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.     

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.     

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