bluuebunny/crossref_metadata_2025 huggingface dataset:
Molecular Orbital Study on the H2O–HCl System
Authors: Shibata Shuzo , Hirota Fumihiko , Ota Yukio
Published: July 2006

The hydrogen bonded system of H2O–HCl was studied by the CNDO/2 method. Calculation of the potential energy for the system showed that the complex of H2O–HCl is considerably stable. The equilibrium structure of the complex and its charge distribution were also investigated.
The Solvent Extraction of the Copper–Pyrocatechol Violet Chelate with Tridodecylethylammonium Bromide
Authors: Shijo Yoshio
Published: July 2006

The solvent extraction of the copper–Pyrocatechol Violet chelate with tridodecylethylammonium bromide (abbreviated TDEA) in benzene as an ion-association system has been investigated by the spectrophotometric method. The copper–PV–TDEA complex can be extracted into such aromatic hydrocarbons as benzene, toluene, and xylene, but not into such polar solvents as n-butanol, ethyl acetate, methylisobutylketone, and nitrobenzene. When a sample solution containing copper and PV, the pH of which has been adjusted to 7.5–8.5, is shaken with TDEA in benzene for 10 s, the maximum extraction of the ternary complex is obtained. The extractability of the complex from 50 ml of an aqueous solution into 10 ml of benzene is 98.3% under the optimum conditions. The absorbance and stability of the complex increase upon the addition of a small amount of ethanol to the extracted layer. Beer’s law is obeyed up to 6.5 μg copper per 10 ml of benzene, and the molar absorptivity of the complex is 7.9×104 cm−1·mol−1·l at 663 nm. The composition of the complex is confirmed to be Cu:PV: TDEA=1: 2: 2 by the continuous variation method. A structure for the complex is proposed.
The Novel Synthesis of l-Hydroxyproline from d-Glutamic Acid
Authors: Eguchi Chikahiko , Kakuta Akio
Published: July 2006

l-Hydroxyproline (1) and d-allo-hydroxyproline (2) were synthesized from d-glutamic acid (3) using the asymmetric center of 3 as that at C4 of 4-hydroxyproline. When the aqueous solution of 1 or 2 was heated at 200 °C for 2 hr, a solution in the equilibrium state, containing 55% of 1 and 45% of 2, was obtained. From this mixture, 1 was obtained by fractional crystallization.
Oxidation by Iron(III) Complexes. VIII. The Reactions of Iron(III) Chloride with Toluene and Substituted Toluenes
Authors: Inoue Hiroo , Izumi Megumu , Imoto Eiji
Published: July 2006

The thermal and photochemical reactions of toluene with anhydrous iron(III) chloride in the solid state result in nuclear chlorination. In a homogeneous system, a side-chain reaction occurs under irradiation with light, although no product is obtained in the thermal reaction. The addition of water to the iron(III) chloride–toluene system in the range of the molar ratio of 1–5 changes the course of the photochemical reaction; in the water/iron(III) chloride molar ratios of 1–1.7, 3, and 4–5, the main products are the diphenylmethane-type compound, o- or p-chlorotoluene (o>p), and benzyl chloride respectively. Pyridine as a ligand acts to give benzyl chloride selectively. The Mössbauer data of the FeCl3/nH2O solid show that the arrangement of the Cl− ion around the Fe(III) ion changes upon the addition of water. The thermal and photochemical reactions of p-methoxytoluene with anhydrous iron(III) chloride give 2,2′-dimethoxy-4,4′-dimethylbiphenyl by oxidative aryl coupling. Water inhibits the aryl coupling reaction.
Reaction of 2-BenzoyIamino-2-methylpropionamidine and 2-Benzoylaminoacetamidine with Bifunctional Compounds
Authors: Uchida Hiroaki , Chinone Akiko , Ohta Masaki
Published: July 2006

The reaction of 2-benzoylamino-2-methylpropionamidine (III) with 1,3-bifunctional compounds was investigated in connection with studies on 2-benzoylaminoacetamidine(I). In case of the reaction of III an appreciable amount of 5,5-dimethyl-2-phenylimidazolin-4-imide (VIII) was formed, the yield of 2-(1-benzoylamino-1-methylethyl)-4,6-dimethylpyrimidine (VI) being low. On the other hand, III reacted with ethyl acetoacetate to give 2-(1-benzoylamino-1-methylethyl)-4-hydroxy-6-methylpyrimidine (IX) in about 50% yield besides VIII. Both III and I were made to react with ethoxymethyleneacetylacetone to yield 5-acetyl-2-(1-benzoylamino-1-methylethyl)-4-methylpyrimidine (X) and 5-acetyl-2-(N-benzoylaminomethyl)-4-methylpyrimidine (XI), respectively. Reaction of I with ethoxymethylenemalononitrile gave 4-amino-2-(N-benzoylaminomethyl)-5-cyanopyrimidine (XII), but did not proceed with benzoin, malondialdehyde, tetraethoxypropane or phenacyl bromide.
Studies of the Equilibria between Tetraarylallyl-type Radicals and Their Dimers
Authors: Watanabe Kohji , Yamaughi Jun , Ohya-Nishiguchi Hiroaki , Deguchi Yasuo
Published: July 2006

Tetraarylallyl-type radicals are stable radicals. In these series, TPA is obtained as radical crystals. However, BDA, BDAA and DDA are obtained as diamagnetic dimerized substances. These are partially dissociated in solution. These can be detected in solution by ESR and optical spectra measurements of these radicals about the equilibrium between the radical monomer and its dimer. The equilibrium constants and the energy of the formation of the dimer are thus determined. The order of the magnitudes of the dimer’s formation energies can be explained in terms of the frontier electron densities of the bond-forming positions of radicals.
The Fractionation of Tritiated Water in an Equilibrium between Organic Hydrates and Their Aqueous Solutions
Authors: Tanaka Haruhiko , Kado Tsutomu , Negita Hisao
Published: July 2006

The fractionation of the tritiated water (HTO) was examined during the crystallization of hydrates, such as (COOH)2·2H2O, (COOK)2·H2O, Cu(HCOO)2·4H2O, and Sr(HCOO)2·2H2O. The dilution of HTO in the organic salts was found to be comparable to that in inorganic salts observed previously. The fractionation of HTO was explained on the basis of an ionic process in an aqueous solution, and the crystal growth mechanism, in a way similar to that described in a previous paper. On the contrary, a considerable dilution was observed for oxalic acid dihydrate. The proton effect on the fractionation in both the ionic and dehydration processes was also discussed.
The Kinetics and Mechanisms of the Reactions of Nitric and Nitrous Acids with Hexaaquochromium(II) Ions
Authors: Ogino Hiroshi , Tsukahara Keiichi , Tanaka Nobuyuki
Published: July 2006

Stoichiometric and kinetic investigations of reactions of the nitric and nitrous acids with hexaaquochromium(II) ions have been carried out in acidic media. The stoichiometries of these reactions found in this work were consistent with the mechanisms proposed by Swaddle,1) in which one mole of nitric acid reacts with four moles of chromium(II) and one mole of nitrous acid reacts with two moles of chromium(II). For the former reaction, it was found that the two-electron reduction of nitric acid by chromium(II) is rate-determining and that the rate constant was 2.2×102 M−1 s−1 at 25 °C and at an ionic strength of 1.0 (NaClO4). For the latter reaction, it was found that the one-electron reduction of nitrous acid by chromium(II) is rate-determining and that the rate constant was 4.5×10−3 M−1 s−1 at 25 °C and at an ionic strength of 1.0 (NaClO4). The rates of the reactions of chromium(II) with anionic species of the parent acids, NO3− and NO2−, were too slow to be detected under the present experimental conditions.
Fundamental Studies on Palladium Catalysts. IX. Characteristics of Hydrogen Sorption and Hydrogenation Activity of Supported Palladium Catalysts
Authors: Yamabe Tsunekichi , Shirono Katsuhiro , Uehara Masaru , Suzuki Sadao
Published: July 2006

The sorption of hydrogen and the hydrogenation of ethylene on palladium/silica–alumina catalysts with palladium contents of 0.58–4.5 wt% were investigated. It was found that Vx (the amount of molecularly-adsorbed hydrogen) and Vz (that of dissociatively-adsorbed hydrogen) increase, while Vy (that of dissolved hydrogen) decreases, with the increase in the specific surface area of palladium, and that the saturated value of Vz is proportional to the amount of chemisorbed carbon monoxide. It was also shown that the increase in the palladium content results in a growth of the palladium crystallites, their number staying approximately constant. The rate of ethylene hydrogenation was found to be first-order with respect to hydrogen and zero-order with respect to ethylene over the temperature range of −20–20 °C. The activity was proportional to the surface area of palladium, and the activation energy was almost constant for these catalysts.
Polymerization of Vinyl Compounds with Hydridodinitrogentris(triphenylphosphine)cobalt(I)
Authors: Kubo Yoichiro , Yamamoto Akio , Ikeda Sakuji
Published: July 2006

The kinetics of polymerization of vinyl compounds (acrylonitrile, methacrylonitrile, and methyl methacrylate) with hydridodinitrogentris(triphenylphosphine) cobalt(I), CoH(N2)(PPh3)3  1 (PPh3: triphenylphosphine) was studied. By comparison with previous studies on the decomposition of 1 in the presence of vinyl compound a polymerization mechanism involving slow initiation followed by rapid propagation and unimolecular termination was proposed. The effects of concentration of monomer and of added triphenylphosphine on the molecular weight of the polymer were studied. The result of copolymerization was explained by the competitive coordination between the monomers involved. Poly(methyl methacrylate)s obtained by 1 in bulk and the solvent were all rich syndiotactic fraction.
Organic Charge Transfer Salts. II. Emission Spectrum of an Organic Charge Transfer Salt, 2,4,6-Triphenylthiopyrylium–1,1,3,3-tetracyanopropenide
Authors: Tamamura Toshiaki , Yokoyama Masaaki , Kusabayashi Shigekazu , Mikawa Hiroshi
Published: July 2006

The emission spectrum of an organic charge transfer salt, 2,4,6-triphenylthiopyrylium–1,1,3,3-tetracyanopropenide, was studied in solutions of various solvents as well as in the solid state. A charge transfer fluorescence was observed both in the solid state and in non-polar rigid solution at 77 K, but not in fluid solution. In rigid solution, as the polarity of solvent increases, the charge transfer fluorescence shows a blue shift of its maximum wavelength and a remarkable decrease in intensity, the phosphorescence of a dissociated cation appearing predominantly. The strong dependence of the emission spectrum on the solvent polarity was explained in terms of the dissociation of the salt and the insufficient reorientation of solvent molecules around the salt in the excited charge transfer state.
Autoxidation of Aromatic Hydrocarbons Catalyzed with Cobaltic Acetate in Acetic Acid Solution. III. Oxidation of p-Toluic Acid
Authors: Kashima Mikito , Kamiya Yoshio
Published: July 2006

The oxidation of p-toluic acid catalyzed with cobaltic acetate was studied kinetically in acetic acid. The maximum absorption rate of oxygen was obtained in the initial stage of reaction, being represented by the same equation as in the case of toluene, ethylbenzene and cumene. That is, the kinetic equation is of first order with respect to the initial concentration of p-toluic acid, of second order with respect to the initial concentration of Co(III), and of inverse first order with respect to the initial concentration of Co(II). The relative reactivity of p-toluic acid per active hydrogen was lower than that of toluene, but higher than that of ethylbenzene and cumene. The apparent chain-length in the oxidation of p-toluic acid was much shorter than that of p-xylene oxidation.
Charge Transfer Complexes and Self-association of Flavin Adenine Dinucleotide
Authors: Takahashi Fujio , Maeda Hirotoshi
Published: July 2006

Spectrophotometric studies on the formation of FAD-l-tryptophane and FAD-d-tryptophane complexes, and the optical rotatory and polarographic studies of FAD have been carried out. The steric influence of ribosyl and ribityl groups on FAD for the complex formation is discussed. The dimerization of FAD in solution is suggested.
Carbonylation of Phenylacetylene by Rhodium Carbonyl Chloride
Authors: Kiji Jitsuo , Yoshikawa Susumu , Furukawa Junji
Published: July 2006

The reaction of phenylacetylene with carbon monoxide catalyzed by rhodium carbonyl chloride (Rh2(CO)4Cl2) gives 3,6 diphenyl-1-oxa-[3,3,0] bicycloocta-3,6-diene-2,4-dione.
The Decomposition of Organic Substances by Laser Heating
Authors: Kim Pil Hyon , Namba Susumu , Taki Ko
Published: July 2006

Gaseous organic substances were decomposed by the laser heating of various solid targets (boiling points are different) which were placed in them. This method gives the products which have never been obtained by means of the conventional heat decomposition.
The Pyrolysis of Hexyl Phosphates and Their Salts
Authors: Okamoto Yoshiki , Kimura Norio , Sakurai Hiroshi
Published: July 2006

The isomer distribution of hexene from the tri-n-hexyl phosphate changes gradually as the decomposition proceeded. However the formation of the isomers other than 1-hexene was appreciably depressed by the addition of anhydrous disodium hydrogen phosphate.
Catalytic Activities of Salicylaldehyde Derivatives. IV. A Synthesis of 2-Formyl-3-hydroxyphenyltrimethylammonium Chloride
Authors: Ando Makoto , Emoto Sakae
Published: July 2006

4-Ethoxy- 1,3-benzodioxan-5-yltrimethylammonium salt, prepared from 4-ethoxy-5-nitro-1,3-benzodioxane via 5-dimethylamino-4-ethoxy-1,3-benzodioxane, was hydrolyzed to obtain 2-formyl-3-hydroxyphenyltrimethylammonium chloride in a good yield.
The Reaction of Styryl Sulfoxides or Sulfones with Boranes
Authors: Miyamoto Norioki , Fukuoka Daisuke , Utimoto Kiitiro , Nozaki Hitosi
Published: July 2006

The title reaction produces β-alkylated styrene 3 in preparative yields. The formation of trans  3 from the cis sulfoxide 2 or the sulfone 7 is explained by considering the vinylic radical 8 as the intermediate.
MO Calculation for Interactions of Cu(II) and Co(III) with Hydroperoxides
Authors: Imamura Sei-ichiro , Sakaki Shigeyoshi
Published: July 2006

By means of MO calculation, cobalt(III) and copper(II) were considered to decompose primary and secondary hydroperoxides through the oxidative fission of their O–H bond. However, in basic solvents such as pyridine, copper (II) was found to promote the fission of their C–H bond of the α-position by the complex formation with them.
The Thermal Decomposition of Formaldehyde in the Presence of Nitric Oxide
Authors: Tadasa Kohji , Imai Naomi , Inaba Tetsuo
Published: July 2006

The pyrolysis of formaldehyde was investigated in the presence of nitric oxide at 500 °C. The kinetics of the reaction suggests that the pyrolysis proceeds by means of a mechanism which is initiated by this reaction:

NO+CH_2O→HNO+CHO

and which involves this reaction:

HNO+HNO→N_2+2OH

as one of the chain-carrying steps.
Partially-occupied d-Orbitals Participating in the Activation of Molecular Oxygen
Authors: Ohkubo Katsutoshi
Published: July 2006

UV spectroscopic and semiempirical SCFMO investigations have been performed on the partially-occupied (formally unoccupied) d-orbitals participating in the activation of the ground state, 3Σg–O2, with special attention being given to the catalytic activities of onium compounds. The order of the red shifts of the (pz)2→(pz)(d) transition of the onium compounds in an oxygen atmosphere is in satisfactory accordance with those of the magnitude, of the partial occupancy of the d-orbitals and of the catalytic activities of the onium compounds in hydrocarbon oxidations. The dxz (or dyz) and dx2–y2 orbitals are most favorably disposed for the interactions between the Group VI and V onium compounds and the (1πg)-orbital of the 3Σg–O2 respectively. The partial occupation of the formally unoccupied d-orbitals results from the d-π delocalization between the onium central atom and the neighboring atoms of substituents and the counter-anion.
Studies on the Mechanism of Methanol Oxidation on Zinc Oxide by Dynamic Treatments of Chemisorbed Species under the Reaction Conditions
Authors: Herd A C , Onishi Takaharu , Tamaru Kenzi
Published: July 2006

The mechanism of methanol oxidation on zinc oxide was studied by quantitatively observing the dynamic behaviour of the surface species during the course of the reaction. It was concluded that the mechanism was similar to that of the decomposition reaction, with an additional step, the oxidation of the carbon monoxide formed. As a key step in the oxidation of methanol, the decomposition of adsorbed methoxide groups in the presence of oxygen at temperatures between 140 and 180 °C has been studied by infrared spectroscopy. The methoxide groups decompose to formate ions until a maximum surface concentration is reached. The rate of decomposition at first increases with methoxide concentration, then decreases as the surface coverage approaches saturation. The observed kinetics can be explained by a mechanism which postulates that negatively charged surface species repel electrons from the surface of the zinc oxide, thus inhibiting decomposition of the methoxide groups.
Radical Addition Reactions to the Carbonyl Group. I. The Reaction of Aliphatic Aldehydes with Di-t-butyl Peroxide
Authors: Maruyama Kazuhiro , Taniuchi Mamoru , Oka Shinzaburo
Published: July 2006

The thermal decomposition of di-t-butyl peroxide in aliphatic aldehydes has been carefully examined. n-Aldehydes and β-substituted aldehyde gave appreciable amounts of sec-alcohols in the reactions, sec-Alcohol arose from the addition of the alkyl radical to the carbonyl group of aldehyde. α-Substituted aldehydes, however, did not give sec-alcohol, but instead gave considerable amounts of enol ether-aldehydes and dialdehydes. The addition of the alkyl radical to the carbonyl group and the decarbonylation of aldehydes were influenced remarkably by the structures of the aldehydes.
The Unsensitized Photooxidation of (+)-Limonene, 1,2-Dimethylcyclohexene, and endo-Dicyclopentadiene
Authors: Sato Tadashi , Murayama Eigoro
Published: July 2006

The unsensitized photooxidation of (+)-lmionene (1), 1,2-dimethylcyclohexene (2) and endo-dicyclopentadiene (3) were carried out with Pyrex-filtered light. The singlet-oxygen oxidation was found to occur concurrently with the radical oxidation to the extent of 41% with 1 and 66% with 2, but not at all with 3. A reaction path via a complex was proposed.
A New Reagent for the Syntheses of N-Monoalkylated Hydroxylamines; N-Tosyl-O-2,4,6-trimethylbenzylhydroxylamine
Authors: Isowa Yoshikazu , Kurita Hideaki
Published: July 2006

The reactions of N-tosyl-O-2,4,6-trimethylbenzylhydroxylamine with primary alkyl halides yielded the protected hydroxylamines. The simultaneous cleavage of N-tosyl- and O-2,4,6-trimethylbenzyl groups with hydrogen bromide in acetic acid gave the corresponding N-monoalkylated hydroxylamines such as N-benzylhydroxylamine, 1-amino-3-hydroxyaminopropane and Dl-3-hydroxyamino-2-aminopropionic acid.
Stable Crystalline Complexes of Diphenylcyclopropenone with Substituted Acetic Acids
Authors: Agranat Israel , Cohen Shmuel
Published: July 2006

Diphenylcyclopropenone (DCP) forms 1: 1 stable crystalline complexes with dichloroacetic acid, phenylacetic acid, diphenylacetic acid, trichloroacetic acid and cyanoacetic acid. The physical properties of these complexes are consistent with a hydrogen-bonded complexation between the carbonyl oxygen of DCP and the acidic hydrogen of the substituted acetic acid.
The Extraction and Spectrophotometric Determination of Vanadium(IV) with Tiron
Authors: Wakamatsu Yoshinobu , Otomo Makoto
Published: July 2006

The vanadium(IV)-Tiron chelate can be extracted into a mixed solvent of 1 : 4 isopentyl alcoholchloroform in the presence of 1,3-diphenylguanidinium salt. Beer’s law was obeyed up to 36 μg vanadium per 10 ml of the solvent.
Notiz über neue \overset+S–\overset−N–Ylid-Komplexe von Platin(II)
Authors: Matsubayashi Gen-etsu , Toriuchi Masaharu , Tanaka Toshio
Published: July 2006

The reaction of (CH3)2SNC(O)R (R=C6H5, C6H4CH3-P)(Y) with K2PtCl4 in water gives a stable ylide complex, PtCl2(Y)(DMSO), in which Y coordinates to the Pt(II) via nitrogen and DMSO via the sulfur to form a cis-configuration.
Micellar Effect of Lauryldimethylsulfonium Halides on the Hydrolysis of p-Nitrophenyl Decanoate
Authors: Okonogi Tsuneo , Yano Yumihiko , Tagaki Waichiro
Published: July 2006

Micellar effects of lauryldimethylsulfonium chloride, bromide, and iodide on the hydrolysis of p-nitrophenyldecanoate were found to be very similar to those of the corresponding lauryltrimethylammonium halides.
The Induced Optical Rotatory Dispersion of Mercury Orange-Phosphoenolpyruvate Carboxylase
Authors: Miyamura Masataka , Suzuki Shuichi
Published: July 2006

On reacting with a SH group, the mercury orange enzyme formed, showed a positive Cotton effect near 500 nm, and the optical activity of which was remarkably induced by adding ADP or PEP. It seemed that ADP or PEP might move to the vicinity of the active amino acid residues.
A Study on Phosphorylation by Means of 8-Quinolyl Phosphates
Authors: Takaku Hiroshi , Shimada Yoshifusa , Arai Kenichi
Published: July 2006

Phosphorylation of phosphates and nucleosides forming unsymmetrical pyrophosphates and nucleotides by the use of 8-quinolyl phosphates has been investigated. According to this method, various pyrophosphates and nucleotides were obtained in high yields.
The Use of Hydroxybenzoic Acids to Polymers. II. Polyether-amides Obtained from the Interfacial Polycondensation of p-Carboxyphenoxyacetic Acid Dichloride with Aliphatic Diamines
Authors: Hirao Ichiro , Kito Taketoshi , Fujimoto Tsutomu , Yoshihara Hideo
Published: July 2006

Five polyether-amides were prepared from the title reaction. The physical properties ([η], Tm  Tg, and decomp. temp.) and the effects of the reaction conditions were examined. These polymers were superior in some physical properties to the polymers obtained from the melt polycondensation.
The Preparation of 2,2-Bis(trifluoromethyl)-1,3-heterocycles from 2,2,4,4-Tetrakis(trifluoromethyl)-1,3-dithietane
Authors: Kitazume Tomoya , Ishikawa Nobuo
Published: July 2006

2,2-Bis(trifluoromethyl)-1,3-heterocyclic compounds, 3, 4, 6, 7, and 8, were prepared by the reaction of 2,2,4,4-tetrakis(trifluoromethyl)-1,3-dithietane (1) with bifunctional compounds such as amino alcohols, o-aminophenol, o-aminothiophenol and o-phenylenediamine.
Die Kinetische Racemat-Spaltung des 1-Phenyläthanols und 1-Phenyläthylamins durch die aktivierten N-Tosyl-l-prolin-ester
Authors: Sakan Takeo , Mori Yutaka , Yamazaki Tomio , Yamashita Tetsushi , Nakamura Nobuo
Published: July 2006

Die optische Ausbeute von 10–50% wird erzielt. Einander entgegengesetztes Reaktionsverhalten zeigen die Magnesiumbromide des 1-Phenylathanols und des 1-Phenylathylamins bei der Umsetzung mit den Reagenzien.
SORPTION OF AMMONIA BY CHARCOAL
Authors: Sameshima Jitsusaburo
Published: July 2006

1. The sorption velocity of ammonia by sugar charcoal has been measured, extending over six months.

2. It was known that the charcoal absorbs ammonia for a very long time, taking more than several months to arrive at the equilibrium condition.

3. The sorption velocity from one hour forward can be expressed by an equation.

x=Klogt+k.

where x is the sorption amount, t the time, and K and k are the constants.

4. The mechanisms of sorption have been discussed.

5. The sorption velocity depends upon the dissolution velocity of ammonia molecules into the narrow molecular cavities of charcoal.
ON THE TRUE NATURE OF “PER-ACIDS” AND THE ALLEGED “ACID NUCLEUS THEORY”
Authors: Hakomori Shin’ichirô
Published: July 2006

1. Starting from three postulates, the presence of “Acid nuleus” has been considered and a new idea “Induction valence” also introduced.

2. That “Oxy-acids” and “Per-acids” are nothing but “Acid nuclei” combined with water or hydrogen peroxide by means of “Induction valence” has been rendered clear.
A NOTE ON NEGATIVE INDUCED REACTIONS
Authors: Miyamoto Susumu
Published: July 2006

(1) The possibility of the existence of negative induced reactions are described with examples, studied by the author.

(2) The definition of the terms actor, inhibitor and acceptor are given in the case of negative induced reactions.

(3) Corresponding to the term induction factor, the term inhibition factor was introduced in the case of negative induced reactions, although its value was not yet calculated in the actual cases.

(4) A classification of negative induced reactions was proposed. The classification will be unable to be confirmed thoroughly by experimental facts, as the examples of negative induced reactions are very few.
C2− Ion as Impurity from Halogen Ion Source and a Possibility of Its Application to Reaction Kinetics Studies
Authors: Kashihira Nobuyuki , Vietzke Egon
Published: July 2006

Negative ions from a hot LaB6 surface were studied with a quadrupole mass filter. C2− ion was formed via a charge exchange process. About 10−11 A of mass-selected C2− ion current was obtained above 40 eV of ion energies. A possibility of employing this to study a reaction kinetics is discussed.
ESR Studies of a New Stable π-Conjugated Bisaryloxyl Biradical
Authors: Mukai Kazuo , Hara Tsukasa , Ishizu Kazuhiko
Published: July 2006

The new stable π-conjugated bisaryloxyl biradical, 4,4′-(m-phenylene)bis(2,6-di-t-butylphenoxyl), was prepared, and the g- and D-tensor values of the biradical were determined from an analysis of an asymmetric ESR spectrum of a frozen solution containing the biradical. A resolved hyperfine structure was observed in the ESR spectrum of a liquid solution of the biradical, giving the hyperfine splitting values theoretically expected for the triplet state of the biradical.
Crystal and Molecular Structure of Bis(1-diphenylphosphinothioyl-3-methylthioureato)nickel(II)
Authors: Iwamoto Toschitake , Ebina Fujio , Nakazawa Hiroshi , Nakatsuka Chiaki
Published: July 2006

The title compound [Ni{(C6H5)2PSNCS-NHCH3}2] was found to crystallize in the monoclinic space group C2/c with a=23.29(1), b=9.457(2), c=16.40(1) Å, β=121.33(8)°, Z=4. The six-membered chelate ring built of five kinds of atoms, Ni, 2S, P, N, and C, was demonstrated.
Diffusion Coefficients of Thallium(I) and Cadmium(II) Ions in Aqueous Nitrate Solutions Determined Chronoamperometrically with a Thin-walled Hanging Mercury Drop Electrode
Authors: Ikeuchi Haruko , Iwai Kyoichi , Kaneko Mamoru , Maya Muneo , Satô Gen P
Published: July 2006

The diffusion coefficients (D) of Tl+ in 0.1 and 0.5 mol dm−3 KNO3 and of Cd2+ in 1.0 mol dm−3 KNO3 in the temperature range 5 °C–35 °C are given with additional data including activation energies. kT/Dη, where η is the viscosity of the nitrate solution, depends primarily on the diffusing species.
2-Alkylation Reactions of Thiophene and 1-Methylpyrrole with Trialkylboranes
Authors: Sotoyama Toshiki , Hara Shoji , Suzuki Akira
Published: July 2006

The reactions of iodine with ate-complexes prepared from trialkylboranes and 2-thienyllithium or 1-methyl-2-pyrrolyllithium were found to give the corresponding 2-alkylthiophenes or 1-methyl-2-alkylpyrroles, respectively, in good yields.
Synthesis of Disubstituted Benzoquinones by the Photochemical Reaction of Acetylenes with Fe(CO)5
Authors: Maruyama Kazuhiro , Shio Toru , Yamamoto Yoshinori
Published: July 2006

Internal acetylenes substituted with alkyl groups and terminal acetylenes substituted with alkyl, aryl, and functionallized alkyl groups are converted to disubstituted quinones by the photochemical reaction with Fe(CO)5 followed by treatment with Ce(IV).
The Solvent Extraction of Several Univalent Metal Picrates by 15-Crown-5 and 18-Crown-6
Authors: Takeda Yasuyuki , Got\={o} Hiroshi
Published: July 2006

The overall extraction equilibrium constants (Kex) for 1:1:1 complexes of 15-crown-5 (15C5) and 18-crown-6 (18C6) with several univalent metal picrates between benzene and water have been determined at 25 °C. The Kex sequences of the univalent metal ion with 15C5 and 18C6 are Ag+>Na+>Tl+>>K+>Rb+>Cs+>Li+ and Tl+>K+>Rb+>Ag+>Cs+>Na+>>Li+ respectively. The Kex series for each same crown ether reflects the stability and the extractability of the univalent metal ion-crown ether complex in the aqueous phase. The Kex sequences for the 15C5 system depends entirely on the extractability of the univalent metal ion-crown ether complex. In the case of the 18C6 system this largely depends on the stability of the univalent metal ion-crown ether complex.
Kinetic Studies for the Acyloxy Exchange Reactions of Acyloxytrimethylsilanes with Carboxylic Acids
Authors: Kozuka Seizi , Kitamura Takuro , Kobayashi Noboru , Ogino Kenji
Published: July 2006

The acyloxy exchange reactions of acyloxysilane with carboxylic acids have been studied kinetically. The rate of reaction has been found to proceed faster with a stronger attacking acid and more basic leaving acyloxy group. The rate was markedly accelerated by the addition of base. The steric effect due to substituents on the silicon atom and hydrogen-deuterium kinetic isotope effects have been examined. A mechanism involving the 5-coordination of the silicon atom prior to the rate-determining proton transfer has been suggested.
Carbon-13 NMR Spectra of Stereoisomeric Substituted 2-Methylcyclo-hexanols and Their Acetates: A Comparison of the Observed and Predicted Chemical Shifts
Authors: Senda Yasuhisa , Ishiyama Jun-ichi , Imaizumi Shin
Published: July 2006

The 13C NMR spectra of stereoisomeric 4-t-butyl-2-methylcyclohexanols, 5-t-butyl-2-methylcyclohexanols, 2-methylcyclohexanols, and their acetates were measured. The observed chemical shifts were compared with the values estimated by using the substituent parameters of methyl, t-butyl, and hydroxyl groups. An appreciable deviation by vicinal substitution was found between the predicted and observed chemical shifts of C-1 and C-2. The substituent parameters of the acetoxyl group on the cyclohexane ring were estimated by means of a comparison of the chemical shifts of cis- and trans-4-t-butylcyclohexyl acetate, and those of t-butylcyclohexane.
Surface Activity of Complex in Mixed Surfactant Solution
Authors: Tajima Kazuo , Nakamura Akio , Tsutsui Takao
Published: July 2006

The dissociation constant of the complex formed in the mixed and very dilute surfactant solution of 3-(dodecylammonio)-propionate (NDA) and sodium alkylsulfates (C10, C12, C14) (SAS) was determined by measuring surface tension and adsorbed amounts of the solution. The composition in the surface and bulk phases did not coincide at the equimolar mixture. The adsorbed monolayer on the solution consists of the coadsorption of NDA–SAS complex (1:1) and free NDA, while the adsorption of free SAS was almost zero in various concentrations studied. Under these conditions the surface activity of the complex alone was obtained. The relationship between the surface activity and bulk concentration for each mixed solution was discussed in terms of relative adsorbability. The surface activity of the complex was one order of magnitude higher than that of NDA and two orders higher than that of SAS.
Vibrational Spectra and Normal Coordinate Analysis of N-Methyl Thiourea
Authors: Dwarakanath K , Sathyanarayana D N
Published: July 2006

The infrared spectra of N-methylthiourea (NMTU) and its N-deuterated and S-methylated species were measured. Assignment of the infrared and Raman spectra of NMTU has been accomplished by correlation with thiourea and by use of infrared band shifts on N-deuteration as well as S-methylation. Normal coordinate analysis was performed for all the fundamentals of NMTU and NMTU-d3, the assignments obtained from the force field calculations being discussed in relation to those in other related thioureas and thioamides. The potential barriers to the internal rotations for the –NH2, –CH3, and –CN groups were estimated from the force constants.
Infrared Studies on Water Adsorption Systems with the Use of HDO.II. Na-Y Zeolite
Authors: Hino Masao , Mikami Yasuko
Published: July 2006

Infrared spectra of the systems of Na-Y zeolite–H2O, D2O, and HDO were measured. It was shown that there are three types of adsorbed water in the zeolite-water system. Type I: adsorbed in a state in which two hydroxyl bonds are highly non-equivalent; it gives absorptions at 3695, 3400, and 1645 cm−1, and is the same type as that on the Molecular sieve 13X. Type II: adsorbed in another state in which the bonds are nearly equivalent; it gives bands at 3610, 3540, and 1645 cm−1. Type II was more resistant to dehydration than Type I, and was irreversible for the back-adsorption of a small amount of water at room temperature, whereas Type I was almost completely reversible. Type III was observed for back-adsorption under this condition; it gives bands at 3635, 3500, and 1655 cm−1. Type III can be transformed into Type II by heat treatment at a temperature which varies depending on the amount of adsorbed water. The other bands were assigned as follows: Bands at 3750 and 3645 cm−1 correspond to stretching of surface structural OH, and that at 3240 cm−1 to overtone deformation of adsorbed water. The sites of adsorbed water molecules of Types I and II were discussed.
The Performance Characteristics of a Permeation Membrane Device for the Preparation of Dilute Standard Gas Mixtures
Authors: Ibusuki Takashi , Toyokawa Fumitoshi , Imagami Kazunari
Published: July 2006

The performance chracteristics of the permeation membrane device for the preparation of dilute standard gas mixtures developed by us was investigated in detail from the practical standpoint. By selecting a siliconerubber and a TFE Teflon for CO or CH4, and NO or SO2, respectively, the steady permeation state was rapidly attained. The small quantities of the gases permeating through the membranes were precisely determined within a relative standard deviation of 1% based on a pressure-differential method. It was confirmed that the permeation rates were reproducible after repeated membrane-temperature, gas-pressure, and gas-cycle changes during an experimental period of more than five months. By changing the gas pressure and the membrane temperature, and by introducing 1–2 1 min−1 of a diluent gas, N2 or air, standard gas mixtures containing 0.5–10 ppm of CO or CH4 and 0.05–0.7 ppm of NO or SO2 were easily obtained. The standard gases concerning CO, CH4, and NO were compared with those in cylinders prepared by the weighing method, and for SO2 the concentration of the gas was checked by the West-Gaeke method. A good agreement in concentration was observed for CO, CH4, and SO2; the discrepancy found for NO was explained in terms of the decrease in the NO concentration in the cylinder.
A Theoretical Interpretation of the Half-wave Reduction Potentials of Chloronitrobenzenes
Authors: Yamabe Shinichi , Minato Tsutomu , Arai Toshio
Published: July 2006

The half-wave reduction potential of chloronitrobenzenes has been studied with ab initio MO calculations. The relation between the energy of the lowest unoccupied MO and the reduction potential is given.
Vibrational Spectra and Rotational Isomerism of Isopropyl Methyl Selenide and Diisopropyl Selenide
Authors: Ohno Keiichi , Mitsui Akitoshi , Murata Hiromu
Published: July 2006

The infrared and Raman spectra of isopropyl methyl selenide and diisopropyl selenide were measured for the liquid and solid states. The fundamental vibrations were assigned and the rotational isomerism was studied on the basis of the spectral observations and the normal coordinate treatment. For isopropyl methyl selenide, the C1 and Cs forms coexisted in the liquid state and the enthalpy difference between them was obtained as ΔH(C2–Cs)=−0.52×0.05 kcal mol−1. For diisopropyl selenide, it was presumed that only the C2 form persisted in the solid state while the C2, Cs, and C1 forms coexisted in the liquid state, the C2 form being the most stable.
Deuterium Tracer Study on Isomerization of Cyclopropane over Thorium Sulfate
Authors: Imizu Yuzo , Hattori Hideshi , Tanabe Kozo , Kondo Toshihiko
Published: July 2006

Mechanistic study on the isomerization of cyclopropane into propene was made over Th(SO4)2 catalyst. With a fresh catalyst, an induction period was observed, disappearing in successive runs. Coisomerization of cyclopropane d0/d6 reveals that the reaction involves an intermolecular H(or D) transfer. Nearly random location of the H(or D) atom in the mono-exchanged propene-d1, and -d5 indicates that the isomerization proceeds via nonclassical carbonium ion in which seven hydrogen atoms are equivalent.
Determination of Heats of Adsorption of Triphenylchloromethane from Its Hexane Solution onto Dehydrated Silica–Alumina Surface
Authors: Taniguchi Hitofumi , Masuda Tatsuo , Tsutsumi Kazuo , Takahashi Hiroshi
Published: July 2006

Heats of adsorption of gaseous triphenylchloromethane (TPC) onto silica–alumina surface were determined from the heat evolved with the immersion of silica–alumina into TPC–hexane solution. The heat of dissolution and the heat of sublimation of TPC and the heat of immersion of the sample into hexane were considered for their determination. It became clear that TPC molecules interacted with silica–alumina surface in two manners. The one was observed in smaller adsorbed amount (below 45 μmol/g), and the other in adsorbed amount from 45 to 100 μmol/g. The former could be attributed to the interaction between TPC and Lewis or oxidizing sites and the latter to the attractive interaction between the adsorbed molecules. The adsorbed amount in the first stage (4.7×1012 molecules/cm2) agreed closely with the number of Lewis acid sites (5.0×1012 sites/cm2) measured by Leftin and Hall.
Stability of Multi-center Bonds in Inorganic Cluster Compounds
Authors: Aihara Jun-ichi
Published: July 2006

An ideal multi-center bond is a bond in which three or more atomic orbitals of the same kind, each from a different atom, interact equally with each other. Since such a multi-center bond can be regarded as a cyclic conjugated system, the graph theory of aromaticity can be applied to it. It was then found that multi-center bonds are aromatically stabilized to a great extent. Most inorganic cluster compounds are polyhedral in shape. This might be rationalized by the fact that polyhedrons are favorable to a formation of a multi-center bond or the like at the core.
Solvent Effects on Raman Intensity and the Determination of Transition Hyperpolarizability Tensor Element
Authors: Fujiyama Tsunetake , Hatakeyama Haruo , Hyodo Shi-aki
Published: July 2006

Raman intensities of methyl iodide were observed in carbon tetrachloride solution at various concentrations. The observed lines were ν1, ν2, ν3, ν5, and ν6. From the observed data, the transition polarizabilities were determined for the ν1, ν2 and ν3 fundamentals of methyl iodide and the transition hyperpolarizabilities were obtained for the ν3 fundamental of methyl iodide in the form of tensor elements.
On the Critical Phenomena in the Decomposition of Hydroperoxides and in the Autoxidation of Cumene with Bis(acetylacetonato)manganese(II)
Authors: Fukuzumi Shun-ichi , Ono Yoshio
Published: July 2006

The decomposition of 1-methyl-1-phenylethyl hydroperoxide and t-butyl hydroperoxide with Mn(II)(acac)2 and the autoxidation of cumene with Mn(II)(acac)2, Mn(III)(acac)3, and MnCO3 have been studied at 323 K. In the decomposition of the hydroperoxides with Mn(II)(acac)2, the peroxyl radicals are observed only when the initial ratio of hydroperoxide to catalyst amount exceeds a certain value. The critical phenomenon is observed in the oxidation of cumene with Mn(II)(acac)2 and also with MnCO3. A scheme for the cause of the critical phenomena has been proposed.
Measurement of Ambient Nitrogen Oxides over an Extended Period of Time by Means of a Solid Absorber Technique
Authors: Yasuoka Takashi , Mitsuzawa Shunmei
Published: July 2006

A new technique using a solid substance for the absorption of nitrogen oxides in the atmosphere was developed in order to obtain an average concentration of nitrogen oxides over a period of several weeks. Nitrogen oxides is absorbed by an absorbent (alkaline earth metal peroxide), and the nitrate produced in the absorber is extracted into water to determine the amount of nitrate by the ion-selective electrode method. The concentration of atmospheric nitrogen oxides is calculated from the amount of nitrate in the extract. A quantitative relation was found between the amount of nitrogen oxides collected on the absorber and that of nitrate in the extract. Hydrogen peroxide produced by the reaction of the absorber and water did not interfere with the measurement of nitrate by the ion-selective electrode technique. Practicability of this technique was demonstrated in comparison with the automatic recording analyzer (NOx meter) with the Saltzman reagent.
Stereochemistry in the Hydrosilylation of Substituted Cyclohexanones Catalyzed by Chlorotris(triphenylphosphine)rhodium and the Silica-linked Rhodium(I) Complex
Authors: Ishiyama Jun-ichi , Senda Yasuhisa , Shinoda Isamu , Imaizumi Shin
Published: July 2006

The homogeneous and heterogeneous hydrosilylation of simple substituted cyclohexanones catalyzed by chlorotris(triphenylphosphine) rhodium, RhCl(PPh3)3, and the silica-linked rhodium (I) complex, (Remark: Graphics omitted.), was examined. The stereoselectivity exhibited by the homogeneous catalyst was found to be nearly the same as that exhibited by the heterogeneous catalyst. The silica-linked rhodium catalyst could be re-used several times without any significant loss of the catalytic activity.
Solvolysis in Carboxamides. VII. Carboxamide Solvolysis of threo-2-Aryl-1-methylpropyl Brosylates. Reactivity-Selectivity Relationships as a Mechanistic Probe
Authors: Saito Seiki , Doihara Kenji , Moriwake Toshio , Okamoto Kunio
Published: July 2006

Solvolysis of a series of threo-2-aryl-1-methylpropyl brosylates (p-MeO, p-Me, H, p-Cl, m-Cl, m-CF3, and p-NO2; 1a–g) has been carried out in four carboxamides, N-methylformamide (NMF), N-methylacetamide (NMA), N,N-dimethylformamide (DMF), and N,Ndimethylacetamide (DMA), as solvent. Fractions of ks and FkΔ pathway were determined on the basis of the upward drift from the Hammett plot of the rate constant (kt); the extra acceleration by p-MeO and p-Me substituents was assigned to the FkΔ fraction. The FkΔ⁄kt values were not in agreement with the amount of retained products (threo-acetate and threo-alcohol) obtained in NMA and DMA solvolysis of 1a–c, although they should be in line with each other on the basis of the bridged-ion theory. The C(2)-deuterated phenyl derivative (1c-2-d) was solvolyzed in NMF, NMA, and DMF to give retained carboxylates (acetate or formate). However, the isotope scrambling at C(2) and C(1) of the carboxylates is incomplete, indicating that a symmetrical ion, such as a phenyl-bridged ion, can not be the intermed be the intermediate of the carboxamide solvolysis. A good correlation of logkt for substrates (1a–g) with log(% threo-acetate% erythro-acetate) or with log (% threo-acetate% olefinic products) was found for solvent systems such as NMA, DMA, and acetic acid, indicating that the reactions of all substituted substrates can be explained by intervention of a common intermediate [R+X−], a classical tight ion-pair from which the final products are derived. Such reactivity-selectivity relationship also holds between log kt’s of 1c in a series of carboxamide and logarithms of threo-erythro ratio in acetate or formate. Through-space interaction between a face of aryl ring and carbenium ion center in the transition state is considered as a possible cause for the anomalous acceleration by the activating aryl groups.
Alkylation of Benzene with Optically Active 3-Chloro-1-butanol, 3-Chlorobutanoic Acid, and Their Esters
Authors: Nakajima Tadashi , Masuda Shinji , Nakashima Satoru , Kondo Takayuki , Nakamoto Yoshiaki , Suga Sohei
Published: July 2006

The alkylations of benzene with optically active 3-chloro-1-butanol, 3-chlorobutanoic acid and their esters in the presence of aluminium chloride gave the corresponding 3-phenyl substituted derivatives in good optical yield. All these reactions were found to proceed with inversion of configuration at the attacking carbon atom. The products were not racemized under the conditions used, while the starting materials were racemized to a considerable extent during the reaction. Taking into account of the optical purity of the starting material recovered before the completion of reaction, net stereospecificity of each reaction was calculated to be about 90% except for the case of 3-chloro-1-butanol and its acetic ester. The high degree of stereospecificity of the reaction can be interpreted by the mechanism involving cyclic intermediate formed from the alkylating reagent and aluminium chloride.
Catalytic Hydrolysis of Dinitrophenyl Sulfate by Poly(ethylenimine) Derivativest
Authors: Kunitake Toyoki , Sakamoto Tetsuo
Published: July 2006

The catalytic hydrolysis of nitrophenyl sulfates by poly(ethylenimine)(PEI) derivatives was investigated at 30 °C in aqueous buffers. PEI derivatives which were made partly hydrophobic by incorporation of higher alkyl groups include alkylated PEI’s, quaternized PEI’s, and PEI’s with imidazole and hydroxamate functions. Nitrophenyl sulfates could not be cleaved by these polymers. The catalytic hydrolysis of 2-hydroxy-5-nitrophenyl sulfate by an PEI with imidazolylmethyl and dodecyl substituents failed to proceed in spite of the contrary report by Kiefer et al. 2,4-Dinitrophenyl sulfate was cleaved fairly readily by PEI derivatives. Simple sulfate transfer was observed in the case of alkylated PEI, but the catalytic hydrolysis proceeded according to the Michaelis-Menten kinetics in the case of quaternized PEI’s. Partly quaternized PEI’s showed highest catalytic efficiencies reported to date for the hydrolysis of dinitrophenyl sulfate.
Reinvestigation of the Mechanism of the Reaction of N,N-Dimethyl-aniline N-Oxide with Acetic Anhydride
Authors: Oae Shigeru , Asai Nobuyoshi , Fujimori Ken
Published: July 2006

The mechanism of the reaction between N,N-dimethylaniline N-oxide 1 and acetic anhydride to give 2-acetoxy-N,N-dimethylaniline 2a has been reinvestigated by means of our more refined 18O-tracer experiments. Other products of the reaction are 4-acetoxy-N,N-dimethylaniline, N,N-dimethylaniline 4, N-methylacetanilide, and bis(4-dimethylaminophenyl)methane. The reaction of 1 with 18O-labeled acetic anhydride is considered to involve the initial formation of carbonyl-18O-labeled N-acetoxy-N,N-dimethylanilinium ion 7a and the subsequent intramolecular rearrangement of 7a into 2a in which the original 18O-label in 7a is unequally partitioned into two oxygen atoms of 2a (phenolic oxygen: ethereal oxygen=ca. 4 : 1). The reaction of 1 with trichloroacetic anhydride gave solely 2-trichloroacetoxy-N,N-dimethylaniline but not any 4 which should be formed via the free radical mechanism. These observations suggest the occurrence of the two concerted path via polarized six-(major) and four-(minor) membered cyclic transition states and rule out the free radical pair mechanism which was proposed ealier by us.
Phosphinyl- and Phosphinothioylamino Acids and Peptides. V. Preparation of Dimethylphosphinothioylamino Acids and Solid Phase Peptide Synthesis
Authors: Ueki Masaaki , Inazu Toshiyuki , Ikeda Shigeru
Published: July 2006

The use of the dimethylphosphinothioyl(Mpt) group for protection of Nα-amino functions of amino acids has been studied as the most readily removable group in the phosphinothioyl series. The Mpt-amino acids have been prepared by the alkaline hydrolysis of Mpt-amino acid esters and Schotten-Baumann type reactions of free amino acids. The Mpt group has been removed using a solution of triphenylphosphine dihydrochloride in dichloromethane. l-Leu5- and d-Ala2, l-Leu5-enkephalins have been synthesized by a solid phase method and synthetic l-Leu5-enkephalin exibited identical activity with an authentic sample.
Raman Spectrum of the Complex of Nitrobenzene with Aluminum Chloride
Authors: Fukushima Kunio
Published: July 2006

Raman spectrum of the complex of nitrobenzene with aluminum chloride in a nitrobenzene solution was measured. The shift frequencies and the degree of depolarization of Raman bands of the nitrobenzene in the complex are different from those of nitrobenzene. The differences were discussed based on the prior assignment of Raman bands of nitrobenzene.