bluuebunny/crossref_metadata_2025 huggingface dataset:
Diamagnetic Behavior of Some Aliphatic Molecules in Crystals
Authors: Mookherji A , Mookherji S N , Neogy D
Published: July 2006

The principal magnetic susceptibilities of single crystals of some aliphatic mono- and di-basic acids and their salts have been measured and the results have been correlated with the fine structure studies of the crystals by X-ray methods. It is observed that the anisotropy per -COOH group is 5 units, which increases by nearly 2 units if two parts of (Remark: Graphics omitted.) groups are not in the same plane.

The observed extra diamagnetism normal to the plane of the carboxylic groups, if attributed to resonance, the calculated energy compares very favourably with that deduced by Pauling from a consideration of the heat of formation of molecules and the lowering of the susceptibility from Pascal’s value is then well understood.
Studies on Heavy-Nitrogen Labeled Compounds. III. Preparation of 15N-Labeled α-Hydroximinopropionic Acid
Authors: Sato Yoshishige , Meshi Teruhiko , Sugimoto Norio
Published: July 2006

By use of K15NO3 as a starting material, α-hydroximinopropionic acid-15N was synthesized in accordance with the following reactions:

K15NO3→K15NO2→15NH2OH→CH3C(=15NOH)COOH

The above reactions were carried out without separating any intermediate products. The yield of α-hydroximinopropionic acid-15N was about 61% on the basis of K15NO3.
A Synthesis of an Octahydrophenanthrene Derivative
Authors: Matsumoto Takeshi , Suzuki Akira
Published: July 2006

Ethyl 1,2,3,4-tetrahydro-2-oxo-5-methoxy-1-naphthyl acetate (IIIb) has been synthesized. Condensation of IIIb with 1-diethylaminobutan-3-one methiodide afforded an anomalous product VI. Treatment of VI with isopropenyl acetate in the presence of p-toluenesulfonic acid gave rise to an acetate VIII, while on treatment with alkali and then with acid, a hydrophenanthrene lactone IX was obtained.
Interaction Polarization of the Hydrogen Bonded Complexes. II
Authors: Kimura Ko , Fujishiro Ryoichi
Published: July 2006

The dielectric measurements were carried out for benzyl alcohol + α, α′-bipyridyl, benzyl alcohol + triethylamine, phenol + α, α′-bipyridyl and phenol + triethylamine by using benzene as a solvent, and the polarization value for each system was calculated. The additional moments due to complex formation were evaluated, as in the previous paper, from both the polarization data and the spectroscopically determined formation constants. Then the weight of structure III was estimated and correlated with the wave number shift Δν of the OH stretching vibration.
Intramolecular Hydrogen Bonding in α-Keto and α-Alkoxycarboxylic Acids. III. Comparison of the Spectra in the Carbonyl Region with Those in the O-H Stretching Region
Authors: \={O}ki Michinori , Hirota Minoru
Published: July 2006

The νC=O and the νO−H absorption of carboxylic acids were measured and the following conclusion was obtained; 1) The carboxylic acids carrying a proton-accepting group at α position give three absorption bands at ca. 1790cm−1, ca. 1760cm−1 and 1740∼1710cm−1, which can be assigned to the trans form of the monomeric acid, the cis form of the mono-meric acid and the dimer, respectively. 2) The Δνmax between the cis and the trans forms can be explained from an intramolecular hydrogen bonding between carboxylic hydroxyl and carbonyl groups.
Intramolecular Hydrogen Bonding in α-Keto and α-Alkoxycarboxylic Acids. IV. Electronic Effect in Aryloxyacetic Acids
Authors: \={O}ki Michinori , Hirota Minoru
Published: July 2006

The electronic effect on the hydrogen bonding formation in aryloxyacetic acid was examined. It is found that the electronrepelling groups enhance the band at the lower frequency in O–H stretching region and the band at ca. 1790 cm−1. The result is completely agreeable with the expectation that the electron density on the oxygen atom in the aryloxyl group controls the hydrogen bonding formation.
Monolayer Studies on Polyanhydro-l-glutamic and Polyanhydro-l-aspartic Acids
Authors: Ikeda Shoichi , Isemura Toshizo
Published: July 2006

To examine the structures of polyanhydro-l-glutamic acid and polyanhydro-l-aspartic acid, we have studied their monolayer properties and compared them with those of poly-Dl-pyrrolidone-2-carboxylic acid and poly-l-succinimide. It was found that polyanhydro-l-glutamic acid is not identical with polypyr-rolidone carboxylic acid but with poly-l-glutarimide, which has a rigidly folded configuration even in monolayer. This conclusion is in agreement with the results obtained by other methods. It was shown, however, that polyanhydro-l-aspartic acid can not be identified with poly-l-succinimide but it might be a copolymer of l-succinimide and l-aspartic acid.
On the Orientational Order-Disorder Transition in Crystalline Aniline Hydrobromide
Authors: Suga Hiroshi
Published: July 2006

Measurements of the heat capacity (−80∼+60°C) and the thermal expansion (−40∼+60°C) of aniline hydrobromide were carried out covering the transition temperature which has been observed recently by X-ray methods. The observed heat capacity versus temperature curve was of the λ-shape, similar to that of the order-disorder phase transition of binary alloy systems. The following results were obtained ; Tc (the temperature corresponding to the heat capacity peak) 22°C, ΔH (heat of transition, −70∼+35°C) ±10cal./mol., ΔS (entropy of transition, the same temperature interval) 1.10±0.05 e. u., ΔCp (drop of heat capacity at Tc)∼9 cal./mol. deg. Also the anomalous behavior of thermal expansion was observed in the vicinity of the critical temperature. These observations showed that the transition was of higher order nature.

Based on the lits of knowledge of the crystal structures above and below the critical temperature, the author has discussed the main feature of the phase transition from the sandpoint of the orientational order-disorder of the −NH3+ ionic group and obtained fairly satisfactory results.
Effect of Solvent on Carbonyl Stretching Frequency of Ketones
Authors: Inuzuka K\={o}z\={o} , Ito Mitsuo , Imanishi Sunao
Published: July 2006

The C=O stretching frequencies in acetone, mesityl oxide, acetophenone and benzophenone were measured in various solvents and the frequency shifts induced by solvents were interpreted by McRae’s theoretical equation. Results show that the observed shifts can be explained in terms of the coöperating interactions between solute and solvent molecules.

Next, the intensity of the C=O group vibration bands of these ketones was observed and compared with bond moment derivatives calculated by diatomic molecular appoximation. Small changes of about 1 D/Å were observed for polar and nonpolar solvents. The increase of the bond moment derivative value in a hydrogen bonding system was attributed to the charge transfer force.
Magnetic and Spectrophotometric Studies on the Decoloration of Thiocyanatoiron(III) Complexes in Solutions. II. Effect of Acids
Authors: Miyake Chie
Published: July 2006

Magnetic and spectrophotometric measurements have been carried out for the purpose of determining which of the proposed three types of dimers is most probable. The results obtained show that the second one with chloride ion bridges can safely be neglected. The existence of the first type with hydroxo bridges can be considered to be plausible.
Magnetic and Spectrophotometric Studies on the Decoloration of Thiocyanatoiron(III) Complexes in Solutions. III. Structure of Thiocyanatoiron(III) Complex in Organic Solvents
Authors: Miyake Chie
Published: July 2006

Thiocyanatoiron(III) complex was extracted by organic solvents. The magnetic moment of the complex was found to be 6.0 Bohr magnetons which is characteristic of the iron(III) complexes possessing the outer orbital type of binding. The absorption spectrum in the visible region of the complex shows the maximum of absorbance at 511 mμ.
Iodine-Catalyzed Thermal cis-trans Isomerization of Stilbene
Authors: Yamashita Shigeru
Published: July 2006

The iodine-catalyzed thermal cis → trans conversion of stilbene has been studied kinetically in n-hexane in temperature range 62.0∼68.8°C. The reaction rate obtained spectrophotometrically has been found to be proportional to the concentration of cis-stilbene and to the square root of iodine concentration. The overall activation energy has been found to be 25 kcal./mol. The results have been interpreted in terms of the thermal dissociation of iodine molecules followed by the formation of a transient complex between cis-stilbene and atomic iodine.
Bile Acids and Steroids. XX. Studies on the Hog Bile Acids (Part 4). Synthesis of 3β, 6β-Dihydroxy-5β-cholanoic Acid and 3β, 6α-Dihydroxy-5α-cholanoic Acid
Authors: Kawanami Jun’ichi
Published: July 2006

(1) 3β, 6β-Dihydroxy-5β-cholanoic acid was synthesized from methyl 3β-hydroxy-Δ5-cholenoate in high yield.

(2) 3β, 6α-Dihydroxy-5α-cholanoic acid was also synthesized from 3β-hydroxy-6-oxo-5α-cholanoic acid or 3, 6-dioxo-5α-cholanoic acid.
Ultraviolet Spectra of N-Heterocyclic Systems. I. The Anions of Uracils
Authors: Nakanishi Koji , Suzuki Noboru , Yamazaki Futaba
Published: July 2006

In aqueous solutions uracil exists predominantly in the diketo form, whereas in alkaline solutions it exists as an approximately 1:1 mixture of two deprotonated forms. The two deprotonated anions show ultraviolet absorptions similar to the anions of 1-methyluracil and 3-methyluracil, and the main contributing canonical structures which give rise to the general absorption feature of the anions are discussed. The peak shifts accompanying N-alkylation or deprotonation may be summarized in a simple empirical rule. Individual ionization constants have also been estimated.

The results of uracil can be extended to thymine, uridine, thymidine, and their phosphates. The pesent method can probably be extended to other systems containing two dissociable protons.
Infrared Spectra of Acyclic Imides. I. Two Modifications of Diacetamide in the Crystalline State
Authors: Uno Toyozo , Machida Katsunosuke
Published: July 2006

Two crystal forms have been found for diacetamide (the form A and the form B). Infrared spectra of these two forms of diacetamide and diacetamide-d have been measured in the region 3600 to 400 cm−1 and many differences of absorption bands have been observed. It has been shown that these differences of absorption bands can be explained to result from rotational isomerism. The trans-trans planar structure of the –CONHCO–group has been proposed to correspond approximately to the molecular structure of the unstable form (the form B) of diacetamide. The frequency shifts of absorption bands on deuteration in the potassium bromide region has been discussed to give support to this interpretation. An assignment has been given to each absorption band in the potassium bromide region for the form A and the form B of diacetamide and diacetamide-d.
The Scattering of Beams of Alkali Atoms in Various Gases. II. Sodium Atom Beam in Non-reactive and Reactive Gases
Authors: Kodera Kumasaburo , Tamura Teijiro
Published: July 2006

Collision radii considerably larger than those of classical kinetic values have been obtained.Among the measured values of collision radii, that for neon is rather smaller and that for hydrogen is considerably larger than those obtained by the other investigators. For molecules of rather large molecular weight, relative sizes among them are reasonable but they increase with the resolving power of the apparatus used. These large values of radii and their increase with the resolving power may be explained by the existence of considerable mutual interaction such as Van der Waals’ force between colliding particles.
Kinetics of the Reduction of Selenious Acid by Sulfur Dioxide. II. Reduction in Acidic Solution with Sulfuric Acid
Authors: Hamada Keinosuke
Published: July 2006

(1) The reduction of selenious acid in sulfuric acid by sulfur dioxide is a reversible reaction, because the reaction has an equilibrium and the process of the reaction is in good accordance with the equation which expressed mathematically the reversible reaction, that is,

−d(a−p)⁄dt=dp⁄dt=k2(a−p)2−k2′p2

(2) Up to the present time the rate constant k2 of the forward reaction was derived by substitution of the experimental data for xmin the following equation,

k 2={2.303xm⁄2a(xm−1)t}×log[(x−xm)⁄{(2xm−1)x−xm}]

The general equation for k2, which does not depend on xm, has been obtained as follows,

k 2′=2.054×1015×[H+]2×exp(−E⁄RT)(E=22.5 kcal.⁄mol.)

The rate constant k2′ of the reverse reaction can be calculated by

k 2′=2.413×10−11×{1⁄(a2[H+]2)}×exp(−E⁄RT) (E=−8.06kcal.⁄mol.)

(3) It has not previously been reported that α selenium is dissolved in dilute sulfuric acid (below 85% by weight), as shown by the present experimental procedure.

(4) The results obtained from this study are useful in the recovery and refinining of selenium. Then application to the recovery and refining of selenium will be expressed in another succeeding paper.
Calculation on the Electronic States of the Acrolein Molecule by the Semi-Empirical Molecular Orbital Method
Authors: Inuzuka K\={o}z\={o}
Published: July 2006

It was found that the semi-empirical method proposed by Pariser and Parr can be applied to the n–π* transition as well as the π–π* transition in acrolein. In acrolein the (n, π*) triplet state is the lowest state. A weak band in the red side of the 0–0 band is a hot band and it is not the n–π* singlet-triplet transition band. The n–π* triplet band anticipated from calculation could not be found.
The Relation between Reactivity and Selectivity
Authors: Ogata Yoshiro , Tabushi Iwao
Published: July 2006

The proportionality between logpf and log(pf/mf) reported by Brown1) seems to express the proportionality between inter- and intramolecular selectivities. The standard rate constant k0 may be a measure for the reagent activity; the parallelism between 1/k0 and |ρ| or selectivity is observed in very limited reactions.
Mass Spectrometric Study on Adsorption of Water Vapor on a Graphite Surface
Authors: Inouye Hokotomo
Published: July 2006

Peak shapes in mass spectra obtained by voltage scanning using a mass spectrometer with such a modified ionization chamber as that described above are characterized by the places of formation and the initial kinetic energy of the ions. Thus, from the shape of the peak, one may be able to decide the place of formation of the ions and, though not so precisely, to estimate their initial kinetic energy.

When the method was applied to the ions formed by electron bombardment at a graphite surface covered with adsorbed water vapor, it was found that (1) H2O+ and HO+ were formed from residual or desorbed H2O only in the gas phase, (2) H2+, H+ and CO+ were formed both on the surface and in the gas phase, and (3) H+ which formed on the surface had the initial kinetic energy of about 10 V. These results will confirm the fact that the adsorbed water molecule is dissociated into adsorbed H2 and surface oxide of carbon that probably takes a configuration such that CO is adsorbed on the surface.
On the Fluorine Shift of Aromatic Fluorine Compounds
Authors: Yonezawa Teijiro , Fukui Kenichi , Kato Hiroshi , Kitano Hisao , Hattori Shuzo , Matsuoka Shinichiro
Published: July 2006

In order to make a quantitative analysis of the F19 magnetic shielding parameters in conjugated molecules, an extension of the idea previously proposed by Saika and Slichter is made. Calculations are carried out with respect to several fluorobenzene derivatives and fluorin-ated polycondensed aromatic compounds by using the molecular orbital method. The agreement of our calculated shifts with observed shielding data is almost satisfactory.
Electronic and Vibrational States of Acrolein
Authors: Inuzuka K\={o}z\={o}
Published: July 2006

The position, blue-shift and theoretical calculation3) of the state energy of the electronic transition of acrolein in 24241∼30294 cm−1region suggest that the transition is of the n−π* type. From the vibrational analysis of acrolein vapor spectrum, it is known that the vapor spectum of acrolein has four progressions corresponding to the C=O, C=C and C-C stretching, and skeletal bending frequency in the lower state.
Spectrophotometric Determination of Nitrite in Nitrate and Sulfate
Authors: Katsube Yukiteru , Uesugi Katsuya , Yoe John H
Published: July 2006

A simple procedure has been developed for the determination of trace amounts of nitrite in large amounts of nitrite and surlfate, with disodium 1-(4′-aminobenzeneazo)-2-amino-8-hydroxy-naphthalene-2′,6-disulfonate. The method is accurate and precise.
Electronic Spectra of Substituted Aromatic Hydrocarbons. I. Phenol and Aniline
Authors: Baba Hiroaki
Published: July 2006

The electronic spectra of monosubstituted benzenes are examined from the viewpoint of semi-empirical MO theory. To allow for electronic interaction, the simple LCAO method is refined in the light of purely theoretical procedure, configuration interaction being included. The refined method is particularly convenient for dealing with the spectra of substituted organic compounds.

The origins of the absorption bands for phenol and aniline are clarified on the basis of the calculated excitation energies, oscillator strengths and changes of charge distribution accompanying electronic transitions. The nature of the second excited state of aniline is discussed in detail, in connection with the problem of electron transfer.
Studies on d-Glucosamine Derivatives. VI. α-1-C-Phenyl-2-acetamido-2-deoxy-d-glucopyranoside and its Derivatives
Authors: Yoshimura Juji
Published: July 2006

The sirup obtained as a by-product with β-1-C-phenyl-2-acetamido-2-deoxy-3,4,6-tri-O-acetyl-d-glucopyranoside by the action of phenylmagnesium bromide on acetobromo-d-glucosamine hydrobromide has been deacetylated and chromatographed to yield the α-anomer. Several α-derivatives have been described, among which, α-1-C-(p-nitrophenyl)-2-dichloroacetamido-2-deoxy-d-glucopyranoside which is a chloramphenicol derivative showed no antibiotic activities. The application of Hudson’s rules of isorotation to the anomeric compounds in this series is discussed.
Differential Thermal Analysis of the Systems Aluminum Soap-Hydrocarbon
Authors: Shiba Sukekuni
Published: July 2006

The phase behaviors of the system aluminum stearate, palmitate, and laurate-Nujol are studied by differential thermal analysis. Phase diagrams are obtained, and it is found for stearate and palmitate that soaps dissolve in hydrocarbon at the lower transition points of the soaps, and that the higher transition points disappear by addition of hydrocarbon. Differences in phase behaviors are found between laurate and other soaps. Some discussions are made on the colloidal structures of the dispersed systems aluminum soaps-hydrocarbon.
Studies on Metal Complex Species Using an Anion Exchange Resin, I. Derivation of Equations and Application to Mercury (II)-Nitrate Complex
Authors: Waki Hirohiko
Published: July 2006

1) The equations for determining the composition of a metal complex using an anion exchange resin have been derived by considering the complex formation equilibria in both the resin phase and the solution phase.

2) The method based on these equations was successfully applied to the investigation of mercury (II)-nitrate complex at various external nitrate concentrations by means of the sodium nitrate-sodium perchlorate mixed solution.

3) Mercury (II) adsorbed from a sodium nitrate solution exists in the form of Hg(NO3)3− at the external nitrate concentration of 0.5∼1 m, Hg(NO3)42− at 3∼5 m and a mixture of Hg(NO3)3− and Hg(NO3)42− at the middle of these concentrations, though no anionic complex appears to be present in an ordinary nitrate solution.
n−π Absorption Spectra of Some Aliphatic Aldehydes
Authors: Oshima Hiroko
Published: July 2006

The n-π absorption spectra of propionaldehyde, n-butyraldehyde and isobutyraldehyde were measured in various solvents and the effects of substituents and solvents on the n-π absorption spectra were investigated. For the former effect red shifts instead of blue shifts reported as the characteristic of n-π transitions were observed. The latter effect was studied using McRae’s equation. Hydrogen bonding between solute and solvent molecules is also considered.
Studies on the Chemical Equilibrium Lag during the Rapid Expansion through the Rocket Nozzle
Authors: Tsuchiya Soji
Published: July 2006

The pyrometer fitted for the temperature measurement of exhaust gas of the rocket, was constructed, and the exhaust temperature of the JP4-nitric acid rocket having 100 kg. of thrust, was observed. From the obtained exhaust temperature, it has been ascertained that the expansion of the gas through the present nozzle proceeds with chemical equilibria neither shifting nor frozen, and that relaxation occurs. From the approximate analysis of chemically relaxed flow, the relaxational process is assumed to occur at −(dt⁄dT)=3∼8×10−8 sec./deg., T\fallingdotseq2600°K and T\fallingdotseq10 atm.
Thermal Decomposition of Potassium Chlorate
Authors: Tobisawa Sh\={o}tar\={o}
Published: July 2006

The curves of dx/dt against t were obtained with accuracy; in consequence, the complication of the curves appeared, and the complication may be associated with the irregularities of the bubbling and splashing.
Electron Paramagnetic Resonance Study of Diphenyl Nitric Oxide in Single Crystals
Authors: Deguchi Yasuo
Published: July 2006

Electron paramagnetic resonance experiments of diphenyl nitric oxide single crystals were performed. Variation of exchange narrowed line were measured by changing the magnitude of magnetic dilution in crystals. Angular variations of g-value and of hyperfine spectra were investigated. The value of the exchange integral in pure crystal and the spin density on 14N atom in the molecule were determined.
Polarographic Studies of Some Organo-sulfur Compounds. I. A.C. and D.C. Polarography of Potassium Thiobenzoate
Authors: Okamoto Koichi
Published: July 2006

The polarographically new sulfur compound, potassium thiobenzoate, was investigated, using A.C. and D.C. polarographs. Comparatively complicated three oxidation waves were observed in both polarograms.

According to the various investigations about the properties of these waves, it was found that the whole reaction was the oxidation of PTB to its disulfide, benzoyl disulfide. The 1st wave was mainly due to this oxidation reaction and the two others were mainly due to the adsorption and the desorption of PTB at the surface of D.M.E.

The reversible oxidation-reduction system consisting of PTB and benzoyl disulfide would not be expected owing to the adsorption and desorption processes that interfered with the normal oxidation of PTB to benzoyl disulfide, if the studies were done with a dropping mercury electrode.
Oxidation of Terpene Compounds with tert-Butyl Chromate. VII. Oxidation of d-p-Menthene-3
Authors: Fujita Kozo
Published: July 2006

On oxidation with tert-butyl chromate, d-p-menthene-3 gave d-carvenone as a main product and dl-p-menthen-3-one-5 as a by-product.

In this oxidation, it is found that, when an endocyclic double bond is in the position between C(3) and C(4) in monocyclic terpenes of p-menthane type, two active methylenes adjacent to the endocyclic double bond are selectively oxidized to carbonyls as in the case of the terpenes containing an endocyclic double bond in the position between C(1) and C(2), and that, between the two active methylenes, the one remote from the isopropyl group attached to C(4) is preferentially attacked rather than the other which is close to the same group.
A Study of Dehydration and Hydration of Oxalic Acid by Means of the Deuterium Exchange Reaction
Authors: Okazaki Nobukazu , Takemura Eiko
Published: July 2006

The deuterium exchange reaction in the course of the hydration of anhydrous oxalic acid with heavy water vapor and subsequent dehydration of the product has been studied.

Two exchange mechanism have been suggested to be operative; the hydrate formation mechanism and the surface exchange mechanism. A distinction may be made between the two by the dependence of exchange reaction on the molar ratio of the reactants.

Anhydrous oxalic acid prepared by dehydration at 100°C takes part in the exchange reaction through hydrate formation; while, with the anhydrous acid prepared by dehydration in vacuo at ordinary temperatures, the surface exchange mechanism comes into play.

For the specimens of anhydrous acid prepared in vacuo, the molar ratio of oxalic acid in the surface to that of the bulk is estimated to be 0.6∼0.7 from the results of the deuterium exchange reaction. Dehydration of oxalic acid dihydrate in the vacuum of electron microscope yields amorphous anhydrous acid.

The recrystallization of amorphous anhydrous oxalic acid was studied by the use of deuterium exchange reaction as a measure of surface area. It has been shown that adsorbed water exerts catalytic effect on the recrystallization. The process is associated with small or zero activation energy. Anhydrous oxalic acid recrystallized in the presence of water has been identified with α-form.

Deuterium exchange reaction between unhydrated oxalic acid and hydrate water occurs in anhydrous oxalic acid partially hydrated with heavy water vapor. The rate of this exchange is practically independent of temperature. The reaction probably consists in the deuteration of the molecules in the interior of the anhydrate lattice.

Treatment of amorphous anhydrous acid with a small amount of water vapor causes a peculiar change in the rate of subsequent rehydration. There is a considerable retarding effect on the rehydration rate for a particular range of the amount of water vapor.
The Rearrangement of N-Deuterated Aromatic Amine Hydrochloride into its Ring-deuterated Analogue in the Solid Phase: The Rearrangements of o- and m-Toluidine Hydrochlorides and the Effect of Anions on the Rate of Rearrangement of Anilinium Salts
Authors: Okazaki Nobukazu , Okumura Akiko
Published: July 2006

The rearrangement of N-deuterated aromatic amine hydrochloride into its ring-deuterated analogues has been studied in the solid and the liquid phases with o- and m-toluidines, and studied kinetically with anilinium chloride and bromide at 173∼194°C and at 210∼225°C, respectively.

The ease of the rearrangement of the hydrochlorides in the solid phase is in the order,

o-toluidine hydrochloride

>aniline hydrochloride

>p-toluidine hydrochloride

which is the reverse of the order of the basic dissociation constants of the amines at 25°C. m-Toluidine hydrochloride is more reactive than o-toluidine hydrochloride.

The numbers of nuclear hydrogen atoms which take part in the rearrangement are, 2 in the solid phase and >3 in the liquid phase rearrangement of o-toluidine hydrochloride, and for m-toluidine hydrochloride 3 and 4 in the solid and the liquid phases respectively. This result, taken in conjunction with the earlier ones with aniline and p-toluidine hydrochlorides, confirms the view that in the solid phase rearrangement the ortho and the para positions are exclusively deuterated, and in the liquid phase deuteration of the meta positions takes place.

The rearrangement of the anilinium salts is characterized by high activation energy (ca. 45kcal.) and large positive entropy of activation (ca. 15cal./deg.).

These results are reasonably interpreted by the intramolecular electrophilic mechanism.

A small difference of the activation energies between the rearrangement of the two anilinium salts (ca. 2 kcal.) may be explained in terms of the different polarizing effects of the halide ions on initial state and possibly also on the activated complex.
Hydrophile-Lipophile Balance Values for O/W Emulsions Stabilized by Nonionic Surfactants. I. Hydrophile-Lipophile Balance Values of Nonionic Surfactants Determined by Emulsification
Authors: Ohba Noriaki
Published: July 2006

The HLB values of several types of nonionic surfactants were determined by experiments in emulsification according to the concept of HLB suggested by Griffin.

The HLB values required to emulsify the mineral oil do not show a consistent value, although the values are limited within a narrow range.

The HLB values calculated according to the law of the additivity for the surfactant mixture, [HLB]a, and the values calculated by the equations proposed by Griffin, [HLB]calcd, were compared. The differences between these two values were most remarkable in the case of sorbitan fatty acid esters and became greater at the higher mole numbers of the ethylene oxide in the molecule, excepting polyoxyethylene sorbitan esters and polyethylene glycol stearates.

Some explanations were attempted for such differences and for the deviations from the assumed additive properties of the HLB system, in connection with the role or behavior of nonionic surfactants in emulsification.
Hydrophile-Lipophile Balance Values for O/W Emulsions Stabilized by Nonionic Surfactants. II. “Required Hydrophile-Lipophile Balance Values” of the Oil Mixture
Authors: Ohba Noriaki
Published: July 2006

To study the additivity of the HLB values of an oil mixture from its component and the characteristics of the oil mixture forming a component of the emulsion, the required HLB values of several oil mixtures were determined by means of the emulsification tests proposed by Griffin.

The oil mixtures examined in this series of experiments consist of two oils, one being a mineral oil of fixed components and the other an oil to be studied as the additive, which is added in varying ratios to the fixed-component mineral oil.

The additivity of the required HLB values in oil mixtures was shown to hold to some extent for the case of saturated fatty acids, n-fatty alcohols, and some acetylated esters. For the rest of the additives, the additivity is not valid.

The required HLB values of these additive oils were remarkably large in the case of fatty acids, alcohols and some acetylated esters, excepting the anomalous value for oleic acid.

The structural effects on the increase of required HLB values seem to be in the following order:

COOH>OH>COOR
Chemical Use of the Absorption of Soft γ-Rays, β-Ray-excited X-Rays and K-Capture X-Rays. II. Application to the Analysis of a Binary Alloy and the Determination of a Heavy Element in a Multi-component System
Authors: Nozaki Tadashi
Published: July 2006

The absorption phenomenon of soft γ-rays, β-ray-exited X-rays and K-capture X-rays was applied to the following two kinds of analyses (1) Analysis of solder (simultaneous determination of the composition of a binary system and the sample thickness), and (2) Determination of an element of high atomic number in a multi-component system). Two photon-beams of energies suitable for each purpose were chosen, and for the letter purpose the retionship between the absorption coefficient of an element and the photon-beam energy was used. The results were in good agreement with those obtained by usual chemical anaiysis.
On the Basicities of the Nitro-derivatives of Benzoanthrones
Authors: Handa Takashi
Published: July 2006

The basicities of the nitro-substituted benzoanthrones were measured. One nitro-substitution decreases the basicity of beazoanthrone by about two pK units, as in the case of nitrosubstituted aniline and anthraquinone. This is explained qualitatively not by the inductive effect but by the resonance effect of the nitro groups on the carbonyl group of benzoanthrone in such way as to estimate approximately the change of resonance energies in the cases of both hydrocarbons and their related quinones. The gradient of the straight line of pK plotted versus log(N∗N) in the case of nitro-substitution is greater than in the case of chlorosubstitution. This means that the contribution of the polarized structure in the ground state to resonance effect is greater in the case of the nitro-derivatives of benzoanthrone than in the case of the chloro-derivatives.
The Reaction of Carbon Monoxide with Organometallic Compounds. VI. Synthesis of Symmetrical Ketones by the Reaction of Carbon Monoxide with Organolithium Compounds
Authors: Ryang Membo , Tsutsumi Shigeru
Published: July 2006

The reaction of carbon monoxide with an organolithium compound at −70°C yielded symmetrical ketones.

Benzophenone (55%), 4,4′-ditolyl ketone (50%), di-n-butyl ketone (40%), di-n-amyl ketone (28%) and diisopropyl ketone (30%) were prepared by this new method.

A reaction path for the formation of ketones was discussed.
Electrolytic Process for the Preparation of Dianisidine Using Rotating Cathode Cell for the Reduction of o-Nitroanisole to Hydrazoanisole
Authors: Udupa K S , Subramanian G S , Udupa H V K
Published: July 2006

The technique of using rotating cathodes for electrolytic reduction of nitro compounds developed in this Institute earlier has now been extended to the study of the reduction of o-nitroanisole in an alkaline emulsion to obtain hydrazoanisole, which is subsequently converted to dianisidine by reaction with acid. The various chemical methods of obtaining hydrazoanisole as well as the previous attempts for obtaining the same by electrolytic reduction of o-nitroanisole are briefly reviewed.

The experimental technique adopted, the isolation of the product and the subsequent conversion of the hydrazoanisole to dianisidine are described.

Cathode potential has been measured at different current densities using lead deposited iron cathode under stationary and rotating condition of the cathode without the addition of nitro compound. The effect of the nitro compound addition on the cathode potential at different current densities has also been studied. The potential of a rotating cathode measured during the course of an experiment is graphically presented and the results discussed.
Dielectric Behavior of Hydrated Crystals. IV. Cupric Formate Tetrahydrate, Cu(HCO2)2·4H2O
Authors: Kiriyama (née Ibamoto) Hideko
Published: July 2006

The dielectric properties of single crystals of cupric formate tetrahydrate have been investigated over the range 30c./sec. to 10 Mc./sec. from the liquid nitrogen temperature to the dehydration point, 46°C. This crystal undergoes a phase transition at –36°C, indicated by a sudden change in the dielectric properties. Above the transition point, large dielectric dispersion and absorptions are present when the applied electric field is along the crystallographic a- and b-axes, whereas along the normal to (0 0 1) plane, the variations in permittivity and the loss factor with temperature and frequency are quite small.

The results for the radio frequency absorption can be explained on the basis of a molecular mechanism involving the axial reorientation of two water dipoles in the formula unit of Cu(HCO2)2·4H2O. The energy barrier H(kcal./mol.) and the frequency factor A(sec−1) associated with the dipole orientation have been obtained as follows : along the a-axis A=1×1011, H=6.7; along the b-axis A=8×109, H=4.5; and in the direction normal to (0 0 1) A=7×1010, H=6.3.

A further absorption at much lower frequencies is remarkable only in the a-axis direction. The observed high dielectric loss suggests the possibility of proton transfer in the hydrogen-bonded chains found in this crystal structure.
High-Kinetic Energy Fragment Ions from Aliphatic Hydrocarbons under Electron Impact. I. Measurement and High-Kinetic Energy Methyl Ions from 1,3-Butadiene
Authors: Tsuchiya Toshikazu
Published: July 2006

With a conventional analytical mass spectrometer and without any additional electrodes, fragment ions produced with excess kinetic energies by electron impact can be detected and studied quantitatively. Mainly methyl KE ions in the spectra of seven hydrocarbons have been measured. A comparison of the results on methyl ions in four hydrocarbons with reported values showed a satisfactory consistency.

An appreciable part of the m/e 15 rearrangement ions of 1,3-butadiene had excess kinetic energies. The mechanism of the formation of the ions has been proposed which assumes a transfer of the hydrogen atom from a second carbon atom of the molecule to the first carbon atom followed by the recoil of the resulting two groups of atoms. The study of the KE ions in the spectra of the ethylene molecule from the standpoint of the H-M assumption shows that the mechanism of the formation of various KE ions is complicated and deserves more detailed study.
The Color of Liquid Caustic Soda Produced by the Ammonia-Soda Process
Authors: Awaya Hiroshi
Published: July 2006

It is found that the coloring of caustic liquor produced by the ammonia-soda process is due to chromate in the milk of lime given to the sodium carbonate solution for causticization. But the solid caustic soda, even produced by the ammonia-soda process, contains a little chromate. The coloring of caustic liquor by chromate is found in products of all ammonia process makers in Japan.

The existence of chromate not only gives the yellow color to the product, but also has an undesirable effect on viscose production in the rayon industry.

Yellow-colored caustic liquor can be discolored by the addition of the reducing reagent. Refining by anion exchange resin is also effective, but there is a risk of the corrosion of the resin by the caustic liquor. As the chromate was identified in the caustic liquor, it was concluded that the abnormal wave of the polarogram caustic liquor was probably due to the hydrolysis current.

By measuring the absorbancy of caustic liquor at the wavelength of 370 mμ, the chromate content can be nearly exactly determined.

As much limestone contains a considerable impurities, it is not desirable to use the milk of lime for the purification of the brine in the electrolytic-soda process also.
On Glumamycin, a New Antibiotic. III. Fatty Acid, a Constituent of the Antibiotic
Authors: Inoue Michitaka
Published: July 2006

Investigation was made of the ether soluble part of glumamycin hydrolysate. After this oily substance was purified by distillation, the distillate corresponded to unsaturated fatty acid, having an epimerical formula C13H24O2.

This unsaturated fatty acid was optically active and by oxidation with ozone gave an optically active saturated fatty acid C10H20O2 and malonic acid C3H4O4. Therefore, the fatty acid constituted glumamycin corresponding to 3-isotridecenoic acid.
The Secondary-emission Electron Multiplier Tube Used on a Mass Spectrometer and its Amplification of Ion Currents
Authors: Sugiura Toshio
Published: July 2006

For the purpose of measuring very small ion currents by the mass spectrometer, a secondary electron multiplier, using the dynodes of copper-beryllium, has been constructed and installed. The amplification by the electron multiplier of various supplied voltages to the conversion dynode was measured for inert gas ions, and the amplification factor and its variation with the supplied voltage to the conversion dynode was compared with both the activated and the electro-polished dynode. For the electron multiplier using the electro-polished dynodes, the amplification was roughly inversely proportional to the square root of the ion mass, while for the activated dynode this was not the case. The average yield of the secondary electrons impacted by electrons on the copper-beryllium dynodes was determined, using the values of γi which had been estimated by extrapolation of the data obtained in a previous study. The increase of the amplification factors of the electron multiplier due to the dynode activation was explained on the basis of an increase in γi and \barδ due to dynode activation, an increase to be attributed to the formation of beryllium oxide layers. In this study, an amplification factor of a 105 order for inert gas ions has been obtained with the electron multiplier constructed with dynodes made from activated copper-beryllium. By using this electron multiplier, ion currents of 10 −19 amperes are easily detectable with a mass spectrometer using a conventional D. C. amplifier.
The Kinetics of the Formation of Calcium Carbide in a Solid-Solid Reaction
Authors: Tagawa Hiroaki , Sugawara Hideo
Published: July 2006

The kinetics of the formation of calcium carbide in the solid state reaction of calcium oxide with carbon has been examined by using a thermobalance in the temperature range 1600 to 1800°C and at 50, 100 and 200 mmHg of carbon monoxide. The reaction ratio vs. time curves were parabolic in all experimental runs, and the reaction followed parabolic kinetics: (1−3\sqrt1−x)2=kt. On the other hand, the decomposition of calcium carbide as a successive reaction occurred from the specimen surface and was described as a zero-order reaction. As the reaction velocity depended strongly on the pressure of carbon monoxide, it is considered that the reaction rate is governed by the diffusion process of gas through the product layer, as well as that of solids into the solid and product layer.
The Decomposition of Methyl N-Nitroso-p-acetamidobenz[14C]oate in Benzene. The Determination of the Products by the Isotopic Dilution Method
Authors: Inukai Takashi , Kimura Kenjiro , Simamura Osamu , Suehiro Tadashi
Published: July 2006

Methyl N-nitroso-p-acetamidobenz [14C] oate was decomposed in benzene, and the product was analyzed by the isotopic dilution method. The results are shown in Table I, and the mechanistic implication is discussed.
Studies of 2-Oxazolidinones. I. A Convenient Synthesis of 3-Substituted 2-Oxazolidinones
Authors: Oda Ryohei , Miyanoki Masahiko , Okano Masaya
Published: July 2006

A convenient synthesis of 3-substituted 2-oxazolidinones starting from three components–aliphatic or aromatic amines, phosgene and ethylene chlorohydrin–has been developed.
Proton Magnetic Resonance of Ammonia-Borane Derivatives
Authors: Ohashi Osamu , Kurita Yukio , Totani Tetsushi , Watanabe Haruyuki , Nakagawa Toshio , Kubo Masaji
Published: July 2006

The proton magnetic resonance spectra of triethylborane, trimethylamine-triethylborane, triethylamine-triethylborane, trimethylamine-trichloroborane and triethylamine-trichloroborane were recorded at room temperature using an NMR spectrometer operating at 40 Mc. The assignments of observed signals were made and the chemical shifts and spin coupling constants were evaluated. The extent of electron transfer from nitrogen to boron in ammonia-boranes is slightly greater than that in borazoles.
Reduction of Pyrones with Complex Metal Hydrides
Authors: Yamada Kiyoyuki
Published: July 2006

Reduction using complex metal hydrides was carried out on monocyclic α-pyrones and benzo-γ-pyrone. It was established that generally the hydrogenolysis of the 1,6-linkage of an α-pyrone ring occurred. In benzo-γ-pyrone, carbon-carbon double bond and ketone were reduced. The effects of the substituents on the reactivity of α-pyrone were discussed.
Studies on Mixture Dyeing. I. The Kinetics of the Mixture of Benzopurpurine 4B and Sky Blue 6B
Authors: Sekido Minoru , Morita Zenzo
Published: July 2006

1. The single and mixture dyeing of Benzopurpurine 4B (C. I. 23500) and Sky Blue 6B (C. I. 24410) were examined kinetically.

2. The diffusion coefficient of each dye decreased with a decrease in the surface concentration. The apparent activation energy of diffusion at a constant surface concentration was evaluated.

3. In mixture dyeing, the dye distributions in the substrate were considerably different from that in the single dyeing, but there was good agreement between the dye distributions experimentally determined and those theoretically calculated in terms of the thermodynamics of irreversible processes.

4. The interaction between two dyes in the substrate increased with an increase in the sodium chloride concentration in the dye bath and with a decrease in the temperature.
Catalytic Activities of Copper-nickel Alloys for Hydrogenating Reactions
Authors: Takeuchi Toyosaburo , Sakaguchi Masakazu , Miyoshi Ikkei , Takabatake Takeo
Published: July 2006

The hydrogenation of ethylene and benzene on two series of copper-nickel alloys, i. e., massive alloys prepared physically and granular alloys prepared chemically, was carried out in order to determine the cause of the disagreement of the catalytic activities which have been found in these alloys. The adsorption of hydrogen on granular alloys was also examined to learn the heat of adsorption and the amount adsorbed; the results were compared with the activities of the alloys.

The activities of massive alloys may be interpreted by the Dowden theory, but those of granular alloys could not. The activities of granular alloys were interpreted in connection with the concentration of nickel at the surface, which can be considered to be different from that in the interior. It was concluded that the amount of hydrogen adsorbed, the heat of adsorption, and the catalytic activity of granular alloy are related to the concentration of nickel at the surface.
Syntheses of Chelating Agents. I. Stability of the Metal Chelate of Benzylamine-N, N-diacetic Acid and its Nitro Derivatives
Authors: Ando Takeshi
Published: July 2006

1. The acid dissociation constants of benzylamine-N, N-diacetic acid, and the stability constants of its chelates with Cu(II), Ni(II), Pb(II), Zn(II), Co(II), Ca(II) and Mg(II) at 25°C and 0.1 ionic strength, have been determined by the pH titration method.

2. o- and p-Nitrobenzylamine-N, N-diacetic acid have been newly synthesized from the corresponding benzylamine.

3. The acid dissociation constants of the above two ligands, and the stability constants of its chelates with Ca(II) and Mg(II), have been determined at 25°C and 0.1 ionic strength.
Concentration and Temperature Profiles in a Tubular Reactor for Methanol Synthesis with an Outer-wall of Uniform Temperature. I. Profiles in a Reactor without a Heat Exchanger in a Catalyst Bed
Authors: Uchida Hiroshi , Ogino Yoshisada , Oba Masaaki , Shimomura Kinya
Published: July 2006

On the basis of the experimental concentration and temperature profiles for one of the synthesis runs, the experimental rate curve has been drawn on a chart in which lines of constant conversion with reaction rates are given as ordinates and temperatures as abscissa. In a step by step calculation of the temperature profiles from the experimental profiles by the use of a set of analytical solutions of the heat balance equation, which includes the respective constant reaction heat terms given by the step by step distribution plot, the heat transfer coefficients are conveniently chosen to match the calculated profiles with the experimental ones. Taking the heat transfer efficiencies thus obtained into consideration, a comparison of the experimental rate curve with the maximum rate curve on the afore-mentioned chart discloses that, for attaining an efficient performance of the reactor, not only should the heat transfer referred to the outer tube surface be improved, but also the temperature rise in the catalyst bed should be controlled by a suitable means.
Investigation of Chemisorption by Desorption Rate Measurement; CO2 on ZnO and NiO; CO on NiO
Authors: Kubokawa Yutaka , Toyama Osamu
Published: July 2006

As an extension of previous work, the study of chemisorption by desorption rate measurement was carried out for carbon dioxide adsorbed on zinc oxide and nickel oxide, and also for carbon monoxide adsorbed on nickel oxide. For the chemisorption of carbon dioxide, the activation energy of the desorption was increased with the decreasing amount adsorbed from 16 to 40 kcal./mol. on zinc oxide and from 7 to 30 kcal./mol. on nickel oxide. In the case of the chemisorption of carbon monoxide, where the two types of chemisorption are seemingly operating, the activation energy of the desorption for the reversible type ranged from 5 to 18 kcal./mol. A method of distinguishing these two types of chemisorption from the behavior on desorption has been proposed, for it has been found that there are two types of chemisorption for the carbon dioxide-zinc oxide system. From the effect of oxygen treatment at high temperatures on the chemisorption, it was concluded that the effect of the surface barrier, emphasized by Hauffe and others, seems to be only of secondary importance in the above system.