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.     

An Improved Synthesis of Retinoic Acid from β-Ionone

A convenient and large-scale preparation of retinoic acid 1 from β-ionone in five steps with 38% overall yield is described.The key steps are the epoxidization of 2 with a new methylated agent and the condensation 4 with tetraethyl methylenediphophonate in one-pot procedure to prepare 6.     

Reactivities of tetraalkyltin complexes toward Pt/HY zeolite

Tetraalkyltin complexes, SnR₄ (R = Me, Et, Pr, Bu) could react with Pt/HY at 193, 243, 273 and 333 K, respectively. The reactions occurred on the surface of the zeolite and the organotin grafted zeolites were characterized in detail. The framework and the microporous structure of the grafted Pt/HY zeolites were retained. However, the modified zeolites showed better size selectivity in the absorption of hydrocarbons.     

Organocatalysis: quantum chemical modeling of nucleophilic addition to α,β‐unsaturated carbonyl compounds

One of the successful transformations within the field of organocatalysis, the organocatalytic asymmetric addition of nitromethane to α,β‐unsaturated aldehydes and ketones, has been studied by quantum chemical modeling. The level of accuracy of the hybrid density functional theory method B3LYP/6‐31G(d) was compared to a high level ab initio benchmark for this reaction. It is concluded that B3LYP/6‐31G(d) performs very well for this reaction type, giving good estimates of critical energies. The reaction between acrolein and nitromethane was studied in detail. The reaction mechanism revealed an intermediate oxazolidin structure, which is currently unknown. Alkyl substitution in various positions on the amine catalyst or α,β‐unsaturated carbonyl compound influences the reactivity in a predictive fashion. The iminium ion, prop‐2‐en‐iminium, is less activated towards nucleophilic attack compared to protonated acrolein. Copyright © 2007 John Wiley & Sons, Ltd.     

Peritectic phase growth in directionally solidified Cu-70% Sn alloy

The growth mechanism of the peritectic η phase involving the peritectic reaction and peritectic transformation in Cu-70%Sn alloy was investigated under directional solidification. The results show that a major growth mechanism in thickening of the peritectic η-layer is not the peritectic reaction but the peritectic transformation. The transformation temperature and isothermal time play crucial roles in determining the volume fraction and the thickness of the peritectic η phase. With the increase of the temperature and isothermal time, the volume fraction of the peritectic η phase increases. The regressed data show that the relationship between the thickness of η phase (Δx) and the transformation temperature (T) meets the following equation In Δx=6.5−1673 1 / T. Additionally, there exists a relationship between the thickness of the η phase (Δx) and the isothermal time (t) at the 9 mm solidification distance below the peritectic reaction interface, Δx=0.72t ^1/2, which is consistent with the theoretical model. Supported by the National Science Foundation of China (Grant No. 50395102)     

Amine‐blocked polyisocyanates. I. Synthesis of novel N‐methylaniline‐blocked polyisocyanates and deblocking studies using hot‐stage fourier transform infrared spectroscopy

A series of substituted N‐methylaniline‐blocked polyisocyanates based on 4,4′‐methylenebis(phenyl isocyanate) and poly(tetrahydrofuran) were prepared and characterized thoroughly with FTIR, ¹H NMR, and ¹³C NMR spectroscopy methods. Compared with unsubstituted N‐methylaniline, a blocking agent with an electron‐releasing substituent at the para position took a shorter time, whereas those with an electron‐releasing substituent at the ortho position or an electron‐withdrawing substituent at the ortho and para positions took longer times for the blocking reaction. The thermal dissociation reactions of blocked polyisocyanates were carried out with an FTIR spectrophotometer attached to hot‐stage accessories under dynamic and isothermal conditions. The dynamic method was used to determine the deblocking temperature, and the isothermal method was used to calculate the deblocking kinetics and activation parameters. The cure times of blocked polyisocyanates with hydroxyl‐terminated polybutadiene were also determined. The deblocking temperatures, the results of cure‐time studies, and the kinetic parameters revealed that the thermal dissociation of the N‐methylaniline‐blocked polyisocyanates was retarded by electron‐donating substituents and facilitated by electron‐withdrawing substituents. The action of N‐methylanilines as blocking agents for isocyanate was explained by the formation of a four‐center, intramolecularly hydrogen‐bonded ring structure during the thermal dissociation of the blocked polyisocyanates. The formation of such a hydrogen‐bonded ring structure was confirmed and supported by variable‐temperature ¹H NMR studies and entropy parameters, respectively. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 1557–1570, 2007