bluuebunny/crossref_metadata_2025 huggingface dataset:
Bis(succinimidato)copper(II) Complexes with Pyridine, Picolines and Lutidines
Authors: Miki Seiko , Yamada Shoichiro
Published: July 2006

Bis (succinimidato)copper (II) complexes with pyridine and its derivatives have been prepared, the derivatives involving α-, β- and γ-picoline, 2,4-lutidine and 3, 5-lutidine. Depending upon the reaction conditions the following types of complexes have been obtained: (1) red complexes of [Cu(sucim)2(amine)2], (2) violet complexes of [Cu(sucim)2(amine)(OH2)], and (3) indigo or dark-blue complexes of [Cu(sucim)2−(amine)2(OH2)n]. When 2,6-lutidine is employed, however, none of the three types is obtained; rather, a blue compound with the formula of Cu(sucim)2(OH2)2 is isolated.

The configuration of the three types of complexes has been examined, mainly on the basis of the electronic absorption spectra. The complexes of types 1 and 2 consist of quadri-coordinate complexes with a square-planar configuration. The compounds of type 3 consist of quinque- or sexa-co-ordinate complexes.

The configuration of these complexes of the three types in non-donor solvents has also been discussed.
The Electrometric Titration of Thorium with Tellurite
Authors: Sharma V K , Gaur J N
Published: July 2006

Potentiometric and conductometric titrations of thorium nitrate solutions with tellurite show a sharp break at the 1:2 (Th:Te) ratio. Direct volumetric titrations using phenolphthalein as an indictator also show the 1:2 ratio, indicating the formation of normal tellurite. The estimation of thorium by potentiometric, conductometric and direct volumetric titrations using. potassium tellurite has been suggested.
The Acyl-Exchange Reactions of N-Acyl Lactams with Amines. A Novel Synthesis of N-Substituted Amides
Authors: Tani Hisaya , Oguni Nobuki , Araki Takeo
Published: July 2006

N-Acetyl and N-benzoyl lactams consisting of a five-to-seven-membered ring were found to be good acylation reagents. Several amines were acylated with these reagents to give the corresponding amides in good yields.

When N-benzoyl-2-pyrrolidone was used, ring-opened by-products were obtained by the reaction with a secondary amine, such as pyrrolidine and piperidine.

Tosylalanyl-2-pyrrolidone reacted with primary amines to produce the corresponding tosylalanine amides. The alanine methyl ester reacted as a primary amine with tosylalanyl-2-pyrrolidone to afford a dipeptide.
An Application and Modification of the Freeze-out Technique by Quiram and Biller for the Determination of Pollutants in the Atmosphere by Mass Spectrometry
Authors: Hoshino Hiroko , Wasada Nobuhide , Tsuchiya Toshikazu
Published: July 2006

Quiram and Biller’s freeze-out method, originally devised to determine hydrocarbons contained in air above l0 p.p.m. and using a mass spectrometer, was tried on a trace (down to 1/100 p.p.m.) of mercury vapor in atmosphere ; it was proved to give satisfactory results. The freeze-out procedure was then slightly modified. To collect the pollutants, the air sample was circulated automatically for ten minutes through the freezing-out trap instead of repeatedly handling the stopcocks. By this procedure, a blended air sample containing various pollutants above 10 p.p.m. have been analyzed. The precision is about ±10%.
The Vacuum Ultraviolet Absorption Spectra of Aniline and Some of Its N-Derivatives
Authors: Kimura Katsumi , Tsubomura Hiroshi , Nagakura Saburo
Published: July 2006

The vacuum ultraviolet absorption spectra of anilne, N-methylaniline, N-ethylaniline, N,N-dimethylaniline, N,N-diethylaniline and N-n-butylaniline have been measured in the vapor phase by a recording vacuum ultraviolet spectrophotometer, with which the absorption measurements have been extended down to 1500 Å. Some new bands have been found in the vacuum ultraviolet region, and in total five π→π* transtion bands with molar extinction coefficients larger than 1500 have been observed commonly for the anilines. In order to clarify the nature of these bands, a theoretical treatment has been made by considering the configuration interaction among the ground, locally excited and charge-transfer configrations. An excellent agreement has been obtained between the experimental and the calculated result. It has been concluded the the anilines studied here exhibit intramolecular charge-transfer bands characteristic if the electron trasfer interaction between the substituent and benzene ring.
The Szilard-Chalmers Reaction of Several Neutron-Irradiated Inorganic Phosphorus Compounds
Authors: Tanaka Kichizo
Published: July 2006

The distribution of the chemical species containing phosphorus-32 formed by the (n,γ) reaction has been studied for several phosphates as functions of the irradiation conditions in a reactor. The variation in the distribution has been discussed in connection with the radiation annealing process during irradiation, and a comparison of the distribution of the chemical species containing phosphorus-32 by three separation methods has been made.

By means of the analysis of the variation curves of the distribution of the chemical species containing phosphorus-32, the apparent rate constants have been estimated. It has been suggested that the variations in the distribution may be approximately expressed by radiation annealing processes, and that they are affected by pile factors.
Synthesis of Benzocyclobutene by Photochemical Desulfonylation
Authors: Odaira Yoshinobu , Yamaji Kenzo , Tsutsumi Shigeru
Published: July 2006

The synthesis of benzocyclobutene by the photochemical desulfonylation of 1,3-dihydroisothianaphthene-2, 2-dioxide has been studied and the following results obtained; 1) The irradiation considerably accelerates the desulfonylation of the sulfone, while the ultravioletlight has no remarkable effect on the molar ratio of the formed benzocyclobutene and 1,2,5,6-dibenzocycloöctadiene. 2) The rate of desulfonylation is independent of pressure, and the reaction pressure plays a very important role in the further reaction of the intermediate o-xylylene biradical produced by the desulfonylation.
The Complexometric Estimation of Ferric Iron
Authors: Singh Balwant , Mankotia M S , Lamba H S
Published: July 2006

Ferric iron has been determined, alone or in the presence of Ba2+, Ca2+, Sr2+, Cr3+ or Hg2+, by titrating it with CyDTA (disodium salt), using pyrocatechol violet and p-anisidine-thiocyanate as indicators at pH 3.09 and 1.42 respectively. Th4+, F−, C2O42−, Cu2+, Ni2+, Co2+ and Mn2+ have been found to interfere in the complexometric estimation of ferric iron with CyDTA (disodium salt).
Magneto-chemical Studies of Some Organo-Silicon Compounds Containing Si–O Bonds
Authors: Mital R L
Published: July 2006

The diamagnetic susceptibilities of a few organo-silicon compounds have been measured with the help of a very sensitive and accurate microbalance, with an accuracy of the order of 0.5×10−12 c.g.s. e.m.u. The mean value of χsi in these compounds containing Si-O bond is 17.0. The environmental role of Si-O liaisons on the value of χsi has been discussed from the structural point of view.
Stereoselective Synthesis of Nerol
Authors: Yukawa Yasuhide , Hanafusa Terukiyo , Fujita Kaneko
Published: July 2006

Nerol, acyclic monoterpene alcohol, has been stereoselectively synthesized using as an intermediate the unsaturated hydroxylic acid VI, in which the carboxyl and the hydroxymethyl groups are evidently in the cis-relation.
A Semi-empirical MO Theory of σ Electron Systems. II. Bond Polarity and Electronegativity
Authors: Hamano Hidekazu
Published: July 2006

A previously proposed theory is applied to a study of the electronegativity scale and the ionic character of bonds. The general validity of the electronegativity scale and also the relation between the Mulliken and Pauling scales are discussed. The previously defined inductive effect is used as a basis for calculations on MXn-type molecules and on n-alkyl halide molecule. The results are then used for the qualitative interpretation of the experimental dipole moments, nuclear quadrupole coupling constants and fluorine chemical shifts.
A Semi-empirical MO Theory of σ Electron Systems. III. The Bond Additivity Rule
Authors: Hamano Hidekazu
Published: July 2006

The aditivity rules for bond energies and bond moments are discussed on the basis of a previously-proposed theory. The results show that the apparent additivities are partially caused by accidental cancellations when summing over the molecule and essentially by the invariance of the trace of the matrix representing the molecular quantity. Bond energies are then constant in different molecules, whereas bond moments are not, mainly because of the inductive effect.
A High Resolution Nuclear Magnetic Resonance Study of the Styrene-Methylmethacrylate Copolymer
Authors: Kato Yoshinori , Ashikari Nobuyuki , Nishioka Atsuo
Published: July 2006

The information concerning D-units in methyl methacrylate polymer chains has inproved our knowledge about the stereoregularity of the polymer. As an extension of the study, we have examined styrene-methylmethacrylate copolymers prepared under various polymerization conditions. In these cases, the α-methyl resonance of methyl methacrylate does not change, except that the peak position shifts towards a higher magnetic field as the styrene component of the polymer chain increases. A direct evidence of the copolymer structure has been obtained by the analysis of the methoxy resonance. A total of six methoxy resonance lines can be observed if any methyl methacrylate monomer unit in the copolymer chain can be classified only in terms of its placement relative to the neighboring styrene monomer units.

Monomer reactivity ratios have been estimated from the NMR spectra. The results are r1 (styrene)=0.56±0.01 and r2 (MMA) = 0.50±0.03.
Color Reactions of 3-Methyl-2-benzothiazolone Hydrazone with Phenol Derivatives. I. The Spectrophotometric Microdetermination of Catechol, Hydroquinone and Resorcinol
Authors: Kamata Eijiro
Published: July 2006

New spectrophotometric procedures for determining microgram amount of catechol, hydroquinone and resorcinol with MBTH have been described. The sensitivities and selectivites of the reaction are largely dependent on the pH and on the conditions of oxidation: 1) In an ammoniacal medium MBTH gives a stable pink color with catechol and, with hydroquinone, a blue color which is srabilized by acetone. Resorcinol gives only a faint color under these conditions. 2) When ferricyanide is used as a oxidant in a weakly alkaline solution, MBTH gives a sensitive orange color with resorcinol. 3) In an acidic ferric-ferrous redox catechol. At pH 3 the reaction is selective for catechol. 4) Ferric chloride in 1.2n hydrochloric acid is favorable for the determination of hydroquinone and resorcinol in a mixture of the two.
The Reaction of Carbon Monoxide with Organometallic Compounds. IX. The Syntheses of Cyclic Ketones and Polyketones by the Reaction of Carbon Monoxide with Polymethylene Dilithiums
Authors: Ryang Membo , Sawa Yoshihiko , Hasimoto Terukuni , Tsutsumi Shigeru
Published: July 2006

The reactions of carbon monoxide with tetramethylenedilithium, hexamethylenedilithium and pentamethylenedilithium at −70°C have yielded the corresponding poly-ketones (monomer unit: –CO(CH2)n−,n=4,5 and 6) and cyclic ketones (cyclopentanone, cyclohexanone and cycloheptanone). In these reactions, high dilutions of polymethylenedilithiums with a solvent (diethyl ether) lead to the formation of cyclic ketones in good yields. For example, cyclopentanone has been obtained in a 40% theoretical yield.
The Stability Constants of the Palladium, Copper, Nickel, Zinc and Manganese Chelates of 3-Hydroxy-3-phenyl-1-o-tolyltriazene and -1-p-tolyltriazene
Authors: Purohit D N , Sogani N C
Published: July 2006

The stabilities of the palladium, copper, nickel, zinc and manganese chelates of 3-hydroxy-3-phenyl-1-o-tolyltriazene and 3-hydroxy-3-phenyl-1-p-tolyltriazene have been determined in a 70% v/v dioxane-water mixture and at an ionic strength of 0.1m potassium chloride, by employing the Bjerrum-Calvin pH titration technique.
The Reaction of Acetylenecarboxylic Acid with Amines. XII. On the Hydrolysis of the Products Obtained by the Reactions of Diethyl Acetylenedicarboxylate with Amines
Authors: Iwanami Yasuo , Kenjo Yoshihisa , Nishibe Koji , Kajiura Makoto , Isoyama Seiko
Published: July 2006

2-Oxo-3-ethoxycarbonylmethylenepiperazine (IV) and its 6-methyl derivative (V) have been synthesized by the reactions of diethyl acetylenedicarboxylate with ethylenediamine and propylenediamine. These compounds (IV and V), the previously-reported diethyl N-(n-butyl)aminofumarate (VIII), 4-methyl-2-oxo-3-ethoxycarbonylmethylene-3,4,5,6- tetrahydro-2H-1,4-oxazine (X), the newly-synthesized 6-chloro-2-oxo-3-ethoxycarbonylmethylene-3,4-dihydro-2H-1,4-benzoxazine (XII), and 2-oxo-3-ethoxycarbonylmethylene-1,2, 3,4-tetrahydrobenzoquinoxaline (XIV) have been hydrolyzed with 6n hydrochloric acid. The compound XIV has been hydrolyzed, with decarboxylation, to give 2-oxo-3-methyl-1,2-dihydrobenzoquinoxaline, while all the other compounds have been hydrolyzed into pyruvic acid, carbon dioxide, and the amines by the splitting of the carbon-nitrogen bond.

These two types of hydrolyses shown by the compounds have been discussed in connection with their tautomerism between enamine and ketimine forms.
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

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

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

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

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

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>p-CH3>p-NO2>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

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

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

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

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

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

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

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>>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

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

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

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

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

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

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

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

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

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

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

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

(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

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

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>(CH2)2>(CH2)3>(CH2)4,(CH2)5,(CH2)6>CHCl>CMe2
Kinetic Energies of Fragment Ions from n-Butane Resulting from Electron Impact
Authors: Inoue Miyako , Danno Akibumi
Published: July 2006

The discrimination effect on the fragment ions from n-butane produced by electron impact has been investigated using a conventional mass spectrometer. From the effect of discrimination, it has been concluded that the relative intensity of fragment ions with initial energies larger than their thermal energy is markedly dependent on the conditions of measurement. On the basis of the information gained about the effect of discrimination on ions, the amount of the kinetic energy for fragment ions from n-butane has been estimated. From the results of our experiments, it is reasonable to consider that considerable portions of C3H3+, C3H4+, C2H4+ and C2H3+ions are produced with high kinetic energies from the dissociation of the doubly-charged molecule-ion, according as the high kinetic enegy of the CH3+ ion is produced.
The Rheological Properties of Concentrated Suspensions. IV. The Viscoelastic Properties of Concentrated Dispersions in Molten Polymers
Authors: Takano Masaharu , Kambe Hirotaro
Published: July 2006

The dynamic viscoelastic properties of molten polyethylene with various fillers have been measured in nitrogen gas at frequencies from 0.01 to 0.75 c. p. s. The dynamic viscosity and dynamic modulus have been measured at the temperatures of 150∼230 °C.

Glass spheres, calcium carbonate powder and barium sulfate powder have been used as fillers. The average diameter of the particles covers the range of 0.04∼91 μ. The polyethylene used was one of a low density, “ Sumikathene F-70-6,” whose number average molecular weight is 28000.

The dynamic viscosity and modulus of molten polyethylene are increased by the addition of fillers. The viscoelastic properties at low frequencies depend differently on the concentration in each suspension. In suspensions of glass spheres of the larger particle sizes (particle diameter : 24.0, 32.3, 49.5 and 91.1 μ), the concentration dependence of the dynamic viscosity, η′, follows a generalized Robinson’s formula :

ln(η′⁄η′0)=Kφ⁄(1−S′φ)

where η′0 is the dynamic viscosity of polyethylene ; φ, the volume fraction of the suspended particles, and K and S′, 2.5 and 1/0.74 respectively, regardless of the particle size. In suspensions of calcium carbonate of the intermediate particle size (particle diameter : 2.4 μ), the dependence of the dynamic viscosity on the concentration and on the amplitude of oscillation is observed more remarkably than that in suspensions of glass spheres. In suspensions of calcium carbonate and barium sulfate of the smaller particle sizes (particle diameter: 0.04, 0.08 and 0.27 μ), the dynamic viscosity and modulus increase appreciably above a critical concentration of the filler, a point which depends on the particle size. Beyond this critical concentration, the particles seemed to be linked with each other by single polymer molecules.

The dynamic viscosity and modulus at lower frequencies increase remarkably as the mean distance between the surfaces of particles becomes less than the molecular dimension of the polymer. In suspensions of the larger particles of glass spheres, this critical concentration can not be observed up to the highest concentration.

The temperature dependence of the dynamic viscosity at lower frequencies approximately agrees with that of unfilled polymers.

The dependence of dynamic properties on the time and on the amplitude of oscillations is observed in suspensions of calcium carbonate and in those of barium sulfate of comparatively small particles. In the barium sulfate suspensions of the finest particles, the dynamic viscosity and modulus increase with time under periodic strains and decrease with the increase in the amplitude of oscillations. The amplitude dependence of the dynamic modulus is more remarkable than that of the dynamic viscosity generally. In such thixotropic suspensions, the dynamic properties were measured with as small a strain as possible.
Determination of Lead and Thallium(I) in Presence of Each Other by Amperometric Titrations
Authors: Jain D S , Gaur J N
Published: July 2006

A method has been described in which thallium(I) can be determined in presence of lead and vice versa. Thallium is determined amperometrically in presence of lead at pH 11.5 and is titrated with potassium chromate, while lead is determined in presence of thallium by titrating with potassium ferrocyanide. It is possible to determine small amounts of lead in large quantities of thallium and vice versa.
Mean-Square Amplitudes and Force Constants of Tetrahedral Molecules. II. Silicon Tetrachloride
Authors: Morino Yonezo , Murata Yoshitada
Published: July 2006

The atomic distances and the mean-square amplitudes of silicon tetrachloride have been determined by the sector-microphotometer method. The possible sources of experimental errors have been thoroughly examined. The quadratic force constants of the potential function have been determined by the use of the mean-square amplitudes thus obtained, by combining them with the vibrational frequencies obtained from the Raman spectrum in the gaseous state. It has been shown that the errors of the force constants originate from those of the mean-square amplitudes by the same order of magnitude as from those of the frequencies.
1-Hydroxy-1,2,3-benzotriazoles as Analytical Reagents. I. 4-Nitro-1-hydroxy-1,2,3-benzotriazole as a Specific Reagent for Silver
Authors: Sharma H L , Mukerji S K
Published: July 2006

4-Nitro-1-hydroxy-1,2,3-benzotriazole (R) has been used as a reagent for the gravimetric estimation of silver. The precipitation of the metal by this reagent is complete between pH 2.8–4.3, and after drying at 120°C the composition of the precipitate corresponds to the formula AgC6H3O3N4. The presence of other metal ions does not interfere in the estimation. For complete precipitation of the metal, double the stoichiometrically required amount of R was used and it was found that variation of the interval between the precipitation and filteration does not effect the result. The solubility of R is 0.2134 g./100 g. of water at 30°C.
The Cationic Copolymerization of Styrene and α-Methylstyrene in Liquid Sulfur Dioxide
Authors: Iino Masashi , Tokura Niichiro
Published: July 2006

The copolymerizations of styrene and α-methylstyrene in liquid sulfur dioxide have been carried out at −40°C using boron trifluoride etherate as a catalyst, and the results compared with the same copolymerizations in methylene dichloride at −20°C. The r1 and r2values have been estimated by NMR spectrometry as 0–0.1 and over 20 in liquid sulfur dioxide, and 0.2–0.3 and 12±2 in methylene chloride. The styrene unit sandwiched between two α-methylstyrene units has been calculated by a comparison of the phenyl doublet with phenyl singlet absorptions. The (S) per cent (S is the sandwiched styrene sequence, M–St–M, in the copolymer, where St is the styrene unit and M is the α-methylstyrene unit) has been estimated. In liquid sulfur dioxide, S is approximately zero. This fact agrees well with the large r2 value. The reason for such a non-alternative nature of the copolymerization in liquid sulfur dioxide had also been discussed.
A Note on the Stereospecific Formation of α-Aminoalcohols
Authors: Ichihara Akitami , Maekawa Haruki , Kanda Reiko , Shirahama Haruhisa , Matsumoto Takeshi
Published: July 2006

The synthesis of the compound which was erroneously proposed for muscarin by Kögl in 1931 has been described.
The Oxidation of Iodide to Iodite and the Reduction of Iodate to Iodite in Iodine Solutions of Permanganate and Some of the Carboxylic Acids
Authors: Gupta Yugul Kishore , Bhargava Anand Prakash
Published: July 2006

Permanganate oxidises small amounts of iodide to iodite in the presence of malonic, citric or malic acid. The colourless reaction mixtures always have an oxidising capacity equivalent to four times the concentration of the iodide originally taken. In mixtures of permanganate and one of these acids, iodate is reduced to its 2/3 oxidising capacity, showing the formation of iodite. A mechanism for this has been suggested. Iodine is the product in the first stage of the oxidation of iodide, which is further oxidised to iodite or iodate or which may react with the oxidation products of the organic acids. Citric acid probably gives a number of such iodinated products, one of which is solid.
A Synthesis of Oxytocin
Authors: Sakakibara Shumpei , Nobuhara Yoshibumi , Shimonishi Yasutsugu , Kiyoi Reiko
Published: July 2006

N-Carbobenzoxy-S-methoxybenzyl-l-cysteinyl-l-tyrosyl-l-isoleucyl-l-glutaminyl-l-asparagin-yl-S-p-methoxybenzyl-l-cysteinyl-l-prolyl-l-leucylglycinamide (IX) was synthesized by the step-wise elongation method, and highly potent oxytocin was obtained from IX by treatment not only with sodium in liquid ammonia, but also with boiling trifluoroacetic acid, followed by the usual aeration procedure. It was demonstrated during the reactions that the newly introduced S-p-methoxybenzyl group could be cleaved more easily than the usual S-benzyl group, and that the new S-protecting group was useful in the preparation of complicated cysteinyl peptides.
Concerning the Structure of Trimethyltin Fluoride
Authors: Yasuda Kiyoshi , Kawasaki Yoshikane , Kasai Nobutami , Tanaka Toshio
Published: July 2006

The structure and the nature of the bonds in trimethyltin fluoride are discussed on the basis of the infrared and the Raman spectra with reference to the results of the X-ray diffraction study by Clark et al. and a few additional X-ray data obtained on the fluoride and related trimethyltin compounds. The most reasonable structure is one in which the planar trimethyltin group is bridged by the fluorine atom forming a non-linear unsymmetrical Sn-F…Sn bond. The distorted bipyramidal configuration around the tin atom can be explained in terms of involvement of the d-orbitals of the tin atom in the bonding.
The Preparations and the Electronic Spectra of Sexa-co-ordinate Molybdenum(III) Complexes
Authors: Komorita Takashi , Miki Seiko , Yamada Shoichiro
Published: July 2006

Several sexa-co-ordinate molybdenum(III) compounds containing some of chloride ions, bromide ions, urea, thiourea N,N-dimethylformamide and pyridine as ligands have been prepared, and their electronic absorption spectra determined.

It has been shown that the spectrum of the sexa-co-ordinate molybdenum(III) compound generally has two spin-forbidden and two spin allowed bands. The ligand field parameters of octahedral molybdenum(III) complexes have been calculated and compared with those of the corresponding chromium(III) complexes.
The Oligomerization of Butadiene with an Iron Complex Catalyst
Authors: Hidai Masanobu , Uchida Yasuzo , Misono Akira
Published: July 2006

The oligomerization of butadiene with the catalyst system of iron(III) acetylacetonate and triethylaluminum has been studied. The products obtained by the use of this catalyst consist of two types, one of which is dimers and trimers, and the other is polybutadiene, with an average polymerization degree of seven. The dimers are 3-methylhepta-1, 4, 6-triene and cycloocta-1, 5-diene. The trimers have been confirmed to be n-dodeca-1, 3, 6, 10-tetraene and a branched isomer.

The effects of the ratio of the catalyst components to the concentration of the catalyst have been also studied.

From these results, it has been concluded that oligomerization proceeds by a mechanism different from that of polymerization.

To elucidate a transition state for oligomerization, the visible light spectra and the magnetic susceptibility of the reaction solution have been measured and a complex in which butadiene coordinates to reduced iron atom has been assumed as the transition state.