棒状CuFe4Ox的可控合成及其异戊醇脱氢反应的催化性能

利用液相沉淀法可控合成了均匀的棒状CuFe₄O_x催化剂。通过原位X射线粉末衍射（XRD）、高分辨透射电子显微镜（TEM）及程序升温还原（TPR）等手段表征其晶相结构、形貌和还原性能。通过还原棒状CuFe₄O_x获得Cu⁰/Fe₃O₄ 纳米棒,原位X射线光电子能谱（XPS）用于确定Cu⁰/Fe₃O₄ 表面的相组成。通过液相沉淀法制备棒状CuFe₄O_x,在120℃保持3 h后加入Na₂CO₃溶液至pH等于9时所得棒状形貌最为规整。以异戊醇脱氢反应作为探针反应,比较了Cu⁰/Fe₃O₄ 纳米棒和Cu⁰/Fe₃O₄ 纳米颗粒的催化反应性能,发现Cu⁰/Fe₃O₄ 纳米棒比Cu⁰/Fe₃O₄ 纳米粒子具有更好的活性和稳定性,表明棒状Fe₃O₄ 担载的Cu纳米粒子具有更好的结构稳定性。     

Resonant-Mie-scattering of aggregates of phosphomolybdate and papaverine for measuring activities and screening inhibitors of cyclic nucleotide phosphodiesterase isozymes

A resonant-light-scattering (RLS) method was proposed to quantify phosphate for screening inhibitors of isozymes of cyclic nucleotide phosphodiesterase (PDE). In acidified mixtures of phosphate, papaverine and molybdate, there were aggregates exhibiting micrometre sizes, no absorbance peaks over 360 nm but strong RLS peaks at 392 nm; Mie scattering thus accounted for the RLS signals. When papaverine was added before molybdate to acidified samples of phosphate, RLS signals at 392 nm were stable from 5 to 25 min since the addition of molybdate; after optimization, phosphate from 0.40 to 3.60 μM was quantifiable. This RLS method tolerated 60 mg L⁻¹ proteins besides common PDE inhibitors and dimethyl sulfoxide in acidified samples of phosphate; the integration of this RLS method with the coupled action of a phosphomonoesterase on PDE product was thus rational to measure PDE activities without the removal of proteins in samples. By quantifying activities of a truncated mutant of human PDE4B2 via this RLS method, Michaelis–Menten constant, inhibition constants of rolipram, papaverine and theophylline varied over three magnitudes and were consistent with those estimated by an improved malachite green assay of phosphate, respectively. Hence, this novel RLS method was promising for screening inhibitors of PDE isozymes.     

Fragrance encapsulation in polymeric matrices by emulsion electrospinning

We present the successful application of emulsion electrospinning for the encapsulation of a model for highly volatile fragrances, namely (R)-(+)-limonene in a poly(vinyl alcohol) (PVA) fibrous matrix. The influence of the emulsion formulation and of its colloidal properties on the fiber morphology, as well as on the limonene encapsulation efficiency, is described. The release profile of the fragrance from the electrospun nanofibers over a fifteen days range shows that this type of nanofibrous matrices with a high fragrance loading capacity is of great potential for applications in various fields, such as cosmetics or food packaging.     

Preparation of l-Threoninol and Its Bisoxazoline Derivative

Abstract

(R,R)-Threoninol was prepared in one step from l-threonine in 86% isolated yield. The product was regioselectively transformed into 2,2-bis[(4R,5R)-4-(hydroxymethyl)-5-methyl-1,3-oxazolin-2-yl]propane in 42% isolated yield.     

Nickel-catalyzed synthesis of 9-monoalkylated fluorenes from 9-fluorenone hydrazone and alcohols

A practical protocol was disclosed for the nickel-catalyzed C-alkylation of 9-fluorenone hydrazone with alcohols using t-BuOK as the base, and 9-monoalkylated fluorene derivatives were obtained in good yields under the benign conditions.     

Practical and Chemoselective Reduction of Acyl Chloride to Alcohol by Borohydride in Aqueous Dichloromethane

A simple methodology for the reduction of acid chlorides to their corresponding alcohols has been developed. Various carboxylic acids were converted to alcohols in excellent yields using NaBH₄-K₂CO₃ in a mixed solvent system of dichloromethane and water (1:1) in the presence of a phase-transfer catalyst at low temperature. The importance of the work is its simplicity, selectivity, excellent yield, and very short reaction time. This new reduction condition has proved to be an excellent chemoselective method for a range of acid chlorides in the presence of various functional groups.     

Oxidation of Benzylic Alcohols to Carbonyl Compounds with Potassium Permanganate in Ionic Liquids

Abstract

The selective oxidation of primary and secondary benzylic alcohols with potassium permanganate in ionic liquids to give corresponding aldehydes and ketones in 83–97% yields has been described.     

Synthetic Access to New Pyridone Derivatives through the Alkylation Reactions of Hydroxypyridines with Epoxides

General methods for the preparation of a variety of pyridone and oxypyridine derivatives are described. 2‐,3‐,4‐Hydroxy pyridine and 2‐pyridinemethanol were alkylated with ethylene‐, propylene‐, and stryrene‐oxide and epichlorohydrin in the presence of different Lewis acids as a catalyst. The best yield of 3a was achieved in the presence of CdI₂/BF₃ · OEt₂. The corresponding pyridone derivatives (3a–d, 7a–d) were obtained from the reaction of 2‐and 4‐hydroxypyridine with oxiranes in good yields, whereas oxypyridine derivatives (5a–d, 9a,b) were obtained from reactions of 3‐hydroxypyridine and 2‐pyridinemethanol with oxiranes. Chlorohydrines (3d, 5d, 7d) were easily converted to corresponding epoxy derivatives (10, 11, 12) in basic medium; then amino alcohols (13–17) were obtained from the reaction of these epoxy derivatives with amines.     

Synthesis of C 2-Symmetric Chiral Amino Alcohols: Their Usage as Organocatalysts for Enantioselective Opening of Epoxide Ring

A series of β-amino alcohols derivatives were synthesized from (R)-2-amino-1-butanol and (S)-1,2-propanediol, and they have been used as organocatalaysts in the racemic ring opening of epoxide in good yields with high enantiomeric excess (up to 97%).     

Stereoselective Synthesis of 1,3-Dienes from Propargylic Alcohols by LiAlH4/AlCl3

Herein we report that LiAlH₄/AlCl₃ is a very efficient reagent for the reductive dehydration of aryl propargylic alcohols in tetrahydrofuran solvent at reflux to give 1,3-dienes with good yields and high E selection. The reaction conditions are mild and easy to operate, and a variety of aryl functional groups, such as bromo, fluoro, butyl, and methoxyl groups, are tolerated. With our protocol, useful (E,E)-1,3-dienes can be synthesized.

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