Novel vinyl phosphonates and vinyl boronates by halogenation, allylation, and propargylation of alpha-boryl- and alpha-phosphonozirconacyclopentenes

[structure: see text] Alpha-phosphonozirconacyclopentenes or alpha-borylzirconacyclopentenes react by bromination, iodination, allylation, and propargylation to generate unique vinyl boronates and vinyl phosphonates not obtainable by other methods. The reaction proceeds in two steps, with both high regio- and stereoselectivity. With the vinyl boronates, the Zr-Csp2 bond is initially cleaved by 1 equiv of electrophile. With the phosphonates, either the Zr-Csp2 bond (allyl bromide, Br(2)) or the Zr-Csp3 bond (I(2), propargyl bromide) may be initially cleaved. The addition of a second equivalent of an electrophile results in disubstitution.     

Selective preparation of (E)-3-oxo-1-alkenylphosphonates by insertion of acyl chlorides and nitriles into zirconacycles

Zirconacycles 1, obtained from diethyl 1-alkynylphosphonates, insert either acyl chlorides or nitriles to provide, after acidic workup, (E)-3-oxo-1-alkenylphosphonates, 2, in isolated yields of 55-83%. Insertion produces only one regio- and stereoisomer. The reaction is quite general and proceeds well with both aliphatic and aromatic acyl chlorides. Acetonitrile and p-methoxybenzonitrile also inserted efficiently. Insertion of isobutyl chloroformate produced the vinylphosphonocarboxylate, 2c, the first representative of this class of compounds.     

Preparation of 5-hydroxy-1-alkenyboronates from 1-alkynylboronates, Cp2ZrCl2/2EtMgBr, and aldehydes

1-Alkynylboronates form five-membered zirconacycles with Cp(2)ZrCl(2)/2-EtMgBr as indicated by deuterium labeling. The zirconacycles add aldehydes to form seven-membered zirconacycles. Hydrolysis of the latter provides 5-hydroxy-1-alkenylboronates in fair to good isolated yields. Both aliphatic and aromatic aldehydes undergo insertion.     

Aspect-ratio dependent oscillatory thermocapillary convection in the floating half zone

The dependency of the critical Marangoni number on the geometrical aspect ratio of the floating half zone is essential to predict the onset of oscillatory thermocapillary convection.The experimental studies in the microgravity conditions on floating half zones of several centimeters in diameter have predicted that the critical Marangoni number increases with the increasing aspect ratio,and the terrestrial experimental studies have predicted the contradictory conclusion for floating half zones of several mil...     

Non-Gravitational Effects with Density-Matching in Evaluating the Influence of Sedimentation on Colloidal Coagulation

The method of density matching between the solid and liquid phases is often adopted to effectively eliminate the effect of sedimentation of suspensions in studies on dynamic behaviour of a colloidal system. However, the associated changes in the solvent composition may bring side effects to the properties investigated and therefore might lead to a faulty conclusion if the relevant correction is not made. To illustrate the importance of this side effect, we present an example of the sedimentation influence on the coagulation rate of suspensions of 2μm （diameter） polystyrene. The liquid mixtures, in the proper proportions of water （H2O）, deuterium oxide （D2O） and methanol （MeOH） as the liquid phase, density-matched and unmatched experiments are performed. Besides the influence of viscosity, the presence of methanol in solvent media, used to enhance the sedimentation effect, causes significant changes （reduction） in rapid coagulation rates compared to that in pure water. Without the relevant corrections for those non-gravitational factors it seems that gravitational sedimentation would retard the coagulation. The magnitude of the contribution from the non-gravitational factor is quantitatively determined, making the relevant correction possible. After necessary the influence of the sedimentation on coagulation rates at corrections for all factors, our experiments show that the initial stage of the coagulation is not observable.     

Comparison of amine-induced cyclization of 6-chloro-1-hexynylphosphonate and isobutyl 7-chlorohept-2-ynoate

The reaction of 6-chloro-1-hexynylphosphonate with primary and secondary amines afforded exclusively 2-aminocyclohexenylphosphonates in 62-85% isolated yields. In contrast, reaction of various amines with isobutyl 7-chlorohept-2-ynoate in acetonitrile at 70 °C gave (E)-sec-butyl 2-(1-alkylpiperidin-2-ylidene)acetates in 65-78% isolated yields. Calculations offer an explanation for the difference in the behavior of the two compounds classes. It is shown that C-C cyclization in the alkyne-phosphonate group occurs via an initial formation of a zwitterionic intermediate, which is stabilized by both an inductive effect of the phosphonate group and a newly formed hydrogen bond. The alkyne-carboxylate group, on the other hand, proceeds via enamine formation as a result of the smaller inductive effect of the carboxylate combined with involvement of an allene-like resonance form. This resonance form both delocalizes the negative charge in the zwitterionic intermediate making it to be less available for attack, and affects the geometry thus preventing formation of the stabilizing hydrogen bond. Hence, the zwitterionic intermediate of the alkyne-carboxylates is less stable leading to formation of an enamine, which is followed by N-C cyclization to give the azaheterocycles.