Synthetic talc as a solid base catalyst for condensation of aldehydes and ketones

Magnesium organo silicates (MOSs; synthetic talc) as such and with amine surface functionalities were synthesized by sol–gel method under non-hydrothermal conditions and characterized by spectroscopic techniques. The synthesized talc samples were observed to be thermally stable up to 200 °C in nitrogen atmosphere and used as catalysts for condensation of aldehydes and ketones. Application of synthetic talc as a solid base catalyst for condensation of aldehydes and ketones is being reported for the first time. The effect of solvent, solvent to reactant molar ratio, amount of catalyst and temperature was studied in detail for self-condensation of propanal. High conversion (86%) of propanal with 95% selectivity of 2-methylpentenal was achieved using dimethyl sulphoxide as a solvent. The kinetic study was carried out for the condensation of propanal catalyzed by amine functionalized MOS under optimum reaction conditions. Catalyst was re-used without significant loss in activity up to three cycles.     

Synthesis and utilization of alternative chain transfer agent in cobalt catalyzed 1,3-butadiene polymerization reaction to produce cis-polybutadiene rubber

The cyclodimerization of 1,3-butadiene was performed to synthesize 1,5-cyclooctadiene by using nickel-phosphite based catalyst system. The optimization of cyclodimerization reaction was done to achieve up to 80% selectivity towards 1,5-cyclooctadiene. 1,5-Cyclooctadiene, thus synthesized, was subsequently employed as a chain transfer agent (CTA) for controlling the molecular weight (M.W.) of cis-polybutadiene rubber (BR) in cobalt-complex catalyzed 1,3-butadiene polymerization reaction. The M.W. of BR was reduced from 6.7 to 1.88 × 10⁵ g/mol by escalating the concentration of 1,5-cyclooctadiene from 0% to 0.5% with respect to 1,3-butadiene (monomer) concentration. Similar reducing trend was observed for the Mooney viscosity and gel content of BR with increasing 1,5-cyclooctadiene concentration. The efficacy of 1,5-cyclooctadiene as a CTA for 1,3-butadiene polymerization reaction was further explored by conducting polymerization reaction in various solvents and at higher monomer conversion (∼70%). The effect of 4-vinyl cyclohexene, which was a dominant byproduct during cyclodimerization of 1,3-butadiene, was also investigated. The presence of 4-vinyl cyclohexene has shown adverse effect in the polymerization reaction and was not functioning as a chain transfer agent. Finally, a feasibility of replacement of commercially used gaseous CTA, 1,2-butadiene, by in-house synthesized liquid CTA, 1,5-cyclooctadiene, was also investigated.     

Linear variance bounds for particle approximations of time-homogeneous Feynman–Kac formulae

This article establishes sufficient conditions for a linear-in-time bound on the non-asymptotic variance for particle approximations of time-homogeneous Feynman–Kac formulae. These formulae appear in a wide variety of applications including option pricing in finance and risk sensitive control in engineering. In direct Monte Carlo approximation of these formulae, the non-asymptotic variance typically increases at an exponential rate in the time parameter. It is shown that a linear bound holds when a non-negative kernel, defined by the logarithmic potential function and Markov kernel which specify the Feynman–Kac model, satisfies a type of multiplicative drift condition and other regularity assumptions. Examples illustrate that these conditions are general and flexible enough to accommodate two rather extreme cases, which can occur in the context of a non-compact state space: (1) when the potential function is bounded above, not bounded below and the Markov kernel is not ergodic; and (2) when the potential function is not bounded above, but the Markov kernel itself satisfies a multiplicative drift condition.     

Diffusion-driven pattern formation in ionic chemical solutions

The driving force in diffusion-driven pattern formation is the difference in the diffusional flux of the key species, which in the case of ionic systems builds up a local electric field at the concentration gradients. The arising additional migrational flux not only decreases but also enhances the instability of the base state, depending on the charge distribution among the components. The opposite charges on the slower diffusing autocatalyst and its reacting counterpart favor pattern formation and shift the onset of instability to a smaller difference in the diffusion coefficients. The same charges, in addition to having the opposite effect, may even lead to the complete stabilization of planar reaction fronts unstable in the neutral system.     

Most recent strategies targeting estrogen receptor alpha for the treatment of breast cancer

Molecular Diversity - Breast cancer is the most prominent, frequently diagnosed and leading cause of death among women. Estrogen is an agonist of estrogen receptor alpha (ER-α), expressed in...     

Spectrophotometric study of the acid-base equilibria of an imidazobenzodiazepine,midazolam, and its determination in pharmaceutical formulations

The acid-base behaviour of midazolam, a psychotropic drug derived from imidazobenzodiazepine family, has been studied spectro-photometrically. This compound hydrolyzes at pH values lower than 4. Reversible cleavage of the azomethine bond takes place and the open-ring compound is in equilibrium with the closed-ring compound (protonated form of the parent drug). Absorbance-time data (measured at 225 nm and for different pH values) have been evaluated by a pseudo-first order logarithmic approach, leading to different apparent kinetic constants, depending on pH and temperature. A simple mechanism of hydrolysis, corresponding to fast protonation and slow hydrolysis with opening of the ring is in good agreement with the kinetic results. From data obtained at pH values greater than 4, the deprotonation constant of the nitrogen atom at position 2 of the imidazole ring has been calculated and a pK_a value of 5.50 ± 0.05 obtained. In addition, a Spectrophotometric method has been developed which allows the determination of midazolam at concentrations from 1.23 × 10^–6 M to 3.38 × 10^–5 M. This method has been applied to a pharmaceutical formulation midazolam; the Dormicum error, in terms of relative standard deviation, was lower than 1.5%.     

Electrogeneration of coulometric reagents: Applications to drug control

Summary The coulometric electrogeneration of titanium(III) is applied to the quantitative reduction of quinone and naphthoquinone compounds of biological interest. Current efficiencies of 100% are obtained at a platinum cathode with titanium tetrachloride as supporting electrolyte in strong acidic media. Benzoquinones, which can be partially or totally destroyed in such media, are determined by using a mixture of TiCl₄ and EDTANa₄. The choice of experimental parameters is discussed in detail. For oxidimetric determinations, silver(II), which is well known as a very strong oxidizing agent (E ⁰+1.90 Vvs. NHE), is produced with 100% current efficiency on a gold anode at low temperature (–10° C). The best conditions for the electrogeneration of vanadium(V) from vanadyl sulphate in dilute sulphuric acid have also been investigated. The use of amperometric or potentiometric end-point detection is discussed. Organic compounds such as hydroquinone and hydrazide derivatives can be titrated with a good accuracy.

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Elektrogeneration coulometrischer Reagenzien. Anwendung zur Arzneimittelkontrolle

Zusammenfassung Die coulometrische Elektrogeneration von Titan(III) wurde zur quantitativen Reduktion von Chinon- und Naphthochinonverbindungen biologischer Bedeutung verwendet. Ausbeuten von 100% wurden an einer Platinkathode mit TiCl₄ als Trägerelektrolyt in stark saurem Medium erhalten. Benzochinone, die in einem solchen Medium ganz oder teilweise zerstört werden können, wurden mit einer Mischung von TiCl₄ und ÄDTA bestimmt. Die Wahl experimenteller Parameter wurde ausführlich diskutiert. Für oxydimetrische Bestimmungen wird Ag(II), das als starkes Oxydationsmittel bekannt ist (E ⁰=+1,90 V vs NHE), mit 100%iger Ausbeute an einer Goldanode bei –10° gewonnen. Die besten Bedingungen für die Elektrogeneration von Vanadin(V) aus Vanadylsulfat in verdünnter Schwefelsäure wurden untersucht. Die amperometrische oder potentiometrische Endpunktanzeige wurde diskutiert. Organische Verbindungen, wie Hydrochinon- und Hydrazidderivate, lassen sich genau titrieren.

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Presented at the 8th International Microchemical Symposium, Graz, Austria, August 25–30, 1980.