bluuebunny/crossref_metadata_2025_split huggingface dataset:
The Radiation-Induced Addition Reaction of Thiols to Chlorofluoroolefins
Authors: Inukai Kan , Ueda Teruo , Muramatsu Hiroshige 
Published: July 2006

Abstract
The addition of thiols to chlorofluoroethylenes was carried out under γ-ray irradiation; chlorofluoroethyl alkyl sulfides were thus obtained. Ghlorofluoroethyl alkyl sulfoxides and sulfones were prepared by the oxidation of the sulfides. The dehydrohalogenation of chlorofluoroethyl alkyl sulfides yielded chlorofluorovinyl alkyl sulfides, whose structure indicated that the thiyl radical attacked the difluoromethylene side of the asymmetrical dichlorodifluoroethylene. Chlorofluorovinyl sulfoxides and sulfones were also synthesized from the sulfides by oxidation with hydrogen peroxide.
The Autoxidation of p-Xylene Catalyzed with Cobalt Monobromide in Acetic Acid
Authors: Kamiya Yoshio , Nakajima Tadahiko , Sakoda K\={o}ichiro 
Published: July 2006

Abstract
The rate of the cobalt-catalyzed autoxidation of p-xylene by adding sodium bromide reaches the steady state within several minutes and increases remarkably at high cobalt concentrations. Although p-tolualdehyde as well as water, the main oxidation products of p-xylene at the initial stage, strongly affect the rate of oxidation, the apparent rate is kept constant over a long period. When cobalt dibromide is used, a pronounced induction period can be observed at high cobalt concentrations, and the rate of oxidation starts to decrease after a short while. The effect of the ratio of sodium bromide to cobalt has shown that cobalt monobromide is an effective catalyst for the propagation step. The rate of the oxidation of p-xylene is found to be of the order of from 1.5 to 2.0 with respect to cobalt at concentrations from 10−3 to 5×10−2mol./l. and at temperatures from 65 to 95°C, and to be first-order with respect to the p-xylene concentration; these findings show excellent agreement with the theory. When cobalt is partly replaced by manganese, a strong synergistic effect can be observed.
Studies of Peptide Antibiotics. VII. The Synthesis of Cyclo-d-phenylalanyl-d-leucyl-l-ornithyl-l-valyl-d-ornithyl-l-prolyl
Authors: Kato Tetsuo , Izumiya Nobuo 
Published: July 2006

Abstract
A cyclic hexapeptide, cyclo-d-phenylalanyl-d-leucyl-l-ornithyl-l-valyl-d-ornithyl-l-prolyl, was once reported to be an antibiotic gramicidin J2, and the synthesis of the compound was described also. However, the natural occurrence of gramicidin J2 was denied recently. For the purpose of comparing its antibacterial activity, if any, with gramicidin S, the synthesis of this compound was carried out. p-Methoxybenzyloxycarbonyl-d-phenylalanyl-d-leucyl-δ-benzyloxycarbonyl-l-ornithyl-l-valyl-δ-benzyloxycarbonyl-d-ornithyl-l-proline p-nitrophenyl ester was prepared, and, after the selective cleavage of p-methoxybenzyloxycarbonyl group, the hexapeptide ester was transformed to the cyclic benzyloxycarbonyl hexapeptide, which was then hydrogenated to afford the desired cyclic hexapeptide as dihydrochloride. The effects of the synthesized cyclic peptide on bacterial growth have been examined. No antibacterial activities were observed in reaction to the microorganisms utilized here.
Cyclopropene Derivatives. IV. The Reactions of Acylcyclopropene
Authors: Obata Naruyoshi , Moritani Ichiro 
Published: July 2006

Abstract
The reactions of acylcyclopropenes, such as 3-benzoyl-1,2-diphenyl- and 3-acetyl-1,2-diphenyl-cyclopropene, were investigated. These ketones gave normal hydrazones with 2,4-dinitrophenylhydrazine. With p-toluenesulfonylhydrazine, the acetyl compound gave ordinary hydrazone, but the benzoyl derivative did not give its hydrazone. The reaction with hydrazine hydrate caused the expansion of the cyclopropene ring and produced pyridazine derivatives in both the ketones. The carbenic decomposition of 3-acetyl-1,2-diphenylcyclopropene p-toluenesulfonylhydrazone with sodium methoxide in diglyme gave diphenylacetylene and 3,4-diphenyl-6-methylpyridazine. On irradiation with ultraviolet light, 3-benzoyl-1,2-diphenylcyclopropene produced 1,2,4,5-tetraphenylbenzene. In the case of 3-acetyl-1,2-diphenylcyclopropene, the same benzene derivative and 1,2,4,5-tetraphenyl-3,6-diacetyltricyclo[3,1,0,02,4]hexane were obtained. The latter material was transformed into a benzene derivative upon further irradiation. Tricyclohexane could be an intermediate in the transformation of ketones to a benzene derivative.
The Synthesis, Resolution and Configuration of β-Hydroxyvaline
Authors: Oh-hashi Jun-ichi , Harada Kaoru 
Published: July 2006

Abstract
Dl-β-Hydroxyvaline was synthesized from sodium β,β-dimethylglycidate by aminolysis with benzylamine, followed by hydrogenolysis. N-Benzoyl-Dl-β-hydroxyvaline was resolved by use of (−)-α-methylbenzylamine to yield (−)-N-benzoyl-β-hydroxyvaline. The configuration of VI was determined by converting it to methyl N-benzoyl-β-chlorovalinate (I) and subsequent hydrogenolysis of I yielded (−)methyl N-benzoylvalinate (II). From II, optically pure d-(−)-valine was obtained upon hydrolysis.
The Effects of Some Antioxidants on the Elastomers Derived from Carboxy-terminated Polybutadiene
Authors: Tokui Harusuke , Yamazaki Kiroku 
Published: July 2006

Abstract
The capability of several sorts of conventional antioxidants was studied by means of the tensile and the swelling tests of the elastomers derived from the carboxy-terminated polybutadiene prepolymer. When exposed for one year, the elastomers containing no antioxidants deteriorated remarkably; they became brittle and, without exception, no longer looked like the so-called “elastomers.” Many kinds of the antioxidants worked out and were found to be effective; their capabilities were evaluated as almost the same as far as the tensile properties of the exposed material were concerned. The changes in the reciprocal value of the average chain length between cross-links, 1/Mc, in the course of the exposure, however, would be a convenient semi-quantitative measure of the induced cross-linking reaction. With this assumption, the swelling test might prove that, among the additives covered, the amine-type antioxidants were most effective in preventing the deterioration induced by the over-cross-linking reaction of the elastomer. The relationship between the amount of the sol-fraction and the cross-linking density for the exposed specimens was fitted to that of the random cross-linking and the scission of the polymer with a random distribution of chain lengths.
Properties of Dilute Solutions of Polyurethanes. II. Branched Polymers
Authors: Sato Hiroshi 
Published: July 2006

Abstract
Linear and branched polyurethanes, both of which contained polycaprolactone (\barMn=1.80×103), were prepared. Each polymer was fractionated from a dimethyl acetamide solution by precipitation with a mixture of n-heptane and ethyl ether, and the fractions were characterized by viscosity and sedimentation. The degree of branching for the fractions of the branched polymer was estimated by using the relation between viscosity and branching, derived by Flory. The ratio of the concentration dependence of the sedimentation coefficient ks to [η] was about 1.7 for the linear polymer, but the ks⁄[η] value increased with an increase in the degree of branching for the branched polymer. The Huggins constant, k′, seems to be independent of the degree of branching.
Heptafulvenes. V. Some Substitution Reactions of 2,3-Dimethoxy-8,8-dicyanoheptafulvenes
Authors: Kitahara Yoshio , Doi Kozo , Kato Tadahiro 
Published: July 2006

Abstract
Methoxyl groups of alkyl-2,3-dimethoxy-8,8-dicyanoheptafulvenes were easily replaced by various kinds of nucleophilic reagents to give the corresponding substituted-8,8-dicyanoheptafulvenes. There exists a difference in reactivity between the two methoxyl groups located at the 2 and 3 positions of 8,8-dicyanoheptafulvenes. The isopropyl group at the 4 position of 2,3-dimethoxy-8,8-dicyanoheptafulvene hindered some substitution reactions of the methoxyl group at the 3 position.
Hydrogenation and Hydrogenolysis. IX. The Hydrogenation of Benzyl Alcohol with Platinum Metal Catalysts
Authors: Nishimura Shigeo , Hama Michiko 
Published: July 2006

Abstract
The rate of the hydrogenation of benzyl alcohol with a rhodium catalyst decreases markedly in the course of the reaction, accompanied by the formation of an increasing amount of cyclohexanecarboxaldehyde with the conversion of the alcohol. The decrease in the rate is only slight with a platinum catalyst, however, and the formation of the aldehyde is much less than with the rhodium catalyst. It has been shown that cyclohexanecarboxaldehyde is an effective catalyst poison in the hydrogenation of benzyl alcohol, but that cyclohexylcarbinol is not. 1-Cyclohexenylcarbinol, an intermediate of the hydrogenation, isomerizes to cyclohexanecarboxaldehyde during the hydrogenation on rhodium and 7 : 3 rhodium-platinum catalysts to a greater extent than on the platinum catalyst. Cyclohexanecarboxaldehyde is hydrogenated only very slowly, but the rate with the platinum catalyst is about four times greater than that with the rhodium catalyst. These results may account for the different behaviors of the rhodium or 7 : 3 rhodium-platinum catalyst and the platinum catalyst observed in the hydrogenation of benzyl alcohol.
Studies of Unnatural Amino Acids and Their Peptides. II. The Syntheses of Dl-β-(4-Thiazolyl)-α-alanine and Its Peptides
Authors: Watanabe Hiroshi , Kuwata Shigeru , Sakata Tatsuo , Matsumura Keizo 
Published: July 2006

Abstract
Dl-β-(4-Thiazolyl)-α-alanine has been synthesized in a good yield by the condensation of 4-thiazolylmethyl chloride and diethyl acetamidomalonate, and by the subsequent hydrolysis of the product. The N-carbobenzoxy derivative of this amino acid could be prepared easily and transformed to its p-nitrophenyl ester and t-butoxycarbonylhydrazide, but it was found difficult to obtain the methyl ester or the benzyl ester directly from this amino acid. Carbobenzoxy-Dl-β-(4-thiazolyl)-α-alanyl-glycine benzyl ester has been synthesized by several coupling methods: its yield decreased in the following order: p-nitrophenyl ester&gt;dicyclohexylcarbodiimide (glycine ester was used as a free base)&gt;dicyclohexylcarbodiimide (glycine ester p-toluenesul-fonate was used without triethylamine)&gt;dicyclohexylcarbodiimide (glycine ester p-toluenesulfonate was used with triethylamine)&gt;mixed anhydride. The alkaline hydrolysis of the protected di-peptide ester afforded the N-protected peptide in a good yield. Decarbobenzoxylation did not proceed smoothly by catalytic hydrogenation, in which hydrogen was absorbed slowly and incompletely, while it proceeded normally with hydrobromic acid in acetic acid.
Copolymerizations of 1-Phthalimido-1,3-butadiene and 1-Succinimido-1,3-butadiene
Authors: Murata Kenichi , Terada Akira 
Published: July 2006

Abstract
1-Phthalimido-1,3-butadiene (1-PB) and 1-succinimido-1,3-butadiene (1-SB) were co-polymerized readily with acrylonitrile, methyl methacrylate and styrene, but somewhat less readily with vinyl acetate. The monomer reactivity ratios for the system with styrene were calculated by the Fineman-Ross method and found to be r1(1-PB)=1.48, r2(St)=0.32 for the 1-phthalimido-1,3-butadiene-styrene system, and r1(1-SB)=1.62, r2(St)=0.28 for the 1-succinimido-1,3-butadiene-styrene system. The Q, e-values for these systems were successively evaluated and obtained as Q (1-PB)=1.57, e(1-PB)=+0.06, Q (1-SB)=1.76 and e(1-SB)=+0.09, when Q (St)=1.0 and e(St)=−0.8. Likewise, such values for N-vinyl phthalimide (VPI) and N-vinyl succinimide (VSI) were investigated in order to compare them with the values obtained above for the imidobutadienes; they were shown to be r1(VPI)=0.09 and r2(St)=6.3 for the N-vinyl phthalimide-styrene system, and r1(VSI)=0.07 and r2(St)=9.6 for the N-vinyl succinimide-styrene system. Subsequently, the following Q and e values were determined: Q (VPI)=0.09, e(VPI)=−0.13, Q(VSI)=0.06, and e(VSI)=−0.17.
Sesquiterpenes from Dictyopteris Divaricata. II. Dictyopterol and Dictyopterone
Authors: Kurosawa Etsuro , Izawa Motowo , Yamamoto Koji , Masamune Tadashi , Irie Toshi 
Published: July 2006

Abstract
The structures of new sesquiterpenes, dictyopterol and dictyopterone, isolated from the essential oil of a brown algae, Dictyopteris divaricata Okamura (“Yezoyahazu”), have been shown to be selinen-1β-ol and selinen-1-one, respectively, on the basis of chemical and spectral data. Dictyopterol is an inseparable mixture of α- and β-isomers.
The Reaction of Halogenated Biacetyl Monoximes with Esters of Amino Acids
Authors: Sugiyama Masatoshi , Masaki Mitsuo , Ohta Masaki 
Published: July 2006

Abstract
1-Chloro-2-oximino-3-butanone (I) was prepared by the nitrosation of chloroethyl methyl ketone with an alkyl nitrite. I was treated with the l-leucine ethyl ester (II) to give 2-(2-oximino-3-oxobutylamino)-4-methylvalerate (III) and 2-[N, N-bis(2-oximino-3-oxobutyl)amino]-4-methyl-valerate (IV). In a similar manner, l-bromo-3-oximino-2-butanone (V) was treated with II to give 2-(3-oximino-2-oxobutylamino)-4-methylvalerate (VI). The reaction of the carbonyl group of III and VI with hydroxylamine and hydrazine was also studied. The treatment of VI with ammonia gave 6-(2-oximinoethyl)-3-isobutyl-2-hydroxypyrazine. Reactions of I and V with other esters of amino acids were also carried out.
The Catalytic Hydrogenation of Aniline in Fluidized Beds
Authors: Echigoya Etsuro , Hagiwara Hiroshi , Sakurai Akio 
Published: July 2006

Abstract
The hydrogenation of aniline in fluidized beds was studied. As a result of the experiments, the following conclusions were obtained: 1) The reaction rate of the catalytic hydrogenation of aniline in the temperature range between 150°C and 180°C was approximately first-order with respect to hydrogen. In the case of a large molar ratio of hydrogen to aniline, however, the reaction rate became zeroth-orcler with respect to aniline. 2) A good agreement was obtained between the conversion by the fluidized-bed experiment and the values calculated on the model of the contact-time distribution for low degrees of conversion. For high degrees of conversion, the deviation of the values calculated using this model from the experimental value was found to be about 10%. It was suggested that this model can well be applied to predicting the conversion for zeroth-order reaction within the limits of uncertainty given above.
Determination of Angular Orientation of Rigid Group in Molecular Crystal: Vector-set Seeking Method
Authors: Katsube Yukiteru , Sasada Yoshio , Kakudo Masao 
Published: July 2006

Abstract
In order to determine the angular orientation of the rigid atomic group, such as benzene ring, in a molecular crystal, a new method for interpreting a distribution of peaks near the origin of two-dimensional Patterson function has been described in this paper. Similar methods for solving the Patterson function by the aid of the rigid groups have been proposed by several authors, but the present method, vector-set seeking method, differs from them in the procedure to find a satisfactory fit of a vector-set of the rigid group on the Patterson function and in a criterion for a correct choice of the angular orientation. Satisfactory results for the known structures of salicylamide and α-pyridone and the unknown structure of m-hydroxybenzamide were quickly obtained by the application of this method.
The Radiolysis of Crystalline Oxalato Metal Complexes. The Effects of Coordinating Metal Ions on the Radiolysis of Oxalate
Authors: Sugimori Akira 
Published: July 2006

Abstract
Coordinated oxalates in metal complexes are more reactive under γ-irradiation than are ionic oxalates. This suggests that the covalency between the metal ion and the ligand in oxalato metal complexes promotes the reactivity of the ligand. The reaction of the ligand is also affected by the central metal ions. In K3[Co(C2O4)3]·3H2O and K3[Fe(C2O4)3]·3H2O, the coupled reduction of central metal ions with the oxidative decomposition of the ligand to carbon dioxide occurs at relatively high G values. In K3[Cr(C2O4)3]·3H2O, the redox reaction of the central metal ion is small and the ligand decomposes into carbon dioxide and carbon monoxide. In K3[Al(C2O4)3]·H2O, the formation of glyoxal and formic acid instead of carbon monoxide is significant.
Studies of the Hydrocracking of Lignin. III. The Hydrocracking of Various Types of Lignin
Authors: Oshima Motoyoshi , Kashima Kan , Watanabe Hiroshi , Tabata Haruo , Kubo Teruo 
Published: July 2006

Abstract
Three types of raw material for lignin hydrocracking were prepared and their reactivities were compared in relation to the refined lignin reported in the authors’ previous paper (Bull. Chem. Soc. Japan, 39, 2750 (1966)). The raw materials were prepared; 1) by autoclaving the alcohol-fermented sulfite waste liquor (heat-precipitated lignin); 2) by drying the liquor (dried SWL), and 3) by concentrating the liquor (concentrated SWL). Although these three types of lignin are less costly to prepare, they showed poor reactivities in the hydrocracking process. Heat-precipitated lignin gave a 16–20% monophenol yield [Analyzed by rectification and gas chromatography (no alkaline extraction was conducted).] at a 100% recovery level of pasting oil. No definite monophenol yield figures could be concluded in the runs with dried or concentrated SWL because of the scattered data. The poor reproducibility of data in the cases of these two types of lignin is discussed.
The Reaction of Aminotropones with Diketene. II. The Structure of the By-product in the Reaction of 5-Aminotropolone with Diketene
Authors: Seto Shuichi , Sasaki Hiroko , Ogura Kyozo 
Published: July 2006

Abstract
The reaction of 5-aminotropolone with diketene gave a minor product and 5-aceto acetamidotropolone, which had previously been described (K. Ogura et al., This Bulletin, 38, 306 (1965)). This unknown compound was obtained as a main product when 5-acetoacetamidotropolone was treated with diketene in the presence of triethylamine. From its oxidative degradation and its NMR spectrum, this compound was proved to be 3-acetyl-4-hydroxy-6-methyl-1-(tropolon-5′-yl)pyridone-2. Furthermore, for the sake of the structural determination, 3-acetyl-4-hydroxy-6-methylpyridone-2 and its deacetylated product were prepared.
The Synthesis of α, ω-Disubstituted Higher Alkanes from α, α, α, ω-Tetrachloroalkanes
Authors: Saotome Kazuo , Komoto Hiroshi , Yamazaki Toshiaki 
Published: July 2006

Abstract
Higher ω-chloroalkanoic acids than ω-chlorooctanoic acid were prepared in good yields (over 90%) by improved methods of the hydrolysis of α, α, α, ω-tetrachloroalkanes. The reactions were carried out in fuming nitric acid, with the addition of nitrogen dioxide during the reaction or in the presence of a small amount of phosphoric anhydride. α, ω-Dichloroalkanes were derived from the ω-chloroalkanoic acids by the Kolbe electrolytic synthesis. Various other novel α, ω-disubstituted alkanes with very long methylene chains, such as glycols, dinitriles, dicar-boxylic acids, and diamines, were also prepared starting from the tetrachloroalkanes.
An Application of the Quasi Chemical Approximation to the NMR Dilution Shift in Some Binary Mixtures
Authors: Satake Iwao , Arita Masujiro , Kimizuka Hideo , Matuura Ryohei 
Published: July 2006

Abstract
The theoretical NMR dilution curves for the ethanol-carbon tetrachloride, water-acetone and water-dioxane systems have been derived without the assumption of any particular type of H-bonded complexes in the solution. The expressions so derived contain the interchange energies as variable parameters. The use of the appropriate values of interchange energies (a few kilocalories) gives reasonable quantitative fits of the experimental dilution curves over the entire concentration range of the solutions. These values suggest that the strength of hydrogen bonding in the present systems is in the order of: water-water&gt;water-acetone&gt;water-dioxane&gt;ethanol-ethanol.
Spectroscopic Studies of Dialkylaluminum Alkoxides and the Trialkylaluminum-Ether Complex. I. Structures and Symmetries
Authors: Tarao Ryokichi 
Published: July 2006

Abstract
The infrared and Raman spectra of [Al(CH3)2OCH3)]3, [Al(C2H5)2OCH3]3, [Al(C2H5)2·OC2H5]2, and Al(CH3)3·(CH3)2O have been measured in the 3000—300 cm−1 region, and the infrared absorption bands and the Raman lines in the skeletal vibration region (720—300 cm−1) have been compared. For [Al(CH3)2OCH3]3 and [Al(C2H5)2OCH3]3, the results are consistent with trimeric structures with symmetry D3h. For [Al(C2H5)2OC2H5]2, the results are consistent with a dimeric structure with symmetry Vh. Thus, the structures with the oxygen bridge proposed by Hoffmann for these polymeric compounds have been confirmed by spectroscopic measurements. The structures with alkyl bridges are very unlikely. For Al(CH3)3·(CH3)2O, the results do not contradict the postulated structure, with symmetry Cs.
Alkali Fusion-Gas Chromatography of Alkyl Sulfates
Authors: Nakagawa Terumichi , Miyajima Koichiro , Uno Toyozo 
Published: July 2006

Abstract
The alkali fusion of alkyl sulfates was investigated by pyrolyzing a mixture of alkyl sulfates and alkali metal hydroxide between 200–500°C. The pyrolyzates were isolated and identified to be 1-olefins, internal olefins, alcohols, and dialkyl ethers by gas chromatography and IR spectroscopy. The mechanism of this reaction was proposed from these results and an attempt was carried out to estimate the alkyl chain carbon number distribution of the commercially available sodium alkyl sulfates.
Syntheses and Structures of Acetylformoin and Related Compounds. VI. Substituent Effects
Authors: Miyagi Yo , Kimura Sadao , Goto Ryozo 
Published: July 2006

Abstract
In the presence of cyanide ions, an α-ketoaldehyde dimerizes to give an acylformoin. The tautomerism of this compound was studied. It was found that the tautomerism between I and II is affected by the solvents and by the substituents. In proton-accepting solvents (EtOH, THF), I predominates. In ethanol-free chloroform, II is dominant for almost all substituents. In ethanol-containing chloroform, some acylformoins exist as I, while the others exist as II. The former case is observed when R=t-Bu and p-X–C6H4 (X=H, t-Bu, Cl, and Br); the latter case, when R=Me, i-Pr, and p–Me-C6H4. In the former case, ethanol reacts slowly with I to give an O-ethyl derivative (III). When R=2,4,6-Me3–C6H2, II predominates in all states. When R=p-Cl–C6H4 and p-Br–C6H4, I and II were isolated as crylstals. The solvent effects are interpreted in terms of the hydrogen-bonding interactions of I with basic and hydroxylic solvents.
(Remark: Graphics omitted.)
Photochemical Substitution of Ferrocene in Halogenated Hydrocarbon–Ethanol Solutions
Authors: Akiyama Takeo , Hoshi Yoshiyuki , Got\={o} Satoshi , Sugimori Akira 
Published: July 2006

Abstract
The photochemical substitution of ferrocene in several halogenated hydrocarbon–ethanol solutions was investigated. Ethoxycarbonyl, formyl, ethoxymethyl, benzyl and allyl groups were photochemically introduced into ferrocene in 25–53% yields by the UV-irradiation of ferrocene in carbon tetrachloride–, chloroform–, dichloromethane–, benzyl chloride–, and allyl bromide–ethanol solutions, respectively. The reactions proceeded effectively by the excitation of the charge transfer complexes formed between ferrocene and halogenated hydrocarbons.