bluuebunny/crossref_metadata_2025 huggingface dataset:
ON THE OXIDATION OF SODIUM SULPHITE BY AIR IN THE PRESENCE OF FERROUS HYDROXIDE AND A THEORY OF NEGATIVE INDUCED REACTION
Authors: Miyamoto Susumu
Published: July 2006

1. A theory of negative induced reaction was proposed. Three kinds of negative induced reactions was considered according to the proposed theory. The oxidation of the mixture of stannous hydroxide and sodium sulphite in sodium hydroxide or in sodium carbonate solution by means of air, the results of which being already reported in the previous papers, can be regarded as an example of negative induced reaction of the first kind, and the oxidation of the mixture of ferrous hydroxide and sodium sulphite in sodium hydroxide solution, here reported, as an example of negative induced reaction of the second kind.

2. The oxidation of the mixture of sodium sulphite and ferrous hydroxide in sodium hydroxide solution by means of air was studied, with an expectation, that it will give an example of negative induced reaction. The oxidation velocity of sodium sulphite in the mixture was only measured, which was sufficient for the present purpose. The velocity decreases rapidly with time, and the result was interpreted as a negative induced reaction of the second kind.

3. To ascertain that the decrease of the observed oxidation velocity of sodium sulphite in the mixture is due to the formation of ferric hydroxide, the reaction product of the primary reaction, the oxidation velocity of sodium sulphite in the presence of ferric hydroxide was studied under the same conditions. The expectation was fulfilled.
STUDIES ON MERCAPTALS OF SUGARS. III. ISO-BUTYL MERCAPTALS OF SUGARS
Authors: Uyeda Yoshisuke
Published: July 2006

Iso-butyl mercaptals of three hexoses, one methyl pentose, one pentose and two dioses are crystallized out as new compounds.

Other sugars, e. g. lactose, fructose, xylose are tried but ended in negative results.
REDUCTION OF TRIMETHYL STANNYL HYDROXIDE IN LIQUID AMMONIA
Authors: Harada Taichi
Published: July 2006

(1) General method of reduction of compounds in liquid ammonia by alkali metals and apparatus were described.

(2) Trimethyl stannyl iodide from methyl iodide and sodium-tin alloy and from which trimethyl stannyl hydroxide was prepared.

(3) Trimethyl stannyl free radical was prepared by the reduction of trimethyl stannyl hydroxide with metallic sodium in liquid ammonia solution.
ON THE OXIDATION OF STANNOUS CHLORIDE IN SULPHURIC ACID SOLUTION BY AIR AND THE DISSOLUTION VELOCITY OF OXYGEN INTO SULPHURIC ACID SOLUTION
Authors: Miyamoto Susumu
Published: July 2006

(1) The oxidation velocity of stannous chloride in sulphuric acid solution was observed under quite the same conditions as in the case of the oxidation of the same substance in hydrochloric acid solution, which was reported in the previous paper. The velocity increases slowly as the concentration of sulphuric acid increases as far as it reaches the dissolution velocity of oxygen into the solution, when the concentration of sulphuric acid attains about 0.8 normal, and the further increase of the concentration of sulphuric acid has almost no effect on the oxidation velocity, which was found to be almost independent of the initial concentration of stannous sulphate. The velocity constants, calculated as a zero-order reaction, were approximately expressed as a linear function of the concentration of sulphuric acid.

(2) The dissolution velocity of oxygen into sulphuric acid of various concentrations was calculated from the oxidation velocity observed. The dissolution velocity has nearly the same value as that into hydrochloric acid solution under the same conditions.

(3) The effect of temperature on the oxidation velocity, when the concentration of sulphuric acid is greater than about 0.8 normal, was ascertained to be negligible under the present conditions.
SORPTION OF GAS BY MINERAL. I. HEULANDITE AND CHABAZITE.
Authors: Sameshima Jitsusaburo
Published: July 2006

1. The amounts and the velocities of sorptions by partially dehydrated heulandite of ammonia, carbon dioxide and ethylene have been measured.

2. It was known that the heulandite absorbs only ammonia in considerable amount.

3. The number of mols of ammonia sorped are nearly identical with that of water evaporated in the process of dehydration. So the ammonia is considered to combine chemically with the dehydrated heulandite. The composition of the substance obtained in the present experiment is probably Ca2Al4Si12O32·4H2O·7NH3.

4. The amounts and the velocities of sorptions by dehydrated chabazites of carbon dioxide, ethylene and ammonia have been measured.

5. Chabazite absorbs carbon dioxide and ammonia rapidly, but ethylene slowly.

6. Chabazite absorbs hydrogen only in small quantity.
Preparation and Properties of Metal Complexes in Non-aqueous Solutions. I. Preparation of the trans-Dicyano-bis(ethylenediamine)cobalt(III) Complex by the Use of Dimethylsulfoxide as Solvent
Authors: Muto Masayuki , Baba Tetsuo , Yoneda Hayami
Published: July 2006

An isomeric form of the hitherto known cis-[Co(CN)2 en2]+ was prepared from cis- or trans-[CoCl2 en2]+ and potassium cyanide in dimethylsulfoxide solution. The new complex was characterized by UV, IR and NMR spectra, and its trans configuration was established.
3,4-Benzotropolone and Related Compounds. VI. Brominated 6-Hydroxy-2,3-benzotropone (or Brominated 3-Hyroxy-4,5-benzotropone). Formation and Reaction
Authors: Hoshino Masamatsu , Ebine Seiji
Published: July 2006

6-Hydroxy-2,3-benzotropone (or 3-hydroxy-4,5-benzotropone) (I) was brominated under various conditions, and the bromination products were subjected to debromination, substitution, and some other reactions. I reacted with a molar equivalent of bromine at 25°C to give 7-bromo-6-hydroxy-2,3-benzotropone (II), and with two molar equivalents of bromine at 25°C to give an adduct of II with bromine (V), which, on heating, was dehydrobrominated to 5,7-dibromo-6-hydroxy-2,3-benzotropone (IV). On the other hand, I reacted with bromine at 100°C to give 5-bromo-6-hydroxy-2,3-benzotropone (III), IV, and 2,2,7-tribromo-4,5-benzocyclohepta-4,6-diene-1,3-dione (VI), depending on the amount of bromine employed. All these bromination products could be debrominated with ease with hydrogen in the presence of catalyst to yield I. When II was heated with hydrobromic acid, the 7-bromo substituent was in part eliminated to give I and migrated in part to give III. When IV and 4,7-dibromo-6-hydroxy-2,3-benzotropone (X) were heated with hydrobromic acid, the 7-bromo substituents were eliminated and the 4- or 5-bromo substituent remained unreacted, producing III and 4-bromo-6-hydroxy-2,3-benzotropone (IX) respectively. When II and IV were heated with hydrochloric acid, the 7-bromo substituents were not eliminated but, rather, substituted with chlorine atoms to give 7-chloro-6-hydroxy-2,3-benzotropone (VII) and 5-bromo-7-chloro-6-hydroxy-2,3-benzotropone (VIII) respectively. These facts suggest that I and its bromo derivative sometimes behave as unsaturated β-diketones (I′).
Studies of Heteroaromaticity. XXIV. 1,3-Dipolar Cycloaddition of C-(5-Nitro-2-furyl)-N-phenylnitrone
Authors: Sasaki Tadashi , Yoshioka Toshiyuki , Izure Iwao
Published: July 2006

C-(5-Nitro-2-furyl)-N-phenylnitrone (I) was prepared from 5-nitro-2-furfural and phenylhydroxylamine in an 80% yield. The 1,3-dipolar cycloaddition reactions of I with various olefins were carried out, and the corresponding 5-substituted isoxazolidine derivatives were obtained. The structual elucidation of these products was made on the basis of the nmr spectral data. Several observations support the theory that these reactions proceed via a concerted one-step process.
A Synthesis of Dl-Tryptophan from Acrolein
Authors: Maeda Itsutoshi , Yoshida Ryonosuke
Published: July 2006

Dl-Tryptophan hydrantoin was obtained from phenylhydrazone of β-(hydanto-5-yl)-propionaldehyde acetal (5-(γ,γ-dialkoxypropyl)hydantoin) by Fischer’s indole synthesis. β-(Hydanto-5-yl)propionaldehyde acetal was prepared by Bucherer’s reaction from 1,1-diacetoxy-4,4-dialkoxybutane obtained by the hydroformylation of acrolein acetate. Attempts to crystallize β-(hydanto-5-yl)-propionaldehyde acetal from Bucherer’s reaction solution were unsuccessful, but 5-alkoxy-1,3-dioxoperhydropyrro[1,2-c]imidazole was obtained by treating the solution with ion exchange resins in alcohol. It could be also converted to tryptophan hydantoin.
Spectroscopic Investigations of α-Keto Phosphorus Compounds
Authors: Osaki Takayoshi , Otera Junzo , Kawasaki Yoshikane
Published: July 2006

The NMR, IR, and UV spectra of some α-keto phosphorus compounds, (C2H5)2PCOR, (C2H5)2P(S)COR, and [(C2H5)2CH3PCOR]+I− (R=C6H5 and CH3), were measured. The carbonyl stretching frequency and the n-π* transition show considerable red shifts, but the shifts are smaller than those of α-keto organosilicon compounds. The lowering of the carbonyl π* level, which resulted from the interaction with a vacant d orbital of the phosphorus atom, was found to be largely responsible for the red shift of the n-π* transition in the α-keto phosphorus compounds, particularly in [(C2H5)2CH3PCOR]+I−. The rise in the n level of the carbonyl group was found to be rather small.
Studies of the Synthesis of Furan Compounds. XXIX. Syntheses of 2-(5-Nitro-2-furyl)vinyl-1,8-naphthyridines
Authors: Hirao Ichiro , Kato Yasuhiko , Fukano Yoshimasa , Yanai Shinpei
Published: July 2006

In continuing our study of the relationship between structures and antibacterial activity, 2-[2-(5-nitro-2-furyl)vinyl]-5-hydroxy- and 4-[2-(5-nitro-2-furyl)vinyl]-2,7-dihydroxy-1,8-naphthyridine and their related derivatives have been synthesized. In these compounds, 2-[2-(5-nitro-2-furyl)vinyl]-5-hydroxy- (I) and 2-[2-(5-nitro-2-furyl)vinyl]-5-hydroxy-6-ethoxycarbonyl-1,8-naphthyridine (II) showed broad spectra of antibacterial activity, and the activity of I was greater than that of II. Other compounds exhibit a strong antibacterial activity against Diplococcus pneumoniae, Streptococcus hemolyticus, and Staphilococcus aureus, but they show a weak activity against the other microorganisms tested.
The Synthesis and the Stereochemistry of 4-Chromanones and 4-Chromanols with Bulky Substituents
Authors: Kabuto Kuninobu , Kikuchi Yoriko , Yamaguchi Shozo , Inoue Naoto
Published: July 2006

The synthesis and the stereochemistry of 4-chromanones and 4-chromanols with bulky substituents have been investigated. In 3-substituted chromanones, the t-butyl group exists mainly in the quasi-axial position, while the phenyl group is still in the quasi-equatorial environment. The preferred conformations of the isopropyl, and of the t-butyl group in cis- and trans-2-substituted chromanols, are equatorial, whereas trans-3-t-butylchromanol and its benzoate exist mainly as the conformations in which the t-butyl group is in the axial position. The conformational preference of these compounds can reasonably be explained by considering the steric interactions (A(1,3) strain, gauche, and diaxial repulsion) of these groups. The magnitude of the A(1,3) strain due to the hydroxyl group was estimated to be 1.3 kcal/mol.
Chemistry of α-Haloaldehydes. II. Base-catalyzed Condensation of α-Haloaldehydes with Methyl Chloroacetate
Authors: Takeda Akira , Tsuboi Sadao , Hongo Toru
Published: July 2006

The Darzens-type condensation of α-haloaldehyde (2) with methyl chloroacetate has been studied. The reaction of aliphatic α-chloroaldehydes afforded 4-chloro-2,3-epoxyalkanoates (4). The reaction of 2-bromo-2-methylpropanal (2d) with methyl chloroacetate gave α-chloro-γ,γ-dimethyl-Δα,β-butenolide (7) as a major product. α-Bromo-n-alkanal gave a mixture of many minor products.
Sterically Controlled Syntheses of Optically Active Organic Compounds. XX. Synthesis of Optically Active Alanine from α-Bromopropionamides
Authors: Okawara Tadashi , Harada Kaoru
Published: July 2006

The treatment of N-benzylchloroacetamide with sodium hydride resulted in the formation of N,N′-dibenzyldiketopiperazine which was converted to glycine after hydrolysis and hydrogenolysis. In a similar way, N-alkyl-α-bromopropionamides, in which the alkyl groups were chiral, were treated with sodium hydride and optically active alanine was obtained after hydrolysis and hydrogenolysis. When an optically active (S)-(−)- or (R)-(+)-α-methylbenzyl group was used as a chiral center, the optical activity of alanine was very low. When (S)-(−)-α-ethylbenzylamine was used, optically active (S)-alanine (optical purity 6–25%) was obtained. The use of (S)-(−)-α-(1-naphthyl)ethylamine resulted in the formation of (R)-alanine (opposite configuration, optical purity 23–27%). The overall yield of optically active alanine is in the range 11–36%.
An Interstitial-Electron Model for the Structure of Metals and Alloys. III. Interpretation and Correlation of Properties of Group I–V Metals
Authors: Johnson Oliver
Published: July 2006

The interstitial-electron model for metals supplements the concepts of band theory to give a detailed interpretation of the properties of metals. The instantaneous picture of vacant and electron-occupied interstices given by the model clarifies the complex gradations in electrical conductivity which are not explained by an electron per unit volume term. The consideration of polarization of the itinerant electron cloud by ion cores with high positive fields and of interpenetration of the more deformable ion cores by itinerant electrons is another new feature of the model. The interstitial-electron model leads to the expectation of parallel gradations for electronic heat capacity and magnetic susceptibility and an inverse relation of both of these properties with electrical conductivity. The presence of (\bare2) in the metal structure is associated with a positive Hall Coefficient for a metal, and a new correlation between positive Hall Coefficient and superconductivity for a metal is pointed out.
On the Interaction of Sodium Alkyl Sulfate with Alkylpyridinium Chloride and with Alkyltrimethylammonium Bromide in a Solution
Authors: Mitsuishi Masaru , Hashizume Mieko
Published: July 2006

The interaction between sodium alkyl sulfate and alkylpyridinium chloride or alkyltrimethylammonium bromide has been studied quantitatively by means of the conductometric method. The equilibrium constants of the reactions between them have been found to increase with an increase in the length of the alkyl chain. When the sum of the carbon atoms in an alkyl sulfate and of those of an alkylpyridinium chloride or of alkyltrimethylammonium bromide is less than twenty, no reaction has been found to take place. When it is larger than twentysix, precipitates of the complex have been found. The interaction has been found to depend greately on the length of the alkyl chain. The interaction decreases the heat content and increases the entropy.
Lone Pair Ionization Potentials of Carboxylic Acids Determined by He(I) Photoelectron Spectroscopy
Authors: Watanabe Iwao , Yokoyama Yu , Ikeda Shigero
Published: July 2006

Photoelectron spectra of some simple carboxylic acids and halogen substituted acetic acids were observed. Each spectrum contains a band which is associated with the ionization from an oxygen lone pair (n0) orbital of carboxyl group. The band associated with the n0 orbital is clearly separated from other bands, and its shape and width are quite similar among the various carboxylic acids. In the spectra of halogen substituted acetic acids, n0 band appears around the region of the lone pair bands of halogen atoms. The ionization potentials for oxygen lone pair orbital of carboxylic acids are measured and compared with the results of some semi-empirical SCF MO calculations. The agreements are quite satisfactory when ionization potentials are obtained from the difference of total energies of neutral molecule and its corresponding cation calculated using CNDO/2 or INDO method. MINDO/2 method also gives excellent values when Koopmans’ theorem is applied.
Water Content on Metal Oxides. I. Water Content on Silica Gel, Magnesium Oxide, Zinc Oxide, and Titanium Dioxide
Authors: Morimoto Tetsuo , Naono Hiromitu
Published: July 2006

The surface water content has been determined on silica gel, magnesium oxide, zinc oxide, and titanium dioxide by means of active hydrogen analysis and by the successive-ignition-loss method. Except for magnesium oxide pretreated at 100 °C, it has been found that the water contents obtained from the two methods on every oxide tested are in good agreement with each other. The successive-ignition-loss method gives an extraordinarily high value of water content on magnesium oxide pretreated at 100 °C, probably because of the retention of inner hydroxyl groups. The present results indicate that the two methods are equally reliable for the quantitative determination of the water content on metal oxides. Moreover, the simultaneous application of both methods make it possible to estimate each amount of surface hydroxyl groups and physisorbed water molecules.
Analysis of Metals by Solid-Liquid Separation. Spectrophotometric Determination of Cadmium by Extraction of Cadmium Salt of Oxine with Melted Naphthalene
Authors: Fujinaga Taitiro , Satake Masatada , Yonekubo Tatsuo
Published: July 2006

A method is described for the spectrophotometric determination of a minute quantity of cadmium. A cadmium complex stable at 90°C is easily extracted with melted naphthalene. The resulting mixture of cadmium complex and naphthalene is dissolved in dimethylformamide and absorbance of the solution is measured at 400 nm. Effects of pH, amounts of oxine, naphthalene and diverse salts are given.
The Mass Spectra of 3-Aryl-5-chloromethyl-1,2,3-oxathiazolidine-2-oxides
Authors: Nishiyama Tomihiro , Yamada Fukiko
Published: July 2006

The mass spectra of 3-phenyl- (I), 3-tolyl- (II), 3-chlorophenyl- (III), and 3-trichlorophenyl- (IV), -5-chloromethyl-1,2,3-oxathiazolidine-2-oxides have been obtained. The major path in the electron impact-induced cleavage of all the compounds involves the loss of SO2 and Cl from each molecular ion (M). The M–SO2–Cl ions show the loss of CH=CH2, followed by the loss of the hydrogen radical and HCN. On the other hand, in compounds II, III, and IV, the M–SO2–Cl ions show the loss of the ring-substituted methyl or chloro radical. The above fragmentation pathways associated with metastable transitions or the chlorine isotopic clusters for each ion of III or IV have been outlined and discussed for each group of compounds.
Synthesis and Biological Activity of Peptides Related to Eledoisin. III. C-Terminal Hexapeptide Amides Modified in Methionine and Isoleucine Residues
Authors: Sugano Hiroshi
Published: July 2006

New analogs of hexapeptide related to eledoisin containing N-methylmethionine and α-hydroxy-γ-methylthiobutyric acid in place of the methionine, and α-hydroxyisovaleric acid in place of the isoleucine, were synthesized in order to obtain some information about the role of the amide bond in the peptide backbone. The former two were practically inactive in the rabbit pressure assay. These results indicated that the amide bond between the leucine and the methionine residues was important for the depressor activity of eledoisin. The last one showed very little activity. The results supported the suggestion made previously that the amide bond between the phenylalanine and the isoleucine residues is important in eliciting the biological response. The role of the amide bonds in the peptide backbone of eledoisin was also discussed.
The Formation of Tin-Nitrogen Bonds. V. The Selective 1-Substitution Reaction of Tetrazoles by the Reaction of 5-Substituted 2-(Tri-n-butylstannyl)tetrazoles with Methyl Iodide, Methyl p-Toluenesulfonate, Dimethyl Sulfate, and Ethyl Bromoacetate
Authors: Isida Tyûzô , Akiyama Tetsuo , Nabika Kiyoshi , Sisido Keiiti , Kozima Sinpei
Published: July 2006

The selective 1-substitution reaction of tetrazole was developed by the treatment of 5-substituted 2-(tri-n-butylstannyl)tetrazoles with methyl iodide, methyl p-toluenesulfonate, dimethyl sulfate, or ethyl bromoacetate at room temperature. This selectivity was introduced by blocking the 2-nitrogen with the tri-n-butyltin group against the 2-substitution. In the case of 5-substituted 2-(trimethylstannyl)tetrazoles, a low selectivity was observed. The possible reaction pathways have been discussed.
A Study on the Photochemistry of α,β-Unsaturated γ-Lactones. II. Photoisomerization of 3-Ethylidene-4,5-dihydro-2(3H)-furanone
Authors: Ohga Kazuya , Matsuo Taku
Published: July 2006

On irradiation of cis-3-ethylidene-4,5-dihydro-2(3H)-furanone with 2537 Å light, both the cis-trans isomerization of the exocyclic double bond and transformation into the β,γ-unsaturated isomer, 3-vinyl-4,5-dihydro-2(3H)-furanone, were observed. By the use of sensitizers such as acetone, acetophenone, p-methoxyacetophenone and benzophenone, it was possible to induce cis-trans isomerization exclusively. On the basis of the solvent effect and the wavelength dependence of the reactions, transformation into the β, γ-unsaturated isomer and cis-trans isomerization were suggested to proceed via T2(n,π*) and T1(n,π) states, respectively.
Chemical Studies on the Mistletoe. II. The Structure of Viscumamide, a New Cyclic Peptide Isolated from Viscum album Linn. var. coloratum Ohwi
Authors: Okumura Yasuaki , Sakurai Atsushi
Published: July 2006

A new cyclic peptide, viscumamide (C30H55N5O5) was isolated from Viscum album Linn. var. coloratum Ohwi, and the structure Ia (Remark: Graphics omitted.) was assigned to this substance from gas-chromatographic studies on the products of partial hydrolysis.
The Electrochemical Fluorination of Benzenes and Pyridines
Authors: Inoue Yoshio , Nagase Shunji , Kodaira Kazuo , Baba Hajime , Abe Takashi
Published: July 2006

The electrochemical fluorination of several aromatic compounds (benzene, fluorobenzene, chlorobenzene, m-dichlorobenzene, anisole, o-chloroanisole, thiophenol, p-chlorothiophenol, m-thiocresol, 2-chloropyridine, and 3-chloropyridine) has been carried out. Perfluorocyclohexane was the principal product from benzene and fluorobenzene. In addition, chloro-derivatives of perfluorocyclohexane were produced from chlorobenzenes. Anisoles gave fully-saturated perfluoroethers, together with cleaved products. Extensive cleavage was observed in the fluorination of thiophenols and chloropyridines, and fluorocarbons and sulfur hexafluoride or nitrogen trifluoride were characteristic products. New compounds were also formed, trifluoromethyl 2-chlorodecafluorocyclohexyl ether from o-chloroanisole, and 3-chlorodecafluoropiperidine and 2-chloroundecafluoropentane from 3-chloropyridine.
Application of the RRKM Theory to Energized Ethylene Formed in the Vacuum-ultraviolet Photolysis of n-Paraffins
Authors: Akimoto Hajime , Obi Kinichi , Tanaka Ikuzo
Published: July 2006

The Rice-Ramsperger-Kassel-Marcus treatment has been applied to the energized ethylene produced in the vacuum-ultraviolet photolysis of C2H6, C2D6, C3H8, C3D8, n-C4H10 and n-C4D10. The energy spread in the energized ethylene has been evaluated assuming modified statistical distribution of liberated energy among fragment species. The calculated nonequilibrium unimolecular decomposition rate constant for the process C2H4(C2D4)→C2H2(C2D2)+H2(D2) could satisfactorily reproduce the experimental pressure dependence of ethylene to acetylene ratio. Non-statistical kinetic energy Ek seems to appear for the primary decomposition of the n-paraffins. Its value ranges from zero for the elimination of methane and ethane from propane and n-butane, respectively, at 147.0 nm to about 25 kcal mol−1 for the elimination of hydrogen from ethane at 123.6 nm.
ESR Studies on Radical Anions of Calicene Derivatives
Authors: Konishi Shiro , Niizuma Shigeya , Kokubun Hiroshi , Koizumi Masao
Published: July 2006

Two calicene derivatives, 1,2,3,4-tetrachloro-5,6-diphenylcalicene and 1,2,3,4-tetrachloro-5,6-di-n-propylcalicene, were reduced with an alkali metal in degassed tetrahydrofuran and the ESR spectra of the resluting monoanion radicals were investigated. It was found that in both anion radicals the unpaired spin does not exist on the five-membered ring, and is localized only on the other part. In the latter anion radical, the five-membered and three-membered rings were found to be twisted toward each other at about 45°, a line width alternation caused by hindered internal rotation of two adjacent n-propyl groups being observed. The potential barrier for the hindered rotation was determined to be about 1.5 kcal/mol.
The Crystal Structure of Dinicotinic Acid
Authors: Takusagawa Fusao , Hirotsu Ken , Shimada Akira
Published: July 2006

The crystal structure of dinicotinic acid has been determined by X-ray diffraction method. Two kinds of twinning crystals were obtained by changing the pH of the aqueous solution by recrystallization. The crystals are monoclinic with the space group of P21/c and with cell dimensions of a=9.702, b=11.153, c=6.587 Å, and β=107.8°. The crystal structure was solved by an inspection of the sharpened Patterson map. The final R value is 5.93% for 1181 observed reflections. The dinicotinic acid molecule takes an intermediate structure between the neutral molecule and the zwitter ion with an approximate C2v symmetry. The bond lengths and angles related by the C2v symmetry are equal within the limits of experimental error for those of the two carboxyl groups. The C(2)–N(1)–C(6) bond angle is 119.8°, which lies between those of protonated and unprotonated species of the pyridine ring. The molecules lie approximately on planes parallel to the (001) plane at z=1⁄4 and 3/4. Each molecules on the same plane is joined through two kinds of hydrogen bonds (O–H···O; 2.594 Å, O···H···N; 2.515 Å), related by two-fold screw axes, with four neighboring molecules. In the O···N hydrogen bond, the hydrogen bonding distance and angle are 2.515 Å and 174° and the O–H and N–H distances are 1.23 and 1.29 Å, which are equal within the limits of experimental error. Therefore, it may be considered as an example of the single minimum hydrogen bond of the O–H···N hydrogen-bond type. The existence of two kinds of twins may be interpreted on the basis of the layer structure.
Absorption Band in the Near-Ultraviolet Region Observed for Binuclear Copper(II) Complexes
Authors: Kida Sigeo , Nishida Yuzo , Sakamoto Masatomi
Published: July 2006

Elucidation of the origin of near-ultraviolet absorption believed to be characteristic of binuclear copper(II) complexes was attempted. The absorption was attributed to charge transfer transitions from nonbonding orbitals of bridging oxygen atoms to the vacant metal d-orbital. Appearance of the band in the near-ultraviolet region was interpreted in terms of the red-shift due to the decreasing s-character of the nonbonding orbitals enforced by the steric requirement of the complex. On this basis, the spectra of dialkoxo- or dihydroxo- bridged complexes and of copper alkanoates can consistently be explained.
Oxidation of p-Tolyl Triphenylmethylhydrazo Sulfone
Authors: Kojima Minoru , Kamigata Nobumasa , Minato Hiroshi , Kobayashi Michio
Published: July 2006

In order to synthesize and study the decomposition of p-tolyl triphenylmethylazo sulfone, p-tolyl triphenylmethylhydrazo sulfone was oxidized by various oxidizing agents. Although it was oxidized fairly easily by mercury(II) oxide or potassium permanganate, the azo compound formed was unstable and decomposed immediately with evolution of nitrogen. The main products were p-tolyl triphenylmethyl sulfone and p-tolyl p′-benzhydrylphenyl sulfone; both are ascribable to the recombination of p-toluenesulfonyl and triphenylmethyl radicals.
Variations of Heat of Immersion of Ferric Oxyhydroxides in Water with Structural Changes by Heating
Authors: Ishikawa Tatsuo , Inouye Katsuya
Published: July 2006

The relationship between the activity of ferric oxyhydroxides (α-, β-, and γ-FeOOH) and structural changes has been investigated by determining the heat of immersion in H2O and H2O vapor adsorption. For each ferric oxyhydroxide, the monolayer capacity of H2O adsorption and the heat of immersion decreased with the progress of transformation into α-Fe2O3. Above the transformation temperature the heat of immersion increased with the outgassing temperature. The heat of immersion of α-Fe2O3 obtained by outgassing each ferric oxyhydroxide at 400 and 500 °C increased with the accompanying increase in crystallite size. β-FeOOH showed higher heat of immersion and larger monolayer capacity per unit surface area than other ferric oxyhydroxides. It is presumed that the higher heat of immersion and larger monolayer capacity observed for β-FeOOH are ascribed to micropores in β-FeOOH crystals produced by the removal of molecular water originally contained.
X-Ray Analysis of the Domain Structure of the 1:1 Complex of Carbazole–TCNQ
Authors: Kobayashi Hayao
Published: July 2006

The crystal structure of the 1:1 complex of carbazole–TCNQ was investigated by X-ray diffraction. Analysis of sharp spots and diffuse streaks in the diffraction patterns revealed that the crystal is composed of an ordered domain and a disordered one. The ordered domain is made up from two types of ordered molecular arrangements, whereas the disordered one consists of a one-dimensionally disordered structure. The structures of the two ordered domains are closely related with each other. They both contain mixed stack columns of alternating carbazole and TCNQ usually observed in charge transfer (CT) complexes. The existence of various types of domain structures as shown by diffraction patterns of many crystals grown from acetone, acetonitrile and tetrahydrofuran solutions can be interpreted in terms of the combinations of ordered and disordered domains. No CT band appears in the visible absorption spectra of the acetone solution of carbazole–TCNQ, whereas the spectra of the powdered crystals show a CT band at about 18000 cm−1. The calculation of SCF-MO-CI of the system of the carbazole–TCNQ, pair indicates a weak CT interaction.
An Experimental Study of Gibbs-Donnan Membrane Equilibria Across Permselective Membranes Which Involve the Ions of Strong Inorganic Electrolytes
Authors: Tamamushi Reita
Published: July 2006

The Donnan membrane equilibria arising across permselective collodion matrix membranes were studied both by a static and a flow method in systems which contain only simple strong electrolytes at relatively high concentrations, up to 0.4 equiv/l. Experimental details of the flow method and its advantage in studying the ion activity behavior are presented. From the measurements of equilibrium concentrations and Donnan membrane potentials the ratios of ion activity coefficients were calculated for the following pairs of electrolytes in mixed solutions: sodium chloride–sodium nitrate, sodium sulfate–ammonium sulfate, potassium oxalate–ammonium sulfate, and potassium oxalate–ammonium oxalate. The experiments prove the feasibility of determining the ratios of ion activity coefficients in mixed solutions at concentrations where other methods lose their usefulness.
Conformation of Poly(S-benzyl-l-cysteine) in Solution
Authors: Maeda Hiroshi , Inoue Takashi , Tsunoda Masa-aki , Ikeda Shoichi
Published: July 2006

Conformation of poly(S-benzyl-l-cysteine) was investigated by measurements of optical rotatory dispersion, infrared absorption and viscosity in dichloroacetic acid (DCA)–chloroform mixtures. Transition from random coil to the β-structure was confirmed to occur when DCA content of the solvent was reduced below 40% (v/v). Both dispersion parameters a0 and b0 increased as the polymers were transformed into the β-structure. Viscosity of the polymer solution changed only slightly with accompanying the transition. This was interpreted in terms of the formation of intramolecular β-structure. In the region where the β-structure was dominant both optical rotatory parameters and viscosity were independent of solvent composition. Such behavior has been rarely observed in the β-coil transition of other polypeptides. The β-structure of poly(S-benzyl-l-cysteine) was shown to be more stable than that of poly(O-benzyl-l-serine) as referred to respective random coil conformations.
Studies on the Interactions of 1-Substituted 2,4-Dinitrobenzenes with Hydroxide Ion in Aqueous Dimethyl Sulfoxide by Means of the Rapid Scan Spectrophototometer
Authors: Hasegawa Yoshinori , Abe Takehiro
Published: July 2006

The initial interactions of m-dinitrobenzene, 2,4-dinitroanisole, 2,4-dinitrofluorobenzene, and 2,4-dinitrochlorobenzene with hydroxide ion in aqueous dimethyl sulfoxide were studied with a rapid scan spectrophotometer. In all the cases, the first transient colored-species assigned to 1-hydroxy-3-substituted-2,6-dinitrocyclohexadienates were observed at initial stages before the formations of the second colored-species having the π-electronic structures of 1,3-dinitropentadienyl anion were complete.
Restricted Rotation Involving the Tetrahedral Carbon. VII. Rotation About the Carbon-Group IV Single Bond
Authors: Suzuki Fumio , Oki Michinori , Nakanishi Hiroshi
Published: July 2006

9-t-Butyl-, 9-trimethylsilyl-, 9-trimethylgermyl- and 9-trimethylstannyl-1,2,3,4-tetrachloro-9,10-dihydro-9,10-ethenoanthracenes were prepared by the addition of tetrachlorobenzyne to 1-(CH3)3M-substituted naphthalene. The carbon compound showed very high barrier to rotation, whereas the coalescence phenomenon of three methyl signals was observed for silicon, germanium, and tin compounds. The barrier (ΔG\eweq) to rotation at 298 K was obtained as 19.1±0.5, 17.2±1.2, and 11.7±0.4 kcal/mol for Si, Ge, and Sn compounds, respectively. The decrease in the barrier on increasing the atomic size was attributed to the release of repulsive interaction to a greater extent, since the longer bond length should result in the larger displacement of the methyl group even though the bond angle deformation is the same.
An Attempt at Simultaneous Observation by Polarizing Microscopy and by Differential Thermal Analysis
Authors: Sasaki Kunihisa Kazuko
Published: July 2006

An apparatus for differential thermal analysis using a polarizing microscope has been developed. With this device it is possible to observe the state of a sample under the heating or cooling conditions with a polarizing microscope and to obtain the DTA curve simultaneously. The transformations of several substances—potassium laurate, ammonium nitrate and tripalmitin— were observed. The results are in agreement with those obtained by X-ray diffraction. The relation between the appearance of Phase III of NH4NO3 and the water content of the sample was considered on the basis of the microscopic observations. In the case of tripalmitin, two types of transformations were observed under cooling conditions. The relation between the DTA curve of tripalmitin and the heating rate has also been studied. The apparatus may be useful for the study of liquid crystals.
Faraday Parameters of the Magnetic Circular Dichroism of Praseodymium Trichloride and Thulium Trichloride in Poly (vinyl alcohol) Film
Authors: Kato Yoshifumi , Nishioka Kyusaku
Published: July 2006

The magnetic circular dichroism and absorption spectra of PrCl3 and TmCl3 in polyvinylalcohol film are measured in the range of 300–700 nm. The absorption bands observed are five for PrCl3, the transitions from the ground state, 3H4, to the excited states, 1D2, 3P0, 3P1, 1I6, and 3P2, of Pr3+, and four for TmCl3, the transitions from the ground state, 3H6, to the excited states, 3F3, 3F2, 1G4, and 1D2, of Tm3+. In order to separate the C term of the Faraday parameters, the temperature variation of the spectra is carried out at room temperature to 77 K. The Faraday parameters are derived from the experiment by the use of three methods; the method of moments, the graphical method, and curve fitting. The characteristics of these methods are discussed, and the uncertainty of the parameters obtained is estimated to be 30% or more. A group-theoretical consideration is applied for the interpretation of the results; this consideration fairly well explains the sign of the C terms obtained for PrCl3, but not for TmCl3.
Properties of Ampholytic Surfactant, N-Alkyl-β-alanine
Authors: Okumura Takeo , Tajima Kazuo , Sasaki Tsunetaka
Published: July 2006

Ampholytic surfactant, N-alkyl-β-alanine, was synthesized and its infrared absorption spectra, surface tension, isoelectric points and critical micelle concentrations of aqueous solutions were measured at various electrolyte concentrations, pH and temperature. The measurements of isoelectric points and infrared spectra confirmed a zwitterionic sructure of N-alkyl-β-alanine. The critical micelle concentrations determined by surface tension measurements are 1.3×10−2 and 9×10−4mol/l respectively for the decyl and dodecyl homologs at 30 °C, the values decreasing with the increase in pH, electrolyte concentration and temperature.
The Crystal Structure of (±)-1-Benzyl-5-phenyl-1-azacycloheptan-4-one Hydrochloride, C19H21NO·HCl
Authors: Fukuyama Keiichi , Shimizu Shozo , Kashino Setsuo , Haisa Masao
Published: July 2006

The crystal structure of (±)-1-benzyl-5-phenyl-1-azacycloheptan-4-one hydrochloride has been determined by the heavy-atom method from three-dimensional X-ray data. The crystals are monoclinic, space group P21⁄c, with four formula units in a unit cell of dimensions: a=5.967(8), b=11.20(1), c=25.96(2) Å, and β=93.8(3)°. The structure was refined by the block-diagonal least-squares method to an R index of 0.076 for 1299 independent observed reflections. The benzyl and phenyl groups are bonded equatorially to the azacycloheptanone ring which takes a chair-like conformation. The chloride ion is hydrogen-bonded to the ring nitrogen atom at a distance of 3.075(4) Å.
Counterion Effect on the Titration Behavior of Poly(itaconic acid)
Authors: Muto Nobuhiko
Published: July 2006

The effect of counterions on the titration behavior of poly(itaconic acid) (PIA) was studied by titrating PIA in aqueous solutions containing alkali metal salts and a tetramethylammonium salt at 25°C. The acidity of the primary carboxylic groups of PIA increases in the order (CH3)4N+<Li+<Na+<K+, whereas that of the secondary carboxylic groups increases with the decrease in the crystallographical radii of the counterions, in the order (CH3)4N+K+<Na+Na+>Li+ on the binding strength to the primary carboxylate groups in the first dissociation step is interpreted in terms of the radii of the hydrated cations; it can be ascribed to the stable ring structure of the monoanion of the itaconic acid residue, resulting from the hydrogen bonding between two adjacent carboxylate groups. In apparent complete dissociation, about 80, 60, and 40% of the itaconate residues bind to Li+, Na+, and K+ ions, respectively, when it is assumed that no (CH3)4N+ ions are bound to the carboxylate groups.
Vibration-Rotation Spectrum of Methyl Fluoride II. Analysis of ν3+ν6 Band
Authors: Nakagawa Jim , Suzuki Isao , Shimanouchi Takehiko , Fujiyama Tsunetake
Published: July 2006

The ν2+ν6 band of methyl fluoride has been measured with a high-resolution infrared spectrometer. The molecular constants are obtained with the least-squares method. The effect of the x,y-type Coriolis interaction is discussed and the theoretical spectra are compared with the observed spectrum.
The Decomposition of Hydrogen Peroxide with Metal Complexes. I. The Catalytic Decomposition of Hydrogen Peroxide by the Ammine-Copper(II) Complex Ions in an Aqueous Solution
Authors: Hayakawa Katumitu , Nakamura Sumio
Published: July 2006

The catalytic decomposition of hydrogen peroxide by the ammine-copper(II) complex ions has been studied using kinetic measurements, UV and visible spectroscopy, electron-spin resonance spectroscopy, and polarography. It was found that there were two reaction paths in the catalytic decomposition of hydrogen peroxide. In the first case, a linear part was observed in the plot of the amount of oxygen evolved vs. time. In this case, a brown intermediate was formed which was later found to be a diamagnetic peroxo-copper complex and to contain some of the stable oxygen anion radical just after the mixing of the reactants. The activation energy of the reaction was found to be 23±1 kcal mol−1. In the second case, no linear part was observed in the kinetic curve. In this case, the reaction had a reaction order in hydrogen peroxide varying from the first- to the second-order depending on the initial concentrations of the reactants. The nature of the brown compound and the active species of the reaction is discussed.
Stereochemical Studies of N-Methyl-(S)-alaninatocobalt(III) Complexes with Chiral Tetramines. II. Cobalt(III)-N-Methyl-(S)- and (R)-alaninate-N,N′-Bis(β-aminoethyl)-1), 2(R)-diaminocyclohexane Systems
Authors: Saburi Masahiko , Yoshikawa Sadao
Published: July 2006

The preparation and structural assignments of N-methyl-(S)- and -(R)-alaninatocobalt(III) complexes with N,N′-bis(β-aminoethyl)-1(R),2(R)-diaminocyclohexane (abbreviated as (R)-baetchxn) are described. The Λ-β2-(SSR) isomer has been obtained for Co(N-Me-(S)-ala)((R)-baetchxn)2+ ion. The two isomers, which have been found for the Co(N-Me-(R)-ala)((R)-baetchxn)2+ ion under equilibrium condition at pH 7, are assigned as the Λ-β2(SSR) and Λ-β2(SSS) configurations, taking into account the stereospecific coordination of the (R)-baetchxn. The stereoisomerism of Δ-β2-Co(N-Me-(S)-ala)(trien)2+ ion is also discussed. The structures of two species observed in the PMR measurements of Co(N-Me-(R)-ala)((R)-baetchxn)2+ ion and assigned to Λ-β2(SSR) and Λ-β-(SSS) configurations, respectively, are determined, based on the chemical shifts of α-methine protons of N-methylalaninate moieties.
Aminosugars. XXII. Syntheses and Properties of 6-Deoxy-6-and 3-Deoxy-3-guanidino-d-hexoses
Authors: Yoshimura Juji , Sekiya Tetsuo , Ogura Yoshio
Published: July 2006

Methyl 6-deoxy-6-guanidino-α-d-glucopyranoside, 6-deoxy-6-guanidino-d-galactose, 3-deoxy-3-guanidino-d-allose (7), and 3-deoxy-3-guanidino-d-glucose were synthesized by guanidination of the corresponding amino-sugars. The acetate of 7 was proved to exist in a bicyclic structure; 2′,4′,6′-tri-O-acetyl-d-allopyrano[l′,2′,3′;4,5,6]-2-acetylimino-1,3-diacetyl-perhydropyrimidine, whereas others exist as the usual pyranoses. Properties of the new compounds and the synthetic methods were examined.
A Macrocyclic Enzyme Model System. Acyl Transfer from p-Nitrophenyl Carboxylates to Paracyclophane Oxime
Authors: Murakami Yukito , Sunamoto Junzo , Kano Koji
Published: July 2006

The deacylation reactions of p-nitrophenyl carboxylates by 10-hydroxy-11-hydroxyimino[20]paracyclophane (Oxime-I) have been investigated in an alkaline aqueous acetone. Oxime-I was acylated by p-nitrophenyl laurate (PNPL) and decanoate (PNPD), but was not affected by p-nitrophenyl acetate (PNPA) and hexanoate (PNPH). Meanwhile, 2-hydroxycyclodecanone oxime (Oxime-II) and acetoxime (Oxime-III) did not undergo any reaction with all of the present carboxylic esters under the same conditions. These results suggest that the acylation reactions of Oxime-I with PNPD and PNPL proceed primarily through incorporation of the substrates into the cyclic oxime cavity. The formation of an intra-complex was also suggested by an evidence that the copper(II) ion markedly retarded the reaction rate of PNPL with Oxime-I below the catalyst-absence level. The binding constant for PNPL with Oxime-I was considerably large in comparison with the usual micelle-substrate or synthetic polymer-substrate complexes. On the basis of thermodynamic parameters for the binding and the subsequent acylation, the driving force for the incorporation and the geometry of the intra-complex have been discussed.
Perkin Synthesis of Bromobenzalphthalides. Their Reactions with Amines and Hydrazine
Authors: Islam A M , Khalil A M , El-Maghraby A A
Published: July 2006

The isomeric 5-bromo- and 6-bromo-3-benzalphthalides were prepared by condensation of 4-bromophthalic anhydride with phenylacetic acids. The reaction of such isomeric bromobenzalphthalides with primary aromatic amines give the corresponding bromobenzalphthalimidines. Bromophthalazinone derivatives were obtained in good yields by the reatcion of bromobenzalphthalides with hydrazine hydrate.
Gel Filtration of Starch–Iodine System
Authors: Kodama Makoto , Sasaki Tsunetaka
Published: July 2006

The well-known starch-iodine reaction was taken up to study the applicability of gel filtration to the problem of physical chemistry. Gel filtration by the frontal analysis was carried out, the following results being obtained. (1) Soluble starch- and amylose–iodine systems give elution volumes of iodine containing constituents (Vsi and Vai, respectively) distinctly smaller than that of iodine, which decrease with increasing concentration of iodine, C, and starch, approaching the elution volume of starch. This is a direct experimental evidence of starch–iodine complex formation. (2) An equation derived for Vsi  vs. C and Vai  vs. C relations holds satisfactorily. The concentration of free iodine in equilibrium with the complex is calculated by the equation. (3) Presence of iodide ion facilitates the complex formation, but its decomposition is instantaneous when it is isolated from free iodine. (4) Some iodide ions are found to be incorporated in the complex. (5) Amylopectin also forms a complex with iodine, but the amount of iodide incorporated is not large. (6) Potentiometric titration of starch with iodine exhibits a similar behavior to the gel filtration measurement.
The Crystal Structure of the Cupric Complex with Succinimide. II. Potassium Tetrakis(succinimidato)copper(II) Hexahydrate and Lithium Tetrakis(succinimidato)copper(II) Monohydrate
Authors: Tsukihara Tomitake , Katsube Yukiteru , Fujimori Kumiko , Kawashima Kiyoshi , Kan-Nan Yoshiaki
Published: July 2006

As part of a program for the study of the crystal structure of copper(II)-complex with succinimide, the crystal structures of potassium tetrakis(succinimidato) copper(II) hexahydrate and lithium tetrakis(succinimidato) copper(II) monohydrate have been determined by means of X-ray analysis. In the potassium-salt, the copper atom has a square planar coordination and the potassium ion has a trigonal prismatic environment formed by six oxygen atoms. In the lithium-salt, the copper atom has a flattened tetrahedral coordination, and each lithiun ion is tetrahedrally surrounded by four oxygen atoms. The conformational difference between the complex anion of the potassium-salt and that of the lithium-salt seems to result from the different sizes of the alkali-metal ions.
Studies of the π–π* Absorption Bands of p-Quinones and o-Benzoquinone
Authors: Kuboyama Akira , Matsuzaki Sanae , Takagi Hiroshi , Arano Hiroshi
Published: July 2006

The π–π* absorption spectra of p-benzoquinone, α-naphthoquinone, anthraquinone, and their derivatives, mainly in n-heptane up to the vacuum UV region, were obtained. On the other hand, MO calculations of the n-electronic systems of these p-quinones and o-benzoquinone were carried out by means of the P-P-P method. The π–π* absorption bands of these quinones could be favorably assigned on the basis of the calculated results.
Effect of Cesium Counterion on the ESR Spectrum of Tetracyanoethylene Anion Radicals
Authors: Ogasawara Masaaki , Inaba Seizo , Yoshida Hiroshi , Hayashi Koichiro
Published: July 2006

Evidence was obtained by ESR for the ion-pair formation between the tetracyanoethylene anion radical and the cesium counterion in tetrahydrofuran. The hyperfine lines of the ESR spectrum of cesium tetracyanoethylenide were exceptionally broad at high salt concentrations in tetrahydrofuran, while they were remarkably narrowed by the addition of a small amount of DMF or triglyme (cation-solvating agents) or by replacing the counterion with the tetra-n-butylammonium ion. This indicates that the broad linewidth is due to the unresolved hyperfine splitting of the cesium counterion. In addition, the concentration dependence of the ESR spectrum indicates that the line broadening is to be interpreted not only in terms of the Heisenberg spin exchange, but also in terms of the equilibrium between the ion-pair and the free ion. The cesium hyperfine coupling constant was estimated by simulating the line shape to be 40 m Gauss in the ion-pair state between the tetracyanoethylene anion radical and the cesium ion in the tetrahydrofuran solution.