bluuebunny/crossref_metadata_2025 huggingface dataset:
The Infrared Spectra and Some Properties of Tris-(acetylacetonato) Lanthanide(III) Complexes
Authors: Misumi Seizo , Iwasaki Noriko
Published: July 2006

The infrared spectra of tris-(acetylacetonato) complexes of praseodymium(III), neodymium-(III), europium(III), gadolinium (III), dysprosium(III), and erbium(III) have been measured in the range between 4000 and 100 cm−1 in order to obtain information about the nature of lanthanide metal-oxygen bond; some properties of these complexes were studied, also. The calculated frequencies and assignments were used to elucidate the complex spectra and to show the relations between the calculated force constants and some physicochemical properties. Although the molecules of each complex were 1 : 3 complexes, the calculation of the vibrational frequencies was made by using a simplified model of the 1 : 1 complex (C2v), because it may be supposed that this tris-(acetylacetonato) complex does not always have a regular octahedral symmetry in spite of the composition of Ln(acac)3. The calculated frequencies were in good agreement with the observed ones; the lanthanide metal-oxygen stretching vibrations were found at 420–432 cm−1 (A1-ν5) and 304–322 cm−1 (B1-ν14). The lanthanide metal-oxygen stretching force constant increases with an increase in the atomic number, while the corresponding C=O stretching frequency (A1-ν1) decreases in the same order. For example, the values of K(Pr–O) and K(Er–O) are 2.10 and 2.29 md/Å respectively. As the result of the lanthanide contraction, the force constant of the lanthanide metal-oxygen bond increases with a decrease in the M–O bond length, thus increasing the stability constant, log β, and slightly increasing the electronegativity.
The Yields of Radioactivities Induced by (γ, n) Reactions with 20 MeV Bremsstrahlung
Authors: Oka Yoshinaga , Kato Toyoaki , Nomura Koichi , Saito Tatsuya
Published: July 2006

The yields of radioactivities resulting from the (γ, n) reactions on 37 elements covering the periodic table have been determined by means of 20 MeV linear accelerator bremsstrahlung and gamma-ray spectrometry. The yield values, as measured in the number of photodisintegrations per mole per roentgen for each of the (γ, n) reactions, increase in the main regularly with atomic number from 103 through 107 order of magnitude. Anomalously small yield values are obtained in the irradiation of the nuclides with neutron or proton number of the magic numbers. The present results permit studies of general behavior of the photoneutron reactions and of the application of their products to the photoactivation analyses of many elements distributed throughout the periodic table.
The Hunsdiecker Reaction of Silver Acrylate and Methacrylate
Authors: Furukawa Shu , Naruchi Kiyoshi , Matsui Shigetake , Yuuki Michio
Published: July 2006

The Hunsdiecker reaction of silver acrylate and methacrylate has been investigated; 1, 1, 2-tribromoethane was obtained from the former, and bromoacetone from the latter. Since bromoacetone has also been obtained by the reaction of 2-bromopropene-l with acetyl hypobromite, it is conceivable that, in the case of the Hunsdiecker reaction of silver methacrylate, methacryloyl hypobromite (the intermediate of the Hunsdiecker reaction) oxidized 2-bromopropene-l (the primary product of the Hunsdiecker reaction) to bromoacetone, with an accompanying rearrangement of the bromine atom.
Reactions of Triethylaluminum with Electron Donors
Authors: Takashi Yûkichi
Published: July 2006

As a study of the roles of the electron-donor compounds in the three-component Zieglertype catalysts, the reactions of triethylaluminum with various electron donor compounds, e. g., triethylamine, pyridine, diethyl ether, tetrahydrofuran, dioxane, and triethylstibine, have been investigated by means of the proton magnetic resonance. The internal chemical shifts between the α- and β-protons of the substituent groups bound to key atoms in the reaction mixtures have indicated that (1) each donor gives only one type of complex which is ordinarily expected, and (2) the coordination of the donor to triethylaluminum lowers the electronegativity of the aluminum atom. Qualitative information about the ligand exchange reactions of the donor complexes has also been obtained. All the complexes obtained showed remarkable electrical conductivities, indicating ionic structures.
Kinetic Studies of Solvolysis. XIII. The Solvolyses of Optically-active α-Phenylethyl Chloride in Binary Mixtures of Phenol and Water—The Sn1 Hydrolysis with the Retention of the Configuration
Authors: Okamoto Kunio , Hayashi Masayuki , Komatsu Koichi , Shingu Haruo
Published: July 2006

The competitive Sn1 hydrolysis and Sn1 phenolysis of optically-active α-phenylethyl chloride in aqueous phenols (75 to 90 wt% phenol) give partially-retained α-phenylethyl alcohol and α-phenylethyl phenyl ether in the presence of added triethylamine at 14 and 30°C. The extent of the retention of the configuration is almost independent of the reaction temperature, whereas it shows a tendency to increase from 13 to 23% for the alcohol and from 5 to 20% for the ether with an increase in the phenol concentration. A predominant four-center (Sni-like) attack of a water molecule, with the assistance of a specific solvation of phenol molecules, has been suggested as a possible interpretation for the unusual hydrolysis with a retained steric course for this simple secondary alkyl system. In connection with the nature of the specific solvation of phenol molecules, the applicability of the concept of the back-side shielding of the Sn1 ion-pair intermediate by a phenol molecule has been discussed.
The Redistribution Reaction of Ethyl Groups and Chlorine Atoms in the Ethylaluminum Chloride + Ether System
Authors: Tarao Ryokichi , Takeda Saburo
Published: July 2006

The redistribution reactions of ethyl groups and chlorine atoms in the 2AlEtnCl3−n+ether system were studied by the Raman spectroscopic method. It was found that the reaction of AlEtCl2 with Et2O (molar ratio, 2:1) gave rise to AlEt2Cl and AlCl3·Et2O, although not quantitatively. On the contrary, the reaction of AlEt2Cl with Et2O (molar ratio, 2:1) did not produce any AlEt3 or AlEtCl2·Et2O at all. These and several related observations demonstrate that, by the reaction between AlEtnCl3−n and AlEtmCl3−m·Et2O (n, m=0, 1, 2, 3), AlEt2Cl is preferentially produced as long as there is any possibility of its formation.
Formation of Complexes from Azobenzenes and Cyclopentadienyl Cobalt Derivatives
Authors: Joh Takashi , Hagihara Nobue , Murahashi Shunsuke
Published: July 2006

New complexes (III) have been found to be formed in the reaction between aromatic azo compounds and cyclopentadienyl cobalt derivatives. The same complexes have also been obtained from the reaction of o-quinonediimine or o-phenylenediamine derivatives with cyclopentadienyl cobalt dicarbonyl. These complexes reacted with carbon monoxide to yield benzimidazolone derivatives, and with hydrogen to give o-phenylenediamine derivatives. The structure of the complexes has been formulated on the basis of the infrared spectra, the proton magnetic resonance, and chemical evidence.
Thermische Zersetzung von Benzoylphenylacetylperoxyd in Lösung
Authors: Suehiro Tadashi , Tsuruta Hideki , Hibino Shuji
Published: July 2006

Benzoylphenylacetylperoxyd zersetzt sich in Benzol anscheinend nach 1. Ordnung und bei 25°C erhält man Geschwindigkeitkonstant, Aktivierungsenergie und Aktivierungsentropie je (2.05±0.04)×10−4 Sek−1, 21.7 kcal·Mol−1 und −5.0 cal·Grad−1. Die Bildung von freien Radikalen während der Zersetzung beträgt, nach der spektroskopischen Bestimmung mittels Diphenylpikrylhydrazyl, erst unter 10 Mol%. Produktenanalyse der Umsetzung vom Peroxyd in Lösung durch Gaschromatographie zeigt das Auftreten von Benzyl-Kation und die monomolekulare Entstehung von Benzoesäurebenzylester, und durch Infrarot-Spektrum, die Bildung von Benzylkohlensäurebenzoesäureanhydrid. Die Zersetzung wird beschleunigt durch Säure unter gleichzeitiger Zunahme des Produktes Diphenylmethanderivates in Aromaten mit Elektron-Donator Substituent, und auch durch die Poläritat von Lösungsmitteln. Alle diese bedeuten, dass Peroxyd zerfällt in keiner normaler Weise der homolytischen Spaltung von O–O Bindung, sondern zersetzt sich in drei parallel laufenden Reaktionen 1) zum Benzyl-Kation, 2) zum Benzoesäurebenzylester und 3) zum Benzylkohlensäurebenzoesäureanhydrid in ungefähr gleichen Massen.
The Structural Change in Zinc Oxide in the Process of Mechanical Treatment
Authors: Takahashi Hiroshi , Tsutsumi Kazuo
Published: July 2006

The structural change in zinc oxide by mechanical treatment was studied. In the process of the mechanical treatment of zinc oxide, the crystallite size and the lattice distortion as measured by the X-ray diffraction method, the specific surface area as measured by the BET method, and the density as measured by a pycnometer changed monotonously with the treatment time. Such monotonous changes correspond to a primary structural change in zinc oxide.
ESR Study of the Ion Pairs of the Phthalonitrile Anion with Alkali Metals
Authors: Nakamura Kazuo , Deguchi Yasuo
Published: July 2006

From the ESR spectroscopic point of view, there are two distinct species of ion pairs of the phthalonitrile anion with the lithium ion in ethereal solvents. One corresponds to the locating of the cation in close proximity to a cyano group. Its ESR spectrum exhibits the loss of twofold symmetry in the spin distribution on the anion (spectrum I) or an alternating line width (spectrum II), depending on the transfer rate of the cation between the two cyano groups. The other species refers to the locating of the cation probably in the spacing between the two cyano groups. The appearance of its spectrum (spectrum III) is similar to that of the free anion. The DME or THF solution gives spectrum II; the ethyl ether solution, spectrum III, and the THP or MeTHF solution, the superposition of spectrum I or II upon III. A similar two species are found in the sodium ion pair. The negative spin density at the meta-carbon atom to the cyano group where the cation is located has been found. The solvent and the temperature effects on the alkali metal splittings, a semi-quantitative treatment of the alternating line width, and the variations in the proton and nitrogen coupling constants are also described.
The Addition Reactions of Ethanol to Ethylene Induced by Gamma-ray Irradiation in the Gaseous Phase. II. A Kinetic Analysis of the Results
Authors: Kurihara Hirondo , Hotta Hiroshi
Published: July 2006

In order to analyze the results obtained in Part I (H. Hotta and H. Kurihara, Bull. Chem. Soc. Japan, 40, 714 (1967)), a general kinetic expression for the system which involves side chain reactions is derived by a modification of the Gale and Wagner method (J. Am. Chem. Soc., 86, 4531 (1964)) on the basis of the G-values without the steady-state approximation. By the use of this expression, the chain transfer constants are found to be C1′=0.093 and C2′=0.074 in the gaseous phase, and about C1′=0.007 in the liquid phase. These values are compared with the reported chain transfer constants for related systems.
Thermodynamics of the Hydroxymethylation of Melamine and Urea with Formaldehyde
Authors: Sato Kenji
Published: July 2006

The hydroxymethylation of melamine and urea with formaldehyde in an aqueous solution was studied thermodynamically. The entropy, enthalpy, and free energy of activation for the early stages of the reaction, i. e., the formation of mono-methylol derivatives, and also the changes in the entropy, enthalpy, and molecular heat, etc., were determined in connection with the functionalities. It was confirmed that no marked differences exist between the rate constant of melamine and that of urea, but that the ΔS\eweq and ΔH\eweq values of urea are considerably smaller than the respective values of melamine. Prominent differences do exist between ΔS and ΔH\eweq, the ΔS\eweq and ΔH\eweq terms of melamine amount roughly to 105 times and 105 times those of urea respectively, regardless of the functionalities. These results imply a conspicuous difference between their reaction mechanisms, a difference which is explicable in terms of the characteristics of their amino-group nitrogen. Besides, the solvent effect of dimethylsulfoxide in the hydroxymethylation of melamine was investigated; it will be discussed in connection with the solvation.
Extraction of Scandium(III) with Tri-n-butyl Phosphate from Chloride Solutions
Authors: Morris D F C , Sutton K J
Published: July 2006

The distribution of scandium(III) between tri-n-butyl phosphate and aqueous solutions containing chloride has been measured using 46Sc as a tracer. The extraction of anionic scandium chlorocomplexes seems to be unimportant in the systems studied and it appears that different solvates of the trichloride ScCl3 can exist in tributyl phosphate extracts.
Studies of the Complex Formation between Uranium and Thiosalicylic Acid
Authors: Kumar A N , Nigam H L , Katyal M
Published: July 2006

Orange-yellow coloured complexes formed by the interaction of uranium and thiosalicylic acid in 40% ethanol have been investigated by spectrophotometric, potentiometric, and magnetic susceptibility measurements. Spectrophotometric studies reveal that a 1 : 1 complex is mainly formed below pH 4.5, while at higher pH’s (5.5) a 1 : 2 (metal : ligand) complex is mainly formed. Magnetic susceptibility measurements point towards the diamagnetic character of the complexes. The stereochemical configuration of the complex ions has been discussed.
Simple Malonate and Maleate Complexes of Oxovanadium(IV)
Authors: Sathyanarayana D N , Patel C C
Published: July 2006

Oxovanadium(IV) malonate tetrahydrate, VO(malon)·4H2O and oxovanadium(IV) maleate dihydrate, VO(mal)·2H2O are prepared and characterised. Magnetic moments agree with quadrivalent vanadium. The differential thermal analysis and infrared spectra of both the complexes have been studied. Molar conductance, molecular weight by cryoscopic method and the electronic spectrum of the malonate have also been obtained. A comparison of oxalate, malonate and maleate complexes of the type VO(LL)·x H2O (LL, being one of the bidentates) is attempted to arrive at a series from cryoscopic data, thermal decomposition temperature and vanadium-oxygen stretching frequency. The series obtained showing the ‘stability’ is: oxalate>malonate>maleate and is expected to be the same as the naphelauxetic series.
The Chemistry of Protactinium. III. A Study of the Sulfate Complex of Protactinium(V) by the Solvent Extraction Technique Using TTA as the Chelating Agent
Authors: Mitsuji Toshikazu , Suzuki Shin
Published: July 2006

The behavior of pentavalent protactinium in sulfuric acid solutions was investigated by paper electrophoresis and by the TTA-benzene extraction method. From the results of this investigation, it is recognized that the Pa(OH)2(SO4)+ ion exists predominantly in dilute sulfuric acid solutions (pH 0.4–2.2), and that the complexing reaction of pentavalent protactinium by the sulfate ion may proceed as;

Pa(OH)4++2H++SO42−\ightleftarrowsPa(OH)2(SO4)++2H2O.

The stability constant of Pa(OH)2(SO4)+ was also determined by the solvent extraction method to be 6.4 at an ionic strength of 1.38.
Some Aspects of Solid State Reactions between Oxides
Authors: Yamaguchi Goro , Tokuda Toshio
Published: July 2006

Solid state reactions in air between two oxide pieces of a single crystal or a polycrystal were conducted and observed; the couples were MgO and Al2O3,ZnO and Al2O3,MgO and Fe2O3,MgO and Cr2O3, MgO and SiO2, MgO and TiO2, and CoO and TiO2. In all the reactions except the MgO-Fe2O3 reaction, the two pieces were easily separated after the reaction. Moreover, in all the reactions except the MgO-SiO2 reaction, the reacted substances adhered selectively to one of those two pieces. The host crystals (to which the reacted substances adhered) were Al2O3 in the cases of MgO-Al2O3 and ZnO-Al2O3, Fe2O3 in the case of MgO-Fe2O3, MgO in the case of MgO-Cr2O3, and TiO2 in the cases of MgO-TiO2 and CoO-TiO2. In the reaction between MgO and SiO2, 2MgO·SiO2 adhered to MgO and MgO·SiO2 adhered to SiO2. In the reactions of MgO-TiO2 and CoO-TiO2, three layers of different compounds were formed, all adhering to TiO2. The mechanism of the diffusion of ions through the reacted layer was hard to determine in detail. It was pointed that the investigators must be careful in confirming the field of diffusion and in discriminating the diffusion through the diffusion field of the lattice from that through the surface and the space. Only in the cases of MgO-Al2O3 and ZnO-Al2O3 was the mechanism clearly determined to be the counter diffusion of cations through the spinel lattice formed, by means of a natural mark.
Infrared Spectra and Molecular Vibrations of Ethylene Glycol and Deuterated Derivatives
Authors: Matsuura Hiroatsu , Miyazawa Tatsuo
Published: July 2006

The infrared spectra of ethylene glycol and ethylene glycol-d2 have been measured in the liquid and crystalline states in the region 4000—300 cm−1. The infrared and Raman spectra suggest that ethylene glycol molecule takes only the gauche conformation as to the C-C bond in both states (the likely models are TGT, TGG and GGG). To establish the vibrationarassignments, the normal coordinate treatments of ethylene glycol and its three deuterated derivatives have been carried out for these models by the use of GF matrix method. The modified Urey-Bradley force field has been used and the force constants have been transferred from similar molecules. The potential energy distributions have also been calculated and the nature of the observed infrared bands and Raman lines in the liquid state has been discussed. The empirical assignments of the methylene rocking modes by the previous investigators have been revised by the present normal coordinate analyses.
Structure of Dimethylthallium Compounds Soluble in Non-polar Solvents
Authors: Kurosawa Hideo , Yasuda Kiyoshi , Okawara Rokuro
Published: July 2006

Several dimethylthallium derivatives were studied by means of a study of their IR and NMR spectra and by measurements of their physical properties. These new compounds, (CH3)2· TlSC6H5, (CH3)2TlOC6H4Cl-o, and (CH3)2Tl[B(C6H5)], are described. By correlation with earlier reports, it is possible to classify dimethylthallium derivatives into two groups according to the nature of the hybridization of the Tl-bonding orbitals. The experimental results can be interpreted in a straightforward and consistent manner.
The Photochemical Reaction of Ethylene Glycol with Ferric Chloride-Pyridine Complex
Authors: Inoue Hiroo , Tamaki Kentaro , Komakine Nobuyuki , Imoto Eiji
Published: July 2006

The photochemical reaction of ethylene glycol with ferric chloride-pyridine complex are carried out under a nitrogen atmosphere with 100 W mercury lamp at room temperature. Glyoxal, formaldehyde, acetaldehyde and water are obtained as the main products. When the molar ratio of pyridine to ferric chloride is below 1–2, the amounts of glyoxal and formaldehyde produced increase with increasing the amount of pyridine, though that of acetaldehyde decreases. In the process, Fe(III) is photo-reduced to Fe(II). Thus, the remarkable effect of pyridine on the photochemical reaction is observed. From these results, the mechanisms of the action of the excited Fe(III) in the presence and absence of pyridine are assumed here.
Reactions of Allenes. I. The Synthesis of Unsaturated Monocarboxylic Esters by the Carboxylation Reaction of Allenes; Reaction Conditions and Products
Authors: Kunichika Sango , Sakakibara Yasumasa , Okamoto Tadashi
Published: July 2006

The carboxylation reaction of propadiene and 1,2-hexadiene with carbon monoxide and methanol in the presence of a catalyst was studied. Propadiene was carboxylated to give methyl methacrylate in a fairly good yield (62% based on the propadiene consumed) by the use of a catalyst composed of nickel carbonyl and methacrylic acid or water under a relatively low pressure. A small amount of methyl vinylacetate was also present. The predominant side reaction was a polymer formation reaction. The carboxylation of 1,2-hexadiene, however, did not proceed smoothly, and a great amount of tarry materials was obtained. The carboxylation products obtained in low yields (max. 15%) were exclusively the materials formed by a carbonyl attack on the central carbon of the allenic structure, that is, methyl trans-2-methyl-2-hexenoate and methyl 2-butyl-2-propenoate.
Homolytic Chlorination of Aliphatic Compounds. I. Photochlorination of Chloroethanes
Authors: Migita Toshihiko , Kosugi Masanori , Nagai Yoichiro
Published: July 2006

The effect of the structure on the rate of hydrogen abstraction from chloroalkanes by a chlorine atom has been investigated by carrying out the competitive photochlorination of eight different chloroethanes in the presence of 2,2-dichloropropane to which the relative site reactivities have been referred. The results show that the successive introduction of a chlorine sub-stituent at the 1-position decreases the reactivity of the 2-position, but that, in some cases, it increases that of the 1-position. A linear free-energy relationship is found to exist between the reactivities of the R group in R-R′ (R=methyl, chloromethyl or dichloromethyl; R′=methyl, chloromethyl, dichloromethyl or trichloromethyl) and Taft’s σ* constants for the R′ group. These facts are elucidated in terms of the inductive and resonance effects of the substituent groups.
Studies on Antibiotics and Related Substances. XXIX. Syntheses of 2-Acetamido-5-oxo-6-heptenoic Acid and 2-Acetamido-4-oxo-5-hexenoic Acid
Authors: Kinoshita Mitsuhiro , Nakada Saburo , Umezawa Sumio
Published: July 2006

In continuing our study of the relationship between structural and antitumor activity, α-acetylamino acids containing a terminal methyleneketo group (namely, 2-acetamido-5-oxo-6-heptenoic acid, and 2-acetamido-4-oxo-5-hexenoic acid) and related derivatives have been synthesized. Their structures were confirmed by a study of their chemical reactions and their ultraviolet and infrared absorption spectra. It has been found that methyl esters of the α-acetylamino acids showed significant antitumor activity, whereas the free N-acetyl acid failed to show such activity.
Preparation of Esters of Phosphoric Acid by the Reaction of Trivalent Phosphorus Compounds with Diethyl Azodicarboxylate in the Presence of Alcohols
Authors: Mitsunobu Oyo , Yamada Masaaki , Mukaiyama Teruaki
Published: July 2006

Trivalent phosphorus compounds, phosphine or trialkylphosphites, have been oxidized by means of diethyl azodicarboxylate and either benzyl or allyl alcohol to give the corresponding phosphine oxide or trialkyl phosphates. The reaction was then extended to the phosphorylation of alcohols. When allyl diethyl phosphite was treated with diethyl azodicarboxylate in the presence of an alcohol at room temperature, a corresponding alkyl diethyl phosphate and diethyl N-allyl hydrazodicarboxylate were obtained in good yields. On the other hand, when phenol was treated with allyl diethyl phosphite and diethyl azodicarboxylate, diethyl phenyl phosphate, allyl phenyl ether and diethyl hydrazodicarboxylate were obtained. The mechanism of their formation will also be discussed.
Electron Spin Resonance Spectra of X-Irradiated Single Crystals of 3, 3′-Dithiodipropionic Acid: “B cos2θ” Rule for Sulfur Radicals
Authors: Kurita Yukio
Published: July 2006

The ESR of X-irradiated single crystals of 3, 3′-dithiodipropionic acid was measured at room temperature. From the analysis of the anisotropy in the spectra, the free radical produced was confirmed to be of the HO2OC·H2CH2·S form. The principal values of the g factor are 2.003, 2.025, and 2.055, while the isotropic coupling constants for the two β protons are 12.4 G and 5.3 G. In this free radical the unpaired electron is mainly concentrated in a 3pπ orbital of the sulfur atom. For the isotropic coupling constant of the β proton in this type of radical, the “Bcos2θ” rule is applied successfully using the value of 12.8 G for B.
Reaction of Aliphatic Ketones with α-Cyano-α, β-unsaturated Acid Derivatives
Authors: Sato Kikumasa , Kurihara Yoshie , Inoue Seiichi
Published: July 2006

The reaction of several aliphatic ketones with α-cyano-α, β-unsaturated acid derivatives has been studied. Ethylidenecyanoacetic acid reacted with a large excess of acetone in an autoclave at 150–160°C to give 3-methyl-5-oxohexanonitrile, which was considered to be produced by the decarboxylation of the Michael-type adduct of acetone onto the acid. Similar adducts were obtained by the reaction of the acid with methyl ethyl ketone, cyclohexanone, and ethyl laevulinate. The reaction of ketones with ethyl ethylidenecyanoacetate did not afford Knövenagel-type condensates, but Michael-type adducts in appreciable yields, for example, ethyl 2-cyano-3,4-dimethyl-5-oxohexanoate from methyl ethyl ketone. Diethyl ethylidenemalonate also gave Michael-type adducts. These results seem to suggest that the γ-methyl group of ethylidenecyanoacetic acid or its ester is not active enough to give Knövenagel-type condensates with aliphatic ketones, and that, therefore, the Knövenagel-type reaction is preceded by the Michael-type addition reaction of ketones onto the activated carbon-carbon double bond.
Photo-induced Reactions. V. The Photochemical Reaction of a 2-Cyclohexenone, Pummerer’s Ketone
Authors: Matsuura Teruo , Ogura Katsuyuki
Published: July 2006

The ultraviolet irradiation of Pummerer’s ketone (VIII) in methanol yielded a 1:1 methanol adduct IX in a good yield; this is a new type of product in the photochemical reaction of a 2-cyclohexenone, i.e., a photochemical Michael-type addition of an alcohol to form a 3-alkoxy-cyclohexanone. The irradiation of VIII in isopropyl alcohol yielded an adduct, XI, analogous to IX and a photoketone, XIII, isomeric to VIII. The photoketone was also obtained by the irradiation of VIII in t-butyl alcohol, dioxane, or benzene. The mechanisms of these reactions are discussed.
Aminocyclitols. XVII. A Facile Synthesis of 2-Deoxystreptamine
Authors: Suami Tetsuo , Lichtenthaler Frieder W , Ogawa Seiichiro , Nakashima Yasuo , Sano Hiroshi
Published: July 2006

Bromination of myo-inosadiamine-l,3 dihydrochloride or its di-N-acetyl derivative with acetyl bromide and acetic anhydride yielded pentaacetyl-2-bromo-2-deoxy-scyllo-inosadiamine-1,3 (III), which upon reductive debromination afforded pentaacetyl-2-deoxystreptamine (IV). The configurations of the new compounds obtained were established by nuclear magnetic resonance and chemical evidences. A mechanism of the bromination reaction is presented, based on the configuration of the bromo-compound.
The Electron Spin Resonance of Mn2+ Ion in Polyphosphate
Authors: Miura Masaji , Hasegawa Akinori , Watanabe Masayuki
Published: July 2006

A part of cation in polyphosphate was replaced with Mn2+ ion. Zero-field splitting parameter D due to the crystal field with axial symmetry was estimated according to Allen’s method from the ESR spectrum of Mn2+ ion. The value of D changes with the change in the state of polyphosphate, crystalline or glassy. As the degree of polymerization of sodium polyphosphate glass decreases, the value of D increases and approaches to the value corresponding to the crystalline state. These phenomena were interpreted as due to the disorderness of glassy state. The value of D was found to change with the variation of the kind of cation in polyphosphate. This was explained in terms of the effective cationic field.
Dissociation Pressures of Various Metallic Oxides
Authors: Kodera Kumasaburo , Kusunoki Isao , Shimizu Shinkichi
Published: July 2006

Gases evolved during a vacuum heat treatment of various oxides were analyzed by means of an omegatron mass spectrometer. Carbon dioxide, carbon monoxide and water were detected as main gases evolved at lower temperatures. Oxygen due to thermal dissociation of ZnO, CdO, NiO, CuO, Cu2O, and WO3 was found at high temperatures. In the case of MoO3, however, evolution of oxygen was not observed. The equilibrium pressures of the evolved gases over these oxides have been measured with a McLeod gauge and a Knudsen gauge. The oxygen dissociation pressures of ZnO, CdO, NiO, CuO, and Cu2O were measured and compared with the calculated values.
The Non-Newtonian Viscosity of Dilute Aqueous Solution of Methylcellulose
Authors: Iso Naomichi , Yamamoto Daijiro
Published: July 2006

The viscometric behavior of a dilute aqueous solution of methylcellulose was studied by tilting capillary viscometers. The intrinsic viscosity was obtained by the extrapolation of Martin’s plots on the assumption that the plots were linear down to an infinite dilution. The intrinsic viscosity obtained increased with the rate of shear over the range of 200–1200 sec−1. Huggins’ constant, k′, the temperature coefficient of the intrinsic viscosity, d[η]/dT, and the energy of the activation of flow, Ev, decreased with the rate of shear. From the data of d[η]/dT and Ev thus obtained, it has seemed reasonable to assume that the methylcellulose chain has a relatively small flexibility and a strong tendency toward alignment with a flowing stream. This may be the main reason why the viscosity of the dilute aqueous solution of methylcellulose is non-Newtonian.
A Study of Charge-Transfer Complexes. VII. Interactions between the Alkyl- or Arylsubstituted Pyrroles and Chloranil or Tetracyanoethylene
Authors: Matsuo Taku , Shosenji Hideto
Published: July 2006

The charge-transfer (CT) bands of complexes of alkylsubstituted pyrroles and chloranil or tetracyanoethylene (TCNE) were found to consist of two closely situated peaks. The peaks were assigned to transitions originated from the highest occupied, and second-highest occupied orbitals of the donor. The energy of the CT absorption band is hardly affected even by the presence of a bulky substituent such as a t-butyl group at the pyrrole nitrogen. Hence, the acceptor molecules were thought not to be close to the 1-position of the pyrryl group. In the case of 1-phenylpyrrole, the first CT bands are at almost the same positions as those of the corresponding complexes of 1-methylpyrrole. The bands show red shifts if methyl groups are introduced either on the pyrryl group or on the phenyl group, so that the planes of the two groups are twisted around the N–C bond between them. Thus the acceptor molecules were concluded to interact mainly with the pyrryl group.
Microwave Spectrum of o-Difluorobenzene
Authors: Hatta Aritada , Hirose Chiaki , Kozima Kunio
Published: July 2006

The microwave spectrum of o-difluorobenzene has been studied in the 7.8- to 28-Gc/sec region, R- and Q-branch transitions of the a-type being assigned for the lowest vibrational state. The rotational constants obtained are A=3263.55 Mc/sec, B=2227.91 Mc/sec, and C=1323.87 Mc/sec. Four possible sets of structural parameters were obtained. seems probable that the angle made by two C–F bonds is larger than 60°. The value of the dipole moment obtained is 2.46±0.03 D.
Radicals Produced by UV Irradiation of Acridan and Acridine in Glassy and Crystalline Medium at 77°K
Authors: Niizuma Shigeya , Koizumi Masao
Published: July 2006

Choosing two groups of solvent a) methanol, ethanol, isopropanol (glassy at liquid nitrogen temperature) and b) t-butanol, benzene, tetrahydrofuran (crystalline at liquid nitrogen temperature), ESR studies have been made on the irradiated solutions of A] acridine (A)+acridan (AH2) (1:1), B] A alone, and C] AH2 alone at 77°K. 1) 365 mμ irradiation of A] and B] in the solvents of a) group does not cause any photochemical reaction, whereas in the solvents of b) group, the A*+AH2→2AH· reaction occurs. A resultant singlet ESR line has been assigned to AH·. 2) Irradiation of A] and C] with the entire output from a superhigh pressure mercury lamp gives, for solvents of group a), the ESR spectra which can be attributed mainly to alcohol radicals (RCHOH) but gives electronic absorption spectra ascribed only to AH· ; for the solvents of group b) the results were almost the same as in 1).
The Crystal and Molecular Structure of an Isomer of Bis-(1,2-diethoxycarbonyl-ethyl)tin Dibromide
Authors: Yoshida Mamoru , Ueki Tatzuo , Yasuoka Noritake , Kasai Nobutami , Kakudo Masao , Omae Iwao , Kikkawa Shoichi , Matsuda Sumio
Published: July 2006

Low mp isomer of bis-(1,2-diethoxycarbonyl-ethyl)tin dibromide (mp 114–115°C) crystallizes in a monoclinic form: a=11.85, b=20.24, c=9.79 Å, β=101.3°; space group, P21/a; and four molecules are contained in a unit cell. Crystal structure was established by the heavy atom method. The coordination about the tin atom is nearly octahedral. Two bromine atoms attached to the tin atom are in cis-positions. Two ligands, 1,2-diethoxycarbonyl-ethyl groups, are both bound to the tin atom by carbon and oxygen, forming five-membered rings. These rings are rather puckered, and one is in d-form and another in l-form.
The Chemistry of Protactinium. VI. A Study of the Sulfato-Complex of Pa(IV) by Means of TTA-Benzene Extraction
Authors: Mitsuji Toshikazu
Published: July 2006

The behavior of Pa (IV) during extraction with TTA was investigated in perchlorate, chloride, and sulfate solutions (pH 0.4–1.1). In perchlorate and chloride solutions, the extraction equilibrium may be written as:

Pa(OH)_2^2++4HT\ightleftharpoonsPaT_4+2H_2O+2H^+

On the other hand, the extraction by TTA from the sulfate solution may be described as:

Pa(SO_4)(OH)^++4HT\ightleftharpoonsPaT_4+HSO_4^-+H_2O+2H^+

Therefore, the formation of the sulfato-complex of Pa(IV) is considered to occur as follows:

Pa(OH)_2^2++HSO_4^-\ightleftharpoonsPa(SO_4)(OH)^++H_2O

The equilibrium constant for the above reaction has been determined to be 320 at the ionic strength of 0.50 (temperature: 10±0.5°C).
The Reaction of the Ester with Acyl Chloride in the Presence of Aluminum Chloride. VIII. The Attempted Synthesis of the Carbethoxy Derivative of Polymalonylphenylene
Authors: Matsui Kiyotada , Motoi Masatoshi , Nojiri Tetsuro , Wakabayashi Kohtsuchi
Published: July 2006

The treatment of ethyl acetoacetate with terephthaloyl chloride in the presence of two equivalents of aluminum chloride in nitrobenzene at 55°C affords a polymer which may be designated as an aluminum chelate of the polymalonylphenylene derivative with some carbethoxy groups.
A Kinetic Study of the Metal Ion-catalyzed Glycolysis of Benzonitrile
Authors: Ikeda Takashi , Kitabatake Michitoshi , Ito Masatomo , Noguchi Yoshitaka
Published: July 2006

The kinetics of the lead ion-catalyzed glycolysis of benzonitrile were studied in the presence of water. The experimental results indicated that the rate of the formation of ammonia followed the first-order rate law with respect to the concentrations of benzonitrile and of water. For the concentration of the catalyst, the rate found was of a 0.44 order. It was observed that the product, β-hydroxyethyl benzoate, exhibited an inhibiting effect on the glycolysis. The effects of substituents on benzonitrile were found to fit the Hammett rule. The reaction was remarkably influenced by the type of glycol used. The reaction also proceeded through the hydrolysis of benzonitrile, followed by the glycolysis of the benzamide thus formed. The rate of the glycolysis of benzamide was about one-third that of benzonitrile, which is the main reaction in the system. The reaction of imidate formation possessed a small equilibrium constant at a high temperature, but it had a high reaction rate. The proposed mechanism for these glycolysis reactions is as follows: the addition of glycol to benzonitrile yields imidate, which then forms a chelate compound with a metal ion. The imidate activated by the formation of the chelate is easily hydrolyzed by water to form ester and ammonia. This ester tends to chelate to the metal ion and so inhibits the reaction.
The Kinetics of the Metal Ion-catalyzed Glycolysis of Terephthalonitrile
Authors: Ikeda Takashi , Kitabatake Michitoshi , Ito Masatomo , Ishioka Ryoji
Published: July 2006

The kinetics of the lead ion-catalyzed glycolysis of terephthalonitrile have been studied in the absence of and in the presence of water. In the absence of water, scarcely any formation of β-hydroxyethyl p-cyanobenzoate is observed, but some orthoesters are formed. The reaction rate data obtained in the absence of water are found to fit a reversible consecutive reaction scheme in which some basic compounds are involved as the intermediates. In proportion to the increase in the concentration of water, such intermediates as the orthoesters and basic compounds are hydrolyzed more rapidly to form β-hydroxyethyl p-cyanobenzoate, but simultaneously the hydrolysis of terephthalonitrile and the basic intermediates also takes place in the reaction mixture, thus yielding amide.
Stereochemical Studies of Monoterpene Compounds. V. The Rotational Conformation of the Acetyl Group of 10-Nor-8-oxomenthols and 10-Nor-8-oxocarvomenthols
Authors: Suga Takayuki , Shishibori Tsuyoshi , Matsuura Tamon
Published: July 2006

The preferred rotational conformation of the acetyl group of (+)-10-nor-8-oxoneomenthol (I), (−)-10-nor-8-oxomenthol (II), (−)-10-nor-8-oxocarvomenthol (III), and (+)-10-nor-8-oxoneocarvomenthol (IV) has been examined by a combination of conformational analysis by a priori calculation and variable-temperature circular dichroism and infrared spectrum measurements. Compound I exhibited an inversion in the sign of the Cotton effect upon a change in the solvent. This phenomenon was interpreted as indicating the conformational change Ia\ightleftarrowsIb. The cause of the change was ascribed to the formation and subsequent rupture of the intramolecular hydrogen bond. Compound II exhibited a solvent-depending circular dichroism curve similar to the curve of I; this was explained as indicating the existence of a conformational equilibrium between the free conformer, IIa, and the internally-hydrogen-bonded conformers, IIb, IIc, and IId. Furthermore, compounds III and IV were found to take preferentially the IIIa–IIIb and IVa–IVb conformations respectively.
Acid-Catalyzed Isomerization of 1,3,4,5-Tetra-O-acetyl-2-deoxy-l-sorbopyranos-2,3-ene
Authors: Katsuhara Mitsuru , Wakahara Shigeru , Tokuyama Kanji
Published: July 2006

An acid-catalyzed reaction in acetic anhydride was found to isomerize 1,3,4,5-tetra-O-acetyl-2-deoxyl-l-sorbopyranos-2,3-ene (V) to four new unsaturated compounds. When the reaction was allowed to continue for a longer period, they underwent polymerization, but did not afford 2-hydro-xyacetylfuran acetate (XXVIb). The reaction in acetic acid containing water was shown to mainly convert V into XXVIb. This reaction pathway was thought to be different from the above.
Synthetic Studies of α-Tocopherol. II. Synthesis of Trimethyl-benzoquinone
Authors: Ichikawa Takehiko , Owatari Hiroko , Kato Tetsuya
Published: July 2006

Trimethylbenzoquinone (XII), a raw material for the synthesis of trimethylhydroquinone (XIII), was synthesized from trimethylcyclohexenones and trimethylcyclohexene by oxidation. Ethyl α-propionylpropionate (II) prepared from ethyl propionate was condensed with methyl vinyl ketone to yield 4-methyl-4-ethoxycarbonylocta-3,7-dione (IV), which was then dehydrated with beryllium chloride to give 2,3,6-trimethyl-6-ethoxycarbonyl-2-cyclohexen-1-one (V). The product (V) was heated with alkali to give 2,3,6-trimethyl-2-cyclohexen-1-one (VI). The refluxing of a solution of IV in a mixture of acetic acid and hydrochloric acid also gave rise to VI. When II was condensed with crotonaldehyde, 2,5,6-trimethyl-2-cyclohexen-1-one (VIII) was obtained in a single step. 1,4(or 1,5)-Dimethyl-5-(or 4)-formyl-1-cyclohexene (IX), obtained by the Diels-Alder reaction of crotonaldehyde with isoprene, was reduced by hydrazine hydrate to give 1,4,5-trimethyl-1-cyclohexene (X). X was oxidized with t-butyl chromate and acetic anhydride to give 3,5,6-trimethyl-2-cyclohexen-1-one (XI). VI, VIII, XI, and X were oxidized with t-butyl chromate and acetic anhydride to give XII in 53, 52, 22, and 12% yields respectively. The oxidation of VIII by selenium dioxide gave XII in a 23% yield, but only a trace of XII was formed by the similar oxidation of X.
Synthesis of 4,5-Di- and 1,4,5-Trisubstituted Imidazole Derivatives from 4,5-Dicyanoimidazole
Authors: Yamada Yoshitaka , Kumashiro Izumi , Takenishi Tadao
Published: July 2006

The chemical reactivities and the synthesis of various derivatives of 4,5-dicyanoimidazole formed by heating a solution of hydrogen cyanide in liquid ammonia were studied, as were the partial hydrolysis, hydrogenation, and addition reaction of cyano groups and the alkylation, cyano-ethylation, and vinylation of the imidazole ring. From these experiments, a few new compounds were synthesized, which had been expected as intermediates of polymers containing imidazole rings.
Measurement of Adsorbed Amount of Sodium Dodecylsulfate at Gas-Solution Interface by Radiotracer Method Using Tritium-Labeled Compounds
Authors: Muramatsu Mitsuo , Tajima Kazuo , Sasaki Tsunetaka
Published: July 2006

Sodium dodecyl-2,3-3H,3Hsulfate (SDS) was synthesized from non-radioactive dodecanol, and the adsorbed amount of SDS at the gas-water interface, Γ, was directly measured by the radiotracer method with the use of 2π gas-flow windowless counter and humidified propane as a flow-gas. Because of a very soft nature of tritium β-rays, surface radioactivity is exclusively due to the solute adsorption compared with the large contribution from the bulk of the solution as in the case of 14C or 35S labeled detergents. Therefore the use of 3H labeled compounds enables the determination of the amount of adsorption in high accuracy, even in the region of high concentration beyond the critical micelle concentration (CMC) of SDS solution. However, no reliable reports have appeared as yet on the studies of adsorption of surfactant at gas-solution interface using 3H labeled compounds. Our measurement was carried out under exactly specified conditions, namely using chemically and radiochemically pure sample and under the condition free from evaporation. It was confirmed that Γ increased with the increase of SDS concentration and approached the saturation value of 5.9×10−10 mol/cm2 or 28.2 Å2/molecule at the concentration higher than 6×10−3 mol/1000 g solution and beyond CMC. Furthermore, Γ proved to be independent of the acidity of solution above pH 4, while it increased with increasing acidity below pH 4. The phenomenon is explained by the presence of hydrolytically formed dodecylsulfuric acid whose surface activity is higher than that of SDS.
Radiolysis of CoIII-EDTA in Aqueous Solution; The Effect of pH
Authors: Matsuura Niro , Shinohara Nobuyoshi , Nishikawa Masaru , Takizawa Masao
Published: July 2006

The hydrogen and hydrogen peroxide produced in the radiolysis of CoIII-EDTA (CoIIIY−) in various pH’s have been measured. G∞(H2) in the deaerated system sharply dropped from the value of 3.2 at pH<1 to the value of 0.8 at pH>4 where G∞ denotes a limiting value which is reached with increasing solute concentration. G∞(H2O2) in the aerated system was found to be 2.5–2.0. G∞(–CoIIIY−) (=4.4) was not affected by the addition of N2O. G∞(N2) and G∞(H2) were found to be 2.6 and 0.8 respectively. From the results, it is concluded that H atoms and OH radicals reduce Co(III) to Co(II) through the dehydrogenation from the ligand, while eaq− reduce the complex without any degradation of the ligand.
The Electronic and Vibrational Spectra of Oxalyl Bromide
Authors: Shimada Hiroko , Shimada Ryoichi , Kanda Yoshiya
Published: July 2006

The infrared and Raman spectra of oxalyl bromide have been observed. The spectral features suggest that this molecule is planar and trans at room temperature. An assignment has been given for all the fundamental vibrational frequencies. The ultraviolet absorption spectrum of oxalyl bromide has been studied in cyclohexane and in the vapor. The spectrum consists of four absorption systems. These were ascribed to a 3Au(n, π*)←1Ag, a 1Au(n, π*)←1Ag, the second 1Au(n, π*)←1Ag and a 1Bu(π, π*)←1Ag transitions, respectively. Vibrational analyses have been made for the 3Au(n, π*)←1Ag and the first 1Au(n, π*)←1Ag systems.
An X-Ray Determination of the Structure of Motiol Iodoacetate
Authors: Nishi Yoriko , Ashida Tamaichi , Sasada Yoshio , Kakudo Masao
Published: July 2006

The molecular configuration of motiol has been determined by the X-ray crystal analysis. The crystal of motiol iodoacetate, C32H52O2I, is monoclinic with two molecules in a unit cell of dimensions; a=17.37, b=6.78, c=13.04 Å and β=99.6°, the space group being P21. The crystal structure was solved by the heavy atom method. The atomic coordinates and anisotropic temperature factors were refined by block-diagonal matrix least-squares method. The structure determined is, in general, compatible with that derived chemically. The rings A and D are of a chair form, and the rings B and C are of a semi-chair. The molecule bends at the rings B and C to make a bow as a whole. All but one of the methyl groups are in axial junction.
Anticatalytic Effect of Mn(II) in the Silver Catalyzed Oxidations by Peroxydisulphate
Authors: Sengar H G S , Gupta Y K
Published: July 2006

Mn(II) has been found to be an anticatalyst in the silver catalyzed oxidations of oxalate, citrate, tartrate, malonate and arsenious acid and the limiting value of the rate constants in each case is about 0.4 l/mol-min at 35°C which is very much comparable to the rate constant for the separate silver catalyzed oxidation of Mn(II), H2O, Ce(III), N2H4 and vanadyl ion. A mechanism has been proposed in which the simultaneous oxidation of Mn(II) and the organic substrate or arsenious acid takes place and when sufficiently large concentration of Mn(II) is present, the latter oxidation is almost completely suppressed. The oxidations of citrate and tartrate are consecutive reactions. The first faster reaction is followed by the second slower reaction.
The Reaction between Hydrocarbon and Hydrogen Cyanide in Silent Electrical Discharge. I. The Formation of Cyclohexyl Cyanide from Cyclohexane and Hydrogen Cyanide
Authors: Kawamoto Kazuaki , Sonoda Noboru , Tsutsumi Shigeru
Published: July 2006

In order to examine the possibility of the direct introduction of a cyano radical into cyclohexane by means of silent discharge, a mixture of cyclohexane and hydrogen cyanide was discharged in an ozonizer under various conditions. As a result, cyclohexyl cyanide was obtained. The yield of cyclohexyl cyanide depended upon the voltage of discharge, the residence time in the discharge tube, the temperature of the discharge tube, and the structual characteristics of the apparatus. In the refluxing method the maximum yield of cyclohexyl cyanide was obtained when the discharge was carried out at a low temperature. Besides cyclohexyl cyanide, the reaction products were confirmed to consist of bicyclohexyl, cyclohexene, methylcyclohexane, ethylcyclohexane, 3-cyclohexylcyclohexene, methylenecyclohexane, 1-hexene, n-hexane, n-pentane, methylcyclopentane, a solid brown deposit, and cracked gas. The principal reactions can be interpreted as being the formation of cyclohexyl and cyano radicals and the combination of these radicals, their dehydrogenation, their isomerization, their polymerization, and their decomposition.
Kinetic Studies of Solvolysis. XV. Racemization Caused by the Molecular-Complex Formation in the Acetolysis of Optically Active 2,4,7-Trinitro-9-fluorenyl (+)-Camphor-10-sulfonate
Authors: Okamoto Kunio , Nitta Issei , Shingu Haruo
Published: July 2006

Optically active 2,4,7-trinitro-9-fluorenyl (+)-camphor-10-sulfonate (II) has been synthesized by asymmetric attack of (+)-camphor-10-sulfonic acid to 9-diazo-2,4,7-trinitrofluorene. Acetolysis of II is accelerated by added phenanthrene, anthracene, and hexamethylbenzene at 116–120°C. This acceleration is attributed to molecular complex formation between II and these hydrocarbons. The complex formation has been examined by spectrophotometry or by the isolation of the crystalline complex of II. The acetolysis product, i.e., optically active 2,4,7-trinitro-9-fluorenyl acetate (III), has been racemized in the greater degree in the presence of the more aromatic hydrocarbons. This racemization is ascribed to the prolonged life of the Sn1 ion-pair intermediate caused by the rapid equilibration between the uncomplexed and the complexed Sn1-intermediate; the kinetic nature of this interaction has been discussed.