Catalytic reactions which involve the cleavage of an sp(3) C-H bond adjacent to a nitrogen atom in N-2-pyridynyl alkylamines are described. The use of Ru(3)(CO)(12) as the catalyst results in the addition of the sp(3) C-H bond across the alkene bond to give the coupling products. A variety of alkenes, including terminal, internal, and cyclic alkenes, can be used for the coupling reaction. The presence of directing groups, such as pyridine, pyrimidine, and an oxazoline ring, on the nitrogen of the amine is critical for a successful reaction. This result indicates the importance of the coordination of the nitrogen atom to the ruthenium catalyst. In addition, the nature of the substituents on the pyridine ring has a significant effect on the efficiency of the reaction. Thus, the substitution of an electron-withdrawing group on the pyridine ring as well as a substitution adjacent to the sp(2) nitrogen in the pyridine ring dramatically retards the reaction. Cyclic amines are more reactive than acyclic ones. The choice of solvent is also very important. Of the solvents examined, 2-propanol is the solvent of choice.

No abstract

In the medical ultrasound field, microbubbles have recently been the subject of much interest. Controlling actively the effect of the microbubbles, a novel therapeutic method has been investigated. In this paper, our works on high intensity focused ultrasound (HIFU) lithotripsy with cavitating microbubbles are reviewed and the cavitation detection method to optimize the HIFU intensity is investigated. In the HIFU lithotripsy, collapse of the cloud cavitation is used to fragment kidney stones. Cloud cavitation is potentially the most destructive form of cavitation. When the cloud cavitation is acoustically forced into a collapse, it has the potential to concentrate a very high pressure. For the control of the cloud cavitation collapse, a novel two-frequency wave (cavitation control [C-C] waveform) is designed; a high-frequency ultrasound pulse (1-4 MHz) to create the cloud cavitation and a low-frequency trailing pulse (500 kHz) following the high-frequency pulse to force the cloud into collapse. High-speed photography showed the cavitation collapse on the stone and the shock-wave emission from the cloud. In vitro erosion tests of model and natural stones were also conducted. In the case of model stones, the erosion rate of the C-C waveform showed a distinct advantage with the combined high- and low-frequency waves over either wave alone. For the optimization of the high-frequency ultrasound intensity, the subharmonic acoustic pressure was examined. The results showed relationship between the subharmonic pressure from cavitating bubbles induced by the high-frequency ultrasound and eroded volume of the model stones. Natural stones were eroded and most of the resulting fragments were less than 1 mm in diameter. The method has the potential to provide a novel lithotripsy system with small fragments and localized cavitating bubbles on a stone.

The treatment of aryl-1-alkynes, such as 4-aryl-1-butyne, 5-aryl-1-pentyne, and 6-aryl-1-hexyne, with catalytic amounts of transition metal chlorides, such as PtCl(2) and [RuCl(2)(CO)(3)](2), at 80 degrees C in toluene results in cycloisomerization to give dihydronaphthalenes or dihydrobenzocycloheptenes, in which the cyclization mode is dependent on the length of the tethers. The reaction is limited to substrates containing terminal alkynes. A key step of the reaction is the intramolecular interception by an aromatic ring of the vinylmetal complex 2, which contains a cation center at the beta-position, generated from the electrophilic addition of transition metal halides toward an alkyne. The more electron-rich aryl systems are more reactive.