bluuebunny/crossref_metadata_2025 huggingface dataset:
The Dissociation of Carbon Monoxide in an Induction-coupled Argon Plasma Jet
Authors: Nishimura Yukio , Takenouchi Takeyoshi , Sakai Wataru
Published: July 2006

The major products were solid carbon, CO2 and O2. As the inside diameter of the probe decreased, the concentration of O2 in the quenched gas increased and that of CO2 decreased. The product distribution was independent of the argon-flow rate.
The Photosensitized Isomerization of 2-Butenes by Sensitizers Adsorbed on Porous Vycor Glass
Authors: Otsuka Kiyoshi , Morikawa Akira
Published: July 2006

The triplet-triplet energy transfer from ketones adsorbed on the Vycor glass to 2-butenes was rapid enough for us to neglect the transfer to the surface when the transfer is exothermic. Different photoisomerization mechanisms were suggested for different groups of sensitizers.
The Molecular Structure of Boron Triiodide as Determined by Gas Electron Diffraction
Authors: Kakubari Hironobu , Konaka Shigehiro , Kimura Masao
Published: July 2006

The B–I distance of BI3 was determined to be 2.118±0.005 Å. A modified Schomaker-Stevenson rule holds for the boron-halogen bond lengths of the boron trihalides except for the fluoride. The B–F distance is much shorter than the value predicted by the rule.
Comparison of the Catalytic Activities of Metal Oxides for Hydrogen-Deuterium Equilibration and Ortho- Parahydrogen Conversion
Authors: Otsuka Kiyoshi , Keii Tominaga
Published: July 2006

The corrected activities, rates divided by square of spin magnatic moment of a metal ion, in ortho-parahydrogen conversion on first series transition metal oxides at 77°C were shown to give a very similar activity pattern to that obtain in hydrogen-deuterium equilibrtation.
The Conversion Reaction of Alkali 4-Hydroxyisophthalates into Hydroxybenzoic Acids
Authors: Ota Koki
Published: July 2006

When alkali 4-hydroxyisophthalates are heated with phenol or alkali phenolates, p-hydroxybenzoic acid is formed from potassium salts and salicylic acid is formed from sodium salts preferentially.
The Synthesis of Methoxylated Aromatic Carotenoids
Authors: Okukado Nobuhisa
Published: July 2006

Four methoxylated aromatic carotenoid derivatives (IVa–d) were prepared by the condensations of the ylids derived from the phosphonium salts (Ia–d) with didehydrocrocetindial (II) followed by partial hydrogenation of the acetylenic bond.
Functionalization of trans-Decalin. I. Synthesis of 1-Oxo-trans-decalin-4a, 6-carbolactone
Authors: Torii Sigeru , Kunitomi Tsuyosi , Okamoto Tsutomu
Published: July 2006

The synthesis of 4a-carbomethoxy-cis- and trans-Δ6-octalin-1-ones (2a and 2b), 4a-carboxy-trans-Δ6-octalin-1-one (3b), and 1-oxo-trans-decalin-4a,6-carbolactone (5) from the adduct of 3-carbomethoxy-2-cyclohexen-1-one with butadiene was described.
The Ion-exchange Behavior of Some Cations on Crystalline Zirconium Phosphate
Authors: Hasegawa Yoshitsugu , Tomita Isao
Published: July 2006

The distribution coefficients of Ag+, Tl+, K+, NH4+, Mg2+, Ca2+, Sr2+, Ba2+, Co2+, Zn2+, Y3+, and Ce3+ have been determined on a crystalline zirconium phosphate ion-exchanger in chloride solution media, and the affinity sequences are presented. pH titration curves and X-ray powder diffraction data were obtained for calcium and barium ions. The ion-exchange capacity of the exchanger for barium ions was found to be 4.4 meq/g, but the X-ray powder patterns were rather unusual as compared to those of other ions studied previously.
Metal Complexes of Amino Acids. VI. μ-l-Aspartato and μ-l-Glutamato Complexes of Cobalt(III)
Authors: Yasui Takaji , Kawaguchi Hiroshi , Kanda Zenjiro , Ama Tomoharu
Published: July 2006

Some binuclear and trinuclear complexes containing μ-l-aminocarboxylato ligands, (+)d- and (−)d-[en2-Co(OCOCH(NH2)(CH2)nCOO)Co(OH2)en2](ClO4)4, (+)d-[en2Co(OCOCH(NH2)(CH2)nCOO)Co(NH3)5]-(ClO4)4 and (+)d- and (−)d-[en2Co{(OCOCH(NH2)(CH2)nCOO)Co en2}2](ClO4)5 (n=1 for l-aspartato and n=2 for l-glutamato), have been newly prepared. The structure and vicinal CD effect of these complexes were discussed on the basis of their absorption, 13C NMR and CD spectra data. Their geometrical structures were assigned as cis to the μ-l-aminocarboxylato-OH2 binuclear complexes (with respect to the β-COO or γ-COO end of μ-aminocarboxylato bridge and the aquo ligand), and as trans to the di-μ-l-aminocarboxylato trinuclear complexes (with respect to the β-COO or γ-COO ends of two μ-aminocarboxylato bridges).
The Photo-Fries Rearrangement of Bis(methoxymethoxy)phenyl Cinnamates
Authors: Onodera Jun-ichi , Obara Heitaro
Published: July 2006

The irradiation of bis(methoxymethoxy)phenyl cinnamates in benzene solution gave 2′-hydroxy-bis(methoxymethoxy)chalcones in 5.4–7.6% yields and 2′,3′,4′-, 2′,3′,5′-, and 2′,4′,6′-trihydroxychalcone were obtained by the hydrolysis of the resulting chalcones.
Estimation of Chlorine Content in Single Crystals of Chromium Chalcogenide Spinels by Atomic Absorption Spectrophotometry
Authors: Ametani Kohei
Published: July 2006

Analyses using the silver atomic absorption indicated that all the crystals grown by the vapor transport method were contaminated with chlorine. Particularly in crystals containing copper, a large amount of chlorine was incorporated. In crystals with an intended composition CuCr2S3Cl, the chlorine content was much higher than the expected amount.
The One-electron Reduction of Carbonium Ions. VII. A Kinetic Study of the Reduction of the Aryl- and n-Alkyl-substituted Tropylium Ions with Cr(II)
Authors: Okamoto Kunio , Komatsu Koichi , Fujimori Masami , Yasuda Sumio
Published: July 2006

A series of substituted phenyltropylium (I) and n-alkyltropylium ions (II) has been synthesized, and the kinetic measurements for the one-electron reduction of these ions have been carried out with Cr(II) in 10% HCl at 25°C. A linear correlation is observed between the logk2 values, for I (X-C6H4-C7H6+, X=p-OH, p-OCH3, p-CH3, H, p-Cl, p-Br, p-CN, m-OCH3) and for II (CnH2n+1-C7H6+, n=0,1–6), and the transition energy of the charge-transfer band of these ions, with pyrene as a donor. In addition, the values of logk2 for I exhibit a good linear free-energy relationship with pKR+ and also with the σ -value (ρ=+1.31), but not with σ+. The n-alkyl group is shown to diminish the reducibility of the tropylium ion, and a slight alternation effect of the length of the n-alkyl chain on the K2’s is observed.
The One-electron Reduction of Carbonium Ions. VIII. The Reducibility of Hetero-substituted Tropylium Ions as Measured by the Competitive Reduction Method with Zinc Powder
Authors: Okamoto Kunio , Komatsu Koichi , Sakaguchi Osamu
Published: July 2006

A series of hetero-substituted tropylium salts (X-C7H6+·Y−), including three new compounds, have been synthesized. Their relative reactivities in one-electron reductions with zinc powder have been determined by the use of a competitive-reaction method, which gave the following reactivity sequence: CH3O-C7H6+ (krel.=0.0295), t-C4H9-C7H6+ (0.146), CH3S-C7H6+ (0.255), C7H7+ (1.00), C6H5-C7H6+ (2.50), (C6H5)3Si-C7H6+ (7.50), Cl-C7H6+ (16.8), CH3OCO-C7H6+ (35.7), NC-C7H6+ (163). The values of logkrel. for the t-C4H9−, H-, and C6H5-C7H6+ ions exhibit a good linear relationship with those of logk2 in the chromous-ion reduction. A linear correlation is also observed between logkrel. and the transition energy for the charge-transfer band of the respective cations, with pyrene as a donor. A plot of logkrel. against σp (for the ring substituent, X) gives a greater ρ-value (+4.0) than in the case of X-C6H4-C7H6+ (+1.31), reflecting the influence of the direct substitution on the tropylium ring.
Synthetic Photochemistry. IV. The Reaction of Betaines with Singlet Oxygen
Authors: Takeshita Hitoshi , Mori Akira , Ohta Shumei
Published: July 2006

Singlet oxygen was allowed to react with three 3-hydroxypyridine derivatives, I, II, and III, in order to investigate its general behavior toward dipolar substrates. The occurrence of an easy C=C cleavage process to give furanones (V and XI) through the dioxetones was a characteristic feature. In addition, maleimides (IV and IX), oxamates (VIII, XII and XIV), and a carbamate (XIII) were isolated as highly oxidized products.
The Structure of the Pechmann Condensation Product of p-Orsellinic Acid with Ethyl Acetoacetate
Authors: Hirata Toshifumi , Suga Takayuki
Published: July 2006

The product obtained by the Pechmanr condensation, followed by the decarboxylation, of p-orsellinic acid with ethyl acetoacetate has been established not to be such 4,5-dimethyl-7-hydroxycoumarin as previously reported, but to be 2,5-dimethyl-7-hydroxychromone.
Double Tridentate Complex of Triquinoyl with Boric Acid
Authors: Goto Toshio , Nagao Masanori
Published: July 2006

Triquinoyl forms with boric acid a strongly acid double-tridentate complex, dipotassium salt of which is almost insoluble in water. The formation of this complex supports dodecahydroxycyclohexane structure for triquinoyl.
The Stability of Inosine in Acid and in Alkali
Authors: Suzuki Yoshihisa
Published: July 2006

The rate constants of the decrease in inosine at several temperatures between 50 °C and 140 °C in water were determined over the pH range from 1 to 13. They can be expressed as a sum of four simultaneous bimolecular reactions. Their thermodynamic parameters were obtained.
Vopour-Liquid Equilibrium in the 2-Butanol–Water System and the Effect of Uranyl Nitrate
Authors: Yui Norio , Kurokawa Y\={o}ichi , Otsuki Hiroyuki
Published: July 2006

Vapour-liquid equilibrium have been investigated by a modified Randall’s method. The activities of solvent showed positive deviation from Raoult’s law. There was a sign of salting effect on 2-butanol by uranylnitrate hexahydrate.
The Reaction of α-Olefins and Epoxyalkanes with the Dimethyl Sulfide–Sulfur Trioxide Complex
Authors: Nagayama Masuzo , Okumura Osamu , Yaguchi Katsumi , Mori Akira
Published: July 2006

2-Dimethylsulfonioalkane-1-sulfonates were formed by the reaction of α-olefins with the dimethyl sulfide-sulfur trioxide complex. The treatment of these products with alkali gave Δ1-alkene-1-sulfonates quantitatively. In the reaction between 1,2-epoxyalkanes and the dimethyl sulfide-sulfur trioxide complex, 1-dimethylsulfoniomethyl-1-alkyl sulfate was formed exclusively. 1-Dimethylsulfonio-1-alkenes were quantitatively formed upon the treatment of these products with alkali. The chemical structures of these compounds have been established, and the reaction routes were discussed.
Fourier Analysis of AC Polarography. Elimination of Non-Faradaic Effects and Determination of Kinetic Parameters for Cd(II)-Na2SO4 System
Authors: Hirota Michio , Umezawa Yoshio , Kojima Hiroyuki , Fujiwara Shizuo
Published: July 2006

The on-line Fourier analysis of the AC polarographic current was found to give accurate results for electrode kinetics provided that the compensation of the iR drop and of the non-faradaic current was attained: The iR drop was compensated by a positive feedback technique. The charging current was cancelled by addition of a pseudo-charging current, inverse in phase to the former. Both the phase angles and amplitudes of the fundamental and second harmonic AC responses for the system of Pb(II) in 1M NaClO4 ([H+]=12 mM) agreed with theoretical prediction. As an illustration, the kinetic parameters of Cd(II)-1 n Na2SO4 system have been determined to be ks=(0.20±0.03) cm/s and α=0.30 (0.27<0.30<0.35) from the second harmonic AC polarogram.
A Polarographic Study of the Dissociation Reactions of the Ethylenediaminemonoacetatocobalt(II) (Co(II)-EDMA) and Ethylenediaminediacetatonickel(II) (Ni(II)-EDDA) Complexes
Authors: Kodama Mutsuo
Published: July 2006

The rates and the mechanisms of the dissociation reactions of the Co(II)-EDMA complex in a phosphate buffer solution and the Ni(II)-EDDA complex in an ethylenediaminediacetate solution were studied by analyzing their kinetic waves by means of conventional DC polarography. The dissociation of the Co(II)-EDMA complex gave this rate law: −d[Co(II)-EDMA]⁄dt=kp·[Co(edma)+]·[H2PO4]−. On the other hand, the dissociation of the Ni(II)-EDDA complex was found to proceed through a reaction mechanism which involves ligandolysis, corresponding to this rate law: −d[Ni(edda)0]⁄dt=k0×[Ni(edda)0]. On the basis of the relative rate constant, the detailed reaction mechanism was discussed. In the dissociation of the Co(II)-EDMA complex, the phosphate anion acts just as a proton donor. In the case of the Ni(II)-EDDA complex, the ligandolysis of the coordinated water has a profound effect on the dissociation rate of the edda2− anion from the nickel (II) ion.
The Amination and Dimerization of Norbornadiene with Nickel, Palladium, and Rhodium Complexes
Authors: Kiji Jitsuo , Nishimura Satoshi , Yoshikawa Susumu , Sasakawa Eiichi , Furukawa Junji
Published: July 2006

The reactions of norbornadiene in amine by the use of nickel, palladium and rhodium complexes have been studied in the presence of protic acid. A catalytic system of Ni(COD)2 (1)-n-Bu3P gives a mixture of 5-exo-(o-tolyl)-2-norbornene (3) and 5-exo-(N-amino)-2-norbornene (4). Bis(triphenylphosphine)(maleic anhydride)palladium (5) gives 3-(N-amino)nortricyclene (6). Dichlorotetrakis(cyclooctene)dirhodium (10) gives a [2+4] cycloaddition product (11). All these reactions mechanisms are discussed from the point of view of an acid-promoted reaction on low-valent transition metal complexes.
X-Ray Photoelectron Spectroscopic Study of the Reaction of Evaporated Iron, Nickel, and Palladium with Nitric Oxide
Authors: Kishi Kosaku , Ikeda Shigero
Published: July 2006

The reaction of the evaporated iron, nickel, and palladium with NO was investigated by X-ray photoelectron spectroscopy. On both iron and nickel larger part of NO dissociates to give two or more N(1s) and O(1s) photoelectron peaks which are ascribable to the surface oxide, nitride, and NO species. The proportion of these species is estimated roughly from the intensity ratios of the N(1s) and O(1s) peaks at 15 NO: 65 O: 20 N (iron) and 7 NO: 65 O: 28 N (nickel) when the metals are exposed to 5 Torr of NO gasfor 1 s, and 35 NO: 55 O: 10 N (iron) and 10 NO: 75 O: 15 N (nickel) when exposed to 10 Torr of NO for 10 min. On palladium the N(1s) for chemisorbed NO is observed. The N(1s) binding energies of the surface NO are compared with the N(1s) binding energies and the infrared NO frequencies of the corresponding transition metal nitrosyls.
The Equilibria for the Inosine–Calcium Hydroxide–Water and Inosine–Strontium Hydroxide–Water Systems
Authors: Suzuki Yoshihisa , Nomura Yasuichi
Published: July 2006

Solubility data have been obtained for the inosine–Ca(OH)2–H2O and inosine–Sr(OH)2–H2O systems at 10 °C. Three different solid phases of the calcium salt of inosine were found in the former system. The first is the normal hemi-calcium salt, (inosine) 2·Ca·2H2O; the second, an abnormal salt, (inosine)3·Ca·3H2O, and the third, another abnormal salt, (inosine)4·Ca·9H2O. The former two salts have stable regions in the system, while the last one does not. The system including Sr(OH)2 is simple, and no other salt-formation was found except for that of normal hemi-strontium salt, (inosine)2·Sr·2H2O. The X-ray powder diffraction data of the above four salts are given. The solubilities of the two normal hemi-alkaline-earth-metal salts of inosine in water were determined at 10—60 °C and formulated as follows:

Ca-salt, logS & = 0.00406·t - 0.4725

Sr-salt, logS & = 0.00551·t - 0.4116

where S represents the gram weight of anhydrous salt per 100 g of water.
The Electrodepositions of Copper and Nickel from Their Trifluoroacetate–N,N-Dimethylformamide Baths
Authors: Takei Tatsuko
Published: July 2006

This paper will deal with the electrodepositions of copper and nickel from Cu(CF3COO)2–HCON(CH3)2, Cu(CF3COO)2–HCON(CH3)2–citric acid, Ni(CF3COO)2–HCON(CH3)2, and Ni(CF3COO)2–HCON(CH3)2–additives baths. The properties of these baths and the mechanism of the electrodeposition of copper from the Cu(CF3COO)2–HCON(CH3)2–citric acid bath were studied. The solubility of Cu(CF3COO)2 in 100 g of HCON-(CH3)2 was 180 g at 20 °C. The specific conductances of the Cu(CF3COO)2–HCON(CH3)2 and Ni(CF3COO)2–HCON(CH3)2 baths were lower than those of the Cu(CF3COO)2–HCONH2 and Ni(CF3COO)2–HCONH2 baths. Cu2O was electrodeposited at the cathode, while copper was not easily obtained from the Cu(CF3COO)2–HCON(CH3)2 bath. By dissolving citric acid in the bath, copper electrodeposition was made easier. Bright and smooth copper deposits were obtained at current densities in the range of 2.0–11.0 A/dm2 from the Cu(CF3COO)2 500 g/l–HCON(CH3)2–citric acid 200 g/l bath at 60 °C, the current efficiencies for cathode and anode being about 75% and above 100% respectively. The cross-section of the copper deposits showed that the deposits have a granular structure. The rate of the electrodeposition of copper from the Cu(CF3COO)2–HCON(CH3)2–citric acid 200 g/l bath at current densities ranging from 1.0 to 3.5 A/dm2 was found to be controlled by the charge–transfer reaction. A black powder nickel deposit was obtained from the Ni(CF3COO)2–HCON(CH3)2 bath. By dissolving NH4Cl, H3BO3, sulfamic acid or CCl3COOH in the bath, adherent bright and smooth nickel deposits were obtained. While the cathode current efficiency was lower in the bath containing sulfamic acid, the anode current efficiency was lower in the bath containing H3BO3 or CCl3COOH. NH4Cl and AlCl3 have the disadvantage that they are dissolved in HCON(CH3)2 only with difficulty. Since the bond between the metallic ion and the solvent in the HCON(CH3)2 bath is stronger than that in the HCONH2 bath, and since dielectric constant of the solvent in the former is lower than that in the latter, metal electrodeposition from the former is more difficult.
Polarographic Behavior of Glycol Dimercaptoacetate
Authors: Saxena R S , Bhatia S K
Published: July 2006

Polarographic behaviour of glycol dimercaptoacetate has been studied in 25% ethanol at d.m.e. in the pH range 1.56–11.56 in presence of 0.1 M KNO3. In the acidic media, the current-voltage curves consist of three waves; a prewave due to the adsorption of anodic reaction product at the mercury drop surface, main anodic wave due to the electroxidation of –SH groups and a third wave at more positive potential due to the insoluble film formation on the electrode surface whose solubility depends on pH of the solution. In the alkaline media only two waves, a prewave and the main anodic wave, are observed. The effects of various factors such as different buffer, Hg-pressure, temperature, ethanol and depolarizer concentrations on the wave characteristics have been investigated. The electrode reaction is irreversible at higher pH but in acid media it is reversible and diffusion controlled involving a two electron transfer process, with the formation of (Remark: Graphics omitted.) complex. The overall dissociation constant (pK) of the sulphydryl groups has been found to be 8.20 at 20 °C. At pH 4.80, the maximum number of moles adsorbed on unit area is 6.83×10−10mol/cm2  i.e. 4.12×1014 molecule/ cm2. Adsorption coefficient and molar adsorption energy are calculated to be 1.445×104 and 31.2 kcal/gm mol respectively. The respective values of kinetic parameters, viz. transfer coefficient (α) and formal rate constant (K°b.h) for the irreversible wave at pH 11.56 are 0.76 and 2.6×10−9 cm/s.
Application of Chemical Reactions of Thin-Layer Chromatoplates. III. Monoterpenes
Authors: El-Garby Younes M , Mokhtar A
Published: July 2006

Some characteristic reactions of monoterpenoids were carried out on inert thin-layer chromatoplates under controlled conditions and the products of the reactions were compared with the expected substances on the same chromatogram. The reactions performed were: acetylation at 40 °C on silica gel and on alumina plates, saponification on silica gel and on alumina chromatoplates, benzoylation at 0 °C, dehydration with thionyl chloride, oxidation with chromium trioxide in acetic acid and in dry pyridine, formation of 2,4-dinitrophenylhydrazone derivatives, chloride formation, reduction with lithium aluminium hydride, reaction of p-toluenesulphonyl chloride with some monoterpene alcohols and a modified Clemmensen reaction on monoterpene ketones.
Ionization Potentials of Radicals as Determined by the Unrestricted MINDO/2 Method
Authors: Ichikawa Hiroshi , Ogata Michihiko
Published: July 2006

The parametrization in the MINDO/2 theory has been applied to the unrestricted Hartree-Fock method to give the appropriate ionization potentials of various radicals.
Blue-colored Matter Appearing in an Alkaline Solution of Benzoin and Benzil in Aqueous Dimethyl Sulfoxide
Authors: Abe Takehiro , Iwaizumi Masamoto
Published: July 2006

Blue-colored matter appearing in the alkaline solution of benzoin and benzil in aqueous dimethyl sulfoxide (DMSO) was confirmed to be a benzil anion-radical by visible and ESR spectroscopy.
Isomerization of 2-Pinene over Monohydrates of Metal Sulfates
Authors: Ohnishi Ryuichiro , Matsui Akira , Tanabe Kozo
Published: July 2006

Catalytic activity of the monohydrates of various metal sulfates for the isomerization of 2-pinene was found to be related to the infrared wave numbers of the rocking mode of the water of crystallization and the transition temperatures from the monohydrates to the anhydrates, but not to the electronegativity of metal ions.
The Crystal Structure of dl-Bi-1,4-dioxanyl
Authors: Furusaki Akio , Misumi Shunjiro , Matsumoto Takeshi
Published: July 2006

The two forms of bi-1,4-dioxanyl (mp 157.5–158.0 °C and 133.5–134.0 °C), obtained by the photochemical reaction of 1,4-dioxane with acetophenone, have been assigned unequivocally to the meso and dl forms respectively by the X-ray method.
A Study on the Hydrolysis of Cadmium Ion in Aqueous 3M (Li)ClO4 Solution
Authors: Matsui Haruo , Ohtaki Hitoshi
Published: July 2006

The equilibrium constants of hydrolytic reactions of cadmium ion have been determined in a 3M (Li)ClO4 aqueous medium at 25 °C as follows: log*β1,1=−10.3±0.1 and log*β1,2=−9.13±0.01.
O–H Stretching Absorption and Conformation of the β-Methyl Derivatives of 1-Tetralol, 4-Chromanol, 4-Thiochromanol, and 4-Thiochromanol 1,1-Dioxide
Authors: Hanaya Kaoru , Onodera Shinji , Kudo Hideaki
Published: July 2006

The conformation of eight benzyl alcohol derivatives has been examined by the measurements of OH stretching absorptions. Preference of the OH quasiaxial structure was shown.
The Determination of Ruthenium in a Sulfuric Acid Solution by Atomic Absorption Spectrophotometry
Authors: Iwata Reiko , Ogata Ikuei
Published: July 2006

The addition of sodium salts was found to make possible the determination of ruthenium in a sulfuric acid solution by atomic-absorption spectroscopy, something which is usually impossible because of the serious depressive interference of sulfuric acid.
Synthesis of 2,3,6-Trimethylbenzyl Alcohol
Authors: Kawai Tadashi , Yamazaki Yasuo , Yuhashi Shuei
Published: July 2006

2,3,6-Trimethylbenzyl alcohol was prepared by the Cannizzaro reaction of 2,3,6-trimethylbenzaldehyde; mp 83–85 °C. It was found that the substance regarded by Golivets et al. as 2,3,6-trimethylbenzyl alcohol is an eutectic mixture of 2,3,6- and 2,4,5-trimethylbenzyl alcohol.
The Photochemistry of 3,3-Dialkoxy-1-phenylpropan-1-ones
Authors: Nishio Takehiko , Aoyama Hiromu
Published: July 2006

The irradiation of 3,3-dialkoxy-1-phenylpropan-1-ones (Ia-b) in a benzene solution afforded β-ketoesters (IIa-b), phenyl β-alkoxyvinyl ketones (IIIa-b), and tetrahydrofuranols (IVa-b).
Reaction of Polymethylbenzyl Cyanides with Fuming Nitric Acid. A New Route to Polysubstituted 3-Isochromanone Synthesis
Authors: Suzuki Hitomi , Hanafusa Terukiyo
Published: July 2006

Treatment of pentamethylbenzyl cyanide and bis(cyanomethyl)tetramethylbenzenes with fuming nitric acid in dichloromethane led to the regiospecific nitrooxylation of the methyl group adjacent to the cyanomethyl group, giving the corresponding benzyl nitrates in good yields. On acid hydrolysis, these nitrates were readily converted into 3-isochromanone derivatives.
The Preparation of 1,5-Diaryl-3-Phenylsulfonylformazans from Phenylsulfonylacetarylamides and Their Arylazo Derivatives
Authors: Sami Shawali A , Elansari A L
Published: July 2006

Azo coupling of phenylsulfonylacetarylamides(I) in presence of NaOAc gives the hydrazones (II). In presence of NaOH (and not NaOAc) both I and II couple with diazonium salts to give the formazans (III), mechanism is suggested for the formation of III.
The Photoionization of Molecular and Crystalline Anthracene
Authors: Aihara Jun-ichi , Inokuchi Hiroo
Published: July 2006

The photoionization efficiency curve of gaseous anthracene was examined by comparing it with the photoemission yield curve of solid anthracene. The direct ionization processes were found to dominate the two curves primarily. Some σ-valence orbitals of this compound were associated with considerably low ionization potentials. The cube law for the photoemission yield near the threshold was also established.
Optically-active Vibrations and Elastic Constants of Calcite and Aragonite
Authors: Yamamoto Akio , Shiro Yuji , Murata Hiromu
Published: July 2006

Treatments of the normal coordinate and the elastic constant were undertaken for two calcium carbonate crystals. By the use of the least-squares technique, we obtained sets of the force constants which reproduce satisfactorily both the observed vibrational frequencies and the macroscopic elastic constants. The intermolecular interactions, the elastic strains of the internal coordinates, and the nature of the splitting of the normal frequencies in these crystals were briefly discussed.
The Electrochemical Reduction of Purine in Nonaqueous Solvents
Authors: Yao Toshio , Musha S\={o}ichir\={o}
Published: July 2006

The electrochemical reduction of purine, which is the model compound for the reduction of the biologically-important purine bases, has been investigated in nonaqueous solvents (acetonitrile and DMF) by polarography, cyclic voltammetry, controlled potential electrolysis, and the ESR technique. In neutral solutions, purine is initially reduced in a one-electron, diffusion-controlled process at a fairly negative potential to produce an unstable radical anion, which then abstracts a proton from the parent purine to produce a free radical and an electro-inactive purine anion. The free radical is quickly deactivated by fast dimerization to form a purine dimer and by a further one-electron reduction to produce, ultimately, 1,6-dihydropurine. The addition of various acids to purine solutions results in the appearance of a new, drawn-out wave at a more positive potential than the original purine reduction wave, which is attributed to the two-electron reduction of N-protonated purine species to produce 1,6-dihydropurine.
Synthesis of Nε-Hydroxy-l-lysine
Authors: Isowa Yoshikazu , Ohmori Muneki
Published: July 2006

Optically active Nε-hydroxy-l-lysine monohydrochloride (l-I·HCl) was synthesized from Nε-tosyl-Nε-benzyloxy-l-lysine (l-II) obtained by the procedure employed for the preparation of Nδ-tosyl-Nδ-benzyloxy-l-ornithine. Removal of the protecting groups of l-II was carried out by the following two methods: a) treatment of l-II with boron tris(trifluoroacetate) in trifluoroacetic acid gave l-I in one step, which was isolated as 2-nitroindane-l,3-dione salt; b) deprotection of l-II via  Nε-benzyloxy-l-lysine (l-VIII), detosylation with hydrogen bromide in acetic acid and phenol, followed by debenzylation with hydrogenolysis, gave l-I·HCl having properties identical with those of the natural product obtained from mycobactine.
Studies of Acyl and Thioacyl Isocyanates. XIV. The Reactions of Benzoyl and Thiobenzoyl Isocyanates with Hydrazones
Authors: Tsuge Otohiko , Kanemasa Shuji
Published: July 2006

Benzoyl (1) and thiobenzoyl isocyanates (2) reacted with benzaldehyde arylhydrazones and methylhydrazone to give the corresponding semicarbazones as isolated products respectively. In the reactions with acetone arylhydrazones and methylhydrazone, however, the s-triazolidin-5-ones whose structures corresponded to the ring tautomers of semicarbazones, were isolated as sole products from the reaction of 1, and 2 afforded the (4+2) cycloadducts of 2 to the C=N bond of hydrazones and s-triazolidin-5-ones. It has been found that in some cases, the semicarbazones isomerize into their ring tautomers, and the isomerization obeys good first-order kinetics taking into account the equilibrium. Although 1 did not react with p-tosyl- and benzoylhydrazones, 2 easily added to both hydrazones to yield the corresponding (4+2) cycloadducts.
The Crystal and Molecular Structure of Tyramine Hydrochloride
Authors: Tamura Kyoko , Wakahara Akio , Fujiwara Takaji , Tomita Ken-ichi
Published: July 2006

The structure of tyramine hydrochloride has been determined by X-ray diffraction method using the data collected by counter diffractometer techniques. Crystals are orthorhombic, with space group Pbcn, Z=8, a=19.961, b=10.756, and c=8.243 Å. The structure was solved by the direct method with the symbolic addition procedure, and refined by least-squares method. The atoms constituting the tyramine cation lie on the two planes, that is, that of the phenol ring and that of the extended side chain. The dihedral angle between these two planes is 71°. The extended conformation about the C–C bond of aminoethyl group is such that the NH3+ group is trans with respect to the phenol ring. Half-weighted two independent chlorine ions are found on the two-fold axis with distance of 4.5 Å, having some different modes of hydrogen-bonding system for these two ions.
Superacids and Their Derivatives. V. Kinetics and Mechanism of the Cationic Polymerization of 3,3-Bis(chloromethyl)oxacyclobutane Initiated by Ethyl Trifluoromethanesulfonate. Evidence for Ester Type Propagating Species
Authors: Kobayashi Shiro , Danda Hidenori , Saegusa Takeo
Published: July 2006

Kinetic analysis of the cationic ring-opening polymerization of 3,3-bis(chloromethyl)oxacyclobutane (BCMO) initiated by ethyl trifluoromethanesulfonate (EtOSO2CF3) was carried out by direct determination of the instantaneous concentrations of monomer, initiator, and propagating species by means of 1H and 19F NMR spectroscopy. It was established that the polymerization of BCMO proceeds via an ester type propagating species (4). The propagating species of the first (P1*) and subsequent propagations (Pn*, n≥2) were directly observed. The rate constants of initiation (ki) and propagations of the first (kp1), second (kp2) and subsequent steps (kpn, n≥3) were determined. Activation parameters as well as the solvent effect supported the proposed mechanism, in which the rate-determining step is a dipole-dipole reaction between monomer and propagating ester species to form the intermediate cyclic oxonium ions (7, 8, and 10) as unstable transient species.
Preparation of Diethylaluminium Chelates, R2P(S)–X–AlEt2(X=NMe, S) and Some Reactions with Carbonyl Compounds
Authors: Urata Kouichi , Yogo Toshinobu , Itoh Kenji , Ishii Yoshio
Published: July 2006

New monomeric organoaluminium chelate compounds; N-diethylaluminium N-methyl dialkylthiophosphinic amide and dialkyldithiophosphinate; R2P(S)–X–AlEt2 (X=NMe, S), were prepared. Spectroscopic results of these compounds indicate an intramolecular coordination of sulfur atom of P=S bond to the organoaluminium moiety. Addition reactions of Me2P(S)–NMe–AlEt2 and Et2P(S)–S–AlEt2 with phenyl isocyanate gave the corresponding 1/1 adducts and only small amount of elimination product was obtained. A reaction of Me2P(S)–NMe–AlEt2 with benzaldehyde gave Me2P(S)–NMe–CH(Et)Ph and PhCH=NMe (by two ways of addition-elimination).
Synthesis of Sequential Polypeptides of l-Leucine and Glycine
Authors: Iio Takayoshi , Takahashi Sho
Published: July 2006

The following sequential polypetides of l-leucine and glycine were synthesized: (Leu3Gly)n, (Leu2Gly)n, (LeuGly)n, and (LeuGly2)n. Polymerization was achieved by self-condensation of the corresponding peptide p-nitrophenyl esters. Hydrolysis of the polypeptides were carried out in 90% aqueous trifluoroacetic acid and the time course of liberation of leucine from each polymer was presented. Apparent first-order rate constants (×102), 1.93, 2.86, 2.91, and 4.4 hr−1 were obtained for liberation of leucine from (Leu3Gly)n, (Leu2Gly)n, (LeuGly)n, and (LeuGly2)n, respectively.
The Synthesis of 1,3,4-Benzotriazepin-5-one Derivatives from Isatoic Anhydrides
Authors: Takahashi Masahiko , Onizawa Saburo , Satoh Tomonobu
Published: July 2006

The reaction of isatoic anhydrides (1) with 2-pyridylamidrazone afforded N-(2-aminophenyl)-2-pyridylamidrazones (2), which were then cyclized with acid to 1,3,4-benzotriazepin-5-one derivatives (3). The treatment of isatoic anhydride with 2-pyridylcarbonohydrazide gave 1-(2-aminophenyl)-2-(2-pyridinecarbonyl)-hydrazine (5), which was then dehydrated with polyphosphoric acid to 3-(2-aminophenyl)-5-(2-pyridyl)-1,3,4-oxadiazole (6), but not to 3.
The Synthesis and Oxidation of 4-(N-Arylmethylideneamino)-2,6-di-t-butylphenols
Authors: Manda Eiichiro
Published: July 2006

4-(N-Arylmethylideneamino)-2,6-t-butylphenols (I) were synthesized through the condensation of 4-amino-2,6-di-t-butylphenol hydrochloride and arylaldehydes, and the infrared and electronic spectra of phenols (I) were discussed. The oxidation of phenol (I) with lead dioxide gave a stable phenoxyl radical (II) in solution, and 4,4′-bis[4-(N-arylmethylideneamino)-2,6-di-t-butyl-2,5-cyclohexadien-1-one] (III) was isolated as a crystalline oxadation product, which was in equilibrium with the radical (II) in solution.
Fragmentations in Doubly Charged Ion Mass Spectra of Aromatic Carbonyl Compounds
Authors: Sakurai Hiroshi , Tatematsu Akira , Nakata Hisao
Published: July 2006

2E Doubly charged ion mass spectra of forty-six aromatic carbonyl compounds were determined. The spectra are quite different from those of singly charged ions. Several characteristic fragmentations including a novel [M–CO] peak are discussed. It is suggested that certain isomer pairs can be differentiated by comparing these spectra even when their conventional spectra are almost identical.
Isotope Effects in the Reactions of 80Br Activated by Isomeric Transition with Various Deuterated Propanes
Authors: Tachikawa Enzo , Numakura Kenshi
Published: July 2006

Product studies of the reactions of recoil 80Br with propanes in binary mixtures with ethane showed that the difference in the energy-loss efficiency of C3H8 and C3D8 in collision with 80Br was less than 10%. Then, the yields for the substitution of 80Br for atoms or groups have been compared in various deuterated propanes. A reactivity integral-isotope effect has been observed in the yields of products from CD3CD2CD3 and CD3CH2CD3, except in the case of isopropyl bromide from the latter compound. However, it has been observed only in the yield of iso propyl bromide from CH3CD2CH3. These results indicate that the chemical and physical properties of both replaced and residual atoms or groups play a role in the observed isotope effects. With a “complex” formation mechanism, it is suggested that an isotope effect appears mostly when the kinetic energy of the reacting 80Br is at the lower-energy end of the reaction-energy range.
The Surface Activity of Tetra-n-alkylammonium Halides in Aqueous Solutions. The Effect of Hydrophobic Hydration
Authors: Tamaki Kunio
Published: July 2006

Surface tensions are reported for aqueous solutions of a series of homologous tetra-n-alkylammonium chlorides, bromides, and iodides (R4NX) at 25 °C, and the experimental results are discussed with particular reference to the bulk properties of these salts in water. It is found that Me4NX salts are surface inactive in aqueous solutions and that they may be classified as simple salts. On the other hand, it is found that Et4NX and higher homologous salts are surface active in aqueous solutions and that the surface activity increases with the number of carbon atoms in the alkyl chains; thus, they are hydrophobic structure-makers in the water phase. The surface tensions for aqueous solutions of Me4NX salts are only slightly dependent on the kind of counter-ion, such as Cl−, Br−, and I−. In the cases of Et4NX, Pr4NX, and Bu4NX salts, the effectiveness of the anions for the same cation on the surface activity increases progressively in this order: I−>Br−>Cl−.
Contribution of d Orbitals in SiH SiH2, SiH3, and SiH4
Authors: Higuchi Jiro , Kubota Shozo , Kumamoto Toshio , Tokue Ikuo
Published: July 2006

Semi-empirical calculations have been carried out for SiHn (n=1, 2, 3, and 4) adopting the electron pair bond approximation using hybrid orbitals with d orbitals of Si determined by minimizing the energy of each ground state. The results are satisfactory as a whole for explaining the experimental data of these molecules. The contribution of d orbitals obtained is not very large, but it is important in discussing the energy levels and molecular structures of some low-lying electronic states. It is also shown that the maximum overlap method is not always adequate in determining hybrid orbitals including d orbitals.
Reactions of π-Allylic Palladium(II) Complexes of Acetoacetate Esters with Pyridine and Its Derivatives
Authors: Baba Shigeru , Sobata Tamotsu , Ogura Tetsuya , Kawaguchi Shinichi
Published: July 2006

The π-allylic palladium(II) complexes of ethyl and benzyl acetoacetate esters react with pyridine and its derivatives to afford the terminal-carbon-bonded complexes PdCl(CH2COCH2COOCH2R)L2, where R=CH3 or C6H5, and L=pyridine or its derivative. The NMR spectra unequivocally establish the bonding type in these complexes. The pyridine and 4-methylpyridine complexes are a mixture of cis and trans isomers in a ratio of 1: 5, while 2-methyl- and 2,6-dimethyl-pyridine complexes are trans exclusively. The relative stabilities of these complexes are compared.
Stereoselectivity in the Formation of Oxalato-l-aspartatoethylenediaminecobalt(III) Complex
Authors: Takeuchi Mitsuaki , Shibata Muraji
Published: July 2006

The complex [Co(ox)(l-aspH)(en)] has been prepared by the reaction of the dioxalatoethylenediaminecobalt-(III) complex with l-aspartic acid and separated into four diastereoisomers by means of ion-exchange chromatography: mer-Δ-, mer-Λ- and facΔ-[Coox(l-aspH)en]·H2O, and facΛ-[Coox(l-aspH)en]·2.5H2O. They were characterized by their absorption, CD and PMR spectra. Stereoselectivity has been found in the mer-Δ and fac-Λ isomers with degrees exceeding 80%. Related isomeric complexes containing l-glutamate or l-leucinate ion in place of l-aspartate have also been investigated, much less selectivity (∼60%) being observed.
Formation of Alkyl Radicals by Photoionization of Alcohol Radicals Trapped in Glassy Matrices
Authors: Shiotani Masaru , Chachaty Claude
Published: July 2006

Experiments were carried out in order to elucidate the formation mechanism of C2H5 · radicals formed by the UV irradiation (250<λ<350 nm) of CH3\dotCHOH radicals. The kinetics of the formation of the C2H5· radical was examined by means of ESR in neutral, acidic, and alkaline ethanol glasses at 77 K. The initial rate of the formation of C2H5· was nearly independent of the concentration of added acid (H2SO4), but it decreased sharply with that of added NaOH. Moreover, the limiting yield of C2H5· decreased with the concentrations of both the acid and the base. Our experimental results suggest that the C2H5· radicals are formed by this reaction:

C_2H_5OH_2^++e^-→C_2H_5·+H_2O

The C2H5OH2+ ion and the electron result from the photoionization of CH3\dotCHOH radicals according to these reactions:

& CH_3\dotCHOH\xrightarrowhv(CH_3CHOH)^++e^-

& (CH_3CHOH)^++C_2H_5OH→CH_3CHO+C_2H_5OH_2^+
Reactions of Methylcalcium Iodide. II. Carboxylation, Metalation, and Metal-Halogen Exchange Reactions
Authors: Kawabata Nariyoshi , Yoshimura Hirotsugu , Yamashita Shinzo
Published: July 2006

Utility of methylcalcium iodide in several organic reactions in tetrahydrofuran was shown. Carboxylation of methylcalcium iodide at −70 °C gave acetic acid in 57–63% yield. Metallation of indene and fluorene by methylcalcium iodide at −30 °C gave 3-indenyl- and 9-fluorenylcalcium iodides in 99 and 93% yields, respectively. Metal-halogen exchange reactions of methylcalcium iodide with halobenzenes were rather slow.
Kinetic Studies on the Selenization of Silver
Authors: Mizusaki Jun-ichiro , Fueki Kazuo , Mukaibo Takashi
Published: July 2006

In order to elucidate the kinetics of selenization of silver by liquid selenium, the Ag/Ag2Se interface reaction rate, the ionic conductivity of Ag+ in Ag2Se layer, the Ag2Se/Se(1) interface reaction rate, and the over-all reaction rate were determined. The Ag/Ag2Se interface reaction rate was found to be given by

υ=1.6×10^9{exp(-32300/RT)}(a_Se) eqv cm^-2·s^-1

The following mechanism was proposed for the interface reaction.

2Ag(Ag)+Se(Ag_2Se)→2Ag^+(Ag_2Se)+Se^2-(Ag_2Se)

It was found that the driving force of the Ag2Se/Se(1) interface reaction is very small and Ag2Se is in equilibrium with Se(1). On an assumption that the over-all reaction is controlled by both the Ag/Ag2Se interface reaction and the diffusion of Ag+ in Ag2Se, the over-all reaction rates were calculated. The results agree with the observed ones.
MCNDO/2 Calculation of the Radiative Lifetimes of the Triplet States of the Nucleic Acid Bases
Authors: Kamiya Mamoru , Akahori Yukio
Published: July 2006

The radiative lifetimes of the lowest excited triplet states of the nucleic acid bases were calculated using a first-order perturbation treatment of the spin-orbit coupling. The calculated lifetimes were in the sequence of pyrimidines>purines; that of thymine was found to be largest. The relation between the radiative lifetimes and biological photo-deactivation was discussed.
The Dipole Moment of Benzaldehyde
Authors: Kawashima Yoshiyuki , Kozima Kunio
Published: July 2006

The dipole moment and its components along the principal axes were determined by measuring the Stark effects of the rotational transitions. The most probable direction of the moment was discussed.
The ESR of Alkyl Phenyl Nitroxide Radicals Studied as Hindered Rotation
Authors: Nishikawa Toshio , Someno Kazuo
Published: July 2006

The ESR spectra were obtained in the series of N-methyl, N-ethyl, N-n-propyl, N-isopropyl, N-n-butyl, and N-tert-butyl phenyl nitroxide radicals. Two tendencies were found in the hyperfine splitting constants and were explained as hindered rotation.
The Spectrophotometric Determination of Boron in Condensed Water from Fumaroles
Authors: Isozaki Akinori , Utsumi Satori
Published: July 2006

A simple and accurate spectrophotometric method for determining boron in condensed water from fumaroles has been developed. The proposed method is based on the methylene blue-tetrafluoroborate ion pair. It was possible to determine micro amounts of boron with satisfactory results without any interference of foreign ions.
The Alkylation of m-Cresol with Propylene by Supported Metal Sulfates
Authors: Nitta Masahiro , Yamaguchi Katsumi , Aomura Kazuo
Published: July 2006

The alkylation of m-cresol with propylene over supported metal sulfate catalysts was studied at 250 °C under atmospheric pressure. The activity of the catalyst varied with the kind of sulfate and the calcination temperature, whereas the selectivity to thymol was independent of those factors and depended on the type of carrier instead.
Pyrolysis of Dialkyl 2-Acyloxyalkylphosphonates
Authors: Okamoto Yoshiki , Kawai Toshikazu , Sakurai Hiroshi
Published: July 2006

The pyrolysis of dialkyl 2-acyloxyalkylphosphonates at 220–240 °C gave the corresponding alkyl carboxylates and olefins by the elimination of metaphosphoric acid (HPO3)n.
Metal Phosphinylides and Phosphinothioylides. III. Reactions of Lithium Diphenylphosphinylide and Diphenylphosphinothioylide with Acetone and Bromoacetone
Authors: Yoshifuji Masaaki , Gomi Hideyuki , Inamoto Naoki
Published: July 2006

Reaction of acetone with [Ph2PO]Li gave 1-hydroxy-1-methylethyl- (2a), 1,1-dimethyl-3-oxobutyldiphenylphosphine oxides (3a) and 2,6-bis(diphenylphosphinyl)-2,6-dimethylheptan-4-one (4a). The corresponding sulfide 2b was obtained in the case of Ph2P(S)H, and 3b and 4b in the case of [Ph2PS]Li (5b). Bromoacetone reacted with 5b through substitution reaction.
The Reaction of Several o-Methoxy Aromatic Aldehydes with Ethylthioxide. Novel Substitution and Condensation
Authors: Iwata Masaaki , Emoto Sakae
Published: July 2006

The reaction of o- and p-anisaldehyde with potassium ethylthioxide in diglyme at 90–120 °C gave the corresponding demethylated products, while 2,6-dimethoxy-benzaldehyde and 9-(2-p-cymenyl)-2-methoxy-1-anthralde-hyde afforded two novel condensation and substitution products, VII and VI respectively.
The Application of an MC-SCF Theory to Organic Chemical Reactions
Authors: Kikuchi Osamu , Aoki Katsutoshi
Published: July 2006

MC-SCF equations have been derived with the help of Segal’s partition-basis-set technique; these equations can be used for the calculation of the potential curves of many organic reactions. They were applied to two typical organic reactions, and the results were compared with those obtained by CI methods. The corrections of the SCF-CI energies by the MC-SCF procedure were small for the present system.
Charge-Transfer Transitions Associated with Tricyanovinyl Aromatics
Authors: Sasaki Akira , Aihara Jun-ichi , Matsunaga Yoshio
Published: July 2006

Four tricyanovinyl aromatic compounds were spectroscopically investigated in various phases. The solidstate spectra distinctly display both intra- and inter-molecular charge-transfer bands in the visible region. The formation of the charge-transfer self-complex is, however, markedly hindered in the fluid phases. The dual charge-transfer properties were also examined for these compounds.
The Infrared Intensities of Stretching Fundamentals in Gaseous and Crystalline Cyanoacetylene
Authors: Uyemura Masakatsu , Maeda Shiro
Published: July 2006

The absolute intensities of the stretching fundamentals of cyanoacetylene and cyanoacetylene-d were measured in gaseous and crystalline (77 K) states. As had been expected from the previous result for hydrogen cyanide, a striking intensity increase upon crystallization was observed not only for νCh(Cd) also for the other fundamentals. The observed intensities were reduced to dipole-moment derivative with respect to the internal coordinates, ∂μ⁄∂r. Then, by taking advantage of the strictly linear geometry of hydrogen-bonded chains in the crystals, it was demonstrated that the derivative with respect to the hydrogen-bonded distance, [∂μ⁄∂rN···H], was primarily responsible for the remarkable change in ∂μ⁄∂r; this was in accordance with the previous conclusion for hydrogen cyanide. A discrepancy from this view which appeared for ∂μ⁄∂r3 was interpreted as being mainly caused by the vibronic behavior of π-electrons.
Deuterium Isotope Effects on the Redex Decomposition of Hydroxymercurated Propene and 2-Butenes in an Aqueous Solution
Authors: Shinoda Sumio , Saito Yasukazu
Published: July 2006

Kinetic deuterium isotope effects on the redox decomposition of hydroxymercurated propene, cis-, and trans-2-butenes in an aqueous solution (CH3CH(OH)CHRHg+→CH3COCH2R+Hg(0)+H+; R=H, CH3) were determined by following the reaction in situ by means of PMR spectroscopy. Taking advantage of the PMR characteristics, the identity of the reaction conditions was confirmed by comparing the rates for the reactant mixtures (e.g., CH3CH(OH)CH2Hg++CH3CD(OH)CH2Hg+). The mercurials, deuterated on either β-carbon (CH3CD(OH)CH2Hg+, CH3CD(OH)CHCH3Hg+) or α-carbon (CH3CH(OH)CDHHg+, CH3CH(OH)CDCH3Hg+), gave primary and secondary deuterium isotope effects of 1.35–1.40 and 1.17–1.19 respectively. A possible structure of the activated complex was proposed in accord with the observed nature of the intramolecular hydrogen shift.