allen T. Ekubo Mark R. J. Elsegood Nuria Lastra-Calvo Aman Mantry Arturo Martinez-Insua-Rodriguez 《Phosphorus, sulfur, and silicon and the related elements》2017,192(5):570-575
New tetraalkylaminophosphonium chlorides were readily prepared by four-fold condensation of commercially available [P(CH2OH)4]Cl with a range of fifteen aryl based primary amines, in EtOH, at ambient temperature. All compounds have been characterized by FT–IR spectroscopy and elemental analysis. Solution 31P{1H} NMR studies of these chloride salts reveal their instability with respect to various PIII/PV species. The structures of three examples have been determined by single crystal X-ray diffraction and confirm the pseudotetrahedral arrangement around the PV center. Extensive N–H···Cl hydrogen bonding is observed. 相似文献
152.
J. Graham Dawber R. Glynn Skerratt John C. Tebby Albert A. C. Waite 《Phosphorus, sulfur, and silicon and the related elements》2013,188(10):1261-1268
Abstract Third order rate constants have been determined for the alkaline hydrolysis of four series of alkylphenylphosphonium salts and alkylphenylbenzylphosphonium salts at various temperatures in 50%–70% v/v aqueous tetrahydrofuran and 70% v/v aqueous methanol. Thermodynamic activation parameters have been calculated for the reactions of each substrate and the effects of varying the ratio of alkyl to phenyl groups have been compared, as well as the effects of changes in the nature of the alkyl group. Solvation, as revealed by trends in entropy of activation, plays a largely counter-balancing role with respect to enthalpy and energy of activation. The role of the isokinetic effect is discussed. In aqueous tetrahydrofuran, solvation effects on the hydrolyses of phosphonium salts change as the mole fraction of water changes, and for aqueous methanol the trends in the thermodynamic activation parameters actually reverse. 相似文献
153.
154.
R. Hekmatshoar S. Souri M. Rahimifard 《Phosphorus, sulfur, and silicon and the related elements》2013,188(8):1605-1609
Protonation of the highly reactive intermediate produced in the reaction between triphenylphosphine and dialkyl acetylenedicarboxylate 1a–c by methyl-2-hydroxy-3-naphthoate lead to vinyl triphenylphosphonium salts which undergo aromatic electrophilic substitution reaction with phenolate-conjugated base to produce 2a–c. 相似文献
155.
156.
Nobumasa Kamigata 《Phosphorus, sulfur, and silicon and the related elements》2013,188(3-4):667-678
Abstract The synthesis and stereochemistry of tricoordinated optically active selenium and tellurium compounds are described. Telluronium salts, telluronium imides, and seleninic acids were prepared and optically resolved by fractional recrystallization of diastereomeric mixtures or by chromatography using a chiral column of racemic mixtures. Diphenyl dichalcogenides also were optically resolved by chiral crystallization. Their absolute configurations were determined or estimated based on X-ray crystallographic analysis, specific rotations, and circular dichroism spectra. The kinetic studies and the mechanism for the racemization were also studied. 相似文献
157.
158.
Cristofor Simionescu Severian Dumitriu Marcel Popa Cristina Coman Vlad Artenie 《高分子科学杂志,A辑:纯化学与应用化学》2013,50(6):677-686
Pepsin was immobilized on BIOZAN R (Hercules) with dicyclohexylcarbodiimide as activator. The reaction product obtained has a protein content of 35–110 mg/g of polymer and a proteolytic activity between 20.85–28.75 μmol tyrosine/L·min·g of polymer). The coupling reaction rate is maximum under the following conditions: pepsin/BIOZAN R ratio = 0.52 g/g, DCCI/BIOZAN R ratio = 0.2 g/g, pH = 3.4, reaction time = 4 h. 相似文献
159.
The influence of cyclodextrins (CDs) on the formation of azocrown ethers comprising pyrrole, imidazole and substituted imidazole has been studied. Pyrrole, imidazole, 2-methyl-, 4-methyl- and 4-phenylimidazole were coupled with bis-diazonium salts derived from bis-1,5-(2-aminophenoxy)-3-oxapentane or bis-1,8-(2-aminophenoxy)-3,6-dioxaoctane to form macrocyclic compounds with two azo units. The syntheses were performed under standard conditions in the presence of α-, β- or γ-CDs and the yield of the reaction products was compared with the results of plain experiments, i.e. without CDs. The results are discussed in terms of co-conformation of azole molecules embedded in CD cavity. Pyrrole or imidazole or imidazole derivatives were coupled with bis-diazonium salts to form macrocycles with two azo units. The syntheses were performed under standard conditions in the presence of α-, β-, or γ-cyclodextrin and the yield of the reaction products was compared with the results of plain experiments, i.e. without CDs. The results are discussed in terms of co-conformation of azole molecules embedded in cyclodextrin cavity. 相似文献
160.
M. Sc. Durga Prasad Hari Prof. Dr. Burkhard König 《Angewandte Chemie (International ed. in English)》2013,52(18):4734-4743
The use of diazonium salts for aryl radical generation and C? H arylation processes has been known since 1896 when Pschorr first used the reaction for intramolecular cyclizations. Meerwein developed it further in the early 1900s into a general arylation method. However, this reaction could not compete with the transition‐metal‐mediated formation of C(sp2)? C(sp2) bonds. The replacement of the copper catalyst with iron and titanium compounds improved the situation, but the use of photocatalysis to induce the one‐electron reduction and activation of the diazonium salts is even more advantageous. The first photocatalyzed Pschorr cyclization was published in 1984, and just last year a series of papers described applications of photocatalytic Meerwein arylations leading to aryl–alkene coupling products. In this Minireview we summarize the origins of this reaction and its scope and applications. 相似文献