Efficient chemoselective deprotection of silyl ethers using catalytic 1-chloroethyl chloroformate in methanol

Fast and chemoselective desilylation of silyl-protected alcohols was achieved using a catalytic amount of 1-chloroethyl chloroformate in methanol. With a minimal amount of 1-chloroethyl chloroformate as the source for anhydrous HCl, extremely efficient cleavage of silyl ethers of primary and secondary alcohols was accomplished, and chemoselective deprotection of one silyl ether in the presence of another silyl or other acid-labile group was possible through controlling the amount of the chloroformate and reaction time.     

Facile syntheses of 3-spiro- and 3,6-bridged 2,5-piperazinediones

The intramolecular addition of hydroxyl group of 3-(3-hydroxyl)propylidene-2,5-piperazinedione to 3-position and the same substitution of 3-(3-hydroxy)propyl derivative to 6-position gave the corresponding 3-spiro- and 3,6-bridged 2,5-piperazinediones, respectively.     

Self-assemblies of new rigid angular ligands and metal centers toward the rational construction and modification of novel coordination polymer networks

Self-assemblies of rigid angular ligands with 120 degrees molecular angle and metal centers have been investigated with the aim of achieving the rational construction and modification of coordination polymer structures. The reactions of Co(NCS)(2) with 1,3-bis(trans-4-styrylpyridyl)benzene (L(1)()), 2,6-bis(trans-4-styrylpyridyl)pyridine (L(2)()), 1,3-bis(trans-4-styrylpyrimidyl)benzene (L(3)()), and 1,3-bis(trans-4-styrylquinoly)benzene (L(4)()) afford complexes [Co(L(1)())(2)(NCS)(2)]( infinity ) (1), [Co(L(2)())(2)(NCS)(2)]( infinity ) (2), Co(L(3)())(2)(NCS)(2)(CH(3)OH)(2) (3), and [Co(L(4)())(NCS)(2)]( infinity ) (4), respectively. The resulting complexes exhibit open framework, stairlike hydrogen-bonded chain and single-stranded helical coil structures, which are controlled by the variation of the geometry around the coordination site in ligands. Moreover, the coordination of L(1)() and L(2)() to Mn(hfac)(2) (hfac = 1,1,1,5,5,5-hexafluoroacetylacetonate) yields single-stranded helical coordination polymers of [Mn(L(1)())(hfac)(2)]( infinity ) (5) and [Mn(L(2)())(hfac)(2)]( infinity ) (6), respectively.     

Electronic structure and field emission of multiwalled carbon nanotubes depending on growth temperature

The electronic structure of multiwalled carbon nanotubes (CNTs) has been investigated, depending on the growth temperature, using synchrotron X-ray photoelectron spectroscopy (XPS) and field emission measurements. The vertically aligned CNTs are grown via pyrolysis of ferrocene and acetylene in a broad temperature range 600-1000 degrees C. The CNTs have a cylindrical structure with a uniform diameter of 20 nm. As growth temperature increases, due to an improved crystallinity of the graphitic sheets, the width of the XPS C 1s peak becomes narrower and the intensity of the valence band increases. Field emission from the as-grown CNTs exhibits a large enhancement of current density with growth temperature, strongly correlated with the electronic structure revealed by XPS.     

A Mild Isomerization Reaction for β,γ‐Unsaturated Ketone to α,β‐Unsaturated Ketone

A series of β,γ‐unsaturated ketones were isomerized to their corresponding α,β‐unsaturated ketones by the introduction of DABCO in iPrOH at room temperature. The endo‐cyclic double bond (β,γ‐position) on ketone was rearranged to exo‐cyclic double bond (α,β‐position) under the reaction conditions.     

Spin—rotational relaxation study of molecular reorientation in the presence of internal extended rotational diffusion

Molecular reorientation in the presence of internal rotation is investigated and an analytical expression for the spin—rotational rate of a nucleus attached to the internal rotor is obtained in terms of the internal angular-momentum correlation time. A model of a symmetric-top molecule undergoing anisotropic rotational diffusion is extended to include a modified extended diffusion of internal rotation. The result is applied to liquid toluene and the internal angular-momentum correlation time is evaluated from the ¹³C nuclear spin—rotational relaxation rate of the methyl carbon. A comparison with the previous result on the dipole—dipole relaxation data is made and the consistency of the present theory is discussed.     

Manipulating the Through‐Space Spin–Spin Interaction of Organic Radicals in the Confined Cavity of a Self‐Assembled Cage

We show a new approach to manipulating the through‐space spin–spin interaction by utilizing the confined cavity of a self‐assembled M₆L₄ coordination cage. The coordination cage readily encapsulates stable organic radicals in solution, which brings the spin centers of the radicals closer to each other. In sharp contrast to the fact that the radical in solution in the absence of the cage is in a doublet state, in the presence of the cage through‐space spin–spin interaction is induced through cage‐encapsulation effects in solution as well as in the solid state, resulting in the triplet state of the complex. These results were confirmed by ESR spectroscopy and X‐ray crystallography. The quantity of triplet species generated by encapsulation in the cage increases with increasing affinity of the radicals to the cage. We estimated the affinity between several types of guests and the cage in solution by cyclic voltammetry. We also demonstrate that the through‐space interaction of organic radicals within the self‐assembled coordination cage can be controlled by external stimuli such as heat or pH.     

Metabolism and pharmacokinetic studies of propionylpromazine in horses

The propionylpromazine concentrations in plasma after intramuscular administration to horses were determined using gas chromatography with nitrogen-phosphorus detection. After hydrolysis by beta-glucuronidase/arylsulphatase, the parent drug and three metabolites were detected in urine. The metabolites were identified as 2-(1-hydroxypropyl)promazine, 2-(1-propenyl)promazine and 7-hydroxypropionylpromazine by gas chromatography-mass spectrometry. No N-demethylated or sulphoxidated metabolites of propionylpromazine were observed in the horse urine.