An efficient novel synthesis of beta-(azuleno[1,2-b]benzothienyl)- and beta-(azuleno[2,1-b]benzothienyl)-alpha,beta-unsaturated ketones by the tropylium ion-mediated intramolecular furan ring-opening reaction and X-ray investigation of methyl ketone derivative

Intramolecular reaction of 2-tropylio-3-(5-substituted 2-furyl)benzothiophenes (3), prepared from the corresponding 2-cycloheptatrienyl-3-(5-substituted 2-furyl)benzothiophenes (2), afforded the beta-(azuleno[1,2-b]benzothienyl)-alpha,beta-unsaturated ketones (4), which are otherwise difficult to obtain, in moderate yields. The reaction involves a ring-opening process of the furan ring by intramolecular attack of the tropylium ion onto the 2-position of the furan ring. Similarly, beta-(azuleno[2,1-b]benzothienyl)-alpha,beta-unsaturated ketones (8) were obtained from the corresponding 3-tropylio-2-(5-substituted 2-furyl)benzothiophenes (7) albeit in lower yields. The molecular and crystal structures of the methyl ketone derivative, 8a, are discussed on the basis of X-ray structure analysis.     

Cyclopropanation and carbonyl olefination utilizing 2-(Alk-1-yn-1-yl)-2-(trialkylsilyl)-1,3-dithianes via regioselective generation of titanium alkynylcarbene complexes

Cp(2)Ti[P(OEt)(3)](2)-promoted reactions of 2-(alk-1-yn-1-yl)-2-(trialkylsilyl)-1,3-dithianes (RS)(2)C(Si)CCR with terminal olefins and carbonyl compounds produced (trialkylsilylethynyl)cyclopropanes and 1-(trialkylsilyl)alk-3-en-1-ynes, respectively. These compounds were suggest to be produced via the formation of intermediary titanium alpha-(trialkylsilylethynyl)carbene complexes Cp(2)Ti=C(R)CCSi in preference to their regioisomers, alpha-(trialkylsilyl)alkynylcarbene complexes Cp(2)Ti=C(Si)CCR.     

Cage-shaped borate esters with tris(2-oxyphenyl)methane or -silane system frameworks bearing multiple tuning factors: geometric and substituent effects on their Lewis acid properties

Boron complexes that contain new tridentate ligands, tris(o‐oxyaryl)methanes and ‐silanes, were prepared. These complexes had a cage‐shaped structure around a boron center and showed higher Lewis acidity and catalytic activity than open‐shaped boron compounds. The cage‐shaped ligands determined the properties of the borates by altering the geometry and were consistently bound to the metal center by chelation. The synthesized compounds were L?B(OC₆H₄)₃CH, L?B(OC₆H₄)₃SiMe, and its derivatives (L=THF or pyridine as an external ligand). Theoretical calculations suggested that the cage‐shaped borates had a large dihedral angle (C_ipso‐O‐B‐O) compared with open‐shaped borates. The geometric effect due to the dihedral angle means that compared with open‐shaped, the cage‐shaped borates have a greater Lewis acidity. The introduction of electron‐withdrawing groups on the aryl moieties in the cage‐shaped framework increased the Lewis acidity. Substitution of a bridgehead Si for a bridgehead C decreased the Lewis acidity of the boron complexes because the large silicon atom reduces the dihedral angle of C_ipso‐O‐B‐O. The ligand‐exchange rates of the para‐fluoro‐substituted compound B(OC₆H₃F)₃CH and the ortho‐phenyl‐substituted compound B(OC₆H₃Ph)₃CH were less than that of the unsubstituted borate B(OC₆H₄)₃CH. The ligand‐exchange rate of B(OC₆H₄)₃SiMe was much faster than that of B(OC₆H₄)₃CH. A hetero Diels–Alder reaction and Mukaiyama‐type aldol reactions were more effectively catalyzed by cage‐shaped borates than by the open‐shaped borate B(OPh)₃ or by the strong Lewis acid BF₃?OEt₂. The cage‐shaped borates with the bulky substituents at the ortho‐positions selectively catalyzed the reaction with less sterically hindered substrates, while the unsubstituted borate showed no selectivity.     

Spectrophotometric determination of cobalt(II) with 2-(3′-sulfobenzoyl)pyridine benzoylhydrazone

A simple method has been described for the Spectrophotometric determination of cobalt(II) with 2-(3′-sulfobenzoyl)pyridine benzoylhydrazone (SBPBH). In aqueous solution, cobalt(II) reacts with SBPBH to form a yellow complex, which is not destroyed even by the addition of 3.8 M perchloric acid. The absorption maximum of the complex in 1.5 M perchloric acid medium was found to be 400 nm; the molar absorptivity was 2.17 × 10⁴ liters mol⁻¹ cm⁻¹. The proposed method is fairly selective and has been applied to the determination of cobalt in standard alloy steel samples.     

The annealing behavior of hydrogen implanted into Al-1.5 at.% Si alloy

We have studied effects of added elements as well as defects on trap-sites of hydrogen in metals. For the purpose, we observed depth profiles and thermal behaviors of hydrogen implanted into Al-1.5 at.% Si alloy samples in an implantation-temperature range of liquid nitrogen temperature (LNT) to 373 K at different doses. The results were compared with those for pure aluminum samples. It was found that hydrogen is trapped as molecules in grain boundaries of Al/Si.     

Aplyronines D–H from the sea hare Aplysia kurodai: isolation,structures, and cytotoxicity

Five cytotoxic macrolides, aplyronines D–H (4–8), were isolated from the Japanese sea hare Aplysia kurodai. They are new congeners of the antitumor compound aplyronine A (1), which was previously isolated from the same organism. Their structures were determined by spectroscopic analysis (NMR and MS). The cytotoxicity of these new compounds was evaluated in comparison with that of aplyronines A–C (1–3), suggesting the importance of the 7-O-seryl ester group for mediating the potent cytotoxicity of aplyronines.     

Effect of Alkynyl Group on Reactivity in Photoaffinity Labeling with 2-Thienyl-Substituted α-Ketoamide

Minimalist photo-reactive probes, which consist of a photo-reactive group and a tag for detection of target proteins, are useful tools in chemical biology. Although several diazirine-based and aryl azide-based minimalist probes are available, no keto-based minimalist probe has yet been reported. Here we describe minimalist probes based on a 2-thienyl-substituted α-ketoamide bearing an alkyne group on the thiophene ring. The 3-alkyne probe showed the highest photo-affinity labeling efficiency.     

Proton Conduction at High Temperature in High-Symmetry Hydrogen-Bonded Molecular Crystals of RuIII Complexes with Six Imidazole-Imidazolate Ligands

A new H-bonded crystal [Ru^III(Him)₃(Im)₃] with three imidazole (Him) and three imidazolate (Im⁻) groups was prepared to obtain a higher-temperature proton conductor than a Nafion membrane with water driving. The crystal is constructed by complementary N−H⋅⋅⋅N H-bonds between the Ru^III complexes and has a rare Icy-c* cubic network topology with a twofold interpenetration without crystal anisotropy. The crystals show a proton conductivity of 3.08×10⁻⁵ S cm⁻¹ at 450 K and a faster conductivity than those formed by only HIms. The high proton conductivity is attributed to not only molecular rotations and hopping motions of HIm frameworks that are activated at ∼113 K, but also isotropic whole-molecule rotation of [Ru^III(Him)₃(Im)₃] at temperatures greater than 420 K. The latter rotation was confirmed by solid-state ²H NMR spectroscopy; probable proton conduction routes were predicted and theoretically considered.     

Thermal stability of phthalate esters: Effect of substituents on the β-carbon atom

In order to clarify the mechanism conferring heat resistance on phthalate esters, those with a substituent on the β-carbon atom, such as bis(2-aminobutyl) phthalate, bis(2-nitrobutyl) phthalate, bis(2,4-diphenylbutyl) phthalate and dineopentyl phthalate, were synthesized and their thermal stabilities were studied by thermogravimetry and differential thermal analysis. The analytical results for these phthalate esters were compared with those for dibutyl phthalate, with a straight alkyl chain. As the temperatures required for a 3% weight loss of phthalate esters with a substituent, an electron-donating group (amino group) or an electron-accepting group (nitro group) on the β-carbon atom move to the higher end of the range, the effect of the adjacent group was recognized. The presence of a phenyl group in phthalate esters considerably improved the heat resistance. It is considered that the high heat resistance of bis(2,4-diphenylbutyl) phthalate is due to the obstruction of the planar configuration for cis elimination by the phenyl group and hindrance by the phenyl group of the formation of the six-membered cyclic transition state owing to the interaction between non-bondable molecules.     

Preparation of a polymeric membrane with lipoamide structure and its application to electron transport across membrane

A lipoamide (LAm) structure was introduced into a polymeric membrane by chemical modification of poly(γ-methyl-D -glutamate) (PMG). A. redox reaction proceeded across the membrane mediated by pendant LAm groups as solid carriers. It is suggested that the electron transport process in the membrane is derived from the exchange reaction between reduced LAm (thiol) and LAm (disulfide).