bluuebunny/crossref_metadata_2025_split huggingface dataset:
Studies of the Organic Reactions of Metal Carbonyl. II. The Reaction of Olefin Oxide with Cobalt Hydrocarbonyl
Authors: Takegami Yoshinobu , Yokokawa Chikao , Watanabe Yoshihisa , Masada Hiromitsu 
Published: July 2006

Abstract
The reactions of olefin oxides with cobalt hydrocarbonyl have been studied.
The effect of the reaction conditions on the nature of the reaction, especially that of propylene oxide, has been examined in detail. Propylene oxide gave only the products with β-hydroxy-n-butyryl structure under these reaction conditions: temperature, 25∼45°C; atmosphere; nitrogen or carbon monoxide; and mole ratio of propylene oxide, 1.4∼6.2. The inhibitory effect of a nitrogen atmosphere on the formation of carbonylated products (ester and aldehyde) has been observed ; under nitrogen, some side reaction was highly promoted, and the formation of carbonylated products was thereby prevented.
The reactions of ethylene oxide, cyclohexene oxide, styrene oxide and epichlorohydrin have also been studied. In the reactions of styrene oxide, the mole ratio of styrene oxide had a significant effect on the nature of the reaction; at a relatively small mole ratio, the reduction gave, mainly two isomeric alcohols, but as the mole ratio increased, the carboxylation reaction seemed to increase. Epichlorohydrin gave a product with a γ-chloro-β-hydroxy-n-butyryl structure, which corresponds to that which propylene oxide gave.
The order of the reactivity of these olefin oxides is as follows: cyclohexene oxide (about 5) and styrene oxide&gt;propylene oxide (1)&gt;ethylene oxide&gt;&gt;epichlorohydrin (1⁄20∼40) ; (the numbers indicate the relative reactivities).
This fact seems to indicate that, in general, internal (and conjugated) olefin oxides are more reactive than terminal olefin oxides. By analogy with the relative reactivity of propylene oxide and epichlorohydrin with cobalt hydrocarbonyl, perchloric acid and ammonia, it may reasonably be considered that cobalt hydrocarbonyl reacts as an acid.
Pentene-1 appeared to be less reactive than propylene oxide.
Studies of the Organic Reactions of Metal Carbonyl. III. The Hydroformylation of Olefin Oxides
Authors: Yokokawa Chikao , Watanabe Yoshihisa , Takegami Yoshinobu 
Published: July 2006

Abstract
The hydroformylation reactions of ethylene oxide and propylene oxide have been carried out; the character of this type of reaction may be summarized as follows:
1) Propylene oxide reacts with water gas, in the presence of dicobalt octacarbonyl serving as a catalyst, to give β-hydroxy-n-butyraldehyde as the major product, but it is important to keep the reaction temperature between 80 to 100°C in order to hold the high selectivity of this reaction.
2) At temperatures below 80°C, the reaction does not take place; on the other hand, at temperatures above 100°C, the isomerization of propylene oxide to acetone predominates, and the other side-reactions, such as the dehydration of the hydroformylation products, hydrogenation, condensation and polymerization, take place simultaneously.
3) Ethylene oxide seems to undergo hydroformylation under the same conditions as those used for the propylene oxide, but only a small amount of acrolein is obtained as the hydroformylation product. The expected product, i.e., β-hydroxypropionaldehyde, is formed, but this compound is easily converted into acrolein and the latter seems to polymerize to give a large amount of a resinous or oily material.
An Automatic Recording Analyzer for the Determination of Dissolved Oxygen in Boiler Feed Water
Authors: Tanno Kazuo 
Published: July 2006

Abstract
An automatic recording analyzer for the determination of dissolved oxygen (in concentrations up to 50 p.p.b.) in boiler feed water by Winkler’s method has been described. The instrument is so designed as to perform automatically most of the operations involved in manual analysis, such as sampling, the addition of reagents, titration, recording, and cleansing. The series of required operations (all of the operations in both sample and blank analyses) is completed in 30min. and is automatically repeated. A more important feature of the instrument is that hydrazin-treated feed water, as well as feed water not treated with hydrazin, can be analyzed with accuracy. The oxygen content, however, cannot be read directly on the recorder chart and must be calculated from the recorded quantities of the titrant used. The precision of oxygen determination is within 2 p.p.b. The reproducibility is better than that of manual analysis.
Heat Capacity and Thermodynamic Functions of K2CuCl4·2H2O and (NH4)2CuCl4·2H2O from 13 to 310°K
Authors: Suga Hiroshi , Sorai Michio , Yamanaka Tadashi , Seki Syûzô 
Published: July 2006

Abstract
The heat capacity of copper potassium chloride dihydrate and copper ammonium chloride dihydrate crystals have been measured between 13 and 310°K. The latter crystal shows a λ-type anomaly in the heat capacity curve which seemed to be due to the orientational order-disorder process of ammonium groups. The heat capacity of (NH4)2CuCl4·2H2O exhibits a maximum value of 76.290 cal. deg.−1 mol−1 at 200.50°K. By plotting the temperature derivative of heat capacities, the normal contribution from the lattice to the heat capacity of (NH4)2CuCl4·2H2O has been estimated. In this case the corresponding values for K2CuCl4·2H2O has been taken as a reference. By subtracting the estimated normal heat capacity from the experimentally measured one, approximate values of the entropy change, ΔS=1.945 cal.deg.−1 mol−1, and the heat capacity jump, ΔCp=13.24 cal. deg−1 mol−1, associated with the orientational ordering of the linearly-arranged ammonium ion system have been given.
The values of the heat capacity, entropy, enthalpy, and Gibbs free energy of both crystals have been tabulated at selected temperatures. The standard values of the entropy and enthalpy are: K2CuCl4·2H2O, S0=84.95 cal. deg−1 mol−1, H0–HO0=11980 cal. mol−1; (NH4)2·CuCl4·2H2O, S0=92.30 cal.deg.−1mol−1, H0–HO0=14220 cal. mol-−1.
An Attempt to Determine Eosine’s S*→T Transition Probability and Evidence for the Participation of a D–D Redox Mechanism
Authors: Ohno Takeshi , Usui Yoshiharu , Koizumi Masao 
Published: July 2006

Abstract
Using ATU and EDTA as a reducing agent, an attempt was made to determine the transition probability of the singlet excited state to the triplet state. The values obtained are 0.032 for ATU and 0.080 for EDTA. The cause of this difference is not known at present.
Deactivation of the triplet state by a leuco dye as well as by the ground state dye was confirmed. In the case of ATU, it was established that a D-D mechanism operates when the concentration of ATU islow and the con centration of dye is high. This conclusion was supported by the fact that at a constant low concentration of ATU the 1/φ—[D]o plot deviates from linearity, when the dye concentration becomes high.
The Pectic Acid from the Pulp of Jackfruit (Artocarpus Integrifolia). II
Authors: Gupta U K Sen , Das A 
Published: July 2006

Abstract
The jackfruit pectic acid has been converted into ethylene glycol ester, which, on reduction with sodium borohydride, gives a galactan. Methylation studies of the original polysaccharide and of the reduced pectic acid suggest the presence of chains of 1→4 linked α-d-galacturonic acid residues in the pectic acid which is associated with a glucan.
Structure of the Polysaccharides from Unripe Mango (Mangifera Indica LINN). III
Authors: Das A , Gupta U K Sen 
Published: July 2006

Abstract
The polysaccharide isolated from the mesocarp of unripe mango has been found to be a mixture of three component polysaccharides, viz., a glucan, and araban and a galacturonan. By a methylation study, the glucan has been found to have the same structural pattern as that of the glucan isolated from ripe mango. The araban portion yielded 2,3,5-, 2,3- and 2-O-methyl-l-arabinose. On the basis of these results, a probable structure has been assigned to the araban. The isolation of only 2,3-di-O-methyl-d-galacturonic acid shows that the galacturonan portion is 1→4 linked.
On the Sn–H Bond in Some Organotin Hydrides
Authors: Kawasaki Yoshikane , Kawakami Katsuhiko , Tanaka Toshio 
Published: July 2006

Abstract
The nuclear magnetic resonance spectra of the proton attached directly to the tin atom in several organotin hydrides (RnSnH4−n ; n= 1, 2, 3) have been measured. The observed shielding values increase in the order of i-C3H7&lt;n-C4H9\simeqn-C3H7\simeqC2H5&lt;CH3 in tri-alkyltin hydrides. This order is consistent with that of the hyperconjugation effect of the alkyl group. On the other hand, the change in the shielding of the protons bound directly to the tin atom with a step-by-step substitution of SnH4 by an alkyl group is similar to that of hydrocarbons or alkylsilanes. The infrared spectra of organotin hydrides show that there is a close correlation between the τ values and the Sn-H stretching frequencies.
Vibrational Assignments and Intramolecular Force Field of Trimethylaluminum
Authors: Ogawa Teiichiro , Hirota Kozo , Miyazawa Tatsuo 
Published: July 2006

Abstract
A vacuum infrared cell for reactive or intermediate species has been devised by the use of polyethylene sheets as optical windows. The infrared spectra in the 4000–3100cm−1, 2500–1500 cm−1, 1250–750 cm−1 and 700–65 cm−1 regions can be measured with this liquid cell.
The vibrational assignments of the observed spectra have been carried out. The band at 367 cm−1 has been assigned to ν17, and the band at 175 cm−1, to ν18 and ν14.
The normal vibrations have been calculated, and the potential function of this molecule has been studied. A bond has been concluded to lie between two aluminum atoms. The characteristics of the potential function and the bond structure of trimethylaluminum have also been discussed.
Studies of the Liquid-Liquid Partition Systems. I. The Distribution of Radon(0) between Various Organic Solvents and Aqueous Solutions
Authors: Sekine Tatsuya , Yamasaki Akira 
Published: July 2006

Abstract
(1) The distribution of radon between various organic solvents and water has been determined at 25°C. Radon is always distributed better into the organic phase. The distribution constants of radon in these liquid-liquid partition systems are in the range from 25 to 80.
(2) The distribution of radon between aqueous calcium chloride solution of various concentrations and carbon tetrachloride has been determined at 25°C. A remarkable salting-out effect for radon has been observed.
(3) A solvent extraction method for the separation of radon from radium(II) and the decay products in aqueous solutions has been suggested.
Thermodynamic Properties and Order-Disorder Phase Transitions of the Potassium Cyanide Crystal
Authors: Suga Hiroshi , Matsuo Takasuke , Seki Syûzô 
Published: July 2006

Abstract
The heat capacities of the potassium cyanide crystal have been measured over the temperature range from 13 to 310°K by using a low temperature adiabatic calorimeter. It has been found that there are two regions of anomalous heat capacity, with maxima at 82.9±0.2°K and 168.3±0.1°K respectively. The heats and entropies of transition have been evaluated by utilizing a ΘD-versus-temperature plot. The entropy of the lower transition amounts to about R ln 2, which means that the transition is due to the orientational order-disorder rearrangement of the cyanide ion with respect to its head and tail. A perfectly-ordered structure for the orientation of the cyanide ions has been suggested. A certain small anomaly in heat capacity has been found around 190°K, one which seems to be associated with some change in higher-order structural defects created by the upper transition phenomenon.
The torsion-rotational heat capacity of the cyanide ions has been separated from the total on some reasonable assumptions. The results show that the cyanide ions below the lower transition point are subjected to torsional oscillation with the wave number of about 160 cm−1, a value which corresponds to the barrier height of 7.5 kcal. mol−1 based on a simple harmonic oscillator model. On the other hand, they are in a hindered rotational state with a barrier height of approximately 1.35 kcal. mol−1 in the cubic phase, the barrier height diminishing from 7.5 kcal. mol−1 gradually in a single phase or abruptly via the transition points.
The thermodynamic functions for this crystal have been evaluated by integrating the heat capacity data. The values at 298.15°K are, in units of cal.mol−1deg−1: Cp°=15.84, S°=30.71, (H°–H°O)⁄T=13.94 and –(G°–H°O)⁄T=16.77 respectively.
Oxidation of Alcohols with t-Butyl Chromate. II. The Oxidation of Primary Aromatic Alcohols
Authors: Suga Takayuki , Kihara Keiichi , Matsuura Tamon 
Published: July 2006

Abstract
The oxidation with t-butyl chromate has been carried out with benzyl alcohol, its p-substituted derivatives and trans-cinnamyl alcohol, and also with β-phenylethyl alcohol. In the former alcohols, the corresponding aldehyde was obtained as the main product, but the corresponding ester was not formed. On the other hand, the latter alcohol, containing a methylene group adjacent to the hydroxymethyl group, produced the corresponding ester, aldehyde and acid, as in the case of a saturated primary aliphatic alcohol.
The Synthesis of dl-Muscarine and dl-Allomuscarine
Authors: Maekawa Haruki , Ichihara Akitami , Matsumoto Takeshi 
Published: July 2006

Abstract
The synthesis of dl-muscarine (I) and dl-allomuscarine (II) starting from ethyl crotylmalonate has been described. Trans oriented methyl and hydroxyl groups in these compounds have been introduced stereospecifically into the tetrahydrofurane ring.
The Determination of the Water Content in Acetaldehyde by Means of the Karl Fischer Reagent
Authors: Muroi Kaname , Ogawa Kunihiko , Ishii Yaeko 
Published: July 2006

Abstract
Approximately 5 ml. of the sample has been added to 5 ml. of a 3:1 solvent mixture of of pyridine-propylene glycol in a titration flask. The difference in boiling point between acetaldehyde and water made it possible to evaporate almost all the interfering acetaldehyde from the solution with nitrogen gas passed into the flask at a velocity of about 0.91./min. The water remaining in the solution was titrated with the Karl Fischer reagent SS (Mitsubishi).
Because this reagent is free from alcohol, which would show an interfering reaction in Eq. 1, and because it is somewhat lower than the general Karl Fischer reagent in its concentration of C5H5N·SO2, which is the main component responsible for the interfering reaction in Eq. 3, it proves to be the most satisfactory for the present titration method.
A small quantity of water in purified acetaldehyde was determined by the present method, and subsequent anlysis of water content values showed an excellent reproducibility.
A Theoretical Treatment of the Kinetics of the Oxidation of Metals
Authors: Yoshisaki Hiroshi , Isano Toyojiro 
Published: July 2006

Abstract
We have attributed the deficiency of the parabolic law to its original assumption of a uniform gradient of the concentration of the reactant, and, beginning with a general assumption of a turbulent gradient, we have deduced an alternative equation, one somewhat more complicated than the parabolic one. In discussing the behavior of the new equation, it was found that the mode of progression largely changes its profile as a result of the fluctuation of the coarseness of the surface to be oxidized.
A Study of Monolayer Penetration by the Radiotracer Method
Authors: Matsubara Akira 
Published: July 2006

Abstract
The surface pressure - area isotherms of monolayers of cholesterol, hexadecyl alcohol and octadecyl amine on sodium alkyl sulfate solutions and the surface excess of alkyl sulfate have been measured by the film balance and the radiotracer methods respectively. These measurements were carried out with (1) the monolayers spread on the alkyl sulfate solutions, (2) those below which the detergent solutions were injected, and (3) those formed by the spreading of the insoluble speciesdetergent mixtures on water.
All the surface pressure - area curves showed remarkable expansions; the results were essentially the same as those observed by Schulman et al. and by others.
On the other hand, the surface excess of alkyl sulfates showed no appreciable increase in the case of cholesterol and hexadecyl alcohol, and it was too low to form a stoichiometric complex between the insoluble species and the alkyl sulfate; only in the presence of the octadecyl amine did it increase to an amount sufficient to form the 1 : 1 stoichiometric salt.
Thus it has been concluded that the expansion of the surface pressure - area curve can not be an indication of the stoichiometric complex formation. It has been pointed out that the surface pressure of the detergent solution increases with the compression, even in the absence of a monolayer; this is the main cause for the expansion of the surface pressure - area curve of the penetrated monolayer. The phenomenon of monolayer penetration has been explained in terms of the formation of the adsorbed layer of alkyl sulfate, and the reactivity for penetration has been related to the surface activity of detergents.
Complex Compounds of Gallium with Mandelic Acid
Authors: Srivastava T N , Rupainwar D C 
Published: July 2006

Abstract
pH and conductometric studies of the gallium chloride - mandelic acid - water system show the existence of three chelates in solution with a metal-to-ligand ratio of 1:1, 1:2 and 1:3. The solubility of freshly-precipitated gallium hydroxide in aqueous solutions of mandelic acid of varying concentrations, however, indicates the presence of only, 1:2- and 1:3-type species. These two complexes have here been isolated in the crystalline state. Their structures may be represented by
(Remark: Graphics omitted.)
and
(Remark: Graphics omitted.)
respectively. The 1:1 complex indicated by electrometric titrations appears to be fairly unstable, as it could neither be inferred from solubility experiments nor isolated in the crystalline state.
The Polymerization of Butene Isomers
Authors: Shimizu Akihiko , Otsu Takayuki , Imoto Minoru 
Published: July 2006

Abstract
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&gt;&gt;NB&gt;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&gt;&gt;TB&gt;–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

Abstract
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 &lt; dialkylaluminum halide-ether &lt; 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

Abstract
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

Abstract
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

Abstract
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.