Study on the Reaction of α-Ketohemithioacetal

Aromatic α-sulfinyl carboxylic acids can be rearranged to hemithioacetals or other derivatives of glyoxylic acid under the action of acid reagents was first reported by Pummerer¹. Later, Russell and coworkers applied this rearrangement to β-ketosulfoxides, synthesized α-ketohemithioacetal², which can be transformed to α-keto alcohol, α-keto aldehyde and α-hydroxy alcohol, α-hydroxy acid³. Furthermore, Hall and Poet reported that α-ketohemithio-acetal can be rearranged to the corresponding α-hydroxythioester in the presence of magnesium nitrate and sodium acetate or tertiary amine⁴. However, few reports of reaction of α-ketohemithioacetal can be seen in literature.     

Study on the Reaction of α-Thiobenzoylthioformylmorpholine

a-ThiocaIbonylthiOformnddesareOfalmostunexploredclassOfcomPOundsll],althoughtheyhavebeenpreParedsincel98Ol2-3].ThisattractSustoexploretheirchendStryandutilityinSynthesisOfheteropcles.Accordingtoourpreviousmethodl`1,a-benzOylthiOfOrmyl-morpholine1wasprePaIedfirst,fOllowedbysumirizationOfcarbonylwithLawessenreagnttoaffordtheexpeCtedcr-thjobenzoylthiOformylmorpholine2,whchhastWothiotnylgrous.onthebasisOfstructUreof2,itcanbereactedwithcomPOundsbearingdrinctionalgrouP,suchasdidrineandsen…     

Theoretical Study on the Mechanisms and Kinetic Parameters for the Initiation Reaction of Grubbs–Hoveyda Catalyst

Russian Journal of Physical Chemistry A - In this work, typical alkenes and Grubbs–Hoveyda catalyst (Cat1) were selected to study the mechanism and kinetic parameters (the entropies,...     

Infrared Kinetic Study of the Catalyzed and Uncatalyzed Reaction of Butanol-1 with α-NaphthyIisocyanate in Various Solvents

The condensation reaction of α-naphthylisocyanate with n-butanol has been studied in toluene and in bis(2-methoxyethyl) ether (diglyme) by IR spectroscopy at different temperatures (20–60°C). A kinetic study shows that it is first order with respect to each reactant even when the reaction is catalyzed by tin octoate. A general mathematical treatment indicates that secondary reactions may occur in some conditions of temperature, solvent and catalyst, but do not take place in our system. The activation enthalpy and entropy have been determined.     

Study of the Three-component Reaction of α-Nitrocarbonyl Compounds, Aromatic Aldehydes, and Cyanothioacetamide

The reaction of benzaldehyde, -nitro ketone, and cyanothioacetamide in the presence of morpholine has given the novel 3,4-trans-2-R-5-cyano-2-hydroxy-3-nitro-4-phenyl-1,2,3,4-tetrahydropyridine-6-thiolates. It was found that the reaction occurs via the formation of 1-amino-2-cyano-4-nitro-5-oxo-3-phenyl-1,2-pentene-1-thiolate. In the case of -nitroacetophenone, 3,4-trans-4,5-trans-5-cyano-2-hydroxy-3-nitro-2,4-diphenylhexahydropyridine-6(1H)-thione was also obtained. The use of -nitroesters in place of the nitro ketones in the reaction leads to morpholinium 2-aryl-1-carbethoxy-3-cyano-1-nitro-3-thiocarbamoylpropyl-1-ates as the single product.     

Spectrophotometric Study of Reaction Between Platinum and α,β,γ,δ-Tetra-(2-Chlorophenyl) Porphyrin

The present paper describes the complex reaction of α, β,γ, δ-tetra-(2-chlorophenyl} porphyrin with platinum in the presence of the mixture surfactant, sodium dodecylbenzene sulfonate and OP, and a new highly sensitive method for spectrophotometric determination of micro amounts of platinum. Beer's Law was obeyed when the concentration of platinum was in the range of 0?.2μg/25ml. The molar absorptivity was found to be 3.1×106 L mol-1 cm-1 at 417nm.     

Liquid Phase Isomerization of α-Pinene. Study of the Reaction on Sulfated ZrO2

The -pinene isomerization reaction was studied on sulfated zirconium oxide catalyst for different experimental conditions. The catalysts are active for producing camphene when they present Brönsted acidity and when zirconium oxide crystallizes in the tetragonal phase. The -pinene conversion and its selectivity to camphene can be optimised by proper selection of operating conditions such as temperature, catalyst concentration and reaction time. The use of this catalyst in the appropriate conditions can result in selectivity to camphene of about 70%.     

Ab initio Calculation and Kinetic Study for the Abstraction Reaction of H with Sihcl3

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Theoretical Studies on the Mechanism of Photocycloaddition Reaction Between 6 Azauracil and Acetone

The mechanism of photocycloaddition reaction between 6-azauracll and acetone was studied by using semiemptrical SCFMO AMI method. It was found that this reaction is not a concerted one. The calculated results are as follows:(1) A T1 state exciplex is on the T1 state energy surface; (2) T exciplex as a reactant will proceed along the energy surface of T1 state to form a diradical intermediate. The energy barrier of this reaction step is 63. 6 kJ/mol; (3) The T1 state diradical intermediate happens to be close in energy to the ground state intermediate with a similar geometry. Such a situation turns out to be very favorable for an intersystem crossing (jump from the T, state to the ground state) ; (4) The final product will be formed from the ground S0 state intermediate via an energy barrier 88. 2 kJ/mol.     

Experimental and Theoretical Study of Phosphine-Catalyzed Reaction Modes in the Reaction of α-Substituted Allenes with Aryl Imines

A new phosphine-catalyzed reaction of α-substituted allenes with aryl imines, in stark contrast to classic cycloaddition reactions, has been developed. This reaction delivers valuable highly functionalized itaconimides with excellent stereoselectivities by a new «un-cyclizing» reaction mode involving β′-carbon of α-substituted allenes. Moreover, the present «un-cyclizing» reaction can also be carried out in a one-pot fashion and scaled up to the gram scale by using aryl aldehydes, without the need to isolate the aryl imines. Mechanistic studies and control experiments reveal the crucial role of H₂CO₃ for the present reaction mode. In addition, density functional theory (DFT) calculations were performed to understand the possible mechanism.     

Theoretical Study on the Mechanism of Sonogashira Coupling Reaction

The mechanism of palladium-catalyzed Sonogashira cross-coupling reaction has been studied theoretically by DFT （density functional theory） calculations. The model system studied consists of Pd（PH3）2 as the starting catalyst complex, phenyl bromide as the substrate and acetylene as the terminal alkyne, without regarding to the co-catalyst and base. Mechanistically and energetically plausible catalytic cycles for the cross-coupling have been identified. The DFT analysis shows that the catalytic cycle occurs in three stages： oxidative addition of phenyl bromide to the palladium center, alkynylation of palladium（Ⅱ） intermediate, and reductive elimination to phenylacetylene. In the oxidative addition, the neutral and anionic pathways have been investigated, which could both give rise to cis-configured palladium（Ⅱ） diphosphine intermediate. Starting from the palladium（Ⅱ） diphosphine intermediate, the only identifiable pathway in alkynylation involves the dissociation of Br group and the formation of square-planar palladium（Ⅱ） intermediate, in which the phenyl and alkynyl groups are oriented cis to each other. Due to the close proximity of phenyl and alkynyl groups, the reductive elimination of phenylacetylene proceeds smoothly.     

Theoretical Study on the Mechanism of the Cycloaddition Reaction between Alkylidene Carbene and Ethylene

The mechanism of cycloaddition reaction between singlet alkylidene carbene and ethylene has been investigated with second-order Moller-Plesset perturbation theory (MP2). By using 6-31 G^* basis, geometry optimization, vibrational analysis and energetics have been calculated for the involved stationary points on the potential energy surface. The results show that the title reaction has two major competition channels. An energy-rich intermediate (INT) is firstly formed between alkylidene carbene and ethylene through a barrier-free exothermic reaction of 63.62 kJ/mol, and the intermediate then isomerizes to a three-membered ring product (P 1) and a four-memberd ring product (P2) via transition state TS1 and TS2, in which energy barriers are 47.00 and 51.02 kJ/mol, respectively. P1 is the main product.     

A Theoretical Study on Nonadiabatic Trapping Models of the Reaction NH H←→N H_2

ThehydrogenatomtransferreactionNH H-N H,isanimportantreactioninradicalreactionsandthegas-phrasethermatdecompositionofammonia.Therewereseveralstudiesonthisreactioninexperiment]andtheory='3.Inthispaper,wehaveemployedtheunifiedstatisticaltheory'(UST)tos...     

Comparative Study on the Effect of NaBr on the Interaction Between Alkyltrimethylammonium Bromide and β-Cyclodextrin

The effect of NaBr on the interaction between alkyltrimethylammonium bromide (CnTAB (n = 14 for TTAB and 16 for CTAB)) and ß-CD was studied by surface tension method. The first decrease in the γ_cmc of TTAB/ß-CD in the presence of NaBr mainly due to the elongated effective chain length of the hydrophobic part of the TTAB/ß-CD complexes; while the increase in the γ_cmc of both of the TTAB/ß-CD and CTAB/ß-CD in the presence of NaBr could be attributed to the close pack of CnTAB at the air/water interface.     

Study on the Regulation of Diorganogermanium Compounds on the Maillard Reaction of Histidine and Glycine by Fluorescence Spectrum

TheMaillardreactioncomprisesoftwostages,earlyandadvanced.AminoacidsorproteinsreactwithglucosetoformastableAmadoricproductthroughSchiffbaseadducts,whichareconverted,uponfurtherincubation,toadvancedglycosylationendproducts(AGE)withafluorescentorbrownproperty'.Ge-132((GeCHZCHZCOOH)O3Q)caninhibittheMaillardreactioneffectively'.Inthispaper,weinvestigatetheearlystagesoftheMaillardreactionofHisandGlyunderphysiologicalconditionsinwhichthenuorescentpropertyisthemostimportantcharacter.Theregul…     

Synthesis of α, ω perfluoropolyether iodides

Perfluoropolyether (PFPE) diacyl halides of formula XCOCF₂O[(CF₂O)_n(CF₂CF₂O)_m]_pCF₂COX, with X = Cl, F and molecular weight (MW) 400-4000 g mol⁻¹ are smoothly converted in high yields to the corresponding α, ω diiodides in the absence of solvent, employing KI or LiI at 210 °C with extrusion of CO. During the reactions, β-elimination of COF₂ from the terminal difluoromethylene oxide units (CF₂O, C₁ unit) occurs to some extent until a tetrafluoroethylene oxide unit (OCF₂CF₂, C₂ unit) is encountered yielding a OCF₂CF₂I terminus. This considerably alters the MW distribution of the final diiodide especially for low MW PFPEs. Operating in supercritical conditions of CO (scCO) or both scCO and CO₂ (scCO₂) on low (<600 g mol⁻¹) MW diacyl halides, lowers β-elimination from 95 to 52 mol% if KI is used or from 43 to 30 mol% if LiI is used. With higher MW (>600 g mol⁻¹) β-elimination is lowered from 15 to <1 mol% in scCO conditions employing KI.     

Study on the α-Thiocarbonylthioformamide Ⅲ——Reaction with trimethyl phosphite

α-Thiocarbonylthioformamide is a stable and almost unexplored class of compounds¹ which attracts us to study their properties and reactions. According to literature three-valenced phosphorus compound is easy to react with thiirane² and thiocarbonate³ to form C=C double bond. So we want to explore the reaction of α-thiocarbonylthioformamide with three-valenced phosphorus compound. In initial experiment, we explored the reaction of α-thiobenzoylthioformmorpholine (1a) with trimethyl phosphite in dry diethyl ether at room temperature.     

Electrochemical Study on the Interaction Between Neutral Red and DNA

IntroductionDeoxyribonucleic acid( DNA) is the most im-portant germ plasma of most organisms.It playsan importantrole in the process ofstoring,copyingand transmitting germ messages.There have beenmany papers studying on the interaction betweensmall molecules and DNA since the1 960′s.Nowthe researches have become a field of common in-terest[1] .Those researches have contributed to theunderstanding of the way of the interaction be-tween DNA and protein.What is more,those re-searches are he…     

Study on the Mechanism of the Rearrangement Reaction of 3-n-Butylphthalide by Deuterium-Labelling

InthePangetal.report[l],l-methyl-5-cchp'tetrahdronaPhthalenewasobtalnedfromthetreatInentof3-ntwlphthalideusingAlCl3ascatalStinCS2byaproposedl,4-hydridetransfrprocess.InordertoexPlorethemechasticdetallsofthereaction,wepreParedastableisotope-labelledcomPound--I',l'ch-dotero-3-n-butylphthalideasfollowstl,lall-deutero-ldiutanolwasobtalnedbyreduedonreachonofethy1butwatewithNaBD4andAJCl3indiglpoeI2],treatmentoftheproductwithphosphoroustribroITildetogive1,1-dideutero-lbromobutane,whichunderwe…     

Density Functional Study on the Reaction Mechanism for the Reaction of Ni^＋ with Ethane

The mechanism of the reaction of Ni^ (^2D) with ethane in the gas-phase was studied by using density functional theory.Both the B3LYP and BLYP functionals with standard all-electron basis sets are used to give the detailed information of the potential energy surface (PES) of [Ni,C2,H6]^ . The mechanisms forming the products CH4 and H2 in the reaction of Ni^ with ethane are proposed.The reductive eliminations of CH4 and H2 are typical addition-elimination reactions.Each of the two reactions consists of two elementary steps:C-C or C-H bond activations to form inserted species followed by isomerizations to from product-like intermediate.The rate determining steps for the elimination reactions of forming CH4 and H2 are the isomerization of the inserted species rather than C-C or C-H bond activations .The elimination reaction of forming H2 was found to be thermodynamically favored compared to that of CH4.