bluuebunny/crossref_metadata_2025 huggingface dataset:
Organic Sulfur Compounds. XII. The Ultraviolet and Infrared Spectra of the Substituted Benzenesulfinic Acids and Their Esters
Authors: Kobayashi Michio , Koga Nobuko
Published: July 2006

The ultraviolet spectra of several substituted benzenesulfinic acids and their ethyl esters have been recorded, and the assignments of the absorption have been disucssed briefly.
Molecular Vibrations and Structures of Polyalkyl Polysulfides. II. Polyethylene Disulfide
Authors: Hayashi Michiro , Shiro Yuji , Murata Hiromu
Published: July 2006

The polarized infrared spectra of oriented sheets of polyethylene disulfide were measured in the 4000—200 cm−1 region; the fiber period was thus found to be 8.8 Å by X-ray diffraction. It is found that this polymer does not have twofold symmetry axes intersecting the helical axis at right angles. The infrared-active normal vibrations of the four likely structural models were calculated by the use of a modified Urey-Bradley force field. The structure of polyethylene disulfide was concluded to be the GGG′G conformation along the sequence of the –S–CH2–CH2–S–S– bonds of the 31 helical model. This model is very similar to the structure of polymethylene disulfide reported in the previous paper. The above structure was then discussed in comparison with two models proposed previously (J. R. Katz, Trans. Faraday Soc., 32, 77 (1936); Y. Minoura, J. Soc. Rubber Ind. Japan, 28, 399 (1955)).
The Polarographic Behavior of the Condensation Product of Glyoxal with o-Phenylenediamine, and Its Application to the Determination of Glyoxal
Authors: Musha Sôichirô , Wasa Tamotsu , Naito Tameo
Published: July 2006

In buffer solutions containing excess o-phenylene-diamine (OPD), glyoxal is condensed with OPD and the condensation product produces two diffusion-controlled reduction waves (E1⁄2=−0.211 and −0.358 V. vs. SCE, pH=1.6) at pH values below 2.5 and a single well-defined reduction wave (E1⁄2=−0.782 V., pH=8.5) at pH values above 2.5. In the pH range between 2 and 8, an ill-defined reduction wave, which seems to be a catalytic hydrogen wave brought about by the reduction product, is also observed at a more positive potential than a normal hydrogen wave. A linear relationship between the limiting current and the concentration of glyoxal has been obtained under the following conditions, which are recommended for the practical determination of glyoxal; (1—2)×10−2  m for the concentration of OPD, 7—10 for pH, 25°C for the temperature, and 30—60 min. for the condensation time. The application was made to the determination of the purity of a commercial glyoxal aqueous solution, and also to the determination of the glyoxal which is present in ethylene glycol as an impurity. A mechanism for the electrode reactions of the condensation product (i. e., quinoxaline) of glyoxal with OPD was postulated.
Molecular Rearrangement in Polyphosphoric Acid. II. The Conversion of 1,2-Dihydro-2-phenylimino-4H-3, 1-benzoxazin-4-one to 3-phenyl-2, 4(1H, 3H)-quinazolinedione
Authors: Kurihara Masaru , Yoda Naoya
Published: July 2006

The treatment in polyphosphoric acid of the N-(phenylcarbamoyl)-anthranilic acid prepared by the reaction of anthranilic acid with phenyl isocyanate has been shown to yield 1,2-dihydro-2-phenylimino-4H-3, 1-benzoxazin-4-one or 3-phenyl-2, 4(1H, 3H)-quinazolinedione, depending on the reaction temperature. An intramolecular rearrangement has been found to occur by the treatment of exocyclic iminobenzoxazinone with polyphosphoric acid to afford quinazolinedione. The mechanisms of conversion in polyphosphoric acid have been proposed to account for the experimental results, and the structure of 2-phenylimino-4H-3, 1-benzoxazin-4-one has been presumed by means of infrared and ultraviolet spectroscopies and elemental analyses. The products of the reaction of N-methylanthranilic acid with phenyl isocyanate have been shown to be 1-methyl-3-phenyl-2, 4(1H, 3H)-quinazolinedione, 1-methyl isatoic anhydride and N-methyl-2-(phenylcarbamoyl)-carbanilide. Furthermore, the formation of the mixed anhydride of carboxylic acid and phosphoric acid as a reaction intermediate has been postulated.
Cyclopropene Derivatives. II. The Reaction of Diazoketone with Triple Bond
Authors: Obata Naruyoshi , Moritani Ichiro
Published: July 2006

The additions of some keto-carbene to a triple bond were studied. Since keto-carbene rearranges easily to a ketene derivative (Wolff rearrangement), the carbenic addition will always be in competition with the rearrangement. In the case of benzoylphenylcabene, the rearrangement is preferred, and no cyclopropene derivative is obtained. However, benzoyl and acetylcarbene, both having hydrogen instead of phenyl as a substituent, could be successfully added to diphenylacetylene and di-n-butylacetylene, thus giving 1, 2-disubstituted cyclopropene derivatives. Thus, it was found that the acylcyclopropenes were synthesized in a single step by the utilization of the carbenic addition of keto-carbene to a triple bond.
The Synthesis and Reactions of Benzo-1, 4-thiazinotropone Derivatives
Authors: Nozoe Tetsuo , Asao Toyonobu , Takahashi Kazuko
Published: July 2006

Three isomeric benzo-1, 4-thiazinotropones were obtained. Benzo-1, 4-thiazino[3,2-b]tropones substituted with the chloro, the bromo, the nitro or the acetamido group at the seven-membered ring were synthesized by the reaction of di- or trihalotropolone, or 3-bromotropolones with the nitro or the acetamido group, with o-aminothiophenol. The bromination of benzo-1, 4-thiazino[3,2-b]tropone (I) and its 8-isopropyl derivative (II) afforded 7- and/or 9-substituted compounds. In the case of nitration, 5-oxide and 5-oxide of 7-nitro derivative were obtained. The reaction of I or II with thionyl chloride unexpectedly gave the 7, 9-dichloro derivative of I, or four kinds of chloro derivatives of II.
The Effects of Magnesium Fluoride on the Thermal Behavior of Serpentine
Authors: Mase Hanzo , Fukuda Tomoyuki
Published: July 2006

By means of thermogravimetric, differential thermal, and X-ray diffraction techniques, the thermal behavior of a mixture of serpentine (heated at 730°C for 1 hr.) with 31 per cent magnesium fluoride and or mixtures of serpentine with 10, 15.5, 20, 31, 40, and 62 per cent magnesium fluoride were examined at various temperatures up to 1450°C and for various heating periods. The presence of magnesium fluoride affects the shapes of serpentine thermogravimetric and differential thermal curves, but it hardly affects the starting temperatures of the dehydroxylation of the serpentine (730°C) at all. The thermogravimetric curves showed a gradual weight loss above the dehydroxylation temperature of serpentine. In the differential thermal curves, the height reduction of two serpentine exothermic peaks (830°C and 1100°C), and the appearance of two or three endothermic peaks above 1000°C were observed; moreover, a mixture of the preheated serpentine with 31 per cent magnesium fluoride showed a new exothermic peak at 775°C. These effects of magnesium fluoride were discussed. The main heating products of serpentine in the presence of magnesium fluoride were fluorine norbergite, forsterite, magnesioferrite, and magnesium oxide, whereas those of serpentine alone were forsterite and enstatite.
The Effect of Substituents on the Half-Wave Potential of the Polarographic Reduction of Pyridine N-Oxide Derivatives
Authors: Kubota Tanekazu , Miyazaki Hiroshi
Published: July 2006

Polarograms of twenty-three pyridine N-oxide derivatives substituted at γ- and β-positions were extensively measured at various pH’s. The half-wave reduction potential, E1⁄2, was expressed by the form −E1⁄2=a[pH]+b. The wave height due to the reduction of the \eqslantgtrN→O group decreased with an increase in the pH in a pH region over ∼6. This phenomenon was common to all the compounds studied here; it was thought to be useful in identifying an aromatic N-oxide group by the polarographic method. The E1⁄2 plot against Hammett’s σ value of the substituent satisfied a linear relation well, and the slope of Hammett’s ρ value was positive. This indicates that the reduction process is nucleophilic. The linear relation was explained qualitatively on the basis of the MO theory by applying the second-order perturbation method.
A Molecular Orbital Treatment of 13C–H Spin-Spin Coupling Constants
Authors: Yonezawa Teijiro , Morishima Isao , Fujii Mutsuo
Published: July 2006

A molecular orbital interpretation of the directly-bonded 13C–H spin-spin coupling constant without the concept of hybridization is presented. The observed values of JC–H for some saturated and conjugated compounds are shown to be proportional to the square of the bond order between the 2S atomic orbital of the hydrogen atom and the 2S atomic orbital of the carbon atom, P2, which is calculated using the extended Hückel molecular orbital method.
The Relation between Ultrasonic Velocity and Viscosity in Aqueous Solutions of Electrolytes
Authors: Prakash Satya , Prakash Som , Laxmi Shobhay
Published: July 2006

From the experimental data on the ultrasonic velocity and viscosity of thorium nitrate, lanthanum acetate and lanthanum chloride, it has been found that the product of adiabatic compressibility and viscosity is fairly constant over the concentration range studied. From those data the relation between ultrasonic velocity and viscosity has been derived which can explain the variation in sound velocity with the concentration.
Studies of the Alkaline Earth Complexes in Various Solutions. I. Barium(II) Complexes with Sulfate and Oxalate Ions in 1m Sodium Perchlorate Media
Authors: Sekine Tatsuya , Sakairi Mitsuo , Hasegawa Yuko
Published: July 2006

The distribution of barium(II) at a very low concentration was determined between a carbon tetrachloride solution of 0.1 m thenoyltrifluoroacetone and 0.2 m tributylphosphate and aqueous solutions of 1 m Na(ClO4) at 25°C. The net distribution ratio is decreased when a part of the perchlorate ions are replaced by sulfate or oxalate ions. This decrease was explained in terms of the complex formation of Ba2+ with these ligands. The stability constants were determined graphically from the experimental data as follows:

(Remark: Graphics omitted.)
Physical Chemistry of Binary Plastic Crystals. I. The System of Carbon Tetrachloride and t-Butyl Iodide
Authors: Chihara Hideaki , Otsuru Masako , Seki Syûzô
Published: July 2006

The binary system, carbon tetrachloride- t-butyl iodide, was studied by the proton magnetic resonance, the dielectric measurements and the X-ray diffraction. The complete phase diagram, constructed by the differential thermal analysis, shows a solid solution region where carbon tetrachloride is more than 50 mole%. Detailed studies of the solid solution containing 6.6 mole% of t-butyl iodide reveals that the solution can be described by the theory of regular solutions; its molecular polarization above the transition temperature obeys the Debye formula giving the dipole moment of t-butyl iodide a value of 1.6 debye units. The high-resolution nuclear magnetic resonance experiments with the same phase shows that carbon tetrachloride molecules diffuse in the solid solution with an energy of activation of 6.8 kcal./mole. The transition temperature varies with the composition, and below it the rotational motion of the solute molecules is more hindered. Pure t-butyl iodide shows motional narrowing around –150°C in the NMR line shape, above which temperature a reorienting molecular model can account for the magnitude of second moment of the nuclear magnetic resonance absorption.
The Radiation-Induced Addition Reaction of Thiols to Chlorofluoroolefins
Authors: Inukai Kan , Ueda Teruo , Muramatsu Hiroshige
Published: July 2006

The addition of thiols to chlorofluoroethylenes was carried out under γ-ray irradiation; chlorofluoroethyl alkyl sulfides were thus obtained. Ghlorofluoroethyl alkyl sulfoxides and sulfones were prepared by the oxidation of the sulfides. The dehydrohalogenation of chlorofluoroethyl alkyl sulfides yielded chlorofluorovinyl alkyl sulfides, whose structure indicated that the thiyl radical attacked the difluoromethylene side of the asymmetrical dichlorodifluoroethylene. Chlorofluorovinyl sulfoxides and sulfones were also synthesized from the sulfides by oxidation with hydrogen peroxide.
The Autoxidation of p-Xylene Catalyzed with Cobalt Monobromide in Acetic Acid
Authors: Kamiya Yoshio , Nakajima Tadahiko , Sakoda K\={o}ichiro
Published: July 2006

The rate of the cobalt-catalyzed autoxidation of p-xylene by adding sodium bromide reaches the steady state within several minutes and increases remarkably at high cobalt concentrations. Although p-tolualdehyde as well as water, the main oxidation products of p-xylene at the initial stage, strongly affect the rate of oxidation, the apparent rate is kept constant over a long period. When cobalt dibromide is used, a pronounced induction period can be observed at high cobalt concentrations, and the rate of oxidation starts to decrease after a short while. The effect of the ratio of sodium bromide to cobalt has shown that cobalt monobromide is an effective catalyst for the propagation step. The rate of the oxidation of p-xylene is found to be of the order of from 1.5 to 2.0 with respect to cobalt at concentrations from 10−3 to 5×10−2mol./l. and at temperatures from 65 to 95°C, and to be first-order with respect to the p-xylene concentration; these findings show excellent agreement with the theory. When cobalt is partly replaced by manganese, a strong synergistic effect can be observed.
Studies of Peptide Antibiotics. VII. The Synthesis of Cyclo-d-phenylalanyl-d-leucyl-l-ornithyl-l-valyl-d-ornithyl-l-prolyl
Authors: Kato Tetsuo , Izumiya Nobuo
Published: July 2006

A cyclic hexapeptide, cyclo-d-phenylalanyl-d-leucyl-l-ornithyl-l-valyl-d-ornithyl-l-prolyl, was once reported to be an antibiotic gramicidin J2, and the synthesis of the compound was described also. However, the natural occurrence of gramicidin J2 was denied recently. For the purpose of comparing its antibacterial activity, if any, with gramicidin S, the synthesis of this compound was carried out. p-Methoxybenzyloxycarbonyl-d-phenylalanyl-d-leucyl-δ-benzyloxycarbonyl-l-ornithyl-l-valyl-δ-benzyloxycarbonyl-d-ornithyl-l-proline p-nitrophenyl ester was prepared, and, after the selective cleavage of p-methoxybenzyloxycarbonyl group, the hexapeptide ester was transformed to the cyclic benzyloxycarbonyl hexapeptide, which was then hydrogenated to afford the desired cyclic hexapeptide as dihydrochloride. The effects of the synthesized cyclic peptide on bacterial growth have been examined. No antibacterial activities were observed in reaction to the microorganisms utilized here.
Cyclopropene Derivatives. IV. The Reactions of Acylcyclopropene
Authors: Obata Naruyoshi , Moritani Ichiro
Published: July 2006

The reactions of acylcyclopropenes, such as 3-benzoyl-1,2-diphenyl- and 3-acetyl-1,2-diphenyl-cyclopropene, were investigated. These ketones gave normal hydrazones with 2,4-dinitrophenylhydrazine. With p-toluenesulfonylhydrazine, the acetyl compound gave ordinary hydrazone, but the benzoyl derivative did not give its hydrazone. The reaction with hydrazine hydrate caused the expansion of the cyclopropene ring and produced pyridazine derivatives in both the ketones. The carbenic decomposition of 3-acetyl-1,2-diphenylcyclopropene p-toluenesulfonylhydrazone with sodium methoxide in diglyme gave diphenylacetylene and 3,4-diphenyl-6-methylpyridazine. On irradiation with ultraviolet light, 3-benzoyl-1,2-diphenylcyclopropene produced 1,2,4,5-tetraphenylbenzene. In the case of 3-acetyl-1,2-diphenylcyclopropene, the same benzene derivative and 1,2,4,5-tetraphenyl-3,6-diacetyltricyclo[3,1,0,02,4]hexane were obtained. The latter material was transformed into a benzene derivative upon further irradiation. Tricyclohexane could be an intermediate in the transformation of ketones to a benzene derivative.
The Synthesis, Resolution and Configuration of β-Hydroxyvaline
Authors: Oh-hashi Jun-ichi , Harada Kaoru
Published: July 2006

Dl-β-Hydroxyvaline was synthesized from sodium β,β-dimethylglycidate by aminolysis with benzylamine, followed by hydrogenolysis. N-Benzoyl-Dl-β-hydroxyvaline was resolved by use of (−)-α-methylbenzylamine to yield (−)-N-benzoyl-β-hydroxyvaline. The configuration of VI was determined by converting it to methyl N-benzoyl-β-chlorovalinate (I) and subsequent hydrogenolysis of I yielded (−)methyl N-benzoylvalinate (II). From II, optically pure d-(−)-valine was obtained upon hydrolysis.
The Effects of Some Antioxidants on the Elastomers Derived from Carboxy-terminated Polybutadiene
Authors: Tokui Harusuke , Yamazaki Kiroku
Published: July 2006

The capability of several sorts of conventional antioxidants was studied by means of the tensile and the swelling tests of the elastomers derived from the carboxy-terminated polybutadiene prepolymer. When exposed for one year, the elastomers containing no antioxidants deteriorated remarkably; they became brittle and, without exception, no longer looked like the so-called “elastomers.” Many kinds of the antioxidants worked out and were found to be effective; their capabilities were evaluated as almost the same as far as the tensile properties of the exposed material were concerned. The changes in the reciprocal value of the average chain length between cross-links, 1/Mc, in the course of the exposure, however, would be a convenient semi-quantitative measure of the induced cross-linking reaction. With this assumption, the swelling test might prove that, among the additives covered, the amine-type antioxidants were most effective in preventing the deterioration induced by the over-cross-linking reaction of the elastomer. The relationship between the amount of the sol-fraction and the cross-linking density for the exposed specimens was fitted to that of the random cross-linking and the scission of the polymer with a random distribution of chain lengths.
Properties of Dilute Solutions of Polyurethanes. II. Branched Polymers
Authors: Sato Hiroshi
Published: July 2006

Linear and branched polyurethanes, both of which contained polycaprolactone (\barMn=1.80×103), were prepared. Each polymer was fractionated from a dimethyl acetamide solution by precipitation with a mixture of n-heptane and ethyl ether, and the fractions were characterized by viscosity and sedimentation. The degree of branching for the fractions of the branched polymer was estimated by using the relation between viscosity and branching, derived by Flory. The ratio of the concentration dependence of the sedimentation coefficient ks to [η] was about 1.7 for the linear polymer, but the ks⁄[η] value increased with an increase in the degree of branching for the branched polymer. The Huggins constant, k′, seems to be independent of the degree of branching.
Heptafulvenes. V. Some Substitution Reactions of 2,3-Dimethoxy-8,8-dicyanoheptafulvenes
Authors: Kitahara Yoshio , Doi Kozo , Kato Tadahiro
Published: July 2006

Methoxyl groups of alkyl-2,3-dimethoxy-8,8-dicyanoheptafulvenes were easily replaced by various kinds of nucleophilic reagents to give the corresponding substituted-8,8-dicyanoheptafulvenes. There exists a difference in reactivity between the two methoxyl groups located at the 2 and 3 positions of 8,8-dicyanoheptafulvenes. The isopropyl group at the 4 position of 2,3-dimethoxy-8,8-dicyanoheptafulvene hindered some substitution reactions of the methoxyl group at the 3 position.
Hydrogenation and Hydrogenolysis. IX. The Hydrogenation of Benzyl Alcohol with Platinum Metal Catalysts
Authors: Nishimura Shigeo , Hama Michiko
Published: July 2006

The rate of the hydrogenation of benzyl alcohol with a rhodium catalyst decreases markedly in the course of the reaction, accompanied by the formation of an increasing amount of cyclohexanecarboxaldehyde with the conversion of the alcohol. The decrease in the rate is only slight with a platinum catalyst, however, and the formation of the aldehyde is much less than with the rhodium catalyst. It has been shown that cyclohexanecarboxaldehyde is an effective catalyst poison in the hydrogenation of benzyl alcohol, but that cyclohexylcarbinol is not. 1-Cyclohexenylcarbinol, an intermediate of the hydrogenation, isomerizes to cyclohexanecarboxaldehyde during the hydrogenation on rhodium and 7 : 3 rhodium-platinum catalysts to a greater extent than on the platinum catalyst. Cyclohexanecarboxaldehyde is hydrogenated only very slowly, but the rate with the platinum catalyst is about four times greater than that with the rhodium catalyst. These results may account for the different behaviors of the rhodium or 7 : 3 rhodium-platinum catalyst and the platinum catalyst observed in the hydrogenation of benzyl alcohol.
Studies of Unnatural Amino Acids and Their Peptides. II. The Syntheses of Dl-β-(4-Thiazolyl)-α-alanine and Its Peptides
Authors: Watanabe Hiroshi , Kuwata Shigeru , Sakata Tatsuo , Matsumura Keizo
Published: July 2006

Dl-β-(4-Thiazolyl)-α-alanine has been synthesized in a good yield by the condensation of 4-thiazolylmethyl chloride and diethyl acetamidomalonate, and by the subsequent hydrolysis of the product. The N-carbobenzoxy derivative of this amino acid could be prepared easily and transformed to its p-nitrophenyl ester and t-butoxycarbonylhydrazide, but it was found difficult to obtain the methyl ester or the benzyl ester directly from this amino acid. Carbobenzoxy-Dl-β-(4-thiazolyl)-α-alanyl-glycine benzyl ester has been synthesized by several coupling methods: its yield decreased in the following order: p-nitrophenyl ester>dicyclohexylcarbodiimide (glycine ester was used as a free base)>dicyclohexylcarbodiimide (glycine ester p-toluenesul-fonate was used without triethylamine)>dicyclohexylcarbodiimide (glycine ester p-toluenesulfonate was used with triethylamine)>mixed anhydride. The alkaline hydrolysis of the protected di-peptide ester afforded the N-protected peptide in a good yield. Decarbobenzoxylation did not proceed smoothly by catalytic hydrogenation, in which hydrogen was absorbed slowly and incompletely, while it proceeded normally with hydrobromic acid in acetic acid.
Copolymerizations of 1-Phthalimido-1,3-butadiene and 1-Succinimido-1,3-butadiene
Authors: Murata Kenichi , Terada Akira
Published: July 2006

1-Phthalimido-1,3-butadiene (1-PB) and 1-succinimido-1,3-butadiene (1-SB) were co-polymerized readily with acrylonitrile, methyl methacrylate and styrene, but somewhat less readily with vinyl acetate. The monomer reactivity ratios for the system with styrene were calculated by the Fineman-Ross method and found to be r1(1-PB)=1.48, r2(St)=0.32 for the 1-phthalimido-1,3-butadiene-styrene system, and r1(1-SB)=1.62, r2(St)=0.28 for the 1-succinimido-1,3-butadiene-styrene system. The Q, e-values for these systems were successively evaluated and obtained as Q (1-PB)=1.57, e(1-PB)=+0.06, Q (1-SB)=1.76 and e(1-SB)=+0.09, when Q (St)=1.0 and e(St)=−0.8. Likewise, such values for N-vinyl phthalimide (VPI) and N-vinyl succinimide (VSI) were investigated in order to compare them with the values obtained above for the imidobutadienes; they were shown to be r1(VPI)=0.09 and r2(St)=6.3 for the N-vinyl phthalimide-styrene system, and r1(VSI)=0.07 and r2(St)=9.6 for the N-vinyl succinimide-styrene system. Subsequently, the following Q and e values were determined: Q (VPI)=0.09, e(VPI)=−0.13, Q(VSI)=0.06, and e(VSI)=−0.17.
Sesquiterpenes from Dictyopteris Divaricata. II. Dictyopterol and Dictyopterone
Authors: Kurosawa Etsuro , Izawa Motowo , Yamamoto Koji , Masamune Tadashi , Irie Toshi
Published: July 2006

The structures of new sesquiterpenes, dictyopterol and dictyopterone, isolated from the essential oil of a brown algae, Dictyopteris divaricata Okamura (“Yezoyahazu”), have been shown to be selinen-1β-ol and selinen-1-one, respectively, on the basis of chemical and spectral data. Dictyopterol is an inseparable mixture of α- and β-isomers.
The Reaction of Halogenated Biacetyl Monoximes with Esters of Amino Acids
Authors: Sugiyama Masatoshi , Masaki Mitsuo , Ohta Masaki
Published: July 2006

1-Chloro-2-oximino-3-butanone (I) was prepared by the nitrosation of chloroethyl methyl ketone with an alkyl nitrite. I was treated with the l-leucine ethyl ester (II) to give 2-(2-oximino-3-oxobutylamino)-4-methylvalerate (III) and 2-[N, N-bis(2-oximino-3-oxobutyl)amino]-4-methyl-valerate (IV). In a similar manner, l-bromo-3-oximino-2-butanone (V) was treated with II to give 2-(3-oximino-2-oxobutylamino)-4-methylvalerate (VI). The reaction of the carbonyl group of III and VI with hydroxylamine and hydrazine was also studied. The treatment of VI with ammonia gave 6-(2-oximinoethyl)-3-isobutyl-2-hydroxypyrazine. Reactions of I and V with other esters of amino acids were also carried out.
The Catalytic Hydrogenation of Aniline in Fluidized Beds
Authors: Echigoya Etsuro , Hagiwara Hiroshi , Sakurai Akio
Published: July 2006

The hydrogenation of aniline in fluidized beds was studied. As a result of the experiments, the following conclusions were obtained: 1) The reaction rate of the catalytic hydrogenation of aniline in the temperature range between 150°C and 180°C was approximately first-order with respect to hydrogen. In the case of a large molar ratio of hydrogen to aniline, however, the reaction rate became zeroth-orcler with respect to aniline. 2) A good agreement was obtained between the conversion by the fluidized-bed experiment and the values calculated on the model of the contact-time distribution for low degrees of conversion. For high degrees of conversion, the deviation of the values calculated using this model from the experimental value was found to be about 10%. It was suggested that this model can well be applied to predicting the conversion for zeroth-order reaction within the limits of uncertainty given above.
Determination of Angular Orientation of Rigid Group in Molecular Crystal: Vector-set Seeking Method
Authors: Katsube Yukiteru , Sasada Yoshio , Kakudo Masao
Published: July 2006

In order to determine the angular orientation of the rigid atomic group, such as benzene ring, in a molecular crystal, a new method for interpreting a distribution of peaks near the origin of two-dimensional Patterson function has been described in this paper. Similar methods for solving the Patterson function by the aid of the rigid groups have been proposed by several authors, but the present method, vector-set seeking method, differs from them in the procedure to find a satisfactory fit of a vector-set of the rigid group on the Patterson function and in a criterion for a correct choice of the angular orientation. Satisfactory results for the known structures of salicylamide and α-pyridone and the unknown structure of m-hydroxybenzamide were quickly obtained by the application of this method.
The Radiolysis of Crystalline Oxalato Metal Complexes. The Effects of Coordinating Metal Ions on the Radiolysis of Oxalate
Authors: Sugimori Akira
Published: July 2006

Coordinated oxalates in metal complexes are more reactive under γ-irradiation than are ionic oxalates. This suggests that the covalency between the metal ion and the ligand in oxalato metal complexes promotes the reactivity of the ligand. The reaction of the ligand is also affected by the central metal ions. In K3[Co(C2O4)3]·3H2O and K3[Fe(C2O4)3]·3H2O, the coupled reduction of central metal ions with the oxidative decomposition of the ligand to carbon dioxide occurs at relatively high G values. In K3[Cr(C2O4)3]·3H2O, the redox reaction of the central metal ion is small and the ligand decomposes into carbon dioxide and carbon monoxide. In K3[Al(C2O4)3]·H2O, the formation of glyoxal and formic acid instead of carbon monoxide is significant.
Studies of the Hydrocracking of Lignin. III. The Hydrocracking of Various Types of Lignin
Authors: Oshima Motoyoshi , Kashima Kan , Watanabe Hiroshi , Tabata Haruo , Kubo Teruo
Published: July 2006

Three types of raw material for lignin hydrocracking were prepared and their reactivities were compared in relation to the refined lignin reported in the authors’ previous paper (Bull. Chem. Soc. Japan,  39, 2750 (1966)). The raw materials were prepared; 1) by autoclaving the alcohol-fermented sulfite waste liquor (heat-precipitated lignin); 2) by drying the liquor (dried SWL), and 3) by concentrating the liquor (concentrated SWL). Although these three types of lignin are less costly to prepare, they showed poor reactivities in the hydrocracking process. Heat-precipitated lignin gave a 16–20% monophenol yield [Analyzed by rectification and gas chromatography (no alkaline extraction was conducted).] at a 100% recovery level of pasting oil. No definite monophenol yield figures could be concluded in the runs with dried or concentrated SWL because of the scattered data. The poor reproducibility of data in the cases of these two types of lignin is discussed.
The Reaction of Aminotropones with Diketene. II. The Structure of the By-product in the Reaction of 5-Aminotropolone with Diketene
Authors: Seto Shuichi , Sasaki Hiroko , Ogura Kyozo
Published: July 2006

The reaction of 5-aminotropolone with diketene gave a minor product and 5-aceto acetamidotropolone, which had previously been described (K. Ogura et al., This Bulletin, 38, 306 (1965)). This unknown compound was obtained as a main product when 5-acetoacetamidotropolone was treated with diketene in the presence of triethylamine. From its oxidative degradation and its NMR spectrum, this compound was proved to be 3-acetyl-4-hydroxy-6-methyl-1-(tropolon-5′-yl)pyridone-2. Furthermore, for the sake of the structural determination, 3-acetyl-4-hydroxy-6-methylpyridone-2 and its deacetylated product were prepared.
The Synthesis of α, ω-Disubstituted Higher Alkanes from α, α, α, ω-Tetrachloroalkanes
Authors: Saotome Kazuo , Komoto Hiroshi , Yamazaki Toshiaki
Published: July 2006

Higher ω-chloroalkanoic acids than ω-chlorooctanoic acid were prepared in good yields (over 90%) by improved methods of the hydrolysis of α, α, α, ω-tetrachloroalkanes. The reactions were carried out in fuming nitric acid, with the addition of nitrogen dioxide during the reaction or in the presence of a small amount of phosphoric anhydride. α, ω-Dichloroalkanes were derived from the ω-chloroalkanoic acids by the Kolbe electrolytic synthesis. Various other novel α, ω-disubstituted alkanes with very long methylene chains, such as glycols, dinitriles, dicar-boxylic acids, and diamines, were also prepared starting from the tetrachloroalkanes.
An Application of the Quasi Chemical Approximation to the NMR Dilution Shift in Some Binary Mixtures
Authors: Satake Iwao , Arita Masujiro , Kimizuka Hideo , Matuura Ryohei
Published: July 2006

The theoretical NMR dilution curves for the ethanol-carbon tetrachloride, water-acetone and water-dioxane systems have been derived without the assumption of any particular type of H-bonded complexes in the solution. The expressions so derived contain the interchange energies as variable parameters. The use of the appropriate values of interchange energies (a few kilocalories) gives reasonable quantitative fits of the experimental dilution curves over the entire concentration range of the solutions. These values suggest that the strength of hydrogen bonding in the present systems is in the order of: water-water>water-acetone>water-dioxane>ethanol-ethanol.
Spectroscopic Studies of Dialkylaluminum Alkoxides and the Trialkylaluminum-Ether Complex. I. Structures and Symmetries
Authors: Tarao Ryokichi
Published: July 2006

The infrared and Raman spectra of [Al(CH3)2OCH3)]3, [Al(C2H5)2OCH3]3, [Al(C2H5)2·OC2H5]2, and Al(CH3)3·(CH3)2O have been measured in the 3000—300 cm−1 region, and the infrared absorption bands and the Raman lines in the skeletal vibration region (720—300 cm−1) have been compared. For [Al(CH3)2OCH3]3 and [Al(C2H5)2OCH3]3, the results are consistent with trimeric structures with symmetry D3h. For [Al(C2H5)2OC2H5]2, the results are consistent with a dimeric structure with symmetry Vh. Thus, the structures with the oxygen bridge proposed by Hoffmann for these polymeric compounds have been confirmed by spectroscopic measurements. The structures with alkyl bridges are very unlikely. For Al(CH3)3·(CH3)2O, the results do not contradict the postulated structure, with symmetry Cs.
Alkali Fusion-Gas Chromatography of Alkyl Sulfates
Authors: Nakagawa Terumichi , Miyajima Koichiro , Uno Toyozo
Published: July 2006

The alkali fusion of alkyl sulfates was investigated by pyrolyzing a mixture of alkyl sulfates and alkali metal hydroxide between 200–500°C. The pyrolyzates were isolated and identified to be 1-olefins, internal olefins, alcohols, and dialkyl ethers by gas chromatography and IR spectroscopy. The mechanism of this reaction was proposed from these results and an attempt was carried out to estimate the alkyl chain carbon number distribution of the commercially available sodium alkyl sulfates.
Syntheses and Structures of Acetylformoin and Related Compounds. VI. Substituent Effects
Authors: Miyagi Yo , Kimura Sadao , Goto Ryozo
Published: July 2006

In the presence of cyanide ions, an α-ketoaldehyde dimerizes to give an acylformoin. The tautomerism of this compound was studied. It was found that the tautomerism between I and II is affected by the solvents and by the substituents. In proton-accepting solvents (EtOH, THF), I predominates. In ethanol-free chloroform, II is dominant for almost all substituents. In ethanol-containing chloroform, some acylformoins exist as I, while the others exist as II. The former case is observed when R=t-Bu and p-X–C6H4 (X=H, t-Bu, Cl, and Br); the latter case, when R=Me, i-Pr, and p–Me-C6H4. In the former case, ethanol reacts slowly with I to give an O-ethyl derivative (III). When R=2,4,6-Me3–C6H2, II predominates in all states. When R=p-Cl–C6H4 and p-Br–C6H4, I and II were isolated as crylstals. The solvent effects are interpreted in terms of the hydrogen-bonding interactions of I with basic and hydroxylic solvents.

(Remark: Graphics omitted.)
Photochemical Substitution of Ferrocene in Halogenated Hydrocarbon–Ethanol Solutions
Authors: Akiyama Takeo , Hoshi Yoshiyuki , Got\={o} Satoshi , Sugimori Akira
Published: July 2006

The photochemical substitution of ferrocene in several halogenated hydrocarbon–ethanol solutions was investigated. Ethoxycarbonyl, formyl, ethoxymethyl, benzyl and allyl groups were photochemically introduced into ferrocene in 25–53% yields by the UV-irradiation of ferrocene in carbon tetrachloride–, chloroform–, dichloromethane–, benzyl chloride–, and allyl bromide–ethanol solutions, respectively. The reactions proceeded effectively by the excitation of the charge transfer complexes formed between ferrocene and halogenated hydrocarbons.
Crystal and Molecular Structure of ω-Amino Acids, ω-Amino Sulfonic Acids and Their Derivatives. IV. The Crystal and Molecular Structure of γ-Aminobutyric Acid (GABA), a Nervous Inhibitory Transmitter
Authors: Tomita Ken-ichi , Higashi Hideko , Fujiwara Takaji
Published: July 2006

The structure of γ-aminobutyric acid (GABA), C4H9NO2, was determined by single-crystal X-ray diffraction analysis using the data collected on a four-circle diffractometer. The compound was crystallized from an aqueous ethanol solution as needles of the monoclinic space group P21/c with four molecules in the following unit cell; a=7.193, b=10.120, c=8.260 Å and β=111.05°. The structure was solved directly by a symbolic addition method and refined by a least-squares procedure. The final R is 9.3%. The molecular geometry is not a planar trans-zigzag configuration as found in γ-guanidinobutyric acid hydrochloride or homotaurine, but a gauche configuration with respect to Cα–Cβ bond. The expected zwitterionic structure is evident from the locations of the hydrogen atoms in a difference Fourier map, each molecule being connected with three N–H···O hydrogen bonds to form a three-dimensional network.
Studies of Enamines. III. The Reaction of 4-(1-Piperidyl)- and 4-(1-Pyrrolidinyl)-3-penten-2-ones with Aryl Isothiocyanates
Authors: Tsuge Otohiko , Inaba Akitaka
Published: July 2006

The reaction of enamino ketones, derived from acetylacetone and piperidine or pyrrolidine, with aryl isothiocyanates has been investigated. In contrast with phenyl isocyanates, phenyl isothiocyanates react with the enamino ketones to yield the corresponding 3-phenylthiocarbamoyl derivatives (1 : 1 adducts). The reaction with 1-naphthyl isothiocyanate forms 3-naphthylthiocarbamoyl and/or 2-thiopyridone derivatives, depending on the reaction conditions.
Molecular Structure of Ethane. Comparison of the Structure Parameters of CH3CD3 in the Torsionally Excited State and in the Ground State
Authors: Iijima Takao
Published: July 2006

The structure parameters of ethane have been re-examined by the use of the spectroscopic moments of inertia and the electron diffraction results, on the basis of the large amplitude theory for the torsional motion. The results have been applied to the CH3CD3-species in order to see whether or not the change of the moment of inertia in the torsionally excited state observed by Hirota and Matsumura is consistent with the theoretical prediction on the deformation of the molecular frame upon torsion proposed by Veillard. The conclusion has been affirmative. The elongation of the C–C distance by 0.0028 Å and the decrease of the HCH angle by 0.05° in the torsionally excited state as expected from the theoretical calculation have been found to be consistent with the experimental result of microwave spectroscopy.
Kinetic Studies of the Solvent Extraction of Metal Complexes. II. The Rate of the Extraction of Iron(III) with Thenoyltrifluoroacetone into Carbon Tetrachloride
Authors: Sekine Tatsuya , Yumikura Jun-ichi , Komatsu Yu
Published: July 2006

The rate of the solvent extraction of iron(III) in 4.0 M perchlorate ionic media with 2-thenoyltrifluoroacetone (TTA) into carbon tetrachloride has been measured under various conditions. The rate was found to be first order with respect to the concentration of iron(III) in the aqueous phase, first-order with respect to TTA in the organic phase, but independent and inversely first-order with respect to the hydrogen-ion concentration. From these results, it was concluded that the rate-determining step in this extraction is the formation of the first complex between the undissociated form, TTA(HA), and Fe3+ in the higher acid concentration range, but that the reaction between the anionic form, TTA(A−), and Fe3+ also becomes a rate-determining step as the acid concentration decreases. It was also found that chloride ions accelerate the extraction; this was interpreted by more rapid reactions between TTA (in the both forms, HA and A−) and an iron(III) chloride complex. From these results, the rate constants for the rate-determining reactions were calculated to be KHA=100.57 M−1 min−1 and KA=106.84 M−1 min−1 in 4.0 M(H, Na)ClO4 at 25 °C by means of these equations: −d[Fe3+]⁄dt=KHA[Fe3+][HA] (where [HA] is the total concentration of both enol and keto forms of uncharged TTA in the aqueous phase) and −d[Fe3+]⁄dt=KA[Fe3+]·[A−]. The FeCl2+ species reacts with both HA and A− more rapidly than does the Fe3+ species, and the rate constants of the reactions of the former are in both cases higher than those of the latter by a factor of 28.
Emission Processes in Cadmium Photosensitization
Authors: Tsunashima Shigeru , Toyono Tsutomu , Sato Shin
Published: July 2006

The possibility of the cadmium-photosensitized luminescence of NH3, CO2, CO, and CH4 was examined at 250 °C. In the case of NH3, a very strong band emission was observed at 432 nm, with a band width of about 100 nm. The sensitized luminescence of NH3 was attributed to the emission from an excited complex between triplet cadmium and NH3. In the case of CH4, a weak emission was observed at about 420 nm. In the cases of CO2, CO, and N2, however, no positive evidence of the sensitized luminescence was obtained. From the pressure dependence of the quenching of the 326.1 nm resonance line, the efficiencies of CO2, CO, NH3, and N2 for quenching the triplet cadmium atoms were estimated to be 0.16, 0.03, 3.3×10−4, and 4.9×10−5, respectively, the efficiencies of cis-2-butene being assumed to be unity.
Solubilization Behavior of the Surfactant–Polyethylene Glycol Complex in Relation to the Degree of Polymerization
Authors: Tokiwa Fumikatsu , Tsujii Kaoru
Published: July 2006

The solubilization behavior of the complexes composed of a surfactant and polyethylene glycol (PEG) toward an oil-soluble dye, Yellow OB, has been studied in relation to the degree of polymerization, n, of PEG. The solubilizing powers of the anionic surfactants, sodium dodecyl sulfate and sodium p-octylbenzene sulfonate, become greater on the addition of PEG, the extent depending on n. They increase as n increases. It is proposed that there are at least two different types of complexes, i.e., “oligomeric” and “polymeric” PEG–surfactant complexes. The boundary between the oligomeric and polymeric PEG’s is estimated to be around an n value of 10–15. With an oligomeric PEG–surfactant complex, the solubilization of Yellow OB would occur mainly in the hydrocarbon part of the surfactant micelle. With a polymeric PEG–surfactant complex, on the other hand, the solubilization would take place in the region of a complex rich in PEG. Electrical-conductivity and absorption-spectral data on the complexes are also included in this paper.
The Contact-term Contributions to Lanthanide-induced 13C Paramagnetic Shifts in Acridine, Quinoline, and Isoquinoline
Authors: Hirayama Masatoshi , Hanyu Yoshiaki
Published: July 2006

1H and 13C paramagnetic shifts induced by Eu(DPM)3 and Pr(DPM)3 in acridine, quinoline, and isoquinoline in CCl4 are observed. It has been found that, while the 1H shifts can be interpreted solely in terms of a pseudo-contact interaction, there is a much larger contact-term contribution to 13C shifts induced by Eu(DPM)3 than by Pr(DPM)3 in these compounds; this contribution to the 13C shifts cannot be explained by a simple combination of σ- and π-contact terms.
The Microwave Spectrum and Quadrupole Coupling Constant Tensor of Bromomethylsilane
Authors: Hayashi Michiro , Kuwada Kazunori
Published: July 2006

The microwave spectra of four isotopic species of bromomethylsilane have been measured, viz., the 79Br and 81Br species of BrCH2SiH3 and BrCH2SiD3. The observed rotational constants have been well explained by a model of which the structural parameters have been transferred from the corresponding parameters determined for ethylbromide and chloromethylsilane. The principal quadrupole coupling constants have been determined through the analysis of the first- and second-order effects of quadrupole coupling on the hyperfine structure of the observed spectra. It was concluded, within the experimental error, that the quadrupole coupling constants tensor of this molecule has the cylindrical symmetry around the largest principal axis, the direction of which coincides approximately with the C–Br internuclear line.
Charge Transfer Interaction between the Cation Radicals of Some Aromatic Diamines and Triethylamine
Authors: Sakata Tadayoshi , Okai Toshihiro , Sugimoto Hiroaki , Tsubomura Hiroshi
Published: July 2006

Electronic spectra of the cation radicals of some aromatic diamines in triethylamine were found to differ remarkably from those in other solvents such as ether or alcohol as regards (1) swelling of the absorption at around 25000 cm−1, (2) broadening of the first band system and (3) red shift of the same system. It was concluded that these phenomena are due to the charge transfer interaction between cation radicals and triethylamine.
A Study of Complex Formation by the Cation Exchange Method. Bivalent Metal Complexes with Univalent Anions
Authors: Ohyoshi Emiko
Published: July 2006

An attempt was made to estimate the amount of the cationic complex MA+ adsorbed on a cation exchanger. This method is based on the fact that the ratio of the distribution coefficients of M2+ and MA+ should vary with the ionic strength of the medium. The Ni(II) acetate system studied by Fronaeus has been reexamined. The results show that the distribution coefficient of NiAc+ (Ac=acetate) is negligible compared with that of Ni2+ upon the variation of the ionic strength from 0.2 to 1.0. It was found that Fronaeus overestimated the distribution coefficient of NiAc+ and that this caused the value of β2 to be much greater. In conclusion, the two functions, \varphi1 and f, introduced by Fronaeus could not be determined with high accuracy; for the stability constants obtained by Fronaeus’s method, they must be confirmed by conducting the experiment at a different ionic strength.
Synthesis of Pyrimidines and Condensed Pyrimidines
Authors: Kobayashi Shigeru
Published: July 2006

A new one-step synthesis of pyrimidines and condensed pyrimidines by heating carboxamides or cyclic lactams with formamide in the presence of POCl3 in a sealed tube is described.
Photochemistry of Heterocyclic Compounds. VII. The Photochemical Behavior of Phthalazine and Quinoxaline in Acidified Alcohols
Authors: Wake Shigeo , Takayama Yuichi , Otsuji Yoshio , Imoto Eiji
Published: July 2006

Irradiation of phthalazine (1) and quinoxaline (2) in acidified methanol yielded 1-methylphthalazine (3a) and 2-methylquinoxaline (4), respectively. The quantum yields for the formation of 1-alkylphthalazines, which were obtained upon irradiation of 1 in acidified alcohols, varied with the sort of alcohols used and decreased in the order of methanol>ethanol>>2-propanol. When a mixture of 1 and 2,6-di-t-butylphenol (6) was irradiated in benzene containing trifluoroacetic acid under evacuated conditions, the oxidation of 6 occurred to form 3,5,3′,5′-tetra-t-butyldiphenoquinone (7) without destruction of 1. Detailed mechanistic studies suggest that the photoalkylations of 1 and 2 in acidified alcohols proceed through an electron-transfer from solvents to an excited state of the protonated diazines.
Substituent Effects in the Benzofuran System. II. Electrophilic Bromination
Authors: Okuyama Tadashi , Kunugiza Kiyomitsu , Fueno Takayuki
Published: July 2006

Bromination of benzofuran (BF) and its derivatives (5-CH3, 6-CH3, 5-CH3O, and 5-Cl) has been studied kinetically in acetic acid and by product analysis under various conditions. Product analysis revealed that bromine adds to BF in trans fashion, electrophilic bromine attacking at the 2-position. Analysis of substituent effects on the rate of bromination showed that the electronic effects are transmitted through both the bond 8–3 and the bonds 9–1–2 by a comparable magnitude. The transition state of the reaction was concluded to closely resemble a cyclic bromonium ion intermediate.
Charge-transfer and Proton-transfer in the Formation of Molecular Complexes. IX. Polynitrobenzoic Acid Complexes with Aromatic Monoamines
Authors: Matsunaga Yoshio , Osawa Ryuzo
Published: July 2006

When 2,4,6-trinitrobenzoic acid is combined with aromatic monoamines, true benzoates are mostly formed. However, not only a white true benzoate, but also a red 2 : 1 complex of the CPT type, in which charge-transfer and proton-transfer interactions operate simultaneously between the component molecules, were obtained with aniline. In addition, the brown 2,4,5-trimethylaniline complex reported by Noelting and Sommerhoff was found to be of a similar nature. The phenomenon of complex isomerism was observed upon combination with o-chloroaniline; that is, the colorless salt isomerizes into an orange-colored charge-transfer complex at about 133 °C. Only the complexes with p-dimethylaminobenzaldehyde and o-nitroaniline, which have the lowest pKa values among the amines examined, and those with the halogenated 2-naphthylamines are of the charge-transfer type. The 3,5-dinitrobenzoic acid complexes were also examined. Complexes of the CPT type with a 3: 2 composition were isolated with aniline and p-toluidine.