bluuebunny/crossref_metadata_2025_split huggingface dataset:
Nuclear Magnetic Resonance Spectra of Polymethyl Methacrylate in Solution. II. The Calibration of the Infrared Absorption Method and Some Applications to the Study of the Polymerization Mechanism
Authors: Kato Yoshinori , Watanabe Haruaki , Nishioka Atsuo 
Published: July 2006

Abstract
In the preceding paper it was reported that the degree of the stereoregularity of polymethyl methacrylate could be determined from the NMR spectrum through the analysis of three peaks due to the α-methyl groups. It has been found that the infrared spectrum can also give an equivalent result if it is once calibrated by the NMR method.
We have considered a statistical method to interpret any locus in the ternary diagram which corresponds to the change in the stereoregularity of polymers with the polymerization temperature and with the type of catalyst. By introducing two parameters, the average sequence length of I-, D- and S-blocks have been calculated.
On the other hand, the acetone-extraction of the samples prepared in anionic polymerization has been carried out in order to determine the degree of stereoregularity of both the extract and the residue. From the plots in the ternary diagram, we have discussed some mechanisms of the anionic polymerization. We may conclude that two different mechanisms take place in the course of the ploymerization using an R2Mg catalyst in contrast with the polymerization catalyzed by RMgBr.
Heats of Mixing for Binary Mixtures. The Energy of Hydrogen Bonding between Alcohol and Ketone Molecules
Authors: Murakami Sachio , Amaya Kazuo , Fujishiro Ryoichi 
Published: July 2006

Abstract
A microcalorimeter of the twin type has been constructed, one which is operated semiautomatically. Using this apparatus, the heats of mixing for alcohol-ketone, alcohol-hexane, and ketone-hexane solutions have been measured. From these heats of mixing, the hydrogen bond energy of the O–H…O= type has been estimated to be about 4kcal. by means of the thermochemical cycle.
The Theory of the Indicator Transition in Chelatometry
Authors: Nakagawa Genkichi , Tanaka Motoharu 
Published: July 2006

Abstract
General equations have been proposed for the indicator transition in the chelatometry of a metal in the presence of other metals, using HA or the NY-HA system as an indicator. The validity of these equations has been confirmed experimentally in several examples of practical importance. If the constants involved are all available, it is possible, by the aid of the proposed equations, to predict the optimum conditions for any type of chelatometry.
The Electronic Structures and Spectra of Pentalene and Heptalene
Authors: Nakajima Takeshi , Yaguchi Yoshiko , Kaeriyama Ryoji , Nemoto Yuzo 
Published: July 2006

Abstract
The semiempirical SCF technique has been applied to pentalene and heptalene. Self-consistency has been achieved for the two symmetry types, D2h and C2h, and the total binding energy examination indicates that in both the molecules the asymmetrical structure (C2h) is more favorable energetically than the symmetrical one (D2h). The calculated uneven charge distributions, the high free valence values, and the low ionization potentials supply the reasons for the instability of these molecules. The theoretical spectral calculations for the asymmetrical structures are in good agreement with the available experimental data. It may be concluded that, in these molecules, there exists a remarkable bond length alternation, and that in this sense they cannot be considered aromatic. They show, rather, characteristics of cyclic polyolefins.
Kinetic Studies of Solvolysis. IX. The SNl-type Cleavage of t-Butyl p-Substituted-phenyl Ethers and Optically-active α-Phenethyl Phenyl Ether by Hydrogen Halides in a Phenol-Dioxane Solvent
Authors: Okamoto Kunio , Takeuchi Ken-ichi , Shingu Haruo 
Published: July 2006

Abstract
1) Hydrogen chloride cleaves t-butyl phenyl ether at 70.0°C in 20 wt.% phenol-dioxane. The reaction is kinetically first-order in each reactant. The second-order rate constants show an increase with increasing phenol concentrations, and p-nitrophenol accelerates the reaction.
2) The hydrogen bromide cleavage of t-butyl phenyl ether at 19.2°C in 20wt. % phenol-dioxane gives a second-order rate constant greater than that of hydrogen chloride.
3) The rate sequence of the hydrogen chloride cleavage of t-butyl p-substituted-phenyl ethers at 70.0°C in 20 wt.% phenol-dioxane is H&gt;p-CH3&gt;p-NO2&gt;p-Cl, and there is no linear relationship between those rate constants and Hammett’σ constants.
4) The hydrogen chloride cleavage of (+)-α-phenethyl phenyl ether at 30.0°C in 50.0 wt.% phenol-dioxane obeys good second-order kinetics for both polarimetric and titrimetric runs. The value of the polarimetric rate constant exceeds that of the titrimetric constant, and from the final reading of the polarimetric run it has been concluded that the α-phenethyl chloride produced in the cleavage partly retained the configuration.
5) It has been concluded that the hydrogen halide cleavage of those phenyl ethers in phenol-dioxane proceeds through the protonated ether produced by a rapid equilibration between hydrogen halide and those ethers, and that the protonated ether reacts by an Sni-like mechanism. For the cleavage of the opticallyactive ethers, a detailed mechanism involving two parallel series of cleavage reactions of antipodal protonated ethers has been suggested wherein the partial racemization of the product is explained as resulting from the interconversion between the antipodal intermediates. For each series of Sni-type reactions, the possibility of a two-stage or three-stage mechanism has been discussed.
Polymerization of Acrolein Initiated by Gamma-rays
Authors: Toi Yoshio , Fujii Toshikatsu , Hachihama Yoshikazu 
Published: July 2006

Abstract
The bulk polymerization of acrolein initiated by gamma-rays at various temperatures has been studied. Most of the polymers obtained at −20° and 10°C are insoluble in organic solvents. On the other hand, most of the polymers obtained at −78°C are soluble in pyridine, dimethylformamide, and dimethylsulfoxide at room temperature. The aldehyde content of the soluble polymer is 75∼85% of the theoretical amount, and its intrinsic viscosity is 0.32∼1.20.
The influence of the polymerization temperature on the solubility of the polymer in organic solvents has been discussed, as has the polymerization mechanism.
The Purification of Silicon Tetrachloride from Traces of Boron with N,N-Diphenylacetamide
Authors: Nakagawa Masanao 
Published: July 2006

Abstract
A standard solution of boron in silicon tetrachloride (1 p.p.m. or 1 p.p.b. order) has been distilled in the presence of N,N-diphenylacetamide. The residue of the distillation has been analyzed for boron by the spectrophotometric measurement of the methylene blue complex of boron tetrafluoride ions. The boron of an order of 1 p.p.m. has been about 100% recovered when the solution in silicon tetrachloride has been distilled after being stirred for 24 hr. with the amide. The recovery of the boron of an order of 1 p.p.b. has also been satisfactory. The silicon tetrachloride distilled off in the presence of the amide, therefore, believed to be almost free of boron.
The Oxo Reaction of Unconjugated α, ω-Diolefin
Authors: Morikawa Masanobu 
Published: July 2006

Abstract
Pimelaldehyde and 2-methylheptanedial have been obtained from 1, 4-pentadiene and 1, 5-hexadiene respectively by carrying out the oxo reaction in alcohol at a lower temperature (below 100°C) using a rhodium catalyst.
The Complex Formation of Boron Fluoride with Lower Olefins at Low Temperatures. II. Isotope Effects and Absorption Spectra of Boron Fluoride-Butene Systems
Authors: Nakane Ryohei , Watanabe Tsunao , \={O}yama Toshiyuki 
Published: July 2006

Abstract
The equilibrium constants of isotopic exchange between boron fluoride gas and boron fluoride in 1-butene and cis-2-butene solutions have been found to be 1.017±0.002 and 1.020±0.002 at −112°C, and 1.012±0.002 and 1.015±0.002 at −95°C. In boron fiuoride-trans-2-butene system, the equilibrium constant is 1.011±0.002 at −112°C and 1.006±0.002 at −95°C.
When 1-butene and ethylene are dissolved in liquid boron fluoride, the intensity or the wave number of the V ← N absorption bands in mono-olefins is changed and the fine structure of these bands disappear.
Thus, the following conclusion, more decisive than that of the preceding work, has been obtained:
Boron fluoride can form liquid σ-complexes with polar mono-olefins with electron-releasing substituents. On the other hand, with nonpolar mono-olefins it cannot form σ-complexes but only unstable π-complexes. Although σ-complexes are not the intermediate products in reactions by boron fluoride catalysts, it is possible that these reactions proceed through π-complexs. However, the rate-determining step does not involve the initial formation of π-complexes.
It has also been suggeted that the equilibrium constant may be proportional to the ratio of dative to no-bond structure in the complex, and it has been found that the larger the equilibrium constant, the higher become the stability and the catalytic activity of the complexes.
The Spectra of Intermediates and the Mechanism of Their Formation in the Color Reactions of Polynitroanisoles with the Methoxide Ion
Authors: Abe Takehiro 
Published: July 2006

Abstract
By the simple LCAO MO treatment, introducing the reaction parameter, the following expectations have been obtained for the color reactions of polynitroanisoles with the methoxide ion: 1) Meisenheimer’s intermediates are more easily formed and are more stable as the numbers of nitro groups increase. 2) The energies of activation for the formation of the intermediates become smaller as the numbers of nitro groups increase. These expectations are in agreement with the experimental results.
Infrared Spectra of Metal Chelate Compounds. X. A Normal Coordinate Analysis of Dithiooxalato Complexes
Authors: Fujita Junnosuke , Nakamoto Kazuo 
Published: July 2006

Abstract
The infrared spectra of dithiooxalato complexes of platinum(II), palladium(II), nickel-(II) and cobalt (III) have been obtained in the range between 4000 and 280 cm−1. A normal coordinate analysis has been carried out for the 1 : 1 (metal/ligand) model of the dithiooxalato platinum (II) complex. The results indicate that the Pt–S stretching bands are at ca. 430 and 320 cm−1 and that the corresponding force constant is 2.30×105 dyn./cm.
The Mercury-photosensitized Decomposition of Neopentane at High Temperatures
Authors: Sato Shin , Tsunashima Shigeru 
Published: July 2006

Abstract
The mercury-photosensitized decomposition of neopentane has been investigated over the temperature range 25°C to 500°C. If the quenching of excited mercury atoms by neopentane molecules is assumed to occur both physically and chemically, as follows:
(Remark: Graphics omitted.)
it has been shown that k2&gt;&gt;k3 and that the quenching cross section of reaction is about 0.6 Å2, which is almost temperature independent, and E3\simeq4 kcal. Above 250°C, neopentyl radicals decompose to methyl radicals and isobutene molecules with an activation energy of 17±2 kcal.
The Reaction Mechanism of α-Bromo-α, β-unsaturated Ketones with Amines
Authors: Inokawa Hiromi 
Published: July 2006

Abstract
It has been considered that, in the reaction of α-bromo-α, β-unsaturated ketones with amines, α-bromo-β-amino ketones are produced first by the 1,4-addition of amines and converted to ethylenimine ketones in the presence of excess amines. The ethylenimine ketones react with hydrogen chloride to give α-chloro-β-amino and β-chloro-α-amino ketones, the yields of these ketones depending on the variation of the fractional positive charge at the α-carbon atom and on the delocalization energy on the β-carbon atom by R′.
Colloid Chemical Studies of Starching Materials. V. Rheological Properties of Concentrated Polyvinyl Alcohol Solutions
Authors: Nakagaki Masayuki , Nishii Takako 
Published: July 2006

Abstract
The dynamic viscosity, dynamic rigidity and steady-flow viscosity at 30°C have been measured for 11∼12% solutions of four specimens of polyvinyl alcohol, GH-17, GH-23, NH-17 and HN-26, 20, 60 and 110 hr. after the preparation of the solutions.
In the dynamic measurement by a top-drive coaxial oscillation rheometer, the relations of η and G vs. ω did not depend on time and have all been explained by Rouse’s theory except for NH-26, the latter showing time and ω dependencies of the structure. In the steady-flow measurement by a coaxial rotation viscometer, the viscosity of all the polymers showed both time and velocity gradient dependencies.
Confirmation of 5-Pyrophosphomevdonate as an Intermediate in the Enzymatic Synthesis of Bacterial Phytoene from Mevalonate
Authors: Suzue Ginzaburo 
Published: July 2006

Abstract
In phytoene biosynthesis from mevalonic acid and 5-phosphomevalonic acid by the enzyme preparation from the mutant of Staphylococcus aureus, a phosphorus-containing substance has been isolated as an intermediate compound. After purification by paper chromatography, column chromatography and paper electrophoresis, this substance has been shown to contain phosphorus and mevalonic acid in the molar ratio of 2:1. From its behavior with regard to prostatic phosphomonoesterase, together with the above-mentioned results, this substance has been concluded to be 5-pyrophosphomevalonic acid.
The Ring-opening Addition Reactions of Exo-imino Cyclic Compounds with Carboxylic Acids
Authors: Mukaiyama Teruaki , Tamura Yorikazu , Fujisawa Tamotsu 
Published: July 2006

Abstract
The rate constants, the activation energies and the entropies of the activation of the ring-opening addition reactions of exo-imino cyclic compounds, such as ethylene N-phenyliminocarbonate, 2-phenylimino-3-methyloxazolidine and N-substituted 2-iminotetrahydrofurans, with carboxylic acids in various solvents have been determined in order to study the mechanism of these reactions.
The rate of the reactions increases as the acidity of carboxylic acids increases, and the linear Hammett relation is observed in the reactions of ethylene N-phenyliminocarbonate or 2-phenylimino-3-methyloxazolidine with meta- and para-substituted benzoic acids.
The relative rate of the reactions of the three exo-imino cyclic compounds, ethylene N-phenyliminocarbonate, 2-phenylimino-3-methyloxazolidine and 2-phenyliminotetrahydro-furan, with carboxylic acids is as follows:
(Remark: Graphics omitted.)
These results show that the ring-opening addition reaction involves two stages, namely, the initial formation of the intermediate salt from the exo-imino cyclic compound with carboxylic acid, followed by the reaction of the salt with the other acid to give the ring-opening addition compound.
Infrared Spectroscopic Studies of Acido-pentammine Cobalt(III) Complexes, Sulfato, Nitrito, Nitrato and Carbonato Complexes
Authors: Tanaka Nobuyuki , Sugi Haruko , Fujita Junnosuke 
Published: July 2006

Abstract
The infrared spectra of twelve acido-pentammine cobalt(III) complexes have been obtained in the range between 5000 and 250 cm−1, and the vibrational frequencies of the co-ordinated oxyanions have been assigned from the normal co-ordinate treatment based on Wilson’s method and on the Urey-Bradley potential field. The results of the calculation show that the co-ordination effects on these oxyanions are fairly large and that the bonds between cobalt and oxygen atoms have a considerably covalent character.
The Photometric Determination of Traces of Platinum in Electrolyte using Copper Sulfide as a Collector
Authors: Ujihira Yûsuke , Hirano Shizo 
Published: July 2006

Abstract
A method of separation has been developed for the photometric determination of trace amounts of platinum in electrolytes for the electrolysis of chlorate by the use of carrier precipitation with copper sulfide.
After a sample solution had been treated with concentrated hydrochloric acid, the preliminary separation of platinum was made by carrier precipitation with copper sulfide, and, following the ignition of the precipitate, the ashes was introduced into a hydrochloric acid solution. The orange-colored substance which was produced by the addition of the stannous chloride solution was extracted into ethyl acetate, and the color intensity of the ethyl acetate phase was measured at 420 mμ.
The recovery of platinum was quantitative, and the removal of macro amounts of salt and divers ions was satisfactory.
Experiments using synthetic sample solutions indicate that trace quantities of platinum in electrolytes for the electrolysis of sodium chlorate could be determined by this method with an accuracy of from 5 to 10% in the range between 0.02 and 0.00 p.p.m.
Reactions of Methylene Radicals with Benzene and Toluene in the Gas Phase
Authors: Terao Terumi , Shida Shoji 
Published: July 2006

Abstract
The reactions of methylene radicals produced by the photolysis of ketene with benzene and with toluene in the gas phase have been studied. The reaction of methylene with benzene gave cycloheptatriene and toluene in a ratio 7 to 3. The ratio varied neither with the pressure raised by the added nitrogen or carbon dioxide nor with the wave lengths of the incident radiation.
The products obtained in the reaction of methylene with toluene were ethylbenzene, m-xylene, p-xylene and an unidentified product, their percentages being 25, 40, 25 and 10% respectively. About a five-fold increase in the amount of ethane has been observed over that observed in the reaction with benzene or in the photolysis of pure ketene. This fact indicates that the abstraction of the hydrogen atom by methylene from the methyl in toluene does occur, but that that from the benzene ring does not. Oxygen did not alter the relative yield among the products in the reactions of methylene with either benzene or with toluene. This suggests that the products are formed by the reactions of singlet methylene with benzene and toluene via norcaradiene-type intermediates.
It has quantitatively been shown that the reactivity of methylene redicals is very high with aromatics, ethylene and acetylene, as with ketene.
The Rearrangement Polymerization of Propenylbenzene
Authors: Murahashi Shunsuke , Nozakura Shun’ichi , Tsuboshima Kazuhiko , Kotake Yahide 
Published: July 2006

Abstract
1) Propenylbenzene has been found to polymerize by a cationic mechanism in two ways. Both the structure -(CHPh-CH(CH3))n- (I) resulting from the usual opening of the double bond and the structure -(CHPh-CH2-CH2)- (II) resulting from the rearrangement along the backbone chain of the resultant polymer occur.
2) The relative ratio of structures I/II has been pursued using the ratio of infrared absorptions, CH3/CH2, as a measure.
3) The rearrangement polymerization is generally preferred by mild catalysts, such as BF3-etherate, while the polymerization to I has been found to predominate in polymerization with BF3.
4) On the basis of the observed effect of reaction variables on the rate of polymerization and on the I/II ratio, a propagation mechanism has been proposed which includes the “gegen” ion attack on the methyl hydrogen of propenylbenzene.
5) Termination reaction by a “gegen” ion or an initiator has been shown to be important in polymerization catalyzed by BF3-complexes.
On the Synthesis of a Hemopeptide
Authors: Inouye Sumiko , Sakakibara Shumpei , Akabori Shiro 
Published: July 2006

Abstract
Carbobenzoxy -S- benzyl -l- cysteinyl-glycyl-glycyl -S- benzyl-l-cysteinyl -l- histidine benzyl-ester has been synthesized, and then it has been hydrogenated to the free peptide by treatment with sodium in liquid ammonia. The free peptide has been coupled with protohemin in the liquid ammonia to form a hemopeptide, which has then been purified by counter-current distribution. The visible and infrared absorption spectra of the product have been compared with those of natural hemopeptide, which was obtained from beef-heart cytochrome c by peptic degradation. The peroxidative activity of the synthetic hemopeptide is about 100 times as strong as that of hemin, but it is inferior to that of natural hemopeptide.
The Solid State Polymerization of Trioxane by the Simultaneous Sublimation of the Monomer and Iodine
Authors: Miyama Hajime , Kamachi Mikiharu 
Published: July 2006

Abstract
It has been found that the polymerization of trioxane occurs in the solid state by subliming the monomers and iodine simultaneously on a cooled surface and raising the temperature over 10°C. This method gives a polymer of a high degree of polymerization in a good yield. As a result of chemical kinetic treatments, the polymerization rate has been found to be proportional to [C]0.25 [M]2/[P]2, where [C], [M] and [P] are the concentrations of iodine, the monomer and the polymer respectively. The reaction mechanism has been discussed in connection with the results of ESR and X-ray and measurements.
Monolayer Studies of the Interactions between Histidyl Polypeptides and Metal Ions. I. The Effect of Cupric Ions on the Monolayer Properties of Histidyl Polypeptides
Authors: Yamashita Takuya , Isemura Toshizo 
Published: July 2006

Abstract
The effects of salts on the monolayer properties of poly-1-benzyl-l-histidine and copoly-2:2:2: l-(glycine, O-benzyl-Dl-serine, β-benzyl-l-aspartate, 1-benzyl-l-histidine) have been investigated.
In the presence of potassium chloride, sodium sulfate, and sodium acetate (pH 5.6), the film expansion has been observed; this has been interpreted in terms of the salt formation between side chains and anions. The addition of cupric sulfate to a subsolution causes the film to expand to increase in surface viscosity and potential, for which cross linkage by complex formation between side chains and metal ions might be responsible.
On the other hand, the monolayer of the copolymer is not affected by the presence of cupric sulfate because of the smaller content of histidyl residue.
Flammulin, an Antitumor Substance
Authors: Watanabe Yumi , Nakanishi Koji , Komatsu Nobuhiko , Sakabe Tomohei , Terakawa Hirofumi 
Published: July 2006

Abstract
(1) Flammulin, an antitumor substance of Flammulina velutipes, has been demonstrated to be a basic simple protein with a molecular weight of about 24000 and to be homogeneous in electrophoresis and sedimentation.
Analyses of amino acids indicated the following composition:
Lys5, His5, Arg14, Asp37, Thr20, Seri12, Glu18, Pro19, Gly22, Ala34, Half-cys3, Val5, Met0, isoLeu6, Leu9, alloisoLeu1, Tyr4, phe8, Try1, (CONH2)25.
Photoconductivity of Polyacenaphthylene and Its Nitrated Derivatives
Authors: Inami Akira , Morimoto Kazuhisa , Hayashi Yoshiki 
Published: July 2006

Abstract
The photoconductive properties of polyacenaphthylene and nitrated polyacenaphthylene have been studied using both the sandwichcell method and the relative-surface-potential method. The polyacenaphthylene shows little photoconductivity, while the nitrated polymer obtained by the partial nitration of polyacenaphthylene shows considerable photoconductivity. The photocurrent depends on the degree of nitration.
Preparation of Some Bis(fluorodimethylsilyl)alkanes
Authors: Kumada Makoto , Naka Kiyomi , Yamamoto Yoshihiro 
Published: July 2006

Abstract
It has been established that the demethylation of bis(trimethylsilyl)alkanes of the general formula Me3SiRSiMe3 by concentrated sulfuric acid, followed by fluorination with ammonium hydrogenfluoride, can successfully be used for the method generally applicable to the preparation of bis(fluorodimethylsilyl)- alkanes, FMe2SiRSiMe2F. Although Si-Me cleavage was the main reaction in most cases, some part of the reaction gave a cleavage between silicon and the R grouping.The ease of the cleavage of R from silicon was found to decrease in the following order:
CH2,CHMe&gt;(CH2)2&gt;(CH2)3&gt;(CH2)4,(CH2)5,(CH2)6&gt;CHCl&gt;CMe2