bluuebunny/crossref_metadata_2025 huggingface dataset:
Studies on the Liquid-Liquid Partition Systems. VI. Solvent Extraction Study of the Dissociation of Sulfurous, Selenious and Tellurous Acids in Acid Perchlorate Media
Authors: Sekine Tatsuya , Iwaki Hidehiko , Sakairi Mitsuo , Shimada Fumitake , Inarida Mariko
Published: July 2006

Liquid-liquid distribution behavior of sulfur(IV), selenium(IV) and tellurium(IV) in acid perchlorate media was studied at 25°C. The distribution of sulfur(IV) into carbon tetrachloride was determined by iodometry and that of selenium (IV) into methylisobutyl carbinol or of tellurium(IV) into hexane containing trioctylphosphine oxide was determined by radiometry. The changes in the distribution ratio caused by the changes in the hydrogen ion concentration were explained in terms of the distribution of sulfurous, selenious or tellurous acid as the non-charged form into the organic phase and the dissociation of these acids in the aqueous phase. The distribution constants as well as the dissociation constants of these acids were determined by a graphical method. In acid perchlorate media, sulfurous and selenious acids exist as neutral and mononegative species while tellurous acid exists as monopositive, neutral and mononegative species, and the neutral species exists only in a narrow hydrogen ion concentration range.
Electronic Spectra and Electronic Structures of Benzonitrile N-Oxide and Its Derivatives
Authors: Yamakawa Masumi , Kubota Tanekazu , Akazawa Hideko , Tanaka Itaru
Published: July 2006

The electronic spectra of 2,6-dimethylbenzonitrile N-oxide and its some derivatives were recorded in n-heptane and were compared with those of benzonitrile and phenylacetylene. The analyses of the electronic spectra of aromatic nitrile N-oxides were done by the following procedures. First, simple molecular orbitals (SMO) of benzonitrile and phenylacetylene were calculated using some parameters determined by the use of the overlap integrals and valence state ionization potentials. Then, by comparing the eigenvalues of the SMO thus obtained with the observed spectra the spectroscopic exchange integrals have been obtained for 1A1 and 1B1 bands, where interactions between two configurations were taken into consideration for the 1B1 bands. The SMO of benzonitrile N-oxide was next calculated on reference to the physicochemical nature of aromatic nitrile N-oxides studied before. The parameters were chosen so as to fit with the observed values of dipole moments of benzonitrile N-oxide and its some methyl derivatives. Electronic spectra of the nitrile N-oxides were then analyzed using the above SMO’s and spectroscopic exchange integrals. The substituent effect on the electronic spectrum of benzonitrile N-oxide was also discussed by the similar treatment. Characteristic strong band appearing in the near UV region was assigned to the 1A1 band having a change transfer (CT) nature, where the CT from the oxygen atom to the residual conjugated system makes a larger contribution than that of the reverse direction. In addition, the physicochemical nature and reactivity of nitrile N-oxides were discussed on the basis of their molecular diagrams, which were obtained from the SMO’s mentioned above.
A New Determination Method of Relative Rate Constants for Reactions with OH-radicals in Radiolysis of Aqueous Solutions
Authors: Morita Makio , Fujimaki Masao
Published: July 2006

Radioactivity of water increased linearly with dose when aqueous solution of 3H-formate (2 μCi/ml and 2×10−8  m) was irradiated with γ-rays in the presence of oxygen. The increase of the radioactivity was found to be reciprocally proportional to the non-labeled formate concentration where the amount of 3H-formate was kept invariable. Addition of ferrocyanide and 2-propanol, effective OH-radicals scavengers, depressed the radioactivity increase to near zero. These facts show that the abstraction of tritium from 3H-formate by OH-radicals causes the increase of the radioactivity of water. A competition method to measure relative rate constants for reactions with OH-radicals was deviced on the present results. Some values obtained by this method were in agreement with published data.
Intramolecular Hydrogen Bonding in Monoterpene Alcohols Containing π-Electronic System
Authors: Shishibori Tsuyoshi
Published: July 2006

The nature of intramolecular hydrogen bonding in diastereoisomeric pairs of 10-nor-8-oxomenthols (VIII and IX) and 10-nor-8-oxocarvomenthols (X and XI) has been studied by infrared spectroscopy. It was found that 10-nor-8-oxoneomenthol (IX) contains the OH···O type intramolecular hydrogen bond, while 10-nor-8-oxomenthol (VIII) contains the OH···π interaction in addition to the OH···O hydrogen bond. 10-Nor-8-oxocarvomenthols (X and XI) were internally unbonded. In addition, the extent and the limitation of the intramolecular OH···π interaction has been investigated for the diastereoisomeric pairs of a series of p-menth-8-enols: p-menth-8-en-4-ols (I and II), isopulegols (III and IV), dihydrocarveols (V and VI), and trans-β-terpineol (VII). Thus, the hydroxyl group in α- or β-unsaturated alcohols I, II, III and IV was found to be internally bonded to the π-electrons on the double bond; the other isomers are internally unbonded.
The Synthesis of 4-Hydroxyfuro[2′,3′:7,8]coumarins 5H-benzofuro[3,2-c]furo[2,3-h][1]benzopyran-5-one
Authors: Kawase Yoshiyuki , Nanbu Mutsumu , Yanagihara Hirokazu
Published: July 2006

4-Hydroxyfuro[2′,3′:7,8]coumarin (16) and its 3-phenyl (10) and 3-(2-methoxyphenyl) (11) derivatives were prepared from the corresponding 4-hydroxy-5-benzofuranyl ketones (15, 8a and 8b) by the action of ethyl carbonate and sodium. The furocoumarin 11 thus obtained was converted to 5H-benzofuro[3,2-c]furo[2,3-h][1]benzopyran-5-one (18), a compound having a new pentacyclic ring system, by the demethyl-cyclization with pyridine hydrochloride, hydroiodic acid or aluminum chloride. The attempted preparation of these compounds through their dihydro compounds is also described; 2,3-dihydro-4-hydroxybenzofuran (1) was acylated with phenylacetic acid, with 2-methoxypheny lace tic acid or with 2,4,5-trimethoxyphenylacetic acid by the action of polyphosphoric acid to give a mixture of the 5- and 7-acylated compounds (3 and 2), and the formers were converted to the corresponding 4″,5″-dihydrofuro[2″,3″:7,8]isoflavones (6), 4″,5″-dihydro-2-methylfuro-[2″,3″:7,8]isoflavones (4) and 4′,5′-dihydro-4-hydroxyfuro[2′,3′:7,8]coumarins (7). The 2,3-dihydro-4-hydroxy-5-benzofuranyl benzyl ketone (3a) and the dihydrofuroisoflavones (4a and 4b) were also obtained by the catalytic reduction of the corresponding furo-compounds.
Synthetic Studies of α-Tocopherol. III. Synthesis of Phytone
Authors: Ichikawa Takehiko , Kato Tetsuya
Published: July 2006

Phytone (XI), an important intermediate in the preparation of α-tocopherol, was synthesized by a selective Wittig reaction between geranyltriphenylphosphonium halide (VII) and the aldehyde group of 2-methyl-6-oxoheptanal (VIII), followed by the hydrogenation of the product. VIII was prepared from 1,3-dimethyl-1-cyclohexene (V) by ozonolysis and reductive decomposition. V could not be obtained in a pure state by the dehydration of 2,6-dimethylcyclohexan-1-ol (II), presumably because of the isomerization of the intermediate carbonium ion. The pyrolysis of the acetate of II (III) was found to give pure V. That the hardly-pyrolizable stereoisomer of III was cis,cis-2,6-dimethylcyclohexyl-1-acetate (VI) is consistent with the cis-elimination mechanism.
The Partial Resolution of Racemic α-Alanine through the Cobalt(III) Complexes of Optically Active Aspartic or Glutamic Acid
Authors: Shibata Muraji , Nishikawa Hiroaki , Hosaka Kinya
Published: July 2006

When a hundred per cent excess of racemic α-alanine was reacted, in the presence of activated charcoal, with a reaction mixture of tricarbonatocobaltate(III) and l-asparate, water-insoluble β-tris(alaninato) cobalt (III) was precipitated. The recovery of alanine from this triscomplex showed a partial resolution; the d form of alanine was preferentially complexed, and the optical purity of the alanine recovered was about 38%. Spectroscopic measurements (absorption, ORD and CD) showed that the predominantly-existing species in the above reaction mixture was the (−)-[Co CO3(l-asp)2]3− anion, and that the reaction of this complex anion with racemic alanine led to the predominant formation of β(−)-[Co(d-ala)2(l-ala)] (the (−) sign refers to the sign of the Cotton effect in the first absorption band region). Similar experiments were carried out with d-aspartate and l-glutamate in place of l-aspartate. Through all the experiments, we have found that the complexes which are effective for the resolution of racemic alanine and the product or tris(alaninato) cobalt (III) have the same sign of the Cotton effect in their first-band regions.
Stability Constants of Some Uranyl Complexes
Authors: Ramamoorthy S , Santappa M
Published: July 2006

Complexes of uranyl ion with benzoic, phenylacetic, phenoxy-acetic, thiomalic and itaconic acids were studied by pH titration method at 31±0.1°C. A 1 : 1 complex is formed in all the cases in the pH range 2.5–3.5 and their stability constants are reported.
Kinetics of Multidentate Ligand Substitution Reactions. II. Substitution Reactions of BT with Nitrilotriacetato Nickelate(II) Chelate and with Ethylenediaminetetraacetato Nickelate(II) Chelate
Authors: Kodama Mutsuo , Sasaki Chifumi , Murata Mitsuko
Published: July 2006

This paper reports a spectrophotometric study of the solution equilibria and the kinetics of the substitution reaction of Eriochrom Black T (BT) with nickel(II)-NTA and with nickel (II)-EDTA chelates. In solutions of pH 8.50–9.50 containing a large excess of uncomplexed NTA over BT and nickel (II)-NTA chelate, BT forms only 1-to-1 normal chelate, NiD−, with the nickel(II) ion, the stability constant of which is 1020.8(μ=0.30). Kinetically, the ligand-exchange reaction of BT with the nickel (II)-NTA chelate was found to proceed through the following two simultaneous reaction paths and to be much faster than that with the nickel(II)-EDTA chelate,

2i) &  NiX^-+HD^2-\ightleftharpoonsNiD^-+HX^2- ii) & & HD^2-\oversetrapid\ightleftharpoonsD^3-+H^+

& rapid\upharpoonleft\downharpoonright& &  NiX^-+D^3-\ightleftharpoonsNiD^-+X^3-

&  NiX_2^4- & & rapid\upharpoonleft\downharpoonright

& & & NiX_2^4- rate-determining step

where NiX−, NiX24−, HD2−, and D3− represent Ni(II)-NTA chelate of 1-to-l composition, Ni(II)-NTA chelate of 1-to-2 composition, doubly deprotonated BT anion and completely deprotonated BT anion, respectively. The substitution reaction of BT with nickel(II)-EDTA chelate was found to proceed mainly through the following reaction path,

& HD^2-\oversetrapid\ightleftharpoonsD^3-+H^+ & NiY^2-+D^3-\ightleftharpoonsNiD^-+Y^4-

& &rate-determining step

and the contribution of the following reaction to the whole reaction is negligible at pH 9.00–10.50.

NiY^2-+HD^2-\ightleftharpoonsNiD^-+HY^3-
Studies on Photo-polarography. I. Polarographic Behavior of Trioxalato-ferrate(III) Ion under Ultraviolet Irradiation
Authors: Yamashita Kazuo , Imai Hideo
Published: July 2006

The polarographic behavior of trioxalatoferrate(III) ion under irradiation of ultraviolet light was studied. Trioxalatoferrate(III) was photo-chemically reduced in the bulk and the polarographic reduction current changed into the oxidation one, which showed a highly kinetic characteristic. The current-time curve during one drop growth of the dropping mercury electrode under irradiation was analyzed, and the rate constant of the photo-chemical reaction (kν) was evaluated. The apparent value given as kν′=I0εkν was 0.35 cm−1, where I0 being the intensity of the incident light and ε the extinction coefficient. The time dependence of the photopotential was elucidated on the basis of the Nernst equation. The possible photonometric determination of dissolved oxygen was suggested from the effect of dissolved oxygen on the half-life of the photo-chemical reaction.
Some Reactions of N-Haloamidines
Authors: Haruki Eiichi , Inaike Toshihiro , Imoto Eiji
Published: July 2006

The reactions of a variety of N-haloamidines with silver oxide, sodium ethoxide, thiourea derivatives, and phenols are described. In these reactions, N-phenyl-N′-chlorobenzamidine gave diphenylcarbodiimide, benzimidazole, N-amidinobenzamidine and 2,4-diphenylthiadiazole respectively, while the other N-haloamidines afforded the corresponding products. The mechanistic implications of these reactions are discussed.
Syntheses of Some Heterocyclic Compounds from α-Benzoylimino-benzyl Cyanide and Related Compounds
Authors: Fujimori Masahiro , Haruki Eiichi , Imoto Eiji
Published: July 2006

The reaction of α-benzamidobenzyl cyanide (I) with thionyl chloride and pyridine in benzene gave α-benzoyliminobenzyl cyanide (II) in a 52% yield. II is a novel compound which can react readily with nucleophilic reagents, such as alcohols, mercaptans and amines. The reaction of II with ethyl-mercaptan and with alcohols gave α-ethylthio-α-benzamidobenzyl cyanide and α-alkoxy-α-benzamidobenzyl cyanide respectively. Furthermore, II reacts with bifunctional nucleophilic reagents to form heterocyclic compounds. The reaction of II with hydrazine and with hydroxylamine afforded 3,5-diphenyl-1,2,4-triazole and 3,5-diphenyl-1,2,4-oxadiazole respectively.
Reactions of Transition-Metal-Olefin Complexes. III. Kinetics of the Oxidation of Substituted Styrenes Catalyzed by Palladium Salts in an Aqueous Tetrahydrofuran Solution
Authors: Okada Hiroyoshi , Noma Takashi , Katsuyama Yoshihisa , Hashimoto Harukichi
Published: July 2006

The kinetics of the oxidation of ring-substituted styrenes catalyzed by palladium(II) salts in a homogeneous aqueous tetrahydrofuran solution containing p-benzoquinone have been investigated at 30°C under a nitrogen atmosphere. The rate equation was found to be identical with the one previously found for styrene, i.e., −d[olefin]⁄dt=(kI+kII[Pd2+][olefin], where kI is the rate constant for ketone-formation and kII is the rate constant for aldehyde-formation. It was found that both the proton and the chloride ion affect the rate inhibition at high concentrations and the rate acceleration at low concentrations. The product ratio of the ketone to the aldehyde decreased monotonously with the increase in proton concentration and with the increase in chloride ion concentration. An increase in the ionic strength from 0.052 to 0.787 increased the rate constants, but the ratio of the products scarcely changed at all. The substituent effects for the sites of nucleophilic attack were specific; i.e., the electron-releasing substituents facilitated the formation of substituted acetophenone and diminished the formation of substituted phenylacetaldehyde. The reverse trend was found for the electron-withdrawing substituents. From these results, there is proposed a mechanism in which two active species, [ArCH=CH2Pd(H2O)-(OH)Cl] and [ArCH=CH2Pd(H2O)(OH)Cl2]−, are involved and in which the rate-determining step is the decomposition of the σ-complexes with the hydride shift to the carbonyl products.
Cleavage Reactions of Alkoxy Radicals Produced by Anodic Oxidation of t-Alcohols
Authors: Maruyama Kazuhiro , Murakami Katsuya
Published: July 2006

The anodic oxidation of t-alcohols in water - dioxane - sodium hydroxide system has been examined. The possibility of production of t-alkoxy radicals by anodic oxidation of t-alcohols in the electrolytic system was found. The relative ease of bond scission of the intermediate t-alkoxy radical was determined by quantitative analysis of the mixture of ketones produced. The relative rates of cleavage decrease in the order: allyl>sec-butyl>isopropyl>ethyl>n-propyl>n-butyl>n-pentyl>isobutyl>methyl. The hyperconjugative effect of β-hydrogen and effect of double bond at β-position to the rate enhancement of cleavage reaction was confirmed.
Studies of Phosphorylation. II. Reaction of 2′, 3′-O-Isopropylideneinosine and -guanosine with Phosphoryl Chloride1
Authors: Kusashio Koji , Yoshikawa Masaharu
Published: July 2006

Several reactions accompanied by the phosphorylation of 2′, 3′-O-isopropylidene nucleosides with phosphoryl chloride in the absence of an organic solvent were investigated. When the reaction temperature exceeded 30°C, 2′, 3′-O-isopropylideneinosine gave 5′-chloro-5′-deoxy 2′, 3′-O-isopropylideneinosine and 5′-deoxy-2′, 3′-O-isopropylidene-3, 5′-cycloinosine. This cycloinosine, was then further subjected to rapid cleavage in a pyrimidine ring to give 5-amino-4-carbamoyl-N5, 5′-cyclo-1-β-d-(5′-deoxy-2′, 3′-O- isopropylideneribofuranosyl)-imidazole, 5-amino-4-cyano-N5, 5′-cyclo-1-β-d-(5′-deoxy-2′, 3′-O-isopropylideneribofuranosyl)-imidazole, and the N5-formyl derivative of the latter. Similar sequences of the chlorination at the 5′-position and the cyclization between 3 and 5′-positions were observed in the case of 2′, 3′-O-isopropylideneguanosine, but the resulting 5′-deoxy-2′, 3′-O-isopropylidene-3, 5′-cycloguanosine was not susceptible to ring cleavage under the conditions used. The factors affecting these reactions were described, and possible mechanisms were proposed.
Infrared Spectra and Stereochemistry of Bis-pyridine Complexes of Tin(IV)
Authors: Tanaka Toshio , Matsumura Yoshio , Okawara Rokuro , Musya Yoshihiko , Kinumaki Susumu
Published: July 2006

Assignments are given for the infrared spectra of bis-pyridine complexes of SnX4, (CH3)2SnX2(X=Cl,Br and I), and (C2H5)2SnCl2 in the 80–1610 cm−1 region. These complexes show the Sn–N stretching band near 200 cm−1. Most pyridine vibrations shift to a higher or a lower frequency upon complex formation. Among these, the ν10, in-plane ring deformation vibration is the most sensitive to the substituents on the tin atom as well as to the complex formation. Thus, the frequency may be a qualitative measure of the tin-pyridine coordination bond strength. The infrared spectra suggest a cis-configuration for the tin tetrahalide complexes and a distorted octahedral configuration for the dimethyltin diiodide complex. The remaining complexes may be assumed to have trans-alkyl and cis-halogen configurations.
The Termination Processes of the Autoxidations of Benzene, Toluene and Ethylbenzene in the Aqueous Phase as Studied by Oxygen-18
Authors: Hotta Hiroshi , Suzuki Nobutake
Published: July 2006

The autoxidations of benzene, toluene and ethylbenzene were investigated at 70°C by using the oxygen-18 enriched Fenton’s reagent. The oxygen-18 atom percentage in the products suggests that all the oxygen of benzaldehyde from toluene and of acetophenone from ethylbenzene is donated by molecular oxygen dissolved in the aqueous phase, while the oxygen of the hydroxylation products, namely, phenol from benzene, benzyl alcohol from toluene and methyl phenyl carbinol from ethylbenzene, is donated partly from water and partly from molecular oxygen. From the latter finding, the rate of the carbonium cation formation from the intermediate radicals without their oxidation to the peroxide is in the order of phenyl>α-methyl-benzyl>benzyl.
Heats of Mixing for Binary Mixtures. V
Authors: Murakami Sachio , Koyama Mituo , Fujishiro Ryoichi
Published: July 2006

The heats of mixing were measured at 25.0°C for binary mixtures of chloroform+tetrahydrofuran,+furan, and +2-methyl furan systems and for cyclohexane+chloroform,+tetrahydrofuran,+furan, and +2-methyl furan systems. Using these data and the treatment described in a previous paper [Bull. Chem. Soc. Japan, 37, 1776 (1964)], the intermodular hydrogen bond energies between chloroform and cyclic ethers were estimated to be ΔH=−12 kJ for the chloroform-tetrahydrofuran-cyclohexane system, ΔH=−4 kJ for the chloroform -2-methyl furan-cyclohexane system, and ΔH=−3 kJ for the chloroform-furan-cyclohexane system. From these results, two types of intermolecular hydrogen bonds between chloroform and cyclic ethers are discussed.
Ion-exchange Properties of Anion-exchanger Containing Cobalticinium Cations
Authors: Ito Takuji , Kenjo Tadao
Published: July 2006

Selectivity coefficients of various anions vs. chloride or nitrate and water uptake at a saturated vapor pressure with polymeric pentamethylene cobalticinium exchanger were calculated from the experimental data and compared with those of anion-exchange resins. The selectivity coefficient sequence was nearly identical with that for quaternary ammonium type anion-exchangers, and the position of hydroxide ion indicated that the cobalticinium type anion-exchanger was a strong base type. Inspection of selectivity coefficients data revealed that strong base anion-exchangers were more selective than weak base anion-exchangers. The cobalticinium type anion-exchanger was found to have a high selectivity coefficient of iodide vs. bromide, even in comparison with strong base anion-exchange resins. Column separation of bromide and iodide using the cobalticinium type anion-exchanger was easily accomplished. The separation factor was three times that of the quaternary ammonium type anion-exchanger. The water uptake at a saturation vapor pressure by the cobalticinium type anion-exchanger in a given form increased with decreasing selectivity coefficient for the same anion. These trends were similar to those for quaternary ammonium type anion-exchanger. The relation between selectivity coefficient sequence of various anions vs. a common anion, and solubilities of the salt whose cation was the ionogenic group and anion adsorbed ion was discussed.
Behavior of Methyl Iodide in the Reaction of Acetic Acid Synthesis from Methanol and Carbon Monoxide
Authors: Mizoroki Tsutomu , Nakayama Mikitake
Published: July 2006

The reaction of methyl iodide with carbon monoxide in the presence of cobalt (II) iodide as the catalyst has been investigated to know the effect of methyl iodide on the acetic acid synthesis from methanol and carbon monoxide catalyzed by the same catalyst. The reaction, CH3I+CO+H2O→CH3COOH+HI, does not take place before the methyl iodide used has been hydrolyzed completely into methanol and sodium iodide by adding enough amount of sodium acetate (CH3I+CH3COONa+H2O→CH3OH+NaI+CH3COOH). Methyl iodide also strongly inhibits the reaction of methanol with carbon monoxide catalyzed by cobalt (II) ion or dicobalt octacarbonyl, although iodide ion promotes the reaction effectively. The promotion effect of iodide ion has been discussed by considering the effect of an additive on carbonylation reactions in terms of a labilizing ligand and a non-labilizing ligand and a possible reaction scheme of methanol with carbon monoxide catalyzed by cobalt(II) iodide has been proposed.
Hot Atom Chemistry of Phosphorus Compounds. II. Chemical Effects of Neutron Irradiation on Phosphoric Esters of Hexoses
Authors: Kiso Yoshiyuki , Kobayashi Mitsue , Kitaoka Yoshinori , Kawamoto Keizo , Takada Jitsuya
Published: July 2006

Phosphoric esters of hexoses were subjected to neutrons and the resulting 32P-labeled recoil products were separated by paper chromatography and paper electrophoresis. The main recoil products were phosphorous and phosphoric acids, independent of the chemical form of the target material and the kind of its salt. A small amount of inorganic acids containing a P–P or P–O–P bond was also found. The yield of the retention product was less than a few percents. The presence of organic diphosphorus compound was supposed by paper electrophoretic analysis. An addition of a small amount of water to the target material before irradiation favored formation of 32P-labeled phosphorus oxyacids in lower oxidation state. The results from irradiation of aqueous solution gave an unexpected chromatographic behavior owing to some unstable complex of recoil 32P atom with water molecule.
Polymerizations by 1,3-Dipolar Cycloaddition Reactions. V. The 1,3-Dipolar Polycycloadditions of Dinitrile N-Oxides with Diolefins
Authors: Iwakura Yoshio , Shiraishi Shinsaku , Akiyama Masayasu , Yuyama Masahiro
Published: July 2006

Terephthalonitrile di-N-oxide and isophthalonitrile di-N-oxide were synthesized from the corresponding hydroxamic chlorides by dehydrochlorination with triethylamine. Their chemical properties and the polycycloadditions with diolefins were examined. The polymers obtained were amorphous and their molecular weights were not so high. The thermal gravimetric analyses of them showed that the polymers were stable up to 300–350°C in air.
Polymerizations by 1,3-Dipolar Cycloaddition Reactions. VI. Syntheses of Polyurethans with Isoxazoline or Isoxazole Linkages
Authors: Iwakura Yoshio , Shiraishi Shinsaku , Asakawa Zin , Akiyama Masayasu , Tanaka Nobuo
Published: July 2006

Polyurethans with isoxazoline or isoxazole linkages in the polymer main chains were prepared by polyadditions of diols with isoxazoline or isoxazole rings and diisocyanates. The diols were prepared by 1,3-dipolar cycloaddition reactions of tere- and iso-phthalonitrile di-N-oxides with allyl or propargyl alcohol. Polyurethans of the same structures were also prepared by 1,3-dipolar polycycloadditions of the nitrile oxides with bisallyl or bispropargyl carbamates.
Dehydrocyclization of 3-Methyl Heptatriene-1, 4, 6
Authors: Komatsu Youji
Published: July 2006

Xylenes, mainly consisting of ρ-xylene and o-xylene, were selectively synthesized by the dehydrocyclization of 3-methyl heptatriene-1, 4, 6 (MHT) using a chromia-alumina catalyst. MHT was easily converted to xylenes in a good yield; this reaction proceeded even under mild conditions, as at 200°C. The effects of the catalyst composition, and the influence of the reaction temperature on the conversion of MHT, the xylene yield, the by-products, etc., were studied.
3d-Orbital Resonance in Divalent Sulfides. XIV. Free Radical Copolymerization of Ketene Diethylmercaptal with Styrene
Authors: Tagaki Waichiro , Tada Tsutomu , Nomura Ryuichi , Oae Shigeru
Published: July 2006

Free radical copolymerization reactions of ketene diethylmercaptal (I) and p-methyl-mercaptostyrene (III) with styrene have been carried out. The Q-values for I and III are found to be 2.7 and 3.3 respectively, and these and other related observations are discussed in terms of electron-sharing conjugation involving 3d-orbital of sulfur atom.
Studies of Photosensitive Resins. III. The Thermal Hardening of Polyvinyl Cinnamate
Authors: Nakamura Kenichiro , Sakata Toshifumi , Kikuchi Shinichi
Published: July 2006

The thermal hardening of polyvinyl cinnamate was investigated. The IR spectrum of the thermally-hardened polyvinyl cinnamate was measured, and the change of its structure by heat was studied. The results showed that the structure of the resin hardened by heat was the same as that of the illuminated resin. The kinetics of the crosslinking by heat was also evaluated; the activation energy for the crosslinking was estimated to be 25.4 kcal/mol. The critical hardening value of polyvinyl cinnamate was also measured and estimated to be about 1.3 crosslinking per polymer molecule.
Nuclear Quadrupole Resonance Study of Antimony Pentachloride and Its Phase Transition
Authors: Chihara Hideaki , Nakamura Nobuo , Okuma Hideo , Seki Syûuzô
Published: July 2006

A phase transition was found in solid antimony pentachloride at 212°K by the nuclear quadrupole resonance and the differential thermal analysis. In the high temperature solid phase, five resonance lines were observed that were all assigned to antimony resonances and that were dependent on temperature only slightly. The quadrupole coupling constant of 121Sb was 84.54±0.01 MHz (asymmetry η=1.0±0.3%). Chlorine resonances were not detected above the transition point. In the low temperature phase, many resonance lines were observed due both to chlorine and antimony; the latter gave the coupling constant for 121Sb 186.43±0.03 MHz (η=79.54±0.02%) and 172.8±0.3 MHz (η=79.2±0.3%). There are two nonequivalent sites for antimony. The structure in the two solid phases was suggested as being trigonal bipyramidal above 212°K and a dimerized Sb2Cl10 bridged by two chlorine atoms with hexa-coordinated antimony atoms below 212°K.
The Cobalt Carbonyl-catalyzed Intramolecular Hydroesterification of Allyl Alcohol with Carbon Monoxide
Authors: Matsuda Akio
Published: July 2006

The intramolecular hydroesterification of allyl alcohol with carbon monoxide to give γ-butyrolactone occurred in the presence of cobalt carbonyl under the pressure of carbon monoxide containing a small amount of hydrogen; propionaldehyde and isobutyraldehyde were produced as by-products. The selectivity toward γ-butyrolactone increased with the use of acetonitrile or its derivatives as the solvent. The addition of pyridine, in the absence of these solvents, was effective only in increasing the reaction rate, not in increasing the selectivity toward γ-butyrolactone. On the other hand, in the presence of acetonitrile as a solvent, the selectivity toward γ-butyrolactone increased together with the reaction rate when a catalytic amount of an organic base such as pyridine was added. The higher the reaction temperature, the higher the pressure necessary to attain a maximum selectivity toward γ-butyrolactone; the best yield of γ-butyrolactone was ca. 60%. The effect of the partial pressures of hydrogen and carbon monoxide on the initial rate of the formation of each product was made clear. The experimental results were explained by a mechanism involving two different paths for the formation of an alkylcobalt carbonyl-intermediate. The order of effectiveness of acetonitrile and its derivatives as solvents has been interpreted in terms of the HSAB principle by Pearson et al.
Electrochemical Fluorination of Glycols and Esters of Dicarboxylic Acids
Authors: Nagase Shunji , Abe Takashi , Baba Hajime
Published: July 2006

The electrochemical fluorination of glycols (1,3-propanediol and 1,4-butanediol), and dimethyl or diethyl esters of dicarboxylic acids (malonic, succinic, and maleic acids) was carried out. Difluoromalonic acid from esters of malonic acid, and perfluorosuccinic acid from esters of succinic acid or maleic acid, were obtained in reasonable yields, while 1,3-propanediol and 1,4-butanediol were cleaved or underwent ring formation and yielded only small amounts of perfluoro-dicarboxylic acids. Perfluoromonocarboxylic acids and fluorocarbons were among the by-products of these esters and glycols.
Hydrogen Abstraction Reaction of α-Heteroatom Substituted Compounds by t-Butoxy Radical
Authors: Uneyama Kenji , Namba Hiroshi , Oae Shigeru
Published: July 2006

Hydrogen abstraction reactions of various α-substituted compounds were examined in chlorobenzene using di-t-butyl peroxide. The reactivities are not satisfactorily correlated with σ* values of the substituents. The relative rates of substituted anisoles, N,N-dimethylanilines and phenyl methyl sulfones give good correlations with Hammett σ values with ρ values of −0.39, −0.42 and −0.2 respectively, but those of thioanisoles requires an additional term due to conjugative effect as described in logk⁄k0=−0.11(σ+0.75ΔσR+) in order to get a good Hammett correlation. These results were discussed in terms of a combination of an inductive effect, an electron-releasing and an electron-sharing conjugation.
Anionic Polymerization of trans-β-Methylstyrene
Authors: Okamoto Yoshio , Yuki Heimei , Murahashi Shunsuke
Published: July 2006

The anionic polymerization of trans-β-methylstyrene by n-butyllithium was carried out in hydrocarbon solvents and in tetrahydrofuran. In hydrocarbon solvents the monomer was consumed by n-butyllithium, but gave no polymer insoluble in methanol. In tetrahydrofuran the polymerization proceeded rapidly, giving a polymer insoluble in methanol. This polymer was produced by the normal addition polymerization of a C=C double bond. The relatively lower degree of polymerization of poly-β-methylstyrene indicated a chain transfer in the reaction. The chain transfer reaction due to the active hydrogen of a methyl group in this monomer was also observed by means of the electronic spectra of the reaction mixtures. The polymer anion was converted to inactive anions at high temperatures.
Studies of Photosensitive Resins. IV. Photosensitization Mechanism of Polyvinyl Cinnamate
Authors: Nakamura Kenichiro , Kikuchi Shinichi
Published: July 2006

The photosensitization mechanism of polyvinyl cinnamate was investigated by measuring the phosphorescence spectra of cinnamic acid and sensitizers. The peak of phosphorescence for trans-cinnamic acid was found to be 20100 cm−1, and the triplet energies of the effective sensitizers were found to be situated near or higher than that of cinnamic acid. It was established that the phosphorescences of sensitizers were exceedingly quenched when cinnamic acid was introduced into their solutions. This finding can be understood if it is assumed that the excitation energy is transferred from the triplet state of the sensitizer to that of cinnamic acid. The critical separation of donor and acceptor and the configuration of the triplet state for cinnamic acid are also discussed.
An MO-theoretical Interpretation of the Nature of Chemical Reactions. I. Partitioning Analysis of the Interaction Energy
Authors: Fukui Kenichi , Fujimoto Hiroshi
Published: July 2006

The molecular interaction energy, without considering the nuclear configuration change, is discussed by partitioning it into the Coulomb, exchange, delocalization, and polarization terms. A succinct approximate expression for each term is derived, and its magnitude is discussed. The expressions obtained as the second-order perturbation terms for the delocalization and the polarization energies are in accord with those of the well-established reactivity indices, the delocalizability, and the self-atom polarizability respectively. The chemical reactivity can thus be measured by the combined sum of these four terms. In usual ionic reactions the Coulomb and the delocalization terms are more important than the exchange and the polarization terms respectively.
The Crystal Structure of the Copper(II) Chelate of N,N′-Ethylene-bis(l-ephedrine)
Authors: Motohashi Michio , Amano Yoshiharu , Uno Toyozo
Published: July 2006

The crystal structure of the copper(II) chelate of N,N′-ethylenebis(l-ephedrine), where two molecules of l-ephedrine are connected through an ethylene group, has been determined by three dimensional X-ray analysis. The dimensions of the orthorhombic unit cell with the space group P212121-D24 are a=8.431, b=15.92, c=16.70 Å,Z=4 and ρ0=1.34g/cm3. The intensity data were collected by multiple film technique, and the structure was determined by the heavy atom method. The positions of the copper atom simulated the symmetry of a higher space group than that of P212121 and the phases calculated from them gave two pseudo mirrors in the Fourier map based on the copper atom only. The structural determination was made with the use of the methods of successive approximations and diagonal and block diagonal least-squares. The problems concerning the pseudo mirrors were solved mainly from the behaviors of the thermal parameters. The final results were obtained by correcting some unsuitable positional and thermal parameters found by the block diagonal least-squares refinement. The final R-factor is 13.0%. The structure shows that two crystalline water molecules do not coordinate to the copper atom and that the N–C–C–N bridge causes distortion of the square planar coordination around the copper atom.
The Reactivities of Nuclear-Substituted Phenyl Methacrylates in Radical Copolymerization with Styrene
Authors: Otsu Takayuki , Ito Toshio , Fujii Yoshihiro , Imoto Minoru
Published: July 2006

In order to clarify the effects of the alkyl substituents on the reactivities of methacrylate monomers toward the attack of a radical, the copolymerizations of a series of nuclear-substituted phenyl methacrylates with styrene were investigated. From the results, the monomer reactivity ratios and the Alfrey-Price Q, and e values were determined. It was found that the relative reactivities toward the polystyryl radical were not correlated with the ordinary Hammett equation, but a linear relationship was obtained with a modified Hammett equation which contained a term of the resonance contribution by the substituents. Accordingly, it was considered that the reactivities of substituted phenyl methacrylates depend on both polar and resonance effects caused by the substituents.
Polarographic and Spectroscopic Studies on the Ion-pair Formation of Trioxalatocobaltate(III) Ions with Cations in Aqueous Solutions
Authors: Tanaka Nobuyuki , Koseki Kazuo
Published: July 2006

The ion association between trioxalatocobaltate(III) anion and uni-, bi- and tervalent cations in aqueous solutions has been studied by polarographic and ultraviolet, visible and infrared spectroscopic methods. The association constants have been obtained by the measurement of the polarographic diffusion current of trioxalatocobaltate(III) ions in the presence of varied concentrations of cations at ionic strength 0.1 (NH4NO3) and 25°C. The influence of ammonium ion was taken into consideration in the treatment of polarographic data. The values obtained are 7.9 for (CH3)4N+[Co(ox)3]3−, 3.7±0.4 for (C2H5)4N+[Co(ox)3]3−, 22±1 for Na+[Co(ox)3]3−, 56±6 for Mg2+[Co-(ox)3]3−, 55±4 for Ca2+[Co(ox)3]3−, 53±3 for Sr2+[Co(ox)3]3−, 55±7 for Ba2+[Co(ox)3]3− and 118±17 for Al3+[Co(ox)3]3−. The association constant of NH4+[Co(ox)3]3− was determined by the conductivity measurement to be 33.6 (logK=1.53) at zero ionic strength. No change was observed in the visible, the ultraviolet and the infrared absorption spectra of trioxalatocobaltate (III) ions upon the addition of various cations even at the concentration at which the ion-pair formation is assumed to occur from the polarographic studies. These facts indicate that, in a sense of equilibrium study, there is no direct interaction between the complex anion and the cation, but one or more water molecules interpose between the two ions.
The Reaction between Hydrocarbon and Hydrogen Cyanide in Silent Electrical Discharge. II. The Formation of Acrylonitrile from Ethylene and Hydrogen Cyanide
Authors: Kawamoto Kazuaki
Published: July 2006

The present investigation was undertaken to examine the possibility of the direct introduction of a cyano radical into ethylene by means of a silent discharge. When a mixture of ethylene and hydrogen cyanide was discharged in an ozonizer under atmospheric pressure, the main liquid product was acrylonitrile, though the formation of telomers, such as ethyl cyanide, n-butyl cyanide and n-hexyl cyanide, was also observed. Besides these compounds, the reaction products were confirmed to consist of s-butyl, n-propyl, isopropyl, n-amyl, and isoamyl cyanides, and a gaseous product. The yield of acrylonitrile was affected by the temperature and voltage of the discharge. It has been found that the yields of the liquid products and the gaseous product increase with the rise in the temperature and voltage of the discharge, while the relative ratio of acrylonitrile to the other liquid product decreases. Judging from the relative concentration of each compound in the reaction products, it may be said that the vinyl radical and the cyano radical are the main intermediates in this reaction system.
UV and Visible Absorption Spectra of Monohalogenated Anthracenes. I. The First Absorption Bands
Authors: Ohno Isao , Iguchi Kaoru
Published: July 2006

UV and visible absorption spectra of monohalogenated anthracenes are measured, and the first absorption band are reported. When anthracene is monohalogenated, the first absorption band slightly shifts toward red or does not shift in accordance with the change in the position and the species of the substituting halogen atom, but the vibrational structure remains unchanged. The sequence of magnitude of red shift due to the position is 9-halo>1-halo>2-halo-anthracene, while that due to the species is different depending on the substituted position: in the 9-position, it is monobromo>monochloro>monofluoro>monoiodo anthracene, and, in the 1 or 2-position, it is monochloro>monofluoro>monobromo\simeqmonoiodo anthracene. For the sequence of red shift due to the species of the substituting halogen atom, there are similarities between the first absorption band of monohalogenated anthracenes and the K or B-band of monohalogenated benzenes. These results are discussed in terms of the simple LCAO MO perturbation treatment.
Studies on the Radical Species in Solid Methylene Blue as Revealed from the ESR Spectra
Authors: Okuda Michio , Kowata Takeo , Usui Yoshiharu , Koizumi Masao
Published: July 2006

The ESR signals of polycrystalline methylene blue (MB) salts have been investigated in respect to a) temperature effect, b) anion effect, c) influence of the addition of donor and acceptor and d) response to visible light irradiation, a) The signal intensity in general increases with the rising temperature, but a sharp difference in the ESR behavior has been found above and below room temperature. Response to the temperature change at low temperature is reversible and the apparent activation energy is ca. 0.03 eV (L-type behavior) whereas the high temperature behavior has a marked tendency of irreversibility and the activation energy is at least one order larger (H-type behavior), b) No essential anion effect has been observed on g-value, line shape and spin concentration for chloride, iodide and phosphate, c) The addition of trinitrobenzene and paraphenylenediamine in 10 : 1 to MB chloride also had no essential effect, d) Corresponding to the L-type and H-type behavior observed in a), visible light irradiation has been found to cause a decrease or an increase in signal intensity respectively at low and high temperature. From these findings it has been concluded that there are at least two kinds of defect (L-type and H-type) and that the formation of radical species occurs only on such defect sites. Some suggestions have been made on the nature of these two types of defects and on the molecular processes occurring at or near these defect sites. The radical formation reaction is most likely to be connected with dyedye interaction, D++D+\ightleftharpoonsD+++D.
Gel Filtration of Surfactants on Sephadex
Authors: Tokiwa Fumikatsu , Ohki Kenji , Kokubo Isao
Published: July 2006

An attempt has been made to apply gel filtration on Sephadex to micellar solutions of surfactants. The data on the gel filtration of surfactants were interpreted by taking into account the fact that there exist both micellized and unmicellized species in the solutions. A simple method for obtaining the retention volume of the micelle (VM) of a surfactant directly from the elution curve was developed. Further, the relation between the values of VM and the micellar molecular weights (MMW) was examined for various types of surfactants. A linear relation was found between VM and log MMW, with the exception of a surfactant with a heterocyclic structure. It appears that gel filtration offers a convenient way for roughly estimating the MMW’s of surfactants.
The Crystal Structure of l-Cysteic Acid
Authors: Konishi Hideaki , Ashida Tamaichi , Kakudo Masao
Published: July 2006

The crystal structure of cysteic acid, C3H7NO5S, has been determined. The crystal is orthorhombic with a space group of P212121, and four molecules are in a unit cell with these dimensions: a=8.35, b=10.16, and c=7.44 Å. The molecule is a zwitter ion, −O3SCH2CH-(NH3+)COOH; its dimensions are generally similar to those found in other amino acids and sulfonic acids. The acidic groups occupy the trans positions with respect to the Cα–Cβ bond, while the amino group is in a gauche position to the sulfonic group and forms an intramolecular hydrogen bond between them.
Certain Interactions between Transition Metal Ions and the NCS Group in Chromium(III) Isothiocyanato Complexes. II. Reinecke’s Salt Type Complexes Involving Nickel(II), Manganese(II) and Iron(III) Ions
Authors: Oki Hisaya , Kyuno Eishin , Tsuchiya Ryokichi
Published: July 2006

Nickel (II), manganese (II) and black iron(III)-tetraisothiocyanatochromate(III) were prepared by the reaction of nickel(II) nitrate, manganese (II) sulfate and iron(III) chloride with Reinecke’s salt, respectively. Each salt exhibits a gradual color change from reddish-purple to brownish-orange, red and black, respectively, when exposed to dry air after preparation, except for the orange iron(III) salt prepared in hydrochloric acid solution, which shows no color change from the original orange. Their absorption spectra give evidence that each salt will dissociate into a metal cation and Reinecke’s anion in aqueous solution. Splittings due to the C–N stretching vibration were not observed in the IR spectra. The effective magnetic moments were evaluated as 3.96, 5.13, 5.0 and 4.81 B. M. for the nickel(II)-, the manganese (II)-, the black iron(III)- and the orange iron(III)-salts, respectively. They show that the salts are nearly low spin types, or a type somewhere between low and high spin. From X-ray diffraction analyses, the unit cell of all the salts were found to be tetragonal.
The Dechloro-addition of β-Chloropropionitrile to Acrylonitrile with a Sodium Amalgam
Authors: Misono Akira , Osa Tetsuo , Asano Takamasa , Suzuki Takeo
Published: July 2006

The reaction of a mixture of β-chloropropionitrile, acrylonitrile, and water with a sodium amalgam was investigated. The main product was adiponitrile, which was formed mainly via a route consisting of three steps: I. The replacement of the chloride of β-chloropropionitrile with sodium. II. The addition of the organometallic intermediate formed to acrylonitrile. III. The replacement of the sodium in the final intermediate with hydrogen. The amount formed through the Wurtz reaction was small. The by-products were propionitrile, acrylonitrile, polymers of acrylonitrile, and organometallic compounds. The details of this reaction are given in this paper.
Catalytic Activity of Polymeric Vitamin B12 Model Compounds
Authors: Sasaki Tadashi , Matsunaga Fujinao
Published: July 2006

[CoX(DH)2·P-4VP] (X: CN, Cl)-type polymeric complexes were prepared from dimethylglyoxime (DH2) and poly-4-vinylpyridine (P-4VP) by a procedure similar to that reported for the preparation of [CoX(DH)2·Pyr] (Pyr: pyridine) (T. Sasaki and F. Matsunaga, submitted to Bull. Chem. Soc. Japan). Moreover, their catalytic activities in the decomposition reaction of hydrogen peroxide were compared with those of the corresponding monomeric complexes [CoX(DH)2·Pyr]; it was found that their activities decreases in the following order:

[CoCl(DH)_2·P-4VP]>[CoCl(DH)_2·Pyr]>>[CoCN(DH)_2·P-4VP]>[CoCN(DH)_2·Pyr]

About the relationship between structure and activity, it was concluded that the activity is much influenced by the nature of the X ligand of cobaloximes. It increases with a decrease in the interaction between the cobalt and nitrogen of a pyridine ring and with a weakening in the basicity of the coordinated bases. The structures of the polymeric complexes are discussed on the basis of their spectral data.
Azetidines. V. Preparation and Deamination of Azetidinylpropylamines
Authors: Chen Teng-Yueh
Published: July 2006

The addition of 3,3-diethylazetidine to acrylonitrile and crotononitrile, followed by reduction, gave the corresponding azetidinylpropylamines. The deamination products of the amines were identical with the alcohols prepared by the addition of diethylazetidine to methyl acrylate and crotonate, followed by reduction with lithium aluminum hydride.
Unperturbed Dimension of Poly(butylene oxide)
Authors: Matsushima Masahiro , Fukatsu Masaaki , Kurata Michio
Published: July 2006

Viscosity and light scattering measurements of poly(butylene oxide) were carried out in various solvents, including a theta solvent, isopropanol. The intrinsic viscosity vs. molecular weight relationships obtained in the range of molecular weight from 2.1×105 to 2.3×106 were:

& [η]=3.39×10^-5M_w^0.84 in benzene at 30°C,

& [η]=4.08×10^-5M_w^0.79 in methyl ethyl ketone at 30°C,

& [η]=8.65×10^-4M_w^0.50 in isopropanol at 29.8°C.

The ratio σ between the end-to-end distance of the polymer chain in the unperturbed state and that in the freely rotating state was estimated to be 1.66.