bluuebunny/crossref_metadata_2025 huggingface dataset:
The Electrical and Structural Features of Vanadium-oxide Films as Formed by the Thermal Decomposition of Vanadium Naphthenate
Authors: Kera Yoshiya , Imori Hisateru , Kida Shigeharu , Degawa Katsumi
Published: July 2006

Vanadium-oxide thin film, which was amorphous, brownish, and transparent, was prepared more conveniently by improving Sekiya-Matsushita’s method by, for instance, decomposing vanadium naphthenate thermally; that is, 10 wt% of a 1-butanol solution of vanadium naphthenate was dropped on slide glass, dried in air, decomposed at 600 °C for 20 min under 0.5 l/min of a N2 stream which was equilibrated with water at 21.5 °C, and then taken out rapidly into the air for cooling. The VO thin film thus prepared usually showed an abrupt change in electric conductivity from 2×10−5 to 1×10−4 Ω−1 at about 60 °C. The electrical feature was greatly affected by the addition of other metal oxides, such as Na2O, TiO2, Cr2O3, MoO3, and ZrO2. Both the conductivity and the gap tended to decrease in the cases of TiO2, Cr2O3, and MoO3, and to increase in ZrO2. On the addition of Na2O, however, the conductivity increased only at temperatures lower than the transition point; thus, the gap decreased greatly, almost disappearing. It was concluded from these facts that the electrical feature of the vanadium-oxide film must be controlled to a great extent by the addition of some compounds of vanadium oxide with the other metal oxides formed at the grain boundary of the VO2 amorphous particles. That is, the larger the conductivity of the compound in the boundary layer, the more clearly the intrinsic feature of the VO2 particles appears, and vice versa.
Bromochlorination of Alkenes with Dichlorobromate(1–) Ion. II. Regio- and Stereochemistry for the Bromochlorination of 1-Phenylpropenes with Dichlorobromate(1–) Ion
Authors: Negoro Takeshi , Ikeda Yoshitsugu
Published: July 2006

The bromochlorinations of 1-phenylpropenes with tetrabutylammonium dichlorobromate(1–) in aprotic solvents (dielectric constants 5–36) were found to be completely anti stereospecific and nonregiospecific, although Markownikoff adduct was mainly formed. In marked contrast, addition of molecular bromine chloride to the same alkenes was found to give nonstereospecific and regiospecific adducts. These results suggest that the addition of bromine chloride in the form of (n-C4H9)4NBrCl2 involves a rate- and product-determining attack of a chloride ion to a three-center bound π complex.
Carbon-13 NMR Spectra of 5-(4-Substituted Benzylidene)-2,3,4,5-tetrahydropyridines
Authors: Takeuchi Yoshito , Bando Takashi , Tomoda Shuji , Nomura Yujiro
Published: July 2006

Carbon-13 chemical shifts for a series of 5-(4-substituted benzylidene)-2,3,4,5-tetrahydropyridines were determined. The substituent chemical shifts (SCS) were correlated with σI and σRo values by means of DSP and DSP-NLR analysis. It was found that as a substituent the C=C–C=N moiety is as mild as C=C and that the former can be approximated as a vinylogue of the C=N moiety. C-13 lanthanoid-induced shifts (LIS) of the parent compound were also discussed.
Base-induced Cyclization of N-[Bis(ethoxycarbonyl)methyl]-2-bromo-3-hydroxybutyramide Derivatives
Authors: Shiozaki Masao , Ishida Noboru , Hiraoka Tetsuo , Maruyama Hiroshi
Published: July 2006

Treatment of (2R,3R)-N-(2,4-dimethoxybenzyl)-N-[bis(ethoxycarbonyl)methyl]-2-bromo-3-hydroxybutyramide (5) with DBU yielded the bicyclic β-actam 13 by a direct cyclization, and its diastereoisomer 14 and the γ-lactam 15  via the trans-epoxide 6. The same treatment of (2S,3R)-isomer (11) gave the direct cyclization product 14 in 93% yield. On the other hand, reaction of 5 and 11 with sodium hydride afforded the 2-azetidinone derivatives (mainly 14 (23%) from 5, and 19 (75%) from 11, respectively) via the corresponding epoxides 6 and 12.
Formations of Novel Dimeric Cyclohexanone Oxime Compounds
Authors: Sato Haruyo , Imamura Shinzo , Kitano Yukishige , Kanda Teruo , Ashida Tamaichi
Published: July 2006

The structure of the dimeric oxime compound obtained by the reaction of 2-chlorocyclohexanone oxime or 1-chloro-2-nitrosocyclohexane dimer with stoichiometrical ammonia was established to be 14-oxa-7,15,16-triazatetracyclo[11.2.1.01,6.08,13]hexadecan-16-ol by spectroscopic methods and X-ray crystallography; the result leads to a revision of the previously proposed structure, bis(2-hydroxyiminocyclohexyl)amine.
Cydoadditions of Trifluoroacetonitrile Oxide with Olefins and Acetylenes
Authors: Tanaka Kiyoshi , Masuda Hideyuki , Mitsuhashi Keiryo
Published: July 2006

The regio- and stereoselectivity of the cydoadditions of trifluoroacetonitrile oxide (1) with olefins and acetylenes were described. The oxide 1, generated in situ from trifluoroacetohydroximoyl bromide etherate in the presence of triethylamine, reacted with various monosubstituted olefins and acetylenes to give exclusively 5-substituted 3-trifluoromethyl-2-isoxazolines and -isoxazoles, respectively, whereas 1 cyclized with 1,2-disubstituted olefins and acetylenes to result in the formation of a mixture of two regioisomeric products. On the other hand, the cycloaddition of 1 with (Z)-β-methylstyrene afforded a mixture consisting of two regioisomeric isoxazolines retaining Z-configuration and one diastereoisomeric isoxazoline.
Preparation of 13-Substituted 8H-Dibenzo[a,g]quinolizin-8-ones by Intramolecular Wittig-Horner Reaction of Dialkyl 2-(o-Acylbenzoyl)-1,2-dihydro-1-isoquinolylphosphonates
Authors: Akiba Kin-ya , Negishi Yoshio , Inamoto Naoki
Published: July 2006

Dialkyl 2-(o-acylbenzoyl)-1,2-dihydro-1-isoquinolyl-phosphonates (1) were prepared by reactions of isoquinoline, o-acylbenzoyl chloride, and trialkyl phosphites. Treatment of 1 with lithium diisopropylamide gave 13-substituted 8H-dibenzo[a,g]quinolizin-8-ones by intramolecular Wittig-Horner reaction. Especially, 13-alkoxy and dimethylamino derivatives were obtained in good yields. A similar reaction of dimethyl 1-[o-(methoxycarbonyl)benzoyl]-1,2-dihydro-2-quinolylphosphonate was also described.
Facile Synthesis of (2R,3R)-Phenylalanine-2,3-d2 and NMR Study on Deuterated Gramicidin S
Authors: Tanimura Kenjiro , Kato Tetsuo , Waki Michinori , Lee Sannamu , Kodera Yasushi , Izumiya Nobuo
Published: July 2006

(2R,3R)-Phenylalanine-2,3-d2 (d-Phe*) was synthesized through catalytic reduction of cyclo(-(Z)-2,3-dehydrophenylalanyl-d-alanyl-) under an atmosphere of 2H2 and successive acid hydrolysis in the yield of 80% in high chiral induction. The d-Phe* thus obtained was used for synthesis of [d-Phe*4,4′] gramicidin S (GS*). The 1H NMR spectrum of GS* in DMSO-d6 showed a sharp singlet at 2.98 ppm for the (3S)-proton of d-Phe* residue. It has been proposed that among rotamers of d-Phe aromatic side chain in GS the one with κ1=180° is predominant. The present observation provides sound evidence for assignments of d-Phe β-protons based on the proposal.
Preparation and Properties of AzaTCNQ− Anion Salts and Mixed AzaTCNQ−/TCNQ\ewdot Salts of N-Alkylpyridinium and Related Cations
Authors: Tanaka Hirohisa , Matsubayashi Gen-etsu , Tanaka Toshio
Published: July 2006

The [Cation]+ATCNQ− type salts were prepared, where ATCNQ− is (4-dicyanomethyl-1-pyridinio)dicyanomethanide anion, so-called AzaTCNQ− anion, and [Cation]+ are N-alkylpyridinium, 4-cyano-N-alkylpyridinium, (4-methyl-1-pyrazinio)dicyanomethanide, N-alkylquinolinium (alkyl=Me and Et), N-methylacridinium, and N-methylphenazinium. Electrical resistivities of these salts as compacted samples fall in the range 106–109 Ωcm at 25 °C. The mixed ATCNQ−/TCNQ\ewdot salts (TCNQ\ewdot=7,7,8,8-tetracyano-p-quinodimethan radical anion) of N-alkylpyridinium and -quinolinium cations also were prepared; [Cation]+ (ATCNQ−)0.1(TCNQ\ewdot)0.9([Cation]+=N-methylpyridinium, N-ethylpyridinium, and N-ethylquinolinium) and [N-methylquinolinium]+(ATCNQ−)0.17(TCNQ\ewdot)0.83 whose electrical resistivities (104–106 Ωcm at 25 °C) are somewhat smaller than those of the corresponding TCNQ\ewdot salts. Stackings of ATCNQ− and TCNQ\ewdot anions are discussed on the basis of electronic reflectance and ESR spectra. The [Cation]+ATCNQ− salts react with iodine in hexane to give [Cation]+ATCNQ−·Ix ([Cation]+=N-methyl- and N-ethylpyridinium and -quinolinium; x=3.2–3.9). They exhibit electrical resistivities of 104–106 Ωcm at 25°C, which are lower by the 102–103 order than the resistivities of the undoped [Cation]+ATCNQ− salts.
Synthetic Studies on Quinoxaline Antibiotics. III. Synthesis of Nortriostin A, a Triostin A Analog Lacking N-Methyl Groups on the Cystine and Valine Residues
Authors: Shin Masaru , Inouye Ken , Higuchi Naoki , Kyogoku Yoshimasa
Published: July 2006

Nortriostin A, which is an analog of a cyclic octadepsipeptide antibiotic triostin A and contains one cystine and two valine residues substituted for the N,N′-dimethylcystine and N-methylvaline residues of the antibiotic, was synthesized with Z–d-Ser[Boc–Ala–Cys(MeBzl)–Val]–OH and Z–d-Ser[H–Ala–Cys(MeBzl)–Val]–OTce as key intermediates. The synthetic analog showed no antimicrobial activity at a concentration of 100 μg/ml and was found to exist as a single structure in solution as examined by 1H-NMR spectroscopy. The latter observation suggests that the conformer equilibrium known to occur with triostin A is a consequence of the presence of N-methyl peptide bonds in the antibiotic molecule.
Dynamic NMR as a Nondestructive Method for the Determination of Rates of Dissociation. V. Proton Affinities of p-Substituted N,N-Dibenzylanilines in Aprotic Solvents
Authors: Oki Michinori , Ohira Manabu , Yoshioka Yasuhiro , Morita Toshiari , Kihara Hiroshi , Nakamura Nobuo
Published: July 2006

Rates of proton exchange between p-substituted N,N-dibenzylanilinium ion and chloride ion in chloroform-d and acetonitrile-d3 were determined by the dynamic NMR technique. Comparison of the kinetic proton affinity of the anilines in the aprotic solvents with the proton affinity of anilines in the gas phase and the basicity in water revealed that they could be linearly correlated. The feature of the kinetic data was a large positive entropy of activation which can be ascribed to the change from an ionic ground state to a covalent transition state. The entropy of activation was somewhat smaller in acetonitrile-d3 than in chloroform-d. This was attributed to the change in the stage of the transition state for the exchange. A small amount of water which could not be removed easily from the aprotic solvents was proved not to harm the results.
Optical Resolution of Dl-Valine, Dl-Leucine, and Dl-Isoleucine by Formation of Adduct with l-Phenylalanine
Authors: Shiraiwa Tadashi , Ikawa Akihiko , Sakaguchi Keiji , Kurokawa Hidemoto
Published: July 2006

An alkaline solution containing l-phenylalanine (l-Phe) and one of Dl-valine, Dl-leucine, and Dl-isoleucine is allowed to selectively form a precipitate composed of l-Phe and the aliphatic d-amino acid by adjusting the pH of initial solution to around 5.5 with hydrochloric acid. 1H NMR spectra in deuterium oxide, elemental analyses, and infrared spectra of the precipitates indicate that they are adducts of the aliphatic d-amino acid and l-Phe in the molar ratio of 1:1. The free aliphatic Dl-amino acids with high optical purity (84–100%) may be recovered from the adducts in 49–63% yield. An attempt was made to obtain both the aliphatic d- and Dl-amino acids by using an aqueous solution containig the aliphatic Dl-amino acid and l-Phe as an initial solution. The aliphatic l-amino acids obtained had optical purity of 47–85%.
Manufacturing Process of Sodium Hydroxide and Nitric Acid from Thermochemically Split Sodium Nitrate
Authors: Takeuchi Norio
Published: July 2006

For the manufacture of sodium hydroxide and nitric acid a new thermochemical process of splitting sodium nitrate has been proposed which consists of (i) splitting of sodium nitrate by iron(III) oxide, (ii) hydrolysis of sodium ferrate, and (iii) absorption of nitrogen dioxide into water. Key reactions (i) and (ii) have experimentally been verified. The overall heat requirement for the process is discussed on the basis of a material and heat flow-sheet of the process constructed.
ortho-Disubstituted F-Benzenes. V. Intramolecular Heteroatom-facilitated ortho-Substitution of F-Benzene Derivatives with Oxazolinyl and Oxazinyl Groups
Authors: Inukai Yoshinari , Takuma Keisuke , Toritani Koji , Sonoda Takaaki , Kobayashi Hiroshi
Published: July 2006

The oxazinyl and oxazolinyl substituents on an F-benzene ring facilitated the substitution of fluorine ortho to the heterocyclic functional groups by carbon and nitrogen nucleophiles. Alkylmagnesium halides and alkyllithium compounds were employed as the carbon nucleophile, and lithium N-methylanilide and N-methylanilinomagnesium halide as the nitrogen nucleophile. The selective ortho-substitution was accomplished by the complexing interaction between the ring-membered nitrogen on the functional substituents and the anionic nucleophile through the interposing metal cation. Effects of the substituents in the orientations and rates of the reactions depended upon the polarity of the reaction solvent and the kinds of anionic nucleophile and counter metal cation.
Electronic Spectra of (DBTTF)3· SnBr6 Complex
Authors: Tanaka Masashi , Kamiya Kohji , Tanaka Jiro , Murata Shizuaki
Published: July 2006

The polarized reflection spectra of (DBTTF)3·SnBr6 complex have been measured and the absorption spectra have been determined by the simulation of the observed reflection spectra. The 4000 cm−1 band polarized parallel to the stacking axis has been assigned to the charge resonance(CR) band. The theoretical analysis of the electronic structure of (DBTTF)3·SnBr6 complex has been made for the explanation of the energy and absorption intensity of the CR band.
A Study on Some Simple and Mixed Ligand N,N-Disubstituted Dithiocarbamates of Thallium(III)
Authors: Soundararajan G , Subbaiyan M
Published: July 2006

Neutral tris (N,N-disubstituted dithiocarbamato) thallium (III) ((TI(III)) has been prepared from acyclic dimethylamine, diethylamine, dipropylamine, dibutylamine, N-methylaniline, dibenzylamine, and from piperidine. Mixed ligand dithiocarbamates were found to form by ligand exchange reactions while mixing the simple, symmetric chelates in nonpolar solvents and got separated on preparative TLC layers of silica gel. These chelates were characterised by elemental analyses, IR, 1H NMR, and electronic spectral studies.
The Reversibilities of the Adsorption and Desorption of Organic Compounds in Water
Authors: Urano Kohei , Kano Hisanao , Tabata Toshimasa
Published: July 2006

The reversibilities of the adsorption and desorption of seventeen organic compounds in water on a granular activated carbon and a polystyrene adsorbent were examined by means of a batch-adsorption method. The adsorptions of many organic compounds were reversible, but the adsorptions of several phenolic compounds and aniline were irreversible for the activated carbon, because these compounds were adsorbed strongly on the surface of activated carbon by the π-electron combination. On the other hand, the adsorptions of all the organic compounds were reversiible for the polystyrene adsorbent.
Oxygen Isotope Shifts in 17O NMR Spectra of the Uranyl Ion
Authors: Jung Woo-Sik , Ikeda Yasuhisa , Tomiyasu Hiroshi , Fukutomi Hiroshi
Published: July 2006

The 17O NMR spectrum of uranyl oxygens enriched with 17O gave three peaks. These peaks are assigned to the signals of three isotopomers, [16O=U=17O]2+, [17O=U=17O]2+, and [18O=U=17O]2+. Chemical shifts for the signals of [17O=U=17O]2+ and [18O=U=17O]2+ were −0.054±0.002 and −0.108±0.002 ppm relative to [16O=U=17O]2+, respectively.
Stereochemistry of Halogen-Metal Exchange Reaction of Vinyl Halide with Grignard Reagent
Authors: Sugita Toshio , Sakabe Yo-ichi , Sasahara Toshiaki , Tsukada Mitsunori , Ichikawa Katsuhiko
Published: July 2006

Halogen-magnesium exchange was confirmed to proceed with stereospecific retention of configuration in the reaction of β-bromostyrene and butylmagnesium bromide.
Reduction of Sulfonic Acids with Triphenylphosphine–Diaryl Disulfide System
Authors: Oae Shigeru , Togo Hideo
Published: July 2006

Diaryl disulfides are effective catalysts to reduce arenesulfonic acids with triphenylphosphine to the corresponding arenethiols in good yields, while alkanesulfonic acids are transferred into the corresponding alkyl aryl sulfides. Arenesulfonic acids bearing electron-donating substituents can be reduced more readily than those having electron-withdrawing substituents, while diaryl disulfides bearing electron-withdrawing substituents are more effective catalysts than diaryl disulfides with electron-donating ring substituents.
A Radical-induced Extrusion Reaction of 2-(Benzylsulfonyl)tropones to 2- and 4-Benzyltropones
Authors: Takeshita Hitoshi , Matsuo Norihide , Mametsuka Hiroaki
Published: July 2006

Several 2-(benzylsulfonyl)tropones were thermolized to give 2- and 4-benzyltropones. The radical mechanism for the thermolysis was elucidated by a deuterium-labelling experiment.
Photochemical Reactions of Spiro[benzo[b]thiophene-2(3H), 1′-cydopropan]-3-ones
Authors: Kamigata Nobumasa , Hagihara Koichi , Hashimoto Satoshi , Iizuka Hirokazu , Kobayashi Michio
Published: July 2006

The photolysis of spiro[benzo[b]thiophene-2(3H),1′-cyclopropan]-3-one 1,1-dioxide (1) in benzene afforded 2-biphenylyl cyclopropyl ketone with extrusion of sulfur dioxide, whereas the irradiation of 1 in toluene or p-xylene formed photoreduced dimer and bibenzyl or 4,4′-dimethylbibenzyl, respectively. The photolysis of spiro[benzo[b]thiophene-2(3H),1′-cyclopropan]-3-one in benzene afforded the valence isomer 2,3-dihydro[1]benzothieno[3,2-b]furan.
The Preparation of N-Protected Amino Alcohols and N-Protected Peptide Alcohol by Reduction of the Corresponding Esters with Sodium Borohydride. An Improved Procedure Involving a Slow Addition of a Small Amount of Methanol
Authors: Soai Kenso , Oyamada Hidekazu , Takase Masako
Published: July 2006

Esters of N-protected amino acids and an N-protected peptide were reduced selectively to the corresponding alcohols in high yields using lesser amounts of sodium borohydride than does the conventional method by the slow addition of methanol to the mixture of ester and NaBH4 in t-butyl alcohol or tetrahydrofuran at 50°C.
Kinetics of Solute-Solvent Interaction in Aqueous Solution of Butyl Carbitol by Ultrasonic Methods
Authors: Nishikawa Sadakatsu , Shibata Masayuki
Published: July 2006

Ultrasonic absorptions in the frequency range 4.5–220 MHz and sound velocities at 2.5 MHz were measured at 25 °C with aqueous solutions of Butyl Carbitol (diethylene glycol monobutyl ether) over the concentration range 0.497–3.00 mol dm−3. Only a single relaxational process was observed and attributed to a perturbation of the equilibrium AB\oversetk12\undersetk21↔A+B, where A is Butyl Carbitol as the solute and B is water as the solvent participating in the reaction. A data analysis has led to the estimates k12=3.4×107 s−1, k21=2.0×108 dm3 mol−1 s−1, the standard volume change of reaction ΔV°=0.32 cm3 mol−1, and the standard enthalpy change ΔH°=5.4 kJ mol−1. The effect of the hydrophobicity of solute molecules on the water structure is discussed by comparing the present results with previous ones for other aqueous nonelectrolyte solutions.
Optical Resolution of Pyridoxal-like Pyridinophanes
Authors: Tachibana Yoji , Komatsu Toshihiko , Ando Makoto , Kuzuhara Hiroyoshi
Published: July 2006

Racemic modifications of the pyridoxal-like ansa compounds such as 15-formyl-14-hydroxy-2,8-dithia[9](2,5)pyridinophanes prepared as a pontential catalyst for stereospecific nonenzymatic reactions were optically resolved through formation of Schiff bases by treatment with amino sugar derivatives or amino acids. Resolutions with the amino sugar derivatives were ascribable to the difference of the solubilities of the diastereomeric Schiff bases, whereas those with the amino acids resulted from the difference of the reaction rates for the formation of the diastereomeric Schiff bases. As the amino sugar resolving agents, 3-amino-3-deoxy-1,2:5,6-di-O-isopropylidene-β-d-idofuranose and the corresponding α-d-glucofuranose isomer were employed and gave (R)- and (S)-pyridoxal-like pyridinophanes, respectively. On the other hand, chiral valine was the most efficient resolving agent among the amino acid tested and the presence of half equimolar Fe3+ markedly increased the optical purities of the products. Employment of (S)-valine gave (R)-pyridinophanes in excess and vice versa.
Studies on the Inelastic Electron Tunneling Spectroscopy of o-Hydroxy-, o-Amino-, and o-Mercaptobenzoic Acid on Aluminium Oxide
Authors: Monjushiro Hideaki , Murata Katsuo , Ikeda Shigero
Published: July 2006

Inelastic electron tunneling (IET) spectra were obtained for o-hydroxybenzoic acid(OHBA), o-aminobenzoic acid (OABA) and o-mercaptobenzoic acid (OMBA) adsorbed on aluminium oxide (AlOx) grown on aluminium film and were analyzed by referring IR results. OHBA is adsorbed on AlOx with both two functional groups, carboxyl and hydroxyl radicals. In the case of OABA, the adsorption occurs mainly with carboxyl group and the interaction between amino group and AlOx is rather weak. Mercapto group of OMBA forms two kinds of hydrogen bonding, and a dissociated species on AlOx. These results indicate that the surface of AlOx used in this study is highly hydrated and hydroxyl groups on the oxide are reactive with the proton donating sites of the chemical species. IET spectra of o-fluoro- and o-chlorobenzoic acid were also observed for comparison.
The Acid-catalyzed Decomposition of Diazo Carbonyl Compounds. II. Synthesis of 2- or 5-Heteroatom-substituted Oxazoles
Authors: Ibata Toshikazu , Yamashita Tsuyoshi , Kashiuchi Makoto , Nakano Shyuji , Nakawa Hiroyuki
Published: July 2006

The BF3-catalyzed decomposition of m- and p-substituted α-diazoacetophenones in excess of methyl thiocyanate and ethyl thiocyanate gave the corresponding 2-methylthio-, and 2-ethylthio-5-aryloxazoles, respectively in good yields along with s-alkyl-n-aroylmethylthiocarbamates and α-ethoxyacetophenones. However, yields of 2-dimethylamino-5-aryloxazoles by the reaction of dimethylcyanamide with α-diazoacetophenones were poor. 5-Dimethylamino- or 5-alkoxy-4-aryl-2-methyloxazoles were prepared by the reaction of N,N-dimethyl-α-(p-nitrophenyl)diazoacetamide or alkyl aryldiazoacetates with nitriles. When ethyl phenyldiazoacetate or methyl p-chlorophenyldiazoacetate were used, ketazines of alkyl arylglyoxylates were obtained together with oxazoles.
The Chemistry of Substituted Norbornenes. Reactions of 5-Vinyl-2-norbornene and 5-Ethylidene-2-norbornene with Formic Acid
Authors: Inoue Yoshiharu , Tanimoto Fumio , Kitano Hisao
Published: July 2006

Addition of formic acid to 5-vinyl-2-norbornene(1) and subsequent hydrolysis afford 6-vinyl-exo-2-norbornanol(5) and 5-vinyl-exo-2-norbornanol(6). Similarly, from 5-ethylidene-2-norbornene(2) are formed 6-ethylidene-exo-2-norbornanol(14), 5-ethylidene-exo-2-norbornanol(15), and 6-ethyltricyclo[2.2.1.02,6]heptan-3-ol(16). The hydroboration of 2 also leads to the formation of 14 and 15. Thus, the vinyl- and ethylidene-exo-norbornanols, 5, 6, 14, and 15, and the corresponding endo-norbornanols, 9, 10, 21, and 22, have been synthesized. A structural analysis of these products by 13C NMR revealed that under certain conditions, the ethylidene group of 2 exerts a great influence upon the reactivity of the norbornenyl ring double bond. Moreover, the fact that 16 derived from the addition of formic acid to 2 consists of both exo- and endo-hydroxy epimers is inconsistent with the previous observations that the exo-isomer is generally the sole product in related systems.
Selective Protection of Carbonyl Groups by Taking Advantage of a Combination of Solid Support and Girard’s Reagent
Authors: Chihara Teiji , Waniguchi Erika , Wakabayashi Tamie , Taya Kazuo
Published: July 2006

Some Girard’s derivatives of 4-phenylbenzophenone were prepared in ethanol solution, in the presence of Amberlite IRC-50 as a catalyst. Supported samples of the derivatives were then prepared by addition of silica gel to the solution, followed by evaporation of the ethanol. The supported samples were reduced with lithium tri-t-butoxyhydroaluminate by being suspended in THF solution. Hydrolysis, followed by extraction of the product, yielded 4-acetyl-α-phenylbenzyl alcohol in an 80% selectivity. In the same way, 4-acetylbenzaldehyde yielded 1-(4-formylphenyl)ethanol in an 81% selectivity. Relatively unhindered carbonyl groups were preferentially protected. Utilization of Girard’s reagents was successfully made as a protecting reagent and also as an extracting reagent of carbonyl compounds.
A Stereocontrolled Total Synthesis of C-Nucleosides
Authors: Sato Tsuneo , Hayakawa Yoshihiro , Noyori Ryoji
Published: July 2006

A stereocontrolled, general synthesis of chiral C-nucleosides has been achieved through a common lactonic C-β-glycoside intermediate which is readily obtainable from non-carbohydrate materials. Osmium tetraoxide-catalyzed vic-dihydroxylation of 8-oxabicyclo[3.2.1]oct-6-en-3-one gives, after acetonidation, (1R*,5S*,6S*,7R*)-6,7-isopropylidenedioxy-8-oxabicyclo[3.2.1]octan-3-one as a single stereoisomer. Baeyer-Villiger oxidation of the ketone affords the key intermediate, 2-(2,3-O-isopropylidene-β-ribofuranosyl)acetic acid lactone. The optically pure lactone having the natural d configuration is obtained through optical resolution of the seco acid by the Pirkle’s method followed by relactonization. α-Aminomethylenation of the lactone with t-C4H9OCH[N(CH3)2]2 yields 2-(2,3-O-isopropylidene-β-d-ribofuranosyl)-2-(dimethylaminomethylene)acetic acid lactone, which undergoes base-assisted condensation with urea followed by deprotection to furnish naturally occurring pseudouridine. Analogously, construction of heterocycles using thiourea and guanidine converts the aminomethylene lactone to unnatural pyrimidine C-nucleosides, 2-thiopseudouridine and pseudoisocytidine, respectively. Showdomycin in natural form can be prepared by two schemes. One approach consists of ozonolysis of the α-dimethylaminomethylene lactone, Wittig reaction using (C6H5)3PCHCONH2, and acid hydrolysis. The second entry makes use of 2-(2,3-O-isopropylidene-)3-d-ribofuranosyl)acetic acid lactone as the intermediate, which is converted to 2-(2,3-O-isopropylidene-)8-d-ribofuranosyl)-2-furfurylideneaceticacid lactone by the aldol reaction with furfural and dehydration. Methanolysis of the furfurylidene lactone and t-butyldimethylsilylation are followed by ozonolysis, Wittig condensation with (C6H5)3PCHCON2, and hydrolysis to give the maleimide C-nucleoside. In addition, 6-azapseudouridine and 6-aza-2-thiopseudouridine are obtainable via intramolecular ring closures of the semicarbazone and thiosemicarbazone of methyl 2-(2,3-O-isopropylidene-β-d-ribofuranosyl)glyoxylate followed by deprotections, respectively. These overall transformations are accomplishable under complete stereochemical control.
Ozonization of Phenothiazine and Its Analogues
Authors: Matsui Masaki , Miyamoto Yoshihiko , Shibata Katsuyoshi , Takase Yoshimi
Published: July 2006

When phenothiazine and phenoxazine were ozonized in dichloromethane, the cation radicals and the ozonate anion radical were detected, whereas, in the ozonization of phenoxathiin and thianthrene, these radicals were not observed. Formation of these radicals was more favorable as greater was the polarity of the solvent and lower was the oxidation potential of the substrate. Ozonization of phenothiazine and phenoxazine in polar solvents was explained by the electron-transfer mechanism accompanied by the electrophilic ozone attack, and that of phenoxathiin and thianthrene by the electrophilic ozone attack alone.
Heat-stable Enterotoxin (STh) of Human Enterotoxigenic Escherichia coli (Strain SK-1). Structure-activity Relationship
Authors: Ikemura Haruo , Watanabe Hiroyuki , Aimoto Saburo , Shimonishi Yasutsugu , Hara Saburo , Takeda Tae , Takeda Yoshifumi , Miwatani Toshio
Published: July 2006

For examination of the structure-activity relationship of STh, five shorter analogs of STh lacking one to five N-terminal amino acid residues of STh were synthesized. The synthetic peptides were confirmed to have the same intramolecular disulfide linkages as those in native STh. These peptides caused fluid accumulation in the intestine of suckling mice at almost the same molar levels as that of native STh. The toxicities of these peptides were also neutralized by antisera raised against native STh. These results indicated that the toxic and antigenic sites of STh are both located in the amino acid sequence between the Cys residue at the 5th position from the N-terminus and the C-terminal Tyr residue.
The Reactions of Hydrogen and Deuterium Atoms with Four Ketenes
Authors: Umemoto Hironobu , Tsunashima Shigeru , Sato Shin , Washida Nobuaki , Hatakeyama Shiro
Published: July 2006

The rate constants of the reactions of hydrogen and deuterium atoms with four ketenes have been measured using a pulse radiolysis-resonance absorption technique. For hydrogen atoms, the temperature dependence was also examined in the range of 240–440 K. The rate constants were well expressed by these Arrhenius equations: k(H+ketene)=3.9×106exp(−975⁄T); k(H+methylketene)=74×106exp(−881⁄T); k(H+ethylketene)=4.4×106exp(−728⁄T); k(H+dimethylketene)=6.0×106exp(−773⁄T), in units of m3 mol−1 s−1. No isotope effect between H and D atoms could be observed except for the gas-kinetic-collision frequency.
Kinetics and Mechanism of the Oxidation of Alcohols by Pyridinium Fluorochromate
Authors: Bhattacharjee Manabendra N , Chaudhuri Mihir K , Dasgupta Himadri S
Published: July 2006

Pyridinium fluorochromate, C5H5NHCrO3F, oxidizes benzyl alcohol, ethanol, and cyclohexanol to benzaldehyde, acetaldehyde, and cyclohexanone, respectively. While each of the oxidation, studied in acetonitrile–nitrobenzene (1 : 1, v/v) medium, is first order with respect to the oxidant, the rate is almost independent of the substrate concentration. The reactions are catalyzed by acid, the acid-catalyzed reactions being very fast, precluded determination of their order in acid medium. The effects of temperatures and solvent compositions were studied and activation parameters evaluated. Probable mechanisms are discussed.
Polarized Raman and Infrared Spectra of 2-Chloro- and 2-Bromopyrimidines
Authors: Nakama Sekiichiro , Shimada Hiroko , Shimada Ryoichi
Published: July 2006

The polarized Raman and infrared spectra of 2-chloro- and 2-bromopyrimidines were studied. Assignments of the normal vibrations for these molecules were made on the basis of polarization behaviors of the Raman and infrared bands and also through the normal coordinate calculation.
Intramolecular Orbital Interactions in 6,6′-Bi(1,4-dithiafulvenyl) Studied by Photoelectron Spectroscopy
Authors: Kobayashi Tsunetoshi , Yoshida Zen-ichi , Awaji Hiroshi , Kawase Tokuzo , Yoneda Shigeo
Published: July 2006

Photoelectron spectra of tetrathiafulvalene (TTF) and 6,6′-bi(1,4-dithiafulvenyl) (BDTF) were measured and compared with each other. The first photoelectron spectral band of BDTF is only slightly shifted relative to that of TTF, though the BDTF molecule is lengthened compared with the TTF molecule by two sp2 carbon atoms. From the LCGO model orbital interaction analysis, this apparent anomaly is ascribed to the near cancellation of the effects of two main factors, the energy and the terminal atomic orbital coefficient differences between the central olefinic group π orbitals. Orbital interaction analysis as demonstrated in this work may be useful for molecular design, especially for orbital energy control.
Extraction of Uranium(VI) by Emulsion Liquid Membrane Containing 5,8-Diethyl-7-hydroxy-6-dodecanone Oxime
Authors: Akiba Kenichi , Takahashi Toshihiko , Kanno Takuji
Published: July 2006

Extraction of uranium(VI) by a liquid surfactant membrane has been studied. The stability of water-in-oil (w/o) emulsion dispersed in the continuous aqueous phase increased with an increase in surfactant concentrations and in the fraction of the organic phase in emulsion globules. Uranium(VI) in dilute acid solutions was extracted into (w/o) emulsions containing 5,8-diethyl-7-hydroxy-6-dodecanone oxime (LIX 63) as a mobile carrier and its concentration decreased according to [U]t=[U]o exp(−kobsdt). The apparent rate constants (kobsd) increased with an increase in carrier concentrations and in external pH values, while they were slightly dependent on the stripping acid concentrations. Uranium was transported and concentrated into the internal aqueous droplets. The final concentration of uranium in the external aqueous phase dropped to about 10−3 of its initial value.
Enthalpies of Transfer of Single Ions and Metal Complexes from Water to an Aqueous Dioxane Solution
Authors: Ishiguro Shin-ichi , Ohtaki Hitoshi
Published: July 2006

Enthalpies of solution of some 1:1 and 2:1 electrolytes were determined in water and in a dioxane–water mixture (the dioxane content; 0.2 mole fraction or 55.0% w/w) by calorimetry at 25 °C. Enthalpies of transfer (ΔHto) of single ions from water to the dioxane–water mixture were obtained by employing the extrathermodynamic tetraphenylarsonium tetraphenylborate (TATB) assumption. Enthalpies of transfer of nickel(II) and copper(II) complexes with glycinate (gly−) and ethylenediamine (en) were also evaluated for [Ni(gly)n](2−n)+ (n=1–3), [Ni(en)n]2+(n=1–3), and [Cu(en)n]2+ (n=1–2) by combining enthalpies of transfer of the relevant single metal ions and ligands with enthalpies of complex formation reactions M+nL=MLn (M=Ni2+ or Cu2+ and L= gly− or en) in water and in the mixture. The enthalpies of transfer of the metal complexes examined here increased almost linearly with an increase in the number of the ligands within the complexes. The values of ΔHto of the ethylenediamine complexes of nickel(II) and copper(II) ions were all negative, as well as those of free Ni2+ and Cu2+ ions. On the other hand, the enthalpies of transfer of the noncharged [Ni(gly)2] and anionic [Ni(gly)3]− complexes were positive, while that of the [Ni(gly)]+ complex was still negative. The result suggested that hydration of the ligands coordinating to the central metal ions plays an essential role in the enthalpies of transfer of the metal complexes from water to the dioxane–water mixture.
X-Ray Structural Study on Molecular Stereochemistries of Six-coordinate Zn(II) Complexes of trans-ZnX2N4 Type. Out-of-plane Displacement of Zn(II) from a Plane Formed by In-plane Four Nitrogens
Authors: Ito Tasuku , Kato Masako , Ito Haruko
Published: July 2006

Molecular structures of trans-bis(isothiocyanato)(1,4,8,11-tetraazacyclotetradecane and 1,4,8,12-tetraazacyclopentadecane)zinc(II) complexes, [Zn(NCS)2(C10H24N4)] (1) and [Zn(NCS)2(C11H26N4)] (2), have been determined by X-ray analyses. Crystal data are: for 1, orthorhombic, space group P21nb, a=14.502(2), b=18.163(2), c=6.552(1) Å, V=1718.0(4) Å3, Z=4; for 2, monoclinic, space group P21/a, a=14.453(2), b=14.436(1), c=9.213(1) Å, β=104.82(1)°, V=1858.3(4) Å3, Z=4. Coordination geometries about Zn(II) in 1 and 2 are of the pseudo-octahedral type with two NCS groups at the trans positions, but the Zn(II) ion in each compound deviates from a plane defined by the four nitrogens of the macrocyclic ligand by 0.179 Å on the average in 1 and 0.193 Å in 2. Structural features of 1 and 2 suggest, complemented with data reported previously for out-of-plane Zn(II) structures, that potential surface regarding the out-of-plane displacement is very flat. The Zn–NCS distance has been found to decrease as an in-plane Zn–N length (or cavity size of the ligand) increases. The observed negative correlation is substantially stronger than those for Ni(II) and Co(III) complexes and discloses the softness of a Zn(II) ion.
The Structures of trans-Dichloro- and trans-Bis(isothiocyanato)nickel(II) Complexes with 1,4,8,11-Tetraazacyclotetradecane, 1,4,8,12-Tetraazacyclopentadecane, and 1,5,9,13-Tetraazacyclohexadecane. The Negative Correlation between the Axial and In-plane Coordination Bond Lengths in Tetragonal Ni(II) Complexes of the trans-NiX2N4 Type
Authors: Ito Tasuku , Kato Masako , Ito Haruko
Published: July 2006

The molecular structures of the six titled compounds, which contain 14-membered, 15-membered, or 16-membered tetraazamacrocyclic ligands, have been determined by single crystal X-ray analyses. On going from smaller to larger rings, the average in-plane Ni–N distance increased by 0.05–0.06 Å for each ring member added. For a series of complexes with given axial ligands (X), the mean axial coordination bond length (Ni–X) was found to decrease as the average in-plane distance (Ni–N) increased. The degree of the negative correlation was stronger for complexes with weaker axial ligands (Cl−) than for those having stronger axial ligands (NCS−). Similar negative interrelationships between the Ni–X and Ni–N distances have been found for complexes which have the same in-plane macrocyclic ligand, but different axial ligands. The molecular stereochemistries of the complexes have been discussed. For all the complexes with the 1,4,8,12-tetraazacyclopentadecane ligand, a structural disorder of the same type has been found: gauche five-membered and skew six-membered chelate rings are randomly interchanged in the crystal. This arises mainly from the similarity of the bite angles of the five- and six-membered chelate rings in the gauche and the skew conformations respectively.
Intramolecular Photocycloaddition of Noncyclic Polyether Compounds Containing α,ω-Dicinnamates End Groups and Uptake of Alkali Metal Thiocyanates with Them
Authors: Hiratani Kazuhisa , Aiba Sei-ichi
Published: July 2006

Noncyclic polyethers containing two cinnamoyl end groups have been prepared, they were cyclized by photosensitized intramolecular addition. The uptake of alkali metal (sodium and potassium) thiocyanates with these compounds and their ability to extract has been investigated before and after the cyclization.
Zeta Potentials of Metal Oxides in Aqueous Solution of Water-soluble Titanate Coupling Agents
Authors: Esumi Kunio , Meguro Kenjiro
Published: July 2006

The zeta potentials of γ-Fe3O4 and TiO2 were measured as a function of the amount of water-soluble titanate coupling agents added in aqueous solution. Compared with untreated samples, the zeta potential of γ-Fe3O4 increased negatively with an increase of the amount of water-soluble titanate coupling agents, while that of TiO2 changed little. Furthermore, after a washing process, it was confirmed by ESCA measurement that a certain amount of water-soluble titanate coupling agent still remained on the surface of the γ-Fe3O4.
cDNA Sequences and Molecular Evolution of Calmodulin Genes of Chicken and Eel
Authors: Iida Yôichi
Published: July 2006

c DNA sequences of calmodulin genes taken from chicken and eel were compared to investigate the molecular evolution of its protein. One notable feature of the amino acid coding region of the gene is that the second positions of codons are more conservative than the first positions, while the third positions are highly diverged to exhibit almost saturation. This kind of behaviour is reminiscent of that of the histone gene.
Preparation of Sodium Bis(l-aspartato)rhodate(III)
Authors: Watabe Masatoshi , Furihata Kenji , Odaka Yoshio
Published: July 2006

Bis(l-aspartato) rhodate(III) complex was prepared and separated into three isomers, and their absorption, CD curves and 1H NMR spectra are presented. The geometrical configurations of three isomers are assigned mainly on the basis of the spectral analogy between this complex and the [Co(l-asp)2]− complex.
Extractive Separation of Osmium and Ruthenium from Thiocyanate Media
Authors: Jaya Sambamoorthy , Ramakrishna Tiruvesaloor V
Published: July 2006

The sequential separation of osmium and ruthenium as thiocyanate complexes by extraction into mesityl oxide and cyclohexanone is described. The conditions for their re-extraction prior to determination from the respective organic layers have been established. Alternatively, the amounts of osmium and ruthenium were established spectrophotometrically from the coloured mesityl oxide and cyclohexanone layers respectively. The developed procedure has been applied to the separation of these metals present in synthetic samples of various minnerals.
The Preparation of Pyridinium μ-Oxo-bis[nitrilotriacetatodioxomolybdate(VI)] and Pyridinium Di-μ-oxo-bis[nitrilotriacetatooxomolybdate(V)] Monohydrate and the X-ray Structure of the Molybdenum(VI) Complex
Authors: Matsumoto Keiji , Marutani Yoshiaki , Ooi Shun-ichiro
Published: July 2006

Nitrilotriacetato complexes of MoVI and MoV were prepared and the X-ray structure of the former complex is described. On the basis of the UV-visible and IR spectra and elemental analyses, the latter complex is formulated as (pyH)2[Mo2O4(ntaH)2]·H2O.
Conversion of Alcohols into Haloalkanes in Tertiary Phosphine/Methyl Halide/4-Methyl-1,2,4-triazolidine-3,5-dione (MTAD) System
Authors: Oshikawa Tatsuo , Yamashita Mitsuji
Published: July 2006

Alcohols were succesfully converted to the corresponding alkyl halides using the betaine provided by tertiary phosphine/4-methyl-1,2,4-triazolidine-3,5-dione (MTAD) system. Stereospecific reaction involving inversion of configuration on the carbon atom (SN2 reaction) was clarified.
A Novel Route to N-Phenyl-C-(trifluoromethyl)nitrilimine from 3-Phenyl-5-trifluoromethyl-2,3-dihydro-1,3,4,2-oxadiazaphosphole
Authors: Tanaka Kiyoshi , Igarashi Toh-ru , Maeno Seiji , Mitsuhashi Keiryo
Published: July 2006

Thermolysis of 3-phenyl-5-trifluoromethyl-2,2,2-tris-(p-tolyloxy)-2,3-dihydro-1,3,4,2-oxadiazaphosphole in the presence of various olefins gave the 1,3-dipolar cycloadducts of N-phenyl-C-(trifluoromethyl)nitrilimine in situ formed. The similar decomposition in aniline afforded N-phenyltrifluoroacetamide phenylhydrazone.
The X-Ray Fluorescence Spectroscopy of Inorganic Solids. VII. The Fe Kβ1,3 Energy Shifts in Oxide Glasses
Authors: Yoshioka Michiko , Maekawa Takashi , Yokokawa Toshio
Published: July 2006

The Fe Kβ1,3 energy shifts in the binary sodium borate, silicate, and phosphate glasses containing small amounts of the iron ion were examined. The Fe Kβ1,3 energy decreases with an increase in the sodium oxide content in the borate and silicate glasses. The data are in accordance with those of previous studies that the coordination number of the Fe(III) ion is four in the borate and silicate glasses and six in the phosphate glasses. The structure of the coordination sphere around the Fe(III) ion in the borate glasses was also discussed.
Syntheses, and Crystal and Molecular Structures of Tris(benzamide)bis(O,O′-diisopropyl dithiophosphato)lanthanoid(III) O,O′-Diisopropyl Dithiophosphate (M=Gd, Tb, Dy, Er, and Yb)
Authors: Nagai Kiyofumi , Nakamura Reiko , Shimoi Mamoru , Ouchi Akira
Published: July 2006

Five isomorphous lanthanoid(III) complexes were synthesized, and the structure of the terbium (1) and erbium (2) complexes were determined by the use of the single-crystal X-ray diffraction method. Crystals of 1 and 2 are monoclinic, with the space group P21/n, and the cell constants are: (1) a=25.076(8), b=15.446(3), c=14.579(8) Å, β=100.77(4)°; (2) a=25.036(20), b=15.228(4), c=14.805(19) Å, β=99.50(12)°. The structures were solved by the heavy-atom method and refined by the block-diagonal least-squares method. The final R values of 1 and 2 are 0.061 and 0.055 respectively. They consist of discrete complex cations and dithiophosphate anions. The central metal atom of the cationic complex is hepta-coordinated, and it is in a pentagonal bipyramidal geometry, where four sulfur atoms of two dithiophosphate ions and one oxygen atom of a benzamide ligand take the equatorial positions, while two benzamide oxygen atoms are in the axial positions.
Ion Exchange from a Nonaqueous Solution. Zinc (II) Bromide and Iodide in Ethylene Glycol
Authors: Kumagai Tetsu
Published: July 2006

The distribution behavior of the zinc ion in sodium bromide and iodide solutions between the cation-exchange resin for forced-flow liquid chromatography and the absolute or aqueous ethylene-glycol phase was investigated radiometrically. From the experimental data, consecutive complex formation constants for zinc bromide and iodide in the glycol have been calculated by the nonlinear least-squares method. The results are as follows: in absolute glycol β1Br=2.60 and β2Br=3.91 for zinc bromide, β1I=2.36 and β2I=3.04 for zinc iodide; in 5 wt% aqueous glycol β1Br=2.30, β2Br=3.32, and in 10 wt% aqueous glycol, β1Br=1.87, β2Br=2.78, respectively.
Development of a Laboratory EXAFS System and Its Application to Aqueous Nickel(II) Ammine Solutions
Authors: Sano Mitsuru , Maruo Tetsuya , Yamatera Hideo
Published: July 2006

A laboratory EXAFS system with a curved crystal has been developed. This apparatus consists of a usual X-ray tube, a spectrometer with a Johan-type curved crystal, and two proportional counters detecting the X-rays. The resolution and performance tests have been carried out and excellent spectra have been obtained for NiO. With this system, aqueous solutions of ammine and ethylenediamine nickel(II) salts have been studied. The spectra were analyzed by the curve-fitting method by reference to the spectra of appropriate crystals containing the corresponding complexes. The values obtained for the Ni–N distances are 2.12±0.01 Å. These values are very close to those of the corresponding complexes in crystals.
Stereocontrolled Synthesis of (±)-Asperlin and Related Stereoisomers Using Organotitanium Reagent
Authors: Hiraoka Hiroaki , Furuta Kyoji , Ikeda Nobuo , Yamamoto Hisashi
Published: July 2006

The naturally occurring antibiotics asperlin and related fungal metabolites containing a 5,6-dihydro-2-pyrone moiety have been synthesized stereoselectively. The propargyltitanium reagent derived from 1-trimethylsilyl-3-(tetrahydropyranyloxy)propyne condensed with crotonaldehyde affords the corresponding erythro alcohol as the major product, which is converted to (±)-asperlin and the related three stereoisomers in seven steps.
Adsorption of Oligomer Type Surfactants on Iron Oxide
Authors: Esumi Kunio , Ogihara Kimihiko , Meguro Kenjiro
Published: July 2006

Adsorption of oligomer type surfactants synthesized from acrylic acid, acrylonitrile, and 1-dodecanethiol on α-Fe2O3 was examined by measuring adsorption isotherms and zeta potentials. It was found that the adsorption behavior of oligomer type surfactants on α-Fe2O3 was influenced by the pH of suspensions and further by the differences of composition of oligomer type surfactants.
Electrodic Properties and Surface Characteristics of Ni–V Alloys for Water Electrolysis Cathode Materials
Authors: Machida Ken-ichi , Enyo Michio , Oguro Keisuke , Nakane Masanori
Published: July 2006

Hydrogen evolution reaction on a series of hydrogen absorbing Ni–V alloys, viz. Ni2V, NiV, and NiV3, before and after pretreatments with aq HF was studied in 1 M NaOH (1 M=1 mol dm−3) at 288–333 K by a galvanostatic overpotential transient technique. Results are related with the surface characteristics revealed by XPS techniques. It is concluded that the Ni in the Ni–V alloys is mainly responsible for their electrochemical properties and that the reaction proceeds via the Volmer-Tafel reaction route with mixed rate-determining characteristics: The activation heats are 7.7, 6.8, and kcal mol−1 (1 cal=4.184 J) for two elementary steps, Volmer and Tafel, and the overall reaction, respectively. The electrocatalytic activity of the Ni–V alloys, particularly NiV3, is drastically enhanced through the treatment with aq HF, and this is in parallel with the formation of porous Ni layers on their surface, namely the increase of the effective surface area. Potentiality of the alloys for water electrolysis cathode materials is indicated by a higher electrocatalytic activities of the Ni–V alloys over ordinary Raney nickel electrodes. Hydrogen absorbability of the alloys was also investigated: NiV3 stored hydrogen up to [H]/[M]=≤0.3 after a cathodic polarization at about −400 mV hydrogen overpotential, but that in Ni2V or NiV was far smaller.