Highly efficient methods for metacyclophane synthesis

Highly efficient methods for synthesizing metacyclophanes such as 2,6-bridged pyrones and pyridines are described. 4-Hydroxy-2-pyrone derivative 3 bridged at the 3 and 6-positions is readily available. This compound was transformed into 2,6-bridged 4-pyrone 4 on heating in ethanol or in hydrochloric acid. Heating 4 with ammonia or methylamine afforded the corresponding 2,6-bridged 4-pyrone 7 or 8. These pyridones were synthesized directly from 3 by treatment with ammonia or methylamine. These methods have a wide applicability to the bridge length of metacyclophane; compounds with a short bridge (n=8) as well as long bridge (n=18) are synthesized in satisfactory yields.     

The synthesis of hexahydrooxoepithiopyridinedicarboximides by the reaction of thioamides with N-substituted maleimides

The synthesis of hexahydrooxoepithiopyridinedicarboxyimide (5: X₂ = N-Ph) by the reaction of thioamides 1 with N-substituted maleimide ( 2a ) was examined. The reaction of primary thioamides, such as thiobenzamide and p-toluthioamide with N-phenylmaleimide gives compounds 5 together with corresponding 4-hydroxy-1,3-thiazoles 4 . However, a similar reaction of secondary thioamides, such as N-methylthioacetamide, thiobenzanilide, with N-phenylmaleimide did not provide compounds 5 without addition of acid. The reaction pathway and the configuration of 5 were also investigated.     

Global aspect of steady-states for competitive-diffusive systems with homogeneous Dirichlet conditions

This paper is concerned with the competitive-diffusive systems

$\text{u}{}_{\mathrm{t}}\text{=d}{}_{\mathrm{l}}\text{u}{}_{\mathrm{xx}}\text{+(a}{}_{\mathrm{l}}\text{?b}{}_{\mathrm{l}}\text{u?c}{}_{\mathrm{l}}\text{v)u}\text{v}{}_{\mathrm{t}}\text{=d}{}_2\text{v}{}_{\mathrm{xx}}\text{+(a}{}_2\text{?b}{}_2\text{u?c}{}_2\text{u)v}\text{(x, t) ? (0, 1) × (0, ∞)}$

, with homogeneous Dirichlet boundary conditions. From a global bifurcation view point, the dependency of steady-states on the parameters a_i, b_i, c_i and d_i (i = 1, 2) is investigated. In particular, bifurcation of coexist ence solutions amd their stabilities are our main interests.     

Microwave‐Assisted Palladium‐Catalyzed Direct Arylation of 1,4‐Disubstituted 1,2,3‐Triazoles with Aryl Chlorides

Treatment of 1,4‐disubstituted 1,2,3‐triazoles with aryl chlorides in the presence of potassium carbonate under palladium catalysis and microwave irradiation at 250 °C for 15 min leads to arylation of the triazole at the 5‐position. A variety of functional groups, including ester and hydroxy groups, are compatible. The procedure is suitable for the regioselective preparation of trisubstituted triazoles. Microwave irradiation accelerates the reaction, thus allowing the rapid synthesis of trisubstituted triazoles, which are difficult to synthesize selectively.     

Hydrogen Gas Sensing of High Electrical Conducting-P2O5-SiO2 Glasses Prepared by Sol-Gel Process

High proton-conducting P₂O₅-SiO₂ glass was applied to the electrolyte of the hydrogen concentration cell for hydrogen gas sensing. 5P₂O₅·95SiO₂ glass was prepared using the sol-gel method and its electrical conductivity and electromotive force were measured at 50°C as a function of both the ambient humidity and hydrogen gas concentration. The electrical conductivities increased with increasing humidity and reached 10^–2 S/cm at 90% relative humidity. The electromotive force of the hydrogen concentration cell, where the glass was used as a membrane, showed good Nernstian response to hydrogen pressure in the high relative humidity region.     

A facile one-pot synthesis of α-fluoro-α,β-unsaturated esters from alkoxycarbonylmethyltriphenylphosphonium bromides

A convenient one-pot synthesis of α-fluoro-α,β-unsaturated esters from ethoxy- and tert-butoxycarbonylmethyltriphenylphosphonium bromide was developed. The fluorinated phosphoranes, generated in situ from alkoxycarbonylmethyltriphenylphosphonium bromides and 1-chloromethyl-4-fluoro-1,4-diazoniabicyclo[2.2.2]octane bis(tetrafluoroborate) (Selectfluor^®), undergo a Wittig reaction with aldehydes to yield α-fluoro-α,β-unsaturated esters with (Z)-selectivity.     

Site-selective RNA cleavage by DNA bearing a base pair-mimic nucleoside

We have synthesized the deoxyadenosine derivative tethering a phenyl group (X), which mimics the Watson-Crick A/T base pair. The RNA/DNA hybrid duplexes containing X in the middle of the DNA sequence showed a similar thermal stability regardless of the ribonucleotide species (A, G, C, or U) opposite to X, probably because of the phenyl group stacking inside of the duplex accompanied by the opposite ribonucleotide base flipped in an extrahelical position. The RNA strand hybridized with the DNA strand bearing X was cleaved on the 3'-side of the ribonucleotide opposite to X in the presence of MgCl2, and the RNA sequence to be cleaved was not restricted. The site-specific RNA hydrolysis suggests that the DNA strand bearing X has the advantage of the site-selective base flipping in the target sequence and the development of a "universal deoxyribozyme" to exclusively cleave a target RNA sequence.     

Ionic-conductivity switching of vinyl malachite green leuconitrile copolymers based on photoinduced carrier generation

Copolymers of bis[4-(N,N-dimethylamino)phenyl]-4-vinylphenylmethanenitrile (vinyl Malachite Green leuconitrile) with methyl methacrylate or ω-methoxyoligo(oxyethylene) methacrylate have been synthesized, aiming at designing one-component-type organic polymers for photoswitchable ion-conducting films. The triphenylmethanenitrile copolymers with ω-methoxyoligo(oxyethylene) methacrylate were found to undergo ionic-conductivity switching by turning on and off UV light at ambient temperature, owing to their low glass transition temperature. © 1993 John Wiley & Sons, Inc.     

Reactions of 1,2-dimethoxytetramethyldisilane with styrenes: Formation of a new type of silacyclopentanes having phenyl substituents on ring carbons

The reaction of 1,2-dimethoxytetramethyldisilane with styrene and α-methylstyrene in the presence of NaOMe catalyst in tetrahydrofuran (THF) gave the new silacyclopentanes 1,1-dimethyl-2,4-diphenyl-1-silacyclopentane (IIIa) and 1,1,2,4-tetramethyl-2,4-diphenyl-1-silacyclopentane (IIIb), respectively. These silacyclopentanes were found to exist as cis-trans mixtures. The use of sodium metal in place of NaOMe afforded similar results. Reactions of a polysilane mixture, MeO-(SiMe₂)_nOMe (n ≧ 3), with the styrenes also gave similar results. In some cases, polysilacycloalkanes such as 1,2,3-trisilacyclopentanes (IV) and 1,2,3,4-tetrasilacyclohexanes (V) were obtained as by-products. A mechanism for the formation of the silacyclopentanes and polysilacycloalkanes is presented. It was found that electron impact decomposition of silacyclopentanes IIIa and IIIb, trisilacycloalkane IV and tetrasilacycloalkane V gave molecular ions corresponding to the silacyclopropane, cyclotrisilane and cyclotetrasilane systems.     

Characterization of gem-difluoropropargyl synthons through HF loss from protonated molecules in methane chemical ionization mass spectra

Electron impact and methane chemical ionization mass spectra were obtained following gas chromatography/mass spectrometry for several gem-difluoropropargyl compounds, which had been synthesized as potential intermediates for synthesis of gem-difluoromethylene-containing C-3 acetylenes. EI spectra were variable with respect to the presentation of molecular ions, depending on substituent functional groups present. Methane-CI spectra were characterized by loss of 19 mass units from molecular weight with all compounds examined. These [M − 19]⁺ ions often presented as base peaks of the CI spectra, and were more reliably present and abundant than [M + 1]⁺ ions for these compounds. These ions could have been formed by elimination of HF from the protonated molecules under conditions of methane chemical ionization.