bluuebunny/crossref_metadata_2025_split huggingface dataset:
Dimerization and Rearrangement of Diphenylcyclopropenone
Authors: Toshima Naoki , Moritani Ichiro , Nishida Shinya 
Published: July 2006

Abstract
The reaction of diphenylcyclopropenone with cyclopentadienylmagnesium bromide did not give the expected tertiary carbinol, but resulted in the formation of tetraphenylcyclopenta-dienone, tetraphenyl-p-benzoquinone, and tetraphenylpyrocatechol in 1%, 2%, and 8% yields respectively. When diphenylcyclopropenone was treated with a mixture of metallic magnesium and iodine, the same products were obtained in increased yields. Similarly, the treatment of diphenylcyclopropenone with sodium amalgam in isopropyl alcohol - acetic acid gave tetraphenyl-p-benzoquinone and tetraphenylpyrocatechol in 4% and 20% yields respectively. These results suggest that diphenylcyclopropenone gives pinacol, 1, l′-dihydroxy-2, 2′, 3, 3′-tetraphenyl-l, l′-bi-cyclopropenyl, under the reaction conditions, but the pinacol is too unstable to be isolated and rearranges to the benzene derivatives.
The Kinetics of the Vapor-Phase Ammoxidation of m-Xylene over Mixed Vanadium Catalysts
Authors: Ito Masatomo , Sano Ken-ichi 
Published: July 2006

Abstract
The kinetics of the vapor-phase ammoxidation of m-xylene over a chromium-vanadium catalyst and an antimony-vanadium catalyst, in which the atomic ratio of chromium or antimony to vanadium was unity, was studied in a flow system and compared with that over a vanadium catalyst. The reaction-rate data obtained were then correlated with the reaction kinetic model proposed for a vanadium catalyst. There was no great difference in the reaction rates of m-xylene over the various catalysts. The ratios of the specific rate constant of m-xylene to that of m-tolunitrile, kx/kM both mixed vanadium catalysts were considerably smaller than that for a vanadium catalyst. The relative ratio for the formation of m-tolunitrile from m-xylene, k1/kx, was nearly equal for a vanadium catalyst and a chromium-vanadium catalyst, but it was larger for an antimony-vanadium catalyst. The order of the relative ratio for the direct formation of carbon oxides and hydrogen cyanide from m-xylene was: vanadium catalyst&gt;chromium-vanadium catalyst&gt;antimony-vanadium catalyst. The order of the selectivity for the formation of isophthalonitrile from m-tolunitrile on these catalysts was similar to the order of kx/kM. It seems that those results may be ascribed to the weaker adsorptivity for m-xylene on mixed vanadium catalysts.
The Cobalt Carbonyl-catalyzed Hydroesterification of Acrylonitrile with Carbon Monoxide and Methanol in the Presence of a Small Amount of Hydrogen and a Limited Amount of Pyridine
Authors: Matsuda Akio 
Published: July 2006

Abstract
The present reaction was studied in connection with our preceding research on the hydroesterification of propylene (This Bulletin, 38, 710 (1965)). The cobalt carbonyl-catalyzed reaction was successfully carried out in the presence of a small amount of hydrogen and a limited amount of pyridine; methyl esters of α- and β-cyanopropionic acids were thus obtained, the former in a larger amount than the latter. As the temperature decreased or as the partial pressure of carbon monoxide increased, the selectivity of the reaction toward the methyl α-cyanopropionate grew larger. The reaction mechanism was mainly investigated by kinetic methods. The infrared spectra of the catalyst solutions were measured at −60°C with a low-temperature cell. It was found by the IR study that acylcobalt carbonyls were formed in the acrylonitrile solution of dicobalt octacarbonyl and pyridine when it was treated under the same conditions (temperature and pressure) as in the reaction. It was found from the results of kinetic studies that the mechanisms of reactions at temperatures above and below 100°C were different; each of these mechanisms was discussed.
The Direct and Alternating Current Polarography of ε-Aminocaproic Acid and Its Linear Oligomers via the Schiff Bases
Authors: Kobayashi Yoshinari 
Published: July 2006

Abstract
ε-Aminocaproic acid (ACA) and its linear oligomers were transformed with formaldehyde to the corresponding Schiff bases, which are polarographically active. The a. c. and d. c. polarographic behavior was almost same among ACA, its linear dimer and trimer, of which the half-wave potentials and peak potentials were identical within the range of experimental errors. In d. c. polarography the diffusion current constant was independent of the degree of polymerization, although the peak-current constant in a. c. polarography was influenced by the degree of polymerization and there existed no linear relationship between the concentrations and the peak currents. This electrode reaction was supposed to be a one-electron reduction. In the presence of ε-carprolactam, the N-hydroxymethylation of the compound interfered with the appearance of polarographic waves.
Studies of Phenyl Ether Derivatives. III. Friedel-Crafts Type Condensation Reactions of Some Phenyl Ether Derivatives
Authors: Oshima Akio 
Published: July 2006

Abstract
By treating the p, p′-disubstituted diphenyl ether with stannic chloride or sulfuric acid in some solvents, two sorts of substances were obtained. One was a compound, (ArCH2C6H5)2O (I), produced by the condensation of two molecules of the aromatic solvent and a molecule of the phenyl ether, the other was a self-condensation product (II) of the phenyl ether itself. Which product is obtained is dependent not upon the substituent in phenyl ether, but upon the sort of solvent. On the basis of the analytical data, molecular-weight measurements, UV- and IR-spectral analyses, and the results of pyrolyzing gas chromatography, the author has deduced the structures A and B for I and II respectively. He has inferred about the mechanism for these phenomena as follows: in each case the reaction can be regarded as a sort of Friedel-Crafts reaction. When the reactivity of the solvent molecule is high enough to bring about normal condensation, the compound (I) is produced. On the other hand, inter- and/or intra-molecular condensations take place between the phenyl ether molecules to yield the compound (II) when the reactivity of the solvent is rather low.
Solvent Effect under High Pressure. A Novel Procedure for the Estimation of the Activation Volume and an Abnormal Acceleration of Reaction under High Pressure
Authors: Kondo Yasuhiko , Tojima Hiroshi , Tokura Niichiro 
Published: July 2006

Abstract
In order to examine the relation between the effects of solvents and the effects of pressure on reaction rates, an apparatus for kinetic runs under pressure was constructed and the rates of the Menschutkin reaction were measured in various solvents under pressure. A graphical method for the calculation of an activation volume from experimental results was then developed and applied to these data. Experimental results in acetonitrile, methanol, and nitromethane showed a linear relation between log(kp⁄k1)⁄P vs. P, but in the case of benzene and nitrobenzene large deviations from the line, that is, abnormal accelerations due to pressure, were observed at 1200 and 1500 (kg·cm−2). Analyzing these data, it was concluded that this abnormal acceleration was due to a freezing of the solvent with the increase in pressure.
Coumarins. III. A Novel Synthesis of o-Hydroxybenzaldehydes
Authors: Amakasu Takeshi , Sato Kikumasa 
Published: July 2006

Abstract
The catalytic hydrogenation of salicyloyl chloride at a mild temperature gave a high yield of salicylaldehyde. A similar partial reduction of substituted salicyloyl chlorides provided the corresponding salicylaldehydes in appreciable yields. Attempts to prepare other isomeric hydroxybenzoyl chlorides were, however, unsuccessful. The relationship between the structure of salicyloyl chlorides and the ease of their conversion to salicylaldehydes is discussed. Moreover, the formylation of phenol with dichloromethyl methyl ether and the selective ortho-formylation are described.
Reaction Rates in Binary Mixed Solvents. III
Authors: Kondo Yasuhiko , Tokura Niichiro 
Published: July 2006

Abstract
The expressions for the activation energies in binary mixed solvents have been derived from the differentiation of the expressions for the rate constants in binary mixed solvents obtained in Part II of this series [Y. Kondo and N. Tokura, Bull. Chem. Soc. Japan, 40, 1433 (1967).] with respect to the temperature. The activation energies in mixed solvents have been expressed in terms of the activation energies of the pure solvents, the equilibrium constant, and the composition of the solvent. From comparison with the experimental results, the model used by the authors has been proved to be valid for a consideration of the effects of solvents on the reaction rates and the activation parameters in binary mixed solvents.
The Deamination of 3-Methylenecyclobutylcarbinylamine
Authors: Ooba Shigehiro , Kato Hiroshi , Ohta Masaki 
Published: July 2006

Abstract
The nitrous acid deamination of 3-methylenecyclobutylcarbinylamine in water gave 2-methylenecyclopentanol and 3-methylenecyclopentanol. The reduction of methyl 3-methylene-cyclobutanecarboxylate with lithium aluminum hydride gave 3-methylenecyclobutylcarbinol.
Studies on the κ-Polysaccharide of the Red Seaweed Gigartina Tenella
Authors: Hirase Susumu , Watanabe Kyoko 
Published: July 2006

Abstract
The polysaccharide extracted from the red seaweed Gigartina tenella has been separated into κ- and λ-polysaccharide by potassium chloride. The former polysaccharide is a gelling component precipitated with potassium chloride, while the latter is a non-gelling component insensitive to the precipitant. Complete hydrolysis and methanolysis, together with quantitative determination, have shown that the κ-polysaccharide is composed mainly of d-galactose, 3, 6-anhydro-d-galactose, and an ester sulfate in the molar proportion 1 : 0.98 : 1.17. Very small amounts of l-galactose and d-xylose have also been isolated from the products of hydrolysis. The partial methanolysis of the κ-polysaccharide yielded dimethyl acetal of carrabiose (4-O-β-d-galactopyranosyl-3, 6-anhydro-d-galactose) in a good yield. It follows from these results that this disaccharide is a chief repeating unit of the carbohydrate moiety of the polysaccharide, as in the case of κ-carrageenan.
Component Sugars of the Polysaccharide of the Red Seaweed Grateloupia Elliptica
Authors: Hirase Susumu , Araki Choji , Watanabe Kyoko 
Published: July 2006

Abstract
The extraction of Grateloupia elliptica with hot water afforded a mucilageous sulfated polysaccharide, which was then purified through precipitation as a complex with cetyl pyridinium chloride. In order to examine the component sugars, the polysaccharide was subjected to complete hydrolysis and methanolysis, the respective products of which were then carefully fractionated both by crystallization and chromatography in order to isolate the individual products. The results obtained, coupled with the data of quantitative estimation, have shown that the bulk of the polysaccharide is composed of d-galactose, l-galactose, 3, 6-anhydro-d-galactose, and sulfate, existing in the approximate molar proportion of 9 : 1 : 2 : 8. In addition to these main components, the presence of small amounts of d-xylose, 2-O-methyl-l-galactose, 4-O-methyl-d-galactose and 2-O-methyl-3, 6-anhydro-l-galactose has also been established. These compounds have been identified on the crystalline basis. The partially-methylated sugars isolated above have seldom or never previously occurred in polysaccharides.
Studies of the Organic Reactions of Metal Carbonyls. XI. The Reaction of Potassium Iron Carbonylates with Olefin Oxides
Authors: Takegami Yoshinobu , Watanabe Yoshihisa , Masada Hiromitsu , Kanaya Isao 
Published: July 2006

Abstract
The reaction between potassium iron carbonylates (KHFe(CO)4, K2Fe(CO)4, K2Fe2(CO)8, and K2Fe3(CO)11) and olefin oxides has been studied. Propylene oxide reacts readily with these carbonylates and carbon monoxide at atmospheric pressure at room temperature. As the reaction product, β-hydroxy-n-butyrate is obtained by the treatment of the reaction mixture with an iodine and hydrogen chloride solution in alcohol, indicating that a complex with a type of β-hydroxy-n-butyryliron carbonyl is formed in the reaction. Ethylene oxide also reacts with the carbonylate to give β-hydroxypropionate.
Studies of the Organic Reactions of Metal Carbonyls. XII. The Oxo Reaction of Ethyl Acrylate by Rhodium Carbonyl
Authors: Takegami Yoshinobu , Watanabe Yoshihisa , Masada Hiromitsu 
Published: July 2006

Abstract
The oxo reaction of ethyl acrylate by rhodium carbonyl has been studied and compared with that by cobalt carbonyl. The reaction conditions (the temperatures, and the partial pressures of carbon monoxide and hydrogen) affect the distribution of the products (α- and β-carbethoxy-propionaldehyde) more remarkably, but in a way similar to that in the reaction by cobalt carbonyl: the proportion of β-carbethoxypropionaldehyde increases greatly with an increase in the reaction temperature, but decreases with an increase in the partial pressure of carbon monoxide or hydrogen. Judging from this similarity, it is probable that rhodium carbonyl reacts with ethyl acrylate as rhodium hydrocarbonyl to give alkyl- and acylrhodium carbonyls in the course of the reaction.
The Isolation of Isomeric 5-Oxazolones and the Assignment of Their Structures by Means of NMR Spectroscopy
Authors: Iwakura Yoshio , Toda Fujio , Torii Yoshinori 
Published: July 2006

Abstract
In the syntheses of 5-oxazolones (2-isopropenyl-4-alkyl-2-oxazolin-5-ones) from N-meth-acryloyl-α-amino acids, new isomerized oxazolones were obtained. By NMR spectroscopy, the structures of isomerized oxazolones were determined to be pseudoxazolones (2-isopropylidene-4-alkyl-3-oxazolin-5-ones). The NMR spectra of several pseudoxazolones were measured and compared with the normal oxazolones.
10, 11-Dihydro-5H-dibenzo[a, d]cycloheptenylidene
Authors: Moritani Ichiro , Murahashi Shun-Ichi , Yoshinaga Kunio , Ashitaka Hidetomo 
Published: July 2006

Abstract
The photolysis of 5-diazo-10, 11-dihydro-5H-dibenzo[a, d]cycloheptene in cis-2-butene gave 5, 5′-bi(10, 11-dihydro-5H-dibenzo[a, d]cycloheptenyl) (81%), 10, 11-dihydro-5H-dibenzo[a, d]-cycloheptene (6%), and 10, 11-dihydro-5H-dibenzo[a, d]cyclohepten-5-one (6%). The ESR spectrum established the triplet ground state of this carbene. The absorption spectrum of this carbene was obtained successfully. These spectra are similar to that of diphenylmethylene. 5, 5-Dibromo-10, 11-dihydro-5H-dibenzo[a, d]cycloheptene was prepared by the bromination of the diazo compound at −30°C. The reaction of this dibromide with alkyllithium in the presence of olefin gave 5, 5′-bi(10, 11-dihydro-5H-dibenzo[a, d]cycloheptenylidene) and 5-alkyl-10, 11-dihydro-5H-dibenzo[a, d]cyclohepten-5-ol. No cyclopropane derivatives were obtained.
The Nuclear Magnetic Resonance Spectra of Olefinic Protons and the Substituent Effects. IV. Intramolecular Interactions between Substituents in trans-1,2-Disubstituted Ethylenes
Authors: Niwa Jun 
Published: July 2006

Abstract
The olefinic proton chemical shifts (δji), measured in parts per million from ethylene, in an extensive series of trans-1,2-disubstituted ethylenes (RjCHjiCHijRi) show uniform deviations from the simple additivity of the substituent-shielding parameters. These deviations may be attributed to the interactions between the Ri and Rj substituents, so the chemical shift, δji or δij, may be expressed as δji=dc(Ri)+dG(Rj)+Iji or δij=dc(Rj)+dG(Ri)+Iij. The abbreviations dc(Ri) and dG(Rj) represent the substituent-shielding parameters, while Iji and Iij represent the respective terms of the interactions. The chemical shifts, δji, in each series of compounds bearing Rj as an invariable substituent are determined by the Hammett’s σ-constants of Ri, and much more closely by dc(Ri). That is, δji=dG(Rj)+ρJσi, and δji=dG(Rj)+ρJ′dc(Ri), where the susceptibility, ρJ, is also related to ρJ′ by a linear function. By assuming that Iji is approximately equal to Iij, the following equations may be derived:
ρJ′−ρ0′=κσj and Iji=κσjdc(Ri)
The applicabilities of these equations were tested graphically for the 70 shifts in series of trans-1,2-disubstituted ethylenes. The results revealded that the chemical shift, δji or δij, was comprehensively expressed as:
δji=dG(Rj)+(−0.59σj+1.08)dc(Ri)
or δij=dG(Rt)+(−0.59σi+1.08)dc(Rj)
with the exception of those compounds bearing halogen substituents. The values of standard deviation and the correlation coefficient were 0.08 and 0.994 respectively.
Fluorenylidene and 2,7-Dibromofluorenylidene
Authors: Murahashi Shun-ichi , Moritani Ichiro , Nagai Toshikazu 
Published: July 2006

Abstract
Photolysis of 9-diazofluorene or 2,7-dibromo-9-diazofluorene in diethyl maleate or diethyl fumarate was found to give cyclopropane derivatives nonstereospecifically. Irradiation of 9-diazofluorene in 1,2-dichloroethylene gave no addition product, but did 9-chlorofluorene in 85–89% yield. The same reaction in carbon tetrachloride gave 9,9′-dichloro-9,9′-bifluorenyl in 48% yield. Thus fluorenylidene has strong abstraction character. These chemical results suggest that fluorenylidene and 2,7-dibromofluorenylidene react in triplet state. Furthermore the ground states of these carbenes were confirmed to be triplet by ESR spectra. Concerning to zero-field parameter little effect of bromine substituent was observed in 2,7-dibromofluorenylidene.
Studies of Organic Catalytic Reactions. V. The Function of the Chelates formed in the Hydrolysis of 2-Cyanopyridine with Metal Oxide Catalysts
Authors: Sakai Koji , Ito Takehiko , Watanabe Ken-ichi 
Published: July 2006

Abstract
When 2-cyanopyridine is refluxed with water in the presence of nickel or copper oxide, it is easily hydrolyzed and affords a chelate compound of the acid with nickel or copper. On the other hand, 3- or 4-cyanopyridine affords only the corresponding free amide by the same reaction. The interfering effect of thiophene is not observed in the reaction of 2-cyanopyridine, but it is observed in the case of the 3- or 4-cyanopyridine. When 2-cyanopyridine is refluxed with an aqueous solution of nickel or cupric chloride, it is hydrated to form a chelate of the amide with nickel or copper. These chelates are hydrolyzed with the metal oxides in water to afford the chelates of the acid. Pyridine-2-carboxylic acid amide is also hydrolyzed to the chelate of the acid, but the hydrolysis of the 3- or 4-amide isomer does not occur under the same conditions. The four chelates of the acid and amide are excellent catalysts for the hydration of 2-cyanopyridine, giving the free amide in a high yield. From these facts, it may be presumed that: 1) The adsorption of 2-cyanopyridine or its amide on the catalysts is stereospecific and results in the formation of a kind of chelate. Upon forming the acid, the metal atom of the catalyst is drawn out of the catalyst to form the chelate. 2) The metal oxide is the most suitable catalyst for the chelate-type adsorption and for the chelate formation. 3) The chelate of the acid formed during the hydrolysis of 2-cyanopyridine acts as another catalyst in the formation of the free amide, then, the amide is further converted into the chelate of the acid by means of the metal oxide catalyst.
Kinetic Studies of Solvolysis. XIV. The Solvolysis of Optically Active α-Phenylethyl Chloride in Binary Mixtures of Methanol and Phenol —The SN1 Methanolysis with the Retention of the Configuration—
Authors: Okamoto Kunio , Komatsu K\={o}ichi , Shingu Haruo 
Published: July 2006

Abstract
The competitive SN1 methanolysis and SN1 phenolysis of optically-active α-phenylethyl chloride in the presence of added triethylamine give α-phenylethyl methyl ether and α-phenylethyl phenyl ether, both with a net inverted configuration, in 50 wt% methanolic phenol, whereas in 85–95 wt% methanolic phenol both the methyl and the phenyl ether have been obtained with a net retained configuration. In the intermediate solvent range (e.g., 75 wt% methanolic phenol), the methyl ether possesses a net inverted configuration, while the phenyl ether has a net retained configuration. Over the entire solvent range examined, the o- and p-α-phenylethylphenols (the C-alkylation products) possess net inverted configurations. This heretofore unusual retained steric course of the methanolysis is explained by the SNi-like four-center attack of a methanol molecule from the retentive side of the SN1 ion-pair intermediate. Much as in the retentive hydrolysis in the aqueous phenols, the specific solvation of the phenol molecules to the SN1 ion-pair intermediate may be suggested as a factor which assists the retentive attack of the methanol molecule.
Oxidation of Methyl Conjugated Octadecadienoate with Monoperphthalic Acid
Authors: Suhara Yasuo , Shibuya Yoshinori , Otsuru Hideki 
Published: July 2006

Abstract
Methyl trans-9-trans-11-octadecadienoate was oxidized with monoperphthalic acid under various conditions. The products obtained were separated into several fractions by washing them with an alkaline solution and then submitting them to column chromatography. The substance thus obtained from each fraction was studied by chemical and spectroscopic procedures. From the results of chemical tests, periodic acid cleavage, and spectroscopic observation in the infrared and ultraviolet regions, it is inferred that the oxidation products in all cases contain all the methyl trans-9,10-epoxy-trans-11- and methyl trans-11,12-epoxy-trans-9-octadecenoates, methyl dihydroxy-trans-octadecenoate, and methyl 9(10)-hydroxy-10(9)-(o-carboxy)benzoyloxy-trans-11-and methyl 11(12)-hydroxy-12(11)-(o-carboxy)benzoyloxy-trans-9-octadecenoates.
Synthetic Studies of Bacitracin. I. Synthesis of a Protected Intermediate Heptapeptide (5—11)
Authors: Ariyoshi Yasuo , Shiba Tetsuo , Kaneko Takeo 
Published: July 2006

Abstract
A protected heptapeptide, the formyl-l-isoleucyl-ε-benzyloxycarbonyl-l-lysyl-δ-5-tosyl-d-ornithyl-l-isoleucyl-d-phenylalanyl-im-benzyl-l-histidyl-l-aspartic acid α-methyl-β-benzyl ester, was synthesized by the azide method and the carbodiimide method. It is an intermediate peptide for the total synthesis of the antibiotic bacitracin A, the structure of which is still ambiguous at a few points. β-Benzyl benzyloxycarbonyl-l-aspartate was prepared by a novel method similar to that used in the synthesis of γ-benzyl glutamate. The α-methyl-β-benzyl l-aspartate prepared could be useful in the synthesis of branched aspartic acid peptide. Phenomena of dimorphism were observed in crystals of δ-tosyl-d-ornithine and δ-tosyl-d-ornithyl-l-isoleucyl-d-phenylalanine ethyl ester hydrobromide, and two crystal forms of each compound were isolated in pure states.
The Crystal Structure of the 1 : 1 Complex of Naphthalene with 1, 2, 4, 5-Tetracyanobenzene
Authors: Kumakura Shigekazu , Iwasaki Fujiko , Saito Yoshihiko 
Published: July 2006

Abstract
The crystal of the equimolar complex between 1, 2, 4, 5-tetracyanobenzene and naphthalene is monoclinic, with space group C2/m, a=9.39, b=12.66, c=6.87 Å, β=107.2 ° and Z=2. The structure was deduced from the hk0 weighted reciprocal lattice and a packing consideration, and refined by the three-dimensional difference synthesis and the block-diagonal least-squares method. The constituent molecules are approximately planar and overlap each other with an average interplanar spacing of 3.43 Å. They are stacked alternately in infinite columns along the c axis. The structure is disordered, with the naphthalene molecules adopting one of alternative orientations with equal probability. The determined structure is consistent with the electronic spectra of the cyrstal.