bluuebunny/crossref_metadata_2025 huggingface dataset:
Reinvestigation of the Nitration of Ethylmesitylene and n-Propylmesitylene. Revision of Early Works.
Authors: Suzuki Hitomi , Sawaki Mikio , Sakimoto Reiji
Published: July 2006

Ethylmesitylene reacts with fuming nitric acid in dichloromethane at −50°C to give mononitroethyl-mesitylene, 3,5-dimethyl-4-ethylbenzyl nitrate, 2-nitro-3,5-dimethyl-4-ethylbenzyl nitrate and a dinitroethyltri-methylcyclohexenone, while on nitration with mixed acid it yields mono and dinitro derivatives as the major products, together with minor quantities of 2-nitro- and 2,6-dinitro-3,5-dimethyl-4-ethylbenzyl nitrates, diphenyl-methanes, and unidentified nitro-carbonyl compounds, possibly nitrobenzaldehydes. Similar results are obtained from the nitration of n-propylmesitylene. If the hydrocarbons are nitrated by adding into a large excess of the nitrating agent, the major product is 2,6-dinitro-3,5-dimethyl-4-alkylbenzyl nitrate soon after the reaction, or 2,6-dinitro-3,5-dimethyl-4-alkylbenzaldehyde when the mixture is left to stand at room temperature. The nitro compound melting at 123°C, obtained by Smith and Kiess from the nitration of ethylmesitylene and described as trinitro-4-ethyl-o-xylene, is identified as 2,6-dinitro-3,5-dimethyl-4-ethylbenzyl nitrate. An uncharac-terized nitration product (mp 135°C) from n-propylmesitylene, obtained by Töhl and Tripke, is found most likely to be 2,6-dinitro-3,5-dimethyl-4-n-propylbenzyl nitrate (mp 139–140°C).
Location of the Sulfate Groups in κ-Carrageenan from Gigartina Tenella
Authors: Hirase Susumu , Watanabe Kyoko
Published: July 2006

Location of the sulfate groups in κ carrageenan from G. tenella has been re-investigated by adapting the method, which was devised by Bouveng for locating the acetyl groups in hemicellulose. In this method, the sulfate groups were replaced by methyl groups through a series of reactions consisting of blocking the free hydroxyl groups with phenylcarbamoyl groups, removing the sulfate groups and methylating the newly formed hydroxyl groups. The blocking substituents were then removed, and the positions of the methoxyl groups were investigated by the standard method. The results have shown, in accordance with the conclusion based on the methylation data, that one forth of the 1,4-linked 3,6-anhydro-d-galactose residues are 2-sulfated and that the 1,3-linked d-galactose residues are 4-sulfated. No evidence was obtained to indicate the presence of d-galactose 2,6-disulfate, which had been presumed by other workers. The problem concerning the acyl migration of the blocking groups during the process has also been discussed.
Reactions of Tris(acetylacetonato)manganese(III) and Bis(acetylacetonato)-manganese(II) with Ethylenediamine and Other Primary Amines
Authors: Nishikawa Yoshinori , Nakamura Yukio , Kawaguchi Shinichi
Published: July 2006

Tris(acetylacetonato)manganese(III) reacts with ethylenediamine (L2) and other primary amines (L) in organic solvents at room temperature producing Mn(acac)2L2. The same Mn(II) complexes were also prepared quantitatively by reactions of Mn(acac)2(H2O)2 with amines. Besides the usual hexa-coordinate monomeric complex, allylamine gave a dimeric compound [Mn(acac)2(CH2=CHCH2NH2)]2, which is the first example of the binuclear manganese(II) complex of acetylacetone. The stoichiometry of the redox reaction between Mn(acac)3 and ethylenediamine was established and discussed in connection with the initiation mechanism of vinyl polymerization.
The Infrared Spectra of Addition Compounds of Hydrogen and Deuterium Cyanides with Boron Tribromide
Authors: Kanesaka Isao , Hase Yoshiyuki , Kawai Kiyoyasu
Published: July 2006

The infrared spectra of addition compounds of hydrogen and deuterium cyanides with boron tribromide have been measured in the frequency region from 4000 to 200 cm−1, and the normal frequencies have been proposed on the basis of the C3υ symmetry for four isotopic compounds, HCN·10BBr3, HCN·11BBr3, DCN·10BBr3, and DCN·11BBr3. The force constants have been calculated on the assumption of a modified Urey-Bradley force field, and the shift of the vibrational frequencies by the coordination has been discussed.
Studies of Mixed Cyano Cobalt(III) Complexes. IV. Preparation and Characterization of trans(O,X)-[Co(X)(aminoacidato)(diethylenetriamine)]+ Complexes with X=CN−, NO2−, or Cl−
Authors: Ohkawa Kuwako , Fujita Junnosuke , Shimura Yoichi
Published: July 2006

A series of new kinds of mixed cobalt(III) complexes, trans (O,X)-[Co(X) (aminoacidato) (diethylenetriamine)]Y, have been prepared and characterized by visible and ultraviolet, circular dichroism, and proton magnetic resonance spectroscopy for X=CN−, NO2−, and Cl−; aminoacid=glycine, α-aminoisobutyric acid, l-alanine, l-valine, l-threonine, and l-proline; and Y=Br−, Cl−, or ClO4−. The proton magnetic resonance spectra of the cyano mixed complexes show the existence of new conformational isomers, endo and exo forms, which concern the ligand CN− and the hydrogen atom attached to the central nitrogen atom of the meridionally coordinated diethylenetriamine ligand.
Convenient Quadratic Formulas for the Two-center Coulomb Repulsion Integrals in the Semiempirical LCAO-MO Method and the Significance of the Pariser-Parr Approximation
Authors: Gondo Yasuhiko , Kanda Yoshiya
Published: July 2006

The coefficients in the Pariser-Parr-type quadratic formulas for the two-center Coulomb repulsion integrals encountered in the planar as well as the non-planar conjugated systems have been expressed as linear functions of the effective nuclear charges of the 2p atomic orbitals involved. The formulas thus obtained are applicable to those conjugated systems consisting of carbon, nitrogen, and oxygen atoms, and may well be useful in variable electronegativity self-consistent field calculations on these systems. With some illustrative applications to spin densities and phosphorescent-state energies, it has been shown that the Pariser-Parr approximation gives better results than the Nishimoto-Mataga one, although the latter is successful in the prediction of electronic transitions within the singlet manifold. Incidentally, this was also the case for the phosphorescent-state zero-field splittings (Y. Gondo and Y. Kanda, This Bulletin, 43, 3943 (1970)). The electric dipole moments have also been discussed.
Equilibrium of Urea Synthesis. II.
Authors: Inoue Shigeru , Kanai Kazumichi , Otsuka Eiji
Published: July 2006

In the preceding paper (This Bulletin, 45, 1339 (1972)) it was reported that the existence of the maximum equilibrium conversion was not due to the experimental method. For this phenomenon, we have presented the following interpretation. While NH4CO2NH2 is converted to urea and water, it dissociates into NH3 and CO2 in the solution (not in the gas phase), and the degree of the dissociation increases exponentially as the temperature becomes higher, while the conversion to urea gradually increases. Therefore, at a certain temperature, the equilibrium conversion reaches its maximum value. Although it is nearly impossible to prove analytically the dissociation of NH4CO2NH2 in the solution, we are sure of it from the following facts: 1) The dissociation of NH4-CO2NH2 is a great endothermic reaction, even under the conditions of urea synthesis. 2) The value of NH3/CO2which gives the minimum equilibrium pressure at a usual temperature is not always equal to 2.0, but varies with the temperature. 3) The effect of H2O/CO2 on the equilibrium pressure varies with the temperature; that is, when the temperature is lower than about 200°C, an increase in H2O/CO2 reduces the equilibrium pressure, but when the temperature is higher than 200°C, an increase in H2O/CO2 makes the equilibrium pressure higher.
Least-Squares Determination of Molecular Structures from Gaseous Electron-Diffraction Data. II. Polynomial Expression of Background
Authors: Shibata Shuzo
Published: July 2006

A new least-squares method has been devised for interpreting electron-diffraction data by comparison of an experimental background with a calculated background. The former is derived from an experimental total intensity by assuming a molecular model. The latter is approximated by a polynomial function. A computer program is written to refine structural parameters of a molecule so as to yield a smooth background. The characteristic of the present method is that it does not need any bias depending upon human judgement throughout an analysis. The distinctive features of the procedure are discussed, and the application of this method to structure determination of several molecules is also described.
Mössbauer Effect of 119Sn in Tetracarbonylcobalt Derivatives of Tin(IV) Halides
Authors: Ichiba Sumio , Katada Motomi , Negita Hisao
Published: July 2006

The 119Sn Mössbauer effect was studied in tetracarbonylcobalt derivatives of tin(IV) halides, XnSn[Co-(CO)4]4−n, where X=Cl, Br or I, and n=0∼4. The isomer shift in each halogen series increased as the halogen atom was successively replaced by the Co(CO)4 group. The values of the isomer shift were between those of tin(IV) halides and XSn[Co(CO)4]3 and did not change lineraly with the number of halogen atoms. The values of the quadrupole splitting were smaller than those of the corresponding organotin halides, XnSnR4−n, and attained their maximum at dihalides. From the Mössbauer parameters, the chemical bonds in the compounds, especially the Sn-Co bond, were discussed.
Fluorescence Emission in the Gas Phase of Several Aromatic Hydrocarbons
Authors: Nakajima Akira
Published: July 2006

The fluorescence and excitation spectra of several condensed aromatic hydrocarbons were measured in the gas phase at low pressures. The emission from the second excited singlet state (S2 emission) could be observed with some of the compounds studied, in which the first weak absorption band is located close to the second much stronger band. The relative yield of the S2 emission always increased with the increase in the excitation wave number. It has been shown that the occurrence of the S2 emission can be explained in a qualitative way by the state densities and the radiative rates. In coronene, an emission to be regarded as originating from the third excited singlet state was observed.
Activation Analysis of Arsenic, Copper, and Antimony in Sea Water
Authors: Gohda Shiro
Published: July 2006

Arsenic, copper, and antimony in sea water were determined by the thermal neutron activation analysis. Convenient pre- and post-irradiation procedures were proposed and some samples were analyzed. Arsenic, copper, and antimony were collected by the cocrystallization with thionalide, and were irradiated for 30 min in the neutron flux of 2×1013 n/cm2/sec. After the thionalide complex was decomposed with nitric acid, the copper and antimony were separated from the arsenic by precipitating with oxine, and the arsenic in the filtrate was coprecipitated with ferric hydroxide. Gamma-ray spectra were obtained and the decays of the 0.44–0.67 MeV photo peak of 64Cu plus 122Sb and the 0.55 MeV peak of 76As were followed. The arsenic, copper, and antimony contents in sea water were estimated to be 1.12–1.71 μg As/l, 1.49–3.35 μg Cu/l, and 0.22–0.57 μg Sb/l.
Spectrophotometric Studies and Analytical Applications of Vanadium(IV) Chelates with 4-(2-Pyridylazo)resorcinol and 1-(2-Pyridylazo)-2-naphthol
Authors: Mushran S P , Prakash Om , Verma J R
Published: July 2006

Oxovanadium(IV), VO2+, gives sensitive colour reactions with 4-(2-pyridylazo)resorcinol (ε=2.54×104 at λmax 550 nm) and 1-(2-pyridylazo)-2-naphthol (ε=1.02×104 at λmax 560 nm). The composition of the complexes VO2+: PAN or PAR was established by the continuous variations, mole ratio, and Asmus straight line methods. Lambert-Beer’s law range, Ringbom optimum range, pH stability range, photometric error, and stability constant values were also evaluated.
The Preparation of Bis(dimethylglyoximato)nitrosylcobalt(II) and its Conversion into the Nitro Complex
Authors: Tamaki Motonori , Masuda Isao , Shinra Koichiro
Published: July 2006

The preparation of diamagnetic CoII(dmgH)2NO (dmgH=dimethylglyoximato monoanion) is reported. The complex shows the IR absorption band of NO at 1641 cm−1, indicating a neutral NO ligand in the complex. The IR and electronic spectra are consistent with the structure of the penta-coordinate, the square-pyramidal configuration of the complex. In the presence of oxygen and water, the complex is oxidized rapidly (NO→NO2−, Co(II)→Co(III)) and converted into CoIII(dmgH)2NO2·OH2. During the reaction, a complex formulated as [CoII(dmgH)2NO·OH2] [CoIII(dmgH)2NO2]·2H2O is obtained. It is considered that, in the complex, the Co(II) is bound with the Co(III) through a NO bridge. The assignments of the IR spectra have been made using 15NO and 15NO2.
The Characterization of Oligomeric Iron(II)-tetraoxime Complexes
Authors: Backes Joseph , Masuda Isao , Shinra Koichiro
Published: July 2006

Several polymeric iron(II) chelates with tetraoxime ligands,

CH3C(NOH)C(NOH)–\overset(α)CH2–\overset(β)CH2–(CH2)n–\overset(β)CH2–\overset(α)CH2–C(NOH)C(NOH)CH3,

where n=2 and 6, were characterized. They show a ligand-to-iron molar ratio of 1 : 1, corresponding to a planar arrangement of the ferrous ion and the four oxime nitrogens; two pyridine or methylpyridine substituents are axially coordinated to the central metal ion. The complexes are diamagnetic in the solid state, and their absorption spectra closely resemble those of the monomeric ferrous dimethylglyoxime compounds. The molecular weight, determined in a pyridine solution by vapor-pressure osmometry (2800 for –(CH2)2– and 3100 for –(CH2)6–), corresponds to 5 or 6 Fe–N4 units within the polymer chain. An NMR investigation including tetraoxime ligands with both aliphatic and aromatic linkages, as well as the corresponding chelates, shows that the protons in the α or in the β position to the oxime groups do not undergo any shift upon chelation. The electronic spectral data and NMR data provide no evidence that the Fe(II) chelate rings within the polymer chain are affected by one another.
The Polarography of N,N′-Ethylenebis(acetylacetoniminato) and N,N′-Ethylene bis(salicylaldehydeiminato) Complexes of Cobalt(III), Nickel(II), and Copper(II) in an N,N′-Dimethylformamide Solution
Authors: Kodama Mutsuo , Fujii Yuki , Sakurai Mitsuo
Published: July 2006

The polarographic behavior of N,N′-ethylenebis(acetylacetoniminato) (baen) and N,N′-ethylenebis(salicylaldehydeiminato) (bisaen) complexes of cobalt(III), nickel(II), and copper(II) in DMF solutions was studied thoroughly. At the dropping mercury electrode, these metal complexes give well-defined cathodic waves corresponding to the reduction of metal(II) to metal(I). A careful and systematic study of the polarographic behavior of β-cis and trans cobalt(III)-baen and -bisaen complexes of the general formulae: CoZY1−a and CoZX21−2b, and that of nickel(II)- and copper(II)-baen complexes, revealed that the unusual stability of the metal(I)-baen and -bisaen complexes can be ascribed mainly to the stable square-planar nature of baen and bisaen. The effect of the replacement of the ligand by the halogen atom was also investigated.
Effect of Ring Size on the Mass Spectral Fragmentation of Cyclic Sulfoxides
Authors: Tamagaki Seizo , Oae Shigeru
Published: July 2006

Mass spectra of six cyclic sulfoxides were determined in order to study the effects of ring size on the rate of OH-elimination from molecular ions. The ratios of the rates for the OH loss, [M+–OH]/[M+], are: trimethylene sulfoxide: 0.23/tetramethylene sulfoxide: 0.06/pentamethylene sulfoxide: 0.24 /hexamethylene sulfoxide: 1.21/9-thiamonoxybicyclo[3.3.1]nonane: 3.14/7-thiamonoxybicyclo[2.2.1]heptane: 0.02. These findings were explained in terms of the difference in the closest approaching distance between the sulfinyl oxygen and the β- or γ-hydrogen atoms. Geometry of the ionized molecular ions appears to be an important factor in determining these ratios. The loss of HSO was also disucssed.
Structure and Reactivity of Small Ring Compounds. IV. Photochemistry of Spirocyclopropyl Ketones
Authors: Sonoda Akio , Moritani Ichiro , Miki Jo , Tsuji Takashi , Nishida Shinya
Published: July 2006

The photochemical transformations of a series of spriocyclopropyl ketones (1–4) have been investigated in dilute n-hexane solutions. Spirocyclopropyl ketones 1 and 2 give mainly the ’Type I’ photoproducts of cycloalkanones, i.e., 1-(2′-propenyl)cyclopropanecarboxaldehyde (5, 34%) and 1-(3′-butenyl)cyclopropanecarboxaldehyde (7, 37%), respectively, in marked contrast to the usual photochemical cleavage of cyclopropyl ketones. Ethylidenecycloalkanones are not detected, but their hydrogenated derivatives, 2-ethylcycloalkanones, are produced in a small amount.

The photoreaction of 1 has been found to be quenched by piperylene, so that it is highly probable that the reaction products are derived from the n-π* triplet states of the ketones.

The irradiations of nonconjugated spiroketones 3 and 4 afford ring-enlarged 4-methylenecycloalkanones, 9 and 10, respectively.
Studies on the Voges-Proskauer Reaction. II. The Structure of a Pigment from the Diacetyl Reaction of 1-Benzyl-1-methylguanidine
Authors: Nishimura Tamio , Yamazaki Chiji , Ueno Tetsuro , Kitajima Shinichi , Ishige Koichi
Published: July 2006

A pigment formed in the diacetyl reaction of 1 -benzyl-1 -methylguanidine was isolated as reddish purple prisms. The reduced pigment was colorless and rapidly converted back to the original pigment on exposure to the air. On the basis of IR, NMR, and mass spectral evidence, the structures of the pigment and the reduced one were established to be 2-(N-benzyl-N-methylamino)-4-methyl-5-(1-oxo-1,2-dihydro-2-naphthylidenemethyl)-imidazole and 2-(N-benzyl-N-methylamino)-4-methyl-5-(1-hydroxy-2-naphthylmethyl)imidazole, respectively.
Isomerism of the Metal Complexes containing Multidentate Ligands. I. Geometric and Optical Isomers of the Bis(diethylenetriamine)-cobalt(III) Ion
Authors: Yoshikawa Yuzo , Yamasaki Kazuo
Published: July 2006

Three possible isomers of bis(diethylenetriamine)cobalt(III) halide were isolated by column chromatography on ion-exchange cellulose and Sephadex, and the mer- and u-facial isomers were completely resolved by column chromatography on SE-Sephadex. These isomers were studied by electronic, infrared, and PMR spectroscopy, and the absolute configuration of the u-facial isomer was assigned on the basis of the circular dichroism spectrum.
Imidothiocarbonates. V. Preparations and Properties of Novel Azomethine Ylides and Thiocarbonyl Ylides from Sulfur-contained Heterocycles
Authors: Ueno Yoshio , Okawara Makoto
Published: July 2006

Preparations and properties of some novel azomethine ylides and thiocarbonyl ylides containing 1,3-dithiolanium moiety have been studied. Azomethine ylides, 3a, b, and c, were prepared by deprotonation of 2-(N-methyl-N-phenacyl)amino-(2a), 2-(N-p-nitrobenzyl-N-methyl)amino-(2b), and 2-(N-carbethoxymethyl-N-methyl)amino-1,3-dithiolanium salt (2c), respectively. Azomethine ylides 3a, b reacted with benzaldehydes to give 1,3-dipolar cycloadducts which are new class of spiro orthocarbonates, otherwise it is difficult to obtain. Elimination of ethylene sulfide from the spiro orthocarbonates easily occurred to give thiocarbonyl compounds. In the absence of dipolarophiles, 3a cyclized intramolecularly to give 1,3-oxazoline-2-thione derivative. Formation of the thiocarbonyl ylides by deproptonation of 2-phenacylthio-1,3-oxazolium and 2-p-bromophenacylthio-1,3-dithiolanium salts, and their different cyclization to spiro compounds were also studied. Reaction of thiocarbonyl ylides 16 with p-nitrobenzaldehyde afforded p-nitrochalcone. Mechanisms of these interesting reactions and their synthetic utility were discussed.
Methylene Analogs of Cyclobutenedione. IV. The Reaction of 3,4-Bis(diphenylmethylene) cyclobutanedione Monoacetal and Its Derivatives with Methanolic Potassium Hydroxide
Authors: Toda Fumio , Ooi Nobuhiro
Published: July 2006

The reaction of 2,2-dimethoxy-3,4-bis(diphenylmethylene)cyclobutanone (II), 2,2-dimethoxy-3,4-bis(diphenylmethylene)cyclobutanol (III), 2-hydroxy-3,4-bis(diphenylmethylene)cyclobutanone (IV), and 2-methoxy-3,4-bis(diphenylmethylene)cyclobutanol (VIII) with methanolic potassium hydroxide was studied. The three methoxy compounds, II, III, and VIII, afforded the ring-opened products, methyl 4,4-dimethoxy-2-diphenylmethylene-3-diphenylmethylbut-3-enate (X), 4,4-dimethoxy-2-diphenylmethylene-3-diphenylmethyl-but-3-enal (XIII), and 4-methoxy-2-diphenylmethylene-3-diphenylmethylbut-3-enal (XVI) respectively. However, the ketoalcohol IV afforded the enolizable cyclobutenedione, 3,4-bis(diphenylmethyl) cyclobutenedione (XXI).
The Photolysis and Thermolysis of Ethyl Azidoformate in the Presence of Ketones
Authors: Hiyama Tamejiro , Taguchi Hiroaki , Fujita Shinsaku , Nozaki Hitosi
Published: July 2006

The photochemical decomposition of ethyl azidoformate (I) in an acetone solution gives the nitrene adduct, oxazirane II, whereas the thermolysis of the solution gives a C–H insertion product, III. The photolysis of I in cyclohexanone gives an α-insertion product, IX, while the thermolysis affords a β-insertion product, X, and an oxazole, XIII, in addition to IX. The multiplicity of the reactive species is examined in terms of the heavy-atom effect.
Mass-spectral Fragmentation of 3-(5-Nitro-2-furyl)-1,2,4-triazoles
Authors: Kato Yasuhiko , Hirao Ichiro
Published: July 2006

The mass spectra of 3-(5-nitro-2-furyl)- (I), 5-methyl-3-(5-nitro-2-furyl)- (II), 5-ethyl-3-(5-nitro-2-furyl)-(III), and 5-trideuteriomethyl-3-(5-nitro-2-furyl)-l,2,4-triazole (IV) and their 1-acetyl, 1-trideuterioacetyl, and 1-propionyl derivatives were examined. The mother compounds, I-IV, gave the most prominent molecular ions and showed the same fragmentation pattern. The molecular ions undergo two modes of cleavages; one is the elimination of NO (1) and CO (2), followed by the loss of C2H2 (3), thus giving the M−84 ions which include the 5-substituents of the triazole ring, while the other is the loss of NO2–CO, which directly gives rise to the fragment M−74 ions. The 1-acyl derivatives gave extremely weak molecular ion peaks. In the first step of the fission of the molecular ions, the elimination of an acyl group occurred, with the rearrangement of a hydrogen atom, thus giving rise to prominent ions. These ions correspond to the molecular ions of the mother compounds, I–IV, and are expected to show a similar fragmentation pathway. The fragmentation of these compounds was also considered to occur in view of the existence of meta-stable ion peaks. The meta-stable peaks appearing at the transition of the loss of NO are flat-topped, releasing kinetic energy of 0.78±0.04 eV.
The Synthesis of an Etiojervane Analog of Corticosterone.
Authors: Masamune Tadashi , Orito Takako
Published: July 2006

The synthesis of C-nor-D-homo-17-epicorticosterone 21-acetate (1) from jervine (3), which possesses the corticosterone configuration at each of the ring junctions, is described. Etiojerv-5-ene-3β,11β-diol-17-one (4), obtained by a seven-step process from 3, was subjected to the Darzens reaction and afforded glycidic ester (7), which was converted by treatment with boron trifluoride into olefin (9). Catalytic hydrogenation followed by reduction with lithium aluminum hydride gave rise to tetraol (15), which was isolated as the acetonide (16). After Oppenauer oxidation of 16, acid hydrolysis and subsequent partial acetylation, the resulting monoacetate (19) was oxidized with dicyclohexylcarbodiimide in dimethylsulfoxide to give compound 1. Spectral and chemical evidence are presented for configurational assignment to both the compound and the synthetic intermediates.
Electronic Absorption Spectra and Geometry of Molecule Ions Generated from Stilbene and Related Compounds. I. Dianions
Authors: Suzuki Hiroshi , Koyano Kinko , Kunii Tosiyasu L
Published: July 2006

Stilbene and some of its alkyl-substituted derivatives were reduced with alkali metals to dianions in 1,2-dimethoxyethane. From comparison of the electronic absorption spectra of these dianions with one another and with the results of semiempirical SCF-MO-CI calculation of the π-electronic state, the geometries of the dianions were inferred to be as follows: (a) the preferred geometry of a sterically unhindered dianion, such as the dianion of stilbene, is probably planar or nearly planar; (b) when alkyl substituents are introduced into the central ethylenic carbon atoms, the steric interference caused by the substituents is relieved chiefly by the rotation about the central ethylenic bond; (c) the steric interference caused by ortho methyl substituents seems to be comparatively small or to be relieved by the rotation about the bonds connecting benzene rings to the ethylenic carbon atoms as well as the ethylenic bond. From the influence of alkali-metal cations on the spectra of the dianions, it was inferred that the dianions exist mainly as contact ion aggregates in which the counter-ions are located near the central ethylenic bond, one probably almost above an ethylenic carbon atom and the other almost below the other ethylenic carbon atom.
The Syntheses and Reactions of Sulfenyl-substituted Sulfonium Ylides
Authors: Hayasi Yosio , Nozaki Hitosi
Published: July 2006

Unstable dimethylsulfonium (phenylthio)methylide (2) is prepared in a THF solution from the corresponding sulfonium salt by treating it with n-butyllithium. Sulfenyl-substituted stable phenacylides 6a and 6b are obtained in three ways. The ylide 6a decomposes at 120°C in benzene to give (E)-9, the dimer of benzoyl(phenylthio)carbene. In contrast, the heating of 6a in ethanol affords ethanolysis products (11, 12) and ethyl benzoate. The alkylation of 6a and 6b with trimethyl- and triethyloxonium fluoroborate gives the vinylsulfonium salt 13. The ylide 2 reacts with (Z)- and (E)-1,2-dibenzoylethylene and with diethyl fumarate to give cyclopropanes, 15 and 16 respectively.
Ligand Effects in the Cooligomerization of Butadiene and Ethylene by a Nickel-based Catalyst System
Authors: Inoue Yoshio , Kagawa Teruhiko , Uchida Yasuzo , Hashimoto Harukichi
Published: July 2006

The cooligomerization of butadiene and ethylene catalyzed by a NiCl2–AlEt3–phosphine system was investigated. The cooligomerization product was 1,cis-4-hexadiene or/and 1,trans-4,9-decatriene. Bidentate ditertiary phosphines had remarkable effects on the reaction. The effects of ditertiary phosphines are also described.
C-C Bond Fission in Carboxamides. Kinetic Studies on Alkaline Hydrolysis of Substituted α-Nitroisobutyranilides
Authors: Sayo Hiroteru , Ohomori Hidenobu , Umeda Tsuneji , Masui Masaichiro
Published: July 2006

Alkaline hydrolysis of substituted α-nitroisobutyranilides, trichloroacetanilide and trifluoroacetanilide was studied kinetically at various hydroxyl ion concentrations in 10% aqueous dioxane. The formation of phenylcarbamate ion as an intermediate was confirmed on hydrolysis of the α-nitroisobutyranilides and trichloroacetanilide but not trifluoroacetanilide. All the substituted α-nitroisobutyranilides except the p-nitro derivative were found to undergo C–C bond fission exclusively. Trichloroacetanilide and the p-nitro derivative of α-nitroisobutyranilide underwent both C–C and C–N bond fission. The mechanism of C–C bond fission in the hydrolysis of α-nitroisobutyranilides was explained on the basis of the solvent isotope effect as a fast reversible addition of a hydroxyl ion followed by a rate-determining decomposition of the tetrahedral addition intermediate to form a phenylcarbamate ion and a carbanion.
Photolysis of Phenylazo p-Tolyl Sulfones
Authors: Kobayashi Michio , Fujii Sadao , Minato Hiroshi
Published: July 2006

Photolysis of phenylazo p-tolyl sulfone and p-chlorophenylazo p′-tolyl sulfone in aromatic solvents at room temperature was investigated. The products were analyzed, and the isomer distribution and partial rate factors in arylation of mono-substituted benzenes were determined. The results indicate that the photolysis involves formation of aryl radicals and p-tolylsulfonyl radicals.
Aromatic Arylation with Aryl Radicals. IV. The Kinetic Hydrogen Isotope Effect in the Aromatic Phenylation with Phenyl Radical
Authors: Kamigata Nobumasa , Minato Hiroshi , Kobayashi Michio
Published: July 2006

Anisole-4d, chlorobenzene-4d, chlorobenzene-d5, nitrobenzene-d5, m-dinitrobenzene-d4, and 1,3,5-tri-t-butylbenzene-d3 were phenylated with phenyl radical generated from PhN2BF4–NaNO2, N-nitrosoacetanilide or phenylazotriphenylmethane(PAT), and the isotope effect in these phenylations was determined. The values of kH⁄kD in the phenylations of chlorobenzene and 1,3,5-tri-t-butylbenzene are not so larger than unity, whereas that in the phenylation at the 2-position of m-dinitrobenzene with PAT was very large (∼11).
Reactive Species Produced by Laser Irradiation. The Reaction of CN Radicals with Hydrocarbons
Authors: Taki Ko , Kim Pil Hyon , Namba Susumu
Published: July 2006

The reactive species, CN radicals, were produced by the irradiation of the focused laser beam on the metal cyanide target. The reaction of CN radicals with low-molecular-weight hydrocarbons gave fragmented hydrocarbons and CN (and NC) compounds, while that with hydrogen gave hydrogen cyanide. From the experimental results, it seems that the products may be formed mainly by the reaction of the reactive species with fragment hydrocarbon radicals which are produced by the collision of the high-temperature reactive species (CN*) with the parent hydrocarbons.
Studies of the Synthesis of Furan Compounds. XXVII. Derivatives of 3-(5-Nitro-2-furyl)acrylonitrile
Authors: Hirao Ichiro , Kato Yasuhiko
Published: July 2006

In a continuation of our previous papers concerning the syntheses with 5-nitro-2-furonitrile, 2-(5-nitro-2-furyl)vinyl-1,2,4-oxadiazoles and -1,2,3-triazoles were prepared from 3-(5-nitro-2-furyl)acrylonitrile (I). When I was treated with diazomethane in ether, 4-[2-(5-nitro-2-furyl)vinyl]-1,2,3-triazole (II) was obtained. II gave N-acetyl (IIa) and N-morpholinomethyl (IIb) compounds when treated with acetic anhydride and when the Mannich reaction was utilized respectively. 3-(5-Nitro-2-furyl)acrylamide oxime (III) was prepared by the usual method from I and hydroxylamine. The treatment of III with benzaldehyde and acid anhydrides or chlorides afforded 3-[2-(5-nitro-2-furyl)vinyl]-5-phenyl-4,5-dihydro-1,2,4-oxadiazoline (IV) and O-acyl-3-(5-nitro-2-furyl)acrylamide oximes (IIIa—IIIe) respectively. The O-acyl-amide oximes were found to cyclize to 3-[2-(5-nitro-2-furyl)vinyl]-5-alkyl-1,2,4-oxadiazole (V–VII) in their thermal analyses.
A Negative Ion-molecule Reaction in Nitroethylene
Authors: Shiga Tetsuo , Yamaoka Hitoshi , Arakawa Kazuo , Sugiura Toshio
Published: July 2006

The formation of negative ions and the negative ion-molecule reaction in nitroethylene by electron impact have been studied. The nondissociative resonance electron capture of the nitroethylene molecule led to the formation of the molecular negative ion. The ionization efficiency curves and the appearance potentials of several fragment negative ions and the molecular negative ion were measured. The dimer negative ion of nitroethylene was found to be formed by the ion-molecule reaction between the molecular negative ion and a neutral nitroethylene molecule, and the rate constant of this ion-molecule reaction was estimated to be approximately 3.2×10−13 cc molecule −1sec−1.
The Solid Complex of Aminomalonic Acid with β-Alanine and Its Thermal Decomposition
Authors: Nishijo Juziro , Imanishi Isamu , Hashizume Genzo
Published: July 2006

For the crystallization of aminomalonic acid with several amino acids from an aqueous solution, solid complex formation was studied by means of an X-ray diffractometer. No complex formation of aminomalonic acid with α-alanine, dl-α-amino-n-butyric acid, l-isoleucine, l-leucine, dl-serine, dl-norleucine, α-amino-iso-butyric acid, dl-valine, dl-threonine, or dl-norvaline was observed. However, with β-alanine, the formation of a solid complex with a molar ratio of 1:1 was ascertained. When this solid complex was analyzed by the differential thermogravimetric method in air at a heating rate of 1.4°C/min, a decarboxylation reaction, accompanied by endothermic and exothermic peaks, was observed at 115–133°C. On the other hand, the decarboxylation of aminomalonic acid alone occurred in the temperature range of 112–138°C. The areas of the endothermic peak, which was attributed to the decarboxylation, and the endothermic peak, which was attributed to the crystallization energies of γ-glycine and β-alanine, were, respectively, about 3 and 3/2 times those of the peaks observed in the case of aminomalonic acid. It was also observed that the exothermic process proceeded in two steps. The X-ray analysis of the products of the decarboxylation process suggested that the complex first melted to become amorphous to X-rays, and that it was then decarboxylated to amorphous glycine and amorphous β-alanine with these subsequent crystallization. The two-step exothermic process was explained in terms of a somewhat earlier crystallization of amorphous glycine than in terms of that of the amorphous β-alanine. The activation energy of the solid complex was estimated to 119.2 kcal/mol from the thermogravimetric curve. This large value of the apparent activation energy may be considered to result because the solid complex turns to an amorphous phase much more sensitive to decarboxylation prior to decomposition, and the steep slope of the thermogravimetric curve which results from the rapid decarboxylation of the amorphous gives the large apparent activation energy.
The Crystal and Molecular Structure of Averufin
Authors: Katsube Yukiteru , Tsukihara Tomitake , Tanaka Nobuo , Ando Kazuto , Hamasaki Takashi , Hatsuda Yuichi
Published: July 2006

The crystal structure of averufin has been determined by means of the X-ray diffraction method. The space group is P21/a, with a=23.70 Å, b=7.24 Å, c=9.48 Å, and β=105.5°. The structure was solved by the interpretation of the three-dimensional Patterson function and was refined by the least-squares method. The molecular structure is in agreement with that proposed by Roffey and Grandjean. In the crystal, the molecules are linked to form a molecular pair by a OH···O hydrogen bond across the center of symmetry.
The Electrical Properties of Iodine Complexes of N-Methyl-and N-Ethyl-phenothiazines and Their Mixtures
Authors: Kan Kazuo , Matsunaga Yoshio
Published: July 2006

The electrical resistivities and Seebeck coefficients of 2: 3 iodine complexes of N-methyl- and N-ethyl-phenothiazines were measured. The former complex exhibits a resistivity of 2.0 ohm cm and an activation energy for semiconduction of 0.20 eV at 20°C. Applying the equation of Johnson and Lark-Horowitz for the Seebeck coefficient of an intrinsic semiconductor, the ratio of the electron mobility to the hole mobility in the N-methyl-phenothiazine complex was found to be 2.08 and the electron mobility was estimated as 0.23 cm2/Vsec. The resistivity of the N-ethylphenothiazine complex is 74 ohm cm, and the activation energy 0.15 eV at 20°C. In this complex, the hole appears to be more mobile by a factor of five than the electron. Lichtenecker’s logarithmic rule is observed neither by the resistivity nor by the activation energy of the mixtures of these two complexes.
The Syntheses of 3-(Carboxyalkyl)salicylaldehyde Derivatives and Their Copper Chelates
Authors: Tanaka Tsuguo
Published: July 2006

In order to study the influence of the side-chain carboxylic acid groups on the formation of the metal chelates, 5-bromo-3-carboxymethyl-, 5-methyl-3-β-carboxyethyl-, and 5-chloro-3-β-carboxyethyl-salicylaldehyde (2a, b  c) were synthesized. The green binuclear copper chelates of these aldehydes, di-μ-aquo-bis-(5-bromo-3-carboxymethylsalicylaldehyde)-, di-μ-aquo-bis-(5-methyl-3-β-carboxyethylsalicylaldehyde)-, and di-μ-aquo-bis-(5-chloro-3-β-carboxyethylsalicylaldehyde)-dicopper (11a, b, c) yielded the green binuclear bis-ethylenediimine chelates (12a, b, c), while bis-(5-bromo-3-carboxymethylsalicylaldehyde)-, bis-(5-methyl-3-β-carboxyethylsalicylaldehyde)-, and bis-(5-chloro-3-β-carboxyethylsalicylaldehyde)-ethylenediimine (14a, b, c) gave a brown (13a) and gray-purple (13b, c) mononuclear copper chelates. The reduction of 14a, b, c with sodium borohydride yielded the ihexadentate ligands N,N′-bis-(5-bromo-2-hydroxy-3-carboxymethylbenzyl)-, N,N′,-bis-(5-methyl-2-hydroxy-3-β-carboxyethylbenzyl)-, and N,N′-bis-(5-chloro-2-hydroxy-3-β-carboxyethylbenzyl)-ethylenediamine (15a, b, c), which proved useful for the spectrophotometric determination of the copper (II) ion from solutions containing copper (II) and nickel (II) ions, and the iron (II) ion from solutions containing iron (II) and nickel (II) ions.
Hydrogenation and Hydrogenolysis. XIV. The Hydrogenation of Ethyl p-Tolyl Ether over Platinum Metal Catalysts
Authors: Nishimura Shigeo , Uramoto Masayoshi , Watanabe Tetsuo
Published: July 2006

The hydrogenation of ethyl p-tolyl ether (1) in ethanol has been studied with five unsupported platinum metals as catalysts, mainly with the purpose of estimating the yields of ethyl 4-methyl-1-cyclohexenyl ether (2) formed as intermediate. Except for ruthenium catalyst, the hydrogenation of 1 in ethanol was accompanied by the formation of acetal 3, ketone 4 and alcohol 5 which seem to be related to the formation of 2. The amounts of 2 and the related compounds which were desorbed from the catalyst surface have been estimated to be 32–33% for Ru, 32–34% for Rh, 72–76% for Pd, 3.7% for Ir and 4.7% for Pt, by application of both kinetic and extrapolation methods. A good agreement was obtained between the results from the two methods. The proportion of hydrogenolysis increased for the catalyst metals in the order Pd<Ru<<Rh<Ir<Pt. With platinum catalyst a noticeable amount of toluene was formed along with methylcyclohexane. The hydrogenation of ethyl 4-methyl-3-cyclohexenyl ether (6), one of the other intermediates of the hydrogenation of 1, has also been studied in ethanol. Hydrogenolysis occurred extensively with palladium and rhodium catalysts, but much less with ruthenium, iridium and platinum catalysts. The hydrogenation route of 1 and its relation to hydrogenolysis and stereochemistry of hydrogenation of 1 are discussed with reference to the formation and hydrogenation of its intermediates.
Platinum(II)-Olefin Complexes Containing Amino Acids. III. Optical Inversion and Substitution of Coordinated Olefins in Optically Active trans(N)-Chloro-l-prolinato-olefinplatinum(II) Complexes in Organic Solvents
Authors: Konya Kazuo , Fujita Junnosuke , Kido Hiroaki , Saito Kazuo
Published: July 2006

Optical inversion of coordinated 2-methyl-2-butene and trans-2-butene in trans(N)-chloro-l-prolinato-olefinplatinum(II), trans(N)-[PtCl(l-prol)(olefin)] (nitrogen of l-prolinate ion is trans to the olefin), i.e. the interconversion between diastereoisomers (Fig. 1), has been kinetically studied in acetone by measuring the decrease in the intensity of circular dichroism (CD) in near ultraviolet region. The rate was measurable only in the presence of olefin, and can be expressed by the relation, Rate=k[complex][olefin]. The Ea and the ΔS\eweq values for the two complexes are 7.8±1.0 and 9.0±1.0 kcal/mol, and −44 and −39 entropy unit, respectively. The coordinated trans-2-butene is replaced by other olefins, 2,3-dimethyl-2-butene, 2-methyl-2-butene, trans-2-butene (optical inversion), and styrene, under similar conditions to give the same rate formula. The second order rate constant increases in the given order. The inversion seems to take place via bimolecular mechanism with excessive olefin as nucleophile. The corresponding complexes containing styrene and its para derivatives give such an inversion much faster in the absence of excess of olefin. With change of para substituents, the rate increases in the order, methoxy<methyl<hydrogen<chloro<nitro. This seems to be related with their electrondrawing ability.
Thermal Decomposition Reactions of Metal Oxalato Complexes in the Solid State. I. Thermographic Studies of Metal Oxalato Complexes
Authors: Nagase Kenzo
Published: July 2006

The thermal decomposition reactions of metal oxalato complexes in the solid state were studied by the TG and DSC methods. The results from TG indicated that the thermal stability of the anhydrous complex decreases approximately with the increase in the electron affinity of the central metal ion. From DSC, the complexes can be divided into two groups, giving endothermic and exothermic peaks on the decomposition of their anhydrous complexes respectively. The two enthalpy changes, ΔH, corresponding to the dehydration and to the decomposition of the anhydrous complexes, are also presented.
Magnetic Susceptibilities and Broad-Line PMR Spectra of Dichloro(pyridazine)copper(II) and Related Compounds
Authors: Emori Shuji , Inoue Motomichi , Kubo Masaji
Published: July 2006

The magnetic susceptibilities of CuX2L (X: halide ion, L: 1,2,4-triazole, pyridazine, phthalazine, 4-amino-1,2,4-triazole) conform to the linear Ising model or Heisenberg model, indicating the presence of linear magnetic chains in the crystals. Fermi contact shift observed in the broad-line PMR spectrum indicates the diffusion of a positive hole from a copper atom to the molecule of heterocycles. The magnitude of the exchange integrals is related to the spin densities on the atoms of the heterocycles.
The Syntheses of 5-Azidotropolones and Their Electrophilic, Nucleophilic, and Thermal Reactions
Authors: Toda Takashi , Horino Hiroshi , Nozoe Tetsuo
Published: July 2006

Several 5-azidotropolones were synthesized by the reaction of sodium azide with tropolone diazonium salts which has been prepared from the corresponding 5-aminotropolones. Most of the 5-azidotropolones thus obtained were stable except for the 4-alkyl derivatives. Their electrophilic substitution reactions took place at their 3- and 7-positions, and also their hydroxyl groups behaved like those of other tropolones. 5-Azidotropolone methyl ether did not react with aromatic amines, but it did with aliphatic amines and guanidine to give 2-aminotropone derivatives and 1,3-diazaazulene derivative. The thermolysis of 5-azidotropolone and its methyl ether afforded 5-aminotropolone and its methyl ether respectively; however, 5-azido-4-phenyltropolone gave indolo[3,2-d]tropolone.
The Second CMC of the Aqueous Solution of Sodium Dodecyl Sulfate. II. Viscosity and Density
Authors: Kodama Michiko , Miura Masaji
Published: July 2006

Our viscosity and density studies of an aqueous solution of sodium dodecyl sulfate have revealed that the 2nd critical micelle concentration (CMC) exists in addition to the 1st CMC and that the 2nd CMC is greatly influenced by such additives as sodium chloride, dodecyl alcohol, and benzene; these results are in good agreement with those obtained from the conductivity measurements described in the previous paper. The reduced viscosity of the micelle (ηsp.m/Cm) vs.  Cm curve showed a knick at the concentration corresponding to the 2nd CMC as obtained by Tyuzyo and his co-workers. The molar volume of the hydrated micelle was calculated by using the equation: ηr.m=1+2.5φm+14.1φm2; it has been found to decrease at about the 2nd CMC, similarly to the partial specific volume (\barv) of SDS obtained from the density measurement. This may be attributed to a change in the micelle structure at the 2nd CMC, caused by a variation in the type of aggregation and by a decrease in the counter-ion binding by the micelle.
The Quenching of Hg(63P1) Atoms by Molecular Hydrogen as Investigated by ESR Spectroscopy
Authors: Farmer James B , Shimokoshi Kazuo
Published: July 2006

The gas phase electron spin resonance technique has been applied to study the quenching efficiency of Hg(63P1) mercury atoms by molecular hydrogen. The concentration of hydrogen atoms produced by the mercury photosensitized decomposition of molecular hydrogen in a flow apparatus was followed as a function of the partial pressure of hydrogen with argon, neon, and hydrogen as carrier gases. The kinetic equations derived from the reaction mechanism proposed was shown to be in agreement with the experimental observations. The total quenching rate kH was evaluated from the experimental results.
The Molecular and Crystal Structures of Two Isomeric Dihydrofukinolidol Sulfites, C15H22O5S
Authors: Furusaki Akio , Watanabé Tokunosuké
Published: July 2006

The molecular and crystal structures of two isomeric dihydrofukinolidol sulfites, C15H22O5S, have been studied by means of an X-ray analysis. The two sulfites, called S-1 and S-2, both crystallize in the orthorhombic space group P212121, with four molecules in each unit cell. The cell dimensions are a=12.544, b=14.457, and c=8.545 Å for S-1, and a=12.919, b=14.375, and c=8.496 Å for S-2. The reflection intensities were measured visually from equi-inclination integrating Weissenberg photographs taken with CuKα radiation. The structures were solved by the tangent formula procedure and refined by the block-diagonal-matrix least-squares method, the anisotropic thermal motions being assumed for all the atoms. The final R factor was 10.8% for S-1 and 11.2% for S-2. The absolute configurations of the molecules were determined by using the anomalous dispersion effects of the sulfur atoms for CuKα radiation. It was found that the six-membered ring containing the sulfite group in S-1 takes the chair conformation, while the same ring in S-2 has the twist boat form. The exocyclic S–O bond in the two sulfites are both axially oriented, and the other corresponding parts of the two isomers are closely similar to each other.
Vapor Pressure of a Mixed System of Asphaltene and Organic Solvent
Authors: Sakanoue Shinji , Endo Mitsuo
Published: July 2006

The vapor pressure of a system in which it is assumed that the maltene component in petroleum asphalt has been replaced by an organic solvent, i.e., a mixed system of an asphaltene component and an organic solvent, was measured over a wide range of composition. The experimental results were then analyzed on the assumption that such a system is a binary system and that the equation μ1=μ1°+RTln(1–v2)+(1–1⁄z)v2+χ1v22 which Flory and Huggins derived for the chemical potential of a solvent of a linear, high-polymer solution which is not relatively dilute is applicable; the volumetric ratio, z, of the asphaltene particle and solvent molecule and the value of the parameter, χ1, of the interaction of the asphaltene and solvent molecules were obtained. The above results made it clear that mixed systems of asphaltene plus chloroform and carbon tetrachloride all form a homogeneous phase over the entire composition range, but in the case of a cyclohexane system, separation into 2 phases occurs in the mixed composition range of 3.0 vol%−40 vol% asphaltene and a dilute phase of 3.0 vol% asphaltene and a concentrated phase of 40.0 vol% coexist. It may be assumed from the above results that there is a possibility of the presence of a state in which separation into 2 phases is also present in the case of asphalt.
Studies of Benzoylsulfene. V. The Reaction of Benzoylsulfene with Enamines
Authors: Tsuge Otohiko , Iwanami Sumio , Hagio Shigeru
Published: July 2006

The reaction of benzoylmethanesulfonyl chloride with enamines derived from cyclohexanone in the presence of triethylamine has been studied. The chloride reacted with 1-(1-morpholino)- and 1-(1-piperidino)cyclohexene in the presence of triethylamine, affording the corresponding acyclic sulfones. On the other hand, the reaction of the chloride with 1-(1-pyrrolidinyl)cyclohexene gave 2-benzoylmethanesuIfonylcyclohexanone and 2,3-dibenzoyl-2,3,4,5,6,7-hexahydrothianaphthene 1,1-dioxide. The latter compound, whose structure corresponded to the compound derived from the 2:1 adduct of benzoylsulfene and the enamine with the elimination of sulfur dioxide and pyrrolidine, reacted with hydrazine hydrate to give 1,4-diphenyl-5a,6,7,8,9,9a-hexahydrothianaphtheno[2,3-d]-pyridazine, which was then transformed into 3,4,6-triphenylpyridazine.