Studies on the Model Synthesis of the Brassinolide and Dolicholide‘s Side Chains

A highly stereoselective synthesis of the side Chain enantiomers of brassinolide and dolicholide through an aldol reaction of 2-(4-methoxy benzyloxyl) proplonylaldehyde (5) with the anion of 1- ( tert -butyldimethylsiloxy )-3-methyl-2-butanone ( 6 ) is described.     

A short synthesis of (±)-tecomanine via a Pauson-Khand-based route

The N-carboethoxy precursor to (±)-tecomanine has been prepared in 11 steps from 2-methyl-1-buten-3-yne. The key step, Pauson-Khand cyclization of a methylated 5-aza-6-nonen-1-yne succeeds, but only in low yield, a consequence of the dialkyl substitution about the azaenyne framework. Nevertheless, the overall sequence to that point is one of the more efficient to be described.     

一类催化反应中的非线性奇摄动边值问题的渐近解

本文研究了催化反应非线性奇摄动边值问题．利用微分不等式理论和方法，得到了问题的解的任意次近似渐近估计．     

Dimethylamino-substituted 7H-Benzo[de]pyrazolo[5,1-a]isoquinolin-7-ones and Their Behavior under Vilsmeier-Haack Conditions

The behavior of dimethylamino-substituted 7H-benzo[de]pyrazolo[5,1-a]isoquinoline-7-ones, synthesized for the first time, under conditions of the Vilsmeier-Haack reaction. It has been shown that, on heating with POCl₃ and DMF, they are converted by electrophilic substitution at the position ortho to the dimethylamino group, followed by cyclization of the iminium adduct to a quinazolinium salt. When an acetyl group is present, the Arnold reaction, leading to the formation of a chloroaryl, accompanies the heterocyclization. The rates and proportion of the reaction products depend on the position of the dimethyl groups relative to the pyrazole ring.     

Association Behavior of 4-Acylpyrazolone Derivative and Tertiary Amine of High Molecular Weight in Antagonistic Synergistic Extraction of Palladium

To find an effective extraction and removal method for palladium(II), which is one of the main fission products from an acidic nuclear spent fuel solution, the extraction behavior of palladium(II) from a nitric acid medium by an acidic chelating extractant, 1-phenyl-3-methyl-4-trifluoroacetylpyrazolone-5-one (HPMTP) and a tertiary amine of high molecular weight, tri-n-octylamine (TOA), has been studied by spectrophotometry. A noticeable antagonistic extraction effect was observed in the extraction system under the given conditions. To understand this phenomenon, a preliminary investigation was performed to explain the mechanism of this reaction. According to the theory of corresponding solutions (TCS), the association reaction between HPMTP and TOA is proposed in the organic phase. An associated species, HPMTP·TOA, formed through hydrogen bonding in a chloroform medium might be the main reason why an antagonistic extraction effect occurred. The association constant between HPMTP and TOA was calculated to be 2.86±0.05.     

Diphenylmethane transformations over boron trifluoride modified alumina and silica-alumina

Transformations of diphenylmethane were investigated in a flow system in the presence of alumina and silica-alumina modified with boron trifluoride at atmospheric pressure and elevated temperatures. Hydrogen transfer reaction was observed on addition of tetralin to the substrate stream. This revised version was published online in August 2006 with corrections to the Cover Date.     

Ti(IV)/BINOL-catalyzed asymmetric aldol reaction of a masked acetoacetic ester: pronounced influence of catalyst concentration on nonlinear effects

Initial concentration of enantioenriched or enantiopure catalysts proved to be an important factor for the achievement of a more pronounced amplification of ee's in the Ti(IV)/BINOL-catalyzed aldol reaction of an O-silyldienolate.     

An Efficient Method for the Synthesis of 3-Cyano-6-hydroxy-2(1H)-pyridinones under Microwave Irradiation and Solvent-free Conditions

Summary. Three component condensation of alkylacetoacetates, primary amines, and alkyl cyanoacetates catalyzed by solid supports under microwave irradiation gave N-alkyl 3-cyano-6-hydroxy-2(1H)-pyridinones with high yields. Upon carrying out the reaction under the same condition on acidic alumina, zeolite HY, silica gel, and montmorillonite K-10, the best yields were achieved by silica gel. Corresponding author. E-mail: balalaie@yahoo.com Received August 28, 2002; accepted September 3, 2002     

Rhodium-catalyzed carbonylation of 2-alkynylbenzylamine: a new route to the synthesis of benzazepinones

Rhodium-catalyzed carbonylation of 2-alkynylbenzylamines under water-gas shift reaction conditions gives a seven-membered heterocyclic product, 2,4-disubstituted-1,4-dihydrobenz[c]azepin-3-ones, in a good yield.     

Evaluation of closed-vessel microwave digestion method for the determination of trace impurities in polymer-based photoresist by inductively coupled plasma mass spectrometry

A closed microwave digestion method followed by inductively coupled plasma spectrometric (ICP-MS) analysis was evaluated for the determination of trace impurities in photoresist. To optimize the digestion procedure, several digestion parameters such as acid, heating temperature and heating time were evaluated. Besides, the digestion efficiency of used photoresist material and the recovery of analyte elements obtained by the use of gravimetric method and ICP-MS measurement, individually, were also compared to clarify the completeness of digestion. According to our experiments, the gravimetric method was found to be not so relevant to the completeness of digestion, because the remaining sample matrix could cause suppression effect in the subsequent ICP-MS measurement. In view of minimizing blank value and working time, a simple single-step heating program was proposed to mineralize 0.25 ml of photoresist material with 5 ml of nitric acid at 180 °C for 10 min. Based on the comparative study of the analytical results obtained by instrumental neutron activation analysis (INAA) and proposed method, the reliability of proposed method for the determination of trace metallic impurities in photoresist material has been confirmed.