bluuebunny/crossref_metadata_2025 huggingface dataset:
Formation of Adducts of Poly(thienylene)s with Electron Acceptors and Electric Conductivities of the Adducts
Authors: Yamamoto Takakazu , Sanechika Ken-ichi , Yamamoto Akio
Published: July 2006

Affinities of poly(thienylene) type polymers toward electron acceptors (iodine and SO3) and electric conductivities of the polymer–electron acceptor adducts have been investigated. π-Conjugated poly(2,5-thienylene) has a high affinity toward iodine to absorb 60 wt% of iodine per the polymer. Poly(3-methyl-2,5-thienylene) has a higher affinity toward iodine and absorbs 136 wt% of iodine per the polymer. In the case of copolymer composed of 2,5- and 2,4-thienylene units the affinity against iodine increases with increase in the proportion of the 2,5-thienylene unit in the copolymer. The poly(2,5-thienylene)–iodine and poly(3-methyl-2,5-thienylene)–iodine adducts show electric conductivities of 5×10−2 S cm−1 and 4×10−1 S cm−1, respectively, at room temperature. The activation energies of the electric conduction are 10 kJ/mol and 7.6 kJ/mol for the poly(2,5-thienylene)–iodine adduct (wt% of iodine=60) and poly(3-methyl-2,5-thienylene)–iodine adduct (wt% of iodine=136), respectively. The electric conductivity of the copolymer–iodine adduct sharply decreases on introduction of the 2,4-thienylene unit into the copolymer. The electric conductivity of the iodine adduct of the copolymer containing only 6% of 2,4-thienylene unit drops to ca. 1/100 of that of the iodine adduct of pure poly(2,5-thienylene). The activation energy of the electric conduction of the polymer-iodine adducts decreases with increase in the content of the 2,5-thienylene unit as well as with the increase in the amount of iodine absorbed. Every poly(thienylene) type polymer has a high affinity toward SO3, a stronger electron acceptor than iodine, to absorb about 70 wt% of SO3 per the polymer. The SO3–polymer adducts have electric conductivities of ca. 10−4 S cm−1.
Studies on the β-Turn of Peptides. II. Syntheses and Conformational Properties of N-(2,4-Dinitrophenyl)tetrapeptide p-Nitroanilides Related to the β-Turn Part of Gramicidin S
Authors: Sato Kazuki , Kawai Masao , Nagai Ukon
Published: July 2006

N-(2,4-Dinitrophenyl)tetrapeptide p-nitroanilides related to the β-turn part of gramicidin S were synthesized and subjected to CD measurements. The β-turn preference of the tetrapeptide derivatives had correlation with the antibiotic activities of the gramicidin S analogs containing similar tetrapeptide sequences at their β-turn part. So, conformational preference of partial sequences of gramicidin S analogs seem to play a significant role for determining their biological activities.
The Mode of Stereoselective Association between Complex Cation and Complex Anion
Authors: Sakaguchi Ushio , Yamamoto Ippei , Izumoto Shinji , Yoneda Hayami
Published: July 2006

Ion-exchange chromatography on the IEX 220 anion-exchange resin has been used to measure the retention volumes of enantiomers of several complex anions when eluted by an aqueous solution of Δ-[Co(en)3]3+, Δ-[Co(sep)]3+, or Δ-[Co{(−)-chxn}3]3+, where en=ethylenediamine, sep=1,3,6,8,10,13,16,19-octaazabicyclo[6.6.6]eicosane, and chxn=trans-1,2-cyclohexanediamine. Comparison of these retention volumes suggests that chiral recognition in solution is effected along the C2 axis of [Co(en)3]3+, [Co(mal)2(en)]−, and [Co(ox)2-(en)]−, and along the C3 (or pseudo C3) axis of [Co(chxn)3]3+, [Co(edta)]−, [Co(tdta)]−, [Co(ox)2(gly)]2−, [Cr(mal)3]3−, and fac-[Co(β-ala)3], where mal=malonate, ox=oxalate, edta=ethylenediaminetetraacetate, tdta=1,4-butanediaminetetraacetate, gly=glycinate, and ala=alaninate. The mode of stereoselective association of these complex ions has been proposed.
The Catalytic Isomerization of Butenes over a Sulfuric Acid–Graphite Intercalation Compound
Authors: Tsuchiya Susumu , Hara Masao , Imamura Hayao
Published: July 2006

The relative rate constants and the activation energies of the isomerization of butenes over sulfuric acid–graphite intercalation compound have been measured. cis-2-Butene is more reactive than 1-butene. The reaction profile shown on the triangular graph is of the trans-convex type.
Structure of a Potent Antithyroid Drug, 6-Propyl-2-thiouracil
Authors: Okabe Nobuo , Fujiwara Takaji , Yamagata Yuriko , Tomita Ken-ici
Published: July 2006

The crystal strure of 6-propyl-2-thiouracil (PTU), an antithyroid drug, has been determined as a 2 : 1 complex with 1,4-dioxane [(C7H10N2OS)2(C4H8O2)]. The crystals are monoclinic, space group P21/a, with a=8.983(5), b=23.706(12), c=4.942(2) Å, β=95.79(3)°, V=1047.1(9) Å3, Z=4, Dx=1.36 Mg m−3, Dm=1.35 Mg m−3, MW=214.29, λ(Cu Kα)=1.5418 Å. Final R=0.098 for 1575 reflexions.
Preparation and Characterization of Cobalt(III)–Phosphine Complexes of the Type [Co(CN)2(acetylacetonate)(L)] (L: Tertiary 2-Aminoethylphosphines, and 1,2- and 1,3-Diphosphines)
Authors: Ohishi Tomoji , Kashiwabara Kazuo , Fujita Junnosuke
Published: July 2006

Four new cobalt(III)–phosphine complexes of the type [Co(CN)2(acetylacetonate)(L)] (L=NH2CH2CH2P(C6H5)2, NH2CH2CH2P(CH3)2, (C6H5)2PCH=CHP(C6H5)2, and (C6H5)2PCH2CH2CH2P(C6H5)2) were prepared. The geometrical structures of the 2-aminoethylphosphine, and 1,2- and 1,3-diphosphine complexes were assigned to have trans(C,N) and cis configurations, respectively on the basis of the 1H and 13C NMR spectra.
An Improved Synthesis of threo-3-Methyl-d-cysteine
Authors: Wakamiya Tateaki , Fukase Koichi , Shimbo Kuniaki , Shiba Tetsuo
Published: July 2006

Synthesis of threo-3-methyl-d-cysteine, a moiety of β-methyllanthionine as a component of the peptide antibiotics nisin and subtilin, was achieved via (2R,3R)-1-t-butoxycarbonyl-3-methyl-2-aziridinecarboxamide derived from d-threonine. An addition of thioacetic acid or thiobenzoic acid to the aziridinecarboxamide gave S-acyl-β-mercapto-α-amino acid amide derivatives which were hydrolyzed directly or after the preformation of disulfide bond to afford the desired amino acid.
Penicillin-Cephalosporin Conversion. VII. An Improved Synthesis of 3-Methylenecephams
Authors: Torii Shigeru , Tanaka Hideo , Siroi Takashi , Madono Tomoyuki , Saitoh Norio , Sasaoka Michio , Nokami Junzo
Published: July 2006

Efficient conversion of 2-(7-oxo-2,6-diaza-4-thiabicyclo[3.2.0]hept-2-en-6-yl)-3-chloromethyl-3-butenoates (4), derived from natural penicillins, into 3-methylenecephams (1) has been performed by a simple two-step operation, which comprises replacement of the allylic chlorine atom of 4 with iodine and subsequent acid-catalyzed hydrolysis, leading to 1 in 70–54% overall yields. In the latter step, the ring opening of the thiazoline moiety and the intramolecular substitution of the iodide with the thiol group proceed simultaneously.
Studies of Inorganic Ion Exchangers. VI. The Formation Region and Dehydration Behavior of Various Titanium(IV) Bis(hydrogenorthophosphate) Hydrates
Authors: Kobayashi Etsuro , Yamazaki Shinsuke
Published: July 2006

The formation region, dehydration behavior, and lattice constants of various types of titanium(IV) bis(hydrogenorthophosphate) hydrates were investigated. α-Ti(HPO4)2·H2O was formed by refluxing an amorphous titanium phosphate (ATP) with H3PO4 at 110–165 °C or by treating it with H3PO4 (up to 11.5 mol dm−3) under hydrothermal conditions at temperatures up to 250 °C. (β-γ)-Ti(HPO4)2·xH2O was obtained by refluxing ATP with H3PO4 (15–16 mol dm−3) above 165 °C. γ-Ti(HPO4)2·2H2O was formed by a hydrothermal reaction of ATP and H3PO4 (10–16 mol dm−3) at 200–300 °C. In the thermal analysis of Ti(HPO4)2, no difference in weight loss was found at temperatures up to 920 °C of α-form irrespective of the drying conditions of the samples. The (β-γ)-form dried under reduced pressure over P2O5 had a composition corresponding to that of a 1/2 hydrate. The γ-form dried at a relative humidity of 75% had a composition identical to that of the dihydrate. In view of the X-ray diffraction, it seemed that the (β-γ)-form (11.6 and 9.2 Å) was changed by drying under reduced pressure over P2O5 to the β-form (9.2 Å) as anhydride. The γ-form (11.6 Å) was dehydrated to the β-form by heating. The change in the inter-layer distance upon dehydration was also confirmed by means of a that of the electron diffraction. Thus, it was considered that the (β-γ)-form was a mixture as a quasi stable form.
Stereochemical Aspects of the Optical Resolution of cis(N)-[Co(N)2(O)4]− Complexes by Reversed-phase Ion-pair Chromatography with Cinchona Alkaloid Cations as the Ion-pairing Reagents
Authors: Izumoto Shinji , Sakaguchi Ushio , Yoneda Hayami
Published: July 2006

The reversed-phase ion-pair chromatography with cinchona alkaloid cations as the ion-pairing reagents has been used to resolve optically several anionic complexes of the type cis(N)-[Co(N)2(O)4]−. Complete optical resolution has been achieved for [Co(edta)]−, cis-[Co(ida)2]−, [Co(cydta)]−, [Co(ox)2(en)]−, and cis-α-[Co(ox)(edda)]− by quinine, quinidine, and cinchonidine but not by cinchonine, where edta=ethylenediaminetetraacetate, ida=iminodiacetate, cydta=trans-1,2-cyclohexanediaminetetraacetate, ox=oxalate, en=ethylenediamine, and edda=N,N′-ethylenediaminediacetate. The adjusted retention volumes have been measured for the enantiomers. From comparison of the retention volumes and separation factors obtained for the alkaloids and their derivatives, the mode of chiral discrimination has been proposed.
Preparation and Some Properties of Cobalt(III) Complexes with d-Penicillaminate and Its Derivatives
Authors: Okamoto Ken-ichi , Wakayama Katsuhiko , Einaga Hisahiko , Yamada Shoichi , Hidaka Jinsai
Published: July 2006

Three kinds of [Co(terdentate-N,O,S)2] type complexes were newly prepared; here terdentate-N,O,S denotes d-penicillaminate (d-pen), S-methyl-d-penicillaminate (d-smp) and S-methyl-l-cysteinate (l-smc). Each of the d-smp and l-smc complexes was chromatographically separated into three possible isomers; the d-pen complex was separated into two isomers. These isomers were characterized from their electronic absorption, CD and 1H NMR spectra. Two isomers isolated for [Co(d-pen)2]− were assigned to trans(N) and trans(O), respectively, on the basis of the spectral behavior of the sulfur-to-metal charge transfer band and the reaction with dimethyl sulfate. Three isomers for [Co(d-smp)2]+ were derived from each of two isomers for [Co(d-pen)2]+ by the reaction with dimethyl sulfate. The electronic absorption and CD spectral behaviors are discussed in relation to the comparison of the thioether and thiolato type complexes.
Studies on Long-range Couplings between 77Se and 13C in Some Aryl Selenides, Dichlorides, and Selenoxides. The Inverse Effect on Couplings in the Selenoxide Formation
Authors: Nakanishi War\={o} , Ikeda Yoshitsugu
Published: July 2006

Long-range coupling constants between 77Se and 13C in selenoanisole, diphenyl selenide, diphenyl diselenide, and their 2-mono- and 2,2′-disubstituted derivatives, selenoxanthone, selenanthrene, dichlorides, and selenoxides were measured to disclose predominant factors governing the magnitude of the coupling. Extraordinary large values for two- and three-bond couplings are found in selenoxanthone. Three factors are operative: the orientational effect, the coordination number, and the effect of ring formation. The last factor accompanies a stronger inverse effect on the coupling of selenoxides than on that of selenides.
The Reaction of Thio-substituted Cyclopropenium Ions with Sulfonium Methylide
Authors: Inoue Shinichi , Hori Takuya
Published: July 2006

The reaction between thio-substituted cyclopropenium ions and sulfonium methylides gives unanticipated ketene derivatives. This reaction is supposed to proceed through an intermediate sulfonium salt formed from ylide addition to the cyclopropenyl ring.
The Structure of the Cyclodextrin Complex. XVI. Crystal Structure of Heptakis(2,3,6-tri-O-methyl)-β-cyclodextrin-p-Iodophenol (1 : 1) Complex Tetrahydrate
Authors: Harata Kazuaki , Uekama Kaneto , Otagiri Masaki , Hirayama Fumitoshi
Published: July 2006

The crystal structure of heptakis(2,3,6-tri-O-methyl)-β-cyclodextrin–p-iodophenol (1 : 1) tetrahydrate, C63H112O35·C6H5OI·4H2O, was determined by the X-ray method. The crystal is orthorhombic with the space group P212121, Z=4, a=14.997(2), b=21.368(2), and c=28.205(3) Å. The structure was solved by the heavy atom method combined with the rigid-body least-squares technique and refined by the block-diagonal least-squares method to the final R-value of 0.094 for 3268 reflections (sinθ⁄λ<0.49). Heptakis(2,3,6-tri-O-methyl)-β-cyclodextrin is in the shape of a truncated elliptical cone. The macrocyclic ring is remarkably distorted from a regular heptagonal structure. The iodophenyl group of the guest is inserted into the host cavity. The phenolic hydroxyl group protrudes from the cavity, forming hydrogen bonds with two water molecules. The iodine atom is located at the center of the macrocyclic ring, while the benzene ring occupies its position at the base side of the cone. The crystal is built up of columns which are formed by the stack of host molecules in a head-to-tail mode along the two-fold screw axis which is parallel to the crystallographic b axis. Four water molecules fill intermolecular spaces in the crystal.
Asymmetric Transfer Hydrogenation of Prochiral α,β-Unsaturated Acids and Their Esters by Achiral or Chiral Alcohols with Ruthenium Chiral Diphosphine Complexes
Authors: Yoshinaga Kohji , Kito Taketoshi , Ohkubo Katsutoshi
Published: July 2006

Asymmetric transfer hydrogenations of α,β-unsaturated acids (MeCH=C(Me)CO2H, PhCH=C(Me)CO2H, CH2=C(CH2CO2H)CO2H, and HO2CCH=C(Me)CO2H) and esters (MeCH=C(Me)CO2R; R=achiral and chiral group) by alcohols (PhCH2OH, (RS)-PhCH(Me)OH, and α-d-glucofuranose derivatives) were carried out with RuCl2(PPh3)3 or Ru2Cl4((+) or (−)-diop)3 (diop=2,3-O-isopropylidene-1,4-bis(diphenylphosphino)-2,3-butanediol) at 160–190 °C. The optical purity (3.4–16.4%) of hydrogenated acids obtained with PhCH2OH and Ru2Cl4((−)-diop)3 is in the order MeCH=C(Me)CO2H>PhCH=C(Me)CO2H>CH2=C(CH2CO2H)CO2H>HO2CCH=C(Me)CO2H, suggesting that the substrates possessing two carboxyl groups would provide an asymmetrically unfavorable coordination to the Ru(II) complex for this asymmetric reaction. In the transfer hydrogenation of MeCH=C(Me)CO2R by PhCH2OH or (RS)-PhCH(Me)OH at 190 °C, the extent of asymmetric induction of Ru2Cl4((−)-diop)3 (1.7–11.4% e.e. with PhCH2OH and 7.4–18.2% e.e. with (RS)-PhCH(Me)OH) decreases with increase in bulkiness of groups R (R=H, Me, Et, n-Bu, and PhCH2) and is not enhanced by the introduction of any groups R with chiral carbon atoms into esters (maximum 15.4% e.e.). The structural change of hydrogen donors from PhCH2OH to (RS)-PhCH(Me)OH appreciably increases the optical purity of the saturated acids and esters, and the chiral α-d-glucofuranose derivatives afford optically active saturated products, even with achiral RuCl2(PPh3)3. Features of the present reaction are discussed in relation to the reaction mechanism.
Electrochemical Additions of the Allyl and the Benzyl Groups of Allyl and Benzyl Halides to Acetone
Authors: Satoh Shohei , Suginome Hiroshi , Tokuda Masao
Published: July 2006

Electrolysis of allyl chloride and five molar excess of acetone in hexamethylphosphoric triamide containing 0.5 M tetrabutylammonium perchlorate gave an addition product, 2-methyl-4-penten-2-ol, in a 53% yield. Allyl groups of 1-chloro-2-methyl-2-propene, 1-chloro-2-butene(3), 3-chloro-1-butene(4), 1-chloro-3-methyl-2-butene(5), and 3-chloro-3-methyl-1-butene(6), and benzyl groups of benzyl chloride, benzyl bromide, and 1-chloro-1-phenylethane can similarly be added to acetone by electrolysis to give the corresponding alcohols in fair to good yields. Among these electrochemical reactions, those of 3, 4, 5, and 6 with acetone give respectively two isomeric homoallyl alcohols, one of the isomers is not accessible by the usual chemical reaction between allylic organometallics and acetone.
Reaction of Malonaldehyde with Nucleic Acid. I. Formation of Fluorescent Pyrimido[1,2-a]purin-10(3H)-one Nucleosides
Authors: Seto Hiroshi , Okuda Taisuke , Takesue Tomoyuki , Ikemura Tadashi
Published: July 2006

The reactions of malonaldehyde with guanosine and 2′-deoxyguanosine proceed slowly under acidic conditions to give new pyrimidopurine nucleosides, 3a and 3b, respectively. These compounds emit strong yellow fluorescence and are hydrolyzed by NaOH into malonaldehyde and guanosine from 3a (2′-deoxyguanosine from 3b). From chemical and spectroscopic evidence, these compounds were deduced to be 3-β-d-ribofuranosylpyrimido[1,2-a]purin-10(3H)-one (3a) and 3-(2-deoxy-β-d-erythro-pentofuranosyl)pyrimido[1,2-a]purin-10(3H)-one (3b). No products were detected in the reaction mixture of malonaldehyde with 1-methylguanosine, adenosine, cytidine, uridine, thymidine, 2′-deoxyadenosine, or 2′-deoxycytidine.
Theoretical Study of Proton and Solvent Effects on Molecular Stacking
Authors: Zuccarello Felice , Raudino Antonio , Buemi Giuseppe , Rigano Carmelo
Published: July 2006

Molecular stacking between π-electron systems was analyzed in connection with effects of external charge and solvent. A perturbation approach was used for calculating intermolecular energies and a discrete plus continuum model was used for solvent effects. The solvent favors stacking in unprotonated systems by hydrophobic forces. In the presence of an external charge the solvent induces dissociative effects on the molecular pairs by electrostatic solvation forces.
Furan Derivatives. V. The Syntheses of 4,5-Dihydro-3H-naphtho[1,8-bc]furans Using Strong Bases
Authors: Horaguchi Takaaki , Narita Hidetaka , Suzuki Tsuneo
Published: July 2006

The reaction of ethyl (4-methoxy-8-oxo-5,6,7,8-tetrahydro-1-naphthyloxy)acetate and potassium hydroxide gave a mixture of 6-methoxy-4,5-dihydro-3H-naphtho[1,8-bc]furan and 6-methoxy-4,5-dihydro-3H-naphtho[1,8-bc]furan-2-carboxylic acid in total yield above 90%. The mechanisms of formation of two products were examined, and potassium 2a-hydroxy-6-methoxy-2a,3,4,5-tetrahydro-2H-naphtho[1,8-bc]furan-2-carboxylate was isolated as a precursor of 6-methoxy-4,5-dihydro-3H-naphtho[1,8-bc]furan. It has become apparent that strong bases such as sodium hydroxide, sodium ethoxide, and sodium hydride were also useful for syntheses of 6-methoxy-4,5-dihydro-3H-naphtho[1,8-bc]furan derivatives.
Solvent Effects on the Nonradiative Relaxation Processes of the Lowest Excited Singlet States of Meso-substituted Bromoanthracenes
Authors: Hamanoue Kumao , Hidaka Toshiharu , Nakayama Toshihiro , Teranishi Hiroshi , Sumitani Minoru , Yoshihara Keitaro
Published: July 2006

From the measurements of the fluorescence lifetimes and the 0-1 emission maxima in solutions, it is concluded that the solvent dependence of the nonradiative transition rates of the lowest excited singlet states of 9-bromoanthracene and 9,10-dibromoanthracene is due to the different extent to which the lowest excited singlet and adjacent higher excited triplet states are stabilized by solvents.
Stereochemistry of Nucleophilic Substitution of Menthyl Derivatives with Anion of Diphenylphosphine Oxide by an Action of Sodium Dihydridobis(2-methoxyethanolato)aluminate
Authors: Yamashita Mitsuji , Soeda Yukio , Suzuki Nobuyoshi , Yamada Manabu , Tsunekawa Kenji , Oshikawa Tatsuo , Inokawa Saburo
Published: July 2006

The reaction of an anion of diphenylphosphine oxide prepared by the action of sodium dihydridobis(2-methoxyethanolato)aluminate on the oxide with various menthyl or neomenthyl halides and sulfonates were studied to clarify the sterochemistry of the substitution. The reaction gave neomenthyl- and methyl-diphenylphosphine oxide in ratios from 100 : 0 to 0 : 100.
A Localized Molecular Orbital Approach to the Bond Moment Theory
Authors: Shinoda Hiroyuki , Miyazaki Tomoo
Published: July 2006

The bond moment theory was reinvestigated by use of localized molecular orbitals derived from INDO canonical orbitals. Bond moments were defined in terms of localized molecular orbital and, together with their derivatives with respect to a C–H stretching motion, were evaluated for some simple molecules; the bond moments of acetylene and hydrogen cyanide in the C–H bending geometry were also calculated. It is concluded that the first-order approximation for the bond moment theory is inadequate to interpret infrared absorption intensity. In the C–H stretching vibration the change in trans-sited bond moment is considerably large.
The Preparation and Photoreation of Spiro[oxirane-2,6′-tricyclo[3.2.1.02,7]oct[3]en]-8′-ones. An Intramolecular Cycloaddition of Photochemically Generated Ketene with the Epoxide Ring
Authors: Nitta Makoto , Omata Akihiko , Nakatani Hazime
Published: July 2006

The oxidations of 1,5-dimethyl- and 1,3,5-trimethyl-6-methylenetricyclo[3.2.1.02,7]oct-3-en-8-ones with 3-chloroperbenzoic acid or thallium(III) acetate resulted in the formation of 1′,5′-dimethyl and 1′,3′,5′-trimethylspiro[oxirane-2,6′-tricyclo[3.2.1.02,7]oct[3]en]-8′-ones (2a and 2b). The oxidation occured stereoselectively on the exocyclic double bond from the exo-side. The photochemical reactions of 2a and 2b resulted in the formation of 4,8-dimethyl- and 4,6,8-trimethyl-3,4-dihydro-1H-2-benzopyran-3-ones, both of which would be derived from an ene-type reaction of the ketene intermediate with the exoxide ring involved in the [4π+2σ] electronic system. The intermediacy of the ketene was assessed by low-temperature infrared spectroscopy as well as by a trapping experiment, the mechanistic pathways were confirmed by conducting the photoreaction in deuterated methanol.
Revision of Structures of Nellionol and Dehydronellionol
Authors: Matsumoto Takashi , Imai Sachihiko , Takeda Shoji , Mitsuki Masanori
Published: July 2006

The structures of nellionol and dehydronellionol were revised respectively to 6α,11,12,16-tetrahydroxyabieta-8,11,13-trien-7-one (12) and 6,11,12,16-tetrahydroxyabieta-5,8,11,13-tetraen-7-one (13) by the following syntheses. A mixture of (15R)- and (15S)-12-methoxyabieta-8,11,13-trien-16-ol, prepared from 13-acetyl-12-methoxypodocarpa-8,11,13-triene, was converted into 11,12,16-triacetoxyabieta-8,11,13-trien-7-one (22) via 16-acetoxy-12-benzoyloxyabieta-8,11,13-trien-11-ol. Treatment of 22 with isopropenyl acetate, followed by oxidation with m-chloroperbenzoic acid and subsequent acetylation, afforded 6α, 11,12,16-tetraacetoxyabieta-8,11,13-trien-7-one, which was hydrolyzed with dilute hydrochloric acid to 12. The ketone 22 was also converted into 13  via 11,12,16-triacetoxyabieta-8,11,13-trien-6-one. The spectral data of 12 and 13 were in good agreement with those of natural nellionol and dehydronellionol.
Synthesis of [0]Orthocyclo[2]orthocyclo[0](1,1′)ferrocenophane and [0]Paracyclo[0](1,1′)ferrocenophane
Authors: Shimizu Iwao , Umezawa Hiroshi , Kanno Toshihiro , Izumi Taeko , Kasahara Akira
Published: July 2006

syn- and anti-[0]Orthocyclo[2]orthocyclo[0](1,1′)ferrocenophan-7-enes were synthesized via an intramolecular reductive coupling of 1,1′-bis(o-formylphenyl)ferrocene with low valent titanium reagents, syn- and anti-[0]Orthocyclo[2]orthocyclo[0](1,1′)ferrocenophanes and [0]paracyclo[2]paracyclo[0](1,1′)ferrocenophane were prepared by the reaction of 1,1′-bis[o-(bromomethyl)phenyl]ferrocene and 1,1′-bis[p-(bromomethyl)phenyl]ferrocene with butyllithium. The transannular π-electronic interactions between two aromatic rings in these compounds were examined on the basis of the NMR and electronic spectra.
Photochemical Activation of Zinc-Carbon and Zinc-Sulfur Bonds in Zinc Porphyrins
Authors: Nukui Masahiro , Inoue Shohei , Ohkatsu Yasukazu
Published: July 2006

Ethyl(N-methyltetraphenylporphinato)zinc (NMTPPZnEt 2) reacts with thiol (RSH: R=Prn, But, Ph) and hydrogen sulfide (H2S) to form N-methyltetraphenylporphinatozinc sulfide (NMTPPZnSR: R=Prn, But, Ph, H). Irradiation with visible light enhances the reactivity of 2 in the reaction with ButSH and brings about the homolytic cleavage of the zinc-sulfur bond of NMTPPZnSPrn in dichloromethane.
Restricted Rotation Involving the Tetrahedral Carbon. IL. Singly peri-Substituted 9-Isopropyltriptycenes Revisited
Authors: Yamamoto Gaku , Oki Michinori
Published: July 2006

9-Isopropyltriptycene derivatives carrying a fluoro, chloro, bromo, or t-butyl substituent in a peri-position were synthesized and their dynamic NMR behavior was studied to see the dependence of the barrier to rotation of the bridgehead substituent upon the bulkiness of the peri-substituent. The data obtained in this work together with those reported earlier disclose that, among the derivatives in which the peri-substituent is not buttressed by the 2-substituent, the peri-methoxy compound has the highest barrier and the barrier decreases as the bulkiness of the peri-substituent increases. 1,2,3,4-Tetrachloro and tetrabromo derivatives show the slightly positive buttressing effect.
Electrochemical Kinetic Parameters of Geometric Isomers of Singly Charged Cobalt(III) Complexes
Authors: Yamada Akifumi , Yoshikuni Tadatsugu
Published: July 2006

The kinetic parameters of electrode reactions of several geometric isomers of singly charged cobalt(III) complexes have been determined by means of Tast polarography. The complexes studied are trans-[Co(NCS)(NO2)(en)2]Cl·H2O, cis-[Co(NCS)(NO2)(en)2]Cl·2H2O, trans-[Co(NO2)2(en)2]NO3, cis-[Co(NO2)2(en)2]NO3, trans-[Co(NO2)2(NH3)4]NO3·0.5H2O, cis-[Co(NO2)2(NH3)4]NO3, trans-[CoCl(NO2)(en)2]NO3, and cis-[CoCl(NO2)(en)2]NO3. These complexes showed two irreversible reduction waves; the first corresponds to CoIII→CoII, and the second, to CoII→Co0. The electrochemical kinetic parameters for the one-electron reduction wave were obtained in 0.1 and 1.0 M acetate buffer solutions. The half-wave potentials for the first wave of the complexes were more positive for the cis isomers than for the corresponding trans isomers. The cathodic rate constants at E=0 for the cis isomers were also larger than those for the corresponding trans isomers. A slight increase in the rate constant with the decrease in ionic strength was observed.
Thermal Properties and Raman Spectra of Crystalline and Vitreous BaZrF6, PbZrF6, and SrZrF6
Authors: Kawamoto Yoji , Sakaguchi Fumiko
Published: July 2006

Differential thermal analysis and Raman spectroscopic studies have been performed of crystalline and vitreous BaZrF6, PbZrF6, and SrZrF6 compounds in order to examine the thermal properties and the F coordination of Zr. The differential thermal analyses clarified the definite phase transformation characteristics of crystalline BaZrF6, and SrZrF6 and also suggested that the low- and high-temperature modifications are present in PbZrF6 as well as in BaZrF6 and SrZrF6. The Raman spectra of crystalline BaZrF6, PbZrF6, and SrZrF6 were discussed in relation to the F coordination of Zr in fluorozirconate compounds. The crystallization behaviors and Raman spectra of vitreous BaZrF6, PbZrF6 and SrZrF6 revealed that Zr in the vitreous compounds is eight-coordinated by F although small amounts of seven-coordinated Zr may exist in vitreous BaZrF6.
Metal Complexes in Organic Synthesis. VIII. Allylic Alcohols as Starting Materials in Palladium-catalyzed Wittig-type Olefinizations
Authors: Moreno-Mañas Marcial , Trius Antonio
Published: July 2006

Allylic alcohols, aldehydes, and triphenylphosphine participate in a one-pot process catalyzed by palladium, which is formally equivalent to the Wittig olefinization. It can be applied to both aliphatic and aromatic aldehydes. The resulting olefins which appear as mixtures of stereoisomers were fully hydrogenated. Two different mechanisms can account for the observed results.
Mechanochemical Decomposition of Dipotassium Peroxodisulfate by Dry Grinding
Authors: Motooka Itaru , Nariai Hiroyuki , Tsuhako Mitsutomo
Published: July 2006

The mechanochemical decomposition of dipotassium peroxodisulfate by dry grinding was investigated by X-ray diffractometry, infrared spectrophotometry, electron spin resonance (ESR) spectrometry, and thermal and volumetric analyses. When dipotassium peroxodisulfate (K2S2O8) was ground, type I of K2S2O8 was transformed into type II and then into type III. With prolonged grinding, the O–O linkage in K2S2O8 was severed to produce KSO4· radicals, which reacted with a little moisture to give KHSO4.
The Determination of 5-Iodouracil Using the o-Hydroxyhydroquinonephthalein–Palladium(II) Complex
Authors: Fujita Yoshikazu , Mori Itsuo , Kitano Shoko
Published: July 2006

A simple and sensitive spectrophotometric procedure was studied for the determination of 5-iodouracil (IU) using the o-hydroxyhydroquinonephthalein(Qn.Ph.)–palladium(II) complex and avoiding any effect of iodide ions. This method could be used in the concentration range of 0–15 μg/10 ml of IU, where the Sandell sensitivity was 0.0020 μg/cm2 for at 630 nm; the coexistence of the iodide ion did not interfere with the determination of IU, even when it was present in a 500-fold excess.
The Stereochemistry of Cross-coupling Adducts of Norbornenes with Butadiene Catalyzed by Ni Complex
Authors: Ishii Yasutaka , Kawahara Masakazu , Noda Toshimitsu , Ishigaki Hiroyuki , Ogawa Masaya
Published: July 2006

The stereochemistry of cross-coupling adducts of norbornenes with butadiene catalyzed by Ni complex generated in situ by NiBr2(Ph3P)2 and NaBH4 in ethanol was investigated. The configuration of four-member cross coupling products could be confirmed by means of independent synthesis.
Synthesis of Lepiochlorin, a Chlorinated Antibiotic, by Use of Electrochemical Haloalkoxylation
Authors: Torii Sigeru , Inokuchi Tsutomu , Kondo Kazumi
Published: July 2006

The fungal metabolite lepiochlorin was synthesized from 2-methyl-4-oxopentanoic acid by the electrochemical chloromethoxylation of 2-methyl-2,4-pentadien-4-olide in MeOH–NH4Cl–(Pt–Pt) system followed by hydrolysis in a mixed solution of dioxane–H2O–concd HCl (25/10/1 V/V/V) in 38% overall yield.
Hydrolysis of p-Nitrophenyl Esters by Hydrophobic Linear Molecule Containing Two Histidine Residues
Authors: Kodaka Masato
Published: July 2006

A new type of linear nucleophile, CH3O–His–CO–(CH2)8–CO–His–OCH3(HisC8His), was designed, and its catalytic behavior for the hydrolysis of p-nitrophenyl acetate, hexanoate and laurate was investigated. It was shown that HisC8His enhanced the hydrolysis of p-nitrophenyl laurate and hexanoate as compared with imidazole both in the absence and presence of methyltrioctylammonium chloride.
An NMR Study on Molecular Interactions in 3-Methylsydnone and Its Aqueous Mixtures
Authors: Tanaka Shoji , Yokoi Masatoki
Published: July 2006

Molecular motion in neat 3-methylsydnone and molecular interaction in 3-methylsydnone–water mixtures were studied by the multinuclear FT-NMR method. The estimated rotational correlation times of the methine carbon and the carbonyl oxygen atom in neat sydnone are 8.6 and 8.1 ps at 40 °C, respectively. According to shift variations of the 13C, 14N, and 17O nuclei of the sydnone molecule in sydnone–water mixtures, the sydnone forms a hydrogen bond with water at the carbonyl oxygen and not at the ring oxygen site. The effect of dissolved paramagnetic ions was investigated on the 13C spin-lattice relaxation time of the carbon atoms of sydnone, and a discussion was made on the possible relative configuration of cation and anion to the solvent sydnone molecule.
One-electron Oxidation Potentials of an NADH Model Compound and a Dimeric Rhodium(I) Complex in Irreversible Systems. A Convenient Determination from the Fluorescence Quenching by Electron Acceptors
Authors: Fukuzumi Shunichi , Hironaka Katsuhiko , Nishizawa Nobuaki , Tanaka Toshio
Published: July 2006

A new methodology for experimental determinations of redox potentials of oxidants or reductants in both reversible and irreversible systems is presented. The Rehm-Weller free energy relationship between the activation free energy ΔG− and the free energy change ΔG for the electron transfer quenching of the excited states of oxidants or reductants by a series of reductants or oxidants is converted to a linear correlation between ΔG\eweq−ΔG and (ΔG\eweq)−1, which can be utilized in convenient determinations of redox potentials of oxidants or reductants. This methodology is established in various reversible systems where the redox potentials of oxidants or reductants determined based on the Rehm-Weller free energy relationship agree well with those determined independently by electrochemical methods. By using this method, one-electron oxidation potentials of two quite different compounds, one is an NADH model compound, 1-benzyl-1,4-dihydronicotinamide (BNAH), and the other [Rh2(dicp)4]2+ (dicp=1,3-diisocyanopropane), in MeCN have been determined as 0.60±0.10 and 0.38±0.10 V vs. SCE, respectively. The relation between the oxidation potential and the oxidation peak potential of BNAH measured by the cyclic voltammetry is discussed in the context of free energy relationships.
Electronic Relaxation Processes from Single Vibronic Levels in the S1(n, π*) State of Pyridine Vapor
Authors: Sushida Kazuyoshi , Fujita Masahisa , Yamazaki Iwao , Baba Hiroaki
Published: July 2006

The rate constants of radiative decay (kF), internal conversion (kIC), and intersystem crossing (kISC) for single vibronic levels in the S1(n, π*) state of pyridine-d0 and -d5 vapors have been determined from measured fluorescence quantum yields (ΦF), intersystem crossing quantum yields (ΦICS), and picosecond fluorescence lifetimes. The ΦISC values are fairly constant in the region of lower excess vibrational energy (<1000 cm−1), while the ΦF values are particularly large for vibronic levels involving non-totally symmetric vibrations, ν16b and ν10a. The latter observation is attributed to both an increase of kF and a decrease of kIC and kISC (relative to the zero-point level) for the ν16b levels (16b2 and l6b26a1), and to an increase of kF for the ν10a levels. The relative values of kF are discussed using the Herzberg-Teller theory of vibronic coupling. The values of kF for 16b1 and 16b2 are significantly larger than that for the zero-point level, though no absorption band corresponding to 16b01 can be observed. In both pyridine-d0 and -d5, the value of kIC is as large as 1.7×1010s−1 even for the zero-point level, which is more than twice the kISC value for the same level.
Fractional Spectrophotometric Determination of Ethylenediaminetetraacetate and nitrilotriacetate as Their Iron(III) Complexes by Use of H- and Na-form Ion Exchange Resin Columns
Authors: Yamaguchi Akihiro , Ohzeki Kunio , Kambara Tomihito
Published: July 2006

The fractional determination of ethylenediaminetetraacetate(EDTA) and nitrilotriacetate(NTA) was carried out by use of hydrogen- and sodium-form ion exchange resin columns. After the conversion of free and complexed EDTA and NTA to the corresponding iron(III) complexes, two aliquots of the sample solution were separately passed through the columns. The iron(III)–EDTA complex was stable in both columns but iron(III)–NTA complex was completely decomposed in the hydrogen-form resin column, therefore, both of iron(III)–EDTA and –NTA were found in the effluent of sodium form resin column but only iron(III)–EDTA was found in the effluent of hydrogen-form resin column. The complexes in the respective effluents were determined spectrophotometrically at 255 nm. The recovery tests of EDTA and NTA from the synthetic sample solutions containing various metal ions were examined and the results observed were satisfactory.
Synthetic Studies on the Validamycins. VIII. Synthesis of Dl-2-Deoxyvalidoxylamine B and Related Compound
Authors: Ogawa Seiichiro , Ito Hiroyuki , Suami Tetsuo
Published: July 2006

Dl-2-Deoxyvalidoxylamine B and its diastereomer have been synthesized by the reaction of the protected Dl-valienamine and the anhydro derivative of (hydroxymethyl)cyclohexanetetrol followed by removal of the protecting groups.
Nonequilibrium Thermodynamics of the Ion and Solvent Transports through Ion-exchange Membrane
Authors: Kimizuka Hideo , Nagata Yoshihiko , Kaibara Kozue
Published: July 2006

A theory for the ion and solvent transports through membrane has been developed on the basis of nonequilibrium thermodynamics. The fluxes were represented as linear functions of the effective driving potentials. The theory is reduced to that of Katchalsky when the concentration ratio of two aqueous solutions is near unity and the solutions are dilute. The effect of solvent flow on the interionic correlations was discussed. It was pointed out that Despic and Hills’ theory of the electroosmotic effect on the membrane conductance is not valid with respect to both theoretical and experimental aspects. The comparison of the present theory with the previous one was also made. The six independent phenomenological coefficients (elements of the conductance matrix) were experimentally determined as a function of concentration with the concentration cell consisting of the amphoteric ion-exchange membrane and aqueous calcium chloride solutions. The membrane properties were discussed in terms of the conductance matrix. The diffusional ion conductance was much greater than the electrical ion conductance, as an indication of the failure of the Nernst-Einstein relation. The cation-anion coupling coefficient was close to unity whereas the ion-water coupling coefficients were less than 0.1. The solvent effects on the interionic conductance elements were found to be small in spite of the fact that the water permeability was extremely high. The distinction between the cationic and amphoteric ion-exchange membranes was explored in terms of the elements of the conductance matrix.
Electric Field Orientation of Poly(p-styrenesulfonate) and Its 9-Aminoacridinium Complex as Studied by Square-pulse Transient Electric Birefringence
Authors: Yamaoka Kiwamu , Ueda Kazuyoshi
Published: July 2006

Electric birefringence was measured at 20 °C and at 535 nm for sodium poly(p-styrenesulfonate) (NaPSS), with and without added sodium chloride, and the 9-aminoacridinium (AA) complex in aqueous solutions. The field strength dependence of both the steady-state EB (Δn(∞)) the field-free decay time (〈τ〉EB) was examined. Charge suppression by added Na+ ions or neutralization by strongly bound AA decreased both Δn(∞) and 〈τ〉EB considerably, altering not only the optical factor Δg and electric moments, but also the backbone chain length. The weight-average values of chain length (lw), pseudopermanent dipole moment (μw), counterion-induced electric polarizability anisotropy (Δαw), and the length-independent values of Δg were estimated by analyzing the experimental data on the basis of the “classical” orientation function which takes into account the continuous distribution of chain length for the polydisperse NaPSS sample. The electric field orientation of NaPSS and the AA-complex could be described by the interaction between an applied field and the electric moment which transforms from counterion-induced type in the extremely low field region (<1.5 kV/cm) to saturated induced permanent type at higher fields.
Potentiometric and Calorimetric Studies on the Formation of Ethylenediamine Complexes of Nickel(II) Ion in Water and Dioxane–Water Mixtures
Authors: Ishiguro Shin-ichi , Oka Yoshihiro , Ohtaki Hitoshi
Published: July 2006

Equilibria between ethylenediamine and protons or nickel(II) ions have been investigated at 25 °C by means of potentiometric and calorimetric titrations in water and in dioxane–water mixtures (the dioxane contents are 0.1 and 0.2 mole fractions, which correspond to 35.2 and 55.0%w/w, respectively) containing 3 mol dm−3 LiClO4 as a constant ionic medium. Thermodynamic parameters (ΔG°, ΔH°, and ΔS°) referring to the formation of the species HL+, H2L2+, NiL2+, NiL22+, and NiL32+ (L denotes ethylenediamine) have been determined in the solutions. All the formation constants of the nickel(II)–ethylenediamine complexes increased with increasing dioxane content in the solvent mixtures, although the formation constants of the ethylenediammonium ions remained practically unchanged. On the other hand, enthalpies referring to the formation of the nickel(II)–ethylenediamine complexes became less negative, and thus entropies for the corresponding reactions increased remarkably with increasing dioxane content in the mixtures. The solvent effects on the thermodynamic parameters of the complex formation of nickel(II) ions with ethylenediamine are discussed in terms of enhancement of solvation of the complexes due to weakening of the hydrogen-bonded structure of the bulk water by the addition of dioxane.
The Cycloaddition Reaction of N-Imidoyl Sulfoximides with Diphenylcyclopropenone to Yield Pyrimidinone or Pyrrolinone Derivatives
Authors: Yoshida Hiroshi , Sogame Shingo , Takishita Yasunori , Ogata Tsuyoshi
Published: July 2006

N-Imidoyl sulfoximide (7) reacted with diphenylcyclopropenone (2) at 130 °C to yield a mixture of 1,2-disubstituted 5,6-diphenyl-4(1H)-pyrimidinone (6) and N-(4-oxo-2-pyrrolin-5-yl)sulfoximide (10), which might be formed by [3+3] and [2+3] cycloaddition reactions between 2 and 7. The yields of 6 and 10 depended on the electronic and steric effects of the substituents of 7.
The Recovery of Lithium from Geothermal Water in the Hatchobaru Area of Kyushu, Japan
Authors: Yanagase Kenjiro , Yoshinaga Tetsutaro , Kawano Kentaro , Matsuoka Toshikazu
Published: July 2006

The recovery of lithium from geothermal water at Hatchobaru in Kyushu, Japan, was investigated. A coprecipitation method using aluminium salts was employed. The lithium concentration in the geothermal water used in the present study was about 10 ppm. To make our experimental results more applicable for geothermal water, a reference lithium solution (10 ppm) was also studied as a control solution. A perfect recovery of lithium was obtained for the reference lithium solution by choosing appropriate conditions. For geothermal water, the yield of Li was not so good as in the control solution. However, an almost complete recovery of lithium was attained for geothermal water by the removal of calcium ions and polymerized silica. The mechanism of Li recovery was also considered.
X-Ray Structure of (10R)-10-Bromo-10-deoxyhexahydrolaurefucin
Authors: Furusaki Akio , Matsumoto Takeshi , Kikuchi Hajime , Suzuki Teruaki , Suzuki Minoru , Kurosawa Etsuro
Published: July 2006

The main product of the bromination of hexahydrolaurefucin with sulfinyl bromide has been established as (10R)-10-bromo-10-deoxyhexahydrolaurefucin by X-ray crystal structure analysis.
A New Apparatus for Surface Pressure Measurements
Authors: Iwahashi Makio , Middleton Steven R , Seimiya Tsutomu , Pethica Brian A
Published: July 2006

A new type of horizontal film balance is described. The principal features of the balance are the use of lightly paraffined silk threads without the conventional floating barrier of the Langmuir surface balance and of a strain gauge as the surface pressure detector.
Nitrosyl(protoporphyrin IX dimethyl ester)iron(II) Complexes with Nitrogenous Bases. The Basicity Dependence of the NO Stretching Frequency
Authors: Yoshimura Tetsuhiko
Published: July 2006

The IR spectra of nitrosyl(protoporphyrin IX dimethyl ester)iron(II) [Fe(ppdme)(NO)] complexes with various nitrogenous bases (B), such as imidazoles, pyridines, cyclic secondary amines, and aliphatic amines, were measured in benzene and 1,2-dichloroethane. The NO stretching frequencies (νNO) of these complexes and the equilibrium constants in equilibrium, [Fe(ppdme) (NO)]+B\ightleftharpoons[Fe(ppdme)(NO)B], decreased and increased respectively with an increase in the basicity, pKa(BH+), of the bases. These results are discussed in relation to the σ- and π-bonding abilities of the bases.
Synthesis and Magnetic, Spectral, and Electrochemical Properties of Strati-bis Cobalt(II) Complexes
Authors: Nakamura Masaaki
Published: July 2006

Strati-bis cobalt(II) complexes, [Co2(sata)]·2H2O and [Co2(sacta)] have been prepared, where H4(sata) and H4(sacta) denote 1,2,3,4-tetrakis(salicylideneamino)-2,3-dimethylbutane and 1,2-bis(salicylideneamino)-1,2-bis (salicylideneaminomethyl) cyclohexane, respectively. Since their magnetic moments are 4.89 and 4.73 BM at room temperature, respectively, the cobalt(II) ions in [Co2(sata)] and [Co2(sacta)] have a high spin d7 configuration. From the temperature dependence of magnetic susceptibilities of these complexes the antiferromagnetic interaction exists between the two cobalt(II) ions. The oxidation potentials for CoII→CoII are observed at lower potentials compared with those of corresponding mononuclear cobalt(II) complexes.
Induced Circular Dichroism in the Complex of Poly(l-arginine) Hydrochloride with Azo Dyes
Authors: Yamamoto Hiroyuki , Nakazawa Ayako
Published: July 2006

The induced circular dichroism (CD) spectra of the poly(l-arginine) hydrochloride–azo dye complexes were measured. The induced CD arose from the azo dyes bound to the polypeptide in the α-helical conformation. The configuration of the transition dipole moments of dye was examined by the exciton chirality method.
Diazomethane Ring-expansion of (−)-D3-Trishomocubanone. Preparation and Chiroptical Properties of a Series of [m.1.1]Triblattanes
Authors: Nakazaki Masao , Naemura Koichiro , Hashimoto Masaki
Published: July 2006

Optically active [3.1.1], [4.1.1], [5.1.1], and [6.1.1]triblattanes were prepared through the diazomethane ring-expansion of (−)-D3-trishomocubanone. The absolute molecular rotations of [m.1.1]triblattanes were found to increase with m begining from m=0 till m=2. On going from m=2 to m=3, [M]D abs. abruptly drops, then the value remains almost constant till m=6.
Surface Treatment of Inorganic Pigments by Nε-Acyllysine
Authors: Esumi Kunio , Yoshida Shigeki , Meguro Kenjiro
Published: July 2006

Inorganic pigments(calcium carbonate, iron oxide, and titanium dioxide) were treated with Nε-lauroyl-l-lysine, which is almost insoluble in both polar and nonpolar solvents. Two methods were employed for the treatment: (1) grinding of various weight proportional mixtures of pigment and the N-acyllysine; (2) adsorption of the N-acyllysine from its calcium ethylate solution on pigment. In method(1), the sufficient hydrophobic treatment was made when the weight percent of the N-acyllysine in the mixture was above about 30%. On the other hand, in method(2), although the amount adsorbed of the N-acyllysine was about in the range of 10−6 mol/g, the treated pigment showed a hydrophobicity. The critical surface tension of the treated samples estimated by using various mixtures of methanol and water was in the range from 23 to 39 dyn/cm.
The Selectivity Characteristics of Surfactant Ion-sensitive Nitrobenzene-membrane Electrode
Authors: Satake Iwao , Noda Shun-ichi , Maeda Tamaki
Published: July 2006

The selectivity coefficients of nitrobenzene-membrane electrode containing dodecyltrimethylammonium dodecyl sulfate as an ion exchanger were determined. For a homologous series of surfactant ions, the logarithm of the selectivity coefficient was found to increase linearly with increasing hydrocarbon chain length. The selectivity sequence for anionic surfactant ions with the same alkyl chain length became alkyl-benzenesulfonate ion>alkyl sulfate ion>>alkanesulfonate ion, while that for cationic ones became alkyltrimethyl-ammonium ion≈1-alkylpyridinium ion>>alkylammonium ion. These results can reasonably be interpreted in terms of the partition coefficient of surfactant ion between aqueous and membrane phases. A tentative estimation based on the theory of liquid-membrane electrode led to −2900 J mol−1 for the standard free energy of transfer of a methylene group from water to nitrobenzene.