The reaction of organophosphorus reagents with substituted‐1,3‐diphenylpropanetrione: New synthesis of azaphospholene derivatives

The reaction of 1,3‐diphenyl‐2‐(phenylimino)‐3‐(ylidenemethyl‐acetate)‐1‐propanone (5) with trisdialkylaminophosphines (6a,b) in refluxing toluene afforded the new oxazaphospholene products (7a–b) . On the other hand, the cyclic azaphospholene adducts 8a–b were isolated from the reaction of 5 with 6a,b without solvent. Trialkyl phosphites 1b–c react with compound 5 to give the respective dialkyl phosphate products (9a,b) . Moreover, trisdialkylaminophosphines (6a,b) react with 2a and 2b to give the dipolar adducts 10a,b and the phosphonate products 11a,b, respectively. Possible reaction mechanisms are considered, and the structural assignments are based on compatible analytical and spectroscopic results. © 2001 John Wiley & Sons, Inc. Heteroatom Chem 12:511–517, 2001     

Reactions of phosphite esters and trisdialkylaminophosphines with 5‐substituted 1,3,4‐thiadiazol derivatives

5‐{[(1E)‐(4‐methoxyphenyl)methylene]amino}‐1,3,4‐thiadiazole‐2‐thiol ( 1a ) reacts with trialkyl phosphites ( 2a–c ) to give the respective dialkyl phosphonate adducts ( 4a–c ). On the other hand, the reactions of trisdialkylaminophosphines ( 3a,b ) with 1a , 5‐{[(1E)‐(4‐phenyl)methylene]amino}‐1,3,4‐thiadiazole‐2‐thiol ( 1b ) yield the corresponding open dipolar structures 6a–c . In the case of the reaction of triethyl phosphite ( 2a ) with 1b , both the dialkyl phosphonate adduct ( 7 ) and the dipolar product ( 8a ) are obtained. Moreover, triisopropyl phosphite ( 2c ) reacts with 1b to give both the S‐alkyl and the N‐alkyl phosphonate adducts ( 9a,b ), respectively. Mechanisms are proposed to explain the formation of the new products, and their structures were confirmed on the basis of elemental analysis and spectral studies. © 2001 John Wiley & Sons, Inc. Heteroatom Chem 12:594–601, 2001     

Effect of Cathode Nozzle Geometry and Process Parameters on the Energy Distribution for an Argon Transferred Arc

The influence of two nozzle geometries and three process parameters (arc current, arc length and plasma sheath gas flow rate) on the energy distribution for an argon transferred arc is investigated. Measurements are reported for a straight bore cylindrical and for a convergent nozzle, with arc currents of 100 A and 200 A and electrode gaps of 10 mm and 20 mm. These correspond to typical operating parameters generally used in plasma transferred arc cutting and welding operations. The experimental set up consisted of three principal components: the cathode-torch assembly, the external, water-cooled anode, and the reactor chamber. For each set of measurements the power delivered to each system component was measured through calorimetric means, as function of the arc’s operating conditions. The results obtained from this study show that the shape of the cathode torch nozzle has an important influence on arc behaviour and on the energy distribution between the different system components. A convergent nozzle results in higher arc voltages, and consequently, in higher powers being generated in the discharge for the same applied arc current, when compared to the case of a straight bore nozzle. This effect is attributed to the fluidynamic constriction of the arc root attachment, and the consequential increase in the arc voltage and thus, in the Joule heating. The experimental data so obtained is compared with the predictions of a numerical model for the electric arc, based on the solution of the Navier–Stokes and Maxwell equations, using the commercial code FLUENT©. The original code was enhanced with dedicated subroutines to account for the strong temperature dependence of the thermodynamic and transport properties under plasma conditions. The computational domain includes the heat conduction within the solid electrodes and the arc-electrode interactions, in order to be able to calculate the heat distribution in the overall system. The level of agreement achieved between the experimental data and the model predictions confirms the suitability of the proposed, “relatively simple” model as a tool to use for the design and optimization of transferred arc processes and related devices. This conclusion was further supported by spectroscopic measurements of the temperature profiles present in the arc column and image analysis of the intensity distribution within the arc, under the same operating conditions.     

The reactions of Wittig–Horner reagents with 1,3-dioxo-Δ2,α-indanmalononitrile

Wittig–Horner reagents ( 1a–e ) react with 1,3-dioxo-Δ^2,α-indanmalononitrile ( 2 ) to give the phosphonate adducts 3, 4, 5, 6, and 7 , respectively. Structural reasoning for the new products was based on compatible analytical and spectral data (IR, ¹H, ³¹P NMR, and MS). The mechanism that accounts for the formation of the new adducts is discussed. © 1997 John Wiley & Sons, Inc. Heteroatom Chem 8 : 253–257, 1997.     

The reaction of Wittig and Wittig–Horner reagents with dicyanomethylene derivatives of fluorenone,xanthone, and thiaxanthone. A novel synthesis of phosphoranylidenecyclobutylidene derivatives

>Wittig reagents 1a,b react with dicyanomethylene derivatives of fluorenone (3) and xanthone (4) to give the corresponding phosphoranylidenecyclobutylidene adducts 6a, 6b, 9a, and 9b. On the other hand, the reaction of Wittig–Horner reagents (2) with the same nitriles 3 and 4 afforded the respective phosphonate adduct 8 and the alkylated product 10. A mechanism that accounts for the formation of the new products is presented. © 1999 John Wiley & Sons, Inc. Heteroatom Chem 10: 263–269, 1999     

Synthesis of N‐Substituted Piperidine Salts as Potential Muscarinic Ligands for Alzheimer's Applications

Several heterocyclic N‐piperidine substituted salts were synthesized that were found to inhibit the specific binding of the antagonist [³H] quinuclidinyl benzilate in radioligand muscarinic binding assays (³H‐QNB) in bioassays. One of the heterocyclic salts, compound 7 , met the significance criteria in these assays (>50% inhibition) at 10 μM of the nonselective muscarinic antagonist (³H‐QNB) in cells of the Wistar rat cerebral cortex. Furthermore, this compound displayed 61% inhibition at 10 μM of the antagonist (³H‐QNB) for the M₅ receptor (IC₅₀ 6.34 μM, K_i 3.93 μM, n_H = 0.996) in human recombinant CHO cell lines. These data obtained from Ricerca Biosciences suggested that compound 7 was selective for the M₅ receptor. Another study from the Czech Academy of Sciences demonstrated that compound 7 was 3 to 8 times more potent at M₂ than other subtypes of muscarinic receptors in competition with antagonist N‐methylscopolamine and selective for the M₁ receptors over M₃ and M₅ in antagonizing accumulation of inositol phosphates induced by muscarinic agonist carbachol.     

Scope and Limitation of the Reactions of 3-Imino Derivatives of Pentane-2,4-Diones with Organophosphorus Reagents

Abstract

3-(Hydroxyimino)pentane-2,4-dione reacts with phosphonium ylides, Wittig–Horner reagents, trialkyl phosphites, and Lawesson's reagents to give the olefinic and cyclic products, the phosphonate adducts, the dialkyl phosphate products, the phosphinodithioic acid, and 2,4-dithione products, respectively. Furthermore, the reaction of 3-(phenylimino)pentane-2,4-dione with Wittig, Wittig–Horner reagents and trialkyl phosphite resulted in the formation of 2,5-diendioate, diethoxy phosphoryl hexanoate and the phosphate products. Possible reaction mechanisms are considered and the structural assignments are based on analytical and spectroscopic results. The antibacterial and antifungal activities for some of the new compounds are also reported.     

Effect of Epoxidation of Diene Component of SBS Block Copolymer on Morphology and Mechanical Properties

In this work, the polybutadiene (PB) block of an asymmetric lamellae forming polystyrene/polybutadiene based triblock copolymer was epoxidized to different extent in order to study its effect on morphology and mechanical behaviour of the copolymer. The products were analyzed by means of different microscopic techniques, Fourier transform infrared (FTIR) spectroscopy and microhardness measurements. It was found that the microphase separation behavior and hence the mechanical properties of the materials were drastically altered through epoxidation of the diene block of the styrene/diene triblock copolymer. With the increase in the extent of epoxidation the lamellar structure changed to distorted lamellae and then to disordered domains. Consequently, inhomogeneous mechanical performance of the samples was observed at higher degree of chemical modification.