bluuebunny/crossref_metadata_2025 huggingface dataset:
Condensation of the Triad System with Carbonyl Compounds. I. Condensation of Ethyl Itaconate with Ketones
Authors: Katsuta Chiaki , Sugiyama Noboru
Published: July 2006

In the presence of sodium ethoxide, ethyl itaconate condensed with ketones (acetone and cyclohexanone) at the terminal carbon atoms of its triad system without any appreciable isomerisation and afforded novel compounds, α-methyl-γ,γ-disubstituted aconic acids (C) and α-alkylidenemethyl-γ,γ-disubstituted aconic acids (D).

(Remark: Graphics omitted.)

The chemical structures of C and D were determined by ultraviolet, infrared, NMR spectra etc.

A reaction mechanism has been proposed (p. 1197).
Potentiometric Determination of the Formation Constants of Thiocyanato Complexes of Mercury(II)
Authors: Tanaka Nobuyuki , Ebata Kazuko , Murayama Teisuke
Published: July 2006

The formation constants of dithiocyanatomercury(II) and tri- and tetrathiocyanatomercurate(II) complexes have been determined by the potentiometric method with a dropping mercury electrode at ionic strength 0.2 and at 15, 25 and 35°C. The values obtained are:

at 15°C, KHg(SCN)2c=1.8×1017,

K Hg(SCN)3 c =7.1×1019,

K Hg(SCN)4 c =1.11×1022;

at 25°C, KHg(SCN)2c=2.7×1016,

K Hg(SCN)3 c =1.39×1019,

K Hg(SCN)4 c =1.32×1021;

at 35°C, KHg(SCN)2c=5.5×1015,

K Hg(SCN)3 c =2.43×1018,

K Hg(SCN)4 c =1.68×1020.

The thermodynamic formation constants of these complexes and the free energy change, the enthalpy change and the entropy change of the formation reactions of these complexes have been calculated.
Infrared and Ultraviolet Spectra of α- and γ-Pyrones
Authors: Yamada Kiyoyuki
Published: July 2006

Effects of substituents on the characteristic bands of pyrones were examined in the infrared spectra. Ultraviolet spectra of various α- and γ-pyrones were recorded and the application of the spectroscopic results obtained, disclosed the problems of tautomerism and isomerism concering some of the pyrone derivatives.
Studies on Long Chain Alkyl Amides of Water-soluble Poly-α-amino Acids. II. Infrared Spectra of Poly-Dl-alanine Dodecylamide
Authors: Ikeda Shoichi , Isemura Toshizo
Published: July 2006

The infrared spectra of poly-Dl-alanine and poly-Dl-alanine dodecylamide were measured on film cast from various solutions, and the conformation of the polymers were elucidated on the basis of the location and intensity of absorptions, mainly in the amide I and III bands.

The polymer showed an absorption at 1661 cm−1 in the amide I band if it was in the random coil form, but it showed two absorptions at 1630 and 1690 cm−1, if it was in the antiparallel β-form. While the amide III band was located at 1244 cm−1 irrespective of the polymer conformation, the band had an additional absorption at 1222 cm−1 for the β-conformation.

From the above correlation of the spectra with the polymer conformation, it was found that poly-Dl-alanine and PADA prepared with high [A]/[I] ratios are in the random coil form but that PADA of [A]/[I] ratios lower than 30 is composed of both the random coil and the antiparallel β-forms when it is regenerated from formic acid solution. PADA contained a greater amount of the β-form as the [A]/[I] value or the degree of polymerization was lower. The [A]/[I] 5 preparation was mostly in the β-form.

In the ionized PADA obtained from aqueous hydrochloric acid solution, the portion of the random coil form increased relative to that in the unionized PADA derived from formic acid solution, and the effect of the ionization was enhanced for the lower [A]/[I] preparations.

Poly-Dl-alanine and PADA in formic acid or aqueous hydrochloric acid solution underwent a partial transformation from the random coil to the β-form during the aging of concentrated solution, which process accompanied gelation. The solution of the lowest [A]/[I] preparation did not gel. In the state regenerated from gel, poly-Dl-alanine and PADA, except for the unionized lower [A]/[I] preparations, had an increased amount of the β-form as compared with that from an initial fluid solution. In the lower [A]/[I] preparations obtained from formic acid solution, the reverse transformation apparently occured, when the films cast before and after the gelation were compared.
Concentration and Temperature Profiles in a Tubular Reactor for Methanol Synthesis with the Outer-wall of a Uniform Temperature. II. Profiles in Reactors with a Heat Exchanger Tube in the Catalyst Bed
Authors: Ogino Yoshisada , Oba Masaaki , Shimomura Kinya , Uchida Hiroshi
Published: July 2006

Among the three types of heat exchanger tubes, a single tube countercurrent type, a double tube countercurrent type, and a double tube concurrent type, only the first one serves to increase the methanol production considerably compared with the effect of the previously tested reactor with no heat exchanger tube. On the basis of the experimental temperature profiles in both the catalyst bed and the single tube-heat exchanger tube, the cooling coefficient with the tube has been calculated to give the value as a function of the bed length. The value, when averaged over the whole bed length, agrees with the calculated value from the heat transfer coefficients, h or h′ and ha, available from certain formulae. By the use of this value, the average temperature profiles in the bed have been calculated on the basis of the experimental concentration profile; the resultant profile agrees well with the experimental one.

As regards the double tube-heat exchanger tubes, the temperature profiles for both the annular-shaped space and the inner tube have been calculated from the experimental bed temperature profiles. The results show that the profiles in the second passage of the tubes always slope down markedly in the upper zone and that, as a consequence, the bed temperature profiles are apt to remain almost identical with that for the previously tested reactor with no heat exchanger tube.
Decomposition of Peroxybenzoic Acid in Solution. I. Decomposition in Alcohols
Authors: Tokumaru Katsumi , Simamura Osamu , Fukuyama Masaru
Published: July 2006

Decomposition of peroxybenzoic acid was studied in methyl, ethyl, isopropyl and tert-butyl alcohol. The primary and the secondary alcohols were oxidized to the corresponding carbonyl compounds, which were sometimes further oxidized. The apparent decomposition rate of peroxybenzoic acid in alcohols decreased in the order: isopropyl alcohol > ethyl alcohol > methyl alcohol >> tert-butyl alcohol. For these decompositions a radical mechanism, which involves the homolytic rupture of peroxybenzoic acid and its induced decomposition by 1-hydroxyalkyl radicals derived from the respective alcohols, was proposed. A possible participation of peroxybenzoate anions in these decompositions was suggested.
Decomposition of Peroxybenzoic Acid in Solution. II. Decomposion in Hydrocarbons
Authors: Tokumaru Katsumi , Simamura Osamu
Published: July 2006

Decomposition of peroxybenzoic acid was studied in n-heptane, cyclohexane, cumene, and toluene. The hydrocarbons were oxidized to the corresponding alcohols, which were often oxidized further. For these decompositions, a radical chain mechanism was proposed, which involves the homolytic rupture of the oxygen-oxygen bond of peroxybenzoic acid as the initiation process and an induced decomposition of this bond by solvent radicals derived from hydrocarbon molecules.
Relations between the Electronic Absorption Spectra and the Spatial Configurations of Conjugated Systems. XII. The Intensity and the Shape of the Conjugation Band
Authors: Suzuki Hiroshi
Published: July 2006

The moment of the transition from the highest occupied orbital to the lowest vacant orbital has been calculated, by the simple LCAO MO method, as a function of the angle of the twist of the “single” bond for biphenyl, styrene and stilbene, each as a representative of alternant hydrocarbon systems. Thereby, it has been shown that the decrease in the intensity of the conjugation band observed with sterically hindered compounds, as compared with the band of the sterically unhindered parent compound, can be explained almost entirely satisfactorily by the decrease in the transition moment associated with the deviation of the most probable configuration of the molecule from the planarity. In this connection, Jaffé and Orchin’s explanation, as well as Braude’s explanation, of the steric hypochromic effect has been criticized.

From a consideration of the potential energy curves of the electronic ground state and of the electronic excited state for the twist of the “single” bond, an explanation has been suggested of the notable fact that the conjugation bands of sterically hindered stilbenes are almost structureless in contrast with the band of trans-stilbene, which has quite a well-resolved fine structure.
Relationship between Acid Dissociaiton Constants of N1-Aryl-sulfanilamides and the Hammett Equation
Authors: Yoshioka Mitsuru , Hamamoto Kaname , Kubota Tanekazu
Published: July 2006

1. Acid dissociation constants of twenty one N1-arylsulfanilamides (ArNHSO2C6H4NH2) were exactly determined by the spectrophotometric method at 27±2°C and in an ionic strength of 0.2.

2. A modified Hammett relationship for nucleophilic reactions (Eq. 6) can be applied to acid dissociation of N1-arylsulfanilamides and also of N-arylbenzenesulfonamides (Ar·NHSO2C6H5).

3. These results show that the modified Hammett relationship should be applied to the dissociation of Ar-NH-SO2- type anilides.
On the Solubility and the Velocity of Dissolution of Corundum under Hydrothermal Conditions
Authors: Yamaguchi Goro , Yanagida Hiroaki , Soejima Shigeo
Published: July 2006

The solubility of corundum was measured under hydrothermal conditions. The equilibrium solubility seems independent of the pressure. The temperature term, f(T), the ratio of the gram equivalent of dissolved corundum to that of sodium hydroxide in the solution, was as follows:

(Remark: Graphics omitted.)

The velocity of dissolution was proportional to the surface area of the corundum crystal and the total gram equivalent of sodium hydroxide in the solution. This is shown as

\fracd(xcor⁄xOH)dt=kS(x∞cor⁄xOH−xcor⁄xOH)

The velocity constant was as follows:

(Remark: Graphics omitted.)

The nucleation of corundum may be initiated at the supersaturation ratio of 0.12 without seed.
Some Spectral Studies of the Aqueous Solution of Pyronine G
Authors: Fujiki K\={o}nosuke , Iwanaga Chieko , Koizumi Masao
Published: July 2006

Th effect of inorganic anions on the dimerization constant of pyronine G in an aqueous solution was examined. It was found that the effect is very specific and can not be explained simply by the effect of the ionic strength. The analysis led to the conclusion that a dimer exists as an ion-pair with the anions attached laterally to dye ions instead of being sandwiched between two dye ions.

The change of absorption spectra in the alkaline solution was interpreted to be due to the formation of carbinol, and from its analysis the formation constant of carbinol was determined.

Carbinol was found to have also its proper fluorescence, and from the pH change of fluorescence spectra the formation constant of carbinol was again decided, the value of which coincided well with that obtained from the absorption spectra.
Studies of 2-Oxazolidinones. II. Products of the Pyrolysis of Some 2-Oxazolidinones
Authors: Oda Ryohei , Miyanoki Masahiko , Okano Masaya
Published: July 2006

The products obtained by the pyrolytic decarboxylation of 2-oxazolidinones have been investigated, chiefly by infrared analysis. In the case of 2-oxazolidinone, the products are 1-(β-hydroxyethyl)-2-imidazolidinone, 1-[β-(1-azilidinyl)ethyl]-2-imidazolidinone (somewhat uncertain), and poly(ethylenimine) having a 2-imidazolidinone ring at the chain end. On the other hand, the only products from 3-p-chlorophenyl- and 3-p-nitrophenyl-2-oxazolidinone are believed to be low molecular weight polymers of the corresponding ethylenimines. From 3-acetyl-2-oxazolidinone, a considerable amount of 2-methyl-2-oxazoline, which seems to arise from the rearrangement of N-acetylethylenimine, is isolated, in addition to the corresponding poly(ethylenimine). On the basis of the products obtained, a possible mechanism for the pyrolysis has been proposed.
Decomposition of Peroxybenzoic Acid in Solution. III. Decomposition in Ethers
Authors: Tokumaru Katsumi , Simamura Osamu
Published: July 2006

Decomposition of peroxybenzoic acid was studied in diethyl, diisopropyl and di-n-butyl ether and explained in terms of the same radical mechanism that was postulated previously. Besides ready induced decomposition of peroxybenzoic acid by solvent radicals and facile abstraction of a hydrogen atom from ether by radicals, attack of peroxybenzoate anions on peroxybenzoic acid was pointed out to be an important contributing factor for the relatively rapid decomposition in ethers.
Cycloheptathiazole Derivatives. I. Synthesis of 7-Hydroxycyclohepta-[d] thiazol-6-one and its Derivatives
Authors: Seto Shuichi , Nishiyama Yukio , Ogura Kyozo
Published: July 2006

It has been found that treatment of 3-bromotropolon-5-yl-thiourea derivatives with a base resulted in facile formation of 7-hydroxycyclohepta[d] thiazol-6-one derivatives, with liberation of hydrogen bromide. Out of such products, 2-benzamido derivative was submitted to oxidative degradation and its structure was confirmed.

Reaction of 3-bromo-5-aminotropolone and carbon disulfide, in the presence of a tertiary amine, was found to form a 2-mercapto derivative. Correlation of this product with the foregoing products proved the structure.
Vinyl Polymerization. LXIV. Graft Copolymerization of Vinyl Monomers to Starch
Authors: Kimura Shoichi , Takitani Takehiro , Imoto Minoru
Published: July 2006

1) Starch was oxidized with ozone in a medium of water or carbon tetrachloride to yield per-oxidized starch (abbreviated as oxistarch-W or oxi-starch-C).

2) The stabilities of the peroxide-group of oxi-starchs were measured.

3) In the present of oxi-starch, polymerizations of methyl methacrylate (MMA), acrylonitrile (AN) and vinyl chloride were carried out. Graft copolymers of starch with vinyl polymers were obtained. Their properties were described.

4) It was confirmed that commercial starch, dialdehyde starch oxidized with periodic acid, starch treated with potassium iodide, and commercial maltose could also initiate the polymerization of methyl acrylate, yielding graft copolymers and vinyl homo-polymers.
Spectroscopic Studies on Molecular Configurations of Some Aliphatic Dinitriles. III. Infrared Spectra of Adiponitrile and Bis-(adiponitrilo)copper(I) Nitrate
Authors: Matsubara Ikuo
Published: July 2006

The infrared spectra of adiponitrile and bis-(adiponitrilo)copper(I) nitrate, [Cu{NC–(CH2)4–CN}2]NO3, have been studied. The spectrum of the complex has been analyzed on the basis of the result of X-ray analysis which disclosed that the ligand adiponitrile takes the TTT(C2h) configuration in the crystals of this compound. This complex reacts with alkali halides such as sodium chloride and potassium bromide, resulting in the isolation of free adiponitrile. Considering the frequency shifts of the nitrate vibrations, the reaction of the complex with alkali halides should be ascribed largely to an ion interchange between the two phases. The increase of 26 cm−1 in the C≡N stretching frequency by complex formation may be understood by considering the linear structure of the Cu–N–C–CH2 group, which suggests that the carbon-nitrogen bond is essentially of a triple-bond character, the contributions of polar resonance structures such as C+=N− being decreased. Adiponitrile shows a marked spectral simplification on passing from the liquid to the crystalline solid state. From a comparison of the solid-state spectrum with that of the complex, and from a consideration of the vibrational selection rules, it has been concluded that adiponitrile takes the GTG′(Ci) configuration in the crystalline solid state. The fact that the solid-state spectrum of adiponitrile is subject to a reversible change depending on the temperature may be explained as due to a slight change in the crystal structure. Many of the bands in the liquid-state spectrum of adiponitrile have been assigned to the vibrations of the TTT and the GTG′ isomers, and the number of the remaining bands suggests the existence of at least one more isomer in the liquid state.
Infrared Absorption Spectra of Hydrazides. I. Hydrazides of Aromatic Acids
Authors: Mashima Mitsuo
Published: July 2006

The infrared absorption spectra of acetylbenzoylhydrazine, trichloroacetylbenzoylhydrazine and dibenzoylhydrazine have been studied in the rock salt region. The assignment of the amide frequencies characteristic to the hydrazides RCONHNHCOR′ and the coupling between vibrations due to two CONH groups have been discussed.
The Chemical Reaction in Silent Electric Discharge. III. The Effect of the Packings on Ozone Formation
Authors: Morinaga Kihei , Suzuki Momotaro
Published: July 2006

1. The ozone formation rate was increased in a packed discharge tube more than in the same type of ozonizer without packing.

2. The linear relationship, which has been proved before, between the pulse current and the ozone formation rate was also obtained in this case, independent of the dielectric constant value of the packing materials.

3. The ozone concentration shows a maximum value at a certain value of the dielectric constant.

4. The rate of ozone formation is independent of the dielectric constant at the higher values of the dielectric constant.

5. A tentative mechanism which is plausible for the elucidation of the results has been discussed.
Thermodynamic Studies on Cobalt Complexes. X. Chemical Equilibrium between Aquopentamminecobalt(III) Complex and Oxalate Ion
Authors: Tsuchiya Ryokichi
Published: July 2006

It was confirmed by absorption spectral and electric conductivity measurements that the product of the reaction of the aquopentamminecobalt(III) complex with an oxalate ion was a hydrogenoxalatopentamminecobalt(III) complex in which the oxalate ion was coordinated as a unidentate ligand. The equilibrium of the reaction,

[Co(NH3)5OH2]3++HC2O4−=[Co(NH3)5HC2O4]2++H2O

was measured spectrophotometrically, by which method the free energy of formation of the hydrogenoxalatopentamminecobalt(III) ion was calculated.

On the basis of this value and the free energy of the formation of the oxalatotetramminecobalt(III) ion obtained in the preceding paper, the differences in free energy and entropy changes between the bidentate and unidentate oxalate ions were calculated. It was verified that the chelate effect of the oxalate ion was due to the entropy effect.
The Effect of the Partial Pressure of Carbon Monoxide and Hydrogen on the Rate of Oxo Reaction
Authors: Iwanaga Ryoji
Published: July 2006

The initial rates of the oxo reaction of methylacrylate in toluene at 100°C were measured under various partial pressures of carbon monoxide and hydrogen; they were then compared with the initial rate of the formation of cobalt hydrocarbonyl from dicobalt octacarbonyl measured under the same conditions in the preceding paper. The initial rate of the oxo reaction under the carbon monoxide pressure above 10kg./cm2 can be represented as follows:

Initial rate (mol.% of aldehyde/acrylate/min.)

=0.16 (PH2)1.5/(PCO)

However, the initial rate decreases with the decreasing partial pressure of carbon monoxide in the range below 10 kg./cm2 of carbon monoxide. In addition, under the partial pressure of carbon monoxide below 10 kg./cm2 some behaviors of cobalt carbonyl different from that under the pressure above 10 kg./cm2 were observed. On the basis of these observations, a possible mechanism of the oxo reaction was discussed.
Studies of the Cage Effect of Solvent. III. Photolysis of Azomethane in Frozen Solutions
Authors: Kodama Sukeya
Published: July 2006

The photolysis of azomethane has been studied in cyclohexane, benzene, styrene, o-xylene and tert-amyl alcohol in the temperature range both above and below the freezing point of a given solution. The results obtained in the liquid solutions are essentially similar to those previously obtained with other solvents, except for styrene. The photolysis in the latter differs in that it gives little methane because of the strong scavenging action of styrene. Nevertheless, ethane with a yield comparable to those in the other solvents is formed even in styrene. It has been found with all the solutions investigated that the yield of ethane is more or less enhanced by freezing. All these findings provide additional evidence that the ethane is formed by the cage combination of a pair of methyl radicals resulting from the decomposition of a substrate molecule. For all the solvents investigated, the temperature dependence of the yield of ethane in the liquid phase conforms to the empirical equation previously presented. The apparent quantum yields obtained by comparing the rates of formation of nitrogen decrease with the lowering of the temperature, as was found previously.
Reduction of Organic Compounds with Urushibara Catalysts under High Pressure. X. Hydrogenation of 2-Butyne-1,4-diol to cis-2-Butene-1,4-diol with Various Urushibara Catalysts
Authors: Taira Shin-ichi
Published: July 2006

The Urushibara iron catalysts were newly developed. Partial hydrogenation of 2-butyne-1,4-diol to cis-2-butene-1,4-diol was successfully attained with the iron catalysts, and some modified Urushibara cobalt catalysts were also found to be applicable.
Effects of Organic Bases on the Rate of the Oxo Reaction of Methylacrylate
Authors: Iwanaga Ryoji
Published: July 2006

It has been found that the rate of the formation of cobalt carbonyl from cobaltic oxide in benzene with the high pressure of 1:1 synthesis gas at 110°C is remarkably accelerated by the presence of a small amount of pyridine.

When the oxo reaction of methylacrylate in benzene is carried out in the presence of an amount of pyridine equi-molar to the cobalt of dicobalt octacarbonyl added as a catalyst, the rate is about doubled. By examining the oxo reaction in the presence of other organic bases, the following results were obtained: the rates are decreased by aliphatic tertiarx amines such as triethylamine and tributylamine, and are scarcely affected by primary and secondary amines such as aniline and dibutylamine. Pyridine homologues except 2,6-lutidine, are as effective as pyridine. On the basis of these results, the mechanism of the effects of organic bases on the rate of oxo reaction has been discussed.
Analysis of the Variation in Coil Character by Carbonized Coal with Q-Meter
Authors: Toyoda Sadaharu
Published: July 2006

The relation between the value of Q/Q1 and the carbonization temperature of coal has been studied for various coals. The shape of the curve depends on the grade of coal. It is significant that the Q/Q1 of both the full-line and the dotted line in strongly caking coal suddenly decreases at higher temperatures. Most of the curves have a second minimum value which is smaller than that of the curve for the aqueous solution. This can be understood by taking account of the difference in dielectric constant between the coal and the aqueous solution. This result seems to support the existence of the dotted line in Fig. 2, as well as the opinion in Ref. 14 that the factor, p, would be very important.
Charge Carriers in Pyrene Crystals
Authors: Inokuchi Hiroo , Ohki Kenji
Published: July 2006

From the rectifying behaviour of photoconduction, the sign of charge carriers in molecular crystals is estimated; the ratio of forward photocurrent and reverse one corresponds to the ratio of mobilities μe⁄μh, where μe is the mobility of electron and μh is that of hole. The ratio for pyrene crystal reaches over a unity with repeating the purification, that is, the predominant charge carrier changed from hole to electron with increasing the purity of the crystals. For violanthrene or dibenzpentacene, the ratio is larger than 4 and for quaterrylene, that is almost a unity.
Studies of Photochemical Reaction. VI. The Synthesis of Methylethyl-α-tetrahydrofurylcarbinol and Ethyl-α-tetrahydrofurylcarbinol
Authors: Shima Kensuke , Tsutsumi Shigeru
Published: July 2006

The photochemical reaction of ethyl methyl ketone and propionaldehyde in tetrahydrofuran has been studied. Methylethyl-α-tetrahydro-furylcarbinol and ethyl-α-tetrahydrofurylcarbinol were easily obtained. In the photochemical reaction of propionaldehyde in tetrahydrofuran, di-α-tetrahydrofuryl was not produced, but it was observed to be produced in the photochemical reaction of acetone and ethyl methyl ketone in tetrahydrofuran.
The Properties and Infrared Absorption Spectra of Nitrilotriacetate Chelates
Authors: Tomita Yuko , Ueno Keihei
Published: July 2006

Infrared absorption spectra have been observed in NTA and its metal chelates, in solid states as well as in solution. The results indicate that NTA does not exist as zwitter ions in the solid state, that it behaves as a quadridentate ligand for such divalent metals as copper, nickel, cobalt, zinc, cadmium and lead, but that it behaves as a terdentate ligand for the alkaline earth metals. It is also found that the wave number of the νC=O band of the coordinated carboxylate group in the NTA chelates tends to shift to a higher value with an increasing chelate stability constant.
A Kinetic Study of the Isotopic Exchange of Indium in Indium N-2-Hydroxyethylethylenediamine-N,N’,N’-triacetate Complex in Water
Authors: Saito Kazuo , Tsuchimoto Michiko
Published: July 2006

1) The kinetics of the isotopic exchange of the indium EDTA-OH complex with uncomplexed indium has been studied in neutral and basic solutions, with 114mIn as tracer.

2) The exchange rate is independent of the concentration of uncomplexed indium and proportional to that of the EDTA-OH complex, giving the relationship R=k·b.

3) In a basic solution buffered by barbiturate, p-hydroxybenzoate, or ammonia, the k value is proportional to the concentration of hydroxide ions and is little affected by the buffer. The Arrhenius activation energy is 25 kcal. per mol., and a mechanism involving the dissociation of hydroxo complex [InZ·OH]− as the rate-determining step was postulated. The exchange is accelerated by glycine.

4) In a neutral solution with a pH value below 8, the rate is small but measurable. It is independent of the pH value and is little affected by barbiturate or p-hydroxybenzoate, and the activation energy is 19 kcal. per mol. The dissociation of a mixed complex containing tartrate as one of the ligands, [InZ·C4H4O6]2−, appears to be the rate-determining step. Glycine accelerates the exchange reaction.

5) The feature of the isotopic exchange of the indium EDTA-OH complex is quite different from that of the EDTA complex; the former seems to be much more labile than the latter and similar gallium complexes.
The Electron Spin Resonance of o-Substituted Benzophenone Ketyls
Authors: Maruyama Kazuhiro , Tanikaga Rikuhei , Goto Ryozo
Published: July 2006

The ESR spectra of the potassium ketyls of d5-phenyl 2-methylphenyl ketone (I), phenyl 2-methylphenyl ketone (II), 2-methylphenyl 4′-t-butylphenyl ketone and 2-methylphenyl 3′-chlorophenyl ketone have been measured in a tetrahydrofuran solution.

II gave four broad lines, and I, a single line with a smaller total width. It is considered that the ortho-substituted phenyl group is bent out of the plane of the three central bonds because of the steric hindrance of the ortho methyl group, and that then the free electron spin is accumulated at a non-substituted phenyl group—especially at the ortho-and para-positions.

The findings on the other ketyls support the above hypothesis.
A Theoretical Assignment of the ESR Spectra of Cyclohexadienyl and Phenyl Radicals
Authors: Morokuma Keiji , Ohnishi Shun-ichi , Masuda Takao , Fukui Kenichi
Published: July 2006

Two kinds of spectra—a triplet with a finer structure of four triplets, and a singlet—are known to be observed in ESR of irradiated benzene, and two different assignments of these spectra have been proposed—one assigning the triplet to the cyclohexadienyl radical and the singlet to the phenyl radical, and the other assigning the triplet to the phenyl radical. In the present paper, in order to give ground for a theoretical choice between the assignments, a valence bond calculation on the spin distribution of cyclohexadienyl and phenyl radicals has been carried out. On the cyclohexadienyl radical, though the numerical value of the spin density for methylenic protons is dependent on the C–Cmethylene bond length, the calculated spectrum is in good agreement with the observed triplet with four triplets. On the other hand, the phenyl radical has been shown theoretically to be an essentially localized radical and to give a singlet spectrum, which also agrees with that of the observed singlet.

Numerical calculations were carried out on the KDC-I digital computer of Kyoto University.
The Electronic Spectra of Aromatic Molecular Crystals. II. The Crystal Structure and Spectra of Perylene
Authors: Tanaka Jiro
Published: July 2006

A new crystalline form of perylene has been found and its crystal structure has been determined by the two-dimensional X-ray diffraction method. The new form is monomeric, while the previously known form has a dimeric structure. The electronic absorption and fluorescence spectra of both forms have been measured ; on the basis of these data, an assignment is proposed for the observed transitions. Although the fluorescence spectrum of the monomer form shows a small shift, that of the dimer form shows a larger shift than would be expected from the absorption spectrum. This is explained as a stabilization of the lowest excited singlet state by a charge-transfer resonance interaction between the molecules in a pair. Because this stabilization increases as the distance between two molecules decreases, it is suggested that the molecules in a pair approach each other after excitation. At the liquid helium temperature the motion of molecules in the crystal will be frozen out, the larger stabilization of the excited level cannot occur, and the green emission which is characteristic of the monomer form is observed from the dimer form. The rate process of the molecular motion at lower temperatures has been analyzed.
The Determination of Water Contents in Low Polymers of Formaldehyde by the Karl Fischer Method. II. The Determination of the Total Amounts of Adsorbed Water and Bound Water by the Methanol Absorption Method
Authors: Muroi Kaname , Ogawa Kunihiko
Published: July 2006

The summed content of adsorbed water and bound water in low polymers of formaldehyde has been determined by the following method : (1) The sample is pyrolized in a steam of dry nitrogen. (2) The water thus formed is absorbed in methanol. (3) The water content of the methanol solution is determined by titrating with a Karl Fischer reagent. A comparison between the present method and the propylene glycol dissolution method reported in the previous paper has made it evident that the present method is easy in its operations and is applicable to polymers having a wide range of polymerization. It has also been found that formaldehyde does not react with methanol below 30°C.
Studies of Isocyanides. I. The Formation of Urethanes and Ureas from Isocyanides
Authors: Okano Masaya , It\={o} Yoshihiko , Sh\={o}no Tatsuya , Oda Ryohei
Published: July 2006

The reactions of isocyanides with alkyl hypochlorite, N-bromoamides, and hydroxylamine have been investigated. Cyclohexyl and phenyl isocyanides give t-butyl carbamates (urethanes) by the zinc chloride-catalyzed reaction with t-butyl hypochlorite, followed by treatment with water. An analogous reaction with N-bromosuccinimide or N-bromoacetamide in the presence of a small amount of water gives the corresponding acylureas. On treatment with hydroxylamine hydrochloride and zinc chloride, cyclohexyl isocyanide affords N-cyclohexylurea.
The Oxidation of ( + )-p-Menth-3-ene with Selenium Dioxide
Authors: Suga Takayuki , Sugimoto Masako , Matsuura Tamon
Published: July 2006

The oxidation of ( + )-p-menth-3-ene by selenium dioxide in a mixture of glacial acetic acid and acetic anhydride was examined with special attention paid to the position of the oxidative attack, i. e., the C2− or C5-position of the hydrocarbon. Careful examination of the reaction product showed that this oxidation yielded only (±)-p-menth-3-en-5-yl acetate (major product), (±)-p-menth-3-en-5-ol and (±)-p-menth-3-en-5-one. Thus, this oxidant selectively attacks an active methylene group at the C5-position of p-menth-3-ene.
The Rheological Properties of Concentrated Suspensions. II. Stationary Flow Properties and the Influence of Additives and of Particle Size
Authors: Takano Masaharu , Kambe Hirotaro
Published: July 2006

The stationary flow properties of concentrated suspensions of barium sulfate in linseed oil and of those in polyisobutylenes have been measured at very low rates of shear with capillary viscometers and a Brookfield viscometer.

The dependence of the plastic viscosity and the yield value on the concentration, the particle sizes, and the polarizabilities of the medium and of the additive have been measured and explained by using a network model and by assuming van der Waals-London attraction between particles.

In suspensions of barium sulfate in linseed oil, the plastic viscosity and the yield value do not change on the addition of water below 2 wt. % based on pigments, and their dependence on the concentration of particles is monotonous. However, these values increase when the particles are covered with sodium stearate above a critical concentration.

In suspensions of barium sulfate in polyisobutylene, the plastic viscosity and the yield value appreciably increase above the critical concentration determined by the particle sizes, and these values decrease when the particles are covered with sodium stearate.

In both cases, a higher plastic viscosity and yield value are observed for suspensions of smaller particles in the same medium.

In suspensions of barium sulfate in polyisobutylene, antithixotropic behavior is observed at very low rates of shear. When the particles were covered by sodium stearate, the abnormal behavior disappears and normally thixotropic behavior is observed.

For plastic systems, the mean free energy of activation for breaking links between particles has been evaluated at 30∼kT. If we assume van der Waals-London attraction between particles, the distance between the surfaces of solid particles is within the range of 10∼55 Å, depending on the particle sizes and the presence of an additive.

Other parameters, the mean number of links to be broken for separating particles, the mean stiffness of links and other data have been approximately evaluated by assuming van der Waals-London attraction between particles.
Synthesis of Cyclic Peptide. I. Preparation of Cyclo-di-β-alanyl from 1,4-Cyclohexanedione
Authors: Watanabe Hiroshi , Kuwata Shigeru , Koyama Sugao
Published: July 2006

1) By the direct Beckmann rearrangement of 1,4-cyclohexanedione dioxime by polyphosphoric acid, trifluoroacetic acid, perchloric acid or sulfuric acid at about 100°C, no expected cyclo-di-β-alanyl but p-phenylenediamine was obtained.

2) By indirect Beckmann rearrangement using di-p-tosylate of 1,4-cyclohexanedione dioxime as an intermediate, the rearrangement occurs certainly though the isolation of the cyclic dipeptide was not successful.

3) By the Schmidt reaction of 1,4-cyclohexanedione, the expected rearrangement proceeded smoothly and from the reaction products cyclo-di-β-alanyl was easily isolated.
The Mechanism of Ethylenimine Formation by the Action of Grignard Reagents on Ketoximes
Authors: Eguchi Shoji , Ishii Yoshio
Published: July 2006

The reactions of aryl alkyl ketoximes with aliphatic Grignard reagents have been carried out under various conditions.

Gas chromatographic analyses of the reaction products showed the formation of an ethylenimine ring in which an α-carbon of the alkyl group in oximes constitutes a member of the ethylenimine ring. The reaction of acetophenon oxime with ethylmagnesium bromide containging lithium aluminum hydride produced 2-phenyl-2-ethylethylenimine, together with styrenimine.

A reaction process similar to that of the Neber rearrangement has then been proposed on the basis of the above findings.
Univalent-Bivalent Ion-exchange Equilibria on Some Permselective Membranes
Authors: Mandersloot W G B
Published: July 2006

The relative affinity coefficient Kji is shown to be dependent on the ratio of external and internal total concentrations, the ratio of the external activity coefficients and of the internal activity coefficients, a pressure-volume term and an electrical term. Kji is therefore dependent on the “ loading ” of the resin \barXj.

Several cation exchange resins exhibit a very strong affinity for calcium at high calcium loading and this affinity increases sharply with \barXCa; this effect is attributed to heterogeneity in the crosslinking of the resin and it is a strong indication that here the pressure-volume term plays a decisive rdle.

The pressure-volume term appears to be of relative importance also in the Cl/SO4 equilibrium on anion exchange resins, particularly when these are highly crosslinked. Heterogeneity in the crosslinking probably causes the sharp increase in affinity for Cl at high SO4 loading and low (0.01 n) external concentration.

Conductivity measurements on the resins in single and mixed forms is useful to get an indication of the binding forces between counterions and fixed ions and these measurements can also reveal interactions which may have a bearing on ion exchange equilibrium.
The Electronic Structures and Electronic Spectra of Benzylidene Methyl Amine N-Oxide and Its Related Compounds
Authors: Kubota Tanekazu , Yamakawa Masumi
Published: July 2006

The ultraviolet absorption spectra of benzylidene methyl amine, its protonaddition compound and benzylidene methyl amine N-oxide have been examined under various conditions. SMO calculations on those compounds have been carried out, and various physicochemical properties have been discussed.

On the basis of these calculations, the spectra of the above compounds have reasonably been assigned by using the spectroscopic exchange integrals βs(1A1) and βs(1B1), which were evaluated from the spectra and the MO, including C. I., of styrene.
The Spectrophotometric Determination of Titanium with Xylenol Orange
Authors: Otomo Makoto
Published: July 2006

A new method for the spectrophotometric determination of titanium has been described. This method is based on the formation of the colored complex between titanium and xylenol orange in a slightly acidic solution. The effects of pH and the reagent concentration on the color development of the complex have been thoroughly investigated, and experimental conditions which make possible the determination of titanium at microgram levels have been devised. The compositions of the two 1 to 1 complexes have been determined from the data of spectrophotometric measurements. The apparant formation constants of these complexes have also been calculated.
Hydroxyl Radicals in the γ-Radiolysis of Aqueous Benzene Solutions
Authors: Tsuda Minoru
Published: July 2006

Some experiments have been made in order to prove the hypothesis that the hydroxyl radical plays an important role in the oxidation of organic compounds by γ-radiolysis in aqueous solutions. Nitrous oxide and hydrogen peroxide have been found to be capable of converting radiation-induced hydrogen atoms (or their stoichiometrically-equivalent species) into hydroxyl radicals. In theγ-radiolysis of aqueous benzene solutions in the presence of nitrous oxide or hydrogen peroxide, the yield of the oxidation products from benzene has been found to equal, as had been expected, the sum of the yields of hydrogen atoms and hydroxyl radicals from water.
The Tracer Study of the Reactions of Diphenyl Sulfone and Diphenyl Sulfoxide with Sulfur
Authors: Oae Shigeru , Kawamura Shunichi
Published: July 2006

Diphenyl sulfoxide-35S was reduced to the sulfide-35S nearly quantitatively by heating with sulfur at 280°C, while diphenyl sulfone did not react with sulfur at the same temperature. At around 300°C, diphenyl sulfone-35S started to react with sulfur and gave diphenyl sulride that lost nearly 75% of the original activity of 35S of the sulfone used. The main reaction of the sulfone was found not to be reduction, but substitution involving induced C-S cleavage and replacement with sulfur chain.
The Cationic Copolymerization of Styrene and p-Brornostyrene in Liquid Sulfur Dioxide
Authors: Tokura Niichiro , Matsuda Minoru , Iino Masashi
Published: July 2006

1) The cationic copolymerization of styrene and p-bromostyrene in liquid sulfur dioxide using boron trifluoride etherate as a catalyst has been carried out; the monomer reactivity ratios (MRR) have been found to be r1=0.8 and r2=0.4. The MRR value was independent of the temperature and of the quantity of the catalyst in the copolymerization.

2) The effect of added solvents in liquid sulfur dioxide has also been examined. However, the MRR’s have been little affected by the added solvents, the rates of the copolymerization have largely been depressed, and the rates were not dependent on the dielectric constants of the added solvents, the rate in pure liquid sulfur dioxide being the fastest.

3) The same cationic copolymerization has been conducted in benzene, carbon tetrachloride, nitrobenzene and ethylene dichloride.

The MRR’s were almost equal in all (r1=1.8 and r2=0.3).
Sterically-hindered Organosilicon Compounds Containing Cyclohexyl Groups. III. Notes on Petrov and Chernysheva’s Tetracyclohexylsilane and Tricyclohexyl-n-butylsilane
Authors: Takakusa Michio
Published: July 2006

Discrepancies among reported melting ponints for tetracyclohexylsilane and tricyclohexylbutylsilane were discussed. Tricyclohexylcyclohexoxysilane was obtained in 2∼5% yield in addition to tricyclohexylchlorosilane from the reaction of cyclohexyllithium with silicon tetrachloride. Petrov’s compound melting at 198°C is most likely to be tricyclohexylcyclohexoxysilane and not a stereoisomeric tetracyclohexylsilane. Tricyclohexylbutoxysilane, m. p. 133°C, was prepared by treating sodium butoxide with tricyclohexylchlorosilane, and it was pointed out that Petrov’s “tricyclohexylbutylsilane” is probably tricyclohexylbutoxysilane.
Electrochemical Fluorination of 2,2,3,3-Tetrafluoro-1-propanol
Authors: Nagase Shunji , Baba Hajime , Kojima Rimpei
Published: July 2006

Perfluoropropionic acid, accompanied by a small amount of trifluoroacetic acid, was obtained in a good yield by the electrochemical fluorination of 2,2,3,3-tetrafluoro-1-propanol. The yield or current efficiency increased with an increase in the anodic current density and cell temperature. Although the yield decreased at lower temperatures, the reaction became milder, giving a smaller amout of trifluoroacetic acid in the product. The composition of the perfluorocarboxylic acids obtained by this fluorination reaction is very similar to that of those obtained by the fluorination of propanol, propyl propionate, diethyl ketone, and dipropyl ether. Only a trace of perfluorocarboxylic acid was formed by the electrochemical fluorination of 3H-tetrafluoropropionic acid.
Spectrophotometric Studies of the Complexes of o-Sulfobenzeneazochromotropic Acid Formed with Thorium
Authors: Miyata Haruo
Published: July 2006

o-Sulfobenzeneazochromotropic acid was prepared in the form of reddish brown needles of monosodium salt, and the value of the first dissociation constant, pKa1, was estimated spectrophotometrically to be 9.76 (25°C, μ=0.1).

The reagent reacts with thorium in the molar ratio 1:1, displacing one hydrogen atom, and the approximate value of the apparent stability constant of the complex, logK′, was estimated to be 3.2∼4.2 at pH values from 2.5 to 3.5, while the concentration of thorium was about (4∼8)×10−5.
The Nuclear Magnetic Resonance Spectra of Olefinic Protons and the Substituent Effects. I. Systems of ω-Substituted trans-Styrenes and 1-Substituted trans-Propenes
Authors: Kasiwagi Hazime , Niwa Jun
Published: July 2006

High resolution proton magnetic resonance spectra of ω-substituted trans-styrenes and 1-substituted trans-properies have been observed and discussed from the viewpoint of substituent effects. The chemical shifts of protons located at the cis-position to substituents depend roughly upon Hammett’s σP constants and presumably correlate better with the combination of potential inductive and resonance parameters, namely 0.40σI+0.70σR, proposed by Taft.

These results suggest that the chemical shifts of olefinic cis-proton may be computed from the viewpoint of the polar nature of the substituents, though the diamagnetic anisotropy and the long-range shielding effect of the substituents must be carefully considered side by side.

When the chemical shifts of protons situated at corresponding positions of structure in several systems are compared, a fairly good correlation is observed among them. This fact implies that the modes of the transmittance of substituent effects is similar in these systems.

The nature of the substituent effects on the chemical shifts of geminal protons is, however, very complicated and might be out of consonance with both the electronegativity and the available substituent parameters.
Studies of the Absorption Spectra of Azo Dyes and their Metal-complexes. II. The Absorption Spectra of Phenolazoacetoacetamide and its Derivatives
Authors: Yagi Yoshiharu
Published: July 2006

Phenolazoacetoacetamides take the hydrazone form. The phenolic hydroxyl group forms an intramolecular hydrogen bond with a hydrazone nitrogen atom in the solid state and in non-polar solvents.

The electronic absorption spectra of these compounds exhibit four groups of characteristic bands: The A bands arise from a transition involving electron migration along the whole conjugate system of the respective compound; the C bands originate in a conjugative electronic transition between a phenolic nucleus and a hydrazone group, and the D bands, in a conjugative electronic transition between a carboxylic acid anilide group and a hydrazone group.

From the investigation of the series of spectra in phenolazoacetoacetbenzylamides, the B bands have been assigned to the conjugation band; they arise from a conjugative electronic transition within a partial chromophore consisting of an acetyl carbonyl and a hydrazone group.
Studies of the Absorption Spectra of Azo Dyes and their Metalcomplexes. III. The Electronic Absorption Spectra of Metalcomplexes Derived from Phenolazoacetoacetanilides
Authors: Yagi Yoshiharu
Published: July 2006

1) The electronic absorption spectra of metallized phenolazoacetoacetanilides exhibit four characteristic groups of bands—A, B, C and D. These groups of bands originate in the band of the respective ligand-dye.

2) The metal-complexes have the structure shown in formula VI.

3) The bathochromic shifts of the A ligand-bands with complex-formation are ascribed to two causes: (i) the polarity of the M–O (M, tervalent metal; O, phenolic oxygen) bond, and (ii) the perturbation of the π-electron system by the dπ-pπ interaction. The shifts of the C ligand bands with the complex-formation are closely related to the polarity of the above-mentioned M–O bond. The cobalt (III)-complex has the covalent M–O bond with which to form a stable chelate ring, whereas the chromium (III)-complex has the ionic M–O bond.

4) The absorption characteristics of the iron (III)- and the aluminum-complexes have been discussed.
Studies of Organic Peroxides. VII. The Decomposition of Symmetrically Substituted Benzoyl Peroxides by Iron (II)
Authors: Hasegawa Shigeo , Nishimura Norio , Mitsumoto Seiichi , Yokoyama Ken’ichi
Published: July 2006

An investigation of the reactions between sym-metrically-parasubstituted benzoyl peroxides and iron (II) has been made. From the apparent first order specific reaction rates, which were obtained from the data of the thermal analysis method, the energy and entropy of activation have been estimated. In this reaction series, the linear enthalpy-entropy relationship was observed. William’s concept of the coördination of iron(II) to the peroxide molecule was assumed, and the effects of substituents on both the enthalpy of activation and the entropy of activation were discussed. It was also found that the Hammett’s equation is approximately applicable, except for nitrosubstituted benzoyl peroxide.