bluuebunny/crossref_metadata_2025_split huggingface dataset:
The Crystal Structure of the 1 : 1 Complex N, N, N′ N′-Tetramethyl-p-phenylenediamine and 1,2,4,5-Tetracyanobenzene
Authors: Ohashi Yuji , Iwasaki Hitoshi , Saito Yoshihiko 
Published: July 2006

Abstract
The crystal structure of the 1 : 1 complex formed between N, N, N′ N′-tetramethyl-P-phenylenediamine and 1,2,4,5-tetracyanobenzene has been determined by X-rays at room temperature. The crystals are triclinic with one formula unit of the complex in a cell of dimensions: a=7.654 Å, b=8.041 Å, c=7.462 Å, α=96.7°, β=85.9° and γ=101.3°. The space group is P\bar1. The structure has been solved by three-dimensional Fourier and least-squares methods. The component molecules are stacked alternately in infinite columns along the c-axis. The structure does not seem to show the usual π–π interaction between the two aromatic rings, but indicates the n–π interaction localized between the nitrogen atoms of the donor and the cyano groups of the acceptor. From the direct integration of the electron density, the quantity of the charge transfer from the donor to the acceptor has been estimated to be 0.24 in electron units.
Radiation Chemistry of Dicarboxylic Acids in the Solid State. I. Radiolysis of Malonic Acid in the Solid State
Authors: Hosaka Akio , Sugimori Akira , Genka Tsuguo , Tsuchihashi Gen-ichi 
Published: July 2006

Abstract
The radiolysis of solid malonic acid by 60Co γ-rays has been studied in vacuo at −196°C, − 78°C, and room temperature. All the products were measured after dissolving the irradiated malonic acid in water. The main products were carbon dioxide with G=4.4 and acetic acid with (G=4.5, as was determined by the reverse isotope dilution analysis. The yields of the other products (hydrogen, carbon monoxide, methane, ethane and carbonyl compounds) were very low. These facts revealed that the following reaction takes place selectively:
(Remark: Graphics omitted.)
The mechanism of the reaction is discussed with reference to the results of product analyses and ESR.
Nickel(II) Complexes of Schiff Bases Derived from Alkanolamines and Salicylaldehyde and 3-Methoxysalicylaldehyde
Authors: Yamada Shoichiro , Kuge Yoshio , Yamanouchi Kuniko 
Published: July 2006

Abstract
Nickel(II) complexes of Schiff bases derived from salicylaldehyde and amines have so far been studied. In the present work, the nickel(II) complexes of N-hydroxyalkyl-salicylideneimines and related compounds are taken up, and the behavior of the hydroxyl group as to its coordination with the nickel(II) ion is examined. Bis(N-hydroxyalky 1-3-methoxysalicylideneiminato)-and bis(N-hydroxyalkyl-salicylideneiminato)-nickel(II) complexes have been prepared in the present work, where R=CH2CH2OH, CH2CH(CH3)OH, C(CH3)2CH2OH and CH2CH2CH2·OCH3. These complexes, except for the complexes with R=CH2CH2CH2OCH3, in the solid state are hexa-coordinated and show paramagnetism corresponding to two unpaired electrons. They are hexa-coordinated in non-donor solvents, except for the nickel(II) complexes with R=C(CH3)2CH2OH, which take a hexa-coordinated configuration in ethanol or methanol, a square-planar configuration in chloroform, and a different configuration in pyridine.
Study of Dielectric Relaxation Mechanism in Some Substituted Pyridines
Authors: Mehrotra N K , Saxena M C 
Published: July 2006

Abstract
The relaxation times of 2-chloro-, 2-bromo-, 3-bromo-, 2-methyl-, 2-acetyl- and 2-hydroxy-pyridines have been determined in the 3 cm microwave region at 20°C using benzene as solvent. It has been concluded from the relaxation times of 2-chloro-, 2-bromo-, 3-bromo- and 2-methylpyridines that these rigid molecules relax predominantly by the process of over-all molecular rotation. The comparatively small relaxation times of 2-acetyl- and 2-hydroxypyridines suggest that these non-rigid molecules relax by both molecular as well as intramolecular rotations. The free energies of activation for dipole orientation for the compounds investigated are always found to be smaller than those for viscous flow, because the process of dipole orientation involves only rotation, while the process of viscous flow involves both rotation and translation.
Kinetic Studies of Bimolecular Nucleophilic Substitution. III. Rates of SN2 and E2 Reactions of ω-Chloroalkylbenzenes with Sodium Acetate in 50 vol% Aqueous Acetone—Alternation Effects in Saturated Carbon Chains
Authors: Okamoto Kunio , Kita Teruo , Shingu Haruo 
Published: July 2006

Abstract
The rate of the bimolecular reactions of a series of ω-chloroalkylbenzenes, C6H5(CH2)nCl(n=1–4), with sodium acetate have been measured in 50 vol% aqueous acetone in the range from 100 to 130°C. The second-order rate constants, k2, have been obtained by measuring the rate of chloride-ion liberation. From the k2 values, i. e., kSN2+kE2, and the olefin percentage in the products, which was determined by measuring the rate of acetic acid formation, the SN2 rate constant, kSN2, and the E2 rate constant, kE2, for each chloride have been calculated. For purposes of comparison, the kSN2 and kE2 values for n-alkyl chlorides, CnH2n+1Cl (n=1–4), in the same solvent at 120°C have been calculated by a similar treatment of the rate in the bimolecular reactions of titled chlorides with sodium acetate. There is an alternation effect on the SN2-rate sequence of the ω-chloroalkylbenzenes, whereas no alternation effect has been observed for the E2 reactions of ω-chloroalkylbenzenes or for the SN2 and the E2 reactions of n-alkyl chlorides. From an examination of these data, together with the results previously reported in the literature, the zigzagging of the rate sequence in the SN2 reactions of ω-substituted alkyl halides has been thought most probably to originate from steric effects. In contrast to the previous observation in the E2 reactions of alkyl bromides with sodium ethoxide, the rate sequence for alkyl chlorides with sodium acetate has been found to be governed by the Hofmann rule.
Kinetic Studies of Bimolecular Nucleophilic Substitution. V. Rates of SN2 and E2 Reactions of 1,2-Dichloroethane with Various Nucleophiles in Aqueous Solutions
Authors: Okamoto Kunio , Matsuda Hisayuki , Kawasaki Hiroshi , Shingu Haruo 
Published: July 2006

Abstract
The rates of the reactions of 1, 2-dichloroethane with sodium hydroxide, sodium phenoxide, trimethylamine, pyridine, and sodium acetate have been measured in aqueous solutions at 110 and 120°C. On the assumption that the substitution reaction of 1, 2-dichloroethane produces two equivalents of the chloride ion because of the greater reactivity of the mono-substitution products (β-substituted ethyl chlorides) than that of the starting substrate, while the elimination product from 1, 2-dichloroethane, i. e., vinyl chloride, does not react with the bases under the reaction conditions employed, the kSN2 and kE2 have been calculated from the rate of the chloride-ion liberation and from the number of moles of the base required to react with one mole of the substrate. For a series of kSN2 values there is no linear relation between the rates and the pKa’s of the conjugate acids, whereas a parallelism exists between the kE2 and the pKa. The stronger the base, the more the elimination is promoted.
Aminocyclitols. XIII. Studies on the Synthesis of Streptamine
Authors: Suami Tetsuo , Ogawa Seiichiro 
Published: July 2006

Abstract
Starting from epi-inositol, two new inosamines: epi-l and epi-6, and two inosadiamines: myo-4, 6 and streptamine, have been prepared by a replacement of sulfonate group by an azide ion. The nuclear magnetic resonance spectroscopy has established the configurations of the products.
The Activity of a Catalyst from Nickel Chloride and Methyl-hydropolysiloxane in the Hydrogenation of Olefins
Authors: Takegami Yoshinobu , Ueno Toru , Masunaga Kunihiko 
Published: July 2006

Abstract
The reaction of anhydrous nickel(II) chloride with methylhydropolysiloxane has been found to give an active catalyst for the hydrogenation of olefins. These two reagents react readily at 120–170°C, with the evolution of hydrogen, to form a black-colored substance which has been used as the catalyst. The catalytic activity has been found to depend on the amount of hydrogen evolved during the reaction and on the methylhydropolysiloxane : nickel chloride ratio. The most active catalyst has been obtained by using the reagents in the Si : Ni ratio of 25 : 1 and by intercepting the reaction as soon as the hydrogen evolution amounted to 1.0 mol per mole of nickel chloride. Cyclohexane has been successfully used as a solvent. However, the presence of diethyl ether or tetrahydrofuran has considerably deactivated the catalyst. The catalyst deactivated by ether has, though, been highly activated by adding a large excess of water.
The Ionic Telomerization of Conjugated Diene Compounds. II. The Solvent Effects on the Cationic Telomerization of Butadiene with Its Hydrochloride
Authors: Asahara Teruzo , Kise Hideo 
Published: July 2006

Abstract
The telomerizations of butadiene with its hydrochlorides (1-chlorobutene-2 and 3-chlorobutene-1) in several sorts of solvents in the presence of Lewis acids were investigated. Titanium tetrachloride in ethyl bromide has a considerable catalytic ability at low temperatures and gives telomers with higher average molecular weights than ferric chloride and aluminum chloride at almost the same conversions of reaction. On the other hand, antimony pentachloride gives only a small amount of product with lower average molecular weights. The telomerizations in methylene dichloride and chloroform give almost the same amounts of telomers with molecular weights higher somewhat in the former solvent than the latter. The telomerization in toluene gives primarily the products of Friedel-Crafts reaction, and a small amount of telomers of butadiene with crotyl chloride is obtained. The use of ethyl ether, acetonitrile and acetic anhydride as solvents at low temperatures in the presence of ferric chloride affords poor yields of the telomers in contrast to the cases of halogenated hydrocarbons. In ethyl ether, an appreciable amount of telomers is obtained only at the temperatures above 0°C. The telomers thus obtained have a lower average molecular weight and a larger degree of residual unsaturation than the telomers obtained in halogenated hydrocarbons. The use of nitromethane and nitrobenzene as solvents leads to the formation of an amount of telomers smaller a little than halogenated hydrocarbons. There are scarcely observed differences in the compositions of fractions in 1 : 1 adducts of butadiene and its hydrochloride obtained in the various solvents. The infrared spectra of the higher telomers are almost the same each other and it was concluded that the reactions proceed on the same mechanism irrespective of the variation of solvents.
Amide Mercaptole. II. The Reactions of N, N-Dimethylbenzamide Diethylmercaptole with Some Heavy Metal Compounds
Authors: Yamaguchi Tatsuaki , Mukaiyama Teruaki 
Published: July 2006

Abstract
The reactions of N, N -dimethylbenzamide diethylmercaptole with mercuric compounds (mercuric oxide, mercuric acetate and mercuric cyanide) or lead(IV) compounds (lead dioxide and lead tetraacetate) have been investigated. Mercuric acetate was found to react easily with the amide mercaptole giving N, N-dimethylbenzamide and acetic anhydride with the elimination of mercury ethylmercaptide. In a similar way, mercuric cyanide gave α-dimethylamino phenylmalononitrile in a good yield. Further, it was shown that the amide mercaptole was oxidized by lead dioxide or lead tetraacetate to N, N-dimethylbenzamide and diethyl disulfide. The high reactivity of the amide mercaptole toward heavy metal compounds was discussed in comparison with common mercaptals.
Studies of Peptide Antibiotics. XL Analogs of Gramicidin S and Cyclosemigramicidin S Containing Glycine or Alanine in Place of Valine
Authors: Kondo Michio , Izumiya Nobuo 
Published: July 2006

Abstract
To investigate the contribution for the antibacterial activity of the valine residues in a gramicidin S molecule, two analogs of gramicidin S, 1, 1′-glycine- and 1, 1′-l-alanine-gramicidin S, were prepared through the cyclization reaction of linear decapeptide active esters in pyridine. 1-Glycine- and 1-l-alanine-cyclosemigramicidin S were also prepared through the cyclization of linear pentapeptide active esters. The effects of the four cyclic peptides thus obtained on bacterial growth were tested; only 1, 1′-alanine-gramicidin S was as active as natural gramicidin S, while the other three analogs showed no activity in relation to any of the microorganisms tested. The results indicate that the side chains of the valines in gramicidin S can be replaced by smaller aliphatic side chains, the methyls, without the influence for the activity.
The Crystal Structure of the Perylene-Tetracyanoethylene Complex
Authors: Ikemoto Isao , Kuroda Haruo 
Published: July 2006

Abstract
The crystal structure of the perylene-tetracyanoethylene (TCNE) complex has been determined by the two-dimensional Fourier synthesis and by difference synthesis. The monoclinic unit cell dimensions are: a=15.79, b=8.28, c=7.31 Å, and β=96.1°. Two perylene and two TCNE molecules are in a unit cell. The space group is P21⁄a. Perylene and TCNE molecules are stacked alternately along the b-axis, making their molecular planes parallel to each other. The center of a TCNE molecule is not directly above that of the neighboring perylene molecule. The mean separation of the molecular planes is 3.23 Å.
Generation of Free Radicals at Subzero Temperatures. I. Methanolyses of Thionyl Chloride and Methyl Chlorosulfite
Authors: Minato Hiroshi , Fujii Atsushi 
Published: July 2006

Abstract
Rates of methanolysis of thionyl chloride and methyl chlorosulfite were measured conductimetrically at +1.0–−91.6°C, and were compared with the rates of other acid chlorides. Activation enthalpies and entropies were obtained.
Proton Magnetic Resonance Study of Solid Hexamethylethane
Authors: Koide Tsutomu 
Published: July 2006

Abstract
The molecular motion of solid hexamethylethane was studied by the proton magnetic resonance method from the liquid nitrogen temperature to 20°C. In the temperature range between about −160°C and −120°C, the methyl group rotates about its own axis, and also the molecule rotates about the molecular axis as a whole. Above −120°C, the molecule rotates almost freely. On the other hand, the molecular motion of hexamethyldisilane in the high temperature phase has been explained in terms of the facts that the molecule rotates freely and also has a degree of translational freedom. The difference in the molecular motion between hexamethylethane and hexamethyldisilane is caused mainly by the difference in the molecular interaction.
Studies of the Solvent Effects on the Chemical Shifts in NMR Spectroscopy. III. The Benzene Solutions of Cyclic Ketones and Lactones
Authors: Ichikawa Yukihiko , Matsuo Taku 
Published: July 2006

Abstract
The high-field shifts of the proton signals of cyclic ketones and lactones in the benzene solutions have been investigated. The solvent effects on the chemical shifts for the β-methylene protons of these compounds are always larger than those for the α-methylene protons. The data may be explained by the use of a model in which benzene molecules are assumed to cluster around the carbonyl group of the solute. The affinity between the solute and the solvent molecules has been mainly ascribed to the fact that both the permanent electric dipole moment and the instantaneous dipole moment of the carbonyl (or carboxyl) group induce electric dipole moments in the near-by benzene molecules. The configuration and the number of the solvent molecules clustering around the solute have been suggested to be determined by the geometrical restriction around the carbonyl group.
The Reactions of the OH Radical Arising from Nitrous Oxide in an Aqueous Hexacyanoferrate(II) Solution Illuminated at 2537Å
Authors: Ohno Shin-ichi 
Published: July 2006

Abstract
A method for the determination of the relative rate constants for reactions of the OH radical is described. The OH radical is generated from the reaction between N2O and the photochemically-produced electron in a solution of 10−3 m hexacyanoferrate(II) irradiated at 2537 Å. The method has been applied to the determination of the rate constants for the reactions of OH with methanol, ethanol, 2-propanol, formate, bromide, glycine, and boric acid relative to that with [Fe(CN)6]4−. The values found are compared with those obtained by other methods, and their significance is discussed.
Ribonuclease T1 Peptides. I. Synthesis of a Protected N-Terminal Undecapeptide Containing Asparagine Residue in Third Position
Authors: Ohno Motonori , Kato Tetsuo , Mitsuyasu Nobuo , Waki Michinori , Makisumi Satoru , Izumiya Nobuo 
Published: July 2006

Abstract
A protected undecapeptide containing the possible N-terminal sequence of ribonuclease T1, namely benzyloxycarbonyl-l-alanyl-S-benzyl-l-cysteinyl-l-asparaginyl-l-tyrosyl-l-threonyl-S-benzyl-l-cysteinyl-glycyl-l-seryl-l-asparaginyl-S-benzyl-l-cysteinyl-l-tyrosine ethyl ester (XXI), was synthesized by coupling of benzyloxycarbonyl-alanyl-S-benzylcysteinyl-asparaginyl-tyrosine azide with heptapeptide ester, threonyl-S-benzylcysteinyl-glycyl-seryl-asparaginyl-S-benzylcysteinyl-tyrosine ester, which is derived from p-methoxybenzyloxycarbonyl-heptapeptide ester by the action of trifluoroacetic acid. The optical homogeneity of the protected undecapeptide (XXI) was established by deblocking of XXI and subsequently digesting the resulting free undecapeptide with leucine aminopeptidase.
Radiolysis of CoIII-EDTA in Aqueous Solution; the Yields of Hydrogen and Hydrogen Peroxide in 0.8 n Sulfuric Acid
Authors: Matsuura Niro , Shinohara Nobuyoshi , Nishikawa Masaru , Takizawa Masao 
Published: July 2006

Abstract
The hydrogen and hydrogen peroxide produced in the radiolysis of CoIII-EDTA (CoIIIY−) in 0.8 n sulfuric acid have been measured. The yields of hydrogen and hydrogen peroxide were found to be G∞(H2)=0.4 and G∞(H2O2)=2.5 for the aerated system, G∞(H2)=3.2 and G∞(H2O2)=0 for the deaerated system where G∞ denotes the yield at the infinite solute concentration. The decomposition mechanism proposed previously was discussed in detail on the basis of the observed G∞(H2) and G∞(H2O2) and of the effect of chloride ion on the decomposition yield G∞(–CoIIIY−). A similar experiment was carried out for EDTA alone and the decomposition mechanism was discussed.
The Radiation Chemistry of Cyclic Dienes. II. The Radiolysis of 1,4-Cyclohexadiene in the Gas Phase
Authors: Nakagawa Tsunehiko , Takamuku Setsuo , Sakurai Hiroshi 
Published: July 2006

Abstract
The γ-radiolysis of 1,4-cyclohexadiene vapor has been investigated at room temperature. The gaseous products are hydrogen, acetylene, and 1,3-butadiene. Benzene, cyclohexene, 1,3-cyclohexadiene, and 1,3,5-hexatriene are identified as the low volatile liquid products. The yield of each product is almost independent of the dose (0.87–9.11)×1019 eV, while it is remarkably dependent on the gas pressure (8–56 mmHg). The G values of hydrogen, the C2+C4 gas fraction, benzene, and cyclohexene are 1.95, 1.25, 28.5, and 14.0 respectively at 42 mmHg. The large yields of benzene and cyclohexene may be explained in terms of a chain mechanism. The pressure dependence of these products is very similar in both the Hg-sensitized photolysis and the γ-radiolysis of this diene vapor. The presence of the long-lifetime intermediates is as expected. The experiments with nitric oxide added as a radical scavenger suggest that the main path of hydrogen formation is the radical process.
Cyanoethyl Complexes of Cobalt—Their Preparation and Their Reactions with Acrylonitrile
Authors: Misono Akira , Uchida Yasuzo , Hidai Masanobu , Kanai Hideo 
Published: July 2006

Abstract
By the addition reaction of acrylonitrile to hydridobis (dimethyl- or diphenylglyoximato)-pyridinecobalt, only 1-cyanoethyl complexes were obtained. The 2-cyanoethyl complex was not formed from that reaction, but from the reaction of 3-bromopropionitrile with the hydride complex. NMR spectroscopy was used to confirm the structure of the complexes. The isomerization of the 2-cyanoethyl complex to the 1-cyanoethyl complex at 70°C was not observed by NMR measurements. The reaction of these complexes with acrylonitrile was carried out under a hydrogen atmosphere. It was observed that 2-methylglutaronitrile was formed from the reaction of the 1-cyanoethyl complex with acrylonitrile. The thermal decomposition and the reaction of the complexes with hydrochloric acid were also investigated.
The Liquid Phase Oxidation of Acrolein. V. Effects of Water on the Oxidation of Acrolein
Authors: Ohkatsu Yasukazu , Osa Tetsuo , Misono Akira 
Published: July 2006

Abstract
Some water was added as a model to a reaction solution containing Co(acac)2 before the beginning of the reaction by two methods in order to examine the effects of water formed during the reaction. These two methods gave different phenomema in the induction periods and different oxygen absorption rates. From these results and those with Co(acac)2·2H2O, the water added is considered to act in two ways, increasing the reaction rate by the coordination with the catalyst and decreasing the reaction rate when not bonded with the catalyst. The latter effect is considered in detail on the basis of the oxygen absorption rate: −dO2/dt=k(acrolein)0.88. (catalyst)0.39(H2O)r, wherein r is −0.1 or −0.21. This rate equation accorded well with the derived rate equation considering the reaction phenomena and the interaction among the catalyst, acrolein, and water in the initiation reaction.
Photoreactions of Cyclopentenone Derivatives
Authors: Moritani Ichiro , Toshima Naoki , Nakagawa Shiro , Yakushiji Masatoshi 
Published: July 2006

Abstract
Photoreactions of conjugated or non-conjugated, five-membered, cyclic ketones were investigated. Irradiation of 2,3,4,5-tetraphenyl-2-cyclopenten-1-one in 2-propanol with ultraviolet light under a slow stream of nitrogen or oxygen gave 1-oxo-2,3-diphenyl-2,3-dihydro-1H-cyclopenta[l]phenanthrene (55%) and 1-oxo-3-hydroxy-2,3-diphenyl-2,3-dihydro-1H-cyclopenta[l]phenanthrene (about 20%). Similar irradiation of 3,4-diphenyl-3-cyclopenten-1-one under a nitrogen stream gave 2-oxo- and 2-hydroxy-2,3-dihydro-1H-cyclopenta[l]phenanthrene in 33% and 11% yields respectively. In both cases, there was observed photocyclization of a cis-stilbene skeleton to a phenanthrene. However, on irradiation of 2,2-dimethyl-3,4-diphenyl-3-cyclopenten-1-one, there was obtained a decarbonylation product, 1,1-dimethyl-1,2-dihydrocyclobuta[l] phenanthrene. The reaction courses of these photoreactions are proposed.
Über die Umsetzung eines Ketenimins mit Cyanessigester und Malonester
Authors: Ichimura Kunihiro , Ohta Masaki 
Published: July 2006

Abstract
The reaction of either N-(p-chlorophenyl)diphenylketenimine or N-(p-chlorophenyl)diphenylacetimidoyl chloride with ethyl cyanoacetate gave the identical α, β-unsaturated ester. Whilst the reaction of the ketenimine with diethyl malonate yielded β, γ-unsaturated diester, the isomeric α, β-unsaturated diester was obtained by the reaction of the imidoyl chloride with the malonate. These remarkable different phenomena could be ascribed to the difference in bulk between cyano and carbethoxy groups. The structures of these products were discussed on the basis of the infrared and ultraviolet spectroscopic data and the reaction mechanisms were proposed. Additionally, the pyrolysis of the products was studied and the β, γ-unsaturated diester was found to give quinolin-4-one together with an α-naphthol derivative under elimination of ethanol, whilst only quinolin-4-one was isolated on the pyrolysis of the isomeric α, β-unsaturated diester.