Simple and convenient synthesis of tertiary benzanilides using dichlorotriphenylphosphorane

Various tertiary benzanilide derivatives were effectively synthesized from substituted benzoic acid and N-monoalkylated aniline using dichlorotriphenylphosphorane in chloroform. Yields were generally high, even when an electron-withdrawing group substituted the aromatic ring of aniline, or when an electron-donating group substituted the aromatic ring of benzoic acid. Allyl, Boc, MPM and the Z group were unaffected under these conditions.     

The crystal and molecular structure of the β-cyclodextrin inclusion complex with aspirin and salicylic acid

The crystal structure of the -cyclodextrin (-CyD) molecular complex with aspirin (acetylsalicylic acid), salicylic acid, and water, (C₄₂H₇₀O₃₅)₂ (C₉H₈O₄)₂ (C₇H₆O₃) 23.3H₂O, was determined by X-ray structure analysis. The crystal data is space group Pl, a=19.777(5), b=15.247(3), c=15.475(4) Å, =102.63(2)°, =116.96(2)°, =104.12(2)°, V=3729(2) ų, D_m=1.409(2) g/cm³, D_X=1.419 g/cm³, and Z=1. The two -CyDs form a dimer unit with hydrogen bond networks among the secondary hydroxyl groups of both -CyDs. This -CyD dimer includes three guest molecules of two different types in its hydrophobic cavity. Two of them are aspirin, which are separately included in each cavity of the -CyD unit, with their hydrophobic benzene rings protruding into the hydrophobic cavities of the host -CyDs. The remaining guest molecule is the hydrolyzed product of an aspirin, that is salicylic acid, which is sandwiched in the space constructed by the -CyD dimer formation, and is statistically disordered at three sites.     

Miscibility and hydrogen-bonding interactions in biodegradable polymer blends of poly(3-hydroxybutyrate) and a partially hydrolyzed poly(vinyl alcohol)

Miscibility and hydrogen-bonding interactions, as well as the morphological properties, of biodegradable polymer blends of poly(3-hydroxybutyrate) (PHB) and a 80% hydrolyzed poly(vinyl alcohol) (PVA80) were studied using Fourier transform infrared spectroscopy (FTIR) and differential scanning calorimetry (DSC). It was found that PHB is miscible with PVA80 in the amorphous phase over the whole composition range. PVA80 or PHB assumes the amorphous state when its content in the blend is lower than 30 or 20 wt %, respectively. Due to the heavy overlapping of C=O stretching bands from both PVA80 and PHB and the nonmeasurable peak shift in the OH stretching band region, hydrogen-bonding interactions between the OH group of PVA80 and the C=O group of PHB were not detectable at room temperature, but were observed at a higher temperature of 180 degrees C. This is because hydrogen-bonding interactions are promoted above the melting points of these two crystalline polymers, by increasing the mixing entropy and reducing the Deltachi effect. Blending PHB with PVA80 does not have a significant effect on the OH groups of PVA80 that are hydrogen bonded with each other. Instead, the C=O groups of PHB dispossess some of the OH groups that are hydrogen bonded to the C=O groups of PVA80, which gives rise to the miscibility between PVA80 and PHB in the amorphous phase.     

Highly selective anti-markownikoff type oxidation of olefinic bonds of allylic alcohol derivatives. Specific synthesis of β-alkoxy α-phenylseleno carbonyl compounds

On treatment with diphenyl diselenide and benzeneseleninic anhydride, 3-$\text{t}$-butyldimethylsiloxy-1-alkenes were converted to the corresponding α-phenylseleno aldehydes exclusively.     

Synthesis of γ-zirconium phosphate by the fluoro-complex method and the intercalation behavior of some α-diimines

The ammonium form of -zirconium phosphate has been synthesized by the direct precipitation method from fluorozirconate solution in the presence of ammonium dihydrogen phosphate. The hydrogen form Zr(HPO₄)₂ · 2H₂O, was obtained by acid treatment of the ammonium form -Zirconium phosphate , Zr(HPO₄)₂ · H₂O, with a relatively large particle size resulted from fluorozirconate solution in the presence of concentrated orthophosphoric acid. The intercalation behavior of such -diimines as 2,2-bipyridine (bpy) and 1,10-phenanthroline (phen) toward -zirconium phosphate was investigated, and it was found that about 0.2 mol of bpy and 0.5 mol of phen have been incorporated respectively per one mol of the host, with the expansion of interlayer distances. Further incorporation of Cu(H) ions into the interlayer space of these intercalates was possible. The bpy intercalate took up more Cu(II) ions than -zirconium phosphate, indicating that effective pillars are constructed between layers and the ion exchange of Cu(II) ions is facilitated thereby.     

PHOTOOXYGENATION OF MAGNESIUM meso-TETRAPHENYLPORPHYRIN*

Abstract— On unsensitized photooxygenation magnesium meso -tetraphenylporphyrin underwent oxidative ring cleavage yielding a bilitriene derivative as the sole product. Kinetic studies by quenching technique using singlet-oxygen quenchers, ß-carotene and α-tocopherol, and by substrate direct disappearance technique (Foote and Ching) indicated that only singlet-oxygen process is involved in the photooxygenation, and that the rate of total consumption of singlet oxygen ( k _Q+ k _R) is 1.0 ± 0.4 times 10⁸ M ^-1s^-1.     

Stable, specific, and reversible base pairing via Schiff base

We here present a novel covalently linked base pair via Schiff base formation between 5-formyluracil (fU) and 5-aminocytosine (AmC). Formation of the Schiff base linkage proceeds reversibly and does not require any additives. The cross-linked DNA is very stable under denaturing conditions, whereas it completely dissociates upon heating at 90 degrees C. The pairing ability of AmC and fU is very specific and is applicable to the detection of fU, which is the major oxidative lesion of T in DNA. We propose the Schiff base linkage as a new artificial base pairing scheme to create functional DNAs.     

Moments of the spectra for rotational transitions induced by collisions or by external perturbations

Considered first is the cross sectiond σ(J′←J)/dω for the rotational transitionJ′←J of a linear rotator in collisions. The set of cross sections for a givenJ and for allJ′ defines a discrete spectral distribution as a function of the transition energy ΔE=E(J′)?E(J). In both the classical and the quantum mechanical sudden approximations the moments \(S(\mu ;J) = \sum\limits_{J'} {(\Delta {\rm E}} )^\mu d\sigma (J' \leftarrow J)/d\omega \) of ordersμ=2n andμ=2n+1 (n=0,1,...) are polynomials of degreen in the rotational energyE(J). The special cases forn=0 indicate thatS(0;J) andS(1;J) are independent ofJ. This is a theorem proved elsewhere. Explicit expressions forS(μ; J) of low orders are presented. They are derived on the assumption of equal relative velocitiesv andv′ before and after the collision. Correction onS(μ;J) for the difference betweenv andv′ is made to the lowest order in terms ofS(μ+1;J) forv=v′. The quantum mechanical results for linear rotators are extended to spherical-top and symmetric-top rotators. These results apply not only to the collision cross section but also to a physical quantity expressible in the form ¦〈Γ′¦F¦Γ〉¦² of a transition probability withany F that is independent of the initial and final rotational states ¦Γ〉 and ¦Γ′〉.     

Molecular chemistry in a zeolite: genesis of a zeolite Y-supported ruthenium complex catalyst

Dealuminated zeolite Y was used as a crystalline support for a mononuclear ruthenium complex synthesized from cis-Ru(acac)2(C2H4)2. Infrared (IR) and extended X-ray absorption fine structure spectra indicated that the surface species were mononuclear ruthenium complexes, Ru(acac)(C2H4)2(2+), tightly bonded to the surface by two Ru-O bonds at Al(3+) sites of the zeolite. The maximum loading of the anchored ruthenium complexes was one complex per two Al(3+) sites; at higher loadings, some of the cis-Ru(acac)2(C2H4)2 was physisorbed. In the presence of ethylene and H2, the surface-bound species entered into a catalytic cycle for ethylene dimerization and operated stably. IR data showed that at the start of the catalytic reaction, the acac ligand of the Ru(acac)(C2H4)2(2+) species was dissociated and captured by an Al(3+) site. Ethylene dimerization proceeded approximately 600 times faster with a cofeed of ethylene and H2 than without H2. These results provide evidence of the importance of the cooperation of the Al(3+) sites in the zeolite and the H2 in the feed for the genesis of the catalytically active species. The results presented here demonstrate the usefulness of dealuminated zeolite Y as a nearly uniform support that allows precise synthesis of supported catalysts and detailed elucidation of their structures.     

Effects of metal ion-carbonyl interaction on miscibility and crystallization kinetic of poly(3-hydroxybutyrate-co-3-hydroxyhexanoate)/lightly ionized PBS

Poly(butylene succinate) (PBS) and PBS-based ionomers (PBSi) with 1.0 and 3.0 mol% sodium sulfonate ionic group were synthesized and blended with poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) (PHB-HHx) via direct melt compounding. FT-IR analysis demonstrated that the sodium metal ion–carbonyl interaction between PHB-HHx and PBS ionomer increased in strength with the ionic group concentration. Both non-isothermal and isothermal analyses showed the crystallization rates of PHB-HHx to decrease as the strength of the sodium metal ion–carbonyl interaction increased. However, the constant value obtained for the Avrami exponent indicated that the presence of PBS ionomer did not interfere in any way with the nucleation mechanism or the geometry of the crystal growth of PHB-HHx. DMTA analysis confirmed that PBS ionomer reduced the crystallinity of PHB-HHx, and this phenomenon increased in proportion to the ionic group content. As the ionic group concentration increased, the sodium metal–carbonyl interaction between PHB-HHx and PBS ionomer became much stronger, resulting in the improvement of the miscibility for the blend. The interaction parameter obtained by analyzing the equilibrium melting temperature was negative for all bend systems, with the ionomer having ionic group content, displaying a more negative value. Based on the Lauritzen–Hoffman secondary nucleation theory, the regime of the PHB-HHx/PBS ionomer blend remained unchanged throughout the crystallization process. In addition, both the nucleation constant and surface free energy were found to decrease as both ionomer content and ionic group concentration increased.