bluuebunny/crossref_metadata_2025 huggingface dataset:
The Polymerization of Butene Isomers
Authors: Shimizu Akihiko , Otsu Takayuki , Imoto Minoru
Published: July 2006

The effect of the methyl substituents of four butene isomers (IB, NB, TB and CB) on their polymerizations and copolymerizations has been investigated. None of these monomers homopolymerized in the presence of an ordinary radical or in that of anionic catalysts, but they were homopolymerized by cationic catalysts. The reactivity of these monomers toward their cationic polymerizations and radical copolymerizations has been found to decrease in the order of IB>>NB>TB–CB. These results have been interpreted on the basis of the steric effect and the chain transfer reactivity of the methyl substituents in these monomers.

These monomers, except for IB, can easily be homopolymerized by the Natta catalyst in the reactivity order of NB>>TB>–CB. The resulting polymers from TB and CB have been confirmed to be the same as the polymer from NB, which consisted of the recurring unit of n-butene-1.
The Infrared Spectra of Alkylaluminum-Ether Complexes
Authors: Takeda Saburo , Tarao Ryokichi
Published: July 2006

Fifteen samples of alkylaluminum-ether complexes (alkyl=methyl or ethyl) have been prepared, and their infrared spectra have been measured in the 2000–350 cm−1 region. Most of the absorption bands in this region have been assigned. In the K Br prism region, the assignments of the absorption bands of the trimethylaluminum-dimethyl ether complex have been made on the assumption that this complex has the Cs symmetry only. The absorption bands of these complexes have been found to shift to lower frequencies in the C–O antisymmetric and symmetric streching vibrations in the order of trialkylaluminum-ether < dialkylaluminum halide-ether < alkylaluminum dihalide-ether complexes. The infrared spectra of five samples of ethylaluminum ethoxides have also been measured in the 2000 −350 cm−1 region.
Optically Active Polymers. III. Polymers of 1,3-Dimethylbutyl Methacrylate
Authors: Imoto Minoru , Kumata Yoshiyuki
Published: July 2006

The polymerization of (+)-1,3-dimethylbutyl methacrylate and its optically impure (−)-isomer have been carried out through different three initiations:

(1) n-BuLi in toluene at −78°C gave isotactic polymers (DI and LI). (2) Azobisisobutyronitrile at 60°C gave atactic polymers (DA and LA). (3) Photopolymerization in the presence of azobisisobutyronitrile at −35–−50°C gave syndiotactic polymers (DS and LS). The tacticities of the resulting polymers have been deduced from their softening temperatures and their infrared spectra. Optically active polymers have been fractionated from a benzene solution by adding methanol. In the cases of DI and DA, the specific rotation [α]d increased with the molecular weight, while in the cases of DS, LS and LA, [α]d remained constant during the change in molecular weight. The optical rotatory dispersion of the polymers has been measured. Drude’s equation does not hold. In the case of DA, however, a straight line was obtained by Moffitt’s equation, giving −64.3 as the b-values.
Kinetic Studies of Ammonia Oxidation in Shock Waves. I. The Reaction Mechanism for the Induction Period
Authors: Takeyama Tetsu , Miyama Hajime
Published: July 2006

The oxidation of ammonia has been studied at temperatures between 1550 and 2300°K by using the shock-tube technique combined with ultraviolet absorption spectroscopy.

The measurements of the induction periods for the appearance of OH have shown that they are strongly dependent on the concentration of oxygen and that the activation energy required is 42.5±1.2 kcal./mol.

The intermediates of the reaction, NH, NO and NH2, have been detected spectroscopically, and the time relations between their appearance and their accumulation have been determined.

As a result, the following mechanism has been postulated as the main steps governing the induction period of the high-temperature oxidation of ammonia:

NH2+O2 → NH+HO2 (I)

NH+O2 → NO+OH (II)

OH+NH3 → NH2+H2O (III)

HO2 → OH+O (IV)

O+NH3 → OH+NH2 (V)

where Reaction I is considered to be rate controlling.
Metal Complexes of Amino Acids. I. The Circular Dichroism of Copper(II) Complexes with Optically Active Amino Acids
Authors: Yasui Takaji
Published: July 2006

On the basis of the CD measurements of the complexes of the [Cu(l-am)2] type, four CD components have been observed in the region of the d→d absorption band, namely, (+), (+), (−) and (−), listing from longer to shorter wavelengths. The l-configuration of the amino acids determines the signs of these CD components.

Judging from the CD curves of the copper-(II) complexes with l-threonine and with l-allothreonine, it has been suggested that the vicinal effect caused by the α-asymmetric carbon atom is stronger than that caused by the β-asymmetric one.

It has also been suggested that, when l-proline or l-hydroxyproline is coordinated to copper, the nitrogen atoms of these ligands are activated by the configurational stereo specificity.
A Molecular Orbitals Study of the Nucleophilic Substitution in Methyl Chloride
Authors: Kato Hiroshi , Morokuma Keiji , Yonezawa Teijiro , Fukui Kenichi
Published: July 2006

The electronic structures of CH3C1 and a “transient” species (Cl…CH3…Cl)− have been calculated by an extended Hückel method. The calculated results of CH3C1 correlate well with the experimental facts. The main features of the electronic structure of (Cl…CH3…Cl)−-may be summarized as follows:

1) The 3py orbitals of the chlorine atoms and the 2py orbital of the central carbon atom (pσ-orbitals) play an important role in the interaction between the C–Cl bonds.

2) The 2s orbital of the central carbon atom at the symmetrical configuration makes no contribution to the C–Cl bonding; rather, this orbital, together with the 2px and 2pz orbitals, participates in the C–H bonding.

3) The 3px and 3pz orbitals of the chlorine atoms form the lone-pair orbitals.

The natures of the MO’s of the symmetrical configuration have also been briefly discussed.

It should be noticed, however, that the present treatment is not yet sufficiently qualified as a method to allow an interpretation of the stable configuration of a molecular system, since it does not explicitly take into account the nuclear repulsion and the electronic interaction. Accordingly, there remains room for criticism with respect to the theoretical significance which the configuration of such a local minimum will have in the true electronic process on the reaction path. This point will be examined further in the future.
The Extraction of Thallium(III) from Hydrochloric Acid Solutions with Ethyl Acetate
Authors: Srivastava T N , Rupainwar D C
Published: July 2006

Ethyl acetate has been employed as a solvent for extracting thallium(III) from its hydrochloric acid solutions. The empirical formula of the extracted metal entity has been found to be HTCl4. Optimum conditions for the extraction of the metal have been determined, and the effect of various factors, e.g., metal concentration, salting-out agents, and the dilution of the solvent, have been investigated. It has been possible to separate thallium(III) from aluminum(III), gallium(III) and indium-(III) by performing a batch-by-batch extraction at a 1.0 n hydrochloric acid concentration.

1) The extracted species is an acid with an approximate formula of HTICl4, the distribution of the species between the two phases depends upon the concentration of the hydrochloric acid present in the system.

2) The extracted species is ionic and may associate in the organic phase to from ion pairs, ion triplets and higher clusters. This is evident from the fact that an increase in the metal concentration causes an increase in the distribution coefficient.

3) There is no primary solvation of thallium, which is tetrahedrally surrounded by chloride ions and which is apparently saturated. This is supported by the observation that the metal could not be extracted from its solution in perchloric acid.

4) The proton of the chlorothallic acid may be solvated (and possibly hydrated, too) in the organic phase, the solvation number being indefinite.

5) Ion pairing results in the formation of an extractable complex and a general mechanism of the type:

H(S)++[TlS)2C14]−\ightleftharpoons[(HS+)(Tl(S2)C14)−]

may be expected, where S is either H2O or ethyl acetate.

The above equation may well represent qualitatively various reactions at different relative water and ethyl acetate activities.

In general, the system is a simple ion-association extraction system and is quite similar to the extraction of iron(III) and gallium(III) chloride with oxygenated solvents.
Effect of the N-Substituent on the Course of the Reaction of α-Aminonitriles with Organometallic Reagents
Authors: Yoshimura Juji , Ohgo Yoshiaki , Sato Tetsuo
Published: July 2006

The reactions between various N-substituted-α-aminonitriles and organometallic reagents have been investigated in order to clarify the effect of the N-substituent on the reaction course.

The results indicate that:

(1) Both Grignard reagent and lithium alkyl attack not nitrile carbon but α-carbon to give substituted product when the α-aminonitrile has an active hydrogen on its aminonitrogen.

(2) In the case of α-dialkylaminonitriles, Grignard reagents attack the α-carbon to give substituted products, but lithium alkyls attack the nitrile carbon.

(3) The aminonitriles bearing acetyl group on its aminonitrogen are not attacked at α-carbon but at nitrile carbon by both the reagents, thus giving addition products.
The Catalytic Effect of the Support on Terpene Compounds in Gas-Liquid Chromatography
Authors: Hayashi Shûichi , Yano Katsumi , Yokoyama Naruo , Matsuura Tamon
Published: July 2006

The catalytic action of several solid supports, that is, glass, rock crystal, quartzite, sea sand, unglazed porcelain and commercial supports, have been examined. Glass shows practically no catalytic action in the examined terpene compounds, except for linalyl acetate and α-santalol, which were decomposed and/or isomerized slightly, but this support does show an adsorption of oxygen-containing compounds. The catalytic action of rock crystal is slightly greater than that of glass, but the adsorptivity of rock crystal is extremely small. Commercial diatomaceous earth supports show a remarkable catalytic action.
The Preparation of Hydride-free Triethylaluminum and Its Reaction with Titanium Tetrachloride
Authors: Takashi Yukichi , Aishima Itsuho
Published: July 2006

Hydride-free triethylaluminum has been prepared by destroying diethylaluminum hydride by reaction with diethylzinc. The reaction of hydride-free triethylalumi and titanium tetrachloride in benzene shows the instantaneous reduction of titanium tetrachloride. It has been concluded that the reduction of titanium tetrachloride is not cussed, caused only by the presence of diethylaluminum hydride as an impurity in triethylaluminum, as has been proposed by Roha. Triethylaluminum treated with ethylene at a highi pressure does not reduce titanium tetrachloride under ordinary conditions, even though it contains appreciable amount of the hydride.

On the basis of the above facts, the reaction of Ziegler-catalyst component has been discussed.
Some Acetylene Complexes of Vanadium
Authors: Tsumura Ryuichiro , Hagihara Nobue
Published: July 2006

Some acetylene complexes of vanadium of the π-C5H5(RC2H)V(CO)2 (R=H, n-C3H7, n-C4H9 and (CH3)3C) and π-C5H5(PhC2Ph)V-(PPh3)(CO) types have been prepared by the photochemical reaction of the corresponding acetylene with π-cyclopentadienyl-vanadium tetracarbonyl and its phosphine derivative irespectively. It has been proposed, on the basis of their infrared and nuclear magnetic resonance spectra, that the acetylene complexes of vanadium have a structure in which the acetylene molecule is bonded via two σ-bondings to a vanadium atom.
The Preparation and Polymerization of Divinyl Carbonate
Authors: Murahashi Shunsuke , Nozakura Shun’ichi , Fuji Saburo , Kikukawa Kiyoshi
Published: July 2006

The preparation of divinyl carbonate has been described. The cyclopolymerization of the monomer has been studied under various reaction conditions, and it has been found that cyclopolymerization is not a predominant mode of propagation, for it leaves not less than half a mole of unsafuration per unit structure. The polymer structure has been analyzed by the infrared method and found to contain the 5-membered cyclic carbonate unit, the 6-membered cyclic carbonate unit and the pendant unsaturated carbonate unit.

The polymerization temperature has been shown to have a significant effect on the 5-membered cyclic unit content, increasing the temperature resulting in an increase in the 5-membered unit. The activation energy difference between the intramolecular 5-membered cyclization and the intermolecular propagation has been estimated to be 6.21±0.29 kcal./mol. in the polymerization in a 50% benzene solution and 8.44±0.48 kcal./mol. in bulk polymerization.
A Geochemical Study of Selenium in Volcanic Exhalation and Sulfur Deposits. III. On the Relation between Selenium and Certain Other Constituents, and on the Behavior of Volcanic Gases
Authors: Suzuoki Tetsuro
Published: July 2006

Continuous observations of fumarolic gases have been made in order to study the chemical nature of volcanic gases. A very wide variation in the content of some gaseous constituents has been observed in continuous observation over several hours, and over four years.

Judging from the field observation and the mode of the content variation of several components with the time and the temperature, it is likely that process of the alteration of volcanic gases occurring in the sub-surface plays an important role in producing the difference in the chemical nature of fumarolic gases among the fumarole areas. In addition, the year-to-year variation of the contents of some constituents might provide an indication of the stage of some processes, such as distillation and occlusion, which have occurred in the sub-surface.

It has been found that components like selenium are useful in an examination of the behavior of volcanic gases at an old solfataric volcano like Nasudake, because it is expected that most of the constituents except for selenium have been accumulated in the sub-surface by the past effusion processes and that the accumulated constituents have been occluded in the primary volcanic gases with the change in volcanic activity.
The Reactions of Benzoyl Cyanide with Trivalent Phosphorus Compounds
Authors: Mukaiyaka Teruaki , Kuwajima Isao , Ohno Kiyotaka
Published: July 2006

The reactions of various p-substituted benzoyl cyanides with trivalent phosphorus compounds have been studied. They react with triethyl phosphite to form 2 : 1 adducts which, upon being heated in xylene, decomposed into the corresponding dicyanostilbene oxide and triethyl phosphate. The reaction with tri-n-butylphosphine, on the other hand, gives cis-dicyanostilbene derivatives. These reactions can be explained by a mechanism through similar intermediates.
The Relative Reactivities of Different C–H Bonds in the Photochemical Sulfoxidation of n-Hexane
Authors: Ogata Yoshiro , Izawa Yasuji , Tsuda Takao
Published: July 2006

The product mixture of isomeric hexanesulfonic acids in the ultraviolet light-induced sulfoxidation of n-hexane under various conditions has been analyzed by gas chromatography. On the basis of the data thus obtained, the relative reactivities of different C–H bonds in n-hexane towards light-excited sulfur dioxide and sulfur trioxide have been estimated. The ratio of the reactivities of C1–H : C2–H : C3–H has been calculated to be 1:0.8–1.3: 3.2–6.2. The higher reaction temperatures tend to lower the reactivity of C2–H. The mole ratio of SO2 vs. O2 has an appreciable effect on the composition of the isomers. The lower reactivity of C2–H than that of C3–H may be explained by the intermediary formation of a six-membered ring.
Studies on Mixture Dyeing. III. The Absorption Spectra of Direct Dye Mixtures in an Aqueous Solution
Authors: Morita Zenzo , Sekido Minoru
Published: July 2006

The absorption spectra of a binary mixture of five representative direct dyes in solution have been investigated. The equilibrium constants for complex formation are in the 107–104 range and are in the order: Chrysophenine G - Sky Blue 6B>Benzopurpurine 4B - Sky Blue 6B>Sirius Red 4B - Sirius Supra Blue BRR>Sirius Red 4B - Sky Blue 6B= Benzopurpurine 4B - Sirius Supra Blue BRR>Chrysophenine G - Sirius Supra Blue BRR. The combination of Chrysophenine G and Sky Blue 6B is a typical one in direct dyes. The equilibrium constant for an aggregation of like dye molecules is very much smaller than the value of 104 at room temperature.
Kinetic Studies of the Solution Polymerization of Trioxane Catalyzed by BF3·O(C2H5)2. I. The Effect of the Catalyst and the Water Concentration on the Rate of Polymerization
Authors: Higashimura Toshinobu , Miki Tetsuro , Okamura Seizo
Published: July 2006

In the solution polymerization of TO catalyzed by BF3·O(C2H5)2, water acted as a co-catalyst in n-hexane, a non-polar solvent; in ethylene dichloride, a polar solvent, water slightly accelerated the rate of polymerization, and in nitrobenzene, a more polar solvent, water did not affect the rate at all. The kinetic order of the catalyst concentration to the polymerization rate was 1.0 in benzene, 0.5 in ethylene dichloride, and zero in nitrobenzene. The induction period was very short when water was excluded as much as possible, but it increased with an increase in the water concentration and with a decrease in the catalyst concentration.

On the basis of these results, it may be concluded that the polymerization of TO by BF3·O(C2H5)2 is initiated by the attack of the proton or the ethyl cation on the monomer.
Investigations on Some Amine Complexes of Cobalt(II) Phthalimide. II. Infrared Spectroscopic Measurements
Authors: Narain Gopal
Published: July 2006

Infrared measurements of a series of complexes prepared with cobalt(II) phthalimide and some amines of the [Co(Phthalimide)2(amine)2or1] type have been made. The spectra confirm that both phthalimide ions and amine molecules are co-ordinated; they further suggest that the coordination of phthalimide is through the nitrogen.
Phosphorylation by Means of Ethyl Phosphorodimorpholidite and α-Bromoamides
Authors: Mitsunobu Oyo , Obata Teisuke , Sugaya Yoshiharu , Mukaiyama Teruaki
Published: July 2006

The phosphorylation of alcohols or phenols by means of ethyl phosphorodimorpholidite and either monobromocyanoacetamide or monobromomalonamide has been studied. Further, adenosine 5′-phosphate has been prepared by the reaction of ethyl phosphorodimorpholidite and monobromocyanoacetamide with 2′,3′-isopropylidene adenosine.
The Kinetics of the Acid-Catalyzed Formation of Peracetic Acid from Acetic Acid and Hydrogen Peroxide
Authors: Sawaki Yasuhiko , Ogata Yoshiro
Published: July 2006

The sulfuric acid-catalyzed reversible formation of peracetic acid from acetic acid and hydrogen peroxide in aqueous acetic acid has been studied kinetically. The rate of peracid formation is proportional to the product of the concentrations of acetic acid and of hydrogen peroxide, increasing with an increase in the concentration of sulfuric acid. The plot of the logarithm of the rate constant vs. −H0 gives a straight line, with a slope of 0.82 and 1.10. The mechanism has been discussed in connection with the analogous acid-catalyzed esterification. The equilibrium constants for the present reaction also increase with an increase in the acidity, and the similar plot of logK1 vs. −H gives a straight line with a slope of 0.22. These facts are explicable by considering the protonation of water.
A Study of the Charge-Transfer Complexes. II. The Complexes of Pyromellitic Dianhydride with Polycyclic Aromatic Compounds
Authors: Matsuo Taku
Published: July 2006

The frequency of the charge-transfer absorption of the PMDA complex has been found to be linearly dependent on the energy level of the highest-occupied MO of the aromatic donor as estimated by the Hiickel MO method. The behavior of the complex in the solid state is almost parallel to that in a solution. On the basis of these linear relationships, it has been suggested that PMDA in ethyl acetate behaves as if it is an electron acceptor weaker than that in a solid complex and chloranil in carbon tetrachloride by about 0.2 eV. and 0.53 eV. respectively in the zero order approximation.

Another suggestion has been made that trans-stilbene may be slightly twisted around its essential single bond in a solution but not in the solid complex.
The Optical Properties of Colored Colloidal Systems. III. A Theory of Spherical Particles, with Especial Attention to Systems Dispersed in Colored Media
Authors: Nakagaki Masayuki
Published: July 2006

In the expression of the complex refractive index of a colored colloidal system (m=m0–ik0), the value of m0 may be smaller than unity and k0 may be negative if the medium is colored. Including these cases, the values of x (corresponding to the optical density), y (scattering) and z (absorption) have been calculated for relatively small α and k0 values. The values of the apparent relative refractive index, m′, have been calculated also. These results have been discussed in detail in order to show the effect of the scattering and absorption on the scattering, absorption and apparent refractive index. It has been concluded that the data of a system in which colorless particles are dispersed in a colored medium will be practically equal to those in a colorless medium if the extinction of light according to the Lambert law is corrected properly.
The Synthesis of N-Terminal Acetylpeptides of Ovalbumin and Mammalian Heart Cytochrome c
Authors: Baba Yoshihiko , Sakiyama Fumio , Titani Koiti , Narita Kozo
Published: July 2006

In previous studies acetylglycylserine and acetylglycylaspartylalylglutamic acid had been isolated from the enzymatic digests of ovalbumin and cytochromes c of bovine and equine hearts respectively. Here, in order to confirm the structures of the acetylpeptides isolated, acetylglycyl-l-serine and acetylglycyl-l-aspartyl-l-valyl-l-glutamic acid have been synthesized. It has been proved that the natural acetylpeptides are identical with the synthetic ones in every respect examined. Some troubles encountered during the synthesis of the acetyltetrapeptide have been discussed.
Studies of Cycloheximide-Related Compounds. II. The Acid-catalyzed Condensation of Glutarimide-β-acetaldehyde with Ketones
Authors: Egawa Yoshiyuki , Umezawa Sumio
Published: July 2006

1) Glutarimide-β-acetaldehyde has been condensed with several aliphatic ketones by acidcatalysts to give mainly α,β-unsaturated ketoderivatives. The condensation with methyl iso-propyl ketone has given δ-(1, 1-dimethyl-2-oxo-n-propyl)-β-carbamoylmethyl-δ-valerolactone (III-1) and 3-(2-hydroxy-3,3-dimethyl-4-oxo-n-pentyl)-glutarimide (III-2). It has been found that the latter is an isomer of the product prepared by Nielsen’s aldol condensation procedure.

2) An analogous condensation with Dl-2,4-dimethylcyclohexanone has given Dl-anhydrocycloheximide and two stereoisomers of Dl-gem-cycloheximide. The condensation with (2r:4r)-2, 4-dimethylcyclohexanone has given a similar result.

3) It has been shown that the acid-catalyzed hydration of anhydrocycloheximide affords α-epi-isocycloheximide.
The Selective Halogenation of Methylhydropolysiloxanes : Syntheses of Methylhalopolysiloxanes and Their Derivatives
Authors: Sakiyama Minoru , Nishizawa Yukinori , Okawara Rokuro
Published: July 2006

Bromine was utilized in the presence of stoichiometric amount of pyridine to brominate silanic hydrogen of methylhydropolysiloxanes. Methylbromopolysiloxanes thus obtained and methylchloropolysiloxanes prepared from photo-chlorination of methylhydropolysiloxanes were hydrolyzed with or without methylchlorosilanes to yield new methylhydroxypolysiloxanes and branched methylpoly siloxanes. Preparation of methylhydrocyclopentasiloxanes was also reported.
The Radiation-induced Addition of Hydrogen Sulfide to Olefins
Authors: Sugimoto Ken’ichi , Ando Wataru , Oae Shigeru
Published: July 2006

The radiation-induced free radical addition of hydrogen sulflde to olefins to give the corresponding thiols has been studied. The addition of the thiols to olefins has been found to undergo a free radical chain reaction, readily yielding the corresponding sulfides in the succeeding step. However, the thiols were found to be the only component when an excess of hydrogen sulfide was used. The reactivity of the radical chain reaction decreases with an increase in the carbon number of α-olefins.
The Radiation-induced Isomerization of 2-Butenes
Authors: Ando Wataru , Sugimoto Ken’ichi , Oae Shigeru
Published: July 2006

A detailed study of the radiation-induced trans-cis isomerization of 2-butenes has been made. The effects of halogenated compounds upon 2-butene can be explained by the attack of the halogen radicals formed in irradiation, and a radical chain process can be suggested for the isomerization.

The addition of hexane or cyclohexane to 2-butene in the gas phase has shown a rapid isomerization of trans to cis; it has been suggested that this is caused by the hydrogen atom formed in the irradiation of hexane or cyclohexane. The facile isomerization of 1-butene to trans2-butene by the presence of such hydrocarbons suggests that the hydrogen is readily exchanged with the other hydrogen of olefin, thus leading to the isomerization.

Radiation-induced isomerizations brought by benzene, sulfur dioxide, nitric oxide, carbon disulfide and other molecules have also been examined. The effect of benzene on the trans-cis isomerization of 2-butene has been explained by production of vibrationally-excited triplet states. Results with sulfur dioxide have shown that radiation-induced isomerization is due not only to the formation of the first triplet state, but also to the addition to the double bond, followed by dissociation.
The Rotatory Dispersion and Stereochemistry of Organic Compounds. VIII. Mono- and Dinitrates of Glucopyranose (Preliminary Report)
Authors: Tsuzuki Yojiro , Tanabe Koko , Okamoto Kikuhiko
Published: July 2006

The RD and ultraviolet absorption have been observed with some derivatives of glucose carrying a nitrate group in the C2 and C3positions in order to study the optical contributions of the C2- and C3-ligands with respect to their configurations.
Solid State Polymerization of Binary Component System
Authors: Miura Masatoshi , Hirai Takako , Kawamatsu Shunji
Published: July 2006

The γ-ray irradiation of a solid solution of 3-chloromethyl-3-ethyloxetane and 3,3-bis-(chloromethyl)oxetane has given a copolymer with the same composition as that of the initial monomer mixture, while a BF3-catalyzed copolymerization has formed a copolymer with a different composition from that of the initial monomer mixture. In the polymerization, the solid solution has behaved like each single component crystal in respect to the relation of polymer yield to the irradiation temperature and to the crystal state of the monomers. The copolymer obtained from small crystals grown by rapid cooling has been found to have a narrower distribution of composition than that obtained from large crystals. With a solid solution of 3-chloromethyl-3-ethyloxetane and 3-fluoromethyl-3-ethyloxetance, the polymerization has been studied and similar results obtained.

The mixed crystal of 3-chloromethyl-3-ethyl oxetane and diketene gives a polymer blend. The curve of the polymer yield versus the irradiation temperature is a superposition of those in the each component crystal. The mixed crystal of 3-chloromethyl-3-ethyloxetane and trioxane gives only a homopolymer of oxetane, and the temperature dependence of the yield is similar to that of oxetane, even in an eutectic composition.
Catalytic Asymmetric Benzaldehyde Cyanohydrin Synthesis with Synthetic Optically Active Polymer. II. Cross-linked Poly-(s)-isobutylethylenimine
Authors: Tsuboyama Sei
Published: July 2006

Asymmetric benzaldehyde cyanohydrin synthesis with TDI cross-linked poly-(s)-isobutylethylenimine has been studied. The cyanohydrin obtained was (+)-isomer; its sign is opposite to what it is in the case of the linear polymer. With the linear and soluble polymer which contains some –NH–CO–N= groups, the (+)-isomer was also found to be produced. These results suggest that (1) the reversal of the sign is independent of the reaction phase, and (2) the configuration of the product is not always controlled by the configuration of the asymmetric carbon in the catalyst but by the conformation of the catalytic center.
A Study of the Interaction between the Stearic Acid Monolayer and the Calcium Ions by the Radiotracer Method
Authors: Matsubara Akira , Matuura Ryohei , Kimizuka Hideo
Published: July 2006

Direct measurement by the radiotracer method has been carried out in order to determine the surface excess of calcium on the stearic acid monolayer. It did not provoke any disturbance in the monolayer, such as “skimming off” or “building up”. At higher pH values the stearic acid monolayer spread on a calcium chloride solution shows a very remarkable inhomogeneity. It has been pointed out that this inhomogeneity must be taken into consideration in determining the composition of the monolayer.

The mixed monolayer of stearic acid and calcium stearate satisfies the equation derived by assuming this monolayer to be a mixture not athermal.
Electron Paramagnetic Resonance Absorption of Chromium Ions Dispersed on Silica-alumina. I. The Influence of Chemical Constitution of the Supporting Materials on the Dispersed State
Authors: Matsumoto Akira , Tanaka Hazime , Goto Nobuhisa
Published: July 2006

Chromic anhydride has been dispersed on several supporting materials of silica-alumina of different compositions, and the so-called γ-line in the EPR of these samples has been observed. When the temperature of heat treatment rises, the intensity of this absorption becomes strong, but after reaching a maximum value it decreases again. The chemical composition of the base materials remarkably influences the behavior of the absorption. The variations in water soluble chromium and oxidation number show corresponding results. However, γ-absorption sites may be distributed in the water-insoluble part of chromium as well as in the water-soluble part. The ratio between them depends on the base materials.

Under the assumption of g anisotropy, the observed absorption lines have been compared with the calculated curves and the half-width at the half power of the absorption with the crystallite in these samples. From these results and from the differences in behavior, the states of chromium ions in various samples have been compared. By comparing the present results with those of other investigators, it has been concluded that, on pure silica gel, chromia is dispersed mainly in the form of thin-layer clusters and that this dispersion gives the characteristic of this matter. On the contrary, an alumina-rich base produces a more dispersive state of chromium and the fixation of chromium rapidly becomes stronger with the heat treatment. The influence of the supporting material on dispersed chromium becomes great and the characteristics are affected by this fact. These differences may be caused principally by the differences among these materials in thermal stability and in the compatibility with chromia.
Vibration-Rotation Spectra, the Coriolis Coupling Constants and the Intramolecular Fore Field of Symmetric Top Molecules. II. Analysis of the Overtones and Combination Tones of Methyl Bromide
Authors: Morino Yonezo , Nakamura Junko , Yamamoto Seiya
Published: July 2006

The infrared spectra of most of the overtones and combination tones of methyl bromide have been obtained. In the perpendicular band, the rotational fine structures have been observed. The values of the Coriolis coupling constants obtained from the analysis of the rotational fine structures are consistent with those obtained from the analysis of the fundamentals. It has been seen that, if one takes 0.03 as the error of the observed values of the Coriolis coupling constants, one can use the observed values to calculate the force constants.

Most of the vibrational anharmonic terms, xij, have been obtained, but they are tentative yet.

The rotational correction terms, α1 and α2 have been estimated from the combination-bands analyses.
A Kinetic Study of the Isotopic Exchange of Thallium(III) between the Thallium(III) Ion and the Thallium N-2-Hydroxyethylethylenediamine-N,N′,N′-triacetate Complex in Water
Authors: Tsuchimoto Michiko
Published: July 2006

1) The kinetics of the isotopic exchange of the thallium(III) EDTA-OH complex with uncomplexed thallium(III) has been studied in acid, neutral and weakly basic solutions, with 204Tl as tracer.

2) The exchange rate is independent of the concentration of uncomplexed thallium and proportional to that of the EDTA-OH complex, giving the relationship R=k·b under appropriate conditions throughout the pH range.

3) In a basic solution buffered by ammonia or barbiturate, the k is proportional to [OH−] and [TEA] and is little affected by the concentration of buffers. The Arrhenius activation energy is 29 kcal./mol.

4) In a neutral solution, near pH 7, the rate is small but measurable. It is independent of the pH value but proportional to the concentration of TEA, and it is little affected by the concentration of barbiturate. The activation energy is 22 kcal./mol.

5) In an acid solution buffered by acetate, the k is proportional to [H+], and [Cl−]1.5 and is little influenced by the concentration of acetate. The Arrhenius activation energy is 11 kcal./mol.

6) The features of the isotopic exchange of the thallium EDTA-OH complex are very similar to those of the thallium(III) EDTA complex.
The Effect of Several Condensed Phosphates on the Dissolution of Strontium Sulfate
Authors: Miura Masaji , Naono Hiromitu
Published: July 2006

The effect of ortho-, pyro-, tri- and trimetaphosphate on the dissolution of strontium sulfate has been studied. Pyro- and triphosphate remarkably retard the dissolution, even in an extremely dilute solution, while orthoand trimetaphosphate exhibit only an insignificant effect. From the results of the measurements of the adsorption of these phosphates onto the crystal surface, it is considered that the retarding action of these phosphates is to be attributed to the adsorption. The kinetic treatments of the dissolution and adsorption lead to the conclusion that the dissolution may be controlled by the specific places on the crystal surface and that such places may be the rate-determining sites for the dissolution.
Studies of Ion Exchange Membranes. XXII. Semicontinuous Preparation of Ion Exchange Membranes by the “Paste Method”
Authors: Mizutani Yukio , Yamane Reiichi , Motomura Hirozi
Published: July 2006

A method for the preparation of ion exchange membranes called the “paste method” has been developed into a semicontinuous preparation.

The roll-coating system being employed, a base membrane 1 m. wide and 50 m. long is prepared continuously; the ion exchange group is then introduced to it.

The ion exchange membranes thus prepared have been proved to have excellent electrochemical and mechanical properties as well as an excellent appearance.
Chelate Formation between Chromate Ions and Disodium-1,8-dihydroxy Naphthalene-3,6-disulphonate
Authors: Banerji Samir K , Qureshi Said-ul-Zafar
Published: July 2006

The formation of a coloured chelate with a λmax at 530 mμ between chromate ion and chromotropic acid (sodium salt)-disodium-1,8-dihydroxy naphthalene-3,6-disulphonate has been reported. The composition of the chelate has been studied by the method of continuous variation, using absorption spectra measurements, with a Hilger Uvispek spectrophotometer; it has been found to be Cr(CAD), (Disodium-1,8-dihydroxy naphthalene-3,6-disulphonate). The chelate has been found to be stable in the pH range 2—5 and so the investigations have been carried out in this range of pH. The chelate formed is deep red in colour and is very sensitive, being formed even at great dilutions.

The stability has been calculated by a method described earlier; the value of logK is 8.21±0.02, and the value of the free energy of formation, ΔF°, has been found to be −5.42±0.11 at 25°C.
Absorption Spectra of Dyes. IX. Electronic Spectra of a 1 : 1 and a 1 : 2 Complex, and CT-Bands
Authors: Hoshi Toshihiko , Tanizaki Yoshié , Ando Noboru
Published: July 2006

1) The absorption spectra of binary mixtures of Chrysophenine G (notation: G) and disazo dyes (P), which were the same as those used in a preceding study,1) have been measured at room temperature (ca. 20°C), and the characteristic spectra of the complexes have been determined by using the equilibrium constants, K1 and K2, previously obtained (at 20°C) for the 1 : 1 (PG) and 1 : 2 (PG2) complex formation.

2) The absorption spectra of the PG and PG2 complex have been compared with the respective corresponding additive spectra (P+G and P+2G), and the correlations among these spectra have been discussed in detail.

3) The MO pattern of the G molecule has been decided empirically by applying Platt’s theory; similarly, that of the P molecule has been decided by assuming that there is at least one symmetry species; then the spectral change caused by the complex formation could be explained in relation to the MO’s of the component molecules.

4) It has been confirmed that there exists an intermolecular charge transfer from P as an electron donor to G as an acceptor. It has also been shown that the first band of a disazo dye (P) consists of two electronic transitions; one is a π→π*(shorter wavelength) and the other an l→π* transition (longer wavelength).
Radiotracer Studies of Metal-Detergent Interaction by Means of a Dip Counter with an Evaporated Metal Film Window
Authors: Seimiya Tsutomu
Published: July 2006

The accumulation of solute on metal surfaces has been studied using a radiotracer technique. A dip GM-counter with an end window covered with an evaporated metal film was immersed in an aqueous solution of 35S-labeled sodium dodecyl sulfate, and the change in counting rate due to the accumulation of solute on the metal surface was traced with time for various metals and pH values of the solution. The accumulation curves obtained turned out to be composed of an initial plateau, representing the region of the physical adsorption of the detergent onto the the metal surface, and/or a rising portion of the accumulation curve, indicative of chemisorption. Assuming the closely packed adsorption of solute, the roughness factors of various metal surfaces have been calculated from these plateau characteristics. The rising portion of the curve corresponds to the formation of a thick metallic soap film. The rate of film growth is controlled by the migration of the detergent or metal ions through the film, and this rate decreases as the thickness of the surface film increases. This leads to the parabolic formula for the surface film growth, which is in good agreement with the experimental results. The effect of the pH of the solution on the rate of the uptake of dodecyl sulfate has also been measured for both copper and lead surfaces. For copper surfaces the rate of the uptake of a detergent shows a maximum at pH 7 and decreases in both acid and alkaline regions. For lead surfaces, the rate is large in the acid region and gradually decreases twoards the alkaline region.
The Stability Constants of Ethylenediaminetetraacetato, Trimethylenediaminetetraacetato and Propylenediaminetetraacetato Complexes of Some Divalent Metal Ions
Authors: Ogino Hiroshi
Published: July 2006

Two methods are presented for the determination of the stability constants of ethylenediaminetetraacetato, trimethylenediaminetetraacetato and propylenediaminetetraacetato complexes of some divalent metal ions. One is a new method which is based on the polarographic measurement of the concentration of an uncomplexed ligand in a solution containing two kinds of ligands and an appropriate metal ion. The other is a modification of the method described in the previous paper. From the results obtained by these methods and those obtained previously, the individual stability constants have been calculated. The values of the logarithmic stability constants of complexes at 25°C and ionic strength 0.2 are: Mn 13.64, Co 15.71, Ni 18.12, Cu 18.46, Zn 15.94, Cd 15.98 and Pb 17.76 for ethylenediaminetetraacetato complexes; Mn <10.8, Co 14.48, Ni 17.29, Cu 18.04, Zn 14.26, Cd 12.69 and Pb 13.04 for trimethylenediaminetetraacetato complexes, and Mn 14.85, Co 17.07, Ni 19.42, Cu 19.64, Zn 17.14, Cd 17.43 and Pb 18.69 for propylenediaminetetraacetato complexes.
Ultraviolet and Visible Absorption Spectra of the Solid States of Aromatic Amine Complexes with Iodine
Authors: Kusakawa Hideaki , Nishizaki Shun-ichiro
Published: July 2006

The ultraviolet and visible spectra of aromatic amine complexes with iodine in the crystalline state have been investigated by means of the KBr disk method or with a squashed powder between quartz plates.

Part of the aniline (ANI) ions in the ANI-iodine system become positive, and the maximum of the spectrum band appears at 255 mμ. p-Phenylenediamine (p-PDA) and 1,5-naphthylenediamine (NDA) complexes with iodine possess the band maxima at the same position as those of ANI and α-naphthylamine. The ground states of these complexes seem to be dative states.

In benzidine (BEN) and o-tolidine (TOL) from polyphenylenediamines, and iodine complex systems bathochromic shifts are observed.

By estimating the ionization potential ID of these aromatic amines from the energies of the charge transfer transition, low values of ID, except for ANI, are obtained.

The electrical resistivities of these specimens are in the order BEN<TOL<NDA≈p-PDA, which is in agreement with that of the energies of the charge transfer transition.
Estimation of Anharmonic Potential Constants. II. Bent XY2 Molecules
Authors: Kuchitsu Kozo , Morino Yonezo
Published: July 2006

The vibrational potential function of the bent XY2 molecule has been expanded in terms of the internal coordinates to the fourth order and a general formulation which relates the coefficients of this expansion (second-, third-, and fourth-order potential constants) to the cubic and quartic constants in the normal-coordinate system has been derived. The third- and fourth-order constants in the internal-coordinate system for H2O, D2O, H2Se, D2Se, and SO2 have been determined by using the experimental α and x values taken from the literature. It has been shown that the third- and fourth-order constants which represent the anharmonic bond-stretching vibration, frrr and frrrr, are much larger than the other higher-order constants and that they are nearly equal (to within 12 per cent) to the anharmonic potential constants of the corresponding diatomic radicals. The method presented in Part I of this paper, which makes use of the “diatomic approximation” for estimating the anharmonic constants and the α and x values, has been applied to the bent XY2 molecules. A comparison of the results with currently available experimental data has shown that the signs and the orders of magnitude are in most cases correctly predicted by this approximation. This method has been further applied as an aid for the detection and analysis of the microwave absorption lines in the case of the SO2 and OF2 molecules in their excited vibrational states.
The Electronic Spectra of Pyrene, Chrysene, Azulene, Coronene and Tetracene Crystals
Authors: Tanaka Jiro
Published: July 2006

The electronic absorption spectra of single crystals of pyrene, chrysene, azulene, coronene and tetracene have been measured by a polarized light. Some crystal absorption bands exhibit appreciable splittings and changes in intensity relations according to the simple exciton theory. Those results are explained by the use of the second-order exciton calculation without the inclusion of the electron overlap effect. The theoretical results give a fairly reasonable explanation of crystal spectra, and it has been shown that the second-order mixing of excited states plays an essential role in modifying the crystal spectra from the pattern of the free molecule.
Combination of Sulfuric Acid with Cellulose during the Hydrolysis with a Small Amount of Concentrated Sulfuric Acid
Authors: Sakai Yoshio
Published: July 2006

The combination of sulfuric acid with cellulose occurring during the hydrolysis of cellulose in a small amount of concentrated sulfuric acid has been investigated. The amounts of the soluble and the insoluble glucose polymers produced from cellulose, and the amount of sulfuric acid combined with them, have been estimated. To obtain an effective concentration of sulfuric acid on the cellulose, the concentration of the sulfuric acid must be greater than about 60%. The sulfuric acid concentration in the cellulose-sulfuric acid-water system can not exceed 75%, even when the initial concentration exceeds 85%. The amount of soluble glucose polymer (g.) produced by the action of 100 g. of sulfuric acid is given by 0.0384 exp(0.0958C+4.06r)/[1+0.00132 exp(0.0815C+4.06r)] (C is “initial” concentration of sulfuric acid (%) and r, sulfuric acid-cellulose ratio).
Absorption of Carbon Dioxide in a Centrifugal Absorber by Mono-and Diethanolamine Solutions
Authors: Matsuda Mamoru , Fujioka Yoshio
Published: July 2006

After a description of a centrifugal carbon dioxide absorber, the effects of variables on the mass transfer coefficient of the absorber have been reported. For the experimental conditions examined, the following conclusions may be arrived at:

(1) When the rate-determining step is gas diffusion, the MEA and DEA liquid of the same concentration have the same mass transfer coefficient as long as the effect of viscosity is negligible.

(2) The transfer coefficient increases linearly as the concentration of an MEA aqueous solution increases.

(3) The relation between the coefficient and the concentration of a viscous DEA aqueous solution is given as:

K G a∝N⁄μ0.5

(4) The relation between the coefficient and the concentration of carbon dioxide in a MEA liquid is given as:

K G a∝e−6.56M

(5) So long as the gas diffusion is the ratedetermining step, the coefficients for two solvents, water and glycerol, differ little.

(6) The coefficient for MEA increases greatly with the liquid flow rate; however, the coefficient for DEA increases only a little.

(7) The coefficient is initially in direct proportion to the square root of the gas flow rate.

(8) The efficiency of the centrifugal absorber remains constant even if the carbon dioxide concentration in the gas stream changes from 3 to 0.2%.

(9) The coefficient is in direct proportion to the logarithm of the rotor revolutions per minute.

(10) Slight modifications, except for packing on the rotor, with the aim of increasing the surface area of a liquid do scarcely anything to improve the absorber.
Oxidation of Alcohols with t-Butyl Chromate. I. The Oxidation of Primary Aliphatic Alcohols
Authors: Suga Takayuki , Kihara Keiichi , Matsuura Tamon
Published: July 2006

Oxidation with t-butyl chromate has been carried out on the straight-chain alcohols with the general formula of R·CH2OH, where R is CH3, CH3(CH2)2, CH3(CH2)3, CH3(CH2)4, CH3(CH2)10, CH3(CH2)14 and CH3(CH2)16, on branched-chain alcohols with a variety of substituents at the carbon alpha or beta to the hydroxymethyl group, and on unsaturated alcohol with an allylic hydroxymethyl group. Thus, a saturated primary alcohol containing the grouping of –CH2·CH2OH, >CH·CH2OH or (Remark: Graphics omitted.)C·CH2OH has been found to produce mixtures of the corresponding aldehyde, acid and ester in comparable yields. On the other hand, an unsaturated primary alcohol with an olefinic double bond on the carbon adjacent to the hydroxymethyl group produces the corresponding aldehyde in a high yield, but not the ester.
The Synthesis and the Reactions of 2,4,6-Tri-(ω-hydroxyalkyl)-1,3,5-triazines
Authors: Nohira Hiroyuki , Nishikawa Yoshihiro , Furuya Yoshiaki , Mukaiyama Teruaki
Published: July 2006

2,4,6-Tri-(ω-hydroxyalkyl)-1,3,5-triazines have been prepared by the reaction of hydrochlorides of cyclic iminoethers, such as 2-iminotetrahydrofuran, 2-iminotetrahydropyrane or 2-iminooxepan, with triethylamine. The reactions of the triazines with o-phenylenediamine or 1,8-naphthylenediamine to give 2-(ω-hydroxyalkyl)benzimidazoles or 2-(ω-hydroxyalkyl)perimidines have also been described.