bluuebunny/crossref_metadata_2025 huggingface dataset:
The Chlorofluorination of Ethylene, Ethane, Fluoroethylene and Methane
Authors: Nagase Shunji , Baba Hajime , Abe Takashi
Published: July 2006

This novel electrochemical chlorofluorination involves the passage of each of the title materials, together with chlorine, through liquid hydrogen fluoride containing sodium fluoride. Chlorofluoroethanes were produced directly from ethylene, ethane, and fluoroethylene, while chlorofluoromethanes were produced directly from methane. Carbon tetrachloride, chloroform, and phosgene could also be used as a source of chlorine for the chlorofluorination reaction. Thionyl and sulfuryl chlorides, and sulfur mono- and di-chlorides did not act as chlorinating reagents.
Studies of the Alkaline Earth Metal Complexes in Various Solutions. II. Beryllium(II) Complexes with Sulfate and Oxalate in 1 m Na(ClO4)
Authors: Sekine Tatsuya , Sakairi Mitsuo
Published: July 2006

The complex formation of beryllium (II) with sulfate and oxalate ions in 1 m Na(ClO4) at 25°C has been studied by a liquid-liquid distribution method. The radioactive tracer beryllium-7 at very low concentration was used in conjunction with thenoyltrifluoroacetone in methylisobutylketone. The stability constants of the beryllium complexes were determined graphically from the distribution data by a curve-fitting method. The data seemed to be explained by the formation of the following complex species;

βn=[BeLn2–2n]⁄[Be2+][L2−]n,

where logβ2=1.78 and logβ3=2.08 for sulfate and logβ1=3.55 and logβ2=5.40 for oxalate. The formation of the primary sulfate complex, BeSO4, or the tertiary oxalate complex, Be(C2O42−)34−, was not concluded within the ligand concentration region studied.
The Crystal Structure of p, p′-Dichlorodiphenoxy-1, 2-ethane
Authors: Yasuoka Noritake , Ando Tadanao , Kuribayashi Shunsuke
Published: July 2006

Crystals of p, p’-dichlorodiphenoxy-1,2-ethane are monoclinic; their space group is P2/c, and they have 4 molecules in the cell with dimensions of:

a=12.79, b=9.89, c=10.37Å; β=98.2°

Two crystallographically-independent molecules, which are slightly different in conformation, are located on the two-fold axis of the crystal. The OCH2CH2O groups are of the gauche form.
The Crystal Structure of 1,2-Diphenoxyethane
Authors: Yasuoka Noritake , Ando Tadanao , Kuriyabashi Shunsuke
Published: July 2006

1,2-Diphenoxyethane crystallizes in two forms, flake-shaped and prismatic. The crystal and molecular structures of the prismatic crystals were determined and described. The orthorhombic unit cell dimensions are: a=34.74, b=12.04, and c=5.58 Å. The space group is Fdd2. The molecule has the symmetry of a two-fold axis, and the OCH2CH2O group exists in a gauche conformation with an internal rotation angle of 66.9°.
Syntheses and Properties of Some Thio Derivatives of Acetylacetonato-nickel(II)
Authors: Ouchi Akira , Hyodo Mitsutoshi , Takahashi Yoshiaki
Published: July 2006

Derivatives of acetylacetonato-nickel(II) in which the coordinating oxygen is replaced by sulfur to various extents have been isolated by the reaction between nickel(II) acetylacetonate and hydrogen sulfide in an ethanolic solution, using hydrogen chloride as the catalyst. These compounds are soluble in organic solvents, such as benzene, acetone, or carbon tetrachloride, but can hardly be dissolved in water. The proton magnetic resonance spectra indicate that the proton of the methyl group attached to the C=S carbon gives greater chemical shifts than that of the methyl group attached to the C=O carbon. The infrared spectra of these compounds are discussed with particular reference to the C=S stretching bands. The electronic spectra of these compounds and the Hückel LCAO-MO calculation of bis dithio compounds are also compared.
Synthetic Studies of Bacitracin. V. Synthesis of Thiazoline Peptides from Cysteine Peptides by Dehydration Procedure
Authors: Hirotsu Yoshihiro , Shiba Tetsuo , Kaneko Takeo
Published: July 2006

Synthesis of thiazoline peptide from cysteine peptide by dehydration with hydrochloric acid in non-aqueous solvent was investigated. By this method, ethyl 2-benzyloxycarbonylaminomethyl-R-Δ2-thiazoline-4-carboxylate and 2 - benzyloxycarbonylaminomethyl-R-Δ2-thiazoline-4-carbonyl-l-leucine ethyl ester were prepared and isolated in pure states. This synthetic method could give a promising route to a total synthesis of bacitracin A. However, the cysteine residue in the latter thiazoline peptide ester was found to be easily racemized under the basic condition.
Structure of Busch’s Endo-thiatriazolines
Authors: Ohta Masaki , Kato Hiroshi , Kaneko Takashi
Published: July 2006

The methods of preparing 2,4-dihydro-1,3,4-thiadiazole-2-thiones are discussed. The structure of the reaction products of these compounds or their methiodides with amines is determined to be 1,3-dihydro-1,2,4-triazole-3-thiones.
Medium-Sized Cyclophanes. III. The Nitration Reaction of [2.2]Metacyclophane with Benzoyl Nitrate
Authors: Fujimoto Meiko , Sato Takeo , Hata Kazuo
Published: July 2006

The nitration reaction of [2.2]metacyclophane was carried out using dilute nitric acid or benzoyl nitrate under various conditions. Dilute nitric acid afforded 2-nitro-4, 5, 9, 10-tetrahydro-pyrene as the sole product, confirming Allinger’s original experiments, whereas benzoyl nitrate furnished a complex mixture consisting of 4, 5, 9, 10-tetrahydropyrene, 4, 5-dihydropyrene and pyrene, together with the nitration product. A series of experiments established that 4, 5, 9, 10-tetrahydropyrene, which was formed by the 1, 4-elimination reaction of Allinger’s intermediate, was the initial product of the reaction. Two competitive reactions, nitration and dehydrogenation reactions of the tetrahydropyrene, were assumed to be occurring, thus accounting for the experimental results.
The Infrared Study of the Adsorption of Ethanol on Alumina
Authors: Arai Hiromichi , Saito Yasukazu , Yoneda Yukio
Published: July 2006

The structure of ethanol adsorbed on alumina has been studied by means of infrared spec-troscopy. At room temperature physically-adsorbed ethanol was observed, but it was completely removed by evacuation at 70°C for 2 hr. On the contrary, another adsorbed species remained after long evacuation at 70°C; it was identified as a surface ethoxide (C2H5OAl<). The concentration of the surface ethoxide on alumina had a linear correlation with the intensity of the CH3 symmetric deformation band at 1387 cm−1. The molar absorption coefficient of the band at 1387 cm−1 decreased parallel with 1/T at a higher temperature. The number of adsorption sites was calculated as 2.1×1014 sites/cm2 when the ethanol was exposed at 70°C to an alumina catalyst which had been evacuated at 550°C for 5 hr.
Mass Spectrometric Studies of Metal Acetylacetonates
Authors: Sasaki Shin-ichi , Itagaki Yasuhiro , Kurokawa Tadashi , Nakanishi Koji , Kasahara Akira
Published: July 2006

The mass spectra of fifteen metal acetylacetonates measured under the electron impact with 70 eV energies are reported. The acetylacetonates can be divided into three groups, A, B, and C, according to their stability in mass spectrometeric measurements. When the electronegativity of the central metal atom is 1.5—1.6, the complexes show abundant molecular ion peaks (group A); when the electronegativity is 1.6—1.8, no molecular ion appears and the M-L cations show as the highest mass (group B); when the electronegativity is greater than 1.8, there are no peaks arising from fragments containing the metal, only acetylacetone peaks being apparent (group C). Furthermore, the mass spectra of hexafluoroacetylacetone and its copper complex were also measured.
High Frequency Inductance Manometer for Gaseous Reaction Studies
Authors: Yasumori Iwao , Ohno Seigo , Miyazaki Eizo
Published: July 2006

A corrosion-free manometer which employs a variable inductor as a transducer has been devised. Its main part consists of a pair of small coils and a glass Bourdon bulb on which a thin aluminum disc is so attached as to be located between the coils. A manometer constructed as an example has the following characteristics: measurable (linear) range of pressure difference, 0–20 mmHg; minimum detectable pressure difference, 7×10−2 mmHg; temperature coefficient of zero-point drift, 0.2% of the full scale (20 mmHg) per degree; negligible temperature coefficient of output voltage per unit of pressure difference; limit of response time, 0.6 sec (under atmospheric pressure)–4 sec (1.1×10−3 mmHg). It is possible to extend the measurable range by changing the rigidity of the Bourdon bulb. From these results, it may be concluded that the manometer is useful in following and recording changes which have half-decay times of longer than a few seconds. When the manometer was applied to the study of the catalytic decomposition of formaldehyde on nickel wire, its usefulness was proved.
The Dissociation Phenomena of o-Phenol- and m-Chloro-o-phenolazochromotropic Acids and the Formation Constants of Magnesium and Calcium Chelates
Authors: Nakashima Susumu , Miyata Haruo , Tôei Kyoji
Published: July 2006

The acid dissociation constants of o-phenol-, m-chloro-o-phenol- and o-anisolazochromotropic acids have been measured by potentiometric titration. The measurements have been carried out at 25.0±0.1°C and μ=0.10 (by KNO3). From these constants, the dissociation of the hydroxyl groups in the reagents has been discussed. The phenolic hydroxyl group was first dissociated, and then one of the naphtholic hydroxyl groups; the other naphtholic group was not dissociated under ordinary experimental conditions. The pKa1 and pKa2 values were 7.60 and 10.60 for o-phenolazochromotropic acid, and 7.56 and 10.35 for m-chloro-o-phenolazochromotropic acid. o-Phenol- and m-chloro-o-phenolazochromotropic acids formed 1 : 1 chelates with calcium and magnesium. The formation constants were measured potentiometrically; the logK’s for calcium were 5.01 and 5.22, and for magnesium, 6.15 and 6.22.
Studies of Peptide Antibiotics. VIII. Synthesis of Gly4,4′-gramicidin S
Authors: Nagata Reiko , Waki Michinori , Kondo Michio , Aoyagi Haruhiko , Kato Tetsuo , Makisumi Satoru , Izumiya Nobuo
Published: July 2006

Gly4,4′-gramicidin S dihydrochloride, cyclo-(l-valyl-l-ornithyl-l-leucylglycyl-l-prolyl)2·2HCl, which is an analog of gramicidin S, was synthesized for the purpose of comparing its antibacterial activity with that of gramicidin S. The cyclization reaction via the linear decapeptide active ester or via the linear pentapeptide active ester yielded the same cyclic benzyloxycarbonyl-substituted decapeptide; this was then converted to Gly4,4′-gramicidin S dihydrochloride by hydrogenolysis. The effect of the Gly4,4′-gramicidin S on bacterial growth was tested; the peptide exhibited weak antibacterial activity against Bacillus Subtilis.
Glass Transition Temperature and Isothermal Volume Change of Selenium
Authors: Hamada Shuichi , Sato Tadao , Shirai Toshiaki
Published: July 2006

The viscoelastic behavior of selenium and of partially-chlorinated selenium was studied by the dilatometric method. The glass transition temperature, Tg, of selenium was determined to be 32.0°C at a cooling rate of 0.2°C/min. The glass transition temperature decreased linearly with the reciprocal of the average chain length of selenium. The chain length was calculated using the degree of chlorination. An abrupt increase in Tg was observed at a chlorine content of about 0.013%. The volume-time curves obtained by the determination of the volume of selenium in the neighborhood of Tg were superposed on each other by sliding them along the abscissa. The values of the shift factor and of Tg fit well in Williams, Landel and Ferry’s equation. The parameters in the WLF equation, C1g and C2g, of selenium were calculated to be 6.86 and 28.6 respectively. Both the parameters increased with an increase in the chlorine content up to 0.0125%, and reached the values of usual polymers above 0.0125%. The WLF fg value of selenium was calculated to be 6.33×10−2. This value decreased with an increase in the chlorine content, and reached the universal value of usual polymers (2.5×10−2) when the chlorine content was more than 0.0125%. The chlorine content corresponds to 0.0125% when all the radicals at both ends of the linear chain molecules of selenium have been used in forming bonds with chlorine atoms. Therefore, it may be concluded that the existence of radicals at the molecular ends of selenium chains brings about an augmentation of the fraction of the free volume at Tg.
Synthetic Studies of the Flavone Derivatives. VII. The Synthesis of Jaceidin
Authors: Fukui Kenji , Matsumoto Takashi , Nakamura Shigehiro , Nakayama Mitsuru , Horie Tokunaru
Published: July 2006

The Hoesch reaction of iretol with methoxyacetonitrile yielded 2,4,6-trihydroxy-3,ω-dimethoxyacetophenone. According to the Allan-Robinson flavone synthesis with O-benzylvanillic anhydride, the acetophenone afforded 4′-benzyloxy-5,7-dihydroxy-3,3′,6-trimethoxyflavone. The catalytic debenzylation of the flavone gave jaceidin, 4′,5,7-trihydroxy-3,3′,6-trimethoxyflavone, which had previously been isolated from Centaurea species. Its triethyl ether was prepared from 3,5-diethoxy-4-methoxyphenol via the corresponding acetophenone, followed by the abovementioned flavone synthesis with O-ethylvanillic anhydride. The ultraviolet spectra of these flavones will also be reported.
The Polarographic Behavior of Aliphatic Aldehydes in Buffer Solutions Containing o-Phenylenediamine
Authors: Wasa Tamotsu , Musha Sôichirô
Published: July 2006

Formaldehyde (I), acetaldehyde (II), propionaldehyde (III), n-butyraldehyde (IV), n-caproaldehyde (V), and n-octaldehyde (VI) condense with o-phenylenediamine (OPD) to yield products, each of which gives a single, irreversible but well-defined oxidation wave (E1⁄2  vs. SCE at pH 8.0: −0.240 V for I, −0.242 V for II, −0.263 V for III, −0.290 V for IV, −0.316 V for V, and −0.338 V for VI). From these findings, it has been deduced that the condensation products of aldehydes with OPD would be benzimidazoline derivatives, which would be oxidized to benzimidazole derivatives at the dropping mercury electrode. Linear relations between the limiting currents of the condensation products with OPD and the concentrations of aldehydes [(1–20)×10−4  m], except for I, were obtained under the following conditions: (pH, 6–8(pHi max); the concentration of OPD, 2×10−2  m; the temperature, 25°C; and the condensation time, 15–60 min. The method was then applied practically in the determination of the purity of a commercial product of II and the quantity of II in the presence of glyoxal.
Intrachain Force Field and Normal Vibrations of Polyethylene Glycol
Authors: Matsuura Hiroatsu , Miyazawa Tatsuo
Published: July 2006

Normal vibrations of polyethylene glycol and the perdeuterated species were treated. Intrachain force field was expressed in terms of local-symmetry coordinates. Force constants were adjusted by the method of least squares, with reference to observed infrared and Raman frequencies. A set of force constants was obtained, which reproduces the observed frequencies with an r. m. s. deviation of 0.9%. The values of the force constants thus refined were discussed in comparison with corresponding values of related molecules. Vibrational assignments of the observed infrared absorption bands and Raman lines were revised on the basis of potential-energy distributions refined in the present treatment.
The Chromium(III) Complexes with Ammoniaisopropionicdiacetic Acid
Authors: Uehara Akira , Kyuno Eishin , Tsuchiya Ryokichi
Published: July 2006

A new chelating agent—ammoniaisopropionicdiacetic acid (abbreviated as AIPDA), one of the derivatives of ammoniatriacetic acid, was prepared. Also, the following chromium(III) complexes containing AIPDA as a ligand were newly prepared: NH4[Cr(OH)(aipda)(H2O)]·4H2O (purple) (I), NH4[Cr(OH)(aipda)(H2O)2]·2H2O (green) (II), [Cr(aipda)(o-phen)]·2H2O (brown) (III), [Cr(aipda)(bipy)]·3H2O (brown) (IV), [Cr(aipda)(l-pn)] (pink) (V), [Cr(aipda)-(py)2] (Pink) (VI) and NH4[Cr(OH)(aipda)(py)]·2H2O (reddish purple) (VII), where apipda, o-phen, bipy, l-pn and py are the abbreviations of the ammoniaisopropionatediacetate ion, o-phenanthroline, 2,2′-bipyridyl, l-propylenediamine and pyridine respectively. On the basis of the chemical and thermal analyses and the measurements of the electronic absorption spectra, the reflection spectra, and the IR spectra, it was found that, in these complexes, AIPDA can behave as a terdentate or a quadridentate ligand to chromium(III), but the 1 : 2 Cr(III) AIPDA complex like the corresponding ATA one could not be obtained because of the steric hindrance resulting from the introduction of a methyl group into ATA. Further information on the conductivities in an aqueous solution and the reflection spectra suggests that V and VI are gradually aquated. The properties of the AIPDA complexes obtained in the present study were compared with those of ammoniatriacetic acid and those of ammoniapropionicdiacetic acid complexes.
Use of a Hanging Mercury Drop Electrode in the Alternating Current Polarographic Analysis of Thallium(I)
Authors: Kodama Mutsuo , Noda Tomohiko
Published: July 2006

The use of a hanging mercury drop electrode (HMDE) in the a.c. polarographic determination of thallium was studied systematically. Analysis was carried out by scanning anodically the potential of HMDE from the limiting-current potential region at a constant scanning rate and by measuring the a.c. peak-height for the anodic stripping process of thallium. Thallium could be concentrated effectively on the HMDE at the initial stage of this procedure and then stripped anodically. By employing this technique, a marked increase in sensitivity could be obtained and 1.0×10−6  m thallium(I) in an EDTA solution was determined accurately. The interference effects of lead, cadmium, zinc, and indium on the determination of thallium were also investigated. When the electrolysis was initiated in the limiting-current potential region of lead(II), the peak-height of thallium was found to be enhanced markedly.
1-Acylindoles. VI. On the Deacylation of the N′-Position’in the Formation of a 1,2,3,4-Tetrahydrocarbazole
Authors: Yamamoto Hisao , Atsumi Toshio
Published: July 2006

The cyclization reaction of cyclohexanone acetylphenylhydrazone to produce a tetrahydrocarbazole derivative has been reinvestigated. Although other workers obtained only a deacylated derivative in the reaction products, we found also an acylated product. It can be concluded from the experimental results that an acyl group of the N1-position of a phenylhydrazine derivative participates only a little in the indole cyclization and that the deacetylation occurs mainly after formation of a new C–C bond.
Calorimetric Study of the Glassy State. III. Novel Type Calorimeter for Study of Glassy State and Heat Capacity of Glassy Methanol
Authors: Sugisaki Masayasu , Suga Hiroshi , Seki S\^{y}uzô
Published: July 2006

An adiabatic Nernst-Type calorimeter with a cell for condensing a sample vapor as an amorphous state was constructed. By making use of this calorimeter, the heat capacities of the glassy, supercooled liquid, and crystalline states of methanol were measured from 20°K to 120°K. It was found that the state of methanol deposited on the chilled substrate at about 95°K from its vapor state shows a glass transition phenomenon at about 103°K accompanied with the sudden increase of heat capacity, ΔCP, amounting to 26 J/(mol°K). The drastic crystallization with the exothermic effect coming to 1.54 kJ/mol was observed near 105°K. The residual entropy for the glassy methanol was found to be 7.07 J/(mol°K). Based on these results it seems very plausible to propose that any non-crystalline solid deposited on the chilled substrate from the vapor state will show the glass transition phenomenon.
Diffuse Reflection Spectra of Some Würster Salts
Authors: Iida Yôichi , Matsunaga Yoshio
Published: July 2006

Nine Würster salts derived from p-phenylenediamine, benzidine, and their N-methyl derivatives were examined for diffuse reflection spectra and classified into three groups, namely, those showing a strong charge-transfer band similar to that in the solution’s dimer spectrum, those showing a strong α-band characteristic of the monomer and a relatively weak charge-transfer band, and, finally, those showing a spectrum which bears no resemblance to either the monomer or dimer spectrum. The mode of intermolecular interaction in these cation-radical salts was speculated upon on the basis of the spectra and the magnetic susceptibilities.
The Chelate Formation of o-Substituted Phenylazochromotropic Acids with Alkaline Earth Metals
Authors: Nakashima Susumu , Miyata Haruo , Toei Kyoji
Published: July 2006

The acid dissociation constants of phenyl, o-, m-, and p-sulfophenyl-, o-carboxyphenyl-, o-phenol- and o-arsonophenylazochromotropic acid and the formation constants of their 1:1 metal chelates with alkaline earth metals have been measured by potentiometric titration. The measurements have been carried out at 25°C and μ=0.10 (KNO3). The influence of these substituents on the acid dissociation constants of the reagents, and on the chelate formation constants was discussed. The dissociation constants of the naphtholic protons of the o-substituted reagents increase as follows: o-OH<o-AsO(OH)2<o-COOH<o-SO3NaCa>Sr>Ba, while for chelates of o-carboxyphenyl- and o-sulfophenylazochromotorpic acids the order is Mg>Ca>Sr≈Ba. The sulfonic group in o-sulfophenylazochromotropic acid, in spite of its remarkable electron-withdrawing effect, depress the acid dissociation, and form more stable barium chelate than phenyl-, m- and p-sulfophenylazochromotropic acid do. The plot of the formation constants, logK, against the sum of the dissociation constants, pKA(=pka1+pka2+pka3), was approximately linear.
The Acylation of 2,3-Dimethyl-bz-hydroxybenzofurans and the Syntheses of Di- and Tri-methylfuroisoflavones
Authors: Kawase Yoshiyuki , Nanbu Mutsumu , Miyoshi Fumihisa
Published: July 2006

The acylation of 2,3-dimethyl-4-hydroxybenzofuran (1) with acetic acid, phenylacetic acid, 2-methoxyphenylacetic acid or 2,4,5-trimethoxyphenylacetic acid, and polyphosphoric acid gave a mixture of the 5- and 7-acyl compounds (2a, b, c, d, and 3a, c, d respectively). Analogously, the isomeric 2,3-dimethyl-6-hydroxybenzofuran (6) gave the 5-acyl compounds (7a, b, c, d), two (7a, b) of which were also obtained by the Friedel-Crafts acylation of the methyl ether of 6 (9), followed by demethylation. On the other hand, the formation of a dimethylfuran ring on 2,4-dihydroxyphenyl ketones by the action of polyphosphoric acid on their 4-(α-acetylethoxy) derivatives (11a, b, c) also afforded mixtures of the ketones (7a, b, c) and isomeric ketones (2a, b, c). The benzofuranyl ketones (2 and 7) thus obtained were converted to the corresponding 4″,5″-dimethyl-furo[2″,3″:7,8]isoflavones (12b, c, d) and isomeric -furo[3″,2″:6,7]isoflavones (14b, c), and also their 2-methyl derivatives (13b, c, d and isomeric 15b, c), by the general method utilizing ethyl orthoformate, piperidine and pyridine, or acetic anhydride and sodium acetate. The furoisoflavones (12b, c and 13b, c) were also prepared by building up the dimethylfuran ring on 7-hydroxyisoflavones by the action of polyphosphoric acid or sulfuric acid on their 7-(α-acetylethoxy) derivatives (16b, c and 17b, c respectively). The alkaline degradation of these furoisoflavones (12 and 13) also gave the benzofuranyl ketones (2).
Spectroscopic Studies of Catalysis by Vanadium Pentoxide
Authors: Tarama Kimio , Yoshida Satohiro , Ishida Shingo , Kakioka Hideo
Published: July 2006

The role of the V=O bond in V2O5 in the adsorption of several gases was studied by measuring the electron spin resonance (ESR) and the infrared (IR) spectra. The ESR spectra of V2O5 supported on γ-Al2O3 were similar to those of VOSO4 on γ-Al2O3. When such electron-donating gases as CO, SO2 and C2H4 were adsorbed on this V2O5-γ-Al2O3, the signal intensity of ESR increased and the splitting of the h.f.s. became clear. Upon treatment with an electron-accepting gas such as O2, a reverse change was observed. In the case of V2O5 supported on SiO2, similar ESR spectra were observed by the adsorption of CO after a mild reduction. The IR spectra of V2O5 have a sharp absorption peak at 1023 cm−1 due to the stretching vibration of the (V=O)3+ bond; this peak became broader by adsorption of such gases as CO and SO2. Simultaneously, the center of the peak shifted to the red region and a weak hump appeared at 980–990 cm−1, probably due to (V=O)2+. These results of the ESR and IR measurements reveal that these electron-donating gases are adsorbed on the (V=O)3+ bonds on the surface of V2O5, and that the increase in electron densities in the adsorption sites results from adsorption of these gases. Furthermore, the role of this (V=O)3+ bond in oxidation reaction was also discussed.
Macro Rings. II. Synthesis of [2.1.1.1.1]Paracyclophane
Authors: Inazu Takahiko , Yoshino Tamotsu
Published: July 2006

A macrocyclic compound which incorporates five benzene rings and intervening methylene bridges as parts of a large ring structure, [2.1.1.1.1]paracyclophane I (n=2), was synthesized and then compared with a corresponding open-chain analog, X.
The Behavior of Radical Anion of Acridine as Revealed from ESR Studies
Authors: Niizuma Shigeya , Okuda Michio , Koizumi Masao
Published: July 2006

Nature of acridine anions produced by the addition of alkali metals to the tetrahydrofuran solutions of acridine has been studied by means of ESR and VU spectra. In excess of acridine (A), a green species G is produced. This has been identified as A−Na+ (or A−K+  etc.). A−Na+ gives under suitable conditions, ESR spectra with hfs consisting more than fifty lines. This species reverts to acridine upon addition of a small quantity of water or ethanol. With the fall of temperature, the intensity of ESR spectra of G decreases remarkably and accompanied with it, UV spectra of G also decline with no change of the spectral shape, logIvs. 1/T plots where I is either the intensity of UV absorption or of the ESR signal are satisfactorily linear; this has been interpreted to be due to a large equilibrium constant of the process, 2A− Na+\ightleftarrows(Na+A−)2 in which (Na+A−)2 is a colorless diamagnetic substance. This interpretation has led to the value of enthalpy of dissociation of (Na+A−)2 as ca. 14 kcal. When sodium is in excess, a diamagnetic violet species is produced. This has been assigned as Na+A2−Na+. The chemical processes pertaining to A−Na+ and Na+A2−Na+ can be summarized as follows:

(Remark: Graphics omitted.)
Structure and Reactivity of α,β-Unsaturated Ethers. IV. The Effects of Ring Substituents on the Acid-Catalyzed Hydrolysis Rate of Phenyl Vinyl Ether
Authors: Fueno Takayuki , Matsumura Itaru , Okuyama Tadashi , Furukawa Junji
Published: July 2006

The rates of hydrolysis of various ring-substituted phenyl vinyl ethers, CH2=CHOC6H4X, have been measured in 80 : 20 dioxane-water containing hydrochloric acid as catalyst. The ring substituents investigated include H, p-CH3O, m-CH3O, p-CH3, m-CH3, p-Cl and m-Cl. The reaction was first order with respect to both the acid and the ethers. It has been found that the effect of substituents on the hydrolysis rates obeys the Hammett ρσ relationship with the reaction constant ρ=−2.21 at 35°C. These results are compatible with the previous conclusion that the acid-catalyzed hydrolysis of alkenyl ethers involves the rate-determining protonation of the ethers at their β-carbon atom, to form intermediate oxycarbonium ions. It has been shown that the observed substituent effect can be rationalized from the π-electronic energy changes of the ethers on protonation, which have been calculated by an empirical molecular orbital method.
Metal Complexes with Amino Acid Amides. I. Preparations and Electronic Spectra of the Nickel(II) and Palladium(II) Complexes
Authors: Komorita Takashi , Hidaka Jinsai , Shimura Yoichi
Published: July 2006

Several planar bis(amino-acid-amidato) complexes of nickel(II) and palladium(II) have been newly synthesized and characterized mainly spectroscopically. The geometrical structures of these [M(N)4]-type complexes have been determined: palladium(II) produced both cis and trans complexes with l-alanine- and l-leucine-amidate ligands, while nickel(II) did only trans forms with glycine-, l-alanine- and l-leucine-amidates. Nickel(II) also produced cationic complexes, Ni(l-alanine-amide)2SO4 and its glycine amide analogue. The circular dichroism spectra and rotatory dispersion of the complexes containing optically active amino acid amide have been measured and discussed as for the assignments of the ligand field absorption bands of the diamagnetic planar complexes. A good correspondence was observed between the circular dichroism spectra of the nickel(II) and the palladium(II) complexes.
Solvent Effects on ρ Values of the Hammett Equation
Authors: Kondo Yasuhiko , Matsui Takeki , Tokura Niichiro
Published: July 2006

The effects of selvents on ρ values have been systematically treated as a two-variable problem within a linear free-energy relationship framework. It is assumed that the standard activation free energy is a continuous function of σ, a substituent variable, and ξ, a solvent variable. The applicability of the resultant equations is proved by a test of the dissociation constants (obtained from the literature) of benzoic acids in various solvents. As a result, it is proposed that these effects on ρ values can be explained in terms of the interaction or cross-term of σ and ξ. The application to the reaction rates of a typical Menschutkin reaction, obtained by experiments in ten nonaqueous solvents, suggests that the solvent dependence in these reactivities is much more complicated.
A Study of the Solvent Effect on the Polymerization of N-Phenylethyleneimine
Authors: Kagiya Tsutomu , Kondo Tomizo , Nakao Kozo , Fukui Kenichi
Published: July 2006

The effect of solvents on the cationic polymerization of N-phenylethyleneimine with formic acid catalyst has been studied quantitatively. The polymerization rates in the various solvents used increase in the following order: diethyl ether\simeqtetrahydrofuran<toluene\simeqcarbon tetrachloride<anisole<methyl acetate<ethylene dichloride<N,N-dimethylacetamide<dimethyl sulfoxide<epichlorohydrin<acetonitrile. In polar solvents with high dielectric constants, the rates are much larger than those in nonpolar solvents with low dielectric constants. However, in the solvents with similar dielectric constants, such as acetonitrile and N,N-dimethylacetarnide, ethylene dichloride, methyl acetate and tetrahydrofuran, and anisole and diethyl ether, the rates decreased with an increase in the nucleophilicity of the solvents, and the dependence of the polymerization rate on the nucleophilicity of the solvents is much larger in polar solvents than in nonpolar solvents. The propagation rate was markedly influenced by the nature of the solvent, whereas the initiation rate was only a little influenced.
Syntheses and Reactions of Functional Polymers. XLV. Synthesis and Properties of Poly(N-glycidyl-2-oxazolidone)
Authors: Endo Takeshi , Numazawa Ryozo , Okawara Makoto
Published: July 2006

N-Glycidyl-2-oxazolidone was synthesized by the reaction of N-sodium-2-oxazolidone with epichlorohydrin. N-Glycidyl-2-oxazolidone was polymerized with such Lewis acids as boron trifluoride etherate and aluminum chloride to give a white powder. These polymers adsorbed phenol and methyl bromide effectively. In addition, the copolymerization of N-glycidyl-2-oxazolidone with styrene was carried out, and the amount of the adsorption of methyl bromide on the copolymers was measured. The amount of the adsorption of methyl bromide increased in the copolymers as the content of 2-oxazolidone moiety increased. A 1 : 1 molar complex of stannic chloride with N-glycidyl-2-oxazolidone was isolated; when the complex was heated, poly(N-glycidyl-2-oxazolidone) was obtained quantitatively.
Studies of the Derivatives of Epichlorohydrin. III. A New Method of Preparing γ-Alkoxy-γ-butyrolactones
Authors: Kuwamura Tsunehiko , Takahashi Hideo
Published: July 2006

When alkyl glycidyl ethers derived from epichlorohydrin and alcohols were treated with sodium cyanide, the corresponding γ-alkoxy-β-hydroxybutyronitriles (I) were obtained. The hydrolysis of I with aqueous alkali metal hydroxide, followed by acidification and distillation, gave γ-alkoxy-γ-butyrolactones (II). The structure of II was confirmed by chemical and physical means. The reaction paths of I to II were also studied.
Effects of Substituents on the Chain-transfer Reactivities of Nuclear-substituted Benzaldehydes to Polymer Radicals
Authors: Yamamoto Tadahiro , Hasegawa Masaru , Otsu Takayuki
Published: July 2006

In order to study the effect of substituents on the chain-transfer reactivities of nuclear-substituted benzaldehydes toward polymethyl methacrylate (poly-MMA) and polystyryl (poly-St) radicals, the chain transfer constants (C) of six kinds of benzaldehydes in radical polymerizations of these monomers were determined at 60°C. The C values of all the substituted benzaldehydes toward the poly-MMA radical were larger than that of unsubstituted benzaldehyde, regardless of the electron-repelling or electron-attracting nature of the substituents, while those toward the poly-St radical increased with an increase in the electron-attracting nature of the substituents. The relative reactivities toward the poly-MMA radical could not be correlated with the ordinary Hammett equation, but they could be with this modified equation: log(k⁄k0)=ρσ+γER, with ρ=+0.2 and γ=0.7. On the other hand, the relative reactivities toward the poly-St radical also fit a modified Hammett equation with ρ=+1.4 and γ=0.65.
Studies on Telomerization of Vinyl Chloride with Carbon Tetrabromide
Authors: Asahara Teruzo , Chou M C
Published: July 2006

The radical telomerization of vinyl chloride with carbon tetrabromide was investigated. The telomers with n=1 and 2 in Br(CHClCH2)nCBr3 were isolated and identified. The molecular weight distribution of the telomers was determined by thin-layer chromatography (TLC), and it was found that the distribution varied a little with the variation of reaction conditions. From the results of the TLC, the chain transfer constants (Cn) of polylvinyl chloride radical to carbon tetrabromide were calculated, and a monotonous increase in Cn with the increasing n was found. The effects of initial ratio of vinyl chloride to carbon tetrabromide, reaction time and temperature on the conversion of vinyl chloride and the average molecular weight of the telomer were investigated. Bromoform was also used as a telogen instead of carbon tetrabromide, and the results were compared in both systems.
Molecular Orbital Treatment of Nitric Oxide Radicals. III. Spin Distributions and g Factors of Aromatic Nitric Oxide Radicals
Authors: Kikuchi Osamu
Published: July 2006

The spin distributions and g factors have been calculated for seveial aromatic nitric oxide radicals. The spin distributions calculated by the open-shell SGF method with configuration interaction, and by the unrestricted SCF method with the annihilation of the quartet component from the single determination wave function, agreed with the experimental values estimated from the ESR spectra. The contributions of the lone-pair orbital of the oxygen and of the N–O σ-bonding orbital to the g factor were calculated, the calculated g factors in solution being in the range of 2.005–2.006; these values were then discussed on the basis of the electronic structures of nitric oxide radicals.
The Reactions of a Mixture of Benzene and cis-2-Butene Photosensitized by Cadmium
Authors: Tsunashima Shigeru , Satoh Shin , Sato Shin
Published: July 2006

Using the cadmium-photosensitized cis-trans isomerization of cis-2-butene, the lifetime of triplet benzene has been estimated to be of the order of 10−5 sec for both benzene-d0 and -d6. This technique provides a new method for measuring the lifetime of the triplet state of some molecules.
Electrodeposition of Water-soluble Resin by a Constant Voltage or by Pulses
Authors: Nakamura Yoshio , Oki Fumio , Nozaki Hiroshi
Published: July 2006

The mechanism of deposition was investigated using maleic-linseed oil as a sample. The deposition was made by a constant voltage or by continuous pulses with high voltages, and the initial current-time relations were observed by means of a synchroscope. When we applied pulses with α⁄β values which were smaller than a value, the current decreased gradually after some time and a deposited film was found on the anode, but the decreases in the current was not found for a long time when the value of β was much larger than the value of α. The induction time was found from the current-time curve observed during a constant voltage deposition. These results were discussed from the standpoint that the deposited film is formed by coagulation resulted from ionic combination with hydrogen ions.
Reactions of Nickel(II), Copper(II) and Palladium(II) Complexes of Bis(acetylacetone)ethylenediimine with Nitric Oxide
Authors: Masuda Isao , Tamaki Motonori , Shinra Koichiro
Published: July 2006

Through reaction with nitric oxide, divalent Ni, Cu, and Pd complexes of bis(acetylacetone)-ethylenediimine have been shown to yield fine crystalline compounds of the general formula M(C12H17N3O3), where M=Ni or Cu, and of M(C12H16N4O4) where M=Ni, Cu or Pd, depending on experimental conditions. They are insoluble in water. The former compounds are rather soluble in common organic solvents, but the latter are sparingly soluble, except in pyridine. On the basis of analytical data and IR-spectral analyses, they are thought not to be nitrosyl metalcomplexes but oxime type complexes.
Ionic Equilibria in Mixed Solvents. IV. Solvent Effect on Dissociation Constants of Acids
Authors: Ohtaki Hitoshi
Published: July 2006

Equilibrium of hydronium ions with alkoxonium ions in water-alcohol mixtures being taken into account, solvent effects on dissociation constants of acids were quantitatively interpreted by the following: free energy changes on transferring ions from an aqueous solution to a mixed solvent and difference in standard states in different solvent compositions. Choosing suitable values for effective ionic radii for ions involved, satisfactory agreements were found between experimental and calculated values of ΔpK, the difference of pK in water and in an aqueous mixture, for positively charged acids (e.g., ammonium, anilinium, etc.) as well as neutral acids yielding a negatively charged conjugate base (e. g., acetic acid, benzoic acid, p-nitrophenol, etc.).
Spectroscopic Studies of the Structures of the Dimer of Diethylaluminum 2-Aminoethoxide (AlEt2OCH2CH2NH2)2 and Related Compounds
Authors: Sato Hideo , Tarao Ryokichi , Higashi Hiromi
Published: July 2006

The infrared and proton nuclear magnetic resonance spectra of the solutions of diethylaluminum 2-aminoethoxide (AlEt2OCH2CH2NH2)2 and related compounds were measured. The infrared frequencies and intensities of the NH2 stretching, scissors, and rocking vibration bands, and the NMR internal chemical shifts of the ethyl groups attached to the aluminum atom were compared with the corresponding data of suitable model compounds. It was concluded by taking the results of these experiments into consideration that (AlEt2OCH2CH2NH2)2 was represented by the structural formula I with two Al←NH2 coordination bonds. Similarly, most of the related compounds studied were reasonably represented by the formulas with two Al←NRR′ coordination bonds, while (AlEt2OCH2CH2N(C6H11)2)2 was assumed to be represented by formula III with two Al←O coordination bonds, exceptionally.
Synthesis of Adamantane Derivatives. III. Synthesis of Adamantane Heterocycles
Authors: Sasaki Tadashi , Eguchi Shoji , Toru Takeshi
Published: July 2006

Preparation of 1-adamantyl and adamantane-1-carbonyl derivatives having benzimidazole, 1,3,5-oxadiazole, oxazoline-2, quinoxaline, 2-aminothiazole, thiazolone, 2-methylthiazole, 1,2,3-thiadiazole, pyrazole or pyrazoline ring is described.
Reactions of α-Cyano-β-methoxy-β-alkylacrylic Esters with Hydrazine and Hydroxylamine
Authors: Baba Hideo , Hori Isaburo , Hayashi Toshio , Midorikawa Hiroshi
Published: July 2006

α-Cyano-β-methoxy-β-alkyl (Me, Et, n-Pr, n-Bu, n-Am, and i-Bu)-acrylic esters (I) react with hydrazine to give β-hydrazino intermediates. The hydrazino group of these intermediates is cyclized preferentially between its terminal NH2 and the cyano group in a neutral or acidic medium to give 5-aminopyrazole derivatives, and preferentially between the terminal NH2 and the ester group in the presence of a base to give 5-pyrazolone derivatives. When the β-alkyl of I is isopropyl, t-butyl], etc., I affords only the 5-pyrazolone derivatives in the reaction with hydrazine. The reactions of I with hydroxylamine gave 5-aminoisoxazole derivatives, but in the case of the β-t-butyl derivative of I they gave 5-aminoisoxazole accompanied by the 5-isoxazolone derivative.
Syntheses of Pterocarpans. III. Synthetic Analogues of Neodulin
Authors: Fukui Kenji , Nakayama Mitsuru , Harano Teruo
Published: July 2006

4′,5′-Dimethoxy-2′-hydroxyfurano[3″,2″:6,7]isoflavone was obtained from isoelliptol isoflavone by selective demethylation with boron tribromide. The treatment of the 2′-hydroxyisoflavone with sodium borohydride in absolute alcohol - tetrahydrofuran afforded 8,9-dimethoxyfurano[3′,2′:2,3]pterocarpan. 8,9-Dimethoxyfurano[2′,3′:3,4]pterocarpan was prepared from elliptol isoflavone by a similar procedure.
Photoreversible Photographic Systems. V. Reverse Photochromism of (Photospiran/Acid) System in Acetone
Authors: Shimizu Isamu , Kokado Hiroshi , Inoue Eiichi
Published: July 2006

1,3,3-Trimethylindolino-6′-nitro-benzopyrylspiran (1) exhibits a photoreversible color change which is called “photochromism”. However, it is transformed from a colorless form (A) into a colored form (C) which has a salt-like structure when acid such as malonic acid is added into acetone without irradiation with light. The color is bleached by irradiation with light. The color reappears thermally as the light source is removed. This photoreversible color change is termed “reverse photochromism”. Another colored form (B) of compound (1) which has a merocyanine dye-like structure is converted into (C) as acid is added into the solution (B). The quantum yield of the photoconversion from C to A by irradiation with visible light depends on the solvent polarity. The quantum yield of the photoconversion from A to B also depends on the solvent polarity.
Freezing of the Droplets of Aqueous Solution Aerosols
Authors: Uzu Yuhei , Sano Isamu
Published: July 2006

By atomizing aqueous solutions both of electrolytes and non-electrolytes, fog droplets of 8μ in diameter were prepared, and their freezing temperatures were measured in a thermostat-like cold chamber fitted with an electrically heated platinum wire. The results were compared with that obtained with fog droplets of pure water of the same size. It was found that non-electrolytes hardly influence the freezing, whereas electrolytes do a great deal. The freezing temperature rises in the presence of an electrolyte and varies with its concentration, the highest temperatures being observed at the concentrations around 1×10−4m for 1-1 type electrolytes and at lower concentrations for 1-2 and 1-3 type electrolytes. K+ is the most effective of the alkali metal cations having the same species of anion in common, and I− of the halide anions having the same species of cation in common. Applying the theory of nucleation, the sizes of the hydrated K+ and the critical nucleus developed from it for ice-nucleation were estimated to be about 6 and 21 Å in radius, respectively.
The Crystal Structure of 5,5-Dimethyl-2-oxo-2-hydroxy-1,3,2-dioxaphosphorinane Monohydrate
Authors: Murayama Wataru , Kainosho Masatsune
Published: July 2006

The crystal structure of 5,5-dimethyl-2-oxo-2-hydroxy-l,3,2-dioxaphosphorinane monohydrate (I) has been determined by the three dimensional X-ray diffraction method. The crystals belong to monoclinic system, with space group P21. The unit cell dimensions are; a=9.50, b=5.86, c=8.31 Å, β=106°8′, and two molecules per unit cell. The six-membered dioxaphosphorinane ring has a chair conformation, with P=O bond in equatorial position. The bond angles and distances of the phosphate group are similar to those found in the corresponding acyclic phosphates.
A Theory of the Gel-forming Polymerization of Polyvinyl Compounds
Authors: Fukui Kenichi , Yamabe Tokio
Published: July 2006

A theory of the molecular-size distribution of the cross-linked polymers to be formed from a mixture of vinyl monomers with a distribution of functionalities by radical polymerization is presented. It is assumed that all the unconverted vinyl groups are equireactive to the propagation, which proceeds without 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. The general theory is applied to three practical cases; the curing reaction of unsaturated polyesters, the polymerization of polyvinyl compounds, and the copolymerization of vinyl and divinyl compounds.
The Dipole Moments of Diphenyl Sulfide, Sulfoxide, Sulfone, and Their Derivatives
Authors: Toshiyasu Yoshio , Taniguchi Yoshio , Kimura Ko , Fujishiro Ryoichi , Yoshihara Masakuni , Tagaki Waichiro , Oae Shigeru
Published: July 2006

The electric dipole moments of diphenyl sulfide, sulfoxide, and sulfone and their derivatives were determined in benzene solutions at 25°C. The observed moments are used to estimate the mesomeric moments on the assumption of the vector addition of group moments. The mesomeric moments of the phenylmercapto, phenylsulfinyl, and phenylsulfonyl groups are estimated to be −0.12, 0.10, and 0.44 D, respectively. The steric effect of ortho-substituents is also discussed on the basis of the dipole moment data.
Secondary Structure of Poly-l-arginine and Its Derivatives
Authors: Hayakawa Tadao , Kondo Yoshiyuki , Yamamoto Hiroyuki
Published: July 2006

The conformations of poly-Nω,ω′-dicarbobenzyloxy-l-arginine, poly-Nω-carbobenzyloxy-l-arginine, and poly-L-arginine hydrobromide were studied by means of their infrared spectra (IR), X-ray photographs, optical rotatory dispersions (ORD), and circular dichroisms (CD). The presence of the α-helical conformation in poly-Nω,ω′-dicarbobenzyloxy-l-arginine and poly-Nω-carbobenzyloxy-l-arginine was confirmed by X-ray photographs and by their IR spectra. The ORD and the CD curves of these polymers were found to be characteristic of the α-helical conformation. It was also found that these polypeptides have a random coil conformation in trifluoroacetic acid. In the (2-chloroethanol : trifluoroacetic acid) solvent system, the typical helix-coil transition of poly-Nω-carbobenzyloxy-l-arginine was observed at 20–30% trifluoroacetic acid. The ORD and the CD curves of poly-l-arginine showed that the polymer took a random coil structure in the pH range from 2.7 to 11.0. However, when the pH is increased from 11.0 to 11.5, the spectra gradually change into the α-helix structure. Moreover, the polypeptide predominantly took the α-helix structure at pH 12.5. From the ORD and CD data, the polypeptide can be considered to have a right-handed α-helix conformation.
Reactions of Cycloalkanone Oxime p-Toluenesulfonates
Authors: Sato Tadashi , Wakatsuka Hirohisa
Published: July 2006

The reactions of cyclohexanone and cyclopentanone oxime p-toluenesulfonates were studied. It was found that cyclohexanone oxime p-toluenesulfonate (IIIa) afforded a tetrahydroazepine derivative (Va), while cyclopentanone oxime p-toluenesulfonate (X) afforded δ-valerolactam p-toluenesulfonate (XIII), when both compounds were heated in benzene.