A three-component cyclocondensation reaction for the synthesis of new triazolo[1,5-a]pyrimidine scaffolds using 3-aminotriazole,aldehydes and ketene N,S-acetal

Molecular Diversity - This study describes the use of 3-aminotriazole, different aldehydes and N-methyl-1-(methylthio)-2-nitroethenamine as a ketene N,S-acetal in a three-component condensation for...     

A new route for the construction of the AB-ring core of Taxol

A new method for the construction of the AB-ring core of Taxol was developed utilizing a new skeletal transformation protocol as a pivotal step. The acid-catalyzed rearrangement of the cyclopentenone-allene photoadduct gave a bridged seven-membered ketone, which was easily transformed, using the intramolecular Suzuki reaction and the oxidative cleavage of the vicinal diol, to the bicyclic diketone.     

Three-dimensional trajectory study of the I + HI → IH + I, H + I2 reactions

The quasiclassical trajectory calculation of the I + HI collision is performed in order to study the exchange and endothermic reaction channels. The rate constant of the exchange reaction I′ + HI → HI′ + I is found to be equal to 7.7 × 10¹¹ cm³/mol s at room temperature of 300 K. The study of the endothermic reaction I + HI → H + I₂ shows that it takes place only in configurations with large bend angles. Due to the non-collinear character of this reaction its threshold (2 eV) exceeds significantly the threshold of the minimal energy (collinear) reaction path (1.55 eV).     

An Efficient and Facile Synthesis of Quinoxaline Derivatives Catalyzed by KHSO4 at Room Temperature

Summary. A facile synthesis of quinoxaline derivatives catalyzed by KHSO₄ in very high yields at room temperature is reported.     

Dipole moments of (styrene-p-chlorostyrene) triblock copolymers in solutions

(Styrene-p-chlorostyrene) triblock copolymers of the ABA and BAB types (A—polystyrene; B—poly-p-chlorostyrene) were prepared by anionic polymerization and their conformational behaviours in solutions were studied from measurements of the dipole moments. Two solvents, toluene and cumene, were used for the study; toluene is a good solvent for both polystyrene and poly-p-chlorostyrene whereas cumene is a selective solvent, good for polystyrene but poor for poly-p-chlorostyrene. It was found that the dipole moments of the block copolymers measured in toluene are the same for the ABA and BAB copolymers; in cumene however the dipole moment of the BAB copolymer is smaller than that of the ABA copolymer. The results give an additional support to our previous conclusion that the conformation of the block copolymers in a good solvent such as toluene could be approximated with a pseudo-random coil form; in a selective solvent, however, some anomalies take place in the conformation of the block copolymers, as deduced from intrinsic viscosity, osmotic pressure and light scattering measurements.     

Highly sensitive determination of haloperidol in human serum by capillary gas chromatography using a surface ionization detector

A method has been developed for highly sensitive determination of haloperidol in human serum involving a simple extraction procedure followed by gas chromatographic separation. Target components were separated from the extracting solvents with a Van den Berg type solventless sample injector before introduction Into a DB-1 capillary separation column. A surface ionization detector (SID), which has highly selective sensitivity for Substituted amines, was employed for quantitation using bromperidol as an internal standard. Chloroform proved to be the best extracting solvent, yielding a quantitative detection limit of 5 ng/ml (S/N = 2). Comparison of the response to target compounds obtained by the SID, FTD (flame thermionic detector), and FID (flame ionization detector) showed the SID to be superior.     

Application of 1,2,3,5,6,7-hexahydropyrrolizinium perchlorate in the synthesis of 7a-substituted hexahydro-1h-pyrrolizines

The method for preparing 7a-substituted hexahydro-1H-pyrrolizines 2 from 1,2,3,5,6,7-hexahydropyrrol-izinium Perchlorate (3) was investigated, by which introduction of a wide variety of functionalities on C(7a) could be achieved easily.     

Classical trajectory calculations of intramolecular vibrational energy redistribution. I. Methanol-water complex

Intramolecular vibrational energy redistributions of the O-H stretching (nuOH) vibration for the methanol monomer and its water complex, the methanol-water dimer, are investigated by using ab initio full-dimensional classical trajectory calculations. For the methanol monomer, in the high-energy regime of the 5nuOH overtone, the time dependence of the normal-mode energies indicates that energy flowed from the initial excited O-H stretching mode to the C-H stretching mode. This result confirms the experimental observation of energy redistribution between the O-H and C-H stretching vibrations [L. Lubich et al., Faraday Discuss. 102, 167 (1995)]. Furthermore, a lot of dynamical information in the time domain is contained in the power spectra, whose density is given by the Fourier transformation of the total momentum obtained from trajectory calculations. For the methanol-water hydrogen-bonded complex, at the high-energy level of the 5nuOH overtone, the calculated power spectrum shows considerable splitting and broadening, indicating significant energy redistribution through strong coupling between the O-H stretching vibration and other vibrations. It is thus clear that the A-H...B hydrogen-bond formation facilitates energy redistribution subsequent to the vibrational excitation of the hydrogen-bonded A-H stretching mode.     

Effect of polycondensation methods on molecular weight distribution of nylon 610

Polycondensation methods greatly influence the molecular weight distribution of poly(hexamethylene sebacamide) (nylon 610) as determined by gel permeation chromatography (GPC). The ratio of weight average molecular weight to number average molecular weight (M_w/M_n) was used as a measure for estimating the molecular weight distribution. The M_w/M_n ratios of nylon 610 obtained from melt, solid phase, and high temperature polycondensation methods were 2 to 3.5, which were expected values for the most probable distribution. However, those for polymers obtained from the direct polycondensation in the presence of triphenylphosphine, interfacial polycondensation and low temperature polycondensation using an acid chloride varied over a wide range from 3.5 to 8.5. The effect of the kind of organic solvents in the interfacial method on the M_w/M_n ratios was especially large, and the molecular weight distribution could be controlled to some extent by selecting an appropriate solvent.