bluuebunny/crossref_metadata_2025 huggingface dataset:
Studies on the Chemical Shifts of Auger Electron Energies for Magnesium and Zinc in Their Compounds
Authors: Nishikida Shunichi , Ikeda Shigero
Published: July 2006

The energy shifts of X-ray excited Auger electrons and photoelectrons for zinc and magnesium in their metals, oxides, halides, and chelate compounds are analyzed in terms of the relaxation effect. Zn 2p3⁄2, 3d photoelectron, Zn L3M45M451G Auger electron, Mg 1s, 2p photoelectron and Mg KL23L231D Auger electron peaks were provided for the investigation. The quantitative estimation of the extra-atomic relaxation energies for core electron emission was performed by combining atomic spectral data, XPS and AES data of the compounds. For zinc compounds, extra-atomic relaxation energies increase in the order of ZnF2<ZnCl2<ZnBr2≈ZnO<ZnI2≈ZnS<Zn(acac)2, whilst the values are not fairly systematic for magnesium compounds. The nearest neighbored atom is found to be the important function for the extra-atomic relaxation energies.
Proton Magnetic Relaxation Time T1 of Water in Acrylamide Gel
Authors: Katayama Seiji , Arata Yoji , Fujiwara Shizuo
Published: July 2006

Proton magnetic relaxation time T1 of water in polyacrylamide gel was measured. The results have been interpreted in terms of the contribution from dissolved oxygen and the intrinsic nature of gel. A minimum of 1⁄T1 appears in a system with a ca. 2.8% concentration of acrylamide, corresponding to the lowest concentration for gel formation.
Characteristic Behavior of Damping Coefficient of Capillary Wave on Surfactant Solution
Authors: Sasaki Minoru , Yasunaga Tatsuya , Ashida Minoru , Kan Haruki
Published: July 2006

The damping coefficient of a capillary wave on decylamine hydrochloride and octylamine hydrochloride solutions decreased abruptly in the vicinity of a critical micelle concentration. The phenomenon observed was well interpreted by an equation derived on the basis of a surface mechanical impedance.
Distribution of Trace Rare Earth Element Ions in the Crystallization Process of Alums
Authors: Kanno Hitoshi , Wakita Hiroshi , Hamaguchi Hiroshi
Published: July 2006

The distribution coefficients of rare earth element ions between alums and aqueous solution were determined.
Preparation of trans-Dichlorocobalt(III) Complexes of N-Alkylethylenediamines
Authors: Kitamura Taku , Saburi Masahiko , Yoshikawa Sadao
Published: July 2006

N-Alkylethylenediamine (RNHCH2CH2NH2; R=butyl, hexyl, isobutyl, and isopropyl) complexes of the type [CoCl2(diamine)2]X prepared by usual airoxidation method except the case of R=isopropyl. The N-ipren (R=isopropyl) complex was obtained by employing methanol as the solvent. A brief consideration of the steric effect of N-isopropyl group was given.
Molecular Structure of 2,2-Dichloropropane as Determined by a Combined Use of the Electron-diffraction Data and the Spectroscopic Moments of Inertia
Authors: Hirota Masashi , Iijima Takao , Kimura Masao
Published: July 2006

The molecular structure of 2,2-dichloropropane has been determined by the joint analysis of the electron-diffraction data and the moments of inertia obtained by Matsumura and Takeo by means of microwave spectroscopy. Under the assumptions that rg(C–H) is in the range of 1.100–1.110 Å and that \varphia(HCH.) is larger than 107.0°, the structure parameter values have been determined (with the limits of error in parentheses) to be as follows: rg(C–Cl), 1.799(3) Å; rg(C–C), 1.523(4) Å; rg(cl…Cl), 2.910(1) Å; rg(C…Cl), 2.702(1) Å; \varphiav(ClCCl), 108.3(3)°, and \varphiav(CCC), 113.0(4) °. The rg-structure determined in the present study is in perfect conformity with the r0-structure determined by Matsumura and Takeo. The C-Cl and C-C distances are shorter than the corresponding distances in 2-chloropropane.
The Effect of Poly(oxyethylene) Alkyl Ethers, Alkanediols, and Alkanols on the Critical Micelle Concentration of Sodium Dodecyl Sulfate
Authors: Manabe Masahiro , Koda Masaharu
Published: July 2006

The effect of the addition of the homologues of poly(oxyethylene) alkyl ethers (CmH2m+1(OCH2CH2)nOH: m=3–6, n=1–4), α,ω-alkanediols (m=4–6,8), and 1-alkanols (m=2–7) on the critical micelle concentration (CMC) of sodium dodecyl sulfate (SDS) was examined. The homologous additives are appropriate for studying the effect of polar groups as well as an alkyl group. The CMC decreases with an increase in the concentration of additive. The rate of CMC-decrease estimated at the infinite dilution of the additive increases with the length of alkyl chain in each homologue. The dependence of the rate on the alkyl chain length is the same for all the homologues with longer chain (m≥4 for ethers and alkanols, and m>6 for alkanediols). This is ascribed to the complete transfer of the long alkyl chain into the interior of micelles. The dependence of rate on the number of polar groups (OH, OCH2CH2) is as follows. The rate for alkanediol is lower than that for alkanol with a given alkyl chain. The rate for ethers increases asymptotically with the length of oxyethylene chain. The result for alkanediol is ascribed to the pronounced hydrophilic nature, and that for ethers to the reduction of electrostatic repulsive force between ionic head groups of the surfactant in micelles.
MINDO/3 Study of 7-Norbornyl, 7-Norbornenyl, and 7-Norbornadienyl Cations
Authors: Furusaki Akio , Matsumoto Takeshi
Published: July 2006

The geometries, charge distributions, and heats of formation for 7-norbornyl, 7-norbornenyl, and 7-norbornadienyl cations have been calculated by the use of the semi-empirical MINDO/3 SCF MO method. Each of these cations is symmetrical with respect to the plane which contains the C(7)–H(7) bond and bisects the C(1)–C(7)–C(4) angle. Both the 7-norbornenyl and the 7-norbornadienyl cations take the nonclassical bridge-structure: the C(2)–C(3) and C(2)–C(7) distances are about 1.43 and 1.67 Å respectively, and the C(2)–C(1)–C(4)–C(7) dihedral angle is about 75°. The classical 7-norbornyl cation also is quite unsymmetrical with regard to the C(1)–C(7)–C(4) plane: the C(2)–C(1)–C(4)–C(7) and C(7)–C(1)–C(4)–C(5) dihedral angles are 94° and 144°, respectively. The calculated barriers to the bridge flipping in the 7-norbornyl and 7-norbornadienyl cations are 3.2 and 33.0 kcal/mol respectively. Although the latter is much higher than its observed value of 19.6 kcal/mol, it seems possible that solvation considerably lowers the barrier height. The present article also touches upon the solvolyses of derivatives of these carbocations.
Vibrational Spectra and Normal Coordinate Calculations for Trimethylaluminium–Ammonia
Authors: Watari Fumio , Shimizu Shigenori , Aida Koyo , Takayama Eiji
Published: July 2006

Studies were carried out on the infrared spectra (33–4000 cm−1) of four isotopic trimethylaluminium–ammonia complexes, (CH3)3AlNH3, (CD3)3AlNH3 (CH3)3AlND3, and (CD3)3AlND3 in the solid state at low temperature, and on the Raman spectra (0–4000 cm−1) in the solid state and in solution of dichloromethane and of benzene at ambient temperature. Assignments for all fundamentals except internal torsion were made on the basis of C3v molecular symmetry. For the sake of confirmation normal coordinate calculations were carried out utilizing a symmetry force field. The Al–N stretching force constant was found to be 1.544 mdyn/Å.
Linear Free Energy Relationships in Heterogeneous Catalysis. XIII. The Dehydration of Aliphatic Alcohols over Silica–Alumina
Authors: Take Jun-ichiro , Matsumoto Tadayuki , Yoneda Yukio
Published: July 2006

In order to survey the applicability of linear free-energy relationships to the catalytic dehydration of aliphatic alcohols, isopropyl alcohol and n-, s-, and t-butyl alcohols were dehydrated over silica–alumina at 54–166 °C. The dehydration was zero order in alcohol over the pressure range of 0.01 to 0.1 atm. The true activation energies were 32.0, 35.3, 31.7, and 29.9 kcal/mol for isopropyl alcohol and n-, s, and t-butyl alcohols, respectively. The zero-order rate constants were exclusively affected by the activation energy. A linear relationship was found between the true activation energy, as well as the logarithm of the zero-order rate constant, and the heterolytic bond dissociation energy for the C–O bond in alcohols, D(R+OH−). The activation energy increased and the rate constant decreased with an increase in the D(R+OH−). These correlations were explained in terms of the heterolytic fission of the C–O bond in the rate-determining step.
Neutron Diffraction Study of the Structure of Liquid Water
Authors: Ohtomo Norio , Arakawa Kiyoshi
Published: July 2006

The structure factor for heavy water at 17 °C up to the Q value of 18 Å−1 has been determined by means of the time-of-flight (TOF) diffraction method using pulsed neutrons produced by LINAG. The result has been compared with structure factors calculated on the basis of the various structure models of liquid water; the “uncorrelated orientation model” and the “watery model” (Page and Powles), the “near-neighbor model” (Narten) and the “revised watery model” (authors). None of these models has been found to fit the neutron diffraction data satisfactorily over the entire range of Q, though our curve is somewhat improved in comparison with the curves for earlier models. Some discussions about the various structure models of liquid water have been made.
Light Scattering Study of Local Structures in Solutions. Structure-Forming Effect of Non-Associative Solvent on Ethanol Aggregate
Authors: Fujiyama Tsunetake , Tanaka Masami
Published: July 2006

Light scattering spectra were observed for binary mixtures of ethanol and carbon tetrachloride, and of ethanol and cyclohexane at various concentrations. The Rayleigh intensities were reduced to concentration fluctuation values. From the observed concentration fluctuation values, the mean association numbers of ethanol at each concentration were calculated. The results were compared with that observed in ethanol-chloroform system, where associative interaction between ethanol and chloroform molecules is expected. The concentration dependencies of the mean association numbers suggested that these non-associative solvent molecules (carbon tetrachloride and cyclohexane) promote the formation of large local structure in ethanol solution.
Selective Hydrogen Atom Abstraction by H Atoms in Radiolysis and Photolysis at 77 K: Decane-d22, Tetramethylsilane, and Xenon Matrices
Authors: Miyazaki Tetsuo , Kasugai Joji , Wada Manabu , Kinugawa Kazuhisa
Published: July 2006

The selective formation of HD and solute radicals in the radiolysis of n-C10D22 doped with n-C10H22 at 77 K is explained quantitatively by the mechanism of a selective hydrogen-atom-abstraction reaction by D atoms. The selective hydrogen-atom abstraction by H atoms is found also in tetramethylsilane and xenon matrices as well as in the alkane matrix. The rate constants of the abstraction reaction by H atoms are compared with the bond energies of the solvent and solute molecules. The bond energy of the solvent molecule is always higher than that of the solute molecule. Even if the difference in the bond energy between the solvent and the solute is very small, the k(solute)/k(solvent) ratio is quite large. The k(solute)/k(neo-C5H12) ratios for different solutes in a neopentane matrix are not influenced by the differences in the bond energy among the solutes. Since an isotope effect on the selective hydrogen-atom abstraction reaction is small, the effect may diminish the possibility of the quantum mechanical tunneling abstraction by thermal H atoms. The energy loss of hot H atoms in a Xe matrix is discussed.
Kinetic Studies of the Dimerization Reaction of Thionine by the Laser Raman Temperature-jump Method
Authors: Inaoka Wataru , Harada Shoji , Yasunaga Tatsuya
Published: July 2006

Kinetic studies of the dimerization reaction of thionine in an aqueous solution have been performed by the laser temperature-jump method with the use of the stimulated Raman effect in high-pressure H2 gas. From the concentration dependence of the relaxation time, the formation and dissociation rate constants of the thionine dimer have been obtained. The data have been confirmed by the equilibrium constant, independently obtained spectrophotometrically. The formation rate constant of the dimer was very large, and the process was revealed to be a diffusion-controlled reaction, similar to those with other dyes.
Charge-Transfer Character in the Intramolecular Hydrogen Bond: Vacuum Ultraviolet Spectra of Acetylacetone and Its Fluoro Derivatives
Authors: Nakanishi Hiroshi , Morita Hiroshi , Nagakura Saburo
Published: July 2006

Near and vacuum UV absorption spectra of trifluoroacetylacetone (TFAC) and hexafluoroacetylacetone (HFAC) were measured at room temperature in the vapor phase and in perfluorohexane in the 30000–80000 cm−1 region, together with a vacuum UV absorption spectrum of acetylacetone in the 60000–80000 cm−1 region. By the aid of the modified CNDO-CI calculation, each of the observed valence-shell transition bands was assigned to the π–π**, π–σ*, or σ–σ* transition. The third σ–σ* bands observed at 65200 cm−1 for acetylacetone, at 78000 cm−1 for TFAC, and at 70400 cm−1 for HFAC were concluded to be rich in the CT character pertinent to hydrogen bond. In particular, the third σ–σ* band of HFAC was found to be the CT band pertinent to hydrogen bonding in the sense that the contribution of the CT configuration to the excited state amounts to 67.4%.
Aluminum Chloride Catalyzed Friedel-Crafts Reaction of Anisole with Epoxide Accompanying Isomerization
Authors: Inoue Masashi , Sugita Toshio , Ichikawa Katsuhiko
Published: July 2006

The reaction of anisole with propylene oxide by aluminum chloride has been studied in various kinds of solvents. While the normal Friedel-Crafts reaction yielded 2-(methoxyphenyl)-1-propanols, 1,1-bis(methoxyphenyl)-propanes were also formed in this reaction; these were not obtained by the subsequent reaction of mono(methoxyphenyl) products with another anisole. The yields of 1,1-bis(methoxyphenyl)propanes increased by increasing the basicity of solvents. The mechanism of the formation of 1,1-bis(methoxyphenyl)propanes can be explained by the isomerization of epoxide to aldehyde and the subsequent condensation with anisole. Various kinds of epoxides also gave 1,1-bis(methoxyphenyl)alkanes in nitromethane.
The Polymorphic Crystallization of Titanium(IV) Oxide under Hydro-thermal Conditions. II. The Roles of Inorganic Anions in the Nucleation of Rutile and Anatase from Acid Solutions
Authors: Izumi Fujio
Published: July 2006

Titanic acid was treated with hydrochloric, nitric, sulfuric, and hydrofluoric acids at 350 °C and 49 MPa to give titanium(IV) oxide. With increasing acid concentration, its polymorphic forms changed from anatase to rutile in hydrochloric and nitric acids, but from anatase to rutile, then back to anatase in sulfuric and hydrofluoric acids. Rutile and anatase crystals were grown from 1.7–9.5 mol dm−3 hydrofluoric acid at 360–560 °C by the temperature-drop method. Lower temperatures and higher concentrations of the acid favored anatase formation. The mechanisms for crystallization of the two forms are discussed by considering the chemical behavior of titanium(IV) complexes involved in their primary nucleation.
The Reaction of Alkyl Halides with Mercury(II) and Potassium Thioacetates and Selenocyanates
Authors: Uemura Sakae , Watanabe Nanao , Toshimitsu Akio , Okano Masaya
Published: July 2006

The reactions of alkyl halides with mercury(II) and potassium thioacetates afford alkyl thioacetates (RSCOMe), SN1 and SN2 type reactions taking place. In neither case is ROCS Me formed. Reactions with mercury(II) selenocyanate usually give only small amounts of alkyl selenocyanates and/or isoselenocyanates as isolated products except the case of benzyl bromide from which benzyl selenocyanate was obtained almost quantitatively. The ambident reactivity of this salt was revealed to be not so strong as that of mercury(II) thiocyanate. The reaction with potassium selenocyanate is also reported for comparison.
Synthesis of Stachyose Tetradecaacetate and An Isomer
Authors: Suami Tetsuo , Otake Toshiki , Nishiyama Shigeru , Adachi Ryoichi , Nakamura Katsumi
Published: July 2006

Condensation of 1′,2,2″,3,3′,3″,4,4′,4″,6′-deca-O-acetylraffinose (1) with 2,3,4,6-tetra-O-benzyl-d-galactopyranosyl chloride in the presence of tetraethylammonium chloride, followed by deacetylation, debenzylation and subsequent acetylation afforded stachyose tetradecaacetate. An isomer in which a terminal d-galctopyranosyl group is attached to the 6″-O of raffinose in β-anomeric linkage, was prepared by condensing 1 with 2,3,4,6-tetra-O-acetyl-α-d-galactopyranosyl bromide in the presence of mercury(II) cyanide. 13C NMR spectra of stachyose tetradecaacetate and the isomer were discussed.
Cyclization of Isothiosemicarbazones. I. A New Route to 2-Mercapto-imidazole Derivatives and 4-Substituted Imidazoles
Authors: Yamazaki Chiji
Published: July 2006

Some 1-arylmethyleneamino-2-mercapto-4-aryl-1H-imidazole derivatives were prepared by the condensation of isothiosemicarbazones of aromatic carbonyl compounds with phenacyl bromides. The 1,2,5-trisubstituted isomers were obtained by substitution of dl-α-bromophenylacetaldehyde for phenacyl bromide in this condensation. The reaction of isothiosemicarbazones of aliphatic carbonyl compounds with phenacyl bromides produced a dark, complex mixture from which the corresponding 1-alkylideneamino-2-mercapto-4-aryl-1H-imidazoles and 3,5-disubstituted 1,2,4-triazines were isolated in poor yields, with the latter being a main product or a sole heterocyclic product depending on the reaction conditions. Reductive cleavage of the cyclized products with zinc dust in acetic acid-acetic anhydride solution gave 1-acetyl-4-aryl-1H-imidazoles, which were readily hydrolyzed to 4-aryl-1H-imidazoles. The susceptibility to acid hydrolysis of the arylmethyleneamino group was dependent on the extent of conjugation between the azomethine double bond and the adjacent aromatic rings. Hydrazinolysis of the azomethine double bond yielded 1-amino-2-mercapto-4-aryl-1H-imidazoles in high yields. Their structures were established on the basis of NMR, IR, UV, and mass spectra as well as elemental analyses. Differentiation between 1,2,4- and 1,2,5-trisubstituted imidazoles was discussed.
Formaldehyde Polymers. 22. Reaction Products of 6,8-Dimethyl-4-chromanone with Formaldehyde—On the Dimeric Products—
Authors: Ninagawa Akira , Matsuda Haruo
Published: July 2006

The reaction of 6,8-dimethyl-4-chromanone with formaldehyde has been carried out in 96% sulfuric acid. From the mother liquors after obtaining 5-hydroxymethyl-6,8-dimethyl-4-chromanone, the methylene and oxydimethylene dimers of 6,8-dimethyl-4-chromanone, 6,6′,8,8′-tetramethyl-5,7′-methylenedichroman-4,4′-dione and bis(6,8-dimethyl-4-oxochroman-5-ylmethyl) ether, respectively, were isolated by recrystallization. 1H- and 13C-NMR spectra of 5-hydroxymethyl-6,8-dimethyl-4-chromanone in 96% sulfuric acid show the existence of 6,8-dimethyl-4-oxochroman-5-ylmethyl cation. The intermediate ion is stable, not reacting in sulfuric acid.
Calorimetric Phenomena of Methanol Adsorption on Active Carbon
Authors: Tsunoda Ryoichi , Fukazawa Yoshiyuki
Published: July 2006

The heats of immersion in methanol of active carbon which preadsorbed methanol from the vapor phase at a given equilibrium pressure were measured. The calorimetric phenomena of methanol adsorption on active carbon were interpreted by comparing them with the distribution of the adsorption potential of methanol on active carbon.
Carbon Deposition on Nickel from a Mixture of Ethylene and Hydrogen
Authors: Kishimoto Shozo , Sotani Noriyuki , Niimi Kazuyo , Urata Toshiko
Published: July 2006

Two periods (acceleration and steady state period) were defined in the process of carbon deposition on cold-worked nickel from ethylene. From the dependence of the former period on annealing temperature, it was found that lattice defects in the crystal play a role in the creation of carbon nuclei and the separation of nickel atoms from the surface.
Esterification of N-(Benzyloxycarbonyl)amino Acids and Amino Acids Using BF3–Etherate as Catalyst
Authors: Yamada Takashi , Isono Nobuyuki , Inui Akemi , Miyazawa Toshifumi , Kuwata Shigeru , Watanabe Hiroshi
Published: July 2006

Methyl and ethyl esters of N-(benzyloxycarbonyl) amino acids were prepared conveniently in good yields using BF3–etherate as catalyst. Esterification of free amino acids was also examined.
Resolution of α-Formyl-ε-acyl-Dl-lysines by Acylase
Authors: Minematsu Yoshihiro , Shimohigashi Yasuyuki , Waki Michinori , Izumiya Nobuo
Published: July 2006

Taka-acylase hydrolyzed an α-formyl derivative of ε-acyl-l-lysine faster than the corresponding α-acetyl derivative. Preparative resolution by crude Takaacylase afforded ε-formyl or ε-benzyloxycarbonyl-l-lysine from the corresponding α-formyl-ε-acyl-Dl-lysine. The action of p-toluenesulfonic acid on α-formyl-ε-benzyloxycarbonyl-d-lysine under mild conditions afforded pure ε-benzyloxycarbonyl-d-lysine.
Studies of Quinazoline Pigments. II. Synthesis of Dimethyl Substituted Pyrido[2,1-b]pyrido[1′,2′:1,2]pyrimido-[4,5-g]quinazoline-7,15-diones
Authors: Yokoyama Yasukazu
Published: July 2006

In the presence of alkali, 4,12-, 3,11-, 2,10-, and 1,9-dimethyl derivatives of 6, 14-dihydropyrido[2,1-b]pyrido[1′,2′:1,2]pyrimido[4,5-g]quinazoline-7,15-dione reacted with nitrobenzene to give 2,5-bis(3-, 4-, 5-, and 6-methyl-2-pyridylamino) terephtharic acids. The intramolecular cyclization of 3-, 4-, and 5-methyl derivatives, gave 4,12-, 3,11-, and 2,10-dimethylpyrido[2,1-b]pyrido[1′,2′:1,2] pyrimido[4,5-g]quinazoline-7,15-dione respectively, but the 6-methyl derivative did not give any cyclization product. The synthesis of the 1,9-dimethyl derivative was accomplished by the dehydrogenation of 1,9-dimethyl-6,14-dihydropyrido[2,1-b]pyrido[1′,2′:1,2] pyrimido[4,5-g] quinazoline-7,15-dione with p-chloranil.
Studies on Nucleosides and Nucleotides. VI. A Facile Cleavage of the Anhydro Bond of 2′,3′-O-Isopropylidene-O2,5′-cycloiiridine with the Use of Proton Acid or Lewis Acid
Authors: Kimura Junji , Mitsunobu Oyo
Published: July 2006

When 2′,3′-O-isopropylidene-O2,5′-cyclouridine (1) was allowed to react with methanol in the presence of p-toluenesulfonic acid at room temperature, 5′-O-methyl-2′,3′-O-isopropylideneuridine was obtained in good yield. Similarly, with the use of boron trifluoride etherate, 1 reacted smoothly with diphenyl phosphate to give the corresponding 5′-phosphorylated product.
A Theoretical Approach to the Rearranged Ion in the Mass Spectrum of Methyl Formate
Authors: Takagi Tsutomu , Oiwa Masayoshi
Published: July 2006

The hydrogen-migration mechanism of the fragmentation of the methyl formate under electron impact has been discussed from the standpoint of the all-valence electron semi-empirical SCF-MO theory (CNDO/2-Unrestricted Hartree Fock), assuming the following models:

(Remark: Graphics omitted.)

The model for the hydrogen migration and the possible driving force are presented based on the partition method. The localized MO calculation has been carried out, by the “energy localization” method of the MINDO MO’s, for the origin and the terminus of the migration as an aid to the understanding of the migration. Although the possibility of the hydrogen migration in other models can not always be neglected, the hydrogen migration via Model 1 may be estimated to be energetically favorable, judging from the variation in the total energy and the conformation influence.
Molecular Motions in Sodium Tetrachloroaurate Dihydrate as Studied by the Proton and Chlorine Nuclear Relaxation Times
Authors: Sagisawa Kensho , Kiriyama Hideko , Kiriyama Ryôiti
Published: July 2006

The 1H and 35Cl relaxation times in NaAuCl4·2H2O have been measured at temperatures between 79 and 350 K. The 1H T1 data revealed that the water molecule of crystallization reorients about its C2 axis with an activation energy of 26 kj mol−1. The 35Cl T1 values of the four NQR absorptions indicated that the reorientation of the water molecule makes no important contribution to the chlorine T1 in spite of the hydrogen bonds between them. A brief analysis of the 35Cl T1 led to a frequency of 58 cm−1 for the torsional vibration of the AuCl4− ion.
The Mechanism of the CO Oxidation over Polycrystalline Platinum
Authors: Matsushima Tatsuo
Published: July 2006

The kinetics of the CO oxidation has been studied on polycrystalline platinum at various partial pressures, total pressures, and temperatures; 0.1<Pco⁄Po2<5, 10−6<P<10−3 Pa, and 300<T<900K. The reaction was first-order in CO and zero-order in O2 for low pressures of CO, while it was inhibited by CO above a certain critical CO pressure, which increased with an increase in the O2 pressure and temperature. Above that CO pressure, the reaction was first-order in O2 and negative-order in CO. The amount of CO adsorbed was determined during the reaction with a flash-desorption technique. Above the critical CO pressure it was almost equal to that determined in the CO/Pt equilibrium system. It decreased sharply around the CO pressure and was very small at lower pressures. The kinetic behavior can be explained in terms of a Langmuir-Hinshelwood process and a change in the rate-limiting step.
Electron Trapping in Irradiated NaOH Ices. Electrons Stabilized at 4 K in Shallow Traps Associated with Na+ Cations
Authors: Kroh Jerzy , Noda Shoji , Yoshida Kiyomi , Yoshida Hiroshi
Published: July 2006

Studies on electron trapping in 8 and 18 mol·dm−3 NaOH glassy ices were performed by means of 4 K γ-irradiation technique. The optical absorption spectra of e−t were found to be considerably red-shifted and broader compared with the spectra in the ices irradiated and examined at 77 K. This trend was more pronounced for the concentrated sample. The red part of the broad spectra was removed either by photobleaching with light of λ>800nm at 4 K or by thermally annealing at 77 K. These results, combined with electron spin resonance data, lead to the conclusion that the shallow electron traps responsible for the red part of the spectra are formed with the participation of Na+ cations in the alkaline ices.
Direct Measurement of Interaction Energy between Solids and Gases. II. Microcalorimetric Studies on the Surface Acidity and Acid Strength Distribution of Solid Acid Catalysts
Authors: Masuda Tatsuo , Taniguchi Hitofumi , Tsutsumi Kazuo , Takahashi Hiroshi
Published: July 2006

The differential heats of adsorption of ammonia on several solid acids were measured by means of a twin conduction type microcalorimeter, and surface acid strength distribution and acidity were evaluated. Silica–alumina showed very high initial heats which were not observed in decationated zeolite and silica–magnesia. The acidity of zeolite was about 6 times as high as that of silica–alumina, showing very charactristic acid site distribution at 100 kJ/mol of adsorption energy, and suggesting the existence of homogeneous acid sites. The surface water modified surface acidic nature transforming strong acid sites into weaker ones. The poisoning of acid sites of silica-alumina with alkali occurred preferentially at sites on which adsorption energy of ammonia was 96–105kJ/mol.
Computation of the Correlation Functions for Fluids Composed of Diatomic Molecules by Means of the Method of Integral Equations
Authors: Kojima Kazumitsu , Arakawa Kiyoshi
Published: July 2006

Pair correlation functions and structure factors of molecular fluids were computed, based on the reference interaction site model (RISM) integral equation coupled with the Percus-Yevick (PY) and the hyper-netted chain (HNG) approximations. The system considered is a fluid of diatomic molecules consisting of two identical spheres of diameter a with each center located at a distance L(L<σ). The total potential energy for the molecular fluid is assumed to be the sum of pair potentials of the Lennard-Jones type. It is shown that the pair correlation functions calculated are in agreement with results of molecular dynamics studies. The structure factors calculated by using two kinds of approximations (PY and HNG) are found to deviate from each other for small values of k(wave vector). Discussions are given on the behavior of the structure factors, S(k). The rise of S(k) at small k is ascribed to the effect of attractive forces between molecules.
The Temperature Dependence of the Solubilities of 1-Phenyl-1,3-butanedione and 4,4,4-Trifluoro-1-phenyl-1,3-butanedione in Water and Aqueous Electrolyte Solutions
Authors: Yoshimura Yasuki , Suzuki Nobuo
Published: July 2006

The temperature dependence of the solubilities of 1-phenyl-1,3-butanedione (benzoylacetone) and 4,4,4-tri-fluoro-1-phenyl-1,3-butanedione (benzoyltrifluoroacetone) in water and in 1.0 mol l−1 aqueous solutions of HClO4, HCl, NaClO4, KCl, NaBr, NaCl, BaCl2, and Na2SO4 was determined over the temperature ranges of 20 to 45°C for benzoylacetone and of 15 to 30°C for benzoyltrifluoroacetone. From these data, the thermodynamic quantities associated with the dissolution in water and with the transfer from water to the aqueous electrolyt solutions were estimated. Both the enthalpy and the entropy of solution of benzoyltrifluoroacetone in water were much smaller than those for benzoylacetone. This was interpreted by assuming a higher hydrophobic hydration for the less polar benzoyltrifluoroacetone. The thermodynamic quantities of the transfer of benzoyltrifluoroacetone from water to the aqueous perchloric acid solution showed characteristic features compared with those of the other electrolyte solutions. The overall salt effect on the dissolution of benzoylacetone and benzoyltrifluoroacetone is discussed in terms of the change in the thermodynamic quantities.
Carbon-13 NMR Spectra of Benzene Mono- and Di-Carboxylic Acids and Their Analytical Applications
Authors: Kosugi Yoshio , Takeuchi Tsugio
Published: July 2006

Carbon-13 NMR spectra of benzoic, and phthalic acids were compared both in D2O with an excess of sodium hydroxide and in a mixture of DMSO-d6 and H2O (4:1). Tight ion pair forms of benzoate anion were considered. A simple additive rule for isomeric phthalic acids was employed to assign the spectral peaks. These carboxylic acids gave characteristic peaks and so can be distinguished from others in mixtures. Quantitative analyses of these carboxylic acids with calibration curves are also possible by a simple preparation of basic D2O solutions. An example of the use of these data is the Henkel process (cf. Fig. 1) for the synthesis of terephthalic acid.
cis-Dioxovanadium(V) and Mixed-Valence Divanadium(IV, V) Complexes Containing: β-Diketonate and Heterocyclic Nitrogen-base Ligands
Authors: Taguchi Hiroshi , Isobe Kiyoshi , Nakamura Yukio , Kawaguchi Shinichi
Published: July 2006

Diamagnetic dioxovanadium(V) complexes, VO2(β-dik)(phen or bpy), were prepared by the direct reactions of VO(β-dik)2 with 1,10-phenanthroline and 2,2′-bipyridine in dichloromethane under aerobic conditions as well as by two other methods. These compounds were concluded to have a cis configuration on the basis of the IR and Raman data. These complexes are solvolyzed to afford the di-μ-methoxo-or di-μ-hydroxo-divanadium(V) species, and are reduced by hydrogen bromide to the oxovanadium(IV) species in dichloromethane. In methanol instead of dichloromethane, VO(acac)2 reacted with 2,2′-bipyridine to produce a novel mixed-valence divanadium(IV, V) complex, V2O3(acac)3(bpy), which was revealed by the magnetic, spectral, and polarographic data to be a trans adduct of VO(acac)2 with VO2(acac)(bpy) via an oxide ligand.
Synthesis and Oxygenation Reaction of Cobalt(II) Complexes with Jäger-Type Open-Chain Ligands
Authors: Kubokura Koichi , Okawa Hisashi , Kida Sigeo
Published: July 2006

Cobalt(II) complexes with Jäger-type open-chain ligands, H2(J-R) (R=en, pn, ph, and tn), were prepared. It was found that Co(J-en), Co(J-pn), and Co(J-ph) are in low-spin state, and Co(J-tn) in high-spin state with a pseudo-tetrahedral configuration. The formation constant of pyridine adduct of Co(J-en)was spectrophotometrically determined to be 2.70, 2.18, and 1.90 M−1 at 0, 20, and 30 °C, respectively. Co(J-en)py forms oxygen adducts, Co(J-en)pyO2 and [Co(J-en)py]2O2, in a 1,2-dichloroethane solution at room temperature, exhibiting a characteristic band at 525 nm. The ease of oxygenation and the characteristic absorption in the visible region were interpreted in terms of the electron-withdrawing ability of acetyl group in the ligand.
Molecular and Crystal Structure of Hydrido(tricarbonyl)-bis(triphenylphosphine)manganese(I),HMn(CO)3[P(C6H5)3]2
Authors: Hayakawa Hiroshi , Nakayama Hiroaki , Kobayashi Akiko , Sasaki Yukiyoshi
Published: July 2006

The crystal structure of the title compound has been determined by single crystal X-ray diffraction techniques. The compound crystallizes in the space group C2/c with unit-cell dimensions a=23.54(1), b=9.672(3), c=15.941(7) Å, β=114.90(4)°, and Z=4. The manganese atom is octahedrally coordinated by two triphenylphosphines in the trans positions, three equatorial carbonyl ligands, and a hydrido hydrogen. The Mn–H bond has a normal covalent length, 1.46(8) Å. The molecule has C2 symmetry, and Mn, O(1), C(1), and Hh are on special positions of (0, y, 1/4).
Nondispersive and Dispersive Atomic Fluorescence Spectrometry of Arsenic by Utilizing the Arsine-generation Technique
Authors: Nakahara Taketoshi , Tanaka Toshiaki , Musha Sôichirô
Published: July 2006

Atomic fluorescence spectrometry with nondispersive and dispersive systems by utilizing the arsine-generation technique is described for the determination of arsenic at the nanogram level, where the premixed argon(entrained air)- and nitrogen (entrained air)-hydrogen flames and a microwave-excited electrodeless discharge lamp were used. For the low-temperature flames, a newly designed burner has been constructed. The best detection limits obtained for arsenic are 2.3 ng in mass and 0.12 ppb in concentration with a nondispersive system in argon(entrained air)-hydrogen flame. Linear analytical working curves covering the mass range of arsenic from 30 ng to around 1000 ng have been obtained with nondispersive and dispersive systems at 193.7 and 197.2 nm in both the hydrogen flames. Several elements including other hydride-forming elements, such as antimony, bismuth, selenium, and tellurium, have caused a decrease in fluorescence signals. The present method, with the most sensitive nondispersive system and argon (entrained air)-hydrogen flame, can be applied to the determination of trace amounts of arsenic in wastewaters.
Furan Derivatives. III. Some Electrophilic Substitution Reactions and Hydrogenation of 4,5-Dihydro-3H-naphtho[1,8-bc]furans
Authors: Horaguchi Takaaki , Abe Teishiro
Published: July 2006

4,5-Dihydro-3H-naphtho[1,8-bc]furans (1a–d) reacted with a variety of electrophilic reagents to give the corresponding 2-substituted 4,5-dihydro-3H-naphtho[1,8-bc]furans. Hydrogenation of 1a–d gave the corresponding 2a,3,4,5-tetrahydro-2H-naphtho[1,8-bc]furans. 2H-Naphtho[1,8-bc]furans (7a–c) which were prepared from 1a–c were gradually converted to the 8-hydroxynaphthalene-1-carbaldehydes in air. The facile cleavage of the ether bond of 7a–c is thought due to ring strain in the 2H-naphtho[1,8-bc]furan ring system.
Calculation of the Carbon-13 NMR Chemical Shifts of Some Organic Compounds Using the Improved Virtual Orbital Method
Authors: Kondo Masahiro , Ando Isao
Published: July 2006

Using the wavefunction obtained from the improved virtual orbital (IVO) method proposed by Huzinaga, the 13C NMR chemical shifts in some organic compounds (acetylene, ethylene, ethane, pentane, benzene, pyridine and acetone) have been calculated and compared with those obtained from the ordinary SCF-MO method. If the molecule considered is small, highly symmetric and non-polar, it can be expected that there is little difference in the calculated values between these two methods. If the molecule considered is rather large or polar, modification of the calculated values are apt to be induced by the IVO method. As far as qualitative tendencies of the chemical shifts of carbon in a molecule are concerned, both methods give similar results.
Total Synthesis of (±)Variotin and Its Analogs
Authors: Ishida Akihiko , Mukaiyama Teruaki
Published: July 2006

1-Sorboyl-2-pyrrolidone was prepared from sorbic acid and 2-ethoxy-1-pyrroline using 1-methyl-2-chloropyridinium iodide as a coupling reagent. Variotin and its analogs were similarly synthesized from lactim ethers and (2E,4E,6E)-8-hydroxy-2,4,6-dodecatrienoic acids without protecting the hydroxyl group at C-8. (2E,4E,6E)-8-Hydroxy-6-methyl-2,4,6-dodecatrienal, a precursor of trienoic acid, was synthesized by the elimination of methanol from (2E,6E)-8-acetoxy-5-methoxy-6-methyl-2,6-dodecadienal prepared from the reaction of 1-trimethylsiloxy-1,3-butadiene with (2E)-4-acetoxy-2-methyl-2-octenal dimethyl acetal.
Boron Trifluoride Hydrate-catalyzed Competitive Benzylation of Benzene and Toluene with Benzyl and Substituted Benzyl Chlorides
Authors: Takematsu Akiko , Sugita Kyoko , Nakane Ryohei
Published: July 2006

The competitive benzylation of benzene and toluene catalyzed by boron trifluoride hydrate was carried out with benzyl, chlorobenzyl, alkylbenzyl, and alkoxybenzyl chlorides in boron trifluoride hydrate and hexane solutions. The relative rates of toluene to benzene were smaller than 1 in the benzylation with benzyl and chlorobenzyl chlorides, while they were larger than 1 with alkylbenzyl and alkoxybenzyl chlorides. Competitive benzylation catalyzed by boron trifluoride was also carried out in a nitromethane solution. The relative rates were reduced by from several to ten times in the former solutions as compared to the latter solution; the kT/kB value became smaller than 1 when the electrophile was such a very strongly electron-deficient reagent as the benzyl or chlorobenzyl cation. On the other hand, the kT/kB value was still larger than 1 when the electrophilicity was lower, as in the alkylbenzyl or alkoxybenzyl cation. The isomer distribution was insensitive to the nature of the solvents. The formation of the meta isomer was always only a small percentage. These results substantiate our previous conclusions obtained in the ethylation and isopropylation catalyzed by boron trifluoride hydrate.
Carbon-13 NMR Spectra of Octahydro-1,4-naphthoquinones and of Their Derivatives
Authors: Irikawa Hajime , Okumura Yasuaki
Published: July 2006

The 13C NMR spectra are reported for hexahydro- and octahydro-1,4-naphthoquinones and their derivatives. The shielding trends of the methyl group are utilized for conformational analysis. A comparison of octahydro- 1,4-naphthoquinones with the corresponding decalins reveals that the effects of the carbonyl group are the large downfield shift of the α-carbons and the upfield shifts of the β- and γ-carbons.
A New Synthesis of α-Phenylsulfonyl-γ-lactones and Their Use for Syntheses of Actinidiolide Derivatives
Authors: Uneyama Kenji , Kuyama Manabu , Torii Sigeru
Published: July 2006

The acid-catalyzed cyclization of 2-phenylsulfonyl-4,8-dimethyi-3,7-nonadienoic acid (5) was performed by treatment with sulfuric acid-acetic acid and/or boron trifluoride in various aprotic solvents to afford 2,2,6-trimethyl-9-phenylsulfonyl-7-oxabicyclo[4.3.0]nonan-8-one (4) in 70–75% yield. Similarly, 2-phenylsulfonyl-2-(2,6,6-trimethyl-1,3-cyclohexadienyl)acetic acid provided 2,2,6-trimethyl-9-phenylsulfonyl-7-oxabicyclo[4.3.0]non-4-en-8-one (7) in 62% yield. The lactones 4a, 4b, and 7 were converted into dihydroactinidiolide, tetrahydroactinidiolide, and 4,5-dihydroactinidiolide. The reaction conditions and mechanism of the cyclization of 5 are discussed.
Studies on Diazo Type Process. VI. Physico-chemical Studies on 1-(p-Dimethylaminophenylazo)-2-naphthol-3,6-disulfonic Acid in Aqueous Solutions
Authors: Suzuki Shin , Das Rebati C , Harada Kieko
Published: July 2006

1-(p-Dimethylaminophenylazo)-2-naphthol-3,6-disulfonic acid is formed in many important commercial “dry process” diazo-printing. Some physico-chemical properties of this dye in solutions have been investigated. Its absorption spectra in various solvents and in water at various acidities have been discussed on the basis of azoquinone hydrazone tautomeric and acid-base equilibria respectively. The dissociation constants of the acid-base equilibria in the pH range of 1–14 in aqueous solutions have been determined at 25 °C and 1.0 M ionic strength. Conductivities of aqueous solutions at various concentrations and temperatures have been interpreted on the basis of the colloidal nature of the dye. The polarograms of the compound have been drawn at various pH’s and discussed. Polarographic method indicates complex formation between Zn(II) salt and the dye in the mole ratio of 1:2.
Nuclear Magnetic Resonance Study of Exchanging Systems. X. Rotational Barriers to trans-cis Isomerization in Esters
Authors: Nakanishi Hiroshi , Fujita Hitoshi , Yamamoto Osamu
Published: July 2006

The 13C NMR spectra of t-butyl formate (1), 1,1-diethylpropyl formate (2), and 2,6-dimethylphenyl formate (3) were measured at various temperatures. It was found that the signals of the trans and cis isomers in 1 and 2 are separated at very low temperatures, and that the signal of 3 only shows a slight line broadening. The complete line shape analyses of these temperature-dependent spectra were performed. The activation energies Ea(t-c) of the isomerization from the trans isomer to the cis were determined to be 10.9 kcal/mol for 1 and 7.2 kcal/mol for 2.
Phthalimides. III. Ammonolysis, Aminolysis, Hydrazinolysis, Pyrolysis, and Action of Grignard Reagents on Phthalimide Derivatives
Authors: Fahmy A F M , Aly N F , Orabi M O
Published: July 2006

N-Hydroxyphthalimide undergoes ammonolysis to give phthalimide. N-(Aroyloxy)phthalimides undergo alcoholysis followed by ammonolysis to give mixtures of phthalimide and ester. N-(Arylsulfonyloxy)phthalimides undergo ammonolysis, followed by Lossen rearrangement to give mixtures of 2,4-quinazolinedione and ammonium salts of arenesulfonic acids. N-Hydroxyphthalimide undergoes aminolysis to give the corresponding N-arylphthalimides. N-Hydroxyphthalimide reacts with hydrazine hydrate and/or phenylhydrazine in acetic acid or ethanol to give the corresponding 1,4-phthalazinedione, or by fusion to give phthalimide and N-phenylphthalimide, respectively. Pyrolysis of N-hydroxyphthalimide gives phthalimide, and N-(aroyloxy)phthalimides give mixtures of phthalimide and carboxylic acids. N-(Arylsulfonyloxy)phthalimides give mixture of phthalimide and arenesulfonic acids. However, pyrolysis of N-(arylcarbamoyloxy)phthalimides gave N-arylphthalimides. N-Hydroxyphthalimide reacts with phenylmagnesium bromide to give 1,1-diphenyl-3-(phenylimino)-1,3-dihydroisobenzofuran via ring opening followed Beckmann rearrangement, while N-(arylsulfonyloxy)phthalimides react with arylmagnesium bromide to give mixtures of [O-(arylamino)phenyl]diarylmethanols, and arenesulfonic acids via ring opening followed by Lossen rearrangement.
Preparation, Infrared and Mass Spectral Studies of 6-Substituted 6,7-Dihydro-5H-dibenzo[d,f][1,3,2]diazaphosphepine 6-Oxides
Authors: Naidu M S R , Reddy C Devendranath
Published: July 2006

Several 6-substituted 6,7-dihydro-5H-dibenzo[d,f][1,3,2]diazaphosphepine 6-oxides have been synthesized and their structures were confirmed by IR and mass spectra. The existence of hydrogen bonding between the amidic hydrogens and the phosphoryl oxygen in theses compounds is indicated by the IR spectra. Under electron impact, the splitting pattern of these compounds takes about four major fragmentation pathways. The stability of dibenzodiazaphospheine cyclic system is indicated by the appearence of ions at m/e 229 and 211 corresponding to the species C12H10N2OP+ and C12H8N2P+, respectively, in all the spectra of the compounds except in the methyl and ethyl substituted compounds.
Chemical Equilibria of Methyl-, Ethyl-, and Propylmercury(II) Chlorides and Their Complexes with l-Cysteine in Liquid-Liquid Distribution Systems
Authors: Niitsu Masaru , Manri Teruo , Iritani Nobuhiko
Published: July 2006

The distribution constants for methyl-, ethyl-, and propylmercury(II) chlorides (RHgCl) between aqueous 1 mol dm−3 (H, Na)Cl and benzene were determined to be 101.04, 101.60, and 102.20 respectively. The formation constants for the complexes of these organomercury(II) chlorides with l-cysteine (R′SH), K=[RHgSR′][H+][Cl−][RHgCl]−1[R′SH]−1, were determined to be 101.71 101.55, and 101.49 respectively.
Photochemical Oxidation of Toluene with Nitrogen Dioxide in Gas Phase. “Effects of Oxygen”
Authors: Ishikawa Hiroshi , Watanabe Kazuo , Ando Wataru
Published: July 2006

The products and mechanism of the reaction of toluene with nitrogen dioxide have been investigated in the presence of oxygen. The volatile products observed were benzaldehyde, o-, m-, and p-nitrotoluene, along with 6-nitro-o- and 2-nitro-p-cresol.
Preparation and Reactions of Di-1,3,5-triazinyl Ethers. I. Preparation of Di-1,3,5-triazinyl Ethers
Authors: Sakurai Ryuta , Hashida Yoji , Matsui Kohji
Published: July 2006

Di-1,3,5-triazinyl ethers have been prepared by the condensation of 2-chloro-1,3,5-triazines with potassium 1,3,5-triazin-2-olate in acetonitrile in the presence of a small amount of cyclic polyether. Di-1,3,5-triazinyl ether was also prepared by the reaction of 2-chloro-1,3,5-triazine with potassium nitrite.
Electroorganic Chemistry. XXXIV. Novel Intramolecular Cyclization through Anodic Oxidation of Enol Acetates
Authors: Shono Tatsuya , Nishiguchi Ikuzo , Kashimura Shigenori , Okawa Masahisa
Published: July 2006

The anodic oxidation of 1-acetoxy-1,6-heptadiene homologues in acetic acid gave mainly intramolecular cyclization products, cyclohexenyl ketones. The cyclization takes place through the electrophilic attack of the cationic center generated from the enol ester moiety to the double bond.
A Simple Preparative Method of Alkylthiotrimethylsilanes
Authors: Kuwajima Isao , Abe Toru
Published: July 2006

Treatment of sym-disulfides with metallic sodium in the presence of trimethylchlorosilane in an appropriate solvent affords the corresponding alkylthiotrimethylsilanes in high yield.
Dissociation Constants of the Cyanohydrins of Substituted Acetonaphthones
Authors: Nadar P Ananthakrishna , Gnanasekaran C , Chandrasekaran J
Published: July 2006

The dissociation constants of the cyanohydrins of 4-substituted 1-acetonaphthones and 6-substituted 2-acetonaphthones were determined at 30 °C in 80% dioxan–water(v/v). 1-Acetonaphthone Cyanohydrin has a greater dissociation constant than 2-acetonaphthone cyanohydrin due to steric interaction between the reaction centre and peri-H. The Hammett equation is well obeyed by both the series. The ρ values are found to be −1.18 and −2.36 for the 1-series and the 2-series respectively. The significant difference in the ρ values suggests that the electronic transmission is different in these two cases.
Bromate Ion Specific Adsorption at Hg/KBrO3(aq) Interface
Authors: Ramanamurti M V , Qayum A , Singh R K
Published: July 2006

Adsorption analysis at polarized Hg/KBrO3 (aq) interface through capacity measurements at 25 °C indicates bromate ion specific adsorption by the cathodic shift of zero charge potential with bulk electrolyte activity confirmed by means of q1 (charge due to specifically adsorbed anions) vs.  qm (electrode charge) curves. At any concentration, q1>qm revealed bromate ion superequivalent adsorption. At fixed qm, q1 increases with electrolyte activity.
Neighboring Group Participation in Solvolysis. VII. Trifluoroacetolysis of ω-Phenylalkyl 6-Methyl-2-naphthalenesulfonates
Authors: Ando Takashi , Yamawaki Junko , Saito Yoshimasa
Published: July 2006

The tide compounds, Ph(CH2)nOMns (n=2–6), were solvolyzed in buffered trifluoroacetic acid in order to elucidate the effect of a phenyl group at a remote position on the reactivity and the course of the reaction. The reactivities varied remarkably with the length of the alkyl chain(n); 2>>3<<4>5>6. The rate enhancement was attributed to anchimeric assistance by a remote phenyl group, and the rate depression to the electron-withdrawing inductive effect of a phenyl group. Studies on reaction products revealed that in trifluoroacetolysis of 4-phenylbutyl menasylate (n=4) the only pathway to take place is the one with δ-phenyl participation, and that even for 5-phenylpentyl menasylate (n=5) 12% of the reaction proceeds via ε-phenyl participation.