bluuebunny/crossref_metadata_2025 huggingface dataset:
The Electronic Structures of Several Aliphatic Carbonyls. The Effects of Polar Substituents
Authors: Yonezawa Yoshiro , Fueno Takayuki
Published: July 2006

The electronic structures of several aliphatic carbonyls, X2CO, CH3COX, and (XCO)2 (X=H, F, CN, CH3), have been investigated by the INDO method. Variations in the calculated electron density, the nπ*-excitation energy, the electron affinity, and the ionization potential with α-X substitution are explained qualitatively in terms of the σ-attracting and π-donating character of F, the π-attracting nature of CN and XCO, and the σ,π-donating property of CH3. The lowest 3nπ* excitation energies and ionization potentials calculated by the UHF method are in reasonable agreement with the experimental values in most cases. The partitioning of the total energy suggests that the C–O bonds of X2CO compounds in the lowest 3nπ* state and the radical anions derived from them are somewhat longer than those of the parent molecules, primarily because of the decrease in the electron-core attraction. The C–C bonds in some (XCO)2 compounds appear to be cloven as easily as the C–X one on thermal activation and electron impact.
Enthalpies of Combustion of Organic Compounds. II. l- and d-Glutamic Acid
Authors: Sakiyama Minoru , Seki Syûzô
Published: July 2006

Enthalpies of combustion of l- and d-glutamic acid in the crystalline state have been measured by oxygen bomb calorimetry. Standard enthalpies of formation at 298.15 K have been determined.
The Determination of Formation Constants by Measurements of Molar-volume Changes
Authors: Watanabe Norio , Takamoto Susumu
Published: July 2006

Density measurements were made with a solution containing equivalent amounts of diethylenetriamine and the copper(II) ion, and with solutions of different concentrations of potassium hydroxide. The measurements were also made with systems in which the above-mentioned solutions were mixed. The molar-volume changes due to the complex formation were calculated from the density. The results were used for the calculation of the formation constant of the monohydroxo-diethylenetriamine-copper(II) ion.
Dielectric Relaxation and Molecular Structure. XVI. Dielectric Behavior of Tertiary Alcohols
Authors: Koshii Taro , Takahashi Hiroaki , Higasi Keniti
Published: July 2006

The relaxation time and the activation energy of the principal dispersion of tertiary alcohols do not increase but decrease with increase in the number of the carbon atoms in the molecule. This observation seems to be in accord with a hypothesis that the principal dispersion is associated with the size of the hydrogen-bonded cluster of alcohols.
The Cycloaddition Reaction of Isonitrile to Ketenimine Formed by the Reaction of Isonitrile with Carbene
Authors: Obata Naruyoshi , Mizuno Haruo , Koitabashi Takeo , Takizawa Takeo
Published: July 2006

The reaction of several 2-, 4-, and/or 6-fnethyl-substituted phenylisonitrile with dihalocarbene and diphenylcarbene has been studied. The reaction of methyl-substituted phenylisonitrile with dihalocarbene gave indolenine or indoloquinoline derivatives via ketenimine intermediate which might be produced by α-addition of carbene to isonitrile. In contrast, the reaction of 2,6-dimethylphenylisonitrile with diphenylcarbene presumably formed by photolysis of diphenyldiazomethane gave N-(2,6-dimethylphenyl)diphenylketenimine, and further caused a cycloaddition reaction with isonitrile to yield indonimine derivatives. The structure of these products are discussed on the basis of the spectral data and chemical reactions. The mechanistic pathway of these reactions and the effect of methyl substituent in the cyclization stage are also discussed.
Synthetic Studies of Laurencin and Related Compounds. I. The Synthesis of t-3-Bromo-r-2,c-8-diethyl-3,4,7,8-tetrahydro-2H-oxocin
Authors: Masamune Tadashi , Numata Satoshi , Matsue Hajime , Matsuyuki Akira , Sato Takehiro , Murase Hisashi
Published: July 2006

The synthesis of the titled bromohydrooxocin (2), one of model compounds for synthetic approaches to laurencin (1), is described, trans- and cis-2,5-Diethyl-2,5-dihydrofurans (25), prepared by treatment of furan with bromine and then with ethyl magnesium bromide, was submitted, after oxidation with ozone, to the Robinson-Schöpf condensation with methylamine to give trans- and cis-2,4-diethylbicyclononanones (19a and 19b), whose configurations were discussed on the NMR spectra. These compounds were converted into trans- and cis-diethylhydrooxocinones (38a and 38b), respectively, according to a six-step process analogous to the Paguette procedure. It is to be noted that (i) thermally induced, intramolecular dienyl 1,5-hydrogen transfer (36 to 37), one of the key reactions in the process, took place without difficulty with cis-aminodiene (36b), while the rearrangement did not proceed smoothly with trans-aminodiene (36a), and (ii) trans-ketone (38a) was isomerized readily into cis-ketone (38b). Further hydride reduction of cis-ketone (38b) followed by bromination with carbon tetrabromide and triphenylphosphine yielded the aimed bromohydrooxocin (2) as a major product, which possessed the same relative configuration concerning the ring substituents as laurencin (1).
The Synthesis of 11-(2′-Dimethylaminoethyl)-5-methyl-5,11-dihydrodibenzo[b,e][1,4]thiazepin and Related Compounds. Neurotropic and Psychotropic Agents
Authors: Ueda Ikuo , Umio Suminori
Published: July 2006

The synthesis of 11-(2′-dimethylaminoethyl)-5-methyl-5,11-dihydrodibenzo[b,e][1,4]thiazepin and related compounds is described. 11-Lithiolated 5-methyl-5,11-dihydrodibenzo[b,e][1,4]thiazepin (18) was employed as the key intermediate in the preparation of these compounds.
Group Interactions in Polyelectrolytes. X. The Animation Kinetics of Poly(vinyl haloacetals) and Related Compounds
Authors: Kawabe Hiroshi
Published: July 2006

Polyvinyl chloroacetal (PVCA) and polyvinyl bromoacetal (PVBA) were prepared from polyvinyl alcohol, whose acetal contents were close to the value expected on the basis of Flory’s calculation for the intramolecular reaction between neighboring substituents. The amination of these polyvinyl haloacetals and polyvinyl chloroethyl ether with 2-aminobutanol and diethanolamine was investigated kinetically in dimethyl sulfoxide. The ΔG\eweq values in the amination of these polymers were much higher than that of chloromethylated polystyrene (CMPS) reported previously; this was because of their higher ΔH\eweq values. The lower ΔH\eweq of CMPS was ascribed to the resonance structure of the activation complex due to the phenyl substituent at the α-carbon of the chloro-methyl group. This was ascertained by comparing the ΔH\eweq value in the amination of phenethyl chloride with that of benzyl chloride. The amination of PVBA was faster than that of PVCA as a result of the lower ΔH\eweq of the former.
Hydrogenolyses of Halo-9,9′: 9′,9″-terfluorenyls with the Raney Nickel Catalyst
Authors: Minabe Masahiro , Suzuki Kazuo
Published: July 2006

2,7-Di- and 2- halo-9,9′: 9′,9″-terfluorenyls were treated with the Raney nickel catalyst to give 9,9′: 9′,9″-terfluorenyl isomers (mp 293 °C (dec) (I) and mp 257 °C (dec) (II)), fluorene (III), 9,9′-bifluorenyl (IV), halofluorene, and/or 1,2,3,4,4a,9a-hexahydrofluorene (V). The conformation around the C9–C9′–C9″ single bonds of these halo-9,9′: 9′,9″-terfluorenyls were concluded to be s-cis, s-cis, identical with those of the parent hydrocarbon I. These assignments were confirmed by hydrogenolyzing 9,9″-dideuterio-2,7-dihalo-9,9′ : 9′,9″-terfluorenyls. The chemical shifts of the 9- and 9″-methine protons in these haloterfluorenyls were explained in terms of the torsional conformations of the molecules.
α,β-Unsaturated Carboxylic Acid Derivatives. VIII. The Synthesis and Reaction of Esters N-Acyl-N-bromo-α-dehydroamino Acid
Authors: Shin Chung-gi , Nanjo Katsumi , Nishino Takashi , Sato Yoshiaki , Yoshimura Juji
Published: July 2006

The addition of bromine to t-butyl 2-(N-acylamino)-2-alkenoate (3) was accompanied by the elimination of hydrogen bromide and the decomposition of the ester group to give 2-(N-acylamino)-3-bromo-2-alkenoic acid, while the bromination of 3 with NBS gave the corresponding N-bromo derivative (7), whose bromine atom gradually migrates to give t-butyl 2-(N-acylamino)-3-bromo-2-alkenoate. The substitution of the bromine of 7 with nucleophiles gave, successively, the corresponding N-methoxy, N-benzyloxy and N-cyano derivatives, while that with sodium azide gave the corresponding migration products. The structures of the new compounds were assigned.
Substituent Effect on the Anomeric Effect in 1,3,5-Trithiane Derivatives
Authors: Oki Michinori , Endo Toshiyuki , Sugawara Tadashi
Published: July 2006

Anomeric effect in a series of 2-alkylthio- and 2-arylthio-1,3,5-trithianes has been studied by PMR spectroscopy to investigate the substituent effect on the anomeric effect. A remarkable steric effect is found in 2-t-butylthio-1,3,5-trithiane: the equatorial conformer is slightly favored over the axial one. The electron-withdrawing substituent in 2-arylthio-1,3,5-trithiane enhanced the anomeric effect. The origin of the steric and electric-electronic effect has been discussed on the ground of conformational analysis.
Kinetics of Reduction of Mercury(II) Chloride to Mercury(I) Chloride Induced by the Decomposition of Trioxalatocobaltate(III) in Acid Aqueous Solutions
Authors: Sato Toshiro , Kimura Masaru
Published: July 2006

The decomposition reaction of trioxalatocobaltate(III) complex in the presence of mercury(II) chloride in acid medium induces the reduction of the latter to mercury(I) chloride (calomel). The results are accounted for by a sequence of a chain reaction which is initiated by the intramolecular redox decomposition of trioxalatocobaltate(III). The formation rate of mercury(I) chloride is expressed as half order with respect to the concentrations of oxalic acid, mercury(II) chloride, and trioxalatocobaltate(III). Mechanisms and kinetics are presented to account for these facts.
Iodotrimethylpivalophenones and Iodotetramethylpivalophenones. Preparation and Properties
Authors: Suzuki Hitomi , Ishizaki Katsuro , Hanafusa Terukiyo
Published: July 2006

Three isomeric iodotrimethylpivalophenones and iodotetramethylpivalophenones have been prepared from the corresponding polymethylbenzenes by using the Perrier procedure of the Friedel-Crafts acylation, followed by the iodination of the resulting ketones with iodineperiodic acid dihydrate. Attempts to convert some of these hindered iodoketones to bis (pivaloyl)polymethylbenzenes via the Grignard reagent have failed.
Photoconductivity of Vinyl Polymers with Large Pendant π-Electron Systems. I. Poly-9-vinylacridine
Authors: Moriwaki Saburo , Okamoto Ken-ichi , Kusabayashi Shigekazu , Mikawa Hiroshi
Published: July 2006

The dark- and photo-conductivities of poly-9-vinylacridine (PVAcr) were investigated in comparison with those of poly-N-vinylcarbazole (PVCz). The dark current was ohmic over the whole voltage region studied up to 150000 V/cm. The photocurrent showed a linear dependence on the applied voltage even in fairly high applied fields up to 130000 V/cm and a spectral dependence corresponding antibatically to the absorption spectrum. The magnitude of the photocurrent with positive electrode illumination (iph+) was only 1.5–2 times larger than that with negative electrode illumination (iph−), the behavior differing entirely from that in a PVCz film. The magnitude of the photocurrent of PVAcr was smaller than that of PVCz by several times for iph− and by a hundred times for iph+. The poor photoconductivity of PVAcr was attributed both to the high concentration of the excimer-forming site acting as an effective exciton trap and to the poor electron-donating character.
A Formulation of Chemical Kinetics in Micellar Solutions
Authors: Shirahama Keishiro
Published: July 2006

Reaction kinetics in the presence of micelles is formulated on the basis of a microheterogeneous reaction in accordance with a current model of micellar catalysis. The necessary molecular parameters are the radius of the hydrocarbon core of a spherical micelle, the thickness of a reaction surface layer, the surface and zeta potentials, and a distribution coefficient of a hydrophobic substrate. The derived expression was applied to the hydrolysis reaction of methylorthobenzoate in the presence of sodium dodecylsufate micelle to describe reaction properties such as a rate-surfactant concentration profile, inhibition by added electrolyte, and activation energy. The micellar effect on the reaction rate was explained by a simple concentration effect of the reactants; the stabilization of the transition state by the micellar surface potential need not be taken into consideration. Inhibition of the orthoester hydrolysis by a cationic surfactant is also predicted.
Ion Association of Some 2 : 2 Electrolytes in Water at 25 °C. I. Studies of Magnesium, Calcium, Manganese, and Tris(1,10-phenanthroline)-ruthenium(II) Sulfate Solutions with a Vapor-Pressure Osmometer
Authors: Yokoyama Haruhiko , Yamatera Hideo
Published: July 2006

The osmotic coefficients of aqueous solutions of magnesium, calcium, manganese, and tris(1,10-phenanthroline)ruthenium(II) sulfates were measured at 25 °C by means of a vapor-pressure osmometer. Then the ionassociation constants of these electrolytes were obtained as a function of the closest distance of approach of ions from the measured osmotic coefficients as well as from the available conductivity and cryoscopy data. The best values of the closest distance of approach and the ion-association constant (given in Table 6) were estimated with the help of theories of ion association. The formation of triple-ions and quadrupoles and the hydration of ions are also discussed in connection with the ion-association constant.
Kinetics of Multidentate Ligand-substitution Reactions. XVIII. Substitution Reactions of Triethylenetetraaminehexaacetate (TTHA) with Nickel(II)–Dien, –EDMA, and –NTA Complexes
Authors: Kodama Mutsuo
Published: July 2006

The kinetics of the substitution reactions of TTHA with nickel(II) complexes of diethylenetriamine (Dien), ethylenediaminemonoacetate (EDMA), and nitrilotriacetate (NTA) were studied systematically by employing the polarographic technique. All the substitution reactions were found to have a common reaction mechanism. They were first-order with respect to TTHA and also first-order with respect to a 1:1-ratio nickel(II) complex of Dien, EDMA, or NTA. In all the substitution reactions, the rate constants for the reactions involving a com-pletely-deprotonated TTHA anion were nearly identical to those for the corresponding DTPA (diethylenetriaminepentaacetate) reactions, suggesting that the TTHA reaction has the same reaction mechanism as the DTPA reaction. In the Dien system, the rate constant for the reaction of the quadrivalent TTHA anion is nearly identical to that of the quinquivalent TTHA anion, whereas, in the reactions of NTA and EDMA complexes, the reaction of the quadrivalent TTHA anion is drastically slower than that of the quinquivalent TTHA anion. These facts suggest that the proton transfer from the entering group to the leaving group plays an important role in determining the rate of the multidentate ligand-substitution reaction.
Non-isothermal Studies of Adduct Molecules of Metallic Halides with Oxo Compounds in Solid State. III.
Authors: Chaudhuri N Ray , Mitra S
Published: July 2006

Non-isothermal studies of some adduct molecules of metallic halides with ethylene glycol dimethyl ether of the type MX2(EGDME)y in solid state were carried out with a derivatograph, where M=Mn(II), Co(II), Ni(II), Cu(II) or Cd(II), X=Cl− or Br−, EGDME=ethylene glycol dimethyl ether and y=0.5–1. These adduct molecules lost ethylene glycol dimethyl ether in single or multiple steps upon heating. Thermally stable intermediate products were isolated and characterised by elemental analysis and IR spectral measurement. The activation energy for each step of decomposition of the adduct was evaluated from the analysis of TG, DTG and DTA curves of the respective derivatograms. Enthalpy change was evaluated from the DTA peak area and the order of reaction was found to be unity for each step of decomposition. Thermal parameters for the above adducts were compared with those for the corresponding type of adducts with oxo-compounds like dioxane or tetrahydrofuran.
Oxidative Cleavage of Aromatic Methoxy Compounds with Photo-excited Aromatic Nitro Compounds
Authors: Saito Isao , Takami Masaaki , Matsuura Teruo
Published: July 2006

Photochemical addition of the aromatic nitro group with aromatic methoxy compounds leading to the cleavage of the aromatic ring was studied. The oxidative cleavage occurs selectively at 1,2-bond with respect to a methoxy group of methoxybenzenes and methoxynaphthalenes. Aromatic nitro compounds having the lowest π,π* triplet are more effective to the oxidative ring cleavage of the methoxynaphthalenes than those having the lowest n,π* triplet. A mechanism involving charge-transfer complex is proposed. The scope and limitation on the use of these photochemical reactions are discussed.
α,β-Unsaturated Carboxylic Acid Derivatives. X. The Synthesis and Reaction of α-Azido-diethoxyphosphinyl-α- and β-alkenes
Authors: Shin Chung-gi , Yonezawa Yasuchika , Sakamoto Hiroshi , Yoshimura Juji
Published: July 2006

α,β-Dibromo-β-diethoxyphosphinylalkane (2) was obtained as a stereo-isomeric mixture (erythro : threo=50 : 50) by the bromination of β-diethoxyphosphinyl-α-alkene, composed of the E-isomer and the Z-isomer (50 : 50). It was found that the reaction of 2 with sodium azide proceeded stereoselectively to give only the. E-isomer of α-bromo-β-diethoxyphosphinyl-α-alkene, which could then be converted into α-azido-β-diethoxyphosphinyl-α-alkene (4), and α-azido-β-diethoxyphosphinyl-β-alkene, whose configuration was determined by the coupling constants between the phosphorus atom and the vinyl protons. Moreover, the irradiation of 4 yielded a new type of β-diethoxyphosphinyl-α-alkene-α-imine, which later rearranged into the corresponding nitrile.
Aminocyclitols. 32. Synthesis of Inosadiamine-1,4
Authors: Suami Tetsuo , Tadano Kinnichi , Horiuchi Sumio
Published: July 2006

Three new inosadiamines have been prepared by nitromethane cyclization of dialdehyde, followed by catalytic hydrogenation. Their structures were established to be scyllo-1,4, myo-1,4, and epi-inosadiamine-3,6 by PMR spectra.
The Synthesis of 1,3,4-Oxadiazolo[3,2-b]isoquinoline and 1,3,4-Thiadiazolo-[3,2-b]isoquinoline Derivatives from Homophthalic Anhydride
Authors: Takahashi Masahiko , Shinoda Takamitsu , Osada Hideshi , Nakajima Toshio
Published: July 2006

The synthesis of 1,3,4-oxadiazolo[3,2-b]isoquinoline and 1,3,4-thiadiazolo[3,2-b]isoquinoline derivatives is described. The reaction of homophthalic anhydride (1) with acylhydrazines (2) afforded 2-acylamino-1,2,3,4-tetrahydroisoquinoline-1,3-diones (3) or 1-(o-carboxyphenylacetyl)-2-acylhydrazines (4). The treatment of 3 or 4 with polyphosphoric acid gave 2-substituted 1,3,4-oxadiazolo[3,2-b]isoquinolin-5(5H)-ones (5) in quantitative yields. The treatment of 3 or 4 with phosphorus pentasulfide gave 2-substituted 1,3,4-thiadiazolo[3,2-b]-isoquinoline-5(5H)-thiones (6). 2-Phenyl-1,3,4-oxadiazolo[3,2-b]isoquinoline-5(5H)-thione (9) was obtained by the reaction of 5a with phosphorus pentasulfide.
Ungewöhnliche Wichterle-Reaktionen. Eine Neue Synthese von Phenalenonen
Authors: Kobayashi Makoto , Matsumoto Takeshi
Published: July 2006

Beim Erhitzen von 1-Methyl-1-(3-chlor-2-butenyl)-5-methoxy-2-tetralon(10) in HCO2H in Gegenwart von HClO4 wurde 4,7-Dimethyl-1-phenalenon(11) erhalten, während das Desmethoxy-Analogon, 1-Methyl-1-(3-chlor-2-butenyl)-2-tetralon(5) ein Phenanthren-Derivat ergibt. Es wurde gezeigt, dass die Bildung von Phenalenon liber die Zwischenprodukte 2,3,9,9a-Tetrahydro-7,9-dimethyl-4-methoxy-1-phenalenon(13) und 2,3-Dihydro-4,7-dimethyl-1-phenalenon(17) verläuft. Unter den gleichen Bedingungen wurde 1-(3-Chlor-2-butenyI)-5-methoxy-2-tetralon(21) über 2,3-Dihydro-7-methyl-4-methoxy-1-phenalenon(23) in 7-Methyl-4-methoxy-1-phenalenon(24) umgewandelt.
The Responses of the Monovalent Cation-sensitive Glass Electrode to the Cationic Activities in Different Solvents
Authors: Nakamura Toshio
Published: July 2006

The responses of the glass electrode to the cationic activities in different solvents have been studied for several monovalent cations in several dipolar aprotic and protic solvents by comparing the potentials of the amalgam electrode with those of the glass electrode.
The Conversion of Penicillin S-Oxides into Cephalosporin S-Oxides
Authors: Ishimaru Toshiyasu , Imamoto Tsuneo
Published: July 2006

The reaction of penicillin S-oxides (1a,b) with N-bromosuccinimide afforded sulfinyl bromides (2a,b) in high yields. The bromides were converted into cephalosporin S-oxides (4a, 4b, 6a, and 7a) in fairly good yields.
Metal Derivatives of Amidoximes. VII. Synthesis of Bis(1,3,5,2-Oxadiazaborol-2-yloxy)tetrabutyldistannoxanes
Authors: Goel A B , Gupta V D
Published: July 2006

Bis(1,3,5,2-oxadiazaborol-2-yloxy)tetrabutyldistannoxanes have been synthesized by the reaction of amidoxime, boric acid and dibutyltin oxide. A probable structure for the dimeric species has been proposed on the basis of molecular weight and IR spectral data.
Topochemical Studies. VII. The Crystal and Molecular Structures of Tetrachlorophthalic Acid Hemihydrate and Tetrabromophthalic Anhydride
Authors: Ito Kuniaki , Moriya Keigo , Kashino Setsuo , Haisa Masao
Published: July 2006

The crystal structures of tetrachlorophthalic acid hemihydrate (TCPH) and tetrabromophthalic anhydride (TBPA) have been determined from visually estimated CuKα data. The crystals of TGPH are monoclinic, space group A2/a, a=19.81(1), b=7.091(5), c=16.22(1) Å, β=101.2(2)° and Z=8. Those of TBPA are monoclinic, space group P21/n, a=13.39(3), b=6.19(2), c=12.66(3) Å, β=91.1(3)° and Z=4. The structures of TGPH and TBPA were solved from the sharpened Patterson maps, and refined by the block-diagonal least-squares method to R values of 0.112 and 0.112 for 1287 and 1278 non-zero reflections, respectively. The molecules of TCPH related by a twofold screw axis are linked together by hydrogen bonds between the carboxylic groups to form a chain along the b axis and the chains are held together by hydrogen bonds through water molecules to form a sheet parallel to the (100) plane. The sheets are stacked by van der Waals forces. The dihedral angles of the carboxylic groups with the benzene ring are 68.2 and 48.9°. The crystals of TBPA are isomorphous to those of tetrachlorophthalic anhydride. The benzene ring of TBPA are distorted by the attachment of five membered ring. There is considerable molecular overlap in TCPH, while in TBPA there is no overlap.
An Evaluation of the Effects of the Phosphorus Ligands on the Stereoselectivity of a Nickel-catalyzed Reaction. The Reaction of Norbornadiene with Acrylonitrile
Authors: Yoshikawa Susumu , Aoki Kunihiro , Kui Jitsuo , Furukawa Junji
Published: July 2006

The effects of nineteen phosphorus ligands on the nickel-catalyzed 4+2 cycloaddition reaction of norbornadiene to acrylonitrile have been studied. The cone angle and the νco stretching frequency of Ni(CO)3L (where L is the phosphorus ligand) are used as measures of their steric and electronic parameters respectively. The steric factor of the phosphorus ligands is correlated with the ratio of the exo- and endo-isomers of the product. Consequently, this effect is important in determining the steric course of the reaction. The electronic property and the solvent effect are less influential.
The Interpretation of Surface Tension Data for Solutions of Ionic Surfactants in the Presence of Electrolyte
Authors: Hall Denver G , Pethica Brian A , Shinoda Kozo
Published: July 2006

An improved method is presented for interpreting surface tension data on solutions of an ionic surfactant to which has been added an electrolyte whose co-ion has the same valence as the surfactant ion. Adequate account is taken of co-ion adsorption and of deviations from ideality of the solution. When a monolayer of surfactant ions is formed and the distributions of free surfactant ions and co-ions in the region adjacent to it are determined predominantly by electrostatic repulsion, it is shown that the separate contributions to the total Gibbs excess of surfactant ions from the monolayer and the adjacent region can be obtained. Finally some experimental data are re-examined and a simple explanation is given for the minimum reported to occur in co-ion adsorption as the surfactant ion concentration is increased at constant co-ion concentration.
Ethanol and Lactic Acid Sensors Using Electrodes Coated with Dehydrogenase—Collagen Membranes
Authors: Suzuki Shuichi , Takahashi Fujio , Satoh Ikuo , Sonobe Nobuyuki
Published: July 2006

Electrochemical and enzymatic reactions were studied for the purpose of making sensors of ethanol and lactic acid. The dehydrogenase–collagen membrane coated onto a platinum plate was prepared by the electroshaping method. The substrates were dehydrogenated and nicotinamide adenine dinucleotide (NAD) was reduced to form the reduced NAD (NADH) by an enzymatic reaction on the collagen membrane. Flavin mononucleotide (FMN) was chosen as an electroactive substance which could oxidize NADH to return NAD. The reduced FMN (FMNH2) was easily oxidized at the anode and a current was obtained. From the above reactions, the concentrations of ethanol and lactic acid in solutions were found to be determined by a current-substrate concentration relation. The accuracy was estimated to be within 10% error. The activity and stability of enzymes immobilized in the collagen membrane were investigated.
Chemistry of Nitrosoimines. XI. Reactions of 3-Substituted 2-Nitrosoimino-2,3-dihydrobenzothiazoles with Benzyl and Allylic Grignard Reagents
Authors: Hisaoka Motoyuki , Akiba Kin-ya , Inamoto Naoki
Published: July 2006

3-Substituted 2-nitrosoimino-2,3-dihydrobenzothiazoles (1) react with benzylmagnesium chloride to give 3-substituted 2,2-dibenzyl- (2), 2-N′-benzylidenehydrazono- (3) and 2-N′,N′-dibenzylhydrazono-2,3-dihydrobenzothiazoles (4). The main reaction (formation of 3 and 4) occurrs on the nitroso group of 1, which proceeds via 1,2-addition intermediate (B). Allylmagnesium bromide and cinnamylmagnesium chloride also react with 3-methyl derivative (1a) to afford 2-N′,N′-diallyl- and 2-N′-(1-phenyl-2-propenyl)hydrazono-3-methyl-2,3-dihydrobenzothiazoles, respectively.
The Dehydration and Dehydrogenation of Ethanol Catalyzed by TiO2–ZrO2
Authors: Arata Kazushi , Sawamura Hiromitsu
Published: July 2006

Ethanol was converted into ether, ethylene, and butadiene over TiO2–ZrO2 with various contents of ZrO2in a flow system. Maximum acidity and activity were obtained at 50% ZrO2. The butadiene formation was explained by both dehydration and dehydrogenation reactions on acidic and basic sites, implying that TiO2–ZrO2 is an acid-base bifunctional catalyst.
Topological Index as Applied to π-Electronic Systems. II. Topological Bond Order
Authors: Hosoya Haruo , Murakami Miyuki
Published: July 2006

Topological bond order plT is proposed to be defined for a bond l in the graph corresponding to the carbon atom skeleton of a hydrocarbon. This quantity is obtained by hand calculation of the topological indices of the graph and its subgraphs. The plT value is linearly correlated well with the Coulson bond order plC for both the chain and cyclic compounds. If the bonds with the same Pauling bond order plP are compared this linear relationship is greatly improved and one gets an empirical relation as

p_l^C=A  p_l^T + B  p_l^P.
Direct Measurement of Interaction Energy between Solids and Gases. I. Heat of Adsorption of Ammonia on Zeolite
Authors: Tsutsumi Kazuo , Koh Hong Qui , Hagiwara Seiichi , Takahashi Hiroshi
Published: July 2006

The differential heat of adsorption of ammonia on synthetic zeolites was calorimetrically measured and the distribution of the surface acidity was discussed in relation to the catalytic activity for cumene-cracking as a function of zeolite compositions. A newly designed apparatus, a twin-conduction-type calorimeter equipped with a semiconductor thermoelement and an adsorption apparatus, was used for the direct measurement of the differential heat of adsorption. The differential heat of adsorption of ammonia decreased with the increase in surface coverage, the acid site on the surface becoming stronger up to 27 kcal/mol for ammonia-adsorption when the ratio of silica to alumina was higher and the content of exchanged ammonium ions was higher. The cumene-cracking reaction was effectively catalyzed by zeolites having such sites with heat of adsorption of ammonia exceeding 25 kcal/mol.
Studies on Interaction of Isocyanide with Transition Metal Complexes. XIII. Preparation of Carbene Complexes of Nickel, Iron, and Cobalt through Protonation of Monoimino and Polyimino Type Complexes
Authors: Yamamoto Yasuhiro , Yamazaki Hiroshi
Published: July 2006

Reactions of η-C5H5Ni(CNR1)[C(R)=NR1] (R=CH3,p-ClC6H4; R1=C6H11, (CH3)3C) and η-C5H5Fe(CO)2-[C(CH2C6H4X-p)=NC6H11] (X=H, Cl) with HBF4 gave the cationic carbene complexes, η-C5H5Ni(CNR1)-[C(R)NHR1]BF4 and η-C5H5Fe(CO)2[C(CH2C6H4X-p) NHC6H11]BF4. η-C5H5Co[–C(=NR)–CPh=CPh–C(=NR)–] (1a; R=2,6-(CH3)2C6H3: 1b; R=p-CH3C6H4) reacted with HBF4 to give η-C5H5Co[–C(NHR)–CPh=CPh–C(=NR)–]BF4 (2a, b). Compound 2a exists as two isomers, induced by the restricted rotation about the C–N bond. Treatment of 1a with HCl gave η-C5H5Co[–C(NHR)–CPh=CPh–C(=NR)–]Cl (3b). The H(N) proton showed some fluxional behavior in its proton NMR spectrum. Reaction of 1b with CF3COOH gave the dicationic complex η-C5H5Co[–C(NHR)–CPh=CPh–C(NHR)–](CF3COO)2  4b. Compound 2 reacted with R1NC(R1=(CH3)3C, 2,6-(CH3)2C6H3) to give η-C5H5Co(CNR1)[–C(=NR)–CPh=CPh–C(=NR)–]5. Reaction of 5 with HBF4 gave again the cationic carbene complex η-C5H5Co(CNR1)[–C(NHR)–CPh=CPh–C(=NR)–]BF4.
Optical Activation of α-Substituted Carbonyl Compounds by Asymmetric Transformation
Authors: Matsushita Hajime , Noguchi Masao , Saburi Masahiko , Yoshikawa Sadao
Published: July 2006

Immonium salts of enamines of racemic α-substituted carbonyl compounds with optically active acids gave, on hydrolysis with water, the corresponding optically active carbonyl compounds. Several reaction conditions were examined and a plausible reaction mechanism, an asymmetric transformation, was proposed. Rates of racemization for the (+)-α-pheiiylpropionaldehyde were also determined.
Micellar and Metal Ion Catalysis in the Pyridoxal-Promoted α,β-Elimination of S-Phenylcysteine
Authors: Murakami Yukito , Kondo Hiroki
Published: July 2006

The effects of metal ions and detergents on the pyridoxal-catalyzed α,β-elimination reaction of S-phenylcysteine have been investigated in 0.01 M borate buffer at 50 °C (the copper ion catalysis at 40 °C in the presence of CTAB micelles). Both copper(II) and nickel(II) ions markedly accelerated the elimination reaction of S-phenylcysteine. Since the catalytic efficiency of nickel(II) seems to be obtained due to the poor coordination ability of the leaving group in the present reaction, the previous working hypothesis which was provided for the elucidation of catalytic roles of metal ions in the α,β-elimination of O-phosphothreonine has now been approved. Among cationic, anionic, and non-ionic detergents employed in this work as apoenzyme models, only CTAB of cationic nature showed a considerable rate acceleration even in the absence of metal ions. The micellar binding constant was evaluated from the saturation-type correlation between reaction rate and CTAB concentration. The surfactant micelles demonstrated some enzyme-like features of catalysis in the pyridoxal-promoted α,β-elimination reaction, where the reaction is controlled by the entropy term. The CTAB catalysis was greatly inhibited by organic and inorganic anions due to the electrostatic nature of the micellar surface. The catalytic mechanisms for the micellar reactions and their significance as an enzyme model system are discussed.
A Method for Determining the Degree of Dissociation of Symmetrical Associated Electrolytes from the Conductivity and Activity Data
Authors: Tamamushi Reita
Published: July 2006

A method is presented for determining the degree of dissociation of symmetrical associated electrolytes from a set of conductivity and activity data. The method was applied to the determination of the dissociation constants of several metal sulfates in aqueous solutions.
Semi-empirical SCF–MO Studies of Platinum Hydrides and the Insertion Reaction of Ethylene into the Pt(II)–H Bond
Authors: Sakaki Shigeyoshi , Kato Hiroshi , Kanai Hiroyoshi , Tarama Kimio
Published: July 2006

Semi-empirical SCF–MO calculations were carried out on trans-PtHX(PH3)2 (X= halogen and CN−). The absolute value of Ept-H decreases in the following order: F>Cl>Br>I>CN; this agrees with the order of the bond strength of the Pt–H bond. The electron density on the H ligand is remarkably large in all the complexes (ca. 1.25 e) and decreases in this order: F>Cl>Br>I>CN. An insertion reaction of ethylene into the Pt–H bond was investigated by the use of the MO method. The intermediate five-coordinate π-olefinic hydride complex has a trigonal bipyramid structure in which Cl and H ligands are positioned trans to each other. Three reaction paths of the insertion were investigated, and the following reaction path seems the best: The H ligand starts first to approach ethylene and then the Cl ligand starts to move to the trans-position of the H ligand. The reactivities of trans-PtHX(PH3)2 increase in this order: F<Cl<Br<I<CN. MO calculations also reveal that the catalytic ability of trans-PtHK(PH3)2 increases as follows in the hydrogen-deuterium exchange reaction of ethylene: F<Cl<Br<I
Studies on Mass Spectrometry of Metal Chelates. III. Mass Spectrometry of 2-, 4-, 5-, 7-Methyl-, and 5-Chloro-oxine Metal Chelates
Authors: Naga Shinobu , Kidani Yoshinori , Koike Hisashi
Published: July 2006

For application of mass spectrometry to metal chelate chemistry, a group of divalent metal chelates (Co, Ni, Cu, Zn, and Pd) of 2-Me-oxine, 4-Me-oxine, 5-Me-oxine, 7-Me-oxine, and 5-Cl-oxine has been investigated. 2-Methyloxine and 4-Me-oxine of these ligands give similar spectra and are considered to have similar fragmentation patterns. The same was found for 5-Me-oxine and 7-Me-oxine. However, the spectra of 2-Me-oxine and 4-Me-oxine metal chelates differ from each other, as do also the spectra of 5-Me-oxine and 7-Me-oxine. Thus fragmentation patterns may vary with the metal chelate formation of the ligands even when they have the same fragmentation patterns. Each metal chelate gave two peaks corresponding to metal-containing ions, a molecular ion (I) of a 2:1 (ligand: metal) chelate, and a fragment ion (II) of a 1: 1 chelate due to the loss of a hgand radical from ion I. In the case of Co, Ni, Zn, and Pd chelates of 2-Me-oxine, a peak corresponding to the loss of a methyl radical from I was observed, apparently caused by steric effect. In the metal chelates of 5-Me-oxme, a peak corresponding to the loss of a hydrogen radical from I was also observed. However, the fragmentation pathway of formation of II from I is commonly observed in all metal chelates. Since this pathway is comparable with the second successive formation reaction (k2) in solution, the peak intensity ratio of the ion of I to that of II was calculated. From the results it was found that the stability of the chelates decreases in the order Zn>Ni>Pd∼Co>Cu and that it depends on the charge-radius ratio (e⁄r) of the central metal ion, or the stability constant (logk2) observed in solution.
Isomerism of the Metal Complexes Containing Multidentate Ligands. V. Preparation and Properties of Optically Active Tris-(diaminosuccinato)cobaltates(III)
Authors: Kojima Masaaki , Yoshikawa Yuzo , Yamasaki Kazuo
Published: July 2006

Tris(diaminosuccinato)cobaltates(III) with meso, racemic, and laevorotatory ligands were prepared and resolved by column chromatography on DEAE-cellulose and by the use of cinchonidine. The resolved complexes and their absolute configurations, assigned on the basis of the electronic and circular dichroism spectra, and on the basis of the elution order in cellulose column chromatography, are Δ-(−)589-[Co(mdas)3]3−, Λ-(+)589-[Co(mdas)3]3−, Λ(lel)-[Co(ldas)3]3−, and Δ(ob)-[Co(ldas)3]3−
The Crystal Structure of α-Barium 12-Tungstosilicate, α-Ba2SiW12O40·16H2O
Authors: Kobayashi Akiko , Sasaki Yukiyoshi
Published: July 2006

α-Ba2SiW12O40·16H2O is monoclinic, space group C2/c, with a=25.09(5), b=12.10(2), c=18.79(3) Å, β=122.5(3)°; Dm=4.95 g cm−3 and Dx=4.78 g cm−3 for Z=4. The crystal consists of the well known Keggin ion SiW12O404−, having a SiO4 tetrahedron in the center, bound by Ba2+ and water molecules to form a three-dimensional framework. Four water molecules could not be located on electron-density maps, which seem to be disordered or “zeolitic”. The structural relationship of the Keggin ion to its isomer, the β-SiW12O404− polyanion found in β-K4SiW12O40·9H2O, is discussed. Mutual transformation between α- and β-isomers can occur through rotation of a W3O13 group which is a building-unit of both α- and β-polyanions.
Reactions of 1,8-Dehydronaphthalene with Cyclic Polyenes
Authors: Kato Masahiko , Takaoka Shigeru , Miwa Toshio
Published: July 2006

The reactivities of 1,8-dehydronaphthalene (1) to cyclic polyenes, i.e., cycloheptatriene, cyclopentadiene, 6,6-dimethylfulvene, furan, and norbornadiene, were examined. It was found that the C–H insertion reaction at the end of the conjugated systems, a new type of reaction of 1, as well as the 1,2-cycloaddition reaction occurs in every conjugated cyclic polyene. A stepwise mechanism for the formation of the C–H insertion product was proposed.
The Crystal and Molecular Structure of (+)-1,2-Dibromo-2-phenylethyl p-Tolyl Sulfoxide
Authors: Iwasaki Fujiko , Mitamura Shuichi , Tsuchihashi Gen-ichi
Published: July 2006

The crystal structure of (+)-1,2-dibromo-2-phenylethyl p-tolyl sulfoxide, a dominant isomer formed by the ionic bromination of (+)-trans-β-styryl p-tolyl sulfoxide, has been determined by the X-ray diffraction method. The crystal is monoclinic; space group, P21; a=16.193, b=5.706, c=8.541 Å, β=93.51°, and Z=2. The final R value is 0.087 for 792 observed reflections. The absolute configuration has been established to be Ss, SC(1), SC(2) from the CuKα anomalous scattering of the bromine and sulfur atoms. The sulfinyl oxygen is gauche to the bromine atom across the S–C(1) bond, and the non-bonding distance between the both atoms is 3.13 Å. The bromine atom is trans to another bromine across the C(1)–C(2) bond. Based on the assigned structure, a mechanism which involves the preferential formation of an intermediary bromonium ion is elucidated for the bromination. The configuration at the sulfur atom is retained during the reaction.
Dielectric Relaxation and Molecular Structure. XIII. The Dielectric Behavior of Mixtures of 1-Propanol with Hydrogenbonding and Non-hydrogen-bonding Solvents
Authors: Koshii Taro , Takahashi Hiroaki , Higasi Keniti
Published: July 2006

The dielectric constants and losses of 1-propanol and its mixtures with benzene, chlorobenzene, 1,4-dioxane, and pyridine have been measured in the frequency range of 1–0.35 GHz in the temperature range of 10–40 °C. The concentrations of the mixture lie between 1–0.6 mol fractions of the alcohol. The dielectric relaxations of the observed systems in the above frequency range are all of the Debye type. The measured data were used to calculate the activation enthalpy, ΔH*, and the entropy, ΔS*. The dependence of ΔH* and ΔS* upon the concentration differs with the nature of the solvent. Both ΔH* and ΔS* decrease upon the addition of a hydrogenbonding solvent, while they increase slightly upon the addition of a non-hydrogen-bonding solvent. The mechanism of the principal relaxation of 1-propanol is discussed on the basis of these observations.
The Hydrogen-Deuterium Exchange of 3,5-Dimethylisoxazoles
Authors: Kashima Choji , Yamamoto Yasuhiro , Tsuda Yoshihiko , Omote Yoshimori
Published: July 2006

By the hydrogen-deuterium exchange reaction in methano d4, 3,5-dimethylisoxazole (1) was found to react regioselectively at the C-5 methyl group. This methyl group was, however, less reactive than the methyl groups of 2-picoline or quinaldine. This reaction was shown to be retarded by the electron-donating substituents, and to be accelerated by the electron-withdrawing substituents, at the C-4 position of 1.
The Photochemical Cycloaddition of the Enol Acetate of Dimedone to Cyclopentene
Authors: Umehara Misao , Oda Tomio , Ikebe Yoshinori , Hishida Shinzaburo
Published: July 2006

The photochemical cycloaddition of the enol acetate of dimedone to cyclopentene yields two stereoisomers I and II of 2-acetoxy-4,4-dimethyltricyclo[6.3.0.02,7]undecan-6-one. The NMR and IR data suggest a cis-anti-cis configuration for I and a cis-anti-trans configuration for II. The NMR and IR spectra determined on III, IV and V, the NaBH4 reduction products of I and II, also support these configurations. Both of the photo adducts, I and II, lose acetic acid in the presence of an alkali to give an α,β-unsaturated ketone (VI), while it undergoes retro-aldol cleavage in the presence of an acid to give 4,4-dimethylbicyclo[6.3.0]undecane-2,6-dione (VII). A comparative study was made of the mass spectra of I, II, and VI.
Synthetic Studies on Phosphorylating Reagent. V. A Convenient Synthesis of 2′,3′-Cyclic Coenzyme A
Authors: Taguchi Yoshihiko , Nishimura Noriyuki , Kakimoto Toshio , Mushika Yoshitaka
Published: July 2006

A convenient method has been developed for the preparation of 2′,3′-cyclic Coenzyme A (5). It was readily prepared in a good yield from the reaction of adenosine-5′ 2-dimethylamino-4-nitrophenyl phosphate (3) with d-pantethine-4′,4″-diphosphate (4) in the presence of acetic acid in pyridine. Compound 3 and the diphosphate 4 were prepared in a good yield from the condensation of adenosine (1) with 2-dimethylamino-4-nitrophenyl phosphate (2) in the presence of dicyclohexylcarbodiimide (DCC) and the phosphorylation of d-pantethine with 2, respectively.

Phosphate 5 was hydrolyzed with 0.1 M-hydrochloric acid and subsequently reduced with 2-mercaptoethanol to confirm its structure of 5. One of the products, Coenzyme A (reduced form) (6) showed 102% activity with phosphotransacetylase.
Chemistry of 1,3-Glycol Derivatives. I. The Reactions of 2,4-Pentanediol Derivatives
Authors: Itoh Osamu , Ichikawa Yasunori , Katano Hiroaki , Ichikawa Katsuhiko
Published: July 2006

Cyclic orthoacetates of meso- and dl-2,4-pentanediol (cis- and trans-2-ethoxy-2,4,6-trimethyl-1,3-dioxane, 1) were prepared and characterized by NMR. The stereochemical courses of the reactions of 1 with water, hydrogen chloride, trityl chloride, and acetic acid were investigated. The reactions with water gave 4-acetoxy-2-pentanol (4) with complete retention of configuration, while those with the other reagents gave 4-acetoxy-2-chloropentane (3) and 2,4-diacetoxypentane with complete inversion. Acetolyses of 3 and the tosylate of 4 gave 2,4-diacetoxypentane predominantly with retention in the absence of water. Hydrolysis of the tosylate gave 4 with almost complete inversion. These results can be explained by the mechanism that the reactions proceed mainly through acetoxonium cation intermediate involving six-membered ring. The fluoroborate salt of this acetoxonium cation was prepared and characterized by NMR.
Chelation Effect of Alizarin Dyes on the Semiconductor–Aqueous Solution Systems
Authors: Matsumura Michio , Nomura Yoichi , Tsubomura Hiroshi
Published: July 2006

The dye-sensitized photocurrents produced by some semiconductor (titanium dioxide single crystal or zinc oxide sinter) in electrolyte solutions containing alizarin dyes were studied. The photocurrent was concluded to be caused by the sensitization of the alizarin dyes chelated to the semiconductor electrodes.
Synthesis, Thermolysis and Photolysis of Trimethylammonium-N-diphenylphosphinylimine
Authors: Kameyama Eiichi , Inokuma Seiichi , Kuwamura Tsunehiko
Published: July 2006

Ammonim-N-phosphinylimine was prepared from the corresponding hydrazinium salt. The ylid gave phosphinylnitrenes on thermolysis, predominantly in the singlet state. On photolysis, the ylid also gave a singlet product.
A Proton Magnetic Resonance Study of the Amide Configurations of 2-Acylaminopyrimidines
Authors: Kondo Michio
Published: July 2006

It has been found, from the 1H NMR spectra at various temperatures, that 2-formylaminopyrimidine (2) exists in a cis configuration in chloroform and dimethyl sulfoxide, whereas 2-acetylaminopyrimidine (3) exists in a rapid rotational equilibrium between cis and trans configurations in CDCl3, but almost exclusively in a trans configuration in DMSO at room temperature.
Studies of the Effect of Ethanol and Sodium Chloride on the Micellization of Sodium Dodecyl Sulfate by Gel Filtration
Authors: Suzuki Hitoshi
Published: July 2006

The effects of the addition of ethanol and sodium chloride to aqueous solutions of sodium dodecyl sulfate (SDS) were studied by the gel-filtration method. With an increase in the concentration of ethanol, the CMC decreased and then increased after passing a minimum, while the micellar weight increased and then decreased, showing a corresponding maximum. Above about 40 vol% ethanol, no micelle formation was observed. The micellar weight and aggregation number in the presence of ethanol were measured in the SDS concentration range of a constant elution rate of micelles. A decrease in the CMC and an increase in the micellar weight of SDS were observed with an increase in the concentration of NaCl from 0 to 10 mmol/1. The gel-filtration study enabled us to make a direct experimental confirmation of the effects of ethanol and NaCl on the micelle formation of SDS.
A Proton Magnetic Resonance Study of the Molecular Configurations of 2′,5′-Dichloroacetoacetanilide in Various Solvents
Authors: Kondo Michio
Published: July 2006

It has been found by 1H NMR spectroscopy that 2′,5′-dichloroactoacetanilide (1) exists predominantly in the keto form containing an intramolecular hydrogen bond between the amide proton and the carbonyl oxygen at the γ-position in chloroform solutions. In pyridine, the line broadening of signals suggests a rapid interconversion between the keto and enol forms. Configurations of the enol form are discussed.
A Study on the Anode Effect in KF-2HF System. II. Difference in Anodic Behavior between Edge Plane and Layer-plane of Pyrolytic Graphite
Authors: Imoto Hiroki , Watanabe Nobuatsu
Published: July 2006

The anodic behavior of pyrolytic graphite has been studied by voltammetry and ESCA analysis in the molten KF-2HF system at 100°C, attention being given to the difference in anodic behavior between the edge plane and layer-plane of the pyrolytic graphite. The polarization current obtained by a linear potential sweep experiment decreased rapidly with increasing potential after the onset of the anode effect. When the edge plane was used as a working electrode surface the current density was recovered on the subsequent sweep toward negative potentials, whereas the current density was hardly recovered on the layer-plane surface of the electrode. The difference in polarization behavior was interpreted on the basis of the difference in the rate of decomposition reaction of graphite fluoride, (CF)n, formed on the electrode surface. ESCA spectra of the electrodes polarized at various potentials indicate that (CF)n was formed even at 2.0 V vs. Pt, below the fluorine evolution potential, on the edge plane of the pyrolytic graphite and that its amount did not increase appreciably with increasing potential. On the layer-plane, however, no formation of (CF)n was observed at 2 V vs. Pt, its amount increasing appreciably with potential at the potentials above 3 V vs. Pt.