bluuebunny/crossref_metadata_2025 huggingface dataset:
Untersuchungen von Diiodogermylen und Triphenylphosphindiiodogermylen und die Kristallstruktur von Triphenylphosphindiiodogermylen
Authors: Inoguchi Yoshio , Okui Shuko , Mochida Kunio , Itai Akiko
Published: July 2006

Reaktivitäten und chemische Eigenschaften von Diiodogermylen und Triphenylphosphindiiodogermylen wurden durch ihre Reaktionen mit Organolithium-Verbindungen oder Butadienen untersucht. Die Kristallstruktur von Triphenylphosphindiiodogermylen wurde röntgenographisch aufgeklärt.
The Wet Oxidation Treatment of Wastewater from SOx Removal Facilities
Authors: Yoshida Takatoshi , Ohta Hiroshi , Sugimoto Kimihiko , Banno Jiro , Hasegawa Kan-ichi
Published: July 2006

The wet oxidation of sodium dithionate was carried out at an elevated temperature between 100 and 300 °C. The decomposition of the dithionate solution proceeded rapidly at 150–170 °C and (approximately) a complete decomposition occurred at temperatures greater than 200 °C within 30 min. The removed percentage of the dithionate under a large excess of air was independent of the concentration. The addition of iron(II) sulfate and hydrogen peroxide accelerated the decomposition. Wet oxidation was effective for the disposal of wastewater containing dithionates.
Study of Short Hydrogen Bonds. I. Structures of 4-Methylpiperidinium Hydrogen Bis(p-methylbenzoate) and Piperidinium Hydrogen Bis(p-methylbenzoate)
Authors: Misaki Shintaro , Kashino Setsuo , Haisa Masao
Published: July 2006

The crystal structures of 4-methylpiperidinium hydrogen bis(p-methylbenzoate) 1 and piperidinium hydrogen bis(p-methylbenzoate) 2 have been determined by X-ray diffraction method. Crystal data: 1, monoclinic, P21⁄n (No. 14), a=19.260(2), b=8.0061(5), c=14.065(1) Å, β=94.391(7)°, V=2162.5(3) Å3, Z=4, Dx=1.141 g cm−3; 2, orthorhombic, Pcan (No. 60), a=10.292(1), b=25.248(4), c=7.763(2) Å, V=2017.2(5) Å3, Z=4, Dx=1.177 g cm−3. Final R values for 1 and 2 are 0.088 and 0.065 for 3446 and 1510 unique reflections, respectively. In both crystals the piperidinium cations and the hydrogen bis(benzoate) anions are held together by two kinds of N–H···O hydrogen bonds. The structure of 2 is disordered around a two-fold axis. Two benzoate residues in the anions are linked by the very short O–H···O hydrogen bonds; in 1 asymmetric [O···O 2.505(3), O–H 1.07(5), H···O 1.48(5) Å, O–H···O 158(5)°]; in 2 crystallographically symmetric [O···O related by the two-fold axis 2.473(4), O···H 1.25(5) Å, O···H···O 163(5)°]. The short hydrogen bonds in hydrogen bis(carboxylate) anions are discussed with reference to the crystal structures of 1 and 2.
A Calorimetric Study on the Formation of [CuCln](2−n)+ (n=1–4) in Acetonitrile–N,N-Dimethylformamide Mixtures
Authors: Ishiguro Shin-ichi , Jeliazkova Bojana G , Ohtaki Hitoshi
Published: July 2006

Complex formation equilibria between copper(II) and chloride ions have been studied by calorimetry in various acetonitrile(AN)–N,N-dimethylformamide(DMF) mixtures containing 0.2 mol dm−3 (C2H5)4NClO4 as a constant ionic medium at 25 °C. Calorimetric titration curves in each AN–DMF mixture examined were well explained in terms of formation of [CuCln](2−n)+ (n=1–4), and their formation constants, enthalpies, and entropies were determined. The overall enthalpy ΔHβ4° in any mixture, even in the acetonitrile-rich 0.025 mole fraction DMF mixture, was practically the same as that (19.2 kJ mol−1) in pure DMF, but largely different from that (−54.5 kJ mol−1) in pure AN. The result indicated that copper(II) ion was markedly preferentially solvated with DMF molecules in AN–DMF mixtures. On the other hand, the overall entropy value ΔSβ4° in any AN–DMF mixture was significantly larger than the values in both pure solvents. As to thermodynamic quantities of stepwise formation of [CuCln](2−n)+ (n=1–4), a remarkable change was found at the second step with varying solvent compositions. The stepwise enthalpy and entropy values of formation of [CuCl2] became more positive as the DMF content of the mixture decreased. Enthalpies of solution of anhydrous CuCl2 crystals were also measured in the same AN–DMF mixtures. The enthalpy ΔH\oversetos(CuCl2) of solution of the neutral [CuCl2] complex largely changed depending on the solvent composition, while ΔH\oversetos(Cu2+, 2Cl−), which is the sum of enthalpies of solution of relevant ions, remained practically unchanged. The result for the [CuCl2] complex indicated that the complex was not strongly preferentially solvated with DMF molecules in contrast to copper(II) ion in the AN–DMF mixtures.
Polymer-Protected Metal Complex for Gas Separation. I. A Solution of Polystyrene-Protected Aluminium Copper(I) Halide as Water-Resistant Carbon Monoxide Absorbent
Authors: Hirai Hidefumi , Hara Susumu , Komiyama Makoto
Published: July 2006

Carbon monoxide absorbents composed of linear polystyrene (PSt), aluminium halide, copper(I) halide, and toluene are prepared. The toluene solutions of polystyrene–protected aluminium copper(I) chloride (PSt–AlCuCl4) rapidly absorb CO at 20 °C under 1 atm (initial partial pressure of CO: 0.90 atm) and the equilibrium molar ratio of absorbed CO to the charged CuCl is 0.78. On the elevation of the temperature from 20 °C to 82 °C under 1 atm, the absorbed CO is released completely. The absorption-release cycles are repeated many times without measurable decrease in the absorbing capacity. The CO absorbing capacities of toluene solutions composed of aluminium halides, copper(I) halides, and polystyrene decrease as follows: AlCl3–CuCl system>AlBr3–CuBr system>>All3–CuI system=0. The CO absorbing activity of the toluene solution of PSt–AlCuCl4 remains virtually unchanged on the contact of the solution with nitrogen gas containing 10 mol% water to the charged CuCl (water content: 9000 ppm), when the molar ratio of phenyl residue of polystyrene (number-averaged degree of polymerization: 420, 50, or 4.0) to AlCuCl4 is unity or larger. This result is markedly in contrast with the fact that the activity of the toluene solution of AlCuCl4 without polystyrene significantly (25%) decreases on the contact.
Preparation and Spectral Properties of Cobalt(III) Complexes with S,S′-Ethylenebis(l-homocysteinate) and S,S′-Trimethylenebis(l-homocysteinate)
Authors: Kanesaka Mikako , Okamoto Ken-ichi , Hidaka Jinsai
Published: July 2006

Three cobalt(III) complexes of [Co(sexidentate-N2,S2,O2)] and [Co(terdentate-N,S,O)2] types were prepared; where sexidentate-N2,S2,O2 denotes S,S′-ethylenebis(l-homocysteinate) (l,l-ebhc) and S,S′-trimethylenebis(l-homocysteinate) (l,l-tbhc), and terdentate-N,S,O denotes l-ethioninate (l-eth). Each of the l,l-ebhc and l,l-tbhc complexes was chromatographically separated into two isomers, trans(O) and trans(N), and the l-eth complex was separated into three isomers, trans(O), trans(N), and trans(S). These isomers were characterized by their electronic absorption, CD, and 13CNMR spectra. The stereoselectivity in the formation of each geometrical isomer for the l,l-ebhc and l,l-tbhc complexes is discussed in relation to the flexibilities of the S,S-bridged backbone chelate ring and the l-homocysteinate moiety.
1,1′-Bis(thiocyanatomercurio)ferrocene as Ligand towards M(NCS)2[M=Mn(II), Co(II), Ni(II), Cu(II), Zn(II)]
Authors: Singh Pashupati Prasad , Singh Meena
Published: July 2006

Complexes having three different metal atoms have been prepared by reacting 1,1′-bis(thiocyanatomercurio)ferrocene with M(NCS)2 [M=Mn(II), Co(II), Ni(II), Cu(II), Zn(II)]. The complexes have been referred to as Lewis acid and have molecular formula Fe(C5H4HgSCN)2M(NCS)2. They have unsaturation at M, hence have been reacted with nicotinamide and 2,2′-bipyridyl and adducts of molecular formula Fe(C5H4HgSCN)2M(NCS)2Lx [x=2 when nicotinamide and 1 when bipyridyl] have been isolated. The Lewis acids and the adducts have been characterized by elemental analysis, molar conductance, magnetic moment, infrared and electronic spectral studies. These studies reveal that the coordination geometry of M is tetrahedral in the Lewis acids of cobalt, zinc, and manganese. The geometry around M in the Lewis acids of nickel and copper is octahedral through axial bonding. The adducts have a bridged structure and the geometry around M is octahedral. Quantitative softness parameters have also been applied to derive certain information.
Novel Synthesis of Furo[2,3-b]indole Derivatives
Authors: Abd El-Latif Fathy Faheem , Gohar Abd El-Kareem Mohammed Nasr , Fahmy Atiat Mohammed , Badr Mahmoud Zarif Amin
Published: July 2006

Isatin reacted with diethyl 3-amino-2-cyano-2-pentenedioate in ethanol and in presence of Et3N to give 3-(1-amino-2-cyano-2-ethoxycarbonylethenyl-2H-furo[2,3-b]indol-2-one. The reaction of (2-oxo-3-indolinylidene)malononitrile (3a) with the diethyl ester gave a mixture of diethyl 3-amino-4-(2-amino-3-cyano-4-quinolylcarbonyl)-2-cyano-2-pentenedioate (80%) and diethyl 3-amino-4-(2-amino-3-cyano-3aH-furo[2,3-b]indol-3a-yl)-2-cyano-2-pentanedioate (20%). Treatment of 3a and 3-[cyano(ethoxycarbonyl)]methylene-2-indolinone (3b) with 2-(ethoxycarbonylmethyl)-2-thiazolin-4-one gave the corresponding two pyrano[4′,5′-c] and furo[2″,3″-b]indole compounds, respectively. When 3a and 3b also reacted, with 3-methyl-2-pyrazolin-5-one or 3-methyl-1-phenyl-2-pyrazolin-5-one, the corresponding four spiro indoline-3,4′-(1′H)-pyrano[2,3-c]pyrazol products were obtained. The reaction of 3b with benzoylacetonitrile gave ethyl 2-amino-3a-[benzoyl(cyano)methyl]-3aH-furo[2,3-b]indole-3-carboxylate.
Reaction of Azomethine N-Oxides. III. Reactions of Some Azomethine N-Oxides with Fluoranil, Phenyl Vinyl Sulfone, and β-Nitrostyrene
Authors: Nour El-Din Ahmed Moukhtar
Published: July 2006

Isomerization of 3H-indole 1-oxides in the presence of tetrafluoro-2,5-cyclohexadiene-1,4-dione (fluoranil) to the thermodynamically more stable lactams was found to proceed via formation of charge-transfer complexes. However, addition of fluoranil to some open chain nitrones did not give the corresponding amides. Both electron-deficient β-nitrostyrene and phenyl vinyl sulfone did not form charge-transfer complexes with nitrones, but instead they undergo 1,3-dipolar cycloaddition giving 4- or 5-substituted isoxazolidines.
The Differential Scanning Calorimetry of 1,3,5,7,2,4,6,8-Tetrathiatetrazocine
Authors: Kudo Yoshiyuki , Hamada Shuichi
Published: July 2006

The molar heat of the decomposition of S4(NH)4 was obtained as 360±7 kJ mol−1 by means of differential scanning calorimetry. This value gave the standard enthalpy of the formation, ΔHf(S4(NH)4, s, 298.15 K), as 318±7 kJ mol−1, which was comparable with that calculated (311 kJ mol−1).
Pseudo-Sugars. XV. A Facile Synthesis of Pseudo-β-Dl-fructopyranose
Authors: Suami Tetsuo , Ogawa Seiichiro , Uematsu Yasushi , Suga Atsuo
Published: July 2006

Pseudo-β-Dl-fructopyranose, Dl-(1,2/3,4)-1-C-hydroxymethyl-1,2,3,4-cyclohexanetetrol, has been synthesized from Dl-1,2-di-O-acetyl-(1,3/2)-3-bromomethyl-5-cyclohexene-1,2-diol by the seven-steps sequence in 21% overall yield.
Synthesis and Absolute Configuration of an Optically Active Bisnoradamantane Derivative, (−)-6-Oxotricyclo[3.3.0.03,7]octane-2-carboxylic Acid
Authors: Naemura Koichiro , Komatsu Masanori , Chikamatsu Hiroaki
Published: July 2006

6-Isopropylidenetricyclo[3.3.0.03,7]octane-2-carboxylic acid (11) was prepared from the dimethylfulvene–ethyl acrylate adduct 5. Optical resolution of 11 was carried out via the (+)-1-(2-naphthyl)ethylamine salt, and (−)-11 was transformed into (−)-6-oxotricyclo[3.3.0.03,7]octane-2-carboxylic acid (14) whose absolute configuration and absolute rotation were established.
Mössbauer Study of Tin in γ-AgI
Authors: Hiraga Kazuhiro , Ichiba Sumio
Published: July 2006

Tin was deposited onto the surface of powdered γ-AgI and introduced into the matrix by solid-state diffusion at 300°C. The 119Sn Mössbauer spectra show that the deposit before heat treatment was epitaxially grown α-Sn and that the diffused tin was in the state of valency 4, occupying both the octahedral and tetrahedral interstices.
Hydrogenation and Dimerization of Bicyclo[2.2.1]hepta-2,5-diene Catalyzed by Cobalt(I) Complexes
Authors: Kanai Hiroyoshi , Watabe Yoshiyuki , Nakayama Taisei
Published: July 2006

Bicyclo[2.2.1]hepta-2,5-diene 1 was hydrogenated to bicyclo[2.2.1]hept-2-ene 2 and tricyclo[2.2.1.02,6]heptane 3 in a 70:30 ratio and dimerized to Binor-S 4 by [CoX(PPh3)3]–BF3·Et2O catalysts (X=halogen). 1 was dimerized to 4–7 having tricyclo[2.2.1.02,6]heptane skeletons by a [Co(SCN)(PPh3)3]–ZnBr2–Zn system in THF.
In Situ Trapping of NO. A Generalized Method for the Synthesis of Metal Nitrosyls
Authors: Khan Mohammad Ishaque , Agarwala Umesh Chandra
Published: July 2006

Several known nitrosyl complexes of Ru, Rh, Ir, Os, Co, and Mo have been synthesized using a more generalized method, using organic N-nitroso compounds. Physical methods such as IR, magnetic measurements, conductance measurements, melting points, and elemental analyses were used for the identification of the products of the reactions.
4-Azidobutyryl Group for Temporary Protection of Hydroxyl Functions
Authors: Kusumoto Shoichi , Sakai Keiichiro , Shiba Tetsuo
Published: July 2006

4-Azidobutyryl esters formed from hydroxyl compounds and 4-azidobutyryl chloride were shown to be cleaved via reduction to 4-aminobutyrate followed by intramolecular O→N-acyl migrations to regenerate the free hydroxyl groups. High susceptibility of azide group to reduction enables the selective removal of this acyl group leaving many other functional groups unchanged.
Prediction of IR Intensities of Bending Fundamentals in 2,4-Pentadiynenitrile by the Combination of ab Initio Calculation and Experimental Parameters
Authors: Uyemura Masakatsu
Published: July 2006

2,4-Pentadiynenitrile is a H(C≡C)nC≡N-type molecule. Molecules with n=0 to n=5 are known as interstellar molecules. Infrared spectra have not been observed yet, because the synthesis of a molecule of this type becomes more difficult as the molecular size increases. In the present study, the frequencies and infrared intensities of bending fundamentals in 2,4-pentadiynenitrile were predicted from an ab initio calculation coupled with empirical corrections. Calculation errors have been estimated by comparing calculated and experimental values in small reference molecules which have local structures similar to those of 2,4-pentadiynenitrile. The errors in 2,4-pentadiynenitrile have also been estimated.
Ylide–Metal Complexes. X. An X-Ray Photoelectron Spectroscopic Study of Triphenylmethylenephosphorane and Gold- and Copper–Phosphorane Complexes
Authors: Yamamoto Yoshihisa , Konno Hidetaka
Published: July 2006

Triphenylmethylenephosphorane, the bis(triphenylmethylenephosphorane)gold chloride and the corresponding copper chloride have been studied by X-ray photoelectron spectroscopy. For the phosphorane, the binding energies, EB, for P 2s and P 2p peaks were observed at 190.1 and 132.6 eV, respectively. The EB value for the P 2p peak agrees with that (132.6 eV) for the phosphonium ion in triphenylmethylphosphonium bromide. The C 1s spectrum was separated into two peaks at EB=285.0 and 283.9 eV, assuming a ratio of 18:1. The peak at 285.0 eV corresponds to the phenyl carbons, and that at 283.9 eV can be assigned to the electronrich methylene carbon. Thus, the structure of the phosphorane is considered to be an ylide formula, (Remark: Graphics omitted.). In gold phosphorane complexes, EB of the C 1s, P 2s, and P 2p peaks were close to those for the phosphorane. The EB of the Cl 2p3⁄2, Au 4f7⁄2, and Au 4f5⁄2 peaks coincided with those for bis(triphenylphosphine)gold chloride. These results indicate the structure of the gold complex to be (Remark: Graphics omitted.). The XPS results also indicate that the structure of the copper complex is similar to that of the gold complex.
Thermal Stability of Electroless Nickel–Molybdenum–Phosphorus Alloy Films
Authors: Koiwa Ichiro , Nishikawa Masao , Yamada Keizo , Osaka Tetsuya
Published: July 2006

The structure and the electric resistivity of electroless Ni–Mo–P alloy films, which were plated from a caustic alkali citrate-glycolic acid bath, have been investigated. The phosphorus content in deposits and the deposition rate decreased with increasing Mo-complex concentration which was formed with sodium gluconate before constructing the bath. The crystallized structure and the formation of solid solutions between the Ni matrix and the codeposited Mo were indicated by X-ray diffraction measurments for high Mo-complex concentration range. On the other hand, amorphous states appeared for the Mo-complex concentration range lower than 0.002 mol dm−3. In the range less than 0.002 mol dm−3 Mo-complex concentration, the resistivity of as-plated Ni–Mo–P films was higher than the binary Ni–P alloy film plated from the bath without the Mo-complex. In the higher Mo-complex concentration range, the resistivity immediately reached a constant value independently of the Mo-complex concentration. After 500 and 800 °C heat treatment under vacuum, the resistivity increased with increasing Mo-complex concentration. Moreover for the higher Mo-complex concentration range, the resistivity after heat treatment became higher than that of as-plated conditions, and the increased resistivity after the heat treatment depended on the Mo content in the deposits. Therefore, the codeposited Mo tended to increase the thermal stability of the films.
Proton-Catalyzed Formation of Methyl Carbamate in the Reaction of Isocyanic Acid in Methanol
Authors: Yashiro Hitoshi , Takeshita Jun-ichi , Okuwaki Akitsugu , Okabe Taijiro
Published: July 2006

The rate of formation of methyl carbamate has been measured by a determination of the HNCO concentration. It can be expressed as follows: rc=kc[HNCO][H+]. This rate equation was confirmed in the concentration range of HCl(0.76–1.53×10−3 mol dm−3). Consequently, this reaction was subjected to a proton catalysis. However, at a H+ concentration lower than 4×10−4 mol dm−3, the observed rate was lower than that calculated by the rate equation, especially at a high HNCO concentration. This was explained by a reduction of the free HNCO concentration due to an association of HNCO with the formed carbamate.
Synthesis of β(1–4)-Linked Disaccharides of N-Acetylglucosamine and N-Acetylmuramic Acid by Their Direct Condensation
Authors: Kusumoto Shoichi , Imoto Masahiro , Ogiku Tsuyoshi , Shiba Tetsuo
Published: July 2006

As a basic study in the synthetic approach to immunoactive cell wall peptidoglycan whose backbone is a β(1–4)-linked saccharide of alternating glucosamine and muramic acid, methods for the direct condensation of these sugar components were studied and O-(N-acetyl-β-muramyl)-(1→4)-N-acetyl-d-glucosamine and O-(N-acetyl-β-d-glucosaminyl)-(1→4)-N-acetylmuramic acid were synthesized. In the synthesis of the latter disaccharide, previous formation of an ester bond between the carboxyl group of muramic acid and the 6-hydroxyl group of glucosamine proved to facilitate the glycoside bond fromation between these sugar moieties.
Studies of Liquid Water by Computer Simulations. IV. Transport Properties of a 2-D Model
Authors: Kataoka Yosuke
Published: July 2006

The constant-temperature constant-pressure molecular dynamics simulations of a water-like system are performed at many temperatures and pressures. A 2-dimensional model of water is used for the system with 576 molecules in a square cell. Thermodynamical quantities are anomalous as in liquid water. The temperature-dependences of the calculated self-diffusion coefficient and the shear viscosity are in agreement with the observed values at low pressures. The effects of compression on these transport coefficients are reproduced qualitatively. The bulk viscosity obtained is larger than the shear viscosity. The order of magnitude of the calculated thermal conductivity is in agreement with the experimental results. The contribution of the rotational motion to the thermal conductivity is calculated in order to discuss the anomalous temperature-dependence of this coefficient.
Formation of New Paramagnetic Complexes between Quinones and Their Semiquinone Anions in the Presence of a Cryptand or a Crown Ether
Authors: Suga Kosaku , Takiguchi Tsuyoshi , Aoyagui Shigeru
Published: July 2006

The formation of new paramagnetic complexes is evidenced by the ESR spectra of anion radicals of duroquinone, p-benzoquinone, and 2,5-di-t-butyl-p-benzoquinone in tetrahydrofuran, which are recorded in the presence of their parent molecules and cryptand 222 or 18-crown-6. The numerical values for the equilibrium constant, standard enthalpy and standard entropy of the complex formation are also determined.
Phase Transition of Quaternary Alkyl Halide Salts of 1,4-Diazabicyclo[2.2.2]octane
Authors: Shimizu Jun , Imamura Kengo , Nogami Takashi , Mikawa Hiroshi
Published: July 2006

A series of quaternary alkyl halide salts of 1,4-diazabicyclo[2.2.2]octane (DABCO) exhibited first-order phase transitions in the temperature range of 62–100 °C Abrupt changes of halide anion conductivities were observed by two to three orders of magnitude at the transition temperatures. The transition temperature and the heat of transition tend to increase with the increase of the alkyl chain length. The temperature dependence of an IR spectrum showed that the band progressions due to long alkyl chain disappeared above the phase transition. This fact suggests that the trans-zigzag conformation of alkyl chains in the low temperature phase is destroyed by the internal rotation of the alkyl chain above the transition temperature.
Effect of Electrochemical Pretreatment on Catalytic Activity of Bismuth Ruthenate Electrodes for Oxygen Evolution in Alkaline Solution
Authors: Iwakura Chiaki , Edamoto Toshiyuki , Tamura Hideo
Published: July 2006

The catalytic activity of a film-type bismuth ruthenate electrode for oxygen evolution was greatly enhanced by the electrochemical pretreatment, including potential holding and cycling. On the other hand, any appreciable enhancement in catalytic activity was not observed for a pellet-type bismuth ruthenate electrode. Such an pretreatment effect was explained on the basis of the participation of higher valence Ru species in the oxygen evolution reaction, rather than the increase of surface area.
Synthesis and Properties of Oxo Complex of Ruthenium(IV), trans-[RuCl(O)(py)4]+, which is Formed by the Oxidation of Nitrosyl Complex of Ruthenium(II), trans-[RuCl(NO)(py)4]2+
Authors: Aoyagi Kimitake , Yukawa Yasuhiko , Shimizu Kunio , Mukaida Masao , Takeuchi Toshio , Kakihana Hidetake
Published: July 2006

Oxidation of trans-[RuCl(NO)(py)4]2+ with NaClO gives oxo complex of RuIV, trans-[RuCl(O)(py)4]+, with bond breaking of the metal-nitrosyl ligand. An X-ray structural study revealed that the complex has a much longer Ru–O bond distance (1.862(8) Å) than those of known mono-oxo complexes. A facile reactivity of the oxoruthenium(IV) complex was observed: with methanol methoxo complex, trans-[RuCl(OMe)(py)4]+, was formed. With PPh3, a two-electron transfer process was indicated by the formation of Ph3PO.
Preparation of Alkyl Dihydrogenphosphates with Monomeric Metaphosphate Anion Generated by Photochemical C–P Bond Cleavage of p-Nitrobenzylphosphonic Acid
Authors: Iwamoto Narimasa , Okamoto Yoshiki , Takamuku Setsuo
Published: July 2006

Alkyl dihydrogenphosphates were prepared by a procedure that probably involves a monomeric metaphosphate anion as an intermediate. The monomeric metaphosphate anions used in this reaction were generated by a photochemical C–P bond cleavage of the p-nitrobenzylphosphonate dianion. The photolysis of a 1:2 molar mixture of p-nitrobenzylphosphonic acid and 1,8-diazabicyclo[5.4.0]undec-7-ene (or 2,2,6,6-tetramethylpiperidine) in excess alcohol gave alkyl dihydrogenphosphate in fairly good yield.
Kinetic Studies of Fast Equilibrium by Means of High-Performance Liquid Chromatography. XIV. Separation of Rotamers of Phenyl Methylcarbamates and Their Rotational Energy Barriers
Authors: Moriyasu Masataka , Yamagami Chisako , Kato Atsushi , Hashimoto Yohei , Takao Narao
Published: July 2006

High-performance liquid chromatography(HPLC) of six phenyl methylcarbamates at low column temperatures on normal phase chromatography using hydroxyl-group chemically-bonded silica gel packing achieved the separation of rotamers. The population ratios of rotamers were determined for different conditions such as solvent composition and concentration. The rotational-energy barriers to intramolecularbond rotation about the carbonyl–nitrogen bonds were determined for four p-substituted phenyl methylcarbamates, and it was found that the energy barriers were higher when electron-withdrawing groups were substituted.
Bulk Copolymerization of Acrylonitrile with Allyl Chloride and Thermal Analysis of the Products
Authors: Okamoto Masao , Suenaga Kiyoshi , Ishizuka Osamu
Published: July 2006

The bulk copolymerization of acrylonitrile (M1) with allyl chloride (M2), carried out at 40 °C, was initiated by 0.05 mol% of α,α′-azobisisobutyronitrile under nitrogen. The compositions of six copolymers were in the range of allyl chloride units, 0.63–6.32 mol%. The monomer reactivity ratios r1 and r2 were calculated to be 6.04 and 0.035, respectively. Only three copolymers were soluble in N,N-dimethylformamide and their intrinsic viscosities were found to be greater than 4.5 dL g−1. The chlorine contents, although 0.42, 0.87, and 1.03 wt%, were sufficiently effective to cause a change in the behavior of the thermal degradation of polyacrylonitrile (PAN). In DTA curves measured at a rate of 5 °C min−1 under nitrogen for copolymers containing ca. 1 wt% of chlorine, a sharp exotherm due to the polymerization of cyano groups shifted to the higher-temperature side (ca. 40 °C) and the differential temperature decreased to about 1/6. Moreover, the weight loss at 350 °C decreased from 19 wt% for PAN to 13 wt%. A similar thermal-degradation behavior was also observed for acrylonitrile–α-chloroacrylonitrile (CAN) copolymers. However, there was a great difference between allyl chloride and CAN units concerning the effect on the thermal degradation of PAN. Namely, only 1.5 mol% of allyl chloride units corresponded to 10 mol% of CAN units.
Viscosity B-Coefficients of 1:1 Electrolytes in Acetonitrile–Water Mixtures at 25 and 35 °C
Authors: Kumar Gopu , Dey Nibaran C , Saikia Birendra K , Haque Inamul
Published: July 2006

Viscosity B-coefficients of the Jones–Dole equation were determined for KCl, KBr, KI, NaBr, CsI, Me4NBr, Et4NBr, n-Pr4NI, n-Bu4NBr, and Na[BPh4] at 25 and 35 °C in various acetonitrile–H2O mixtures. The B-coefficients were split into the ionic components and a comparison was made among different methods available. The effective flow volume, Ve° obtained from B=2.5 Ve° was compared with the crystal ionic volume, Vcryst° and the ionic partial molar volume, \barVion° determined from the density experiments simultaneously carried out. Ion-solvent and solvent-solvent interactions were discussed in terms of the above parameters.
A Synthesis of Methyl 3-O-(β-d-Mannopyranosyl)-α-d-mannopyranoside from Sulfonate Intermediates
Authors: Awad Laila Fathy , El Ashry El Sayed H , Schuerch Conrad
Published: July 2006

Methyl 3-O-(β-d-mannopyranosyl)-α-d-mannopyranoside was synthesized by the reaction of 3,4,6-tri-O-benzyl-2-O-benzylsulfonyl-1-O-tresyl-d-mannopyranose with methyl 2,4,6-tri-O-benzyl- and 2,4,6-tri-O-(p-bromobenzyl)-α-d-mannopyranoside, followed by deprotection. The corresponding 1-O-(β-tolylsulfonyl)derivative gave better yield and stereoselectivity in the reaction with methanol, but was not sufficiently reactive to couple with a hindered secondary alcohol. The 2-O-benzylsulfonyl group is comparable in β-directing effect to 2-O-methylsulfonyl group, but its stereoselectivity is dependent on the structure of the reactant alcohol. It can be selectively removed by the reaction with sodium amide in N,N-dimethylformamide.
Synthesis and Characterization of Imidazolate-Bridged Binuclear Copper(II) Complexes
Authors: Matsumoto Naohide , Murakami Hiroyuki , Akui Toshifumi , Honbo Jukichi , Okawa Hisashi , Ohyoshi Akira
Published: July 2006

An unsymmetrical quadridentate copper(II) complex containing an imidazole moiety ([CuHL](ClO4)) reacts with [1,4,7,10-tetraazacyclododecane]copper(II) perchlorate and [2-[2-(2-pyridyl)ethyliminomethyl]pyridine]copper(II) perchlorate in the presence of one equivalent of triethylamine to give two discrete imidazolate-bridged binuclear copper(II) complexes, 1 and 2 respectively, where [H2L] denotes the 1:1:1 condensation product of acetylacetone, ethylenediamine, and 4-formylimidazole. The analysis of the cryomagnetic data(ca. 80–300 K) on the basis of the Heisenberg model of a binuclear structure gave the antiferromagnetic interaction parameter(2J) of −107.7 cm−1 for 2.
Out-of-Plane Vibrations of [1H5]- and [2H5]Pyridines
Authors: Ozono Yoshimi , Maehara Masayoshi , Nibu Yoshinori , Shimada Hiroko , Shimada Ryoichi
Published: July 2006

Assignments of the out-of-plane normal vibrations of [1H5]- and [2H5]pyridines were reexamined based on the polarization behavior of the Raman bands and also through the normal coordinate calculation.
Formation of Bis(2-oxazolidinone) Derivatives by Reactions of 2-Methoxy-3,3-dimethyl-2-phenyloxirane or α-Bromoisobutyrophenone with Carbon Dioxide and Aliphatic α,ω-Diamines
Authors: Saito Norio , Hatakeda Kiyotaka , Ito Shota , Asano Takashi , Toda Takashi
Published: July 2006

Reactions of 2-methoxy-3,3-dimethyl-2-phenyloxirane or α-bromoisobutyrophenone and carbon dioxide in the presence of aliphatic α,ω-diamines were investigated. 1,4-Butanediamine, 1,6-hexanediamine, 1,8-octanediamine, and 1,4-bis(aminomethyl)benzene afforded corresponding 3-(ω-aminoalkyl)-4-hydroxy-5,5-dimethyl-4-phenyl-2-oxazolidinones and 3,3′-polymethylenebis[4-hydroxy-5,5-dimethyl-4-phenyl-2-oxazolidinones] derivatives, while ethylenediamine gave only mono(2-oxazolidinone) derivative.
Kinetic and Equilibrium Studies of Complex Formation of Nickel(II) with Carboxylate Ligands at High Pressure. IV. Nickel(II) Malate and Nickel(II) Tartrate
Authors: Inoue Tohru , Kojima Kiyotaka , Shimozawa Ryosuke
Published: July 2006

Kinetic and equilibrium measurements were carried out for the complexation reaction of nickel(II) malate and nickel(II) tartrate in an aqueous solution at 20 °C and at pressures up to 100 MPa. From the pressure dependence of the stability constant and the rate constant, the reaction volume, ΔV0, and the activation volume, ΔVf*, for the complex formation were estimated as follows: ΔV0=17.8±0.6 cm3 mol−1 and ΔVf*=13.8±0.6 cm3 mol−1 for nickel(II) malate, and ΔV0=17.8±0.5 cm3 mol−1 and ΔVf*=13.7±1.2 cm3 mol−1 for nickel(II) tartrate. Comparing the ΔV0 values with those obtained for other carboxylate ligands, it was inferred that both malate and tartrate ions form a six-membered chelate complex coordinated by carboxyl and hydroxyl oxygens. The rate-determining step of the overall complexation reaction was assigned to the first bond formation process based on the ΔVf* value with the correction for the volume change associated with the outer-sphere complex formation.
Studies of the Hydrous Tin(IV) Oxide Ion Exchanger. V. The Sodium Isotopic Exchange Rate between the Exchanger in the Na+ Form and Aqueous Solutions
Authors: Inoue Yasushi , Yamazaki Hiromichi , Osawa Akira
Published: July 2006

The sodium isotopic exchange rate between the hydrous tin(IV) oxide ion exchanger in the Na+ form and aqueous solutions was determined radiochemically. When the dried exchanger was used, the rate of the first step was controlled by the rate of the equilibration of water in the exchanger with the solutions, while the second step was found to be controlled by the diffusion of sodium ions in the particles (particle diffusion). When the exchanger had been sufficiently immersed in solutions in advance, the particle diffusion controlled the rate from the beginning. From the dependency of the rate of particle diffusion on the apparent particle size and the specific surface area of the exchanger, and on the sodium-ion concentrations in the solutions, the process controlling the rate is considered to be the diffusion in the primary particles, which are formed at the initial stage of precipitation and which aggregate to form the hydrous tin(IV) oxide gel. The diffusion constants and their activation energy (35±2 KJ mol−1) were also evaluated.
Solvation of Anions in Water–Acetonitrile Mixtures
Authors: Miyaji Kiyoshi , Morinaga Kenichi
Published: July 2006

The enthalpies of transfer from water to mixtures with acetonitrile(ΔHt°) for various anions reach maxima at a mole fraction of acetonitrile(xAN)ca. 0.3, and decrease linearly and in parallel in the intermediate region. A linear relation is found between ΔHt° at xAN 0.3 and the hydration enthalpies for halide and symmetrical ions. This finding and the parallel xAN dependence of ΔHt° in the intermediate region are interpreted on the basis of the linear relation between the solvation enthalpies and the entropies for the halide ions. The reduction in the hydrogen-bonding interaction extending beyond the primary hydration sphere(ΔHINT) for halide ions in the mixtures is estimated based on a modified Eley and Evans hydration model. At xAN 0 to ca. 0.3, ΔHINT compared with that in water agree well with the observed ΔHt°, indicating that the increase in ΔHt° is due to the reduction in the outer hydration sphere interaction. However, they split’gradually at xAN above 0.3. The adequacy of the modifications in the treatment of the solvation enthalpy cycle in the mixtures is re-evaluated from the structural viewpoint. The exothermic change in the intermediate region may be attributable to the reduction in the cavity formation energy.
Kinetic and Mechanistic Investigations of the Reduction by Radicals of Nitro to Hydroxyamino Groups in a Cobalt(III) Cage Compound
Authors: Tsukahara Keiichi
Published: July 2006

A compound containing both a hydroxyamino and a nitro group in a cobalt(III) cage complex was detected and isolated in a DQ\underset.+(1,1′-ethylene-2,2′-bipyridinium radical cation) reduction of the corresponding symmetric dinitro compound, [Co(diNOsar)]3+ (diNOsar=1,8-dinitro-3,6,10,13,16,19-hexaazabicyclo[6.6.6]icosane). The nitro group of this compound was reduced to the hydroxyamino group by SO2−, MDQ\underset.+(1,1′-ethylene-4,4′-dimethyl-2,2′-bipyridinium radical cation), and PDQ\underset.+(1,1′-trimethylene-2,2′-bipyridinium radical cation). Rate constants for the various processes were obtained.
Syntheses and Properties of Hepta- and Dibenzopentafulvalene Derivatives Containing 13-, 15-, 17-, and 19-Membered Rings
Authors: Asao Toyonobu , Morita Noboru , Ojima J\={u}ro , Fujiyoshi Masamitsu , Wada Kazuyo , Hamai Satoru
Published: July 2006

5,10-Dimethy 1-6,8-bisdehydroheptatridecafulvalene 10, 10-methy 1-6,8-bisdehydro-4,5-benzoheptatridecafulvalene 11, 6,8-bisdehydro-4,5:10,11-dibenzoheptatridecafulvalene 12, 5,10-dimethyl-6,8-bisdehydroheptapentadecafulvalene 13, 5,10,15-trimethylheptapentadecafulvalene 14, 7,12-dimethylheptaheptadecafulvalene 15, and 7,12-dimethylheptanonadecafulvalene 16 were synthesized by a reaction of 8-oxoheptafulvene 8 with the corresponding bisdehydroannulenones 1–7. Dibenzo derivatives of 5,10-dimethyl-6,8-bisdehydropentatridecafulvalene 23, 10-methyl-6,8-bisdehydro-4,5-benzopentatridecafulvalene 24, 6,8-bisdehydro-4,5:10,11-dibenzopentatridecafulvalene 25, 5,10-dimethylpentapentadecafulvalene 26, 5,10,15-trimethylpentapentadecafulvalene 27, 7,12-dimethylpentaheptadecafulvalene 28, and 7,12-dimethylpentanonadecafulvalene 29 were also synthesized by the reaction of 9-fluorenylidenemethanone 21 with the corresponding annulenones 1–7. Furthermore, a benzoannelated series of heptapentadecafulvalenes 30–35 was also synthesized. The 1H NMR spectra of these hepta- and dibenzopentafulvalenes are discussed in connection with their tropicity. It can be concluded that a slight polarization of π-electrons through pinch bonds from the seven-membered rings to the many-membered rings in the heptafulvalene system and from the many-membered rings to the five-membered rings in the pentafulvalene system exist regardless of the size of the many-membered rings.
Direct Diacetylmethylation of Aromatic Compounds with Tris(2,4-pentanedionato)manganese(III)
Authors: Nishino Hiroshi
Published: July 2006

The oxidation of naphthalenes with tris(2,4-pentanedionato)manganese(III) in acetic acid gave diacetylmethyl derivatives in good to moderate yields. Using excess amounts of the oxidant, the acetylmethyl-substituted naphthalenes were further oxidized and 3-acetoxy-3-naphthyl-2,4-pentanediones were obtained. The similar oxidation of anthracenes also produced (diacetylmethyl)anthracenes together with diacetylmethylene derivatives which were further oxidized. It was found that this direct diacetylmethylation was effective when the ionization potential of the aromatic compound was lower than 8.12 eV, and that the diacetylmethyl radical which was generated directly by the thermolysis of tris(2,4-pentanedionato)manganese(III) has an electrophilic nature based on the result of the oxidation of substituted naphthalenes. The reaction pathway for the oxidation of anthracene is also discussed.
Zeolite-Promoted Benzylation of Alcohols
Authors: Onaka Makoto , Kawai Motomitsu , Izumi Yusuke
Published: July 2006

Zeolite-promoted benzylation of alcohols with benzyl chloride has been investigated. By use of a series of cation-exchanged zeolites, which have the same crystalline structure but different acid and base properties, it is confirmed that the cooperative function of acid sites and base sites of zeolite is required for the effective benzylation of alcohols although both acid and base strengths are low. It is also found that alcohols show different reactivities in zeolite from those in solution depending on their molecular structures because the benzylation is promoted inside the narrow cavities of zeolite.
Syntheses and Properties of α-Alkyl-Substituted Bisdehydroaza[14]annulenes and the Related Benzannelated Derivatives
Authors: Ojima J\={u}ro , Yagi Yasuhiro , Ejiri Emiko , Ishizaka Shuichi , Kato Tadahito
Published: July 2006

14-Ethoxy-2,5,10-trimethyl-6,8-bisdehydroaza[14]annulene, 14-ethoxy-2-ethyl-5,10-dimethyl-6,8-bisdehydroaza[14]annulene, 2-ethoxy-3,11-dimethyl-5,6-benzo-7,9-bisdehydroaza[14]annulene, and 2-ethoxy-1 1,14-dimethyl-5,6-benzo-7,9-bisdehydroaza[14]annulene were synthesized. Influence of α-alkyl substitution and benzannelation upon the skeleton of the bisdehydroaza[14]annulene ring system is discussed on the basis of 1H NMR and UV spectra of these azaannulenes and their α-alkyl unsubstituted ones.
Syntheses and Properties of Two Ethoxytrimethylbisdehydroaza[16]annulenes and Ethoxytrimethylbisdehydroaza[18]annulene
Authors: Ojima J\={u}ro , Yagi Yasuhiro , Manaka Sumio , Nakada Tetsuya , Shiraiwa Yasunao
Published: July 2006

Syntheses of 2-ethoxy-3,6,11 -trimethyl-7,9-bisdehydroaza[16]annulene, 2-ethoxy-6,11,16-trimethyl-7,9-bis-dehydroaza[16]annulene, and 18-ethoxy-2,7,12-trimethyl-8,10-bisdehydroaza[18]annulene are described. It was found that the molecular skeletons of these α- or β-methylated aza[16]- and -[18]annulene are less planar than those of α- or β-methyl unsubstituted aza[16]- and aza[18]annulene, from examination of their 1H NMR and electronic spectra.
Stereoselectivity of Cydoaddition of N-(Cyanomethyl)- and N-(α-Cyanobenzyl)imines with Olefinic Dipolarophiles. Synthetic Equivalents of Nitrile Ylide 1,3-Dipoles
Authors: Tsuge Otohiko , Ueno Kazunori , Kanemasa Shuji , Yorozu Kiyotaka
Published: July 2006

N-(Cyanomethyl)- and N-(α-cyanobenzyl)imines derived from a variety of aldehydes and ketones can tautomerize into N-protonated azomethine ylides which undergo cycloadditions with olefinic dipolarophiles. These cycloadditions are often accompanied by the elimination of HCN, mostly in a stereospecific manner, showing these imines to be synthetic equivalents of nonstabilized nitrile ylides. Stereoselectivity of the cycloadditions is discussed.
Cis-Trans Isomerism among the Octahedral Anionobis(C-substituted ethylenediamine)nickel(II) Complexes Obtained by Thermal Reactions
Authors: Ihara Yoshinori , Fukuda Yutaka , Sone Kozo
Published: July 2006

Ten octahedral anionobis(C-substituted ethylenediamine)nickel(II) complexes were obtained by thermal reactions of corresponding diaqua salts, and their electronic and IR spectra were examined to see whether they are cis or trans. Most of them were found to be trans, but [Ni(NO3)(m-bn)2](NO3) and [NiCl2(i-bn)2] were cis.
The Electrolyte Effect on the Chemical Equilibria of Bis(β-diketonato)nickel(II) Complexes in Dimethyl Sulfoxide
Authors: Kudo Setsuko , Iwase Akio
Published: July 2006

The electrolyte effect on the homogeneous chemical equilibria of Ni(bfac)2, Ni(ftac)2, and Ni(ttac)2 in dimethyl sulfoxide has been studied by means of polarographic and ultraviolet spectral measurements, where bfac−, ftac−, and ttac− represent the enolate anions of benzoyltrifluoroacetone, 2-furoyltrifluoroacetone, and 2-thenoyltrifluoroacetone respectively. The chemical equilibria of these complexes in 0.05 mol dm−3 TBAP solutions found previously:

Ni(bi-L)2\ightleftharpoonsNi(bi-L)(uni-L)\ightleftharpoonsNi(bi-L)++L−\ightleftharpoonsNi(uni-L)++L−

shifted more to the right in the presence of one of the electrolytes (NaClO4, KClO4, RbClO4, CsClO4, TMAP, or TEAP) at the same concentrations as TBAP; bi- and uni- mean that the ligands coordinate to the metal as bidentate and unidentate respectively. Under the conditions of [NiL2]=1 mmol dm−3 and [MClO4]=0.05 mol dm−3, the molar fractions of the species of the Ni(bi-L)2 type decreased with an increase in the inverse of the cationic radii. Such a tendency was explained mainly in terms of the interaction between the π-electron system of Ni(bi-L)2 and those cations. For the same metal perchlorates, except NaClO4, the stability of Ni(bi-L)2 decreased in the order of: bfac−>ftac−>ttac−.
Double Diels-Alder Reaction of trans-3-Methylene-1,4-hexadiene and 1-Methyl-3-methylene-4-pentenyl Tosylate
Authors: Kanemasa Shuji , Sakoh Hirohiko , Wada Eiji , Tsuge Otohiko
Published: July 2006

A cross-conjugated triene, trans-3-methylene-1,4-hexadiene, is accessible from the Grignard reagent of chloroprene and methyloxirane via 1-methyl-3-methylene-4-pentenyl tosylate. The diene-transmissive Diels–Alder reaction of the triene and the stepwise sequence of double Diels–Alder reaction of the tosylate are investigated. Stereo- and regioselectivity of these reactions in the presence or absence of Lewis acid catalyst are discussed.
Kinetics and Mechanism of the Oxidative Deamination of Amines by Coenzyme PQQ
Authors: Itoh Shinobu , Kitamura Yutaka , Ohshiro Yoshiki , Agawa Toshio
Published: July 2006

Kinetic studies on the oxidative deamination of amines by coenzyme PQQ are carried out under anaerobic conditions. The reaction is first-order in the appearance of the reduced PQQ and in the total amine concentrations. A large kinetic isotope effect (kH⁄kD=7.24) in the oxidation of α,α-dideuteriobenzylamine indicates that the C–H bond cleavage is a rate-determining step. From the results of formation of two types of reduced PQQ (quinol and aminophenol) and low reactivities of secondary and tertiary amines, we propose the mechanism via covalent addition of the amine to the quinone followed by rate-limiting α-proton removal.
Vapor-Phase Isomerization of o-Chlorotoluene over H-Mordenite Treated with CF3Cl
Authors: Okazaki Susumu , Jouhouji Hirofumi
Published: July 2006

Vapor phase-isomerization of o-chlorotoluene was somewhat promoted by H-mordenite (HM). The catalytic activity was appreciably enhanced by treatment with CF3Cl and other chlorofluorocarbons such as CF2ClCF2Cl and CF2ClCF3. In particular, maintenance of the HM catalyst activity was remarkably improved by CF3Cl treatment. The CF3Cl-treated HM also promoted vapor phase isomerizations of p- and m-chlorotoluene. The catalytic activity was relatively long-lasting for the isomerization of p-chlorotoluene. Enlargement of the HM pore size on treatment with CF3Cl and other chlorofluorocarbons may contribute to increasing the catalytic activity and then maintaing it.
Analysis of Proton-Transfer Reaction in Aqueous Solutions of Butylamines by Ultrasonic Methods
Authors: Yoshida Yukio , Nishikawa Sadakatsu
Published: July 2006

Ultrasonic absorption has been measured in an aqueous solution of s-butylamine over the frequency range 6.5–220 MHz and the concentration range 0.0115–3.18 mol dm−3 at 25 °C. The single relaxational phenomenon observed in a range less than 1 mol dm−3 was found to be associated with a perturbation of the equilibrium; R-NH3++OH− (Remark: Graphics omitted.) R-NH3+···OH−. The rate constants of the forward and backward reactions, k12 and k21, have been determined to be 2.1×1010 s−1 mol−1 dm−3 and 1.8×108 s−1, respectively. It was also determined that the next step, R-NH3+···OH− (Remark: Graphics omitted.) R-NH2+H2O, which had been thought to have a considerable influence on the first step, was not very effective regarding the ultrasonic absorption observed in the MHz frequency range. The equilibrium constant in the second step, K32, has been determined to be 3.5×10−2. The standard volume change of the reaction has been calculated to be 26 cm3 mol−1 from the concentration dependence of the maximum excess absorption per wavelength. The relaxation observed in a range greater that 1 mol dm−3 has been estimted to be associated with a molecular aggregation reaction. An ultrasonic study in an aqueous solution of butylamine has also been performed in order to determine the rate constants associated with a proton-transfer reaction at 25 °C.
Chemical Effectiveness of Elastic and Inelastic Energy Loss of He+, Ar+, and Xe+ Ions Bombarding Solid Potassium Nitrate
Authors: Ohno Shin-ichi , Furukawa Katsutoshi , Soga Takeshi
Published: July 2006

Decomposition of crystalline potassium nitrate due to He+-, Ar+-, and Xe+- ion bombardment was studied in the energy range from 20 to 100keV. The cross sections for producing nitrite ions were for the first time determined to be 5.7×10−20m2, 12.6×10−20, and 22.0×10−20m2 for 100keV He+, Ar+, and Xe+ ion, respectively. Comparing the values of these cross sections with the rate of an elastic and inelastic energy loss of these incident ions, which were calculated on the basis of the theory of Lindhard et al., it may be concluded that inelastic energy is about five times more efficient than elastic energy for the decomposition of the solid potassium nitrate.
Benzo-15-crown-5 Linked Spirobenzopyran. I. Photocontrol of Cation-Binding Ability and Photoinduced Membrane Potential Changes
Authors: Sasaki Hiroshi , Ueno Akihiko , Anzai Jun-ichi , Osa Tetsuo
Published: July 2006

Benzocrown ether-linked spirobenzopyran (1) and its analogue (2) which has no crown ring were synthesized. The binding abilities of 1 for alkali metal cations (Na+, K+, Rb+, Cs+) were found to change by UV light irradiation, while 2 did not bind these cations before and after UV light irradiation. The plasticized poly(vinyl chloride) (PVC) membrane entrapping 1 or 2 showed photoinduced potential changes reversibly by UV and visible light irradiation. In the membranes of both 1 and 2 showed normal photochromism of spirobenzopyran. In the case of 1, the magnitude of the photoinduced potential change depended upon kind and concentration of alkali metal cations. However, the magnitude of photoinduced potential change of the membrane entrapping 2 was hardly affected by kind and concentration of alkali metal cations. The results are explained in terms of cooperative action of both crown ether and spiropyran.