bluuebunny/crossref_metadata_2025 huggingface dataset:
Azetidines. I. Addition to Multiple Bonds and Condensation with Carbonyl Groups
Authors: Chen Teng-yueh , Kato Hiroshi , Ohta Masaki
Published: July 2006

The addition of azetidine to α,β-unsaturated esters and to acrylonitrile was studied. Azetidine was condensed with ketones to give the corresponding enamines.
Organic Syntheses by Means of Noble Metal Compounds. XXVIII. Syntheses of a New Type of π-Allylic Palladium Complexes from α, β- and β, γ-Unsaturated Esters and Their Carbonylation
Authors: Tsuji Jiro , Imamura Shinzo
Published: July 2006

A general method of synthesizing a new type of π-allylic complex of palladium from compounds with an allylic hydrogen activated by a carbonyl group is described. Ethyl 3-butenoate and ethyl 2-butenoate give the same carbethoxy-substituted π-allyl complex, with hydrogen chloride eliminated, when treated with palladium chloride. Unsaturated diesters, such as diethyl glutaconate and diethyl 3-hexenedioate, also react with palladium chloride to give the corresponding π-allylic complexes. The structures of these complexes are discussed by means of a study of their NMR spectra. The carbonylation of these complexes proceeds smoothly, and carbon monoxide is introduced to form unsaturated esters. 3-Butenoate and then glutaconate are prepared, starting from allyl chloride, by a series of complex formations and carbonylation reactions. The possible synthetic application of this method of step-by-step introduction of carbon monoxide to other olefins is suggested. Diethyl 3-hexenedioate gives the complex, which is then converted into diethyl muconate by the elimination of palladium by the action of a base or carbon monoxide.
The Surface Area of the Annealed Palladium Foil Catalyst as Determined by a Novel Method of Measuring a Small Surface Area
Authors: Kabe Toshiaki , Mizuno Toshihiko , Yasumori Iwao
Published: July 2006

In order to measure the small surface area of metal foils down to a few ten square centimeters by making use of gas adsorption, an apparatus was developed, which made it possible to estimate the amount of adsorbed xenon at 77.5°K from the desorption of the gas on the surface by moving the foil from the adsorbing bulb into the hot furnace; the change in the surface area of palladium foil catalysts which had been annealed at various temperatures was followed by the use of this method. The roughness factor, the ratio of the real surface area to the geometrical one, of the palladium foil decreased from 1.7 to 1.1 with the progress of annealing at 150–300°C, but it increased to 1.9 after heating at 400°C and then decreased again under treatment at high temperatures to 1.0 for 800°C. The chemisorption of carbon monoxide on the same foil catalyst, which is often used for the surface-area determination, was also studied, and the difference between the adsorbed states of the respective molecule on the palladium surface was briefly discussed in order to compare these methods.
A General Theory of Gel Formation with Multifunctional Interunit Junctions
Authors: Fukui Kenichi , Yamabe Tokio
Published: July 2006

A theory is presented for a general treatment of the molecular size distribution, the gel point, and the post-gelation phenomena with respect to polymerization with formations of various kinds of interunit junctions, assuming (1) that all functional groups are equally reactive, and (2) that no kind of intramolecular interunit junction occurs. These interunit junctions appear concurrently in a system composed of a mixture of monomeric molecules and with a distributions of functionalities. Two cases are treated: (1) when the interunit junction is characterized only by the number of functional groups involved in its formation, and (2) when the interunit junction is characterized not only by the number of groups, but also by the magnitude of the free energy of its formation. The former is illustrated by the poly condensation with bi- or terfunctional interunit junctions or with both. The latter is illustrated by the polycondensation between A and B groups in a mixture of A-monomers with equireactive A groups and B-monomers with equireactive B groups, where a B-monomer is regarded as a kind of interunit junction.
Infrared Spectra of Urea and Thiourea Thin Films on the Metal Surface
Authors: Suëtaka Wataru
Published: July 2006

The infrared spectra of thin urea and thiourea films, several hundred Angstroms thick, on a steel plate were obtained using an optical system in which the beam polarized parallel to the plane of incidence was incident at 70° upon a steel plate covered with film. The spectra obtained showed that the c-axis of the urea crystal was parallel to the metal surface. However, the abnormal behavior of the NH2 bending and the NH2 twisting bands suggests that the urea molecule in the film was deformed from the planar structure. The intensities of the infrared bands of thiourea belonging to the B1 species decreased in the film, and it may be concluded that the c-axis of the crystal is nearly parallel to the metal surface. The considerable rise in frequency of the NH2 wagging band observed in the thin thiourea film may arise from the deformation of the crystal. As for the thioureacollodion film, thiourea A1 bands appeared to be very weak, corresponding to the C=S bond orientation parallel to the metal surface. The dichroism of the thiourea bands in the 3 μ region obtained about the thiourea and thioureacollodion thin films is in agreement with the Badger-Waldron assignment of the absorption bands.
The Liquid Phase Oxidation of Acrolein. IV. A Postulated Configuration of the Divalent Cobalt Acetylacetonate Catalysts in the Initiation Reaction
Authors: Ohkatsu Yasukazu , Osa Tetsuo , Misono Akira
Published: July 2006

A possible configuration of the pale blue precipitated divalent cobalt catalyst, synthesized by the addition of a saturated solution of deionized water in acrolein to a vigorously stirred solution of Co(acac)2 in benzene, is deduced from the infrared spectrum and thermal analyses; it is considered to be Co(acac)2-H2O-acrolein, in which acrolein is coordinated through its aldehyde oxygen. When the precipitated catalyst is used in the oxidation of acrolein, the induction period of oxygen absorption is shorter, the rate of oxygen absorption is higher, and the amount of oxygen absorbed is more than when any other divalent cobalt-acetyl-acetonate are employed. From these results, it is considered that the precipitated catalyst contains a species which is converted into a more active trivalent form faster than the other divalent catalysts. Furthermore, Co(acac)2 and Co(acac)2·2H2O are considered to take part in the oxidation via Co(acac)2-H2O-acrolein.
Acetonation of l-Sorbose by Ketal Interchange
Authors: Maeda Takashi
Published: July 2006

The acetonation reaction of l-sorbose with acetone dimethyl ketal was investigated. The products and the yields were greatly influenced by the reaction conditions. The reaction at 45°C gave 1, 3 : 4, 6-di-O-isopropylidene-β- (VIIa), 1, 2 : 4, 6-di-O-isopropylidene-α- (Va) and 2, 3 : 4, 6-di-O-isopropylidene-α-l-sorbofuranose (IVa) and the β-anomer of Va (VIa). At the refluxing temperature, the reaction afforded IVa and the 2-O-methyl derivative of VIIa (VIIe), while at room temperature it yielded 1, 2 : 3, 4-di-O-isopropylidene-α-l-sorbopyranose (VIIIa), 1, 2 : 4, 5-di-O-isopropylidene-α-l-sorbopyranose (IXa), and 5-O-α-methoxyisopropyl-1, 2 : 3, 4-di-O-isopropylidene-α-l-sorbopyranose (VIIIc).
Use of Anhydrous Hydrogen Fluoride in Peptide Synthesis. I. Behavior of Various Protective Groups in Anhydrous Hydrogen Fluoride
Authors: Sakakibara Shumpei , Shimonishi Yasutsugu , Kishida Yasuo , Okada Masanori , Sugihara Hideo
Published: July 2006

The properties of anhydrous hydrogen fluoride (HF) as a reagent for the acidolysis of various protective groups have been studied. Amino acids with various protective groups were each treated with HF at 0 or 20°C in the presence of anisole, and the reaction products were tested. Thus, HF was found to be much better than the other known reagents, such as hydrogen bromide and trifluoroacetic acid. In the present study, the following groups were shown, for the first time, to be removed safely: the nitro group in nitroarginine, the diphenylmethyl group in diphenylmethylamide, the t-butyl group in S-t-butylcysteine, the isopropyloxycarbonyl group, and the isopropyl ester group. A new and convenient apparatus was designed for the safe handling of HF for peptide synthesis.
Asymmetric Synthesis with Sugar Derivatives. III. Action of Methylmagnesium Iodide on Sugar Esters of Phenylglyoxylic Acid
Authors: Kawana Masajiro , Emoto Sakae
Published: July 2006

Asymmetric synthesis of atrolactic acid was investigated by the reaction of methylmagnesium Iodide with phenylglyoxylic ester containing such an optically active component as 1,2 ; 5,6-di-O-cyclohexylidene-d-glucose, its isopropylidene derivative 5-O-ethyl-1,2-O-isopropylidene-d-xylose, its 5-deoxy-5-S-ethyl derivative, or 5-deoxy-1,2-O-isopropylidene-d-xylose. All of the resulting sugar atrolactates were very easily hydrolyzed with alkali at room temperature to afford the levorotatory acid in 22–38% optical yield. The asymmetric reactions proceeded in accordance with Prelog’s rule, but a Prelog’s scheme for asymmetric induction was slightly modified when the steric course for 3-O-phenylglyoxyloyl-1,2 ; 5,6-di-O-cyclohexylidene- and -isopropylidene-d-glucose was discussed.
On the Elastomers Derived from Polybutadiene-Acrylic Acid-Acrylonitrile Terpolymer as a Fuel Binder
Authors: Tokui Harusuke , Yamazaki Kiroku
Published: July 2006

Some characteristic properties of a polybutadiene - acrylic acid - acrylonitrile terpolymer (PBAN) and of the elastomers derived from it were determined to obtain the fundamental information as fuel binders for propellants. The chemical composition of the prepolymer (RF-2) was determined to be:

[{−CH2−CH=CH−CH2−}84.0{−CH2−CH(CN)−}12.6{−CH2−CH(COOH)−}3.4]n,

and it was found to be a Newtonean fluid. Since the prepolymer was found to be, on the average, 1.2 functional, much mono- or non-functional portion is probably included in it. The tensile properties of the elastomer, based on the cured PBAN, were not as good as those of telechelic elastomers, as far as the same curing agents were concerned. This may be attributed to the influence of the random distribution of the cross-linking sites and to that of the resultant terminal sections of the elastomer. The ultimate tensile strength and ultimate elongation of the PBAN elastomers were in the range of 3–6 kg/cm2 and 100–400% respectively. It should be remembered that the elastomers contained as much as 30–50% sol fractions.
Electron Spin Resonance of Anion Radicals of Aromatic Esters. II. The Anion Radicals of Diesters of o-, m- and p-Phthalic Acids
Authors: Hirayama Masatoshi
Published: July 2006

The ESR spectra have been observed for the anion radicals of several diesters of o-, m- and p-phthalic acids. The radicals were generated by the electrolytic reduction in acetonitrile and also by the reduction with lithium, sodium, potassium and cesium metals in dimethoxyethane (DME) and tetrahydrofuran (THF). The MO calculations of spin densities were made for these radicals by using McLachlan’s method, and the calculated spin densities for the anion radicals of m- and p-phthalates were in good agreement with the experimental splitting constants obtained by electrolysis. In the anion radicals of o-phthalates, the results of calculations taking into account the steric effect between the two ester groups revealed that the twisting angle between each ester group and the ring was 35–45°. From the spectrum of di-t-butyl p-phthalate anion radical prepared by the electrolysis in DME, the t-butyl ester group was found to be in a fixed orientation, probably planar with the ring. It was suggested that an ion complex was formed between the o- or p-phthalate anion radical and each alkali metal cation, and that in the p-phthalatesodium system in DME or THF there existed an equilibrium between an ion complex and a completely dissociated state.
The Crystal Structure of the Phenazine-Iodine Molecular Complex
Authors: Uchida Tokiko
Published: July 2006

The 1 : 1 molecular complex of phenazine and iodine crystallizes in an orthorhombic system with the space group Pbcn. There are four formula units in a unit cell with the dimensions of a=12.85, b=11.69, and c=8.30 Å. The structure was solved by Patterson methods and was refined by two-dimensional Fourier and (F0–Fc) syntheses. The component molecules are arranged alternately along the b axis, the two nitrogen atoms of the phenazine molecule and the two iodine atoms of the iodine molecule lying on a two-fold axis. The molecules of each component are stacked in individual columns parallel to the c axis, where the mean separations of the molecules satisfy the van der Waals distances. The phenazine molecule is planar within the range of experimental error. The interatomic distance of an iodine molecule is 2.75 Å; this is more from that of a free molecule, but not as large as those of the other iodine complexes. The charge-transfer interaction between phenazine and iodine is a little weakened by the steric hindrance of hydrogen atoms attached to the phenazine nucleus.
Photochemical Reaction between Acridine and Acridan in the Presence and in the Absence of Oxygen. I. Studies by the Steady Light Illumination
Authors: Niizuma Shigeya , Ikeda Yoshinori , Koizumi Masao
Published: July 2006

Photochemical reactions between acridine and acridan in benzene solution have been studied. The product is diacridan in the absence of oxygen, while in the presence of oxygen, it is acridine. The reactive excited state in both cases is, most likely, the lowest π-π* triplet state. Contrary to the expectation, the kinetics in the degassed solution is difficult to interpret. The rate of acridine production in the presence of oxygen, gives a sharp maximum near ∼10−4  m of oxygen at fixed acridan concentrations. Its quantum yield is reproduced by Φ=0.25×β[AH2]/(α[O2]+β[AH2]) with α/β=3.3 (1). Two schemes consistent with (1) have been tentatively presented in which one involves the mere deactivation of the triplet acridine by oxygen, and the other assumes the formation of an excited oxygen (or the like), which oxidizes acridan but is partially deactivated by a certain substance.
Fluorescence Quenching and the Charge Transfer in the Excited State. II. Dimethylnaphthylamine-Dimethyl Phthalate in Various Solvents
Authors: Kaneta Kyoichi , Koizumi Masao
Published: July 2006

As an extension of a previous paper (Bull. Chem. Soc. Japan, 39, 2588 (1966)), the quenching action of p-methyl toluate, ethyl benzoate, dimethyl esters of m-, o-, p-phthalic acids on the fluorescence of N, N-dimethyl-2-naphthylamine has been studied in several solvents. The quenching constants of the above substances (in the above sequence) in cyclohexane and dimethylformamide are respectively (0.5, ∼1, 65, 85, 93) and (41, 58, 103, 85, 124). The order, toluate<benzoate<phthalate, is consistent with the charge transfer mechanism of quenching in which fluorescer and quencher act respectively as a donor and an acceptor. In slightly or nonpolar solvents a new emission attributed to an excited CT complex has been found; its intensity has been the strongest in the case of dimethyl m-phthalate. Using this substance as a quencher, solvent effect on the quenching efficiency and the CT emissivity has been studied. It has been found that in weakly polar solvents, these two quantities decrease similarly with the increasing solvent polarity, whereas in highly polar solvents the former is large and the latter is negligible. The results in less polar solvents suggest that the reorientation of the solvated molecules is an essential process for both the quenching and the CT emission. Another evidence for this view has been found in the experiments with mixed solvents. In highly polar solvents, the production of free radical ions is most plausible but the possibility of the formation of a solvated ion pair with no emissivity, cannot be ruled out.
Theoretical Studies of the Second Virial Coefficient of the Copolymer Near the θ Temperature
Authors: Sato Hiroshi , Kamada Kensuke
Published: July 2006

The osmotic second virial coefficients of random and block copolymers are calculated according to the perturbation theory. Evaluation is carried out to the double-contact approximation. The results show that the expressions for the osmotic second virial coefficients of random and block copolymers have different forms in their second term. The so-called “theta” temperature of the block copolymer at which the second virial coefficient vanishes, is found to be higher than that of the random copolymer. These results are compared with some existing experimental results. It is also suggested that the “theta” temperature of a copolymer having a distribution of the sequence length of two monomers is located between those of the random and two-block copolymers.
Structure and Reactivity of Small Ring Compounds. I. Solvolyses of Spiro[2,4]hept-4-yl and Spiro[2,5]oct-4-yl 3,5-Dinitrobenzoates
Authors: Tsuji Takashi , Moritani Ichiro , Nishida Shinya
Published: July 2006

The solvolyses of spiro[2,4]hept-4-yl, spiro[2,5]oct-4-yl,2-methylenecyclopentyl, 2-methylenecyclohexyl, 2,2-dimethylcyclopentyl, and 2,2-dimethylcyclohexyl 3,5-dinitrobenzoates have been examined in 60 wt% aqueous dioxane. The solvolysis rate of spiro[2,4]hept-4-yl 3,5-dinitrobenzoate was 850 times greater than that of the corresponding allyl derivative, the 2-methylenecyclopentyl ester, and 3.0×105 times greater than that of the 2,2-dimethylcyclopentyl ester. Similarly, in the cyclohexyl series, spiro[2,5]oct-4-yl 3,5-dinitrobenzoate solvolyzed 330 times faster than the 2-methylenecyclohexyl ester and 1.9×105 times faster than the 2,2-dimethylcyclohexyl ester. In a buffered solution, the spiro[2,4]heptyl ester gave a mixture of spiro[2,4]heptan-4-ol (46%), bicyclo[3,2,0]heptan-1-ol (28%), and 3-methylenecyclohexanol (10%), besides internally-returned 3,5-dinitrobenzoate of bicyclo[3,2,0]heptan-1-ol (12%). Under the same conditions, the spiro[2,5]oct-4-yl ester produced spiro[2,5]octan-4-ol (71%), bicyclo[4,2,0]octan-1-ol (21%), and 3,5-dinitrobenzoate of bicyclo[4,2,0]octan-1-ol (6%), the product of internal return. The implication of these results are discussed.
Stable Biscarbodiimides
Authors: Iwakura Yoshio , Noguchi Kohji
Published: July 2006

The dehydrosulfurization of bisthioureas containing at least one aromatic residue results in the corresponding biscarbodiimides. Biscarbodiimides with bulky groups, such as t-butyl and 2,6-xylyl, can be isolated without any polymerization and disproportionation; the steric hindrance of the bulky groups makes such isolation possible. Polymerization and disproportionation interrupt the isolation of biscarbodiimides with less bulky groups. Despite their nonpolymerizability, they give rise to the other known addition reaction of aromatic carbodiimides.
Oxidation of Phenyl Radical by Copper(II) Complexes in Acetic Acid and in Acetonitrile
Authors: Wada Keisuke , Yamashita Junzo , Hashimoto Harukichi
Published: July 2006

The reactions between the phenyl radical and copper(II) complexes in acetic acid and in acetonitrile were investigated. It was found that the phenyl radical produced from the thermal decomposition of benzoyl peroxide in acetic acid is oxidized by the copper(II) ion to give a considerable amount of phenyl acetate. With cupric propionate, chloride, and bromide, “ligand-transfer” products, i.e., phenyl propionate, chloro-, and bromobenzene, respectively, were also obtained. In addition, a larger yield of the oxidation product was obtained from a 1 : 1 complex than from a 1 : 3 complex of copper(II)-phenanthroline. These facts, together with the results on solvent effects, can be successfully explained on the basis of a ligand-transfer mechanism rather than an electron-transfer mechanism. The effects of substituents of benzoyl peroxide on the reaction were an electron-transfer mechanism. The effects of substituents of benzoyl peroxide on the reaction were so small that one cannot decide whether the ligand-transfer mechanism is a radical or an ionic one. Some abnormalities were observed in the reaction with cupric acetylacetonate. Additionally, the reaction with cuprous chloride was examined, and the behavior of the copper(I) ion in the reaction discussed.
Studies of Aminosugars. XVII. Production of 3-Amino-3-deoxy-d-glucose by Bacillus Species
Authors: Umezawa Sumio , Umino Kimio , Shibahara Seiji , Omoto Shoji
Published: July 2006

3-Amino-3-deoxy-d-glucose was isolated from a fermentation broth of a Bacillus species designated as Bacillus aminoglucosidicus. This demonstrated for the first time the presence of a monosaccharide aminodeoxypyranose in nature. The aminosugar was isolated in a high yield by using column chromatography with cation exchange resin. The identity of the product with 3-amino-3-deoxy-d-glucose was completely established by comparing the natural product and its derivatives with synthetic 3-amino-3-deoxy-d-glucose and its corresponding derivatives in elemental analyses, infrared spectra and mixed melting point determination.
A Theory of the Electronic Structures and Spectra of Negative Ions
Authors: Tsubomura Hiroshi , Sunakawa Sigenobu
Published: July 2006

Some aromatic anions in solutions show absorption spectra with many sharp bands in the visible and ultraviolet regions. It is pointed out that this is rather remarkable in view of the fact that aromatic molecules have very small electron affinities, nearly zero or even negative, in the gas phase. It is then emphasized that the potential for the electron in the negative ions is much more localized than the Coulomb potential. Accordingly, some of the features of the negative ions are deduced by the use of a simple well-type potential. The important conclusions obtained are: 1) Negative ions may have discrete electronic energy levels not only in the E≤0 region but also in the E>0 region, that is, higher than the detachment energy. 2) The larger the domain of the potential well for the electron, the discrete energy levels can exist at the higher energy. 3) These energy levels at E>0 should, of course, be unstable, mostly leading rapidly to the electron detachment, but their lifetime are the longer, the larger the domain of the potential well. These consequences seem to account well for the above-mentioned spectra of aromatic anions. Other features of the negative ions and the nature of the charge-transfer states in the charge-transfer complexes are also discussed.
Phosphorescence Bands of Quinones and α-Diketones
Authors: Kuboyama Akira , Yabe Sanae
Published: July 2006

Phosphorescence bands, their life times, and the excitation spectra of anthraquinone, α-naphthoquinone, phenanthrenequinone, acenaphthenequinone, benzophenone, benzil, furil, and camphorquinone at 77°K in a rigid solution and in the crystalline state have been studied. In a rigid solution the lifetimes of these phosphorescence bands are in the range (10–0.1 msec). The solvent effect on lifetimes shows clear differences between o- and p-quinones. The behavior of these phosphorescence bands is similar to that of the n→π* bands of these compounds. From these facts, these bands are all safely identified as π*→n bands. The phosphorescence bands of p-quinones in the crystalline state are at far longer wavelengths than those in a rigid solution, and the lifetimes of the former are far longer than those of the latter. The dichroism of excitation spectrum of the phosphorescence band of anthraquinone proved that the phosphorescence band is polarized perpendicularly to the 320 mμ band and parallel to the 270 mμ band.
Photochemical Reaction between Acridine and Acridan in the Presence and in the Absence of Oxygen. II. Studies by the Flash Technique
Authors: Kira Akira , Koizumi Masao
Published: July 2006

Flash photolytic studies have been made to elucidate the behavior of the intermediates and to obtain the rate constants of the elementary reactions, which are related to the reactions between acridine and acridan in benzene solutions. Two transient species, triplet and semireduced acridine, have been detected. The elementary reactions the rate constants of which have been measured are:

AT→A [1] k1=1–2×103sec−1

AT+AT→ [2] k2=6.0×109m−1sec−1

AT+O2→(A+O2*) [3] k3=6×109m−1sec−1

AT+AH2→2AH [4] k4=3×108m−1sec−1

2AH→(AH)2 [5] k5+k6=2–3×109m−1sec−1

→A+AH2 [6]

The quantity of AH produced in the presence of a small quantity of oxygen decreases with an increase in the oxygen concentration; if one assumes that Reaction [3] is mere deactivation, the decrease in acridine is too large to be expected from the values of k3 and k4. Hence, it has been inferred that O2* (or some other reactive intermediate) oxidizes AH2. The decrease in the yield of AH with the increase in the oxygen concentration has been attributed to the deactivation of O2* by a third substance. The other kinetic data have been found to be consistent with this scheme.
Silent Discharge Reactions in Aqueous Solutions. VI. Aqueous Solution of Chloralhydrate in Atmospheres of Helium and Argon
Authors: Yokohata Akira , Tsuda Satoru
Published: July 2006

Although most of the reaction systems hitherto treated are limited to acidic solutions in the series of this present research, this work has been extended to neutral solutions. Silent discharge leads to production of hydrochloric acid from neutral aqueous chloralhydrate. A linear correlation was observed between yield of hydrochloric acid and electric discharge current. This finding has been successfully interpreted in terms of absorbed dose, the value of which can be estimated at a given electric discharge current. Yields of hydrochloric acid were not significantly affected by chloralhydrate concentration between 1×10−2  m and 1×10−3  m. The experiments of the radical scavenging effect of cupric ion and bromide ion showed that KH+Cu2+⁄KH+CCl3CH(OH)2≈0.2 and KOH+Br−⁄KOH+CCl3CH(OH)2≈9, and also that the following formula holds approximately irrespective of kind of gas used in low solute concentration and dose rate used in this work: values of hydrogen atom G(HCl)\simeq3G(OH)+G(H). Moreover, these findings also suggested that the G values of and hydroxyl radical obtained in the acidic aqueous solution can be applied approximately to the neutral region. The relation of G(HCl) to solute concentration was qualitatively identical to gamma-ray irradiation, although they are different in detail because of the difference in value of LET and in the mechanism of radical formation.
Electron Spin Resonance of Anion Radicals of Aromatic Esters. III. The Anion Radicals of Several Diesters of Biphenyl-o, o′- and p,p′-Dicarboxylic Acids
Authors: Hirayama Masatoshi
Published: July 2006

The ESR spectra of the anion radicals of dimethyl, diethyl, and diisopropyl esters of biphenyl-o, o′ and -p,p′-dicarboxylic acids, and of the di-t-butyl ester of the o, o′-derivative, have been studied. The anion radicals were prepared by electrolytic reduction in acetonitrile, and also by reduction with sodium and potassium metals in dimethoxyethane and tetrahydrofuran. The MO calculations of the spin densities were made by McLachlan’s method; all the splitting constants observed were assigned to the ring protons and the α-protons in the ester groups. A comparison of the experimental splittings with the calculated spin densities suggests that the anions ofp, p′-derivatives are in a planar conformation, while those of o,o′-derivatives have a twisted structure in which the twisting angle between the two rings was about 35–60°. A structural model was proposed for an ion complex formed between the anion of the o, o′-derivative and a sodium or a potassium cation.
ESR Study of Phenyl Nitric Oxide Radical
Authors: Kikuchi Osamu , Someno Kazuo
Published: July 2006

ESR spectra were obtained for phenyl nitric oxide radicals derived from phenyl hydroxylamines by oxidation with benzoyl peroxide, and the variation of hyperfine splitting constants with solvent was examined. Hyperfine splitting constants of nitrogen and NH proton varied with the polarity and hydrogen-bonding nature of solvent. This variation was explained by molecular orbital theory where the Coulomb integral of oxygen atom is assumed to vary with solvent. The sigma-pi parameters, QNH (in aH(NH)=ρNQNH), QN and Qo (in aN=ρNQN+ρOQO), were determined from experimental splitting constants of nitrogen and NH proton and the spin density calculated by McLachlan’s method. The values QNH=27.5, QN=30.5 QO=−13.6 were obtained and the latter two values could be used to calculate the nitrogen hyperfine splitting constant for diphenyl nitric oxide radical.
Spectrophotometric Studies of the Solution Equilibria and the Kinetics of the Substitution Reaction between Eriochrom Black T and Cobalt(II)-Ethylenediaminetetraacetate Chelate
Authors: Kodama Mutsuo
Published: July 2006

The solution equilibria and the kinetics of the substitution reaction between Eriochrom Elack T (BT) and cobalt(II)-EDTA chelate were studied spectrophotometrically. At the pH range from 8.50 to 9.50, BT was found to form only 1 to 1 normal chelate CoD with cobalt(II), the stability constant of which is 1020.0(μ=0.30). Kinetically, the substitution reaction was found to proceed through the following two simultaneous reaction paths,

i) HD2−+CoY2−\oversetk1+\ightleftharpoonsCoD−+HY3−

ii) HD2−\oversetrapid\ightleftharpoonsD3−+H+

D3−CoY2−−\oversetk2+\ightleftharpoonsCoD−+Y4−

and k1+ and k2+ were determined to be 0.23 l mol−1 sec−1 and 6.76×102  l mol−1 sec−1, respectively, at 20°C.
Altenin. IV. Compounds related to Altenin
Authors: Sugiyama Noboru , Kashima Choji , Yamamoto Makoto , Mohri Ryotaro
Published: July 2006

Three compounds, ethyl 5-hydroxy-4, 6-dioxoheptanoate, ethyl 2-methyl-5-hydroxy-5-(1-hydroxyethyl)-4-oxotetrahydrofuroate and 5-phenyl-2-ethoxy-2-(1-hydroxyethyl)-3-oxotetrahy-drofuran, which have structures closely related to altenin, were synthesized from 3-acetoxy-2, 4-dioxopentane. These compounds produced the black spot disease in pears. As these compounds all possess the reductone grouping, it appears that this grouping is responsible for the phytopa-thogenic activity.
Studies of Heteroaromaticity. IV. The Thermal 1,3-Dipolar Cycloaddition of Fur- and 5-Nitro-2-furhydroxamoyl Chlorides with Olefinic and Acetylenic Compounds
Authors: Sasaki Tadashi , Yoshioka Toshiyuki
Published: July 2006

The corresponding isoxazolines and isoxazoles were prepared by 1, 3-dipolar cycloaddition with olefinic and acetylenic dipolarophiles by two methods, a) and b). Here, method a) means the routine method via nitrile oxide formation, while method b) means the new type of reaction named in the title. Method b) is concluded to be superior to method a) for the purpose of preparing isoxazoles and isoxazolines. The mechanism of the thermal 1, 3-dipolar cycloaddition is discussed.
Polymers Containing Disulfide Bonds. I. Derivatives of p-Benzene-bis(ω-S-alkylthiosulfate)
Authors: Murayama Ken , Kato Yasuo , Morimoto Saichi
Published: July 2006

Highly crystalline polymers were synthesized by the polymerization of p-benzene-bis(ω-S-alkylthiosulfate) (Remark: Graphics omitted.). Sodium sulfide was effective as a catalyst, but polymers obtained showed much more sulfur content than the theoretical value. The polymers (n≥2) possessed rubber-like characteristics.
Preparation and Properties of Organosilicon Surfactants
Authors: Meguro Kenjiro , Ochi Miyoko , Matsushita Noritaka
Published: July 2006

Surface-active polyethenoxy silicic esters were prepared by the reaction of tetraethyl silicate with various polyethenoxy higher alkyl ethers by the use of tetrabutyl titanate as a catalyst. Their properties as surfactant were compared with those of conventional nonionic surfactants. These compounds are soluble in many kinds of organic solvents, and have good dispersing power on such inorganic pigments as titanium oxide in organic media. The dispersing characteristics of these compounds in the inorganic pigments were tested in benzene, carbon tetrachloride, and monochlorobenzene by measuring the sedimentation volume. It was found that the compounds containing a chain of more than six ethenoxy groups were soluble in water. The surface tension of these water-soluble polyethenoxy silicic esters were determined in various concentration regions. In this paper, the preparation and properties of these compounds will be described.
Studies of Liquid-Liquid Partition Systems. V. The Formation of Mixed Dimers with Two Carboxylic Acids in Carbon Tetrachloride
Authors: Sekine Tatsuya , Isayama Muneo , Yamaguchi Sumiko , Moriya Hiromitu
Published: July 2006

The distribution of acetic, propionic and butyric acids, or of mixtures of two of these acids, between carbon tetrachloride and aqueous solutions has been studied at 25°C. The distribution data have been explained in terms of the partition of the acid monomer molecules and the dimerization of the monomer molecules in the organic phase. A salting-out effect has been observed upon additions of sodium perchlorate to the aqueous phase; this salting-out effect is larger in the order butyric>propionic>acetic acid. From the distribution data, the equilibrium constants for the distribution and the dimerization have been determined, and the formation constants for the mixed-dimer molecules have been compared with the statistical values. It has been concluded that the mixed-dimer molecules are equally stable or only a little less stable than had been statistically expected.
Dynamic Mechanical Behaviour of Organic Molecular Crystals. I
Authors: Danno Takaaki , Kajiwara Takashi , Inokuchi Hiroo
Published: July 2006

The forced resonance vibration method was applied to several needle-like organic crystals, triphenylene (I), 1,2,3,4-dibenzanthracene (II), coronene (III), anthracene-trinitrobenzene (TNB) complex (IV), perylene-TNB (V), coronene-TNB (VI), acridine-iode (VII), and acetyl-acetone-Gu (VIII), and their elastic constants were obtained. The observed Young’s moduli, E1 of these organic crystals were E1(I)=1.19×1010 dyn/cm2, E1(II)=2.81×1010, E1(III)=1.10×1010, E1(IV)=1.24×1011(V)=7.77×1010, E1(VI)=9.99×1010, E1(VII)=1.67×1011 and E1(VIII)=2.87×1010 dyn/cm2. These values are consistent with the E1-values of some aromatic hydrocarbons, as obtained from the acoustic velocity.
Reactions of Metal Chelates. I. The Reactions of Copper(II) Chelates of Some β-Diketones and Their Related Compounds with Glycine, Diglycine and Triglycine
Authors: Nakahara Akitsugu , Hamada Kazuko , Miyachi Isao , Sakurai Ken-ichi
Published: July 2006

The reactions of copper(II) chelates of β-diketones such as acetylacetone, benzoylacetone, dibenzoylmethane and benzoylacetaldehyde and of chelates of their related compounds such as salicylaldehyde and 2-hydroxyacetophenone with glycine or glycylglycine were investigated. Only bis(salicylaldehydato)copper(II) and bis(benzoylacetaldehydato)copper(II) reacted with glycine to form the respective glycinato-Schiff base complexes, whereas the other chelates did not react with glycine under the same condition. On the other hand, all the chelates except bis(dibenzoylmethanato)copper(II) reacted with glycylglycine to form the respective glycylglycinato-Schiff base complexes. The reaction at pH 4.5 between bis(salicylaldehydato)copper(II) and triglycine resulted in the hydrolytic cleavage of peptide bond, producing the salicylideneglycylglycinatocuprate(II) and free glycine. As the results of this investigation, five new copper(II) chelates were synthesized and characterized.
Spectrophotometric Studies on the Ion-pair Formation of Hexamminecobalt(III) and Tris(ethylenediamine)cobalt(III) Complexes with Halide and Sulfate Ions
Authors: Tanaka Nobuyuki , Kobayashi Yumiko , Kamada Minoru
Published: July 2006

The optical density of charge transfer spectra of some tervalent substitution-inert complex cations in an ultraviolet region increases by the addition of halide and sulfate ions. From the change in optical density the association constants were determined at ionic strength 0.07 (NaClO4) and 25°C. The values are 2.2±0.5 for Co(NH3)63+Cl−, 2.2±0.6 for Co(NH3)63+Br−, 0.71±0.5 for Co(NH3)63+ I−, 114±3 for Co(NH3)63+SO42−, 2.9±0.5 for Co(en)33+ Cl− and 102±8 for Co(en)33+SO42− respectively. The difference of these values from the reported values are related to the method for the measurements. Absorption maxima of the third absorption bands are obtained at 196 mμ for Co(NH3)63+ and at 210 mμ for Co(en)33+.
Electron Spin Resonance of Irradiated Single Crystals of Sodium and Potassium 1-Oximinopropionates
Authors: Hayashi Hisaharu , Itoh Koichi , Nagakura Saburo
Published: July 2006

ESR studies have been made with single crystals of sodium 1-oximinopropionate irradiated at −196°C and at room temperature. The principal values and axes of the g and hyperfine tensors of the trapped radicals have been determined. The analysis of the observed data has indicated that the σ-electron radicals CH3C(COO−)=NO are trapped at −196°C and at room temperature. It has been found that the electronic structures of the trapped radicals at these two temperatures are essentially the same, but that the environments of the radicals are very different from each other. After the crystal had been heated at 50°C for a week, the σ-electron radical vanished and the π-electron radicals, CH3C(OH)(COO−)NHO· and CH3CR’-(COO−)NRO·, appeared. The former may be formed in the solid state by adding a crystal water molecule to the unsaturated radical. The trapped radicals in irradiated single crystals of potassium 1-oximinopropionate were also studied at room temperature and after having been heated at 50°C. They are the σ-electron radical and the π-electron radical respectively, with structures similar to those of the sodium salt. The radical pairs have been observed in irradiated single crystals of the sodium salt at −196°C.
Convenient Syntheses of 1,2-Ureylenecyclopentane Derivatives
Authors: Takaya Takao , Yoshimoto Hataaki , Imoto Eiji
Published: July 2006

Three Convenient syntheses of cis-1, 2-ureylenecyclopentane (VI) and cis-cis-3-methyl- 1, 2-ureylenecyclopentane (VIa), from 2-carbethoxycyclopentanone (I) and 5-methyl-2-carbethoxycyclopentanone (Ia) respectively, are described. The Curtius degradation of cis-2-aminocyclopentanecarboxylic acid derivatives took place without cis-trans isomerization. The hydrogenation of ethyl 3-methyl-2-ureidocyclopent-1-ene-1-carboxylate at 70°C gave two isomeric products, the major (IIIa), cis-cis-, and the minor (IIIb), cis-trans-3-methyl-2-ureido-1-carbethoxycyclopentane.
The Alkaline Sulfide Reduction of Aromatic Nitro Compounds. XII. ESR Studies of the Alkaline Sulfide Reduction of the Aromatic Nitro Compound
Authors: Hashimoto Shizunobu , Sunamoto Junzo , Aoki Akira
Published: July 2006

The ESR techniques were used in order to examine the presence of the radical species in the alkaline sulfide reduction of aromatic nitro compounds and in the photooxidation of an aqueous monosulfide solution. The ESR spectra were clear when observed by ultraviolet-light irradiation on an aqueous monosulfide solution: they were the signals of a singlet, with a g-value of 2.002±0.001 and a maximum slope width of 3.1 gauss, and a doublet, with a g-value of 2.00±0.001 and a coupling constant of 114 gauss. The singlet was identified as the signal of the sulfide ion radical, S·−, while it was most reasonable to assume the doublet to be signals due to the interaction of the sulfide ion radical with the hydrosulfide or the hydroxide in the solution. On the other hand, ESR spectra were also observed in the reaction of sodium m-nitrobenzene sulfonate with an aqueous monosulfide solution; these spectra were identical with the sulfide ion radical and the radical-anion of the nitro compound. On the basis of the results obtained, we have discussed the mechanisms of the alkaline sulfide reduction of aromatic nitro compounds and these reduction intermediates.
Syntheses of Reductones. A New Method of Synthesizing 2-Acetoxy-1, 3-dicarbonyl Compounds
Authors: Sugiyama Noboru , Yamamoto Makoto , Takano Tadao , Kashima Choji
Published: July 2006

2-Acetoxy-l, 3-dicarbonyl compounds were synthesized by two methods, one consisting of the condensation of 1, 3-dicarbonyl compounds with an electrophilic reagent, followed by acetoxylation. By this method three new compounds, ethyl 5-phenyl-2-acetoxy-3-oxopentanoate (XVII), ethyl 5, 5-diphenyl-5-hydroxy-2-acetoxy-3-oxopentanoate (XVIII), and ethyl 2-acetoxy-3-oxoheptanoate (XIX), were obtained. The other method consisted of the acetoxylation of 1, 3-dicarbonyl compounds, followed by condensation. By this method three other new compounds, 6-phenyl-6-hydroxy-3-acetoxy-2,4-dioxohexane (IV), 6-phenyl-6-hydroxy-3-acetoxy-2,4-dioxo-hexane (VIII), and 6-phenyl-3-acetoxy-2, 4, 6-trioxohexane (X), were obtained.
Azirines. I. The Reaction of 2-Phenylazirine with Carbanions
Authors: Sato Shimao , Kato Hiroshi , Ohta Masaki
Published: July 2006

An attempt to prepare 2-phenylazirine by treating acetophenone dimethylhydrazone methiodide with methylsulfinyl carbanion gave 2, 4-diphenylpyrrole instead of 2-phenylazirine. The reaction of 2-phenylazirine with the carbanions derived from acetophenone, ethyl benzoylacetate, and benzyl cyanide gave the corresponding pyrrole derivatives by ring enlargement.
Syntheses of Phenyl Formates and Naphthyl Formates with Acetic Formic Anhydride
Authors: S\={o}fuku Sh\={o}suke , Muramatsu Ichiro , Hagitani Akira
Published: July 2006

A new method for the syntheses of phenyl and naphthyl formates has been devised. The formates were obtained in good yields from phenols and naphthols with acetic formic anhydride, which had been prepared from formic acid and ketene. The formyl ester of N-hydroxysuccinimide was also prepared by the same method.
Stereoregularity of Poly-(R)-2-ethylaziridine
Authors: Tsuboyama Kaoru , Tsuboyama Sei , Yanagita Masaya
Published: July 2006

Poly-(R)-2-ethylaziridine (I) was obtained by three different procedures: (A) the polymerization of (R)-2-ethylaziridine (II) by boron trifluoride-etherate, (B) the polymerization of the aziridine in the presence of ammonium chloride in liquid ammonia, and (C) the reaction of (R)-2-amino-l-bromobutane hydrobromide (III) with caustic alkali. The stereoregularity of the polymer I may be assumed to be fairly high as a result of comparing the specific rotations of the above polymers. In order to evaluate this assumption, the addition reaction of the aziridine and diethylamine was carried out as a model experiment under experimental conditions similar to those of the polymerization (A). On the basis of the data as analyzed by gas chromatography, it is concluded that the ring opening at the primary carbon takes place over 99.4%. This implies that the ring cleavage at the primary carbon in the polymerization occurs over 180 units successively. Considering the molecular weight of the polymer I (3500–5000, 50–70 monomer units), one can assume that the configuration of the polymers obtained here perfectly retains that of the monomer and that the polymer is “isotactic.”
Studies of Organic Peroxides. VIII. The Reaction of Benzoyl Peroxide with 5, 5′-Indigo-disulfonic Acid
Authors: Kashino Setsuo , Nishimura Norio , Ino Kohei , Hasegawa Shigeo
Published: July 2006

The reaction of benzoyl peroxide with 5, 5′-indigo-disulfonic acid was studied in ethanol. The effect of the p,p′-substituents of benzoyl peroxide on the reaction rate was investigated. It was found that the reaction is a bimolecular process. Either electron-attracting substituents or electron-releasing substituents promote the reaction. This was interpreted by means of the multicenter mechanism. The electron absorption spectra of the reaction mixture showed the formation of a reasonably stable complex in ethanol. This complex is decomposed by water to 5-isatinsulfonic acid and 5, 5′-indigo-disulfonic acid.
Altenin. III. The Synthesis of Altenin
Authors: Sugiyama Noboru , Kashima Choji , Yamamoto Makoto , Mohri Ryotaro
Published: July 2006

Ethyl 5-hydroxy-5-(1-hydroxyethyl)-4-oxotetrahydrofuroate was synthesized and was identified with altenin.
The Chemiluminescence of Indole Derivatives. I
Authors: Sugiyama Noboru , Akutagawa Masamoto , Gasha Taketoshi , Saiga Yo , Yamamoto Hiroshi
Published: July 2006

The chemiluminescence of forty-one indole derivatives has been investigated by using two types of reaction mixtures: (A) the EtOH-KOH-H2O2-K3Fe(CN)6-Sample and (B) the DMSO-KOH-Sample. In both systems the reactions were carried out in the presence of air. The light intensity of chemiluminescence was measured by the deflection of the microammeter of the photometer or recorded by a connected automatic recorder. The relative light intensity (RLI), the ratio of the maximum intensity of the chemiluminescence of the sample to that of indole, was also measured. The electron-repelling group, such as hydroxyl and substituted aminovinyl group, at the 3- or 5-position enhanced the RLI, but alkyl, acetyl, formyl groups or chlorine at the various positions had little effect or a negative effect on the RLI. Some of the compounds showed a maximum intensity soon after the reagents were mixed, while some others slowly showed a maximum, which then decayed slowly.
Cyclic Acetylenes. X. A Transannular Hypochromism Observed in a Cyclic Diacetylene Containing a Naphthalene Nucleus
Authors: Ando Takashi , Nakagawa Masazumi
Published: July 2006

A cyclic diacetylene (XIa) has been synthesized by the oxidative coupling of 1, 5-bis(propargyloxymethyl)naphthalene (X) with a cyclic dimer (XIb) and a cyclic trimer (XIc). The electronic spectra of XIb and XIc have been found to be almost identical with that of naphthalene with respect to the location of the absorption maxima and the intensities. On the other hand, a marked decrease in the absorption intensities has been observed in the spectrum of the cyclic monomer (XIa). An inspection of the Dreiding model of XIa indicates that the two conformations (A and B) can retain the maximum distance between the dyine unit and the naphthalene nucleus. On the basis of the molecular model, the distance between the two chromophores and the angle between the short axis of the nucleus and the bridging chain have been estimated to be 2.26 Å, 21° for A and 2.12 Åand 38° for B. Employing these data, the hypochromic effect exerted by the diyne chromophore on the absorption of the naphthalene nucleus has been calculated according to the theory of Tinoco and Rhodes, resulting in a fairly good agreement with the observed values. Inversely, the calculation of the distance and the angle between the two chromophoric groups using the observed hypochromic effect has also given reasonable values. Therefore, the hypochromism observed in the cyclic diacetylene (XIa) has been attributed to the operation of dispersion-force interaction between diyne unit and the naphthalene chromophore.
Asymmetric Synthesis in the Methoxy-mercuration of α, β-Unsaturated Esters
Authors: Oda Junichi , Nakagawa Tsutomu , Inouye Yuzo
Published: July 2006

The methoxy-mercuration of (−)-menthyl crotonate, cinnamate, and β-methylcinnamate resulted in partial asymmetric syntheses of the corresponding β-methoxylated derivatives, (−)-R-β-methoxybutyric acid, (−)-S-β-methoxy-β-phenylpropyl alcohol, and (−)-S-β-methoxy-β-phenylbutyl alcohol. The results suggested an ionic mechanism involving a cyclic mercurinium ion as an intermediate, formed by the electrophilic attack of mercuric acetate from the least-hindered side of the double bond in the Cram-Prelog model of the systems, followed by the attack of the methoxy anion from the opposite side. The reaction mechanism leading to the predominant enantiomers was discussed.