bluuebunny/crossref_metadata_2025 huggingface dataset:
Kinetics of the Thermal Intramolecular Redox Reaction of Pentaamminenitrosylcobalt(III) Chloride in the Solid State
Authors: Miyokawa Kikuo , Masuda Hakaru , Wakita Hisanobu
Published: July 2006

The kinetics of the thermal intramolecular redox reaction between NO− and Co(III) in [Co(NH3)5NO]Cl2 has been studied by means of thermogravimetric and thermomagnetic analyses. The reaction is found to follow the first-order equation, with ΔH\eweq=129±6 kJ mol−1 and ΔS\eweq=14±16 J mol−1 K−1. These results are compared with the kinetics of other nitrosylcobalt(III) and hexaamminecobalt(III) complexes.
A Glassy Carbon Electrode Modified with N-(2-Hydroxybenzyl)chitosan for Voltammetric Determinations of Cu2+ and Pb2+
Authors: Kurauchi Yoshiaki , Tsurumori Eiichi , Ohga Kazuya
Published: July 2006

A glassy carbon electrode was chemically modified with N-(2-hydroxybenzyl)chitosan which could act as an agent to preconcentrate Cu2+ and Pb2+. The modified electrode was stable for 30 d and its calibration curves for the voltammetric determination of these ions are linear in the concentration range of (1–10)×10−7 mol dm−3. The usage limitation of this electrode has also been discussed.
Photochemical Decarbonylation of (α-Arylacyl)triphenylgermane
Authors: Kiyooka Syun-ichi , Shibuya Tsutomu , Shiota Fuminori , Fujiyama Ryoji
Published: July 2006

(α-Arylacyl)triphenylgermanes were prepared from the corresponding esters with triphenylgermyllithium at room temperature in good yields. Photochemical decarbonylation of (α-arylacyl)triphenylgermanes took place under UV irradiation to quantitatively give (α-arylalkyl)triphenylgermanes without by-products.
A Lattice Gas Model for Neopentane
Authors: Shinmi Masato , Huckaby Dale A
Published: July 2006

A lattice gas model for neopentane on a bcc lattice was considered. The equation of state and critical point were calculated using a Guggenheim–McGlashan approximation. The liquid phase in the model exhibits the same type of short-range orientational ordering proposed by Nishikawa to exist in liquid neopentane.
Reduction of Halonitrobenzenes with Disodium Ditelluride in N,N-Dimethylformamide
Authors: Zingaro Ralph A , Herrera Chris
Published: July 2006

The reaction of disodium ditelluride in N,N-dimethylformamide with o-halonitrobenzenes results in displacement of the halide, reduction of the nitro group and a ring closure reaction which yields phenazines.
Structural Features and Biological Studies of Dioxomolybdenum(VI) Complexes of Thiosemicarbazones
Authors: Kanoongo Neeta , Singh Ranvir , Tandon Jagdish Prasad
Published: July 2006

Synthesis, characterization, and spectral features of six-coordinated dioxomolybdenum(VI) complexes of the type, [MoO2(tscz)2] (where Htscz represents the thiosemicarbazone moiety) are reported. These have been characterized by elemental analysis, conductance measurements, molecular weight determinations, and magnetic studies. Based on IR, 1H NMR, 13C NMR, and electronic spectral studies, an octahedral geometry with cis-MoO2 structure has been proposed. The antibacterial and fungicidal activities of two representative ligands and their dioxomolybdenum complexes have also been evaluated and discussed.
A Simple Iterative Approach to the Synthesis of cis-cisoid-cis-Tricyclo[6.3.0.02,6]undecane Carbon Skeleton
Authors: Vankar Padma S , Chandrasekaran Srinivasan
Published: July 2006

In an iterative synthesis utilizing only four reagents, cyclopentanone has been converted into cis-cisoid-cis-tricyclo[6.3.0.02,6]undecane carbon skeleton in high yield.
Optical Resolution of C3 Cyclotriveratrylenes and D3 Cryptophanes by Liquid Chromatography on Chiral Stationary Phase Chiralpak-OT(+)
Authors: Tambuté André , Canceill Josette , Collet André
Published: July 2006

A series of C3 Cyclotriveratrylenes and D3 cryptophanes have been resolved by HPLC on Chiralpak-OT (+), allowing the first direct enantiomeric excess assessments for these substances. These results confirm the usefulness of this chiral stationary phase for the resolution of aromatic compounds and extend its scope of application to new classes of highly symmetrical molecules.
Two-Bond Deuterium Isotope Effects on 13C Chemical Shifts of Phenols
Authors: Nakashima Yasuki , Yoshino Akihiro , Takahashi Kensuke
Published: July 2006

Two-bond deuterium isotope effects on 13C chemical shifts of 28 substituted phenols are reported and explained in terms of the additivity of substituent parameters which are correlated with the SCS of 13C NMR.
The Crystal and Molecular Structures of Two 1:2 Complexes of 1,4-Diazabicyclo[2.2.2]octane (DABCO) with 1-(o-Chlorophenyl)1-phenyl-2-propyn-1-ol (CPPOH), and Those of Two 1:2 Complexes of N,N′-Dimethylpiperazine (DMP) with CPPOH
Authors: Yasui Masanori , Yabuki Tetsuro , Takama Masaaki , Harada Shigeharu , Kasai Nobutami , Tanaka Koichi , Toda Fumio
Published: July 2006

X-Ray crystal structure analysis of the title four complexes showed that crystals consist of CPPOH···achiral diamine···CPPOH units. In the first two crystals a DABCO molecule is bound by two (−)-CPPOH molecules (1) or by (+)- and (−)-CPPOH (2) to form 1:2 complex by strong intermolecular O–H···N hydrogen bonds [O–H···N=2.707(3) and 2.755(3) (1) and 2.704(4) and 2.747(4) Å (2)]. The latter two crystals are respectively formed by (+)-CPPOH···DMP···(−)-CPPOH complex (3) [O–H···N=2.771(3) Å] and (−)-CPPOH···DMP···(−)-CPPOH complex (4) [O–H···N=2.768(5) and 2.730(6) Å].
The Model Compounds and the Conformational Analysis of Poly(thiomethylene)
Authors: Miyasaka Taira , Yoshida Takaichi
Published: July 2006

The conformational energies of model compounds of poly(thiomethylene), CH3(SCH2)nSCH3, (n=1–6) were calculated by the molecular-mechanics method. Based on these conformational energy differences, the configuration-dependent properties of poly(thiomethylene) were estimated under the rotational isomeric-state approximations. The first-order interaction energy of the (Remark: Graphics omitted.) bond, obtained from the energy differences among the conformers of CH3(SCH2)3SCH3, is coincident with that estimated from the same bond sequence for poly(1,3-dithiocane). Based on this coincidence, the monomeric sequential length of the model compound, which is representative of poly(thiomethylene), was decided. The propriety of the method of coupling the molecular-mechanics with the statistical-mechanics was also demonstrated.
Preferential Solvation of Ni(II) and Mg(II) Ions in Water–Acetonitrile Mixtures. Enthalpies of Transfer and the Electronic Spectra
Authors: Miyaji Kiyoshi , Nozawa Kiyokazu , Morinaga Kenichi
Published: July 2006

The enthalpies of transfer (ΔHt°) from water to water-acetonitrile (W–AN) mixtures for Ni2+ and Mg2+ ions were estimated using the enthalpies of dilution of the concentrated aqueous electrolyte solutions into water and mixtures, and the enthalpies of solution of water in the mixtures. The ΔHt° values for these ions decreased with an increase in the mole fraction of AN (xAN) in the range of xANca. 0.9. The values of ΔHt° for the Ni2+ ion were more negative than those for the Mg2+ ion throughout the xAN regions, especially in the extremely AN-rich region and in pure AN. The average number of coordinated water molecules, N, for the [Ni(AN)6−N(W)N]2+ ion in the mixtures (xAN=0.2, 0.6, and 0.9), as estimated from the electronic absorption spectra, was always greater than that calculated on the basis of the bulk-solvent composition, indicating that the Ni2+ ion was preferentially solvated by water. These results, including the conductance data, were discussed in terms of the principle of hard and soft acid and base.
Reduction of N3− by [Mo2Fe6S8(SPh)9]3− Modified Glassy Carbon Electrode—Model Study of Nitrogenase
Authors: Tanaka Koji , Kuwabata Susumu , Denno Satoshi , Tanaka Toshio
Published: July 2006

The reduction of N3− by a (Bu4N)3[Mo2Fe6S8(SPh)9] modified glassy carbon electrode has been conducted in a pH region 5 to 12 in water. In neutral and acidic conditions, N3− undergoes two-and six-electron reductions to afford not only N2 and NH3 but also N2H4, and the total amounts of N2 and N2H4 produced were essentially consistent with that of NH3. On the other hand, no N2H4 formation was observed in the pH region higher than 10, where an equal amount of N2 and NH3 was formed. The rate of N2H4 formation was linearly proportional to a concentration of N3H, which exists as an equilibrium mixture with N3− in the aqueous phase, while that of N2 evolution was controlled by the concentration of free N3− in H2O. These observations indicate that N2H4 and N2 result from the coordination of N3H and N3− to the molybdenum–iron sulfur cluster, respectively.
Dinuclear Complexes of Tetrathia[10]metallocenophanes with Silver(I) Ion: Slightly Distorted Square-Pyramidal Coordination of Ag(I) Ion
Authors: Akabori Sadatoshi , Sato Sadao , Sato Masaru , Takanohashi Yoshinori
Published: July 2006

Tetrathia[10](1,1′)ferrocenophane reacts with silver(I) perchlorate and/or trifluoromethamesulfonate to form dimeric 1 : 1 complexes (2c and 2d) in 73 and 60% yields, respectively. The corresponding complexes (2a and 2b) of tetrathia[10](1,1′)ruthenocenophane were also obtained in 45 and 33% yields, respectively. The crystal structure of complex 2c was determined by the X-ray method. The crystal data: monoclinic, space group P21⁄a, a=19.227(3), b=10.619(3), c=9.739(2) Å, β=91.71(2)°, U=1987.8 Å3, Dc=2.02 g cm−3, Z=4, μ(Mo Kα)=23 cm−1, R=0.075. In complex 2c the inner coordination sphere of the silver is completed by a sulfur atom of another ligand bonded axially to produce a five-coordinate silver ion with an overall slightly distorted square-pyramidal geometry. The temperature dependence of the 1H NMR spectra of 2 was also examined. The rate between the silver free ligand 1a and complex 2b at room temperature was very first by the 1H NMR scale.
Syntheses and Properties of Quinonoid Mesoionic Compounds
Authors: Araki Shuki , Aoyama Naomitsu , Butsugan Yasuo
Published: July 2006

Quinonoid mesoionic compounds having a 2,3-diphenyltetrazolium ring were synthesized and characterized spectroscopically. Compounds possessing an inserted benzene ring were found that a dipolar (5-tetrazolylio)phenolate structure contributes importantly to the ground state of the mesoions. On the contrary, a mesoion having an inserted anthracene ring is a less polar compound, anthraquinone methide structures being dominant in its ground state electronic structure.
Synthesis, Structure, and Properties of Triple-Layered [2.2][2.2]Naphthalenophane
Authors: Otsubo Tetsuo , Aso Yoshio , Ogura Fumio , Misumi Soichi , Kawamoto Atsushi , Tanaka Jiro
Published: July 2006

The title compound was synthesized in a similar manner to a simple access to triple-layered [2.2][2.2]paracyclophane. Its structure was elucidated by X-ray crystallographic analysis. The outer naphthalene rings are bent into a boat form and the inner naphthalene ring is bent into a twist form. These naphthalenes are stacked in layers within van der Waals contact. Therefore, there is a strong transannular π-electronic interaction between them, which brings about characteristic bathochromism, hyperchromism, and broadening in the electronic spectrum. These effects are more prominent than those of the double-layered homologue.
Immobilized β-Cyclodextrins. Preparation with Various Crosslinking Reagents and the Guest Binding Properties
Authors: Sugiura Izuru , Komiyama Makoto , Toshima Naoki , Hirai Hidefumi
Published: July 2006

β-Cyclodextrin (β-CyD) was immobilized by crosslinking with 1,2-ethanediol diglycidyl ether, 1,4-buthanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, 1,3-butadiene diepoxide, 1,7-octadiene diepoxide, and epichlorohydrin. The molar ratio of the crosslinking residue to β-CyD (degree of crosslinking) for each macromolecular product was determined by the corresponding elemental analysis. The equilibrium constant K of complex formation of each crosslinking macromolecule for cresols, phenol, nitrophenols, and 2-naphthol was determined, respectively, by the use of electronic absorption spectroscopy in pH 4 and 10 (or 11) buffer solutions. The concept of a hydrophobic enhancement coefficient R was introduced in order to compare the effect of a hydrophobic crosslinking residue upon the complex formation of the immobilized CyD.
The Determination of the Selectivity Coefficient of Na+ versus Li+ on Prussian Blue Thin Film in Propylene Carbonate by Means of a Quartz Crystal Microbalance
Authors: Aoki Katsunori , Miyamoto Takeshi , Ohsawa Yasuhiko
Published: July 2006

The cation selectivity on a Prussian Blue (PB) modified electrode in propylene carbonate was examined by means of a quartz crystal microbalance. It was found that the selectivity coefficient of Na+ versus Li+ on the PB film was about 15.
Formation of Solvent-Separated Ion Pairs in Calixarene Ester–Alkali Picrate Complexes
Authors: Arimura Takashi , Kubota Michio , Matsuda Tsutomu , Manabe Osamu , Shinkai Seiji
Published: July 2006

Association constants (Ka) of calix[n]arene esters (1n: n=4, 6, 8) for alkali picrates have been determined in tetrahydrofuran and compared with the 1n-induced bathochromic shifts of the absorption maxima of alkali picrates. It has been established that (1) 1n’s mostly form the 1 : 1 complexes with alkali metal cations, (2) the Ka values for 1n are generally smaller than those for crown ethers, and (3) the certain M+–1n complexes are considerably solvent-separated because of the “encapsulation effect” of the calixarene cavity. This is the first example for the systematic investigation on the relation between Ka and the geometry of the calixarene ester complexes.
The Preparation of Stable Colloidal Poly(vinyl alcohol) Composites of Cu2O and Cu
Authors: Yokoi Hiroshi , Kadowaki Akihide , Ikoma Shuji
Published: July 2006

Stable colloidal particles of reddish brown Cu2O–PVA and grayish black Cu–PVA composites have been prepared by the reduction of green Cu2+–PVA complexes in aqueous solutions with hydrazine, at the [hydrazine]/[Cu2+] ratios of 1–3 and 15 or more respectively, where PVA represents poly(vinyl alcohol). The average diameters of the Cu2O and Cu particles in these composites have been estimated to be about 200 and 300 Å respectively from the half widths of the X-ray diffraction peaks for the corresponding powder samples.
The Magnetic Predissociation of the B3Π0+u State of the Iodine Molecule
Authors: Baba Masaaki , Kimura Misako , Tsuboi Toshiyuki , Kato Hajime , Nagakura Saburo
Published: July 2006

It is shown that the predissociation of I2 excited to the B3Π0+u state can occur through the coupling with the 24311Πu state by gyroscopic and Zeeman interactions. The interaction matrix elements between the B3Π0+u and 24311Πu states are shown to be nonzero, for the 24311Πu state is mixed significantly with the 24313Π1u state by the spin-orbit interaction. The v, J dependence of the magnetic-quenching ratios of the B3Π0+u−X1Σ+g fluorescence intensity has been measured and analyzed. The rate constants of the magnetic predissociation in the B3Π0+u state have also been evaluated. The magnetic-field dependence of the hyperfine structure has been measured by means of the Doppler-free intermodulated fluorescence method.
Synthesis of 4-[(E)-1-Alkenyl]-2-hydroxybutanolides and (Z)-4-Alkylidene-2-butenolides through Cycloadditions Using a Phosphorus-Functionalized Nitrile Oxide
Authors: Kanemasa Shuji , Nakagawa Norihiko , Suga Hiroyuki , Tsuge Otohiko
Published: July 2006

A sequence of cycloadditions of (diethoxyphosphinyl)acetonitrile oxide with α,β-unsaturated esters, the Raney Ni reduction of the resulting cycloadducts, the Horner–Emmons olefination, and the carbonyl reduction with sodium borohydride leads to 5-[(E)-1-alkenyl]-3-hydroxy-4,5-dihydro-2(3H)-furanones which can be converted into (Z)-5-alkylidene-2(5H)-furanones in two steps.
Catalysis by Heteropoly Compounds. XIII. An Infrared Study of Ethanol and Diethyl Ether in the Pseudoliquid Phase of 12-Tungstophosphoric Acid
Authors: Lee Kwan Young , Mizuno Noritaka , Okuhara Toshio , Misono Makoto
Published: July 2006

Ethanol, diethyl ether, and water absorbed in, and their thermal desorption from, the pseudoliquid phase of 12-tungstophosphoric acid have been studied by means of infrared spectroscopy. For all three molecules, the state of the absorption of 6 molecules per anion, H3PW12O40·6R2O (R; C2H5 or H), was quite stable and the secondary structures were similar. The intensities of the C–H vibrations indicated that the methyl group of the ethanol molecules interacted with the anions and that its interaction became stronger as the amount of absorbed molecules decreased. In the thermal desorption of absorbed ethanol or diethyl ether, a protonated monomer and dimer as well as an ethoxy group were detected by means of infrared spectroscopy. These species are reaction intermediates of the dehydration of ethanol which were assumed previously (J. Am. Chem. Soc., 109, 5535 (1987)). It was also found that, upon the dehydration of H3PW12O40·6H2O, the proton which had been hydrogen-bonded to the oxygen atom of the water molecule ((H2O)2H+) migrated onto the bridging oxygen of the heteropoly anion (PW12O4O403−).
Interactions between the Tris(1,10-phenanthroline)iron(II) Cation and Anionic Surfactants: Diffusion and Conductance Studies
Authors: Tominaga Toshihiro , Maruyama Toru , Koshiba Takayuki , Yamamoto Yuroku
Published: July 2006

Tracer diffusion coefficients for the [Fe(phen)3]2+ cation (phen=1,10-phenanthroline) have been measured in aqueous solutions of sodium 1-hexane-, 1-octane-, 1-decane-, and 1-dodecanesulfonate (NaDSO) in concentration ranges below the critical micelle concentrations of the surfactants and at 298.2 K. The diffusion coefficient decreases with an increase in the concentration of the surfactants. At a fixed concentration, the diffusion coefficient decreases with an increase in the carbon number of the surfactants. The results are compared with our previous results in sodium dodecyl sulfate (NaDS) solutions. The conductivities of the NaDSO and NaDS solutions were also measured at 298.2 K in the presence and absence of [Fe(phen)3]SO4. In the presence of [Fe(phen)3]SO4, the molar conductivities of the surfactants first decrease, then increase, and finally decrease again with an increase in the concentration of the surfactants.
Thermal Isomerization of 1′,3′,3′-Trimethyl-8-nitrospiro[2H-1-benzopyran-2,2′-indoline]-6-carboxylic Acid
Authors: Nishimura Norio , Miyake Jun’ichi , Sueishi Yoshimi
Published: July 2006

The rates of thermal isomerization of 1′,3′,3′-trimethyl-8-nitrospiro[2H-1-benzopyran-2,2′-indoline]-6-carboxylic acid (6-COOH-8-NO2-SP) from its spiro form (SP) to its merocyanine form (MC) have been measured in some solvents and at high pressures. The equilibrium constants between these isomers at atmospheric pressure and at 30 °C are in the range of 0.25 to 2.52 depending on solvents. The activation volumes are 0.2–3.4 cm3 mol−1, while the reaction volumes are −7.9–−22.3 cm3 mol−1. Thus the volume profile was found to have a maximum, as predicted previously.
Comparison between Optical Properties of Sulfates and Hydrogensulfates in Halogen-Bridged Mixed-Valence Platinum(II, IV) Complexes
Authors: Matsushita Nobuyuki , Kojima Norimichi , Ban Toshiro , Tsujikawa Ikuji
Published: July 2006

Syntheses and optical properties of some new halogen-bridged mixed-valence platinum complexes analogous to Wolffram’s Red Salt, [Pt(en)2][PtBr2(en)2](HSO4)4 (PBHS), [Pt(en)2][PtI2(en)2](HSO4)4·4H2O (PIHS), and [Pt(en)2][PtX2](en)2](SO4)2·6H2O {X=Br(PBSW), I(PISW)}, are reported. The powder X-ray diffraction pattern shows that PBHS is isomorphous with [Pt(en)2][PtCl2(en)2](HSO4)4 (PCHS), and that PBSW and PISW are isomorphous. The hydrogensulfates PBHS and PIHS crystallize from an aqueous sulfuric acid solution, whereas the sulfates PBSW and PISW crystallize from an aqueous solution. The single crystal absorption spectra of PBHS, PIHS, PBSW, and PISW have been investigated at 4.2 K. The intense optical absorption due to intervalence charge-transfer transition from Pt(II) to Pt(IV) has been observed for the light polarized parallel to the Pt chain axis (E//chain). From the comparison of the energy of the intervalence charge-transfer absorption edges in PBHS, PBSW, and PISW, one can conclude that the influence of the substitution of the counterions HSO4− with SO42− on the Pt(II)–Pt(IV) mixed-valence state is no less better than that of the substitution of the bridging halogen. The role of the counterion on the mixed-valence state is explained by the hydrogen bond network (Pt–NH···counterion···HN–Pt) on individual chains.
An X-Ray Diffraction Study on the Structure of Solvated Cadmium(II) Ion and Tetrathiocyanatocadmate(II) Complex in N,N-Dimethylformamide
Authors: Ozutsumi Kazuhiko , Takamuku Toshiyuki , Ishiguro Shin-ichi , Ohtaki Hitoshi
Published: July 2006

The structure of solvated cadmium(II) ion and the tetrathiocyanatocadmate(II) complex in N,N-dimethylformamide (DMF) has been determined by means of X-ray diffraction at 25 °C. The radial distribution curve for a cadmium(II) perchlorate DMF solution is well explained in terms of the presence of the octahedral [Cd(dmf)6]2+ complex with the Cd–O bond length of 229.6(4) pm, which is practically the same as that within [Cd(dmso)6]2+ in DMSO and [Cd(H2O)6]2+ in H2O. It is also found that the tetrathiocyanatocadmate(II) complex has a tetrahedral structure, [Cd(NCS)3(SCN)]2−, with three Cd–N and one Cd–S bonds, the distances being 223(2) and 257(2) pm, respectively. The coordination structure of the complex in DMF is different from that found in aqueous solution, [Cd(NCS)2(SCN)2]2−.
Polymer Reagents Derived from Sodium p-Styrenesulfonate: N-Methyl-N-nitroso-p-styrenesulfonamide and p-Styrenesulfinic Acid Polymers
Authors: Kamogawa Hiroyoshi , Kitamura Tomoo
Published: July 2006

N-Methyl-N-nitroso-p-styrenesulfonamide (1) was synthesized starting with sodium p-styrenesulfonate (3). Monomer 1 and sodium p-styrenesulfinate (2), also synthesized starting with 3, were polymerized and polymer of 2 was converted to corresponding free acid (9). The function of polymer of 1 as the reagent attaching the CH2 group to the carbonyl carbon by insertion and that of polymer 9 as the catalyst for cis→trans isomerization were investigated for various compounds, including cyclohexanone and benzaldehyde and ethyl oleate. The effects of these polymer reagents as compared with those of the corresponding model compounds were discussed.
The Preparation of Poly(3-methoxy-2,5-thiophenediyl) with Iron(III) Chloride and Its Properties
Authors: Tanaka Susumu , Kaeriyama Kyoji
Published: July 2006

Soluble and conductive poly(3-methoxy-2,5-thiophenediyl) was obtained by the chemical oxidation of 3-methoxythiophene with iron(III) chloride. The resulting polymer was found to be in a doped state, since it contained 0.1–0.2 counterions (FeCl4− and Cl−) per monomeric unit. This means that the oxidation is a convenient method for preparing conductive polymers in one step. We also obtained a poly-MOT solution and film in a state doped to a great extent, showing no π–π* transition band and a high stability in air. An undoped polymer film was prepared by the electrochemical reduction of the doped film. The undoped film had a π–π* transition band at 2.3 eV, indicating that the effective conjugation length of the polymer could be assumed to be the same as that of the poly(3-methoxythiophene) prepared electrochemically.
Reactions of Sodium Salts of Tosylhydrazones of 2- and 3-Thiophenecarbaldehydes, 1-Methyl-2-pyrrolecarbaldehyde, and Furfural with Acrylonitrile
Authors: Saito Katsuhiro , Sato Tatsuji , Ishihara Hiraku , Takahashi Kensuke
Published: July 2006

Reactions of the sodium salts of tosylhydrazones of several heteroaromatic aldehydes with an equimolar amount of acrylonitrile afforded the corresponding cyclopropane derivatives as the major products accompanied by small amounts of pyrazole derivatives. On the other hand, reactions using ten-molar equivalents of acrylonitrile gave pyrazole derivatives as major products.
Molecular Structures of Diarylcyclobutanes Associated with Reactivities in Ring-Cleavage Reactions: Implications of Conformationally Controlled Through-Bond Coupling
Authors: Shima Kensuke , Kimura Jun , Yoshida Kouhei , Yasuda Masahide , Imada Kiyohisa , Pac Chyongjin
Published: July 2006

Molecular structures of diarylcyclobutanes (1–6) have been determined by single-crystal X-ray analyses. Although the distances and angles of the cyclobutane rings are relatively normal, the torsional angles between the aryl ring and the plane involving the ipso carbon and the aryl-substituted carbons of cyclobutane ring are close to 90° in cases of 1–4, but very small (2.3–11.3°) in cases of 5 and 6; conformations of the aryl substituents are highly restricted by the rigid tricyclic structure or by nonbonding interactions between the vicinal substituents in the cis configuration. Restricted conformations are closely related to the different reactivities of the cyclobutane in photochemical, thermal, and radiation-induced ring-splitting reactions. The structure-reactivity relationships are discussed in terms of the conformation-controlled π–σ orbital interactions associated with the capabilities of the π electron systems in through-bond coupling.
Photochemical Reactions of Aromatic Compounds. XLVI. Stereochemical Reaction Courses in the Photolytic Ring-Cleavage Reactions of Diarylcyclobutanes: Implications of Conformation-Controlled Orbital Interactions in the Excited-State Chemistry
Authors: Pac Chyongjin , Go-an Kazuyoshi , Yanagida Shozo
Published: July 2006

The photolyses of cis-transoid-cis-cyclobutadiindene (1), cis-2-phenylcyclobut[a]indene (2), cis-1,2-diphenylcyclobutane (3), the trans isomer (4), and its dimethyl (5) and tetramethyl (6) derivatives have been investigated to explore stereoelectronic factors controlling the excited-state reaction courses for the ring cleavages. The symmetric ring cleavage occurs regiospecifically in the cases of 1–3 and with 98% specificity in the case of 4. The photolysis of 5 results in both the symmetric and the asymmetric cleavages in a ca. 1 : 3 ratio accompanied by substantial losses of stereointegrity in the olefin formation, and the regiospecific asymmetric cleavage occurs in the case of sterically more congested 6. The ring-cleavage efficiencies systematically decrease in the order 1>2>3>4>5>6 and reveal negative temperature dependences, particularly in the cases of 1, 5, and 6. The features of the reactions are in parallel with stable conformations and conformational mobilities of the aryl groups associated with different π–σ orbital interactions, while the spectroscopic properties of the cyclobutanes are essentially identical with those of benzene chromophores with little electronic perturbation. The photolytic ring-cleavage reactions are discussed in terms of crossing from the localized 1π,π* state to a σ* hypersurface, in which conformation-controlled orbital interactions play important roles. The final products are formed via a pericyclic minimum which might be biradicaloid in nature.
Design and Synthesis of Macromonocyclic Polyamines Composed of Natural Methylene Arrays
Authors: Iwata Masaaki , Kuzuhara Hiroyoshi
Published: July 2006

A general synthetic method applicable to acyclic and cyclic polyamines was developed. The methodology was exemplified by systematical synthesis of twelve macromonocyclic polyamines, 1 ([17]N4) through 12 ([35]N8), composed of the combination of four natural polyamine segments, spermidine, spermine, thermine, and thermospermine. These twelve designed macrocycles are exhausted numbers of possible structures defined by three arbitrarily chosen criteria concerning with methylene chain arrays and nitrogen content (four to eight). The common elements of the structural characteristics were analyzed and were found to be reduced to readily available three classes of simple N,N′-ditosylalkanediamines derived from diamines and triamine. Nitrogen content was increased systematically through the reaction of N,N′-ditosylalkanediamine with one of three ω-phthalimidated electrophiles followed by regeneration of the same functionality at symmetrical both terminals as the starting materials via a series of transformation reaction, in excellent yields. Tractable formamide intermediate profits the facile synthesis of acyclic polyamines with long chains. Cyclization was achieved, under high dilution conditions, through the reaction of α,ω-bis(tosylamide) with α,ω-ditosylates in DMF in the presence of cesium carbonate. The cyclization occurred in practical synthetic yields even in the formation of multi-membered ring when the shorter electrophile and the longest α,ω-bis(tosylamide) reacted.
Synthesis of S-Methyl 2-Hydroxyalkanethioates, 2-Hydroxyalkanoic Acids and Related Compounds via the Addition Reaction of Tris(methylthio)methanide Ion to Alkanals
Authors: Orito Kazuhiko , Seki Yoshikatsu , Suginome Hiroshi , Iwadare Tsukasa
Published: July 2006

In connection with the studies on biological activities on myrmicacin and related compounds, the synthetic method for 2-hydroxyalkanoic acids and the corresponding 1,2-diols was studied. The addition reaction of tris(methylthio)methyllithium to the aldehydes (propanal–dodecanal) gave the corresponding 1,1,1-tris(methylthio)-2-alkanols 1a–j. Treatment of 1 with mercury(II) chloride–mercury(II) oxide in water–acetone afforded S-methyl 2-hydroxyalkanethioates 2a–j, and in methanol methyl 2-hydroxyalkanoates 3c–j were obtained. Reduction of the thioates 2 with lithium aluminium hydride gave 1,2-diols 4c–j and saponification produced the corresponding 2-hydroxyalkanoic acids 5c–j.
Deuterium Isotope Effect on the Rate of Ligand Exchange between Tetrakis(acetylacetonato)thorium(IV) and Free Acetylacetone in CD3CN
Authors: Fujiwara Naoshi , Nakagawa Tomoe , Tomiyasu Hiroshi , Fukutomi Hiroshi
Published: July 2006

A deuterium isotope effect on the rate of acetylacetonate exchange between tetrakis(acetylacetonato)thorium(IV), Th(acac)4, and free acetylacetone in CD3CN has been examined by means of 1H NMR technique. The second-order rate constant, k, which is expressed as a function of the observed first-order rate constant, kobsd, and the concentration of acetylacetone in the enol form, [acetylacetone]enol, by k=kobsd/[acetylacetone]enol was determined for the reaction of deuterated acetylacetone, Dacac, as well as undeuterated acetylacetone, Hacac. The ratio of second-order rate constants for Hacac and Dacac, kH⁄kD, was approximately 9. This large deuterium isotope effect strongly supports a mechanism proposed in a previous paper that the proton transfer process is the rate determining step of the whole reaction.
Indirect Electrooxidation by Using Ruthenium Tetraoxide and Chloride Ion as Recycling Mediators. Optimization for the Oxidation of Diisopropylidene-d-glucose to the Ulose
Authors: Torii Sigeru , Inokuchi Tsutomu , Matsumoto Shigeaki , Saeki Takeaki , Oki Tsunehei
Published: July 2006

Various factors related to the yield and selectivity for the indirect electrooxidation of diisopropylidene glucose (1) to the ulose 2 with ruthenium tetraoxide (RuO4) and chloride ion are investigated. The following is found to be optimum conditions: pH, ca. 10: solvent system, carbon tetrachloride and t-butyl alcohol (ca. 9 : 1); current density, 10–40 mA cm−2; temperature, 20–40 °C; catalyst amount, 2 mol% of RuO2·2H2O (based on 1). The optimized electrolysis affords the desired 2 in 90% yield along with a trace of the cleavaged product 3 (0.2%) by an overoxidation.
Tellurodicarbonic Acid Diesters; Preparation and Properties
Authors: Suzuki Hitomi , Nishioka Yoshinobu
Published: July 2006

Title compounds were obtained as reasonably stable to labile oily substances by reacting alkyl carbonochloridates with sodium telluride under phase-transfer conditions at room temperature or in dry N,N-dimethylformamide under ice-cooling.
Silica-Supported Heteropoly Acid Catalyst for Liquid-Phase Friedel–Crafts Reactions
Authors: Izumi Yusuke , Natsume Noriko , Takamine Harumi , Tamaoki Ikuyo , Urabe Kazuo
Published: July 2006

Silica-supported Keggin-type heteropoly acids such as 12-tungstophosphoric, molybdophosphoric, and tungstosilicic acids efficiently catalyzed Friedel–Crafts alkylation and acylation reactions of aromatic hydrocarbons with 1-octene, benzyl chloride and benzoyl chloride in the liquid phase. The catalytic activity of heteropoly acid was generally enhanced when supported on silica. Silica-supported tungstosilicic acid worked as an insoluble heterogeneous catalyst even to the acylation of p-xylene with benzoyl chloride or benzoic anhydride, though deactivation was observed during repeated use. Considering that supported p-toluenesulfonic acid, an ordinarily used typical strong protonic acid, was far less active than the supported heteropoly acid, the high catalytic efficiency revealed by heteropoly acid appears to be due to a unique property of heteropoly anion which can stabilize alkyl and acyl cations as the reaction intermediates.
Ionic Association of Mixed Nickel(II) Chelates in Alcohols, Ketones, and Nitrobenzene
Authors: Ito Kazuaki , Yamamoto Yuroku
Published: July 2006

The conductances of mixed nickel(II) chelates, [Ni(acac)(N,N,N′,N′-tmen)]X (where acac=2,4-pentanedionato, N,N,N′,N′-tmen=N,N,N′,N′-tetramethylethylenediamine, and X−=ClO4− or NO3−), in alcohols {ethanol (EtOH), 1-propanol (n-PrOH), 2-propanol (i-PrOH), and 1-butanol (n-BuOH)}, ketones {acetone (Me2CO), methyl ethyl ketone (MEK), and methyl isobutyl ketone (MIBK)}, and nitrobenzene (PhNO2) were measured at 25 °C. The obtained ionic association constants (Ka) of [Ni(acac)(N,N,N′,N′-tmen)]ClO4 which were derived by using the extended Fouss–Hsia function indicated that (1) the perchlorate complex is a normal type of uni-uni-valent electrolyte and (2) it is more dissociated than [Co(acac)2(N,N,N′,N′-tmen)]ClO4 in EtOH, n-PrOH, and n-BuOH. Walden products of the cations suggest that the nickel(II) chelate cation in the alcohols is present as an octahedral form with the coordination of two solvent molecules. On the other hand, Ka of [Ni(acac)(N,N,N′,N′-tmen)]NO3 are much larger than those of [Ni(acac)(N,N,N′,N′-tmen)]ClO4. This can be ascribed to the coordination of a nitrate ion to the nickel(II) ion. The effect is large and approximately the same in the ketones and PhNO2, though small in EtOH, n-PrOH, and n-BuOH due to the coordination of solvent molecules.
Zone-Melting Separation of Carbazole and Anthracene from Polynuclear Aromatic Compounds Using Biphenyl as a Medium, Followed by the Synchronous Fluorometric Determination
Authors: Tachibana Masaki , Furusawa Motohisa
Published: July 2006

Biphenyl is favorable as a zone-melting medium for the selective separation of small amounts of carbazole and anthracene and a subsequent determination. A definite amount (20–100 mg) of an aromatic sample was mixed with 4 g of purified biphenyl. The mixture was zone-melted 20 times. The two analytes were accumulated in the beginning part of the zone-molten ingot, but many others were eliminated from the part. After being dissolved in xylene along with the biphenyl, carbazole and anthracene could be simultaneously determined up to 10 ng ml−1 by measuring the synchronous fluorescence intensities at 340 and 384 nm, respectively.
Spectroscopic and Electrochemical Characterization of 18-Molybdodisulfate(VI)(4−), S2Mo18O624−
Authors: Himeno Sadayuki , Hori Toshitaka , Saito Atsuyoshi
Published: July 2006

The formation conditions of a yellow Dawson-type S2Mo18O624− anion have been investigated as functions of the concentrations of Mo(VI), H2SO4, organic solvents, the nature of the organic solvents used, temperature of the solution, and the reaction time. For a 50 mM Mo(VI)/50% (v/v) acetonitrile system, the yellow S2Mo18O624− anion formed in 0.2–1.0 M H2SO4, while a pale-yellow Mo6O192− anion did in 0.04–0.3 M H2SO4. The yellow heteropolyanion is electrochemically reduced in six successive steps to mixed-valence heteropoly blues at the glassy carbon electrode. Each of the first four waves corresponds to a reversible two-electron transfer. The mixed-valence blue species were characterized by their inherent visible and infrared (IR) spectra.
35Cl NQR in SnCl4·2Me2O and SnCl4·2Et2O
Authors: Mishima Mitsuo , Okuda Tsutomu
Published: July 2006

35Cl NQR spectra in SnCl4·2Me2O and SnCl4·2Et2O have been observed. Three crystal modifications of SnCl4·2Me2O have been found. A cis geometry is suggested for one of them, and a trans geometry for the remainder. A transformation between the cis and trans isomers in the solid state is indicated. The Zeeman effect on single crystals of cis-SnCl4·2Me2O and SnCl4·2Et2O has provided detailed information on bond angles and bond character. It is confirmed that the molecular geometry of cis-SnCl4·2Me2O belongs to the C2 group and that SnCl4·2Et2O has a trans geometry. The η values of the Cl atoms in cis-SnCl4·2Me2O are negligibly small and those of the Cl atoms in SnCl4·2Et2O are 0.11. The relatively small η values for the latter are ascribed to π bonding between the Sn and Cl atoms.
Preparation, Crystal Structure, and Solid State Properties of Highly Conductive (Phthalocyaninato)platinum Radical Salts: PtPc(ClO4)0.5 and PtPc(AsF6)x
Authors: Yamakado Hideo , Yakushi Kyuya , Kosugi Nobuhiro , Kuroda Haruo , Kawamoto Atsushi , Tanaka Jiro , Sugano Tadashi , Kinoshita Minoru , Hino Shojun
Published: July 2006

New conducting salts of (phthalocyaninato)platinum (PtPc), PtPc(ClO4)0.5 and PtPc(AsF6)x, were prepared by electrochemical oxidation. A crystal of PtPc(ClO4)0.5 belongs to a tetragonal system with a space group of P4⁄mcc, the lattice constants being a=14.062(1) Å, c=6.510(1) Å, and Z=2. They are metallic at least down to 120 K, the room-temperature conductivity being σ=102–103 S cm−1. XPS indicates that the conduction pathway is located mainly at the ligand chain due to a partial oxidation of the ligand-centered HOMO. ESR experiments have also strongly supported this conclusion. The bandwidth of the ligand-centered conduction band has been estimated to be 1.2 eV from the plasma frequency, hωp=0.87 eV, which is obtained by the polarized reflectance spectrum.
Magnetic and Electric Properties of a Cation Radical Salt Tris(decacyclene) Bis(hexafluorophosphate), (Dc)3(PF6)2
Authors: Sugano Tadashi , Kinoshita Minoru
Published: July 2006

A cation radical salt between a π-electron donor decacyclene and hexafluorophosphate, (Dc)3(PF6)2, was prepared by electrochemical synthesis, and conductivity (90–350 K), electron paramagnetic resonance (4–400 K) and static susceptibility (2–300 K) were measured. The salt was found to be semiconductive with the conductivity of ca. 4×10−2 S cm−1 at room tempertature and the activation energy of 66±3 meV. The magnetic measurements show that this salt is paramagnetic and spin susceptibility is thermally activated with the activation energy of 17 meV resulting from antiferromagnetic intermolecular interaction, although the dication of electron donor might be expected to have triplet spin multiplicity to stabilize ferromagnetic spin alignment in the ground state. The magnetism of (Dc)3(PF6)2 is discussed in terms of charge-transfer interaction among donors.
Stereoselective Synthesis of 2,4-Diamino Acids by Asymmetric Hydrogenation
Authors: Park Nam Gyu , Lee Sannamu , Maeda Hiroshi , Aoyagi Haruhiko , Kato Tetsuo
Published: July 2006

A stereoselective synthesis of unusual basic amino acids, ornithine, 2,4-diaminopentanoic acid, and 2,4-diamino-6-methylheptanoic acid, was achieved by the hydrogenation of cyclic α,β-dehydro dipeptides obtained by the condensation of cyclo(–Gly–l(or d)-aminoacyl–) and protected linear or chiral amino aldehydes. The degree of chiral induction greatly depended on the bulkiness of the side chains of α,β-dehydro amino acids. The Rf values on paper chromatography of (2S,4S or 2R,4S)-diaminopentanoic acid prepared by the present method were different from the reported values of a compound which had been obtained from metabolic products of Clostridium sticklandii and estimated to be 2,4-diaminopentanoic acid.
Synthesis and Reaction of 2,2′-Biquinolyl
Authors: Wakabayashi Shoji , Kubo Yukihiro , Takeda Takashi , Uenishi Jun-ichi , Oae Shigeru
Published: July 2006

A title compound is readily prepared from methyl 2-quinolyl sulfoxide (3) with methylmagnesium bromide in excellent yield and an ipso addition of alkylmagnesium halides to 2,2′-biquinolyl (4) is also described.
Effective Doping of Polymer Anion during Chemical Polymerization of Pyrrole Using Fe(OH)3 Oxidant
Authors: Ohtani Akira , Shimidzu Takeo
Published: July 2006

Polypyrroles were prepared by the chemical polymerization of pyrrole using various combinations of Fe3+ oxidants and electrolytes. The morphology and yield of the resulting polymers were affected by the property of the electrolyte anion in the oxidative solution. The size of the particles of the resulting polymers was decreased by using a high-molecular-weight polymer anion as the electrolyte anion. Both the polymer anion and Cl− were incorporated as a dopant into the polypyrrole matrix during the chemical polymerization of pyrrole, using an aqueous solution containing both FeCl3 and the polymer anion. On the contrary, the polymer anion was effectively incorporated as a dopant into the polypyrrole matrix during the chemical polymerization of pyrrole, using an aqueous solution containing both Fe(OH)3 and the polymer acid. A novel type of chemical preparation of the polypyrrole-polymer anion composite using the Fe(OH)3 oxidant and the polymer acid was developed.
The Crystal and Molecular Structures of Bis[1,2-bis(methylthio)vinylenedithio]-tetrathiafulvalene (TMTVT)
Authors: Nakano Hideyuki , Nogami Takashi , Shirota Yasuhiko , Harada Shigeharu , Kasai Nobutami
Published: July 2006

An X-ray crystal structure analysis of the title molecule (TMTVT) was made. The central portion of tetrathio-TTF was shown to be almost planar, and the outer portions of the two bis(methylthio)vinylenes are bent toward opposite directions each other. TMTVT molecules form a columnar stack toward the c-axis with equal intermolecular spacings.
Highly Stereoselective Palladium(0)-Catalyzed Allylation of Active Methylene Compounds with Allyl Imidates under Neutral Conditions
Authors: Suzuki Osamu , Inoue Seiichi , Sato Kikumasa
Published: July 2006

In the presence of a catalytic amount of Pd(0), active methylene compounds were allylated by allyl imidates under neutral conditions. In allylation with 3,3-disubstituted allyl imidates, e.g., geranyl and neryl imidate the effect of solvent and ligand to the E/Z ratio are investigated. The reaction in dimethyl sulfoxide by addition of diphosphine, e.g., 1,2-bis(diphenylphosphino)ethane, or large excess of triphenylphosphine as additive ligand gave best results. In these conditions, various active methylene compounds were allylated stereoselectively, especially complete retention of starting olefin geometry was achieved with neryl imidate.
On the Reaction of N-Vinyliminophosphoranes with 2,4,6-Cyclooctatrienone. Intermediate Formation of 8-Azabicyclo[5.3.1]undeca-2,4,7,9-tetraene Ring System
Authors: Nitta Makoto , Kanomata Nobuhiro
Published: July 2006

The reaction of N-(1-phenylvinyl)iminotriphenylphosphorane and of N-(1,3,5-cycloheptatrienyl)iminotributylphosphorane with 2,4,6-cyclooctatrienone gave an intermediacy of 8-azabicyclo[5.3.1]undeca-2,4,7,9-tetraene derivatives, which underwent an intramolecular Diels–Alder reaction to construct a tetracyclic ring system.
Synthesis of Novel 10-Se-3 Type Selenatetraazapentalene Derivatives with a Hypervalent Selenium
Authors: Matsumura Noboru , Tomura Masaaki , Yoneda Shigeo
Published: July 2006

Novel selenatetraazapentalene derivatives, 2,3-disubstituted 6,7-dihydro-5H-2a-selena(2a-SeIV)-2,3,4a,7a-tetraazacyclopent[cd]indene-1,4(2H,3H)-dithione, were synthesized by a convenient one-pot reaction using the lithium selenoureide/phenacyl chloride/alkyl isothiocyanate system in good yields.
Reactions of Tetrasulfur Tetranitride with Tropolone and Its Several Halogeno Derivatives. Preparations of 4H-Cyclohepta[c][1,2,5]thiadiazol-4-ones, 6H-Cyclohepta[c][1,2,5]thiadiazol-6-one, and 7H-Cyclohepta-[1,2-c:3,4-c′]bis[1,2,5]thiadiazol-7-ones
Authors: Mori Akira , Nakashima Hisataka , Mataka Shuntaro , Tashiro Masashi , Takeshita Hitoshi
Published: July 2006

The reactions of tropolones with tetrasulfur tetranitride gave 4H-cyclohepta[c][1,2,5]thiadiazol-4-ones, 6H-cyclohepta[c][1,2,5]thiadiazol-6-one, and 7H-cyclohepta[1,2-c: 3,4-c′]bis[1,2,5]thiadiazol-7-ones (9–56% yields) in one step. The yields of the products were not improved so much under high pressure and by the addition of a radical initiator.
Electroorganic Synthesis Using Organometals. 2. Reductive Dehalogenation of Halides with Carbonylferrates Derived from Pentacarbonyliron(0) and Cathodically-Generated Methoxide Ion
Authors: Hashiba Shigeto , Fuchigami Toshio , Nonaka Tsutomu
Published: July 2006

A stoichiometry for the reductive dehalogenation of an organic halide with carbonylferrates was established: One mol of the halide was quantitatively reduced with the carbonylferrates derived from 0.2 mol of pentacarbonyliron(0) and 2 mol of cathodically-generated tetramethylammonium methoxide. The dehalogenation was also examined using a variety of halides under the stoichiometric reaction conditions.
Synthesis of 2-Methylsulfonylmethyl-3,4,5-trimethoxybenzyl Methyl Ether. Confirmation of the Structure of Two Pyrogallols Isolated from Red Alga
Authors: Ohira Susumu , Shirane Fukue , Nozaki Hiroshi , Yahiro Shigeru , Nakayama Mitsuru
Published: July 2006

2-Methylsulfonylmethyl-3,4,5-trimethoxybenzyl methyl ether was synthesized in 4 steps from methyl 3,4,5-trimethoxybenzoate, confirming the structure of the natural phenol.
Solvent Effect on the Hydrogen Bonds between Guanine and Cytosine and between Hypoxanthine and Cytosine
Authors: Ohta Yoshihisa , Nishimoto Kichisuke , Tanaka Hidetsugu , Baba Yoshihiro , Kagemoto Akihiro
Published: July 2006

The solvent effect on the hydrogen bonds between guanine and cytosine and between hypoxanthine and cytosine was studied by means of solution calorimetry and ab initio MO calculations. The experimental enthalpy changes for guanine–cytosine and hypoxanthine–cytosine systems in aqueous solution were estimated to be about −10 and −14 kJ mol−1, respectively. In order to explain these experimental results, the electronic structures of hydrated bases and hydrated base pairs were calculated, assuming two types of hydration schemes. In the first type, it was expected that the complementary base pairs were destabilized in aqueous solution. In the second type, the stabilization energies in aqueous solution were calculated to be −11.9 kJ mol−1 for the hydrated guanine–cytosine system and −18.5 kJ mol−1 for hypoxanthine–cytosine one, respectively, which agreed with the experimental results. This suggests that water molecules bound to base pairs contribute to the stabilization/destabilization of hydrogen bonds between bases. The present calculation showed the possibility of C–Hδ+···O hydrogen-bond formation between the complementary base pair and H2O.
Studies on the Area–Temperature Isobars of Insoluble Monolayers at the Air/Water Interface. I. Development of a Microcomputer-Controlled Instrument for Measuring Precise Area–Temperature Isobars
Authors: Kato Teiji , Wakana Tatsushi , Ohshima Katsunori , Suzuki Katsuhiro
Published: July 2006

A microcomputer-controlled instrument for measuring precise area–temperature (A–T) isobars of insoluble monolayers at the air/water interface was developed. To obtain precise A–T isobars, leakage or dissolution of film material must be checked. Before starting A–T isobar measurements, area or structural relaxations must be completed. A–T isobars of monolayers of cadmium eicosanoate, l-α-dipalmitoyl phosphatidylcholine (DPPC), trioctadecanoyl glyceride (TOG), and cis-9-octadecen-1-ol were measured. Precise A–T isobars can afford two-dimensional isobaric thermal expansivities of insoluble monolayers by differentiation with respect to temperature. The thermal expansivities were evaluated as around 9.0×10−4 K−1 for condensed monolayers and around 30×10−4 K−1 for liquid-expanded monolayers.