bluuebunny/crossref_metadata_2025 huggingface dataset:
The Synthesis of Several Dipivaloylpolymethylbenzenes
Authors: Suzuki Hitomi , Aomori Yasuo , Mishina Tadashi , Hanafusa Terukiyo
Published: July 2006

2,4-Dipivaloyl-1,3,5-trimethylbenzene, 4,6-dipivaloyl-1,2,3,5-tetramethylbenzene, and 3,6-dipivaloyl-1,2,4,5-tetramethylbenzene were prepared by the Friedel-Grafts dipropionylation of the corresponding polymethylbenzenes, followed by the exhaustive methylation of the resulting diketones with potassium t-butoxide and methyl iodide in boiling benzene-t-butyl alcohol. The PMR and IR spectra are reported for these new compounds.
The Sesquiterpenes of Dendropanax trifidus
Authors: Yoshihara Kazuo , Hirose Yoshio
Published: July 2006

The volatile oils of the leaves, cortex and fruits of Dendropanax trifidus were investigated. Germacrene-D is enantiomeric, sesquiterpenes of other series, such as caryophyllene and selinenes, optically corresponding to those in higher plants.
Transformation of o-Nitrobenzenes to Quinolines with Tetracarbonylhydridoferrate
Authors: Watanabe Yoshihisa , Takatsuki Kunihiko , Shim Sang Chul , Mitsudo Take-aki , Takegami Yoshinobu
Published: July 2006

Condensates of o-nitrobenzaldehyde with carbonyl compounds are reduced with tetracarbonylhydridoferrate under mild conditions to give quinolines in good yields.
The Preparation of Isoxazole Derivatives from a Nitro Sugar with Dimethylsulfonium Phenacylide
Authors: Sakakibara Tohru , Sudoh Rokuro
Published: July 2006

The reaction of methyl 4,6-O-benzylidene-2,3-dideoxy-3-nitro-α-d-erythro-hex-2-enopyranoside or 5-benzoyl (methyl 4,6-O-benzylidene-2,3-dideoxy-α-d-erythro-hexopyranosido)[3,2-c]isoxazoline N-oxide with dimethylsulfonium phenacylide gave 5-benzoyl-3-(1,3-O-benzylidene-d-erythro-glyceryl)-4-isoxazolecarbaldehyde in a fairly good yield.
Racemization during the Synthesis of Histidine-containing Peptides
Authors: Terada Shigeyuki , Kawabata Akira , Mitsuyasu Nobuo , Aoyagi Haruhiko , Izumiya Nobuo
Published: July 2006

A convenient test for racemization using an amino acid analyzer was developed and applied to examine the effects of several im-protecting groups and synthesis of histidyl peptides.
An Additional Discussion of the Micropore-volume Determination of Active Carbon Using Dubinin-Radushkevich Plots
Authors: Tsunoda Ryoichi
Published: July 2006

The validity of the recently presented method for determining the micropore volume (V0) from the distribution curve of the adsorption potential based on the Dubinin-Radushkevich plot is further discussed in terms of the relationship between the V0 and the adsorption volume (Vh) at the beginning of the hysteresis loop on the adsorption isotherm.
The Photoreaction of 1-Cycloalkenyl Phenethyl Ketone
Authors: Tada Masaru , Saiki Hiroshi , Mizutani Hidemi , Miura Kyo
Published: July 2006

The UV irradiation of 1-cyclopentenyl phenethyl ketone in benzene or methanol gave a cyclobutane derivative. The irradiation of 1-cyclohexenyl phenethyl ketone in methanol or in benzene containing either BF3–Et2O or CF3COOH gave a cycloheptanone derivative. The formation of the cycloheptanone derivative requires an acid catalyst.
Depolarized Rayleigh Wings of the Liquids and Solutions of Some Symmetric Top Molecules
Authors: Kamogawa Keiji
Published: July 2006

Spectra of depolarized Rayleigh wings were observed for the liquids and CCl4 solutions of C6H6, CH3CN, and CHCl3. The spectral band shape can be reproduced very well by a Lorentz function for the low frequency wing component and a Gauss function for the far wing component. The functions for neat liquids gave the relaxation times for orientational motion, which support free rotation models. The relaxation times of the solutions were found to be independent of concentration, the integrated intensities showing a linear dependence on concentration. The results for the wing component are in marked contrast to those found for the central component of the spectra. The difference is discussed in terms of dynamical structure of the liquids.
Syntheses and Electronic Spectra of 2,2′-Isopropylidenedi-8-quinolinol, Its Nickel(II), and Copper(II) Chelates
Authors: Yamamoto Yoshinori , Miura Akira , Kawamata Akira , Miura Masayoshi , Takei Shinsuke
Published: July 2006

The title ligand, which contains two 8-quinolinol (oxine) functions in one molecule, and the Ni(II) and Cu(II) chelates have been synthesized and characterized. Visible and ultraviolet spectra of the chelates and the ligand in several solvents have been measured. Square-coordination of the ligand to the metal has been revealed by a comparison of the d-d bands between the chelates and quadridentate Schiff base chelates in the literature. Intraligand transition bands of the title chelates and the solvent effects on the frequency shifts have been compared with those of the ligand, 8-hydroxy-1-methylquinolinium hydroxide, bis(8-quinolinolato)palladium(II), -copper(II), and -nickel(II), and have been discussed.
Syntheses and Properties of Some Trimethylantimony(V) Complexes of Dithiocarbonate Derivatives
Authors: Ouchi Akira , Shimoi Mamoru , Ebina Fujio , Uehiro Takashi , Yoshino Yukichi
Published: July 2006

New stable trimethylantimony(V) complexes of some dithiocarbonate derivatives, (CH3)3SbL2, where HL=secondary amine-N-carbodithioic acid or O-alkyl dithiocarbonic acid, have been synthesized by the metathetical reaction between dibromotrimethylantimony(V) and the alkali salts of ligands. In these compounds, the antimony is kept quinquevalent. The 1H-NMR peak of the methyl protons of all of these compounds appears as a singlet even at −60 °C. Therefore, the most probable structure for these compounds is the trigonal bipyramidal one, where two unidentate dithiocarbonate derivative ligands bond to antimony from the apical directions.
Studies on Mixed Valence Complexes of Platinum and Palladium. II. The Crystal Structures of [Pt(tn)2][PtCl2(tn)2](BF4)4, [Pt(tn)2][PtBr2(tn)2](ClO4)4, and [Pt(tn)2][PtBr2(tn)2](BF4)4
Authors: Matsumoto Naohide , Yamashita Masahiro , Kida Sigeo
Published: July 2006

The crystal structures of Pt(II)–Pt(IV) complexes, [Pt(tn)2][PtCl2(tn)2](BF4)4 (1), [Pt(tn)2][PtBr2(tn)2](ClO4)4 (2), and [Pt(tn)2][PtBr2(tn)2](BF4)4 (3) have been determined by the single-crystal X-ray diffraction method, where tn denotes trimethylenediamine. The crystals of these complexes are isomorphous with one another and the space group is A222 with a=10.790(2), b=13.872(2), c=10.287(1) Å for 1, a=11.003(6), b=13.979(6), c=10.355(4) Å for 2, and a=10.925(3), b=13.862(3), c=10.291(1) Å for 3. The structures were determined by the heavy atom method and refined by the block-diagonal least-squares method to give the disagreement factor 0.082, 0.089, and 0.086 for 1, 2, and 3, respectively. Each crystal comprises infinite PtII…X–PtIV–X… chains running parallel to the a-axis. In the chain, tetragonal bipyramidal [PtIVX2(tn)2]2+ (X=Cl or Br) and square planar [PtII(tn)2]2+ units are stacked alternately. Two of the fluorine or oxygen atoms of the counter anion are hydrogen-bonded to the nitrogen atoms of the ligand, contributing to the formation of an infinite chain.
Vinyl Polymerization. 375. Radical Polymerization of Vinyl Monomer in Water Initiated with Tin Mercaptides and Iron(III) Ion
Authors: Nakamura Yoshiaki , Ouchi Tatsuro , Imoto Minoru
Published: July 2006

The polymerization of the vinyl monomer was carried out in water, using either dimethylbis(ethylthio)tin or triethyl(p-tolylthio)tin as an initiator. The polymerization required the coexistence of the iron(III) ion. The initiating species was concluded to be a thiyl radical. Macromolecular tin mercaptide was much more effective than monomeric tin mercaptide.
A Synthesis of (±)-β-Vetivone and Its Related Spirovetivanes via the Base-catalyzed Spiroannelation of Phenolic Tosylates
Authors: Torii Sigeru , Uneyama Kenji , Okamoto Kaoru
Published: July 2006

(±)-β-Vetivone was synthesized by the base-catalyzed spiroannelation of 2-[2-(4-hydroxy-2-methylphenyl)-ethyl]-3-methyl-3-butenyl p-toluenesulfonate followed by methylation and subsequent isomerization of the side chain double bond. The reactivities of the related tosylates, 4-(4-hydroxy-2-methylphenyl)-2-isopropylbutyl p-toluenesulfonate, 3-hydroxy-2-[2-(4-hydroxy-2-methylphenylethyl]-3-methylbutyl p-toluenesulfonate, and 2,3-epoxy-2-[2-(4-hydroxy-2-methylphenyl)ethyl]-3-methylbutyl p-toluenesulfonate have been discussed.
Synthetic Studies on Pyridomycin. III. Chiral Synthesis of (2R,2S)-(−)-2,3-Dihydroxy-3-methylpentanoic Acid from Sugar Derivative
Authors: Kinoshita Mitsuhiro , Hamazaki Hiroshi , Awamura Masaki
Published: July 2006

The Grignard reaction of 3-O-benzyl-6-deoxy-1,2-O-isopropylidene-α-d-xylo-hexofuranos-5-ulose (5) with ethylmagnesium bromide yielded 3-O-benzyl-6-deoxy-5-C-ethyl-1,2-O-isopropylidene-α-d-glucofuranose (6) as a major product in 91% stereoselectivity. Hydrolysis of 6 followed by successive periodate oxidation and lithium aluminium hydride reduction gave 2-O-benzyl-5-deoxy-4-C-ethyl-d-arabinitol. Selective benzoylation of 9 followed by successive 3,4-O-isopropylidenation, debenzoylation, hydrogenolysis, and two-stage oxidation with periodate-hypoiodite afforded (4R,5S)-(+)-5-ethyl-2,2,5-trimethyl-1,3-dioxolane-4-carboxylic acid (15) in 24.6% overall yield from 5. Hydrolysis of 15 gave (2R,3S)-(−)-2,3-dihydroxy-3-methylpentanoic acid. The acetonide 15 is usefull as a synthon for pyridomycin synthesis.
Thermal Curtius Rearrangement of N-Acyl-S,S-diphenylsulfilimine
Authors: Furukawa Naomichi , Fukumura Mitsuo , Nishio Takehiko , Oae Shigeru
Published: July 2006

Several N-acyl-S,S-arylphenylsulfilimines were prepared and subjected to thermal decomposition. They decomposed readily at 130–190 °C to give isocyanates together with diphenyl sulfide, quantitatively. However, N-tosyl-S,S-diphenylsulfilimine did not decompose even upon heating at 200 °C for 24 h. A kinetic study revealed that the rates of pyrolysis of N-aroyl-S,S-arylphenylsulfilimines (p-Y–C6H4(Ph)S→NCOC6H4–X-p) are nicely correlated with the Hammett σ-values, ρX=−1.2 and ρY=+0.92, respectively, being obtained. The activation enthalpies and entropies were ΔH\eweq=38.7 kcal/mol and ΔS\eweq=6.0 e.u. for Ph2S→NCOPh and ΔH\eweq=32.3 kcal/mol and ΔS\eweq=5.5 e.u. for (Remark: Graphics omitted.), respectively. The rearrangement was accelerated considerably by o-methyl substituent in the aryl group. The effect of solvent on the rate of pyrolysis was small. The results indicate that the pyrolysis of sulfilimine proceeds via a concerted migration of the R group from carbonyl carbon to imino nitrogen similar to the Curtius type rearrangement of acid azide.
Synthesis of 4-Cinnamylidene-2,5-cyclohexadien-1-ones
Authors: Kurosawa Kazu , Hashiba Atsuko , Takahashi Hirobumi
Published: July 2006

Lithium aluminium hydride (LAH) reduction of 4′-hydroxychalcones, followed by dehydration, yielded 4-cinnamylidene-2,5-cyclohexadien-1-ones in 19–42% yields. The LAH reduction of 4′-acetoxychalcones also gave the same products in improved yields.
Coenzyme Models. XIII. Micellar Catalysis of 1,4-Dihydronicotinamide Reduction of Isoalloxazines and Acridinium Ion
Authors: Shinkai Seiji , Ide Toyoko , Manabe Osamu
Published: July 2006

The 1,4-dihydronicotinamide reduction of isoalloxazines and acridinium ion was examined in cationic (CTAB, CPyB), anionic (SDS), and nonionic (POOA, Brij35) micelles. The micellar effect is accounted for by micellar stabilization (or destabilization) of the micelle-bound species.
Photochemical Ethoxycarbonylmethylation of Alkylbenzenes with Ethyl Chloroacetate. MO Calculation for Prediction of Orientation
Authors: Ogata Yoshiro , Hayashi Eizi , Kato Hiroshi
Published: July 2006

Photoreaction of ethyl chloroacetate with cumene gives ethyl cumenylacetates (17.5%) in the ratio o : m : p = 17 : 46 : 37. The same reaction with t-butylbenzene gives ethyl t-butylphenylacetate (23%) in the ratio o : m : p = trace : 65 : 35. Addition of BF3 increases the total yield of the substitution products. Orientations together with those for toluene and anisole in ethoxycarbonylmethylation were discussed in terms of INDO-type MO calculation of the lowest singlet excitation energies.
Liquid-phase Oxidation of Anthracene in Acetic Acid by Copper(II) Chloro Complexes
Authors: Koshitani Jinya , Hiramatsu Masayoshi , Ueno Yoshio , Yoshida Takatoshi
Published: July 2006

Copper(II) chloro complexes contribute to the liquid-phase oxidation of anthracene in acetic acid. Products of the oxidation were anthrone, anthraquinone, 9-acetoxyanthracene, and 9-chloroanthracene.
Kinetic Studies of Photosensitized Oxygenation by Singlet Oxygen in Aqueous Micellar Solutions
Authors: Usui Yoshiharu , Tsukada Michio , Nakamura Hiroko
Published: July 2006

Singlet oxygen produced by the dye-sensitized reaction in an aqueous solution penetrates into the interior of the surfactant micelles of sodium dodecyl sulfate (SDS) and dodecyltrimethylammonium chloride (DTAC), reacting with the solubilized acceptors such as 9,10-dimethylanthracene, 2,5-diphenyloxazole, and 1,3-diphenylisobenzofuran. From the acceptor concentration effect on the photooxygenation quantum yield, the reactivity index (β), the ratio of the rate constant of the spontaneous decay of singlet oxygen to that of the reaction with an acceptor, is obtained in the aqueous micellar solution. It has been shown that the lifetime of singlet oxygen is mainly dependent on the solvent composition in the bulk phase from the kinetic analysis of the mixed solvent effect on the quantum yield in SDS and DTAC micellear solutions and that in a homogeneous solution.
Emission Spectra of Naphthalene Derivatives by Controlled Electron Impact
Authors: Ogawa Teiichiro , Miyamoto Nobuaki , Ishibashi Nobuhiko
Published: July 2006

Naphthalene, 1-methylnaphthalene, 2-methylnaphthalene, 1-naphthol, 1-naphthylamine, 2-chloronaphthalene, 1-bromonaphthalene, 2-bromonaphthalene, and tetralin were excited in a very low pressure by controlled electron beam of 150–400 eV. The molecules, except those with a halogen atom, revealed an intense emission band similar to fluorescence. The band was assigned to the transition from their lowest-excited singlet state to their ground state. It was concluded that the most important process of photoemission is the excitation into a higher excited state in the primary collision and the subsequent non-radiative transfer to the lowest-excited state. The molecules showed photoemission of such excited fragments as H, CH, C2, C4H2+, CN, NH, OH, CO, CO+, HCL+, and HBr+. A two-electron process by way of an intermediate was found to be important for the formation of such fragments as CN from naphthylamine.
The Effect of Σ-Π Interaction on the Electronic Structure of Molecules in the Excited States. II. Oscillator Strength
Authors: Maki Izumi , Kitaura Kazuo , Nishimoto Kichisuke
Published: July 2006

The effect of Σ-Π interaction on the oscillator strength of π-π* transition has been investigated in terms of the configuration interaction method considering all singly excited configurations. It has been found that the transition moment associated with π-π* excitation is modified by σ-electrons. The correction term of the transition moment resulting from the Σ-Π interaction can be expressed by the bond index matrix. The present theory has been applied to the calculation of the oscillator strength of benzene and naphthalene derivatives. Agreement between the calculated values and experimental data is satisfactory. The effect of Σ-Π interaction on the transition moment has been demonstrated pictorially.
A Modified Synthesis of 2,15-Hexadecanedione, a Precursor of Muscone, from a Butadiene Telomer
Authors: Tsuji Jiro , Kaito Mitsumasa , Takahashi Takashi
Published: July 2006

8-Acetoxy-1,6-octadiene was oxidized with PdCl2/CuCl/O2 to give 8-acetoxy-6-octen-2-one. Hydrolysis and hydrogenation of the ketone produced 8-hydroxy-2-octanone, which was converted to the tosylate after protection of the ketone. The tosylate was converted into the iodide and bromide. The bromide was converted into the Grignard reagent, and coupled with the iodide by the catalysis of CuI coordinated by 2,2′-bipyridyl to give 2,15-hexadecanedione.
Syntheses of Polymerizable Aromatic Mannich Bases by Means of Amine Exchange Reaction
Authors: Kamogawa Hiroyoshi , Kubota Kuniaki , Nanasawa Masato
Published: July 2006

Amine exchange reactions between p-vinyl-β-dimethylaminopropiophenone and arylamine hydrochloride provided six novel aromatic Mannich bases bearing a vinyl group which were otherwise hardly accessible. Thus, by refluxingin ethanol-water (1:1),p-vinyl-β-(p-anisidino)-,p-vinyl-β-(p-toluidino)-,p-vinyl-β-(p-hydroxyanilino)-, p-vinyl-β-anilino-, p-vinyl-β-(p-carboxyanilino)-, and p-vinyl-β-(p-nitroanilino)-propiophenones were obtained in 62.0, 55.2, 24.5, 32.0, 47.3, and 29.1% yields, respectively. The Mannich bases thus synthesized underwent ready radical polymerizations to afford the corresponding vinyl polymers, bearing aromatic Mannich base units as pendants.
Reaction of Nitrile Oxides with N-Aryl-S,S-dimethylsuIfimides
Authors: Shiraishi Shinsaku , Shigemoto Tadashi , Ogawa Shojiro
Published: July 2006

Both benzimidazole 3-oxides and 1,2,4-benzoxadiazines were formed in reactions of sterically-stabilized benzonitrile oxides with N-aryl-S,S-dimethylsulfimides, whereas only 1,2,4-benzoxadiazines were produced in reactions of 2,6-unsubstituted benzonitrile oxides. The reactions are thought to proceed via the intermediacy of a nitroso compound formed by the nucleophilic attack of sulfimide on the carbon atom of the nitrile oxide and the subsequent release of dimethyl sulfide. The nitrogen or the oxygen atom of the nitroso group of this intermediate can attack the ortho position of the benzene ring originating from sulfimide to form benzimidazole 3-oxide or 1,2,4-benzoxadiazine, respectively, Conjugation of the nitroso group with the C-aryl group can be attained in s-cis form for the intermediate derived from 2,6-unsubstituted benzonitrile oxide, and thus, exclusive O-attack takes place to afford 1,2,4-benzoxadiazines. On the other hand, conjugation of the nitroso group with the C-aryl group cannot be considered for the intermediate derived from 2,6-disubstituted benzonitrile oxide because of the steric hindrance of the substituents. In this case, the intermediate nitroso compound is either in s-cis or in s-trans form. This causes the formation of both benzimidazole 3-oxide and 1,2,4-benzoxadiazine. Characterization data of benzimidazole 3-oxides are also described.
The Michael Type Alkylation of α,β-Unsaturated Sulfoxide and Reaction of the Resulting α-Sulfinyl Carbanion
Authors: Sugihara Hideki , Tanikaga Rikuhei , Tanaka Kazuhiko , Kaji Aritsune
Published: July 2006

Aryl vinyl sulfoxide was alkylated via the Michael-type addition with lithium dialkylcuprates, and the resulting α-sulfinyl carbanions were reacted with various electrophiles (i.e. aldehydes, ketones, and alkyl halides) to afford a-substituted alkyl sulfoxides.
Absolute Stereochemistry of Cacalol
Authors: Terabe Mahito , Tada Masahiro , Takahashi Takeyoshi
Published: July 2006

Descriptions on the absolute configuration at C-5 of cacalol have been confused. Ozonolysis of cacalol afforded (S)-(+)-2-methylhexanedioic acid. The asymmetric center at C-5 of cacalol, cacalone, and of sesquiterpenes related to these compounds was therefore established to be (S)-configuration.
A Molecular-orbital Calculation of Chemically-interacting Systems. Interaction between Two Radicals. Self-reaction of Peroxyl Radicals
Authors: Minato Tsutomu , Yamabe Shinichi , Fujimoto Hiroshi , Fukui Kenichi
Published: July 2006

The path of the termination reaction of peroxyl radicals (self-reaction) was studied by means of a perturbational method and its reaction mechanism was elucidated theoretically. It was ascertained from this calculation that the self-reaction of tertiary alkylperoxyl radicals yielding a tetroxide does not have a four-centered transition state with four oxygen atoms of the two peroxyl radicals participating, but has a two-centered transition state with only the terminal oxygen atoms. The self-reaction of primary or secondary alkylperoxyl radicals is found to have a six-centered transition state. The self-reaction of acylperoxyl radicals is also shown to have a six-centered transition state. The mechanism of these self-reactions is clarified in terms of the mode of the particular orbital interaction.
Photo-effects of Metal Oxide Electrode. I. Photoelectrochemical Processes on a Silver–Silver Oxide Electrode and the Influence of Ethylene Glycol
Authors: Kunugi Akira , Miyoshi Shuji , Nagaura Shigeo
Published: July 2006

The influence of light excitation on the anodic oxidation of a silver electrode in alkaline solutions has been studied. The experimental results have shown that, in addition to the formation of Ag(II) species by a reaction of Ag(I) species with photo-generated holes, illumination in the Ag2O formation region causes the photogeneration of Ag(I) species at the metal/oxide interface. In the presence of ethylene glycol, the so-called current doubling phenomenon was found. This phenomenon has been interpreted in terms of a mechanism involving a catalytic reaction of the glycol with the photogenerated Ag(II) species, and not by a mechanism involving the oxidation of glycol by the photo-generated holes.
The Crystal and Molecular Structures of trans-Dichlorobis(dimethyl-neomenthylphosphine)palladium(II) and trans-Dichloro-bis(dimethylmenthylphosphine)palladium(II), Asymmetric Hydrosilylation Catalysts of Olefin
Authors: Kan Kojiro , Miki Kunio , Kai Yasushi , Yasuoka Noritake , Kasai Nobutami
Published: July 2006

The molecular structures of [PdCl2{(Me2neoMen)P}2] and [PdCl2{(Me2Men)P}2], asymmetric hydrosilylation catalysts of olefin, were determined by means of X-ray diffraction. Both complexes form yellow prismatic crystals. The former belongs to the monoclinic system: a=13.512(5), b=13.082(1), c=8.472(1) Å, and β=97.00(2)°, space group P21 with Z=2; the latter belongs to the tetragonal system: a=9.662(1) and c=32.459(2) Å, space group P43212 with Z=4. Both structures were determined by the heavy atom method and have been refined anisotropically by a least-squares procedure (R=0.0697 for 2606 non-zero reflections for the former and R=0.0713 for 1388 non-zero reflections for the latter). The former molecules is not iso-structural with its nickel analog. The central palladium atom has trans-square planar geometry [Pd–Cl 2.304(5) and 2.297(5), Pd–P 2.344(4) and 2.361(5) Å]. The molecule has an approximate two-fold symmetry around the normal to the coordination plane. The neomenthyl groups are on the same side of the co-ordination plane. The latter molecule has exact C2 symmetry: the two-fold axis passes through the Cl(1), Pd, and Cl(2) atoms which lie on the co-ordination plane. The geometry around the palladium slightly deviates from the trans-square planar [Pd–Cl 2.296(9) and 2.267(9) Å and Pd–P 2.310(6) Å]. The menthyl groups are located on either side of the co-ordination plane.
Spectrophotometric Determination of Iron(III) and Aluminium with Semimethylxylenol Blue
Authors: Ueda Joichi
Published: July 2006

Semimethylxylenol Blue (SMXB) reacts with iron(III) and aluminium to form water-soluble colored complexes. The colored solution of the iron(III) complex shows a maximum absorption at 580–581 nm, while that of the aluminium complex shows it at 554–555 nm. The absorbances of the solutions are constant over the pH range from 1.2 to 1.5 and from 2.5 to 2.9, respectively. Beer’s law is obeyed up to 1.4 μg cm−3 of iron(III) and 1.0 μg cm−3 of aluminium. Their molar extinction coefficients are 3.38×104 and 2.91×104, respectively. As a result of the investigation of the composition of the iron(III) or aluminium complex, the mole ratio of metal and SMXB was estimated to be 1 : 1. Among the 45 diverse ions examined, gallium, tin(IV), bismuth(III), zirconium, and vanadium(V) interfered with iron(III) determination, and gallium, indium, bismuth(III), scandium, titanium(IV), zirconium, vanadium(V), iron(III), fluoride, and oxalate interfered with aluminium determination. Consecutive determination of iron(III) and aluminium was also studied.
Experimental Studies of the Liquid Junction Potential between Electrolyte Solutions in Different Solvents. I. Water–Organic Solvent Junctions
Authors: Izutsu Kosuke , Nakamura Toshio , Kitano Toshihiko , Hirasawa Chieko
Published: July 2006

The liquid junction potential (ljp) between water and organic solvents was investigated by measuring the emfs of cells with free-diffusion junctions of various electrolyte solutions. In most experiments, the concentration of the electrolyte on one side of a junction was kept much larger than that on the other side (c MX in S⁄⁄c′ M′X′ in S′; S or S′ is H2O and c>>c′; thus the ljp was mainly determined by MX. The ljp may practically be expressed by the sum of Ej,ion (concn)(I), Ej,ion (ion-solv.)(II), and Ej,solv. (III). I and II are contributions from ionic species: I is the concentration term, which can be estimated approximately from the Henderson equation, and II is the term due to the difference in ionic solvations in S and S′. III is the contribution from the transfer of solvent molecules. The sum of II and III for the case in which S=H2O is approximately equal in absolute value but opposite in sign to that for the case in which S′=H2O. The change of II with the anion X− is in linear relation with free energy of transfer of the anion from S to S′. The change of III with the bridge solvent is also a linear function of the heat (or free energy) of solution of S into S′. The rate of the change with the heat of solution can be divided in two classes by the species of the cation M+: the rate for R4N+ ions is just a half of that for such ions as Li+, Na+, Mg2+, and Ba2+. The effect of the mixed bridge electrolytes and the mixed bridge solvents was also examined.
Regioselective, Abnormal Ring Opening of the Epoxide of Quinone Epoxide–Cyclopentadiene Adducts
Authors: Ichihara Akitami , Kobayashi Makio , Oda Kengo , Sakamura Sadao
Published: July 2006

Treatment of quinone epoxide–cyclopentadiene adducts with sulfuric acid gave abnormal ring opening products, whose structures were determined by the spectral data and identification of the degradation product. Regioselectivity of the reaction was confirmed. The mechanism of the reaction is discussed.
Evidence of Existence of Two Stereospecific Control Mechanisms in Asymmetric Transformation of 2-Phenylpropanal via Enamines
Authors: Matsushita Hajime , Tsujino Yasuko , Noguchi Masao , Saburi Masahiko , Yoshikawa Sadao
Published: July 2006

The temperature dependence of asymmetric transformation of 2-phenylpropanal via achiral enamine salt of d-10-camphorsulfonic acid was examined. The relation between the rotation of 2-phenylpropanal obtained and reaction temperature showed a notable change in specific rotation of the aldehyde obtained. Two courses are postulated for the optical activation.
Nucleoside Analogs. 5. Synthesis of Carbocyclic Pyrimidine Nucleoside Analogs
Authors: Tadano Kin-ichi , Horiuchi Sumio , Suami Tetsuo
Published: July 2006

Six carbocyclic analogs of uridine and thymidine in which the pentofuranosyl groups are replaced by a carbocyclic cyclopentane system have been synthsized. Their biological activities were determined against HeLa S3 cells.
Photochemical Reactions of 2-(Alkoxycarbonyl)-, 2-Cyano-, and 2-(Phenylthio)-cycloalkanones in Alcoholic Solution. Formation of ω-Substituted Esters
Authors: Tokuda Masao , Watanabe Yasuyuki , Itoh Mitsuomi
Published: July 2006

Photochemical reaction of ethyl 2-oxo-1-cyclohexanecarboxylate (3) in methanol gave ethyl methyl heptanedioate, trans- and cis-ethyl 7-oxo-2-heptenoate, and ethyl 7-oxo-3-heptenoate in 25, 7, 8, and 21% yields, respectively. Photochemical reactions of 3 in ethanol, isopropyl alcohol, and t-butyl alcohol gave the corresponding ω-alkoxycarbonyl esters. Other 2-(alkoxycarbonyl)-cyclopentanones and -cycloheptanone underwent similar reactions to give the corresponding ω-alkoxycarbonyl esters. Photochemical reactions of 2-cyanocyclohexanones in methanol similarly gave ω-cyano esters and ω-formyl α,β-unsaturated nitriles. However, photochemical reactions of 2-(phenylthio)- and 2-(methylthio)cyclohexanones in methanol did not give the corresponding ω-phenylthio or ω-methylthio carboxylic acid esters, products resulting from a preferential cleavage of a carbon-sulfur bond being obtained.
Fluorescence of the Hindered Phenoxyl Radical
Authors: Okamura Tadashi , Yip R W
Published: July 2006

Fluorescence and excitation spectra of the 2,4,6-tritertiarybutylphenoxyl radical which is stabilized by a steric hindrance have been measured in benzene at room temperature. The emitting state seems to correspond with a state visualized in the excitation spectrum.
Magnetic Study of α- and β-Diamminecopper(II) Chlorides and Bromides
Authors: Asai Takeshi , Saheki Hiroshi , Hori Kayako , Kiriyama Ryôiti
Published: July 2006

The magnetic susceptibilities, χ, of α- and β-Cu(NH3)2X2(X=Cl, Br) were measured from 4.2 to 360 K. Those of β-Cu(NH3)2X2 obeyed the Curie-Weiss law above 50 K. The Weiss constants and effective Bohr magneton numbers are −3.5(±1) K and 1.75(±0.01) for X=Cl, and −9.7 K and 1.82 for X=Br. α-Cu(NH3)2Cl2 showed a rounded maximum for χ at 30 K. A linear Heisenberg model with the parameters, J=−23.5(±1) K and g=2.03(±0.03), gave good agreement with observations. α-Cu(NH3)2Br2 had a peak for χ at 47(±2) K. This temperature is probably a Neèl temperature. The strong magnetic interaction of the α-form compounds is related to the compressed coordination octahedron of [Cu(NH3)2X4]2−. All samples used were solid solutions of Cu(NH3)2X2 and NH4X. An analysis of χ suggests that the Cu2+ cations in α-Cu(NH3)2Cl2 are distributed inhomogeneously over a short range. A similar inhomogeneity was also found for the β-Cu(NH3)2X2 samples. In this sense, the β-form may be better described as a solid solution of α-Cu(NH3)2X2 and NH4X rather than as a dimorph.
ESR Studies of Oxygen, Sulfur Oxide, and Sulfur Radicals Adsorbed on NaX Zeolite
Authors: Kanzaki Natsuko , Yasumori Iwao
Published: July 2006

The states of O2 and SO2 adsorbed on NaX zeolite were investigated by means of ESR. No oxygen anion radicals were formed thermally on NaX up to 773 K. The adsorption of O2 on γ-irradiated NaX in a vacuum, however, resulted in an ESR spectrum due to O2−. Several kinds of O2− species and O3− were found to be formed on NaX by γ-irradiation in the presence of O2. These oxygen anion radicals showed different reactivities with N2O, ethylene and propylene, and transferred electrons to SO2 to form SO2−. The SO2− radical was also produced on NaX by raising the temperature from 298 to 573 K after the introduction of SO2. This reacted with O2 to form a radical, like SO4−, but upon evacuating the O2, the reaction was reversed to give the original SO2−. When the temperature of NaX was further raised to 773 K in the presence of SO2, a spectrum assigned to a polyatomic sulfur radical appeared indicating that SO2 decomposition occurred at high temperature. This polymer radical was stable in an O2 atmosphere at room temperature.
Far-infrared Spectra of Low- and High-temperature Phases of CsCuCl3
Authors: Akiyama Kenji , Morioka Yoshiyuki , Nakagawa Ichiro
Published: July 2006

Polarized far-infrared reflection spectra of the CsCuCl3 single crystal have been recorded with the electric vector parallel and perpendicular to the c axis at room temperature. Polarized far-infrared transmission spectra have been measured at liquid-nitrogen temperature. The observed spectra have been interpreted using the factor group analysis based on the space group D62. Far-infrared transmission spectra of the powder sample have also been measured over the temperature range from 175 °C to liquid-nitrogen temperature. The spectrum at 175 °C consists of five bands and reveals a typical feature characteristic of the CsNiCl3 structure (D6h4). The spectral change due to the phase transition has been interpreted based on the structural distortion of the crystal.
Fluorescence Quenching of Naphthalene and Its Derivatives by Acetyl Chloride
Authors: Tamaki Takashi
Published: July 2006

The fluorescence of naphthalene and its methyl or methoxy derivatives has been found to be quenched by acetyl chloride. The quenching constants, determined by the Stern-Volmer treatment of the emission intensity and lifetime have been found to be in good agreement within experimental error. The quenching rate constants have been correlated with the energy terms of electron-donating forces in the excited states of these naphthalenes. The results suggest that the quenching mechanism involves a charge-transfer stabilized complex, in which the excited naphthyl compounds act as donors. Exciplex formation has been supported by oxygen quenching experiments.
Preparative Study on Chiral Orthotelluratobis(diamine)cobalt(III) Complexes and Their Condensation Products
Authors: Hosokawa Yutaka , Shimura Yoichi
Published: July 2006

Five chiral cobalt(III) complexes coordinating an orthotellurate or a ditellurate ligand have been prepared and their optically active isomers isolated. They belong to one of the three following types: first a “mononuclear” [Co(TeO6H4)(diamine)2]+ type (diamine=ethylenediamine (en) and (R)-(−)-1,2-propanediamine); second a “dinuclear” [Co(diamine)2(Te2O10H4)Co(diamine)2]2+ one (diamine=en and (R,R)-(−)-trans-1,2-cyclohexane-diamine); and lastly a “tetranuclear” [{Co(diamine)2}2(Te2O10){Co(diamine)2}2]4+ one (diamine=en). The structures of these complexes have been discussed from the visible to ultraviolet absorption and circular dichroism spectra.
Synthesis and Electrical Resistivity of Bis(dialkyldithiocarbamato)gold(III) Cation-TCNQ Radical Anion Salts
Authors: Yumoto Yoshiji , Kato Futoshi , Tanaka Toshio
Published: July 2006

Seven simple salts and one complex salt of TCNQ\ewdot radical anion with bis(dialkyldithiocarbamato)gold(III) cations, [Au(S2CNR2)2]+TCNQ\ewdot (R=Me, Et, n-Pr, n-Bu, n-C6H13, n-C8H17, and CH2C6H5) and [Au(S2CN(CH2C6H5)2)2]+(TCNQ)2\ewdot, were prepared. The complex salt was also obtained as an acetonitrile solvate, [Au(S2CN(CH2C6H5)2)2]+(TCNQ)2\ewdot·MeCN. The electrical resistivity of the simple salt with R=CH2C6H5 (2.9×104 ohm cm in compacted sample) is much lower than those of the remaining simple salts (1.1×107–2.2×1010 ohm cm). The resistivities of two complex salts are in the order of 102 ohm cm. Electronic absorption spectra and magnetic susceptibility measurements in the solid state indicate that the simple salts with R=Me, Et, n-Pr, n-C6H13, and CH2C6H5 involve the TCNQ\ewdot radical anion monomer, whereas those with R=n-Bu and n-C8H17 involve dimeric (TCNQ)22−. The interaction between TCNQ\ewdot radical anion and neutral TCNQ in the complex salts is extremely weak, as suggested from no appreciable absorption band in the near-infrared region.
Formose Reactions. VI. Formose Synthesis in Methanol
Authors: Shigemasa Yoshihiro , Matsuda Yoshinobu , Sakazawa Chikahiro , Nakashima Ruka , Matsuura Teruo
Published: July 2006

The formose reaction in methanol was compared with that in an aqueous solution. The reaction can occur in aqueous methanol even at a low [CaO]/[HCHO] ratio (0.05), at which the reaction does not take place in an aqueous solution, and the formaldehyde consumption rate decreases with an increase in the methanol concentration. Contrary to the formose reaction in an aqueous solution, the sugar yield in methanol becomes higher with an increase in the formaldehyde concentration. The rates of the sugar degradation and the formaldehyde consumption increase with an increase in the pH. The distribution of products is different from that in an aqueous solution, but both of them are very complex and essentially nonselective.
Effect of Pressure on the Rates of Solvolysis. Hydrolysis of Some Sterically Hindered Chlorides
Authors: Sera Akira , Takeuchi Shinichi , Tachikawa Noboru , Maruyama Kazuhiro
Published: July 2006

The effect of pressure on the rates of solvolyses of substituted 1-phenylethyl and benzyl chlorides has been investigated in an ethanol–water mixture at 25 °C. The activation volumes have been calculated and the dependence of these values on the number and size of the substituents have been interpreted in terms of the competitive contribution of the steric inhibition of resonance and steric hindrance to solvation in the transition states.
Reactive Troponoids and o-Aminophenol. III. The Reaction of 2-Bromo-7-methoxytropone
Authors: Nozoe Tetsuo , Someya Taichi , Okai Harue
Published: July 2006

The reaction of 2-bromo-7-methoxytropone with o-aminophenol gave 2-bromo-7-(o-hydroxyanilino)tropone (9), besides small amounts of cyclohepta[b][1,4]benzoxazin-6(11H)-one (10) and 15H-[1,4]benzoxazino[3′,2′ : 3,4]cyclohepta[2,1-b][1,4]benzoxazine (11). The heating of 9 with a strong acid afforded 6-bromocyclohepta[b][1,4]benzoxazine (13) quantitatively. On the other hand, the heating of 13 with o-aminophenol in ethanol gave 10, while in acetic acid a mixture of 10 and 11 was obtained. The mechanism of the formation of these products is discussed.
Optical Activity and Absolute Configuration of 5,6,11,12-Tetrahydro-2,3,8,9-tetramethoxy-5,11-methanodibenzo[a,e]cyclooctatetraene
Authors: Ogura Fumio , Nakao Akio , Nakagawa Masazumi
Published: July 2006

The title compound (VII) was synthesized in an optically active form and the chiroptical properties were recorded. The absolute configuration was determined by chemical correlation method.
Carbon-13 NMR Spectra of Di-t-alkyl Ethers and Related Hindered Ethers
Authors: Masada Hiromitsu , Murotani Yoshiharu
Published: July 2006

The C-13 NMR spectra of hindered t-alkyl ethers and dineopentyl ether have been presented and the electronic and steric effects discussed. The resonances for the α-, methylene β-, and methyl β-carbons of di-t-alkyl ethers shifted downfield by +45, +1.2, and −0.2 ppm, respectively, relative to the corresponding alkanes.
An X-Ray Diffraction Study on the Structure of Hexa-amminecadmium(II) Ion in Aqueous Solution
Authors: Yamaguchi Toshio , Ohtaki Hitoshi
Published: July 2006

The structure of the hexaamminecadmium(II) ion in an ammoniacal aqueous solution of cadmium chloride was determined by the X-ray diffraction method at the NH3/Cd mole ratio of 9.9. The result showed that a cadmium(II) ion is octahedrally surrounded by six ammonia molecules at the distance of (2.37±0.03) Å.
Asymmetric Synthesis of Alanine by Hydrogenolytic Asymmetric Transamination between (R)-2-Amino-2-phenylethanol and Ethyl Pyruvate
Authors: Harada Kaoru , Tamura Minoru
Published: July 2006

Hydrogenolytic asymmetric transamination between (R)-2-amino-2-phenylethanol and ethyl pyruvate was studied. The optical purity of the resulting alanine was in the range 10–62 %. The effect of solvents and the asymmetric moieties in the syntheses were explained by the chelation hypothesis based on the substrate-catalyst complex.
The Reductions of Carbonyl Compounds with Sodium 1-Benzyl-3-carbamoyl-1,4-dihydropyridine-4-sulfinate
Authors: Inoue Hiroo , Sonoda Ichiro , Imoto Eiji
Published: July 2006

It is found that sodium 1-benzyl-3-carbamoyl-1,4-dihydropyridine-4-sulfinate reduces α-keto carbonyl compounds to α-hydroxy carbonyl compounds with the assistance of MgCl2 and reacts with 9-fluorenone to give an adduct.
High Performance Liquid Chromatographic Analysis of Individual Bile Acids: Free, Glycine- and Taurine-conjugated Bile Acids
Authors: Okuyama Sumihiko , Uemura Daisuke , Hirata Yoshimasa
Published: July 2006

High performance liquid chromatographic analyses of individual bile acids (cholic, chenodeoxycholic, deoxycholic, and lithocholic acids), free and conjugated with glycine and taurine, are described. The analyses of the free and glycine-conjugated bile acids are based on the esterification of the carboxyl group of bile acids with O-(p-nitrobenzyl)-N,N′-diisopropylisourea(PNBDI). The bile acids in the biological samples were extracted by an Amberlite XAD-2 column, and separated by DEAE-Sepharose CL-6B into free, glycine and taurine-conjugated bile acids. After separation, the free and glycine-conjugated bile acids were directly esterified with PNBDI. Taurine-conjugated bile acids are unable to be esterified with PNBDI, the bile acids were hydrolyzed with NaOH to produce the free bile acids, and then esterified. The p-nitrobenzyl ester of bile acids has a characteristic ultraviolet absorption. Consequently the compounds were separated into the individual bile acids by high performance liquid chromatography, and detected by an UV-detector. An analysis of the individual bile acids in human bile is given for an example.
The Silver(I) Salt-promoted Benzylation of Silyl Enol Ethers
Authors: Takagaki Hidetsugu , Yasuda Nobuyoshi , Asaoka Morio , Takei Hisashi
Published: July 2006

Various silyl enol ethers gave the corresponding mono benzyl products in moderate to good yields by the reaction with benzyl bromide in the presence of silver perchlorate in dichloromethane at −78–0 °C.
Investigation of CdS Photoanode Reaction in the Electrolyte Solution Containing Sulfide Ion
Authors: Inoue Tooru , Watanabe Tadashi , Fujishima Akira , Honda Kenichi
Published: July 2006

The study of the photoanodic reaction in the CdS/S2− system was carried out by means of the rotating ring-disk electrode (RRDE) technique. The photoanodic reactions at an n-type CdS electrode are divided into two types; the photoanodic oxidation of redox agents in the electrolyte solution and the photoanodic dissolution of CdS electrode surface. The stabilization of a CdS photoanode could be attained through the preferential progress of the former of these two processes. The ratio between these two processes depends upon the concentration of S2− in the electrolyte solution and the light intensity. Sulfide ion in the electrolyte solution stabilizes CdS photoanode and gives rise to the shift of the flatband potential of CdS electrode by ca. −60 mV/log[S2−]. This dependence of the flatband potential on sulfide ions can be explained by an adsorptive dissociation equilibrium at a CdS electrode surface. The results of the photoanodic reaction were disscussed referring to the charge transfer process with the participation of some surface energy state within a bandgap.
The Visible-UV Absorption and Circular Dichroism Studies of Poly(α-l-glutamic acid)–Copper(II) Complexes with Emphasis on the Extrinsic Cotton Effect
Authors: Yamaoka Kiwamu , Masujima Tsutomu
Published: July 2006

The visible-UV absorption and circular dichroism, CD, of poly(α-l-glutamic acid)–Cu(II) solutions have been measured at 25 °C in the pH range 7 to 3.5 and at the mixing ratio, R, (Glu residues-to-Cu2+) 32 to 4. Complex formation between poly (Glu) and Cu2+ was evident from the three absorption bands of bound Cu(II) around 700, 370, and 250 nm. The molar absorption coefficients, ε, varied with pH and R in a complicated but systematic manner. The pH dependence of ε, however, was not in parallel with the helix-coil transition of poly(Glu)–Cu(II) complexes. The extrinsic CD bands of bound Cu(II) have been detected in the three absorption band regions, and found to depend on both pH and R. The optical dissymmetry factor indicated that the 700 and 250 nm absorption bands of bound Cu(II) are associated with multiple CD bands of opposite signs. The intrinsic CD showed that the Cu(II)- and pH-induced helices of the poly(Glu)–Cu(II) complex are alike regarding the polymer backbone.
Electrical Properties of a One-dimensional Conductor, NaxV2O5
Authors: Kobayashi Hayao
Published: July 2006

The resistivity measurement, DTA analysis, refinement of the crystal structure, and examination of the X-ray diffuse scattering have been carried out on the β-phase of the sodium vanadium bronze. A resistivity minimum was observed around 200 K. The peak position of the logarithmic derivative of the resistance and an anomaly in the DTA curvature indicate that a metal-insulator transition occurs at about 130 K. The X-ray diffuse scattering shows a tendency of the sodium atoms toward cluster formation. It is concluded that the β-phase of sodium vanadium bronze is neither a simple one-dimensional metal nor a simple semiconductor, but can be-have partly as a one-dimensional metal and partly as an anisotropic semiconductor.
Precise Coulometric Titration of the Potassium Hydrogen Phthalate (NBS-SRM 84d). The Use of the Faraday Constant as an International Standard
Authors: Yoshimori Takayoshi , Tanaka Tatsuhiko
Published: July 2006

The purity of the potassium hydrogen phthalate (NBS SRM 84d) was determined by precise coulometric titration. The purity obtained was 99.995±0.002% (standard deviation: 0.003%), and was in excellent agreement with the purities of the same SRM determined already in three laboratories in U.S.A. These results support the recommendation on the use of the Faraday constant as an international standard for titrimetric analysis.
A Mössbauer Study of the Photolysis of Bis- and Tris-oxalato Iron(III) Complexes in a Solid, Solutions, and Frozen Solutions
Authors: Sato Haruo , Tominaga Takeshi
Published: July 2006

The photolytic reactions of bis- and tris-oxalato iron(III) complexes in a solid, solutions, and frozen solutions were studied by means of 57Fe Mössbauer spectroscopy. An iron(II) species was observed as a metastable intermediate product in the photolysis of tris(oxalato) ferrate(III) in a solid and solutions. A mechanism with a sequence of iron(II) intermediates was tentatively proposed for the photolysis and subsequent reactions in this compound. The Mössbauer technique was also used to examine whether or not tris(oxalato)ferrate(III) was diluted uniformly with diamagnetic substances in the mixed crystals and frozen solutions.
Chemiionization of Excited Mercury Atom with 253.7 nm Irradiation in the Presence of N2 and CH4
Authors: Sibata Akiko , Takahasi Makoto , Mikuni Hitoshi , Horiguchi Hiroyuki , Tsughiya Soji
Published: July 2006

Chemiionization of excited mercury atom with 253.7 nm irradiation was studied. Results on the system Hg–N2 previously reported were further confirmed. It was found that CH4 can also induce chemiionization of Hg atoms with 253.7 nm irradiation. The dependence of ionization current on CH4 pressure and light intensity was investigated, the ionization current being found to be proportional to the square of light intensity and to increase with increase in CH4 pressure up to 30 Torr, reaching a constant value. N2 and CH4 are considered to show a similar behavior in ionization current against pressure and light intensity, and other substances such as H2, He, CO, NO, Ar, C2H4, and 1-butene to give no appreciable ionization current. Thus the mechanism in which chemiionization proceeds through the collision of Hg(3P1) with Hg(3P0) is further confirmed.
Layered Compounds. LIX. Facile Syntheses and Spectral Properties of [3.3]Cyclophanes and Related Cyclophanes
Authors: Otsubo Tetsuo , Kitasawa Masashi , Misumi Soichi
Published: July 2006

A simple synthetic method of [3.3]cyclophanes via dithia[4.4]cyclophanes is presented. The spectra of a variety of cyclophanes were examined and compared to those of [2.2]analogues. It was concluded from the absorption spectra that the transannular π-π interactions of the cyclophanes were strongly dependent on both ring-to-ring distance and overlapping mode. From the emission spectra, it was described that cyclophanes of parallel sandwich type formed easily normal excimers, whereas [2.2]metacyclophane and [2.2]- and [3.3]metaparacyclo-phanes formed strained excimers showing marked red shifts of fluorescence bands.
Rate and Mechanism of the Complex Formation of Thallium(III) with 4-(2-Pyridylazo)resorcinol (PAR) in Aqueous Solution
Authors: Funada Ryuichi , Imamura Taira , Fujimoto Masatoshi
Published: July 2006

The kinetics of complex formation of Tl(III) with PAR (LH3+) was studied in aqueous solution at 25 °C, [H+]=0.1–1.0 mol dm−3, and ionic strength I=2.0 mol dm−3 (NaClO4). The formation rate constants k1 and k2 assigned to the reactions of Tl+3 and TlOH2+ with LH3+ were determined to be 4.1×104 and 1.8×105 mol−1 dm3 s−1, respectively. The rate data were discussed in comparison with those for Tl(III)–Semi-Xylenol Orange system.