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151.
The reduction of a variety of carbonyl compounds was efficiently carried out with NaBH4/DOWEX(R)50WX4 system. The reactions were performed to give the corresponding alcohols derivatives in perfect yields in THF at room temperature. Reduction of acyloins and a‐diketones by this reducing system produced efficiently the corresponding vicinal diols. Also, the reduction of aldehydes over ketones has been accomplished successfully by this system. Regioselectivity of this system was also investigated with exclusive 1,2‐reduction of conjugated carbonyl compounds to their corresponding allylic alcohols in high to excellent yields. 相似文献
152.
A simple and novel flow‐injection chemiluminescence (FI‐CL) method was established for the determination of 2‐Methoxyestradiol (2‐ME) in pharmaceutical preparations and biological fluids. The method was based on the significant enhancement of the CL from the KMnO4‐Na2SO3 reaction by 2‐ME in acidic medium. Under optimized conditions, the CL intensity was correlated linearly with concentration of 2‐ME in the range of 5.0 × 10?8‐5.0 × 10?6 M (r = 0.9995). The detection limit (3σ) of 2‐ME was 7.5 × 10?9 M and the relative standard deviation was 0.8% at 5.0 × 10?7 M 2‐ME (n = 8). The proposed method was successfully applied for the flow‐injection CL determination of 2‐ME in pharmaceutical preparations and biological fluids with the recoveries from 92.4 to 106.8%. The possible CL reaction mechanism was also discussed briefly. 相似文献
153.
The condensation of indene or 2-nitrofluorene with aromatic aldehydes catalyzed by bis-(p-methoxyphenyl)telluroxide (BMPTO) under ultrasonic wave irradiation gave corresponding fulvenes in fair to good yield. 相似文献
154.
《合成通讯》2013,43(17):3071-3076
Abstract The treatment of 4-(2′-hydroxyaryl)-2-(N,N-dialkylamino)-1,3-dithiolium perchlorates (1a–g) with sodium sulfide nonahydrate in ethanol at room temperature affords the corresponding 1,3-dithiole-2-thiones (2a–g). When these reactions are conducted in boiling ethanol, 2′-hydroxyacetophenones (3a–g) have been obtained in good to excellent yield. A tentative mechanism for the formation of 3a–g shows that this reaction is regioselective, this being established by the presence of hydroxyl group in 2′-position. That has been confirmed in a control experiment, 4-phenyl-2-(piperidin-1-yl)-1,3-dithiolium perchlorate affording a mixture of condensation products of acetophenone and phenylacetaldehyde, under similar reaction conditions. 相似文献
155.
AbstractA convenient and efficient procedure for the synthesis of 2-substituted-6,7-dihydrobenzo[d]oxazol-4(5H)-ones and 2-aryl-6,7-dihydrobenzofuran-4(5H)-ones through a Rh2(OAc)4-catalyzed C≡X (X?=?N, C) insertion of cyclic 2-diazo-1,3-diketones with nitriles and aromatic alkynes has been developed. This reaction uses readily available starting materials and stable cyclic 2-diazo-1,3-diketone compounds, with desired products formed in good to high yields. A tentative mechanism involving a C≡X bond insertion and 1,5-dipolar electrocyclization/ring opening and cyclization sequence for this reaction is proposed. 相似文献
156.
The determination of the phase diagram of the binary system sodium perchlorate – water is reported. Beside the eutectic point, two polymorph crystal structures of sodium perchlorate dihydrate were determined. The two crystal structures are discussed, compared to each other and to other known sodiumhalide dihydrate crystal structures. The two polymorphs of the perchlorate dihydrate represent the two variants of connected octahedra in the layer structure found for sodium halide dihydrates. 相似文献
157.
C. Carnero Ruiz L. Díaz‐López J. Aguiar 《Journal of Dispersion Science and Technology》2013,34(2):266-273
The effect of glycerol on both micellar formation and the structural evolution of the sodium dodecyl sulfate (SDS) aggregates in the context of the action mechanism of the cosolvent has been studied. The critical micelle concentration and the degree of counterion dissociation of the surfactant over a temperature range from 20°C to 40°C were obtained by the conductance method. The thermodynamic parameters of micellization were estimated by using the equilibrium model of micelle formation. The analysis of these parameters indicated that the lower aggregation of the surfactant is mainly due to a minor cohesive energy of the mixed solvent system in relation to the pure water. The effect of glycerol on the mean aggregation number of the micelles of SDS was analyzed by the static quenching method. It was found that the aggregation number decreased with the glycerol content. This reduction in the micellar size seems to be controlled by an increase in the surface area per headgroup, which was ascribed to a participation of glycerol in the micellar solvation layer. Studies on the micropolarity of the aggregates, as sensed by the probe pyrene, indicated that this microenvironmental parameter is almost unaffected by the presence of glycerol in the mixture. However, an increase in the micellar microviscosity at the surface region was observed from the photophysical behavior of two different probes, rhodamine B and auramine O. These results suggest a certain interaction of the cosolvent in the micellar solvation of SDS micelles. 相似文献
158.
Multiple emulsions stabilized by colloidal microcrystalline cellulose (CMCC, Avicel RC591) at the w/o and o/w interfaces, and by the addition of Span 80 or Span 85 at the w/o interface, were studied by means of brightfield microscopy, freeze-etch electron microscopy, droplet size distribution analysis and rheologic measurements. Stable multiple emulsions were prepared by incorporation of sodium chloride in the innermost aqueous phase, thereby creating an osmotic gradient preventing loss of the inner aqueous phase to the external aqueous phase. Freeze-etch electron microscopy of the multiple emulsions indicated the presence of a network of microcrystalline cellulose at the outer o/w interface. It may be assumed that the surfactant directly stabilized the w/o interface by adsorption at the interface, as well as indirectly by facilitating wetting of the microcrystalline cellulose by the oil. From rheologic measurements, the existence of a three-dimensional network in the external aqueous phase was indicated by the considerable degrees of thlxotropy and significant static yield values of these multiple emulsions. 相似文献
159.
Galal H. Elgemeie Wafaa A. Zaghary Tamer M. Nasr Kamelia M. Amin 《Journal of carbohydrate chemistry》2013,32(6):345-356
Reported is the first method to prepare a new class of thienopyrazole thioglycosides via a one‐pot reaction of the sodium thienopyrazolthiolate salts with 2,3,4,6‐tetra‐O‐acetyl‐α‐D‐gluco‐and galactopyranosyl bromides. The sodium thienopyrazolthiolate salts are prepared using pyrazoldithioic acids and their corresponding mono ‐ and dithiolate salts. 相似文献
160.
《Journal of carbohydrate chemistry》2013,32(9):843-866
Kinetics of the reaction between d‐glucose and Cr(VI) in the absence and presence of surfactant micelles have been studied by a spectrophotometric method in aqueous‐acidic solutions of perchloric acid. It was observed that the reaction has a nonautocatalytic followed by an autocatalytic pathway. The rate of the initial stage increases with increase in [glucose], [HClO4] and temperature. Due to precipitation, the effect of cationic micelles of cetyltrimethylammonium bromide (CTAB) could not be studied whereas the oxidation is catalyzed by anionic micelles of sodium dodecyl sulfate (SDS) and nonionic micelles of Triton X‐100 (TX‐100). The results are discussed in terms of the pseudo‐phase kinetic model. Activation parameters are evaluated and a mechanism consistent with the results is proposed. A rate law for the reaction has also been derived. The redox reaction occurs through a Cr(VI)→Cr(IV) path. 相似文献