bluuebunny/crossref_metadata_2025 huggingface dataset:
An Automatic Adiabatic Calorimeter for Low Temperatures. The Heat Capacity of Standard Benzoic Acid
Authors: Suga Hiroshi , Seki Syûzô
Published: July 2006

An adiabatic calorimeter for the measurements of the heat capacity of a solid and liquid over the temperature range from 13 to 300°K has been constructed. In order to minimize the operating manpower, all the temperature controls were recorded semiautomatically. The energy input was started and stopped automatically by a timer driven by a signal from a transistor clock. The working platinum resistance thermometer was calibrated against a laboratory standard thermometer which had been calibrated by the National Bureau of Standards. In order to verify the performance and the accuracy of this one-man-operated calorimeter, the heat capacity of a Calorimetry Conference Standard sample of benzoic acid crystal has been measured from 15 to 310°K. The results have compared with the data from the NBS and from other laboratories; this comparison served to establish the reliability of this equipment. The estimated errors are ±2% at 20°K, ±1% below 50°K, and ±0.3% above 50°K.
The Calculation of the State Energies of Benzaldehyde. II The SCF Molecular Orbital Method
Authors: Inuzuka K\={o}z\={o} , Yokota Toshio
Published: July 2006

The state energies, charge densities, bond orders and free valences of benzaldehyde have been elucidated by the use of the SCF-MO method with a model of Cs symmetry, including interactions of all the singly-excited configurations. In the singlet state, the numerical values of state energies are more reliable than the previous results, which were derived from the C2v model by the use of Hückel MO. In the triplet state, however, the numerical values of state energies seem to be lower than the previous results.
Asymmetric Hydrogenation with Modified Raney Nickel. V. Studies on the Modified Hydrogenation Catalyst. VI
Authors: Izumi Yoshiharu , Tatsumi Susumu , Imaida Masami , Fukuda Yoshio , Akabori Shiro
Published: July 2006

1) The asymmetric activities of Raney nickel catalysts modified with (+)-2-methylglutamic acid or (+)-2-benzylglutamic acid have been formed to be quite different from that of the catalyst modified with l-glutamic acid.

2) Levorotatory methyl 3-hydroxybutyrate is obtained by the catalyst modified with (+)-2-methylglutamic acid, and the dextrorotatory product by the catalyst modified with (+)-2-benzylglutamic acid. With the catalyst modified with l-glutamic acid, however, the direction of optical rotation of the hydrogenation product is much influenced by the pH and by the temperature of the modifying solution.
A Molecular Orbital Treatment of Hydrogen Bonds. I. Preliminary Results
Authors: Morokuma Keiji , Kato Hiroshi , Yonezawa Teijiro , Fukui Kenichi
Published: July 2006

1) The changes caused by hydrogen bonds in the electronic structure of several molecules have been discussed by the use of the extended LCAO MO method.

2) The delocalization energy have been calculated to be 3.8 kcal./mol.

3) The frequency shifts in the ultraviolet spectrum cannot be explained.

4) In the formic acid dimer it has clearly been shown that the population transfers from the carbonyl group to the hydroxyl group and that a small bond population arises between them.

5) The 2pπ orbital on the hydrogen atom contributes almost nothing to the π delocalization energy.

6) The π hydrogen bond has also been discussed.

7) The defects in the extended LCAO MO method in treating molecules with polar groups or lone pairs have been pointed out, a method for improvement suggested, and some critical discussion of the present treatment added.

The calculation was carried out on the IBM 7090 at the Japan IBM Co., with the permission of the UNICON Committee, whose kindnees we hereby acknowledge.
Band Structure of Circumanthracene
Authors: Harada Yoshiya , Maruyama Yusei , Inokuchi Hiroo , Matsubara Noriko
Published: July 2006

The band structure and mobility tensors of circumanthracene have been calculated by the tight-binding band approximation.

The total bandwidths of the compound have been found to be slightly larger than those of anthracene; the total widths of the electron and the hole band being 0.82 kT and 1.22 kT room temperature.

The values of the calculated mobilities for the electron and the hole are comparable in the b and the c′ directions, but the corresponding values in the a direction are smaller by a factor of about 30∼40, reproducing the anisotropy properties of the bandwidths in the reciprocal lattice directions. Thus, the anisotropy of the band structure of the compound is considerably different from that of anthracene. This behaviour may be associated with the differences in their crystal geometry and molecular structure.

The magnitude of the mobility is three times larger than that of anthracene in the b direction, and two or three times larger in the mean, the calculated ratio being roughly in agreement with the experimentally-estimated one. Hence, it has been concluded the sharp drop in the resistivity in going from anthracene to circumanthracene is due mostly to the great increase in the concentrations of charge carriers, 107 times, as a result of the lowering of the energy gap value.

Finally, it has been pointed out that, although circumanthracene is among the largest polycyclic aromatics, judging from the estimated magnitude of the mobility (several cm2/V.sec), the band model may be not satisfactory enough for us to understand the conduction in the crystal.
The Preparation of Optically Active α-C-Substituted Glutamic Acid
Authors: Izumi Yoshiharu , Tatsumi Susumu , Imaida Masami , Fukuda Yoshio , Akabori Shiro
Published: July 2006

1) The optical resolution of Dl-2-methylglutamic acid has been performed using brucine as a resolving reagent; the two optically active isomers have been obtained.

2) Dl-2-Benzylglutamic acid has been synthesized using benzyl cyanide and diethyl succinate as the starting materials. Moreover, the optical resolution of this amino acid has been performed using strychinine as a resolving reagent. The two optically active isomers were obtained.
Reactive Fiber. IV. The Graft Copolymerization of Glycidyl Methacrylate onto Polypropylene and Polyvinyl Chloride Fibers
Authors: Iwakura Yoshio , Kurosaki Toshikazu , Nagakubo Kuniharu , Takeda Kenji , Miura Masatoshi
Published: July 2006

The graft polymerization of glycidyl methacrylate onto polypropylene or polyvinyl chloride fiber has been carried out by the technique of γ-ray pre-irradiation in vacuo, and the reactions of the grafted fiber with amines have been investigated. In the case of polypropylene, the addition of benzene or tetrahydrofuran to the monomer remarkably increases the grafting rate.

The initial grafting rate is slow in acetone or ethylacetate. The epoxide groups of the grafted polypropylene react with diethanolamine quantitatively, but with methyl glucamine partially, with a yield of 70%. In the case of polyvinyl chloride, benzene or acetonitrile is suitable as a grafting solvent. Graft polymerization proceeds in a narrow range of temperature from 10 to 20°C. Diethanolamine or aniline reacts with yields of 50–60% with the epoxide groups of the grafted polyvinyl chloride. Polyhydroxyamine-treated graft fibers have a good dyeability to both direct and acid dyes.
The Solvent Extraction and Spectrophotometric Determination of Vanadium(V) with Thenoyltrifluoroacetone
Authors: Ikehata Akira , Shimizu Tamako
Published: July 2006

The extraction of the vanadium(V)-TTA complex has been studied using various organic solvents. The complex has been extracted quantitatively in isoamyl acetate and n-butyl acetate. The quantitative extraction has been realized within a range from pH 2 to 3, with the absorption maximum at 410 mμ. The mole ratio of the complex is vanadium (V)-1 : 2-TTA, and Beer’s law is applicable in the range from 0 to 10γ/ml. of vanadium(V) at 420 mμ. The solvent effects on the absorption spectra of this complex have also been studied.
Vibrational Spectra of Triethylfluorosilane
Authors: Tanaka Toshio , Murakami Shigezo
Published: July 2006

The infrared and the Raman spectra of triethylfluorosilane have been measured, and the normal vibrations for the skeletal modes have been calculated by Wilson’s FG matrix method, using a simple Urey-Bradley force field and assuming point group C3v for the molecular symmetry. The skeletal vibrations have been assigned quantitatively on the basis of the normal coordinate treatment, and the hydrogen vibrations have been tentatively assigned. The vibrational spectra of this molecule have also been discussed in comparison with those of triethylchlorosilane and methyltrimethoxysilane.
The Spectrophotometric Determination of Anions by Solvent Extraction with Metal Chelate Cations. XIII. A New Method for the Determination of Picric Acid
Authors: Hayashi Shigehiko , Kotsuji Keiya , Sakurai Toshiyuki , Kimura Kenji , Yamamoto Yuroku
Published: July 2006

The solvent extraction method has been applied to the spectrophotometric determination of minute amounts of picric acid with the 2,2′-dipyridyl iron(II) chelate. The selectivity of the procedure is largely dependent on the pH of the solution. At pH 2.5 the extraction is selective for picric acid in the presence of nitrophenols.
The Chemical Behavior of Low Valence Sulfur Compounds. I. Oxidation of Elemental Sulfur with Compressed Oxygen in Aqueous Ammonia Solution
Authors: Shieh Mu-Chang , Otsubo Hiroshi , Okabe Taijiro
Published: July 2006

1) The oxidation of sulfur with compressed oxygen proceeds through the following sequence of steps: (a) The disproportionation of sulfur to both pentasulfide and thiosulfate. (b) The oxidation of pentasulfide to thiosulfate. (c) The oxidation of thiosulfate to sulfate and sulfamate through a series of complicated intermediates.

2) Sulfamate forms only in the decomposition of trithionate.

3) The over-all reaction of the oxidation is prompted by a rise in the temperature, an increase in the ammonia concentration, and the addition of transition metal ions, especially-copper ions.
The Benzene-Photosensitized cis-trans Isomerization of Butene-2
Authors: Tanaka Masahiro , Terao Terumi , Sato Shin
Published: July 2006

The benzene-photosensitized cis-trans isomerization of butene-2 has been investigated in the gas phase. The results have been discussed on the basis of a mechanism involving triplet energy transfer from benzene to butene-2.

The quantum yield measurements indicate that the reaction occurs at a very high efficiency. The triplet-benzene quenching efficiency of butene-2 has been shown to be considerably greater than that of the ground-state benzene.

The photostationary cis-to-trans ratio has been about unity, unlike the value obtained by Cundall et al. A mechanism which may explain the dependence of the ratio on the pressure and on the energy of the sensitizer has been suggested.
π-Electronic Energy Levels of o-Benzoquinone
Authors: Kuboyama Akira , Wada K\={o}ichi
Published: July 2006

The π-electronic energy levels of o-benzo-quinone have been obtained by using Pople’s SCF MO method, while the electron repulsion integrals have been obtained by the Pariser-Parr method. The absorption band near 360 mμ and the strong band which is thought to exist near 200 mμ have unambiguously been assigned to the first 1A1→1B2 and the second 1A1→1A1 transitions respectively. The calculated singlet excited energy levels are much higher than the observed levels. The reason for this has been examined by SCF MO calculations using modified values of various kinds of electron repulsion integrals and core integrals. It has been concluded that a satisfactory lowering of the calculated singlet excited energy levels cannot be expected unless values of the core resonance integrals (β) are used which are much modified from those generally used. Simple MO parameters for o-benzoquinone adequate to simulate the simple MO’s to the SCF MO’s have been obtained.
The Near-infrared Absorption Spectra of Lanthanide Chlorides Dissolved in Molten LiCl–NaCl–KCl Eutectic
Authors: Mamiya Masato
Published: July 2006

Using a high temperature cell for molten salts, a spectrophotometric investigation in the near-infrated region form 0.8 to 2.6 μ and at temperatures from 400 to 800°C has been carried out with fourteen lanthanide chlorides dissolved in a LiCl–Nacl–KCl mixture of eutectic composition (49.0-17.3-33.7 mol%, m.p. 333°C. Praseodymium, neodymium, samarium, dysprosium, holmium, erbium, thulium and ytterbium have characteristic absorption bands in this region. Most of the near-infrated absorption bands of lanthanide chlorocomplexes have been compared to similar spectra obtained in molten nitrate media. However the several absorption bands have been found to be different in molten nitrate and chloride eutectics. Thus, the absorption bands of europium and terbium have been observed in nitrate, wheras their bands have not been found in chloride, and the absporption bands of praseodymium, samarium and holuium beyond the 1.4 μ range have been found to be located at different wavelengths. these solvent, for the ligand field affects the 4f-electronic energy levels of the above elements.

The absorption peaks of lanthanide ions decrease as the teperature increases, partly due to the change in the concetration of the ions associated with the volume change. However, all the characteristic absorption bands of lanthanide in the near-infrared region have stable molar absorptivities at a constant temperature. These absorption bands can be used for the investigation of chemical constitution and electronic structure, for anlysis and for other purposes.
Studies of Diarylalkanes. III. The Cleavage of Diarylmethanes under the Influence of Aluminum Chloride
Authors: Tsuge Otohiko , Tashiro Masashi
Published: July 2006

The reaction of several diarylmethanes (III –XII) with aluminum chloride under various conditions has been carried out in order to elucidate the effect of the substituent on the cleavage of diarylmethanes. It has been established that the bond between the aromatic ring and the methylene group is cleft and that the cleavage is affected by the relative basicities of the two aromatic rings in the diarylmethane as well as by the basic strength of the benzene derivative which is present in the reaction system.
A New Method of Analyzing Thermogravimetric Data
Authors: Ozawa Takeo
Published: July 2006

A new method of obtaining the kinetic parameters from thermogravimetric curves has been proposed. The method is simple and applicable to reactions which can not be analyzed by other methods. The effect of the heating rate on thermogravimetric curves has been elucidated, and the master curve of the experimental curves at different heating rates has been derived.

The applications of the method to the pyrolyses of calcium oxalate and nylon 6 have been shown ; the results are in good agreement with the reported values.

The applicability of the method to other types of thermal analyses has been discussed, and the method of the conversion of the data to other conditions of temperature change has been suggested. From these discussions, the definition of the thermal stability of materials has been criticized.
The Effect of Hydrogen-Bonding on the g-Value of Diphenyl Nitric Oxide
Authors: Kawamura Takashi , Matsunami Shoichi , Yonezawa Teijiro , Fukui Kenichi
Published: July 2006

The decrease in the g-value of diphenyl nitric oxide in hydrogen-bonding solvents has been examined. This decrease has been analyzed on the basis of Stone’s theory for the g-value of a π-radical. The decrease in the g-value has been shown to be caused mainly by the decrease in the odd-electron density on the oxygen atom and the increase in the energy difference between the odd-electron and lone-pair orbitals. We have also attempted to estimate the blue shift of the n-π* transition from the g-value.
The Kinetics of the Phosphate-catalyzed Epoxidation of Styrenes with a Mixture of Nitrile and Hydrogen Peroxide
Authors: Ogata Yoshiro , Sawaki Yasuhiko
Published: July 2006

The phosphate-catalyzed epoxidation of styrenes with a mixture of nitriles and alkaline hydrogen peroxide have been studied kinetical-ly in 75% methanol. The reactions satisfy third-order kinetics, being first-order in nitrile, hydrogen peroxide and styrene. The rate is essentially constant at various pH’s, while it increases with the increasing polarity of the reaction medium. The energy of activation is low (6–8 kcal.mol−1), and the entropy of activation is highly negative (−50 e. u.). The effect of substituent in benzonitrile is to give a Hammett’s ρ-value of 0.57, while that in styrene resulted in a negative ρ-value of −0.51. It is probable that the peroxycarbimidic acid (I), produced by mobile equilibria from nitrile and hydroperoxide ion, is stabilized by an intermolecular hydrogen bonding with the phosphate dianion, and that this species contributes mostly to the epoxidation of styrene in the following, rate-determining step.
Application of Electrostatic Models to the Colloidal Behavior of Plate-shaped Particles
Authors: Jordine E St A , Steel B J , Wolfe J D
Published: July 2006

The method of images in dielectrics is applied to a model consisting of two infinite dielectric slabs and a point charge. When specific effects of the ions such as hydration energies are taken into account, the model describes the electrical aspects of the swelling of the clay minerals satisfactorily. In addition, a detailed theory of the mechanism of swelling is proposed and is shown to be favored by preliminary experimental studies of vermiculite.
Studies of the Liquid-Liquid Partition Systems. IV. The Solvent Extraction Study of Europium(III) Adduct Chelate Complexes with Six Acetylacetone Derivatives and Tributylphosphate
Authors: Sekine Tatsuya , Ono Masaru
Published: July 2006

The extraction of europium(III) in 0.1 m sodium perchlorate with acetylacetone, benzoylacetone, trifluoroacetylacetone, benzoyltrifluoroacetone, froyltrifluoroacetone and thenoyltrifluoroacetone in chloroform and the adduct formation of these metal chelates with tributylphosphate have been studied at 25°C.

It has been concluded that: (i) The β-diketones which have one trifluoromethyl group extract europium(III) better than those which have no trifluoromethyl group. The difference in the metal extraction with acetylacetone or trifluoroacetylacetone and the metal extraction with the homologues of these β-diketones seems to be mainly due to the aqueous chelate complex formation, (ii) A metal chelate with a β-diketone which has a trifluoromethyl group is a much better acceptor of tributylphosphate to form adduct complexes than a metal chelate with a β-diketone which has no trifluoromethyl group. (iii) The ability of the acetylacetone chelate or the trifluoroacetylacetone chelate to form an adduct is not very much changed by the replacement of the methyl group with a benzoyl, froyl, or thenoyl group.
Reactions of the Iodomethylate of N,N-Dimethylthiobenzamide with Nucleophilic Reagents
Authors: Mukaiyama Teruaki , Yamaguchi Tatsuaki , Nohira Hiroyuki
Published: July 2006

The reactions of the iodomethylate (I) of N,N-dimethylthiobenzamide with nucleophilic reagents have been examined. The iodomethylate I reacted with sodium ethylmercaptide and potassium cyanide to give N,N-dimethylbenzamide methylethylmercaptol and α-dimethylamino-α-methylthiobenzyl cyanide respectively. When primary amines and the monosodium salts of active methylene compounds were treated with the iodomethy late I, benzamidine hydroiodides and α-dimethylaminobenzylidene derivatives of the active methylene compounds were, respectively, obtained, and methyl mercaptan was eliminated. Further, it has been found that diamines, such as o-phenylenediamine, easily condensed with the iodomethylate I to yield such heterocyclic compoundsas 2-phenylbenzimidazole, while methyl mercaptanand dimethylamine were eliminated.
The Dipole Moments of Some Sesquifulvalene Quinones and Related Compounds
Authors: Katagiri Shigeyoshi , Murata Ichiro , Kitahara Yoshio , Azumi Hiroshi
Published: July 2006

The dipole moments of some quinone derivative of sesquifulvalene, the corresponding dione compounds and their several derivatives have been measured in benzene at 25°C. The moments of cyclopentene-3, 5-dione and indane-1,3-dione are in the same direction as the carbonyl resultant, the mesomeric moments being 0.4 D. and 1.3 D. respectively. On the other hand, the direction of the moments of sesquifulvalene-1, 4-quinone and its 2,3-benzo derivative is just reversed because of a large transfer from the seven-membered ring towards the five-membered ring, presumably towards the carbonyl groups. The incremental moments, the difference between the observed and the carbonyl resultant, in these quinones are 4.2 and 3.9 D. respectively, while the moments due to the transfer from the seven-membered ring are 4.7 and 5.2 D., suggesting that such a charge transfer is greater in benzo-sesquifulvalene quinone.
On the Competition of Homogeneous and Heterogeneous Chain Terminations in Heterogeneous Photooxidation Catalysis by Zinc Oxide
Authors: Ikekawa Akiko , Kamiya Mamoru , Fujita Yuzaburo , Kwan Takao
Published: July 2006

The photooxidation catalysis of isopropyl alcohol on zinc oxide has been investigated with special reference to the chain termination, mechanism. It has been proposed that homogeneous and heterogeneous chain terminations, compete in this system. At a low concentration of zinc oxide, the homogeneous termination predominates, while at a high concentration the heterogeneous termination may come into play. As a result, a maximum may appear in the relation of the rate of oxygen uptake to the amount of zinc oxide present. With excess zinc oxide, chain reactions are suppressed, so no maximum may appear in the corresponding plot and the temperature coefficient should be very small. The experimental results have been found to be consistent with the expectations. The effect of doping zinc oxide on the photo-oxidation kinetics has been investigated and discussed, mainly on the basis of the data available on the formation and decomposition of hydrogen peroxide on doped zinc oxide samples.

It has been suggested that lithia-doped zinc oxide is more active than alumina-doped zinc oxide at higher temperatures because of the; accompanying hydrogen peroxide-initiated oxidation of isopropyl alcohol on the former, while it is less active at lower temperatures because, of the efficient decomposition of hydrogen peroxide, giving oxygen and water.
Kinetics of Methane Oxidation in Shock Waves
Authors: Miyama Hajime , Takeyama Tetsu
Published: July 2006

The mechanism of methane oxidation in reflected shock waves has been studied by measuring the induction period of the OH absorption and that of the pressure increase simultaneously, and also by using the single-pulse technique combined with gas chromatography.

As a result, it has been found under the present experimental conditions that the rate-determining step for the over-all reaction of the methane-rich mixtures with the ratio [CH4]/[O2]=6 is CH4 + O2→ CH3 + HO2, and that the rate-determining step for the over-all reaction of the methane-lean mixtures with the ratio [CH4]/[O2]=3/ 7 is CH2O + O2→ HCO + HO2. Also, the rate-determining step for the OH formation of the lean mixtures has been found to be CH3 + O2→ CH2O + OH under the present conditions. In the case of the intermediate mixtures with the ratio [CH4]/[O2]=1.5, the over-all reaction is considered to be controlled mainly by the reaction CH4 + O2→ CH3 + HO2.
The Spectrophotometric Determination of Anions by Solvent Extraction with Metal Chelate Cations. VI. A New Method for the Determination of Mercury(II)
Authors: Kotsuji Keiya
Published: July 2006

A new method for the determination of mercury(II) has been proposed. The method is based upon the solvent extraction of the associated complex formed between the 2,2′-dipyridyl iron(II) chelate cation and the tetraiodo-mercury(II) complex anion and upon the estimation of the absorbance belonging to the chelate cation in the organic phase. The interference of diverse ions is eliminated by using ethylenediaminetetraacetate as a masking agent.
Surface Chemistry of the Polyamide Series. III. Monolayers of Nylons from ω-Aminocarboxylic Acids at the Air/Water Interface
Authors: Yamashita Takuya
Published: July 2006

The surface films of a series of nylons prepared from ω-aminocarboxylic acids and with 2 to 11 CH2 groups per monomer unit (Nylons 3 to 12) have been studied at the air/water interface in order to investigate the correlation of the film properties with the numbers of CH2 groups. The film of Nylon 9 at the oil/water interface and that of polynonamethylene urea at the air/water interface have also been studied.

The film of Nylon 3 on the 40% ammonium sulfate subsolution was of the condensed type and the area occupied per residue was quite small, probably because of the especially strong hydrogen bonds between amide groups. On the other hand, the films of Nylons 4, 5 and 6 on 40% ammonium sulfate and that of Nylon 6 on distilled water were of the expanded type. These polymers might be spread in rather flexible states because of the effect of the increased number of CH2 groups.

Nylons 8 to 12 and polyurea gave condensed films on distilled water, their limiting areas per residue being much smaller than the areas calculated for the fully extended chains. The condensation of the films might be primarily caused by the increased van der Waals attractive force between hydrocarbon groups, as has been proved by the remarkable expansion of Nylon 9 film at the petroleum ether/distilled water interface. The small limiting areas of these polymer films have been interpreted by assuming that the hydrocarbon chains are folded near these areas. Nylon 7 was found to give an intermediate film between expanded films, such as Nylons 4 to 6, and condensed films, such as Nylons 8 to 12.

Interesting differences in the film properties of odd- and even-numbered nylons have been found with Nylons 8 to 12. Odd-numbered nylons occupied somewhat larger areas per residue than even-numbered nylons, and the maximum surface moments of the formers were higher than those of the latters. This is the result of the difference in shapes of the folded chains between the two series of nylons.

The surface viscosities of Nylons 8 to 12, with the exception of the last, were first detected at larger areas than the close-packed areas calculated for the fully-extended chains. The areas found for even-numbered nylons were much smaller than those for odd-numbered ones. This may be attributed to the difference in modes of hydrogen bond formation between amide groups.

A remarkable effect of the concentrated sulfuric acid subsolution on the film properties of Nylons 6 to 9 has been found, and interpreted as being due to the protonation to the amide linkages.
On Glumamycin, a New Antibiotic. VI. An Approach to the Amino Acid Sequence
Authors: Fujino Masahiko
Published: July 2006

To elucidate the amino acid sequence of glumamycin, glumamycin and DNP-glumamycin have been partially hydrolyzed with hydrochloric acid, and various peptides have been isolated by column chromatography on ionexchange resin or talc-celite, paper chromatography and paper ionophoresis. From the structures of the peptides, two possible structures (A and B) for glumamycin have been presumed.
Photolysis of Acetaldehyde in the Presence of Deuterium Sulfide. Deuterium Atom Abstraction from Deuterium Sulfide Molecules by Methyl Radicals
Authors: Imai Naomi , Dohmaru Takaaki , Toyama Osamu
Published: July 2006

The photolysis of acetaldehyde in the presence of deuterium sulfide has been investigated over the temperature range from 200 to 300°C, in order to determine the rate constant for the deuterium atom abstraction from deuterium sulfide molecules by methyl radicals. The effect of deuterium sulfide addition is similar to that of the addition of hydrogen sulfide previously studied. The results obtained with low concentrations of deuterium sulfide can be explained by the following reaction scheme: CH3CHO+hν→CH3+CHO (1), CHO→ CO+H (2), H+CH3·CHO→H2+CH3CO (3), H+D2S→ HD+DS (4), CH3+CH3CHO→ CH4+CH3CO (5),CH3+D2S→CH3D+DS (6), DS+CH3CHO→ HDS+CH3CO (7), CH3CO→ CH3+CO (8), and CH3+CH3→ C2H6 (9). The rate equation derived from the scheme, −d[CH3CHO]/ dt=k5k9−1⁄2Ia1⁄2[CH3CHO] + k6k9−1⁄2Ia1⁄2[D2S], is in agreement with the results. The application of this rate equation leads to k6⁄k5=2.0exp(3000⁄RT), and to k6=1011.6exp(−3800⁄RT) mol−1 cc. sec−1, if k5=1011.3exp(−6800⁄RT) mol−1 cc. sec−1, as has been reported by Ausloos and Steacie. On reinvestigating the effect of hydrogen sulfide addition, it was found that k6′⁄k5=1.5exp(4150⁄RT), where k6′ refers to the CH3+H2S→ CH4+HS (6′) reaction. We thus obtain k′6⁄k6==0.75exp(1150⁄RT).
Amylose-Iodine Complex. IV. The Complex in Dimethyl Sulfoxide-Water Mixtures
Authors: Ono Sôzaburo , Watanabe Takehiko , Ogawa Kozo , Okazaki Nobuhiko
Published: July 2006

The temperature at which the blue color due to the formation of amylose-iodine complex fades completely has been determined with a system of amylose and iodine dissolved in dimethyl sulfoxide-water mixtures. This temperature rises with the increase in the concentration of iodine in mixtures, and also with the increasing concentration of water in the mixed solvents.

The spectrophotometric results show that the nature of the amylose-iodine complex in a dimethyl sulfoxide-water mixture is similar to that of one in water, and that the triiodide ion or a chemical species similar to the ion, i.e., the polyiodide ion, contributes to the formation of the complex.

The viscometric studies show that the amylose molecule takes a deformed helix conformation prior to the formation of the blue iodine complex and that this conformational prerequisite to the complex formation is fulfilled when the water concentration in a dimethyl sulfoxide-water mixture exceeds a critical value.

These results stated above may indicate that the triiodide (polyiodide) ion plays the part of “stabilizer” for the fixation of iodine molecules within the helically-wound chain of the amylose molecule when the amylose exists primarily as a deformed helix in solution.
A Spectrophotometric Study of Xylenol Orange as a Color Reagent for Beryllium
Authors: Otomo Makoto
Published: July 2006

The red color produced by adding a xylenol orange solution in excess to a beryllium solution has been studied spectrophotometrically in order to ascertain the optimum conditions for the determination of beryllium. The absorption curve of the colored system shows an absorption maximum at 495 mμ when measured against a reagent solution of pH 5.8. Beer’s law is obeyed over the range up to 6 μg of beryllium. The composition and the apparent formation constant of the two different complexes have then been obtained by applying some spectrophotometric techniques. Beryllium forms a 1 to 1 complex with xylenol orange below pH 5; it gives, however, mixture of 1 to 1 and 1 to 2 complexes at higher pH values.
Surface Chemical Properties in Aqueous Solutions of Glucosyl Alkylbenzenes
Authors: Tokiwa Fumikatsu
Published: July 2006

The surface tension in aqueous solutions of glucosyl alkylbenzenes having various alkyl chain-lengths has been measured. The surface tension vs. concentration relation of these compounds obeys Szyszkowski’s equation in a relatively wide range of concentrations. For these compounds the free energy, ΔG°, of adsorption was calculated; ΔG° changes by 650–700 cal./mol. for each CH2 added to the alkyl chain, except in the case of going from glucosyl methylbenzene to glucosyl ethylbenzene. The adsorbed monolayer obeys an equation of state of the form Π(A–AO=xkT at relatively high pressures, where AO is independent of alkyl chain-length in the present experiment. Contrary to expectation, the value of x, which is governed by the attractive force between hydrophobic portions, is not influenced by the alkyl chainlengths; the benzene ring in the hydrophobic portion seems to play an important role in this attraction between the hydrophobic portions.
The Effect of Sodium Triphosphate on the Nucleation of Strontium Sulfate
Authors: Naono Hiromitu , Miura Masaji
Published: July 2006

The nucleation from supersaturated solutions of strontium sulfate containing various amounts of triphosphate has been investigated by means of light scattering and nucleation kinetics. The nucleation rate is remarkably reduced by the increase in the concentration of triphosphate and may be represented by an empirical expression, J=Kc−95. Light-scattering measurements have confirmed that practically no nucleation occurs in the supersaturated solution stabilized in the presence of triphosphate.
Estimation of Anharmonic Potential Constants. I. Linear XY2 Molecules
Authors: Kuchitsu Kozo , Morino Yonezo
Published: July 2006

On the basis of a normal-coordinate analysis of a series expansion of the anharmonic potential field, a set of general expressions has been derived for a linear XY2 molecule for relating the cubic and quartic potential constants (k) to the coefficients (f) of the potential function expanded in terms of the internal coordinates. The constants k and f for CO2 and CS2 have been calculated by using the observed values of α and x taken from the literature, and the physical significance of the dependence of k on f has been studied.

The anharmonic constants related to the C-O(C-S) bond-stretching vibrations are represented as functions of the parameters of anharmonicity, a3 and a4, which are shown to be transferable from the CO(CS) diatomic molecule. Most of the k, α, and x values for CO2 and CS2 can be predicted quantitatively by assuming a simple potential function, comprised of ordinary quadratic terms and the anharmonic terms for the bond-stretching vibrations mentioned above, with all other higher-order potential terms ignored.

A number of methods for estimating the parameters a3 and a4, and a general rule regarding their relative magnitudes, have been discussed. The k, α, and x values of the linear radicals, NH2, ND2, and BO2, may be predicted in the present scheme by making simple assumptions about their potential constants.
Current-Voltage Characteristics in Phenanthrene Single Crystals
Authors: Matsumoto Shoichi
Published: July 2006

The obtained current-voltage characteristics of phenanthrene single crystals exhibited three distinct types of behavior: (1) at low voltages, up to 2×104 V.per cm., the dependence of the current on the voltage obeyed Ohms’ law, (2) at intermediate voltages, the current increased with the square of the voltage, and (3) at higher voltages, over 5×104 V.per cm., the current rose steeply with the voltage. These results have been analyzed as space-charge-limited currents phenomena, and a value of 1.2×106 cm−2 has been obtained as the concentration of the bulk-free carriers from the transition voltage between the ohmic region and the square-law behavior. The resistivity calculated by applying this value is in good agreement with the resistivity observed for the ohmic region of current-voltage characteristics.

The trap density of 1.1×1014cm−3 has been evaluated from the voltage where the current rose steeply. Although this value seems to be rather low for an organic solid, it is comparable to the trap densities for organic molecular crystals ever obtained.
The Synthesis of Deoxyaspergillic Acid and Tetrahydrodeoxyaspergillic Acid
Authors: Chigira Yasuhiro , Masaki Mitsuo , Ohta Masaki
Published: July 2006

Deoxyaspergillic acid (I) and tetrahydrodeoxyaspergillic acid (II) were synthesized. 1-Chloro-3-methyl-2-pentanone was directly oximinated with hydroxylamine, and then the oxime was treated with l-leucine ethyl ester to yield N-(3-methyl-2-oximinopentyl)-l-leucine ethyl ester (III), which, on alkali-hydrolysis, followed by acid-hydrolysis, gave N-(3-methyl-2-oxopentyl)-l-leucine (IV). The treatment of the methyl ester of IV with ammonia gave I, and the hydrogenation of III on Raney nickel gave II.
The Phosphorylation of Alcohols by the Reaction of Monobromocyano-acetamide with Monobenzyl Phosphite or Inorganic Phosphorous Acid
Authors: Obata Teisuke , Ueki Masaaki , Mukaiyama Teruaki
Published: July 2006

This paper describes a successful method of preparing monoalkyl phosphates by the reaction of monobromocyanoacetamide with monobenzyl phosphite or inorganic phosphorous acid in the presence of alcohols. When equimolar amounts of monobromocyanoacetamide and either of the above-mentioned phosphorus compounds in alcohols were heated at about 100°C, the corresponding monoalkyl dihydrogen phosphates were obtained as anilinium salts in fairly good yields, together with cyanoacetamide and benzyl bromide or hydrogen bromide. The reaction can be interpreted in terms of a mechanism in which the initially-formed enol-phosphonium salts of cyanoacel amide are easily transformed to the second phosphonium salts by the action of the alcohols present from the salts, alkyl dihydrogen phosphates are produced.
The Pyrolysis and Thermochromism of the Crystalline Powder of Dianthraquinone
Authors: Kuroda Haruo , Sudo Ryoichi
Published: July 2006

The crystalline powder of dianthraquinone changes its color from yellow to green when it is heated above 250°C. A heat-treated powder of a green color exhibits an ESR absorption, the line width of which is about 7 gauss, and the g-value, 2.0032. The intensity of the ESR absorption was studied as a function of the temperature of heat-treatment and the heating time. The activation energy for the formation of the paramagnetic species is estimated to be 74 kcal./mol. The X-ray diffraction patterns of heat-treated specimens indicate that a marked disorder is produced in the crystal structure by the heat treatment and that, finally, the dianthraquinone crystal becomes an amorphous solid. A close correlation can be found between the intensity of ESR absorption and the structural change. Polymerization occurs at higher temperatures and results in the formation of a dark green solid insoluble in organic solvents. It is suggested that the initial process of these thermal changes is associated with the thermochromism of dianthraquinone.
Reactions of 2-Chlorocycloalkanone Oximes. I. Their Preparations and Conversion to 2-Alkoxy-, 2-Acyloxy- and 2-Alkylthiocycloalkanone Oximes
Authors: Ohno Masaji , Naruse Norio , Torimitsu Seiichi , Okamoto Masaru
Published: July 2006

The preparation of 2-chlorocycloalkanone oximes has been investigated in detail. 2-Chlorocyclooctanone oxime is prepared in an excellent yield by the reaction of cyclooctene with nitrosyl chloride under the irradiation of light from a high-pressure mercury lamp. 2-Chlorocyclododecadienone oxime, 2-chlorocyclohexanone oxime and 3-chloronorcamphor oxime are prepared in good yields by the addition of nitrosyl chloride to cis, trans, trans-1, 5, 9-cyclododecatriene, cyclohexene and norbornene respectively in the presence of hydrochloric acid. Their displacement reactions with such nucleophilic reagents as sodium alkoxides, sodium ethanethiolate and sodium salts of carboxylicacids have been studied, and the syntheses of 2-alkoxy-, 2-ethylthio- and 2-acyloxy-cycloalkanone oximes have been successfully achieved.
Reactions of 2-Chlorocycloalkanone Oximes. III. Displacement Reactions with Various Nucleophilic Reagents
Authors: Ohno Masaji , Torimitsu Seiichi , Naruse Norio , Okamoto Masaru , Sakai Ikuo
Published: July 2006

The displacement reactions of 2-chlorocycloalkanone oximes with various nucleophilic reagents, such as ammonia, primary and secondary amines, silver and sodium nitrite, sodium azide, Grignard reagents, and carbanions derived from acetylacetone and ethyl malonate, have been investigated. α-Alkylamino, α-nitro, α-azido, and α-alkyloximes of the 8- and 12-membered rings have been prepared in excellent yields, and those of the 6-membered ring, in moderate yields. It has been shown that 2-chlorocyclohexanone oxime hydrochloride can be treated directly with a large excess of the nucleophilic reagents. 2-Chlorocyclooctanone oxime was used in the free state, and 2-chloro-5, 9-cyclododecadienone oxime was first treated with nucleophilic reagents; the resulting α-substituted oximes of the 12-membered ring were hydrogenated to the corresponding saturated oximes with palladium charcoal. These reactions have shown that α-chlorocyclo-alkanone oximes have a potential synthetic utility.
The Mean Amplitudes and Atomic Scattering Factors of Boron Tribromide
Authors: Konaka Shigehiro , Ito Tetsuzo , Morino Yonezo
Published: July 2006

The mean amplitudes and the interatomic distances of BBr3 have been determined by the sector-microphotometer method of gas electron diffraction. The B–Br and Br–Br distances (rg) have been found to be 1.8932±0.0054 Å and 3.2830±0.0053 Å respectively. The values of the mean amplitudes are dependent on the atomic scattering factors used in the analysis. The complex scattering factors for B and Br, as calculated on the basis of the Hartree-Fock potential, have given mean amplitudes which are consistent with the vibrational frequencies observed by spectroscopy, while the mean amplitudes derived from the use of other scattering factors are less reasonable. It has been shown that the Hartree-Fock function for the Br atom is a better representation of the atomic potential function than the Thomas-Fermi function. The utility of the method of gas electron diffraction for the study of atomic scattering factors and atomic potential functions in some favorable cases has been pointed out.
The Thermal Treatment of Dibenzanthronyls
Authors: Nagai Yoshio , Nagasawa Kotaro
Published: July 2006

The ring closure of 3, 3′-dibenzanthronyl to form dibenzanthrone was previously effected by means of homogeneous melting at 430°C in an open vessel or in vacuo (Y. Nagai et al., J. Chem. Soc. Japan, Ind. Chem. Sect. (Kogyo Kagaku Zasshi), 67, 1977 (1964)). In this report, the thermal treatment of 3, 3′-dibenzanthronyl and its isomers, 3, 4′- and 4, 4′-dibenzanthronyls, in a closed vessel is described. The reaction was carried out in the following way: a glass tube was filled with finely-powdered dibenzanthronyl. The tube was then placed in a stainless-steel bomb and heated to 425–435°C for 25 min. Thus, 3, 3′- or 4, 4′-dibenzanthronyl yielded dibenzanthrone and dibenzanthrene, along with a putative secondary thermal reaction product in the form of a black powder; the nature of this briefly discussed. Similarly, 3, 4′-dibenzanthronyl was converted to isodibenzanthrone and isodibenzanthrene, together with a black powder.
The Vibrational Assignment and Rotational Isomerism of 1,2-Dithiamethyl Ethane
Authors: Hayashi Michiro , Shiro Yuji , Oshima Toshiyuki , Murata Hiromu
Published: July 2006

The infrared and Raman spectra of 1,2-dithiamethyl ethane have been measured in gaseous, liquid and solid states. Vibrational assignments have been made in relation to the rotational isomerism. The normal vibration calculation has been carried out in a modified Urey-Bradley force field. In the gaseous and liquid states, GTG′ and GGG molecular forms exist, while in the solid state the GTG′ form alone persists. The energy difference between GTG′ and GGG molecular forms has been found to be 1.1 kcal./mol. in the gaseous state and very small in the liquid state. The GTG′ form is more stable than the GGG form, in both the gaseous and liquid states.
The Solution Behavior of Polystyrene Derivatives: Poly-p-methoxystyrene
Authors: Kotera Akira , Suzuki Keizo , Saito Takahide , Matsuda Hideomi , Kamata Toshio , Hashino Yoshiko
Published: July 2006

The solution behavior of poly-p-methoxystyrene in toluene and butanone was measured by light-scattering and viscosity methods, and the results were compared with those of polystyrene and poly-p-chlorostyrene in order to discuss the mutual interactions between the solvent and the substituent on the phenyl group. The results show that toluene is a good solvent and butanone a poor one for poly-p-methoxystyrene; these relationships between poly-p-methoxystyrene and solvents are inverse to those for poly-p-chlorostyrene and similar to those for polystyrene, although the extensions of poly-p-chlorostyrene and poly-p-methoxystyrene are much larger than that of polystyrene at the same degree of polymerization because of the strong mutual interaction between, the solvent and the substituent on the phenyl group. It is clear, from the application of Kurata-Stockmayer theory to the experimental results obtained for poly-p-methoxystyrene, that the unperturbed dimension of poly-p-methoxystyrene is larger than that of polystyrene; this result may be interpreted as being due to an increase in the volume of the chain element of the polymer molecule.
Electronic Spectra and Electronic Structures of α- and β-Nitronaphthalenes and 1,8-Dinitronaphthalene
Authors: Kojima Maomi , Nagakura Saburo
Published: July 2006

The absorption spectra of α-, β-nitronaphthalenes and 1,8-dinitronaphthalene were measured in the near and vacuum ultraviolet regions. The peak wavelengths are as follows: α-nitro-naphthalene, 213, 243 and 326.5 mμ; β-nitronaphthalene, 210.5, 259.5, 303 and 342 mμ; 1,8-dinitronaphthalene, 199.5, 229.5 and 303 mμ. The transition energies and oscillator strengths were calculated with these three molecules by considering the configurational interaction among the ground, locally-excited and charge-transfer configurations. By combining the theoretical results with the observed peak wavelengths and the oscillator strengths, the nature of the electronic excitations corresponding to the observed absorption bands was clarified. Concerning 1,8-dinitro-naphthalene, the twisting angle between the nitro groups and the naphthalene ring was estimated to be 60–70° by comparing the observed peak wavelengths and intensities with the calculated values. The effect of solvents on the absorption spectrum of 1,8-dinitronaphthalene was found to be explained by the energy change in the charge-transfer configurations caused by the polarity of solvents. By considering the contribution of the charge-transfer configurations in the ground state, the increment in the dipole moment due to the delocalization of π-electrons was estimated for α- and β-nitronaphthalenes and 1,8-dinitronaphthalene. The estimated dipole moment could explain the fact that the observed dipole moment of β-nitronaphthalene is greater than that of α-nitronaphthalene.
Vinyl-substituted Polysilanes
Authors: Sakurai Hideki , Tominaga Kenji , Kumada Makoto
Published: July 2006

1-Vinylheptamethyltrisilane, 2-vinylheptamethyltrisilane and vinylpentamethyldisilane have been prepared from the corresponding chlorosilanes and vinylmagnesium chloride. In these compounds, intense absorption maxima were observed in the ultraviolet region, and both the λmax and ε increased with an increase in the chain length. Nuclear magnetic resonance and infrared data are also recorded here. Free radical copolymerizations were carried out with styrene and with acrylonitrile, and the monomer reactivity ratios of vinylpentamethyldisilane and 2-vinylheptamethyltrisilane were determined. It has been concluded that the 3d orbital resonance is not important for the stabilization of an odd electron adjacent to the silicon atom in the free radical intermediate in copolymerization in spite of spectral and chemical evidence of enhanced conjugation between the vinyl group and the polysilanyl group.