Search results for "Reactivity"
showing 10 items of 880 documents
A DFT study of the mechanism of NHC catalysed annulation reactions involving α,β-unsaturated acyl azoliums and β-naphthol.
2016
The mechanism of NHC catalysed annulation reactions involving an α,β-unsaturated acyl azolium and β-naphthol has been studied using DFT methods at the MPWB1K/6-311G(d,p) level in toluene. For the C-C bond formation step, which corresponds to the rate- and stereo-determining step of this NHC catalysed reaction, the two competitive addition modes, i.e. the 1,2- and the 1,4-additions, have been studied. In toluene, acyl azolium forms an ion pair (IP) with the counterion chloride anion. Interestingly, β-naphthol forms a hydrogen bond with the chloride anion of IP, increasing the nucleophilic character of β-naphthol and the electrophilic character of the acyl azolium moiety. For the first time, …
[39] Lipoperoxyl radical-scavenging activity of vitamin A and analogs in homogeneous solution
1994
Publisher Summary This chapter describes the assay method for determining the reactivity of all- trans -retinol and other natural and synthetic retinoids, with radicals generated by reaction of the lipid-soluble azo initiator 2,2 ' -azobis(2,4-dimethylvaleronitrile) (AMVN) with methyl linoleate. The chapter discusses the general principles for measuring antioxidant activity. The oxidation of linoleic acid methyl ester (LAME) is the simplest model for studying the oxidation of polyunsaturated lipids and has been widely adopted to evaluate antioxidant activity. Because linoleic acid has two double bonds, peroxidation occurs at the bisallylic hydrogens and generates conjugated diene hydroperox…
Oxygen atom transfer catalysis by dioxidomolybdenum(VI) complexes of pyridyl aminophenolate ligands
2021
Abstract A series of new cationic dioxidomolybdenum(VI) complexes [MoO2(Ln)]PF6 (2–5) with the tripodal tetradentate pyridyl aminophenolate ligands HL2-HL5 have been synthesized and characterized. Ligands HL2-HL4 carry substituents in the 4-position of the phenolate ring, viz. Cl, Br and NO2, respectively, whereas the ligand HL5, N-(2-hydroxy-3,5-di-tert-butylbenzyl)-N,N-bis(2-pyridylmethyl)amine, is a derivative of 3,5-di-tert-butylsalicylaldehyde. X-ray crystal structures of complexes 2, 3 and 5 reveal that they have a distorted octahedral geometry with the bonding parameters around the metal centres being practically similar. Stoichiometric oxygen atom transfer (OAT) properties of 5 with…
Influence of some aromatic and aliphatic compounds on the rate of photodegradation of phenol in aqueous suspensions of TiO2
1995
Abstract The influence of 3-nitrophenol, 4-nitrophenol, pentachlorophenol, ethanol, 2-propanol, ethanoic acid and ethanedioic acid on the photodegradation rate of phenol in an aqueous suspension of TiO2 (anatase) irradiated in the near-UV region was investigated. Binary mixtures of organic compound and phenol in molar ratios of 1:1 and 10:1 were used for the photoreactivity experiments performed in a batch reactor. The mineralization rate of all the mixtures was also monitored by measuring the total organic carbon (TOC) concentration. The reactivity results indicate that the photodegradation rate of phenol is mainly determined by the total amount of aromatic substrates present in the reacti…
Well-Defined Multi-Amino-Functional and Stimuli-Responsive Poly(propylene oxide) by Crown Ether Assisted Anionic Ring-Opening Polymerization
2017
Multi-amino-functional poly(propylene oxide) (PPO) copolymers were synthesized by the anionic ring-opening copolymerization (AROP) of N,N-diethyl glycidyl amine (DEGA) and propylene oxide (PO). A solvent free synthesis route using potassium counterions and crown ether for the AROP enabled controlled (co)polymerization with full conversion. The strategy provided access to PPO-b-PDEGA block copolymers, statistical PPO-co-PDEGA copolymers, and, for the first time, PDEGA homopolymer. Molecular weights in the range of 1400 to 4200 g/mol (Mn) and dispersities (Mw/Mn) below 1.1 were obtained. Both the kinetics and resulting microstructure of the statistical copolymerization were investigated by in…
Cyclodextrins in polymer chemistry: Influence of methylated β-cyclodextrin as host on the free radical copolymerization reactivity ratios of isoborny…
1999
Methylated β-cyclodextrin (me-β-CD) was used to complex the hydrophobic monomers isobornyl acrylate (1) and butyl acrylate (2) yielding the water-soluble host/guest complexes isobornyl acrylate/me-β-CD (1a) and butyl acrylate/me-β-CD (2a). The included monomers were copolymerized in water by free-radical mechanism and the kinetics were studied. In order to evaluate these results, the corresponding uncomplexed monomers 1 and 2 were also copolymerized in organic solution. The reactivity ratios of 1a and 2a (r1a = 0.3, r2a = 1.7) differ significantly from the reactivity ratios of the corresponding uncomplexed acrylates 1 and 2 in organic solution (r1 = 1.3, r2 = 1.0). In addition, we found tha…
Towards the Next Generation of Lochmann-Schlosser Superbases: A Potassium Neopentyl/Alkoxy Aggregate used in the Tetra-Functionalization of Ferrocene
2018
Lochmann-Schlosser superbases are formed by mixing alkyllithium with potassium alkoxides. These reagents could prove their synthetic usefulness and reliability in many reactions over five decades. However, despite many efforts, the real source of the exceptional reactivity remained a secret. The seemingly manageable system of four components (lithium, potassium atoms, alkyl groups, and alkoxy groups) and their interaction is obscured by poor solubility and fierce reactivity. Recent progress was achieved by using neopentyllithium, leading to alkane-soluble aggregates with varying lithium/potassium content and a flexible alkyl/alkoxy ratio. Herein, we isolated two new alkane-soluble alkyl/alk…
Deprotonation of Fluoro Aromatics Using Lithium Magnesates.
2004
Abstract 3-Fluoropyridine was deprotonated on treatment with 1/3 equiv of Bu 3 MgLi in THF at −10 °C. The lithium arylmagnesate formed was either trapped with electrophiles or involved in a palladium-catalyzed cross-coupling reaction with 2-bromopyridine. The use of a less nucleophilic lithium-magnesium-dialkylamide, (TMP) 3 MgLi, allowed the reaction of 3-fluoroquinoline, giving the 2,2′-dimeric derivative. 2-Fluoropyridine and 2,6-difluoropyridine were deprotonated using 1/3 equiv of the highly coordinated magnesate Bu 4 MgLi 2 in THF at −10 °C in the presence of a substoichiometric amount of 2,2,6,6-tetramethylpiperidine. 1,3-Difluorobenzene reacted similarly when treated with Bu 3 MgLi;…
Group 13 complexes of dipyridylmethane, a forgotten ligand in coordination chemistry.
2015
The reactions of dipyridylmethane (dpma) with group 13 trichlorides were investigated in 1 : 1 and 1 : 2 molar ratios using NMR spectroscopy and X-ray crystallography. With 1 : 1 stoichiometry and Et2O as solvent, reactions employing AlCl3 or GaCl3 gave mixtures of products with the salt [(dpma)2MCl2](+)[MCl4](-) (M = Al, Ga) as the main species. The corresponding reactions in 1 : 2 molar ratio gave similar mixtures but with [(dpma)MCl2](+)[MCl4](-) as the primary product. Pure salts [(dpma)AlCl2](+)[Cl](-) and [(dpma)AlCl2](+)[AlCl4](-) could be obtained by performing the reactions in CH3CN. In the case of InCl3, a neutral monoadduct (dpma)InCl3 formed regardless of the stoichiometry emplo…
Two-step polymerization of propylene over MgCl2-supported titanium catalyst
1998
The prepolymerization effect on propylene polymerization in the presence of a MgCl 2 -supported titanium catalyst was studied. The catalyst was pre-activated by polymerizing a small amount of propylene in the presence of Et 3 Al and cyclohexylmethyldimethoxysilane under mild conditions, and then it was used in a second step of propylene polymerization. Comparative studies of the polymerization process involving the investigated catalyst and its unmodified counterpart showed the rate-enhancement effect of prepolymerization and the same molecular weights, MWD's and isotacticities of the polymers obtained. Concentrations of active sites and propagation rate as well as transfer rate constants w…