Photo-Fries and Fries reaction of 5,8-dihydro-1-naphthyl esters

Systematic studies were performed on the photo-Fries and the Fries reaction of aliphatic, aliphatic unsaturated, aromatic and aromatic unsaturated esters of 5,8-dihydro-1-naphthol. The Fries reaction of 5,8-dihydro-1-naphthyl acetate in various solvents is also reported.     

A reversible reaction inside a self-assembled capsule

Reversible encapsulation allows the direct observation of the isolated molecules under ambient conditions, at equilibrium and in the liquid phase. Here we show that capsules can amplify and stabilize molecules that are present in only trace concentrations in solution. Evidence is given that reversible chemical reactions take place within the capsule. Stabilization of reaction intermediates is a characteristic property of enzymes and is widely regarded as an essential feature of catalytic activity. Reactive molecules can also be stabilized by encapsulation, a process that involves completely surrounding the reactive species within synthetic receptors. Here, we show that self-assembled capsules can isolate and stabilize molecules that are present in only trace amounts in solution. The system amplifies the concentrations of high-energy species with reduced entropies.     

Amines made easily: a highly selective hydroaminomethylation of olefins

A highly chemo- and regioselective hydroaminomethylation of simple as well as functionalized alpha-olefins using a cationic rhodium precatalyst together with Xantphos as ligand is reported. Studies of the influence of ligands and reaction conditions led to an unprecedented selective hydroaminomethylation procedure. The novel procedure constitutes an economically attractive and environmentally favorable synthesis of secondary and tertiary aliphatic amines.     

State-to-state reaction dynamics: a selective review

A selective review of state-to-state reaction dynamics experiments is presented. The review focuses on three classes of reactions that exemplify the rich history and illustrate the current state of the art in such work. These three reactions are (1) the hydrogen exchange reaction, H+H2-->H2+H and its isotopomers; (2) the H+RH-->H2+R reactions, where RH is an alkane, beginning with H+CH4-->H2+CH3 and extending to much larger alkanes; and (3) the Cl+RH-->HCl+R reactions, principally Cl+CH4-->HCl+CH3. We describe the experiments, discuss their results, present comparisons with theory, and introduce heuristic models.     

An Efficient Steric Controlled Photo-Fries Rearrangement in the Naphthalene Series

For the work on the synthesis of 2-acyl-5-methoxynaphthoquinones as tricyclic analogues of daunomycinone¹, we wanted to develop an efficient regioselective synthesis of 5-methoxy-2-acyl-1-naphthols without using Lewis acids. This requirement precluded the use of the thermal Fries but not the photo-Fries rearrangement. Although the mechanistic aspects of the photo reaction have received much study², the reaction has been little used preparatively³ because it usually gives poor yields of hydroxy ketones even when only one product is possible.     

Spectroscopic studies of a BINAM-based sensor: Highly selective fluorescent recognition of lysine in water solution through a nucleophilic substitution reaction

A BINAM-based compound (R)-1 is found to show significant fluorescence enhancement in the presence of Lys in aqueous solution (1%DMF). This probe achieves highly selective fluorescent recognition of Lys even in the presence of other natural amino acids. It can be used as a sensitive as well as selective fluorescent probe for Lys. The mechanism for the interaction of (R)-1 with Lys was studied by NMR and HRMS.     

糖化学中锡介入的选择性反应

本文从糖锡络合物结构出发,揭示了锡介入方法进行选择性反应的原因.并对该方法在糖化学各类不同类型的反应如酰化,烃化,氧化,磺化所表现的选择性进行了详细的论述.     

Barbier-type reaction mediated with tin nano-particles in water

Tin nano-particles are employed in the Barbier-type allylation reaction of carbonyl compounds in water to afford the corresponding homoallylic alcohols in good yields. The in situ generated allylation intermediates, allyltin(II) bromide and diallyltin dibromide, have been directly observed by using ¹H NMR. A mechanism is proposed based on this observation.     

Hydrophobic effects in a simple Diels-Alder reaction in water

The endo/exo ratio for a simple Diels-Alder reaction carried out in water has been used to argue that hydrophobic effects can dominate the geometries of the transition states.     

Determination of water with a modified Karl Fischer reagent Stability and the mechanism of reaction with water

It is shown that the water equivalent of the modified Karl Fischer reagent (standard Karl Fischer reagent in which dimethylformamide is substituted for methanol), depending on pKa and the concentration of the solvent used for preliminary titration, is not dependent on the water concentration being determined. Also discussed are different aspects of the stability of the Karl Fischer reagent and its modifications. On the basis of the literature data and the findings of this work, a mechanism of interaction between water and the modified Karl Fischer reagent is proposed: in the first stage of the reaction pyridine sulphodioxide is solvated with solvents containing active hydrogen (alcohols, organic acids and water). The lower the value of pK_a of the solvent, the greater the contribution of water to the pyridine sulphodioxide solvation reaction. The results of this work suggest that, especially in particular cases, the water equivalent of the Karl Fischer reagent and its modifications should be determined under the same conditions as the determination of water in the sample.     

Development of porosity in a char during reaction with steam or supercritical water

Two series of activated carbon have been prepared by reaction of a char (from olive stones) with supercritical water (SCW) with the objective of studying the effect of temperature and residence time on the development of porosity. The results have been compared with those obtained using the same char but with classical activation with steam. Both procedures develop porosity, but (i) the reaction rate is critical in the development of porosity for steam but not for SCW activation, and (ii) SCW activation produces a larger development of microporosity at low degrees of burnoff, whereas steam produces more meso- and macroporosity. The differences have been explained by assuming that the mechanism for the carbon-water reaction is common but the transport properties of water in the supercritical state are more favorable to facilitate the access of water to the interior of the char particles. In contrast, when steam is used for the activation of the char, the diffusion of the molecules cannot keep up with the chemical rate and, consequently, the reaction is preferentially taking place at the most accessible surface sites, thus facilitating the development of larger pores and the widening of microporosity.     

Light-induced hetero-Diels-Alder cycloaddition: a facile and selective photoclick reaction

2-Napthoquinone-3-methides (oNQMs) generated by efficient photodehydration (Φ=0.2) of 3-(hydroxymethyl)-2-naphthol undergo facile hetero-Diels-Alder addition (k(D-A)～ 4×10(4) M(-1) s(-1)) to electron-rich polarized olefins in an aqueous solution. The resulting photostable benzo[g]chromans are produced in high to quantitative yield. The unreacted oNQM is rapidly hydrated (k(H2O) ～145 s(-1)) to regenerate the starting diol. This competition between hydration and cycloaddition makes oNQMs highly selective, since only vinyl ethers and enamines are reactive enough to form the Diels-Alder adduct in an aqueous solution; no cycloaddition was observed with other types of alkenes. To achieve photolabeling or photoligation of two substrates, one is derivatized with a vinyl ether moiety, while 3-(hydroxymethyl)-2-naphthol is attached to the other via an appropriate linker. The light-induced Diels-Alder "click" strategy permits the formation of either a permanent or hydrolytically labile linkage. Rapid kinetics of this photoclick reaction (k=4×10(4) M(-1) s(-1)) is useful for time-resolved applications. The short lifetime (τ ～7 ms in H(2)O) of the active form of the photoclick reagent prevents its migration from the site of irradiation, thus, allowing for spatial control of the ligation or labeling.     

The reaction of chlorine water with carbohydrates

Summary On the basis of data from a study of the reaction of chlorine water with carbohydrates and cellulose at various pH values, the conclusion was reached that, in an acid medium, part of the pyrane rings in the cellulose molecule are in the open form.     

Lipase catalyzed Cannizzaro-type reaction with substituted benzaldehydes in water

Lipases were found to catalyze Cannizzaro-type reaction of substituted benzaldehydes in aqueous medium at 30 °C without the addition of any external redox reagent. The ratio of alcohol product to acid product varied with nature of the substituted benzaldehyde, enzyme, and the presence of organic co-solvent.     

Application of a continuous and selective water detector in thermoanalytical investigations

A method for simultaneous TG, DTG and DTA combined with a continuous and direct water determination has been developed. The applicability of the technique is shown by reference to several examples such as limestone-containing metamorphic rock, clay, soil, cellulose and an anion-exchange resin.     

Solid state electrochemical reaction in photocells made using conducting polyaniline and sensitized with methylene blue

The effect of small concentration of methylene blue (MB) on photocurrents was studied in solid state photoelectrochemical cells fabricated using conducting polyaniline (PANI) coated electrodes sandwiched with a solid polymer electrolyte, viz. poly(vinyl alcohol) (PVA) with phosphoric acid. These exhibit good photoresponse to visible light (maximum photosensitivity factor of the order of 10). The current-voltage (I-V) characteristics in such cells reveal that the charge transport is ohmic. Also, an electrochemical reaction (motion of Cl^– from SPE+MB to PANI) is observed at 1.2–1.3 V, which gives rise to a sudden increase of current at this particular voltage. The presence of illumination enhances this electrochemical reaction. The combined effect, i.e. ohmic charge transport and an electrochemical reaction, is observed in the I-V characteristics. Along with the dye concentration, the photosensitivity is observed to be field/voltage dependent. The sensitization effects are due to lowering of the potential barrier formed at the PANI/SPE+MB interface under illumination. Electronic Publication