bluuebunny/crossref_metadata_2025 huggingface dataset:
Synthetic Studies of the Flavone Derivatives. IX. The Syntheses of Axillarin and Its Related Compounds
Authors: Fukui Kenji , Nakayama Mitsuru , Horie Tokunaru
Published: July 2006

By using the method of Allan-Robinson’s flavone synthesis, the condensation of 3,ω-dimethoxy-2,1,6-trihydroxyacetophenone with 3,4-dibenzyloxybenzoic anhydride gave a mixture of 3,6- and 3,8-dimethoxy-3′,4′-dibenzyloxy-5,7-dihydroxyflavone (X and XI). The catalytic debenzylation of the above flavones then gave axillarin (I) and 3,8-dimethoxy-5,7,3′,4′-tetra-hydroxyflavone (IV) respectively. Axillarin 7-O-methyl ether(III) was prepared by the partial methylation of X, followed by catalytic debenzylation.
Solvent Effect under High Pressure. III. The Application of the Electrostriction Model to the Activation Entropy
Authors: Kondo Yasuhiko , Tokura Niichiro
Published: July 2006

The expression which relates the activation entropies of the reactions measured in various solvents with the products of the coefficients of thermal expansion and the molar volumes of the respective solvents has been derived based on the concepts of the electrostriction theory. For three Menschutkin reactions and one acylation reaction linear correlations to be expected from the above expression have been found between the activation entropies and the products of the coefficients of thermal expansion and the molar volumes of the solvents. Moreover, the interrelation between the activation volumes and the activation entropies has been discussed based on this model.
Phosphorus-proton Spin-spin Coupling in the P–O–C–H Group. A Comparison of Cyclic and Acyclic Systems
Authors: Kainosho Masatsune , Nakamura Asao , Tsuboi Masamichi
Published: July 2006

Proton magnetic resonance spectra for eleven compounds with the POCH system have been examined. They are three 4-phenyl-2,2-disubstituted(X,Y)-1,3,2-dioxaphosphorinanes where X=Cl, Y=O (I); X=Cl, Y=S (II); and X=O−K+, Y=O (III); four 5,5-dimethyl-2,2-disubstituted (X,Y)-1,3,2-dioxaphosphorinanes where X=Cl, Y=O (IV); X=Br, Y=O (V); X=Cl, Y=S (VI); and X=OH, Y=O (VII); and four dimethyl phosphates, Y=P(-X)-(-OCH3)2, where X=Cl, Y=O (VIII); X=Br, Y=O (IX); X=Cl, Y=S(X); and X=O−\frac12Ba2+, Y=O (XI). It has been found that the 1,3,2-dioxaphosphorinane ring in each of I–VIII is virtually fixed in a chair form in the solution, and there is no appreciable ring inversion as confirmed by NMR spectra. The phosphorus-proton coupling constant of the POCH system with the gauche relation (Jg) and that with the trans relation (Jt) were determined in each of these compounds (I–VII). The \frac23Jg+\frac13Jt values calculated from the determined Jg and Jt values are always smaller than the \frac23Jg+\frac13Jt values observed for the corresponding acyclic compounds (VIII–XI). This difference was explained in terms of a slight flattening of 1,3,2-dioxaphosphorinane ring from the ideal chair conformation.
Effect of Coexisting Minerals on Graphitization of Carbon under Pressure. III. Accelerating Effect of Calcium Hydroxide
Authors: Noda Tokiti , Inagaki Michio , Hirano Shin-ichi , Saito Hajime
Published: July 2006

The polyvinyl chloride coke was heat-treated under the pressure of 3.2 kbar at 600–850°C for 20–240 min in a simple piston-cylinder type vessel, being sandwiched between two disks of calcium hydroxide. By electron microscopic observations, particles having the six-fold symmetry diffraction pattern of graphite single crystal were found besides particles of amorphous carbon even in the specimen heat-treated at temperature as low as 600°C. Above 800°C, the sharp peak corresponding to the graphitic component appeared on (002) diffraction profiles, overlapping with the broad band of the turbostratic component. The formation of the graphitic component seems to be related to the recrystallization of coexisting calcium hydroxide, as in the case of limestone and calcium carbonate. However, the fact that a small amount of free calcium oxide formed by the decomposition of calcium hydroxide was detected in the heat-treated carbon specimens suggests a chemical theory for the accelerating effect of calcium compounds on the graphitization of carbon under pressure.
Derivatographic Studies on Transition Metal Complexes. II. Thermal Reaction in the Solid State of Chromium(III) and Cobalt(III) Aquo-EDTA-like Complexes
Authors: Tsuchiya Ryokichi , Uehara Akira , Kyuno Eishin
Published: July 2006

The thermal reaction processes in the solid state of the following chromium(III) and cobalt(III) aquo complexes with EDTA or the related aminopolycarboxylic acids were investigated by means of derivatography: [CrHedta(H2O)] (I), [CrHpdta(H2O)]·H2O (II), [CrHtmta(H2O)]·H2O (III), [Cr(OH)Hapda(H2O)2] (IV) and [Co(OH)Hapda(H2O)2] (V) (edta, pdta, tmta and apda are the abbreviated forms of ethylenediaminetetraacetate, propylenediaminetetraacetate, trimethylenediaminetetraacetate and ammoniapropionicdiacetate anions, respectively.). With complex I, the carboxylate anion free from coordination to metal coordinated when the dehydration took place at ca. 280°C. It resulted in the change of the coordination number of EDTA from quinquedentate to sexadentate. In the case of complexes II and III, the transition appeared below ca. 100°C where the coordinated water molecule in the coordination sphere is thermally expelled to the outer sphere as the protonated form due to the coordination of a carboxylate anion. PDTA and TMTA (conjugated acids of pdta and tmta respectively) also changed from quinquedentate to sexadentate ligands in this step. Of complexes IV and V, the coordinated hydroxo group was excluded as a water molecule together with the hydrogen in a free carboxylate anion at ca. 140°C to make the coordination number of APDA(conjugated acid of apda) change from terdentate to quadridentate. The activation energies and the enthalpy changes in each thermal reaction process were determined by the analysis of their derivatograms.
Synthesis of Albonoursin
Authors: Shin Chung-gi , Chigira Yasuhiro , Masaki Mitsuo , Ohta Masaki
Published: July 2006

Treatment of the ester of 2-(2-chloroacetamido)-2-alkenoic acid with ammonia led to the formation of 3-alkylidene-2,5-piperazinedione. By using this method, total synthesis of albonoursin was accomplished. 2-(2-Chloroacetamido)-4-methyl-2-pentenoic acid, derived from the condensation of 4-methyl-2-oxopentanoic acid with chloroacetonitrile or the pyrolysis of 2,2-bis(2-chloroacetamido)-4-methylpentanoic acid, was converted to the ethyl ester, which was treated with ammonia to give 3-isobutylidene-2,5-piperazinedione. The piperazinedione was also synthesized by the esterification of 2-(2-aminoacetamido)-4-methylpentenoic acid, followed by a cyclization of the ester. Condensation of the piperazinedione with benzaldehyde yielded 3-benzylidene-6-isobutylidene-2,5-piperazinedione, and its physical constants are virtually identical with those recorded for the natural albonoursin.
Kinetic Study of the Polymerization of Diallyl Carbonate
Authors: Matsumoto Akira , Takashima Katsutoshi , Oiwa Masayoshi
Published: July 2006

The polymerization of diallyl carbonate was carried out at 60°C, benzoyl peroxide being used as the initiator; here it has been discussed kinetically from the point of view of cyclopolymerization. The rate of polymerization, Rp, was not proportional to the square root or the first power of the initiator concentration, (I), but Rp/(I)1⁄2 and (I)1⁄2 bore a linear relationship. The rate of polymerization, the residual unsaturation, and the degree of polymerization decreased with a decrease in the monomer concentration. The relation between the rate of polymerization over the degree of polymerization, Rp/\barPn,o and the monomer concentration, (M), was also linear, as in Rp/(I)1⁄2 and (I)1⁄2. The ratio of the rate constant of the unimolecular cyclization reaction to that of the bimolecular propagation reaction of the uncyclized radical, Kc, was estimated to be 4.0 mol/l from the dependence of the residual unsaturation on the monomer concentration.
The Reaction of Carboxylic Acids and Hydrocarbons in a Silent Electric Discharge. I. The Reaction of Acetic Acid with Ethylene
Authors: Hiraki Teruo
Published: July 2006

In order to ascertain the possibility of telomerization by a silent discharge, a mixture of acetic acid and ethylene was discharged in an ozonizer under various conditions. The α-C-alkylation of acetic acid which was expected to result from its discharge-induced reaction with ethylene was not observed; neither propionic acid nor higher carboxylic acids were identified by gas chromatography. However, n-butyl acetate was obtained in a good yield. The formation of the acetate can be explained as resulting from the combination of an acetoxy radical with two molecules of ethylene. The yield of the acetate, as well as those of the liquid and gaseous products, increased with a rise in the temperature and in the voltage, with the time, and with a rise in the ratio of ethylene to the acid concentration. Besides this acetate, the liquid products were confirmed to consist of ethyl methyl ketone, acetone, acetaldehyde, hydrocarbons, and ethyl and n-propyl acetates. The gaseous products were carbon dioxide, carbon monoxide, C1–C4-hydrocarbons, and hydrogen. Judging from the relative concentration of each compound in the reaction products, it may be said that the acetoxy radical (CH3COO·) and the acetyl radical (CH3CO·) are the main intermediates in this reaction system.
Studies of the Organic Reactions of Metal Carbonyls. XVII. The Reaction of Potassium Iron Carbonylates with Allyl Halide and Its Derivatives
Authors: Takegami Yoshinobu , Watanabe Yoshihisa , Mitsudo Takeaki , Okajima Toshiharu
Published: July 2006

The reactions of potassium iron carbonylates (K2Fe(CO)4, KHFe(CO)4 and K2Fe2(CO)8) with allyl halide and its derivatives have been studied. Allyl halide and its derivatives react readily with these carbonylates in ethyl alcohol at 30°C to give the corresponding and isomerized olefins. The reaction of allyl chloride in hydrous ethyl alcohol gives propylene in a good yield and 1,5-hexadiene as a by-product. In dry ethyl alcohol, the yield of propylene decreases. The reaction of trans-1-chloro-2-butene gives trans-2-butene (the major product), cis-2-butene, and 1-butene. The reaction of 1-chloro-3-methyl-2-butene and 3-chloro-3-methyl-1-butene gives 2-methyl-2-butene (the major product), 3-methyl-1-butene, and 2-methyl-1-butene. These reactions are considered to proceed via σ- and π-allyl iron carbonyl complexes.
Organic Reactions under High Pressure. IV. Effect of Pressure on the Competitive Nitration of Benzene and Monosubstituted Benzenes. Dependence of the Substitutent Effect on the Pressure
Authors: Asano Tsutomu
Published: July 2006

Partial rate factors for the nitration of six monosubstituted benzenes with nitric-sulfuric acid in acetic acid at 45°C have been determined over the 1–2000 kg/cm2 pressure range. The ρ value for this reaction changed from −7.22 (1 kg/cm2) to −6.92 (2000 kg/cm2). This pressure dependency of the ρ value was not expected for this type of reaction. This phenomenon is interpreted in terms of the dependence of the degree of solvation of the transition states on the substituents. An abnormal deactivation due to pressure has been observed in the case of biphenyl. This deactivation has been attributed to an increase in the deviation from the coplanarity of the two phenyl groups. The dependence of the ortho: para ratios on the pressure is also discussed.
Studies of the Organic Reactions of Metal Carbonyls. XVI. Solvent Effects on the Hydroformylation of Propylene and on the Reaction of Cobalt Hydrocarbonyl with 1-Pentene
Authors: Takegami Yoshinobu , Watanabe Yoshihisa , Masada Hiromitsu , Mitsudo Takeaki
Published: July 2006

In the reaction of cobalt hydrocarbonyl with 1-pentene at 10°C, solvents have a great effect on the distribution of the products, caproylcobalt carbonyl (I) and α-methylvalerylcobalt carbonyl (II). The I-to-II ratio is 72 : 28 in toluene, in toluene-dioxane (1 : 1 in volume), and in tolueneethyl acetate. The percentage of II increases to 40–66% in toluene-diethyl ether, -tetrahydrofuran, -acetone, -ethyl alcohol, and -acetonitrile. In the hydroformylation of propylene, the distribution of the products, n- and isobutyraldehyde, is also affected by the solvents. In toluene, the n-to-iso ratio is about 75 : 25, while in dioxane and in butyl acetate the percentage of the n-aldehyde increases to 79–83%. In methyl alcohol, dimethyl acetals of the aldehydes and n- and isobutyrate are formed. The n-to-iso ratio is the highest in the esters (3.2–8.5), followed by the acetals (0.7–1.6) and the aldehydes (0.4).
Raman and Infrared Spectra of β-Alanine
Authors: Krishnan R S , Katiyar R S
Published: July 2006

The Raman spectrum of β-alanine has been recorded in the single crystal form employing λ 2537 technique. The infrared spectra in Nujol mull and KBr pellet have been taken for the range 400–4000 cm−1. The spectra exhibit the characteristic lines of the zwitter ion and also hydrogen bond vibrations in the region 2400–3000 cm−1. The tentative assignments of the observed lines are given and compared with those of other amino acids.
Theory of the Gel-forming Polymerization of Polyepoxy and Related Compounds
Authors: Yamabe Tokio , Fukui Kenichi
Published: July 2006

A theory of the molecular-size distribution of cross-linked polymers to be formed from a mixture of polyfunctional monomers and mono-functional monomers through step-by-step polymerizations by certain initiators is presented on the assumption that all unconverted functional groups are equireactive for both initiations and propagations, which proceed without termination, transfer, or cyclization. The distribution is obtained by applying the statistical theory of gel formation with multifunctional interunit junctions, which are, in this case, equivalent to cross-linking chains. Some noticeable theoretical results are obtained: (1) the distribution obtained is quite different from that obtained for branched-chain polymers by condensation polymerization; (2) the fraction of converted functional groups at the gel point is independent of the initial concentration of the monofunctional monomer, while it is in proportion to the ratio of the initial concentration of the initiator to that of polyfunctional monomers; (3) there is a certain condition under which the gelation will never take place, even at complete conversion, and (4) the state to be reached after the gel point is quite different from the results obtained previously. The case of a mixture of monomers with any distribution of functionalities is also briefly presented. An explanation of the validity of the distribution beyond the gel point is discussed in the Appendix.
Activity Coefficients of Aqueous Xylose and Maltose Solutions
Authors: Uedaira Hatsuho , Uedaira Hisashi
Published: July 2006

Osmotic and activity coefficients of aqueous xylose and maltose solutions at 25°C are measured by the isopiestic vapor pressure method. Densities of these solutions are also determined at 25°C. The activity coefficients of water in these solutions show that both xylose and maltose solutions do not behave as regular solutions. Second virial coefficients for xylose and maltose are calculated from partial molar volumes of the solute and the solvent at infinite dilution and empirical equations of water activity coefficient. The coefficients calculated for xylose and maltose are 111 and 248 cc/mol, respectively. Second virial coefficients for these sugars and a few other sugars are approximately proportional to the molecular weight. This relation is explained by the van der Waals model.
Zero-point Average Structure of Acetaldehyde
Authors: Iijima Takao , Kimura Masao
Published: July 2006

The zero-point average structure of acetaldehyde has been determined by the use of the moments of inertia and the average distances, obtained by microwave spectroscopy and electron diffraction respectively. The following rz parameters have been determined: 1.515±0.005 Å for C–C, 1.207±0.004 Å for C=O, 1.073±0.002 Å for C–H(methyl), 123°48′±9′ for ∠CCO, and 108°52′±17′ for ∠HCH of the methyl top.
Microwave Spectrum, Barrier to Internal Rotation, and Dipole Moment of trans-Crotonaldehyde
Authors: Suzuki Masao , Kozima Kunio
Published: July 2006

The microwave spectrum of trans-crotonaldehyde has been measured in the frequency region from 8.2 to 36 kMc/sec. The R-branches for the a-type and the R- and Q-branches for the b-type have been assigned. The low J transitions of the a-type and all of the b-type transitions are split into the A-level and the E-level by the internal rotation of the methyl group. The apparent rotational constants for the A- and E-levels have been obtained from the pseudo-rigid rotor approximation as AA=32636.58 Mc/sec, AE=32627.57 Mc/sec, B=2183.30 Mc/sec, and C=2073.32 Mc/sec. From these values it can be concluded that this molecule is of the s-trans form. The barrier height of the hindering rotation of the methyl group is 1730±10 cal/mol. The value of the total dipole moment is 3.72±0.28 D.
ESR Studies on the Reaction of an OH Radical in α,β-Unsaturated Aldehyde
Authors: Ichikawa Takahisa , Kuwata Keiji
Published: July 2006

ESR studies on the UV irradiated α,β-unsaturated aldehyde - hydrogen peroxide mixtures have been done at low temperature in order to examine the reactions of an OH radical with aldehyde: formyl hydrogen-abstraction, methyl hydrogen-abstraction, and addition to an olefinic bond. It has been shown that abstraction of a methyl hydrogen by an OH radical occurs in croton-aldehyde, whereas β-addition of an OH radical to an olefinic bond takes place in methacrolein and acrolein. A formyl hydrogen is unreactive with an OH radical in any case. The distribution of unpaired electron in the radicals was also discussed.
Refinement of the Structure of Tohdite 5Al2O3·H2O
Authors: Yamaguchi Goro , Okumiya Masataro , Ono Shuichiro
Published: July 2006

The structure of tohdite, 5Al2O3·H2O, was determined by Yamaguchi Yanagida, and Ono (1964). Least-squares refinements based on their structure have been carried out using X-ray-powder data. The final R factor of the reflection intensity reduced to 0.08 from the initial value of 0.26.
Coumarins. VI. The Acid-catalyzed Reaction of Phenols with β-Aminocrotononitrile
Authors: Sato Kikumasa , Ohashi Masao , Amakasu Takeshi , Takeda Katsuhiko
Published: July 2006

A new synthesis of 4-methylcoumarins has been developed by means of the acid-catalyzed condensation of phenols with β-aminocrotononitrile. Such monohydric phenols as phenol or cresols reacted with β-aminocrotononitrile in polyphosphoric acid (PPA) to give 4-methylcoumarins in poor yields, along with a good yield of 6-amino-3-cyano-2,4-lutidine (III). In contrast, 7-substituted-4-methylcoumarins were obtained in 23–44% yields from resorcinol and its monomethyl ether. On the other hand, when β-aminocrotononitrile was heated in PPA, the lutidine (III) was obtained in a high yield. Its precursor, 4-amino-1,3-dicyano-2-methylpenta-1,3-diene (XI), was isolated under mild conditions. These results suggest that β-aminocrotononitrile may undergo the preferential self-dimerization to the lutidine (III) rather than the intermolecular condensation with phenols.
Copolymerization of Formaldehyde and Succinic Anhydride in the Presence of Carbon Dioxide
Authors: Yokota Hisao , Toriuchi Yahiko , Kagiya Tsutomu , Fukui Kenichi
Published: July 2006

A Study of the copolymerization of formaldehyde and succinic anhydride was carried out in a liquid carbon dioxide solution without adding any catalyst. A copolymer, in which a small number of succinic units was inserted into the sequence of oxymethylene units because of the low rate of copolymerization of succinic anhydride, was formed. With enhancing the concentration of succinic anhydride, the content of succinic units in the copolymer slightly increased. At reaction temperatures up to 120°C, the molecular weight of the copolymer decreased with a rise in the temperature, whereas the content of succinic units increased to about 3 mol%. The copolymerization proceeded rapidly, so the reaction immediately reached equilibrium. From the results of the study by X-ray diffractiometry, the crystal structure of the copolymer can be said to be similar to that of polyoxymethylene, but the crystallinity of the copolymer decreased as the content of succinic units increased. The rate of thermal degradation, which started from the end-groups of the copolymer was decreased by ester linkgae. The thermal-degradation temperature was enhanced as the content of succinic units increased. The copolymer also showed a high resistivity to the folding of the film, even though it had not been treated so as thoroughly to esterify the endgroups of the copolymer.
Studies on Formaldehyde-Condensation Resin. VII. Isolation of Mono-, Di-, Tri-, and Tetramethylolacetoguanamines
Authors: Uragami Tadashi , Oiwa Masayoshi
Published: July 2006

The reaction of acetoguanamine with formaldehyde was carried out in the presence of basic catalyst under various conditions, and mono-, di-, tri-, and tetramethylol derivatives of acetoguanamine were purely isolated. Their structures were identified by elemental analyses, infrared absorption spectra, NMR spectra, and chemical analyses of methylol groups.
ESR Spectra of the System of the Transition Metal Compound and Trialkyl Aluminum. II. The System of the Vanadium Compound and Trialkyl Aluminum
Authors: Nozawa Yasuo , Takeda Masatami
Published: July 2006

The ESR spectra of the homogeneous organometallic catalyst system of VOA2-AlEt3 (I) and VCl4-AlEt3 (II) were measured in benzene, toluene, n-hexane and tetrahydrofuran solutions. A superhyperfine structure of nine lines with a g-value of 1.9917, and with a hyperfine splitting of 4.2 gauss on each eight line due to the 51V nucleus, was observed in the systems of I and II in the aromatic solvents at any Al/V ratio from 1 to 15. The same type of spectrum was observed in the VA3-Al(isoBut)3 system in a benzene solution at Al/V ratios higher than 3. In the system of II, the single line was observed at Al/V ratios up to 5. At higher ratios the superhyperfine structure appeared to overlap on the single line. On the basis of these facts, it may be considered that the vanadium atom was reduced to the zerovalent state and was then complexed with aromatic solvents in these systems. This suggests the presence of a sandwich complex such as (Remark: Graphics omitted.) where X=H or CH3.
Semi-empirical Unrestricted SCF-MO Treatment for Valence Electron Systems. I. Application to Small Doublet Radicals
Authors: Yonezawa Teijiro , Nakatsuji Hiroshi , Kawamura Takashi , Kato Hiroshi
Published: July 2006

A semi-empirical SCF method for valence electron systems including a differential overlap previously proposed by the present authors is here extended to molecules with an open-shell structure. The unrestricted Hartree-Fock method is applied, and the one-centre and part of two-centre σ-π-type exchange repulsion integrals, playing an essential role in spin-density calculations, are included in the calculations. The calculated spin densities are divided into the mechanistic (spin-polarization and spin-delocalization) contributions. The spin-polarization mechanism is shown to be important even in cases where the spin delocalization mechanism has usually been considered to be dominant (e.g., ethyl and vinyl radicals). The calculated spin densities of π-electron radicals (methyl, ethyl, allyl, and trans-butadienyl anion radicals) and of σ-electron radicals (vinyl, formyl, NO2, CO2−, CN) are discussed. Their hfs constants and mechanistic contributions are calculated; for the methyl and vinyl radicals these are shown to be strongly angular-dependent. The calculated potential curve and the hfs constants of the vinyl radical lead to the CCHa angle, θ\simeq135°; furthermore, the Hα and Cβ  hfs constants are shown to be negative. Generally, the calculated proton hfs constants agree satisfactorily with the experimental data and with other calculations except in the case of the formyl radical. The atomic dipoles of some σ-electron radicals are calculated, and some interesting features common to all the σ-electron radicals studied are found.
Kinetics of the Adsorption of Water and Electrical Conduction in Amorphous Ferric Oxide
Authors: Furuichi Ryusaburo , Sato Norio , Okamoto Go
Published: July 2006

Amorphous ferric oxide was prepared by precipitation in a mixture of ammonium hydroxide and ferric nitrate at 90°C, after which it was calcinated in air at a constant rate of 10°C/min up to 200°C. The rate of the adsorption on the amorphous oxide was measured by a gravimetric method. An equation of the Elovich type was obtained: dq⁄dt=k′p0.63exp(−α′q⁄RTp0.5), where k′ and α′ are constants; q, the amount of adsorbed water, and p, the pressure. This kinetics can be interpreted by a model of a two-stage adsorption process, the van der Waals adsorption and the charge-transfer adsorption, the latter stage being assumed to be rate-determining. The effect of adsorbed water on the direct-current conductivity of the oxide, i, is formulated as i=i0exp(aq). Assuming that the adsorbed water is acting as a donor-type impurity and that the ionization energy decreases with the concentration of impurity, the relation between i and q can be derived from the theory of the semiconduction of an n-type conductor.
The Ultrasonic Study of Aqueous Solutions of Alkyl-Substituted Urea
Authors: Sasaki Katsutaka , Arakawa Kiyoshi
Published: July 2006

An ultrasonic investigation of aqueous solutions of alkyl-substituted urea was made by means of an ultrasonic pulse technique in order to study the influence of the solutes upon the structure of solvent. The ultrasonic velocity and absorption were measured in solutions of 1,3-dimethyl-urea and 1,3-diethylurea in the frequency range from 5 to 45 Mc/sec. The temperature was varied from 10 to 40°C, and the concentration from 0.2 to 4 mol/l. Within the range of frequency no relaxation frequency was observed for both solutions. From the data on absorption coefficent and viscosity, the magnitude of absorption due to structural relaxation was calculated. It was found that structural absorption in dimethylurea solutions is slightly larger, and in diethylurea solutions much larger than that of the urea solutions. From these results, it is concluded that 1,3-dimethylurea is a structure breaker for the open-packed structure in water, the ability being smaller than that of urea, and that, for the behavior of 1,3-diethylurea molecule in water, the structure-forming ability of the ethyl group is found to surpass the structure-breaking effect of the residual part of the molecule.
The Effects of Tetraalkylammonium Salts on the Structure and the Temperature of the Maximum Density of Water
Authors: Wada Goro , Miura Masako
Published: July 2006

The effects of the tetraalkylammonium halides on the temperature of the maximum density of water were measured by means of dilatometry. Contrary to the expectation that the hydrophobic nature of the alkyl radicals would elevate the temperature of the maximum density of water, these salts lowered it, as other, more usual salts do, obeying the Despretz rule. Among the salts represented as R4NBr, where R is either H or an n-alkyl radical, the Despretz constant, kD, increases in the sequence: H<CH3<C2H5<n-C3H7<<n-C4H9, while the deviation of kD from k, which is a hypothetical constant of the ideal mixing where there is no interaction between the solute and the solvent, varies in the following sequence: H\simeqCH3\simeqC2H5\simeqn-C3H7 <<n-C4H9. The latter fact is attributable to the specific occurrence of a clathrate-like structure formed in the aqueous solution, only when R is n-C4H9. This is in accordance with another peculiarity of (n-C4H9)4NBr which shows a minimum in its partial molar volume at a certain concentration in water.
Bond Lengths of Dimethylacetylene as Determined by Gas Electron Diffraction
Authors: Tanimoto Mitsutoshi , Kuchitsu Kozo , Morino Yonezo
Published: July 2006

The bond distances of dimethylacetylene have been determined by electron diffraction to be rg(C–C)=1.4675±0.0013 Å, rg(C≡C)=1.2135±0.0013 Å, rg(C-H)=1.1158±0.0059 Å, and ∠C–C–H=110.7±0.4°, the uncertainties representing the limits of experimental error. The carbon-carbon single bond length has been found to be in good agreement with that in butadiene, as was qualitatively to be expected from Stoicheff’s empirical rule. The carbon-carbon triple bond length appears to be longer than that of acetylene and shorter than that of diacetylene by a few thousandths of an angstrom. The dependence of the triple-bond lengths on the environment is discussed in terms of the change in conjugation and hyperconjugation.
Shielding Effect of Ortho-Substituents on Magnetic Moments and d-d Bands in Chloro-N-phenylsalicylideneiminatocopper(II)
Authors: Kato Michinobu , Muto Yoneichiro , Jonassen Hans B , Imai Kyoko , Katsuki Kazuko , Ikegami Seishi
Published: July 2006

Complexes with the formula, Cu(\overset1O·C6H4·\overset2CH=N–Ph–X)Cl, where Ph-X is a mono- or disubstituted phenyl group, were prepared. A dimeric structure was postulated for these complexes based on the observed subnormal magnetic moments and the chemical formula. For these complexes, a linear relation was observed to exist between the magnetic moments, μeff25°C, and the d–d band positions, \ ildenumax. The d–d bands of the dimeric complexes with o-substituents appeared at shorter wavelengths than those with m- or p-substituents irrespective of the polar nature of the substituents. A similar ortho-effect was also observed for the magnetic moments; complexes with o-substituents were observed to have smaller moment values than those with m- or p-substituents. The oryho-effect was also observed in the d–d bands of the monomeric bis-complexes Cu(\overset1O·C6H4·\overset2CH=N–Ph–X)2 and their d–d bands when X=o-substituents appeared at shorter wavelengths than those with m- or p-substituents. These ortho-effects decreased for the solution spectra of the monomeric complexes.
Synthetic Studies of the Derivatives of Acetylene. I. Reactions of 5-Bromopent-3-en-1-yne
Authors: Sato Kikumasa , Hirayama Masao
Published: July 2006

The preparation of pent-2-en-4-ynylamine and pent-2-en-4-ynylthiol and their derivatives from 5-bromopent-3-en-1-yne was studied. Moreover, in connection with the preparation of the bromide, the rearrangement-bromination of vinylethynylcarbinol was found to give three isomeric bromides, 5-bromopent-trans-3-en-1-yne, 5-bromopent-cis-3-en-1-yne, and 3-bromopent-1-en-4-yne. Pent-2-en-4-ynylamine was obtained from 5-bromopent-3-en-1-yne by two methods, by the hydrolysis of the hexaminium salt and by the cleavage of N-(pent-2-en-4-ynyl)phthalimide. The reaction of 5-bromopent-3-en-1-yne with potassium hydrosulfide and the decomposition of ethyl pent-2-en-4-ynylxanthate by alcoholic ammonia gave pent-2-en-4-ynylthiol.
Synthetic Reactions by Complex Catalysts. XIII. Carbonylation of Amines by Group IB and IIB Metal Compound Catalysts
Authors: Saegusa Takeo , Kobayashi Shiro , Hirota Kiwami , Ito Yoshihiko
Published: July 2006

The present investigation was undertaken in order to examine the catalytic activities of Group IB and IIB metal compounds in the carbonylation of aliphatic and aromatic amines with carbon monoxide, and in order to compare the catalyst activities with those of other metal compounds. It was found that: i) copper compounds are excellent catalysts for the carbonylation of aliphatic amines to produce the corresponding formamides; ii) the catalytic activities of copper compounds are enhanced by the addition of water; and iii) chloroauric acid catalyzes the carbonylation of aromatic amine, whereas copper compounds do not. The temperature effects on the carbonylation of morpholine were also examined.
Intramolecular Hydrogen Bonding in α-Keto- and α-Alkoxy-carboxylic Acids. VII. Ultraviolet Spectra of Phenylglyoxylic Acid in Various Solvents
Authors: Hirota Minoru , Shinozaki Fumiaki
Published: July 2006

The ultraviolet spectra of phenylglyoxylic acid were determined in various solvents as well as in the mixtures of solvents. A very remarkable hypsochromic shift with increase in intensity was observed when the solvent participates in the formation of hydrogen bond as a hydrogen acceptor. The measurement of the spectra in binary mixtures of the solvents shows that the hypsochromic shift is due to the formation of a 1:1 complex of C6H5COCOOH···solvent type. This hypsochromic shift is interpreted by the destruction of the chelate ring formed by the intramolecular hydrogen bond which enforces the acid molecule to the planar conformation. This view is supported by the simple LCAO-MO calculation on this molecule.
Concentration Polarization Phenomena in Ion-exchange Membrane Electrodialysis. II. The Effect of the Condition of the Diffusion-boundary Layer on the Limiting-current Density and on the Relative Transport Numbers of Ions
Authors: Yamane Reiichi , Sata Toshikatsu , Mizutani Yukio , Onoue Yasuharu
Published: July 2006

The effect of the condition of the diffusion-boundary layer in the ion-exchange membrane electrodialysis on the limiting-current density and on the relative transport numbers of ionic species with the same sign was studied. The limiting-current density in the laminar flow is approximately proportional to the first power of the concentration of the solution, the one-half power of the flow velocity of the solution, and, inversely, the one-half power of the membrane length in the direction of the flow. In the natural convection, it is proportional to the five-quarters power of the concentration of the solution. These experimental results agree with the relation of the equations of the limiting-current density for the electrode process. The change in the relative transport numbers of ionic species with the same sign, such as the magnesium and sodium ions or the sulfate and chloride ions, with the flow velocity, the concentration, and the temperature of the solution, the dimension of the membrane in the direction of the flow, and the current density were observed. The results were explained in terms of the change in the condition of the diffusion-boundary layer.
Electrophotographic Properties of Titanium-Dioxide Resin Dispersion Layers
Authors: Iida Takeaki , Nozaki Hiroshi
Published: July 2006

The electrophotographic properties of titanium dioxide-polymer dispersion layers were studied. The titanium dioxide powder of the rutile type and three well-known polymers, polyvinyl acetate, polyvinyl chloride, and polystyrene, were used. The measurements were done on the corona-charging properties, e. g., the resistivity and the capacitance of the layer, the rising gradient of the surface potential, and the fatigue effect of pre-illumination. The results make it clear that the analysis of an equivalent circuit can be applied to the interpretation of the rising gradient of the surface potential and to that of the dark decay to some extent. Moreover, it is found that the logarithm of the potential of the dark decay decreases proportionally to the cube root of the time at the initial step, while, at the next following step, it decays proportionally to the square root of the time. The mechanism of the dark decay of the surface potential is also discussed.
Absorption Spectra and Circular Dichroisms of Metal Complexes. IV. Dichloro-diamine Type Complexes of Platinum(II) and Palladium(II)
Authors: Ito Haruko , Fujita Junnosuke , Saito Kazuo
Published: July 2006

Absorption (AB) spectra of dichloro(l-tetrahydrogenpropylenediaminetetraacetato)platinum-(II) and palladium(II) and dichloro(d-hydrogendiaminopropionato)platinum(II) and palladium(II) were interpreted on the basis of a comparison of their circular dichroism (CD) spectra with those of dichloro(l-propylenediamine)platinum(II) and palladium(II). The d-d bands of edtaH4 and l-pdtaH4 complexes shifted to longer wavelength as compared with those of l-pn complexes. The shift was discussed, based on the effects of the weaker ligand field strength and apical interaction of the acetato groups of these ligands.
Alkaline Hydrolysis of Aryl Benzenethiolsulfonates
Authors: Oae Shigeru , Nomura Ryuichi , Yoshikawa Yoichiro , Tagaki Waichiro
Published: July 2006

The alkaline hydrolysis of substituted phenyl benzenethiolsulfonates has been investigated. The rate was found to be first order with respect to both hydroxide and ester. The second order rate constant for the unsubstituted ester was found to be 3.2×103  m−1 sec−1 (water 45°C). The Hammett ρ values were found to be ρX,Y=H=2.1 and ρY,X=H=1−1 for (Remark: Graphics omitted.) respectively. The reactivities of three esters, i. e. phenyl benzenethiolsulfonate, -thiolsulfonate and -sulfonate were compared.
Base-catalyzed Condensation of o-Nitroacetophenone. IV. Structure of Dehydro-derivative of Compound A, a Condensation Product
Authors: Sakan Takeo , Kusuda Kousuke , Miwa Toshio
Published: July 2006

The alkaline hydrogen peroxide oxidation of compound A, C17H14O5N2, a base-catalyzed condensation product of o-nitroacetophenone, gave a dehydro compound, C17H12O5N2. The structure of the dehydro compound was deduced from the spectral data of its derivatives to be a (o-nitrobenzoyl)-1-hydroxycarbostyril. The forced hydrogenation of the dehydro compound gave 3-(o-aminobenzoyl)-4-methylcarbostyril, which was synthesized by the condensation of o-aminoacetophenone and ethyl o-nitrobenzoylacetate followed by reduction. Therefore, the dehydro compound proved to be 1-hydroxy-4-methyl-3-(o-nitrobenzoyl)carbostyril. On the other hand, the alkaline hydrogen peroxide oxidation of compound A methyl ether gave o-nitrobenzoic acid and 1-methoxy-3-methyldioxindole along with o-nitroacetophenone. These facts are explained by assuming a transition state which would be controlled by the presence of a hydrogen bonding.
Synthetic Studies of Cobalt Carbonyl by Noble Metal Catalysts. II. The Investigation of Reaction Conditions
Authors: Usami Seiji , Nishimura Kotaro , Koyama Takeo , Fukushi Saburo
Published: July 2006

The reaction conditions of cobalt carbonylation catalyzed by palladium have been investigated. Polar solvents have, with some exceptions, been shown to be superior to nonpolar solvents. The fact that the total pressure of synthesis gas and the partial pressure of hydrogen, especially the latter, have a great effect on the initiation temperature of reaction suggests that the presence of hydrogen is very important in the present reaction. The low reactivity and poor yield in the reactions of Raney cobalt indicate that a low-valency intermediate in the course of the cobalt-carbonylation reaction of cobaltous compounds may be somewhat different from the Raney-type Co(0). The initial step of the reaction seems to be affected only a little by various additives e. g., water, triphenyl phosphine, lead naphthenate, and sodium hydroxide. The data previously available suggest that a palladium catalyst may primarily promote the reduction of Co (II) to Co(0) by activating hydrogen. The test of the lifetime of a palladium-on-carbon catalyst for a month indicates that there is no apparent decrease in the catalytic activity within this period.
Photoinduced Reactions. XXXIII. Photochemical Reaction of a para-Quinone Methide
Authors: Matsuura Teruo , Ogura Katsuyuki
Published: July 2006

The photochemistry of a quinone methide (Ia) was investigated. Ia was unchanged on photolysis of an alcoholic solution (0.0064 m) with a high-pressure mercury lamp (Pyrex filter). However irradiation of a highly dilute solution of Ia or a sensitized reaction (acetophenone) gave an alcohol adduct (IIe in methanol and IIf in isopropyl alcohol) which might be formed via triplet excited state(s) of Ia. The methanol adduct IIe was also formed by the irradiation of Ia in methanol with a low-pressure mercury lamp through quartz. In this case the formation of He appears to be initiated by photochemical decomposition of methanol.
Studies on Hydrogenolysis. LIV. Catalytic Hydrogenolysis of Optically Active 2-Methyl-2-phenylaziridine
Authors: Sugi Yoshihiro , Mitsui Sekio
Published: July 2006

In order to obtain further information about the catalytic hydrogenolysis of benzyl-type compounds, the hydrogenolysis of optically active 2-methyl-2-phenylaziridine (I) over several group VIII transition metal catalysts was investigated in ethanol under ordinary pressure and at room temperature. 2-Phenylpropylamine (II) was obtained as the main product over all the catalysts. The configuration of II was inverted over the palladium catalyst. However, the hydrogenolysis over the platinum catalyst occurred with a significant retention of the configuration. Further, in the case of Raney nickel and Raney cobalt catalysts, the configurations of II were retained with the low stereoselectivities, and a small amount of 2-phenyl-2-propylamine (III) was also produced in addition to II. These results are attributable to the free-energy difference at the transition states to form π-benzyl intermediates, which depends on the affinity of these metals for the nitrogen lone-pair, the catalyst hindrance, and other factors. The SN2-type reaction is favored over the palladium catalyst. On the other hand, the SNi-type reaction is favored over platinum, Raney nickel, and Raney cobalt catalysts, where the radical-cleavage reaction will participate in addition to the SNi-type reaction over the latter two catalysts. The differences in behavior between styrene imines and styrene oxides on the catalyst surface were also discussed.
The Effect of Organic Additives on the Autoxidation of Benzene and Toluene in the Aqueous Phase and the Kinetic Analysis
Authors: Hotta Hiroshi , Suzuki Nobutake , Isoda Kazuo
Published: July 2006

The effect of organic additives on the autoxidations of benzene and toluene was studied at 180°C in a ferrous sulfate aqueous solution. The additives were benzene, toluene, ethylbenzene, cumene, cyclohexene, cyclohexane, n-hexane, t-butyl alcohol, isopropyl alcohol, and ethyl alcohol. The yields of the phenol and benzaldehyde produced were measured as functions of the initial volume fraction of the additive. The yields decreased with the addition of a trace of the additive, and the yields increased still more with further addition. In order to interpret these results, the general expression for the yield of the main product was derived by the Gale-Wagner method and was analyzed numerically by using the IBM 7044. The mole fraction of the additive, corresponding to the maximum yield, can give information regarding the relative reactivity of the additive as compared with the results of the above numerical analysis. It is concluded from the present study that the experiment of the flow system for the autoxidation of toluene containing various additives is necessary to get exact kinetic information concerning these additives by using the present numerical analysis, because the equation is derived on the assumption that the concentration of the additive is constant.
An X-Ray Emission Spectroscopic Investigation of the Chemical Bond of Sulfur. III. The Profile of SKβ Band in Sulfur Compounds
Authors: Takahashi Yoshihito , Yabe Katsumasa
Published: July 2006

The profile of the SKβ band in various sulfur compounds, including many organic compounds, was separated into peaks, and the wavelength values and the intensities of the separated peaks were discussed in relation to the chemical bonding. The band of sulfone and sulfoxide consists of three or four peaks. We named the peaks A, B, C (the strongest), and D, beginning from the longer-wavelength side. The relative intensity of the peak A (generally named Kβ′) increases as the number of valence electrons of the sulfur atom decreases. The peak B may be attributed to the non-polar single bond of sulfur in sulfone and sulfoxide. The clear peak, D, appears only in the band of sulfite and sulfoxide. The band of the compounds of thiourea type consists of two peaks. Using the results of the above study, the chemical structures of aldehyde-bisulfite adducts and 2-mercaptobenzimidazole, etc., were discussed.
Energy Transfer between Benzene and Toluene in the Singlet States at 90°K
Authors: Nakahara Akihiko , Koyanagi Motohiko , Murakami Yoshio , Edamura Takao , Kanda Yoshiya
Published: July 2006

The fluorescence spectrum of toluene in benzene has been photographed at 90°K and analyzed accurately. Systematic studies of concentrations made it possible to estimate the efficiency of energy transfer from the singlet state of the host molecule to that of the guest molecule. The fluorescence spectrum of pure benzene has also been studied at 4.2°K and 90°K for comparison, and the effect of toluene as an impurity in the benzene spectra has been discussed.
A Study of the Properties of Dilute Polymer Solutions by the Archibald Ultracentrifugal Method
Authors: Kotera Akira , Matsuda Hideomi , Miyazawa Yuji , Joko Etsuo
Published: July 2006

A modification of the Archibald method for determining the molecular weight of a polydisperse sample in ideal and non-ideal solutions is developed in this paper. A reliable value of the weight average molecular weight is obtained from the plot of an apparent weight average molecular weight against the centrifugal time rather than against the amount of the solute sedimented from the meniscus. This fact is explained on the assumption of a fractionation effect of the solute caused by the centrifugal potential.
Oscillopolarographic Behaviour of Lanthanide Ions in Potassium Iodide Solutions
Authors: Iwase Akio , Yokoyama Chieko
Published: July 2006

The oscillopolarographic depolarization effect of lanthanide ions in KI solutions was investigated using dropping (DME) and hanging-drop (HME) mercury electrodes. The lanthanide-ion incision depth in the dE⁄dt=f(E) curve, measured in a 1m KI solution (pH 3.65) with a DME, was found to be much deeper than that in a 1m KCl solution. The temperature coefficient was negative for the La and Sm incision depths in the temperature range from 25° to 50°C. The incision depths of the La (pH 4.0) and Sm (pH 4.5) ions in a solution with an ionic strength of 0.7 (KCl added) were found to depend on the I− concentration. These facts seem to show that I− is adsorbed on DME, and that the adsorbed I− (at −1.4 V) promotes the electrode reaction of lanthanide ions.
Imidazoles. II. A General Synthesis for 1-Hydroxyimidazoles
Authors: Akagane Katsuo , Allan F J , Allan G G , Friberg T , Muircheartaigh S Ó , Thomson J B
Published: July 2006

The reaction of α-dione monoximes with aldehydes and ammonia affords a general and facile synthetic route to 1-hydroxyimidazoles. By selection of the starting materials substituents can be readily introduced into the 2,4 and/or 5 positions of the imidazole ring which is formed via the intermediacy of a gem-aminoalcohol. The reactions of the N-hydroxyl function are discussed.
The Polymerizations and Copolymerizations of α-Methoxy-acrylonitrile and Methyl α-Methoxyacrylate
Authors: Otsu Takayuki , Yamada Bunichiro , Yoneno Hiroshi
Published: July 2006

A study of the polymerizations and copolymerizations of α-methoxyacrylonitrile(MeOAN) and methyl α-methoxyacrylate(MeOA) has been made. These monomers were homopolymerized with a radical initiator at 60°C, but did not give any polymer with such ionic catalysts as BF3O-(C2H5)2 and C6H5MgBr at 0°C. From the radical copolymerizasions of these monomers with styrene at 60°C, their Q, and e values were determined to be as follows:

Q=0.72, e=0.40 for MeOAN

Q=0.47, e=0.04 for MeOA

These monomers were also copolymerized with acrylonitrile, and the copolymerization parameters were determined.