bluuebunny/crossref_metadata_2025 huggingface dataset:
Use of Propagators in the Hückel Model. VII. Thermochemical and Photochemical Rearrangement in Cycloheptatriene, Tropone, and Related Compounds
Authors: Yamamoto Masaaki , Nishikawa Kiyoshi , Aono Shigeyuki
Published: July 2006

Hückel propagator theory has been applied to the analysis of photochemical and thermochemical rearrangement reactions, such as [1,3] sigmatropy, valence isomerization of norcaradiene, Cope rearrangement et al. In treatments employing the frontier orbital theory, the molecule is sometimes separated into two parts, and the orbital interaction between specified orbitals of two fragments is taken into account. In the propagator theory, the molecule is always considered as a whole, assuming a resonable transition state. In this transition state, the bond order between sites responsible for the reactions under consideration is estimated, and then the perturbing interaction between these sites is introduced. Then we can evaluate the extra energy to determine whether the reaction occures or not.
Ultralow Interfacial Tension in the Vicinity of the Upper Critical Solution Temperature of the Mixture of Water and Isobutyric Acid
Authors: Aratono Makoto , Motomura Kinsi
Published: July 2006

The ultralow interfacial tension of the binary liquid mixture of water and isobutyric acid has been measured as a function of temperature under atmospheric pressure in the vicinity of the upper critical solution temperature. It has been observed that the interfacial tension decreases monotonously as the temperature increases and is reduced to zero at the critical solution temperature. The results have been analyzed on the basis of the thermodynamics of interfaces. It has been found that the formation of interface is accompanied by increases in entropy and energy, which vanish at the critical solution temperature. This behavior has been considered in terms of the partial molar thermodynamic quantities of components. The brief discussion of the critical exponent has been also given for the present system.
Effect of Inner-shell Excitations on the W-Value of Propane
Authors: Suzuki Isao H , Saito Norio
Published: July 2006

The dependence of the propane W-value on photon energy has been precisely measured near innershell excited states using monochromatized synchrotron radiation. The W-value showed an oscillatory variation in this energy region. A model has been proposed in which inner-shell excitation is assumed to give rise to a change in the energy of the electron ejected from the molecule having absorbed a photon. It has been found that the model can reproduce the oscillatory variation feature of the W-value. A postcollision interaction is suggested to take place just above the C–K edge of propane.
A High-resolution 13C NMR Study of Some Ethylene Oxide Oligomers, Cryptands and Crown Ethers Complexed with a Variety of Metal Ions in the Solid State. Conformational Change of Ligand Molecules as Viewed from the Conformation-dependent Displacements of 13C Chemical Shifts
Authors: Tabeta Ryoko , Saitô Hazime
Published: July 2006

We recorded high-resolution solid-state 13C NMR spectra of ethylene oxide oligomers, cryptands, and crown ethers complexed with metal ions, determined by cross polarization-magic angle spinning (CP-MAS) NMR method. It is found that peak-intensities of these complexes are significantly enhanced by the presence of metal ions which act toward conformational fixation of flexible ligand molecules. The 13C chemical shifts of ethylene oxide oligomers complexed with HgCl2 or CdCl2 as open-chain analogues of crown ethers were successfully related with a pair of torsion angles of nearby single bonds. 13C Chemical shifts of cyclic ionophores were displaced (up to 6 ppm) together with conformational changes of ligand molecules. In addition, the 13C chemical shifts of the carbons neighbored with nitrogen atoms of cryptands [2.2.2] and [2.2.1] were well related with a pair of torsion angles of neaby bonds. Further, we found that several kinds of metal complexes with cis-syn-cis and cis-anti-cis isomers of dicyclohexano-18-crown-6 gave rise to substantially different spectral profiles, resulting in the occurrence of significant conformational changes of these ligand molecules as a result of complex formation.
Spin Label Investigation of the Crown Ether. Complex Formation between the Veratrole Analogue of Phenoxyl-labeled Benzo-15-crown-5 and Alkali and Alkaline Earth Metal Salts in Frozen Solution
Authors: Mukai Kazuo , Tanii Michiyo , Yurugi Yohko , Tajima Kunihiko , Ishizu Kazuhiko
Published: July 2006

A stable “phenoxyl-veratrole” (2), a veratrole analogue of “phenoxyl-benzo-15-crown-5” (1), was prepared and the complex formation between 2 and the alkali and alkaline earth metal salts has been studied by the ESR technique. Existence of the 2:1 complex of 2 with K+, Rb+, and Cs+ salts was confirmed by the observation of the triplet ESR spectra in ethanol rigid matrix at 77 K. Essentially the same g- and D-tensor values were observed for all the 2:1 complexes, indicating similar conformation of the ligand molecule 2. By comparing the observed D and E parameters with those of the 2:1 complexes reported for the alkali and alkaline earth metal complexes of 1 in a previous paper (Ref. 10), the structure of the 2:1 complex in ethanol rigid matrix was discussed. On the other hand, the results of the ESR measurements of the Li+, Na+, and alkaline earth metal complexes suggested a 1:1 complex formation between 2 and the metal salts.
Thermal Reactions of the Nickel(II) Complexes Containing 1-Phenyl-1,2-ethanediamine in the Solid Phase
Authors: Ihara Yoshinori
Published: July 2006

Nickel(II) complexes [Ni(phenen)2](ClO4)2 and [Ni(H2O)2(phenen)2]X2 (phenen=1-phenyl-1,2-ethanediamine, X=Cl, Br, or NO3) were prepared, and their thermal behavior was investigated in the solid phase. The nitrate showed a thermochromism consisting of two steps, violet→yellow→violet, which corresponds to a structural change from an octahedral diaqua complex to a square planar anhydride, and then to the octahedral dinitrato complex, respectively. Both the chloride and bromide were converted into the octahedral dianiono complexes by thermal deaquation-anation, retaining their octahedral configuration. However, no change was observed in the perchlorate, which is invariably square planar.
A Synthesis of a Versatile Intermediate Leading to Thienamycin Analogs
Authors: Maruyama Hiroshi , Shiozaki Masao , Hiraoka Tetsuo
Published: July 2006

l-Threonine was converted to a versatile azetidinone derivative stereospecifically in 3 steps. This azetidinone was further transformed to (3S,4R)-3-[(R)-1-hydroxyethyl]-1-(4-methoxybenzyl)-4-[(phenylthio)-carbonylmethyl]-2-azetidinone (S-Phenyl thioester), a key intermediate for the synthesis of thienamycin and it’s biologically active analogs. Since the thiol part of this S-phenyl thioester can be exchanged easily with other complex or useful thiols under mild conditions, important S-thioester precursors for the production of carbapenem analogs were obtained in high yield.
Stereoselective Oxylactonization. Preparation of 2-Deoxy-Dl-ribono-1,4-lactone Derivatives from 3-Silyloxy-4-alkenamides
Authors: Ichikawa Yuh-ichiro , Miwa Tetsuo , Narasaka Koichi
Published: July 2006

The oxylactonization of 3-silyloxy-4-alkenamides proceeds stereoselectively by treatment with m-chloroperbenzoic acid to give the corresponding 2-deoxy-Dl-ribono-1,4-lactone derivatives.
Diene-transmissive Diels-Alder Reaction Using 2-Ethoxy-3-methylene-1,4-pentadiene and 2-(2-Bromo-1-ethoxyethyl)1,3-butadiene
Authors: Kanemasa Shuji , Sakoh Hirohiko , Wada Eiji , Tsuge Otohiko
Published: July 2006

A new cross-conjugated triene, 2-ethoxy-3-methylene-1,4-pentadiene, and a triene equivalent, 2-(2-bromo-1-ethoxyethyl)-1,3-butadiene, have been synthesized and their diene-transmissive Diels-Alder cycloadditions are investigated. The initial Diels-Alder reaction selectively occurs not across the diene part substituted with the alkoxyl moiety but the monosubstituted diene. Some cross types of diene-transmissive Diels-Alder reaction are demonstrated using the triene equivalent and two different dienophiles.
Total Synthesis of (−)-Deoxocassine and Its Diastereomers
Authors: Kurihara Kazuo , Sugimoto Takashi , Saitoh Yutaka , Igarashi Yukinobu , Hirota Hiroshi , Moriyama Yoshihiko , Tsuyuki Takahiko , Takahashi Takeyoshi , Khuong-Huu Qui
Published: July 2006

(−)-Deoxocassine [(2R,3R,6S)-6-dodecyl-2-methyl-3-piperidinol] and its diastereomers with 2R-configuration were synthesized starting from d-alanine by a route involving the intramolecular aminomercuration of an ε,ζ-unsaturated amine.
Viscosity B Coefficients for Polymethylenebis(trimethylammonium) Dibromides in Aqueous Solutions
Authors: Tamaki Kunio , Fujiwara Akifumi
Published: July 2006

The viscosity B coefficients of the Jones-Dole equation for N,N′-polymethylenebis(trimethylammonium) dibromides [(CH3)3N(CH2)nN(CH3)3]Br2 (n=3–8, 10, and 12) and for comparison for alkyltrimethylammonium bromides CnH2n+1N(CH3)3Br (n=2–6) in aqueous solutions at 25 and 35 ° have been determined, and the effect of structural changes in the solvent water upon the dissolution of both series of electrolytes is discussed.
Substituent Effect on Stereoselectivity for Cobalt(III), Chromium(III), and Manganese(III) Complexes of Ring-substituted 1-l-Menthyloxy-3-benzoylacetones
Authors: Nakamura Michio , Okawa Hisashi , Kida Sigeo
Published: July 2006

Stereoselectivities of tris(1-l-menthyloxy-3-benzoylacetonato)M(III) ([M(l-moba)3] (M=CoIII, CrIII, MnIII)) and its homologs [M(l-moba-Br)3] and [M(l-moba-Me)3] (possessing bromo and methyl substituents at the 4-position of the aromatic ring, respectively) were examined by CD spectra. The stereoselectivity increased in the order [Co(l-moba-Br)3]<[Co(l-moba)3]<[Co(l-moba-Me)3], and this trend was explained in terms of the electronic effect of the substituents on the interligand CH/π-interaction.
Peterson Olefination of (α-Methoxybenzyl)silane with Aldehydes and Ketones Leading to Vinyl Ethers
Authors: Kanemasa Shuji , Tanaka Junji , Nagahama Hideki , Tsuge Otohiko
Published: July 2006

(α-Methoxybenzyl)trimethylsilane is deprotonated with butyllithium and then allowed to react with a variety of carbonyl compounds giving vinyl ethers which are convertible into methyl ketones under mild conditions.
A Molecular Mechanical Calculation along the Intrinsic Reaction Coordinate
Authors: Cho Seikichi
Published: July 2006

A normal coordinate analysis was applied to nonequilibrium states composed of atoms. A normal coordinate, Qk, can be the intrinsic reaction coordinate if, and only if, all the first-order differentials have vanished except the k-th one. The HNC-to-HCN isomerization reaction was treated with the ab initio STO-3G potential surface: we thus observed several interesting features.
15N NMR Spectra of Cobalt(III) Complexes Containing 15NO2−
Authors: Odaka Yoshio , Yamasaki Akira , Watabe Masatoshi
Published: July 2006

The nitrogen-15 nuclear magnetic resonance spectra of the cobalt(III) complexes containing 15NO2− were first measured; the coordination chemical shifts, Δδ (=δcomplex–δfree), were found to be from 135.0 to 161.5 ppm. The relationship between Δδ and the geometrical configuration was discussed in terms of the paramagnetic anisotropy of the cobalt(III) ion.
Induced Circular Dichroism of Bis(tropolonato)copper(II) with Optically Active Amines
Authors: Murakami Tasuku
Published: July 2006

Bis(tropolonato)copper(II) forms adducts with chiral aromatic amines and exhibits circular dichroism(CD) induced for d-d and intra-ligand transitions. The applicability of the dispersion-induced CD theory to this complex system is discussed.
The Total Synthesis of (±)-Megaphyllone Acetate, A Cytotoxic Neolignan
Authors: Matsumoto Takashi , Imai Sachihiko , Yamaguchi Tadashi , Morihira Masakazu , Murakami Masao
Published: July 2006

Conversion of 3-methoxy-4,5-methylenedioxybenzaldehyde into (2RS,3SR,4RS)-2-methoxycarbonyl-4-(3-methoxy-4,5-methylenedioxyphenyl)-3-methyl-4-butanolide (11) was carried out in seven steps via 1-acetoxy-1-(3-methoxy-4,5-methylenedioxyphenyl)propanone. The butanolide 11 was further converted into (2RS,3SR,3aRS,5RS)-3,3a,4,5-tetrahydro-5-methoxy-2-(3-methoxy-4,5-methylenedioxyphenyl)-3-methyl-3a-(2-propenyl)6(2H)-benzofuranone (22) in eight steps. Reduction of 22 with lithium aluminium hydride followed by acetylation with acetic anhydride in pyridine afforded (±)-megaphyllone acetate.
Photoredox Chemistry of Chloro and Bromo Complexes of Copper(II) in Methanolic Medium
Authors: David Pazhayirayyathu Geeverghese , da Silva Paulo Augusto Correa
Published: July 2006

Investigation of the photoreduction of copper(II) to copper(I) in methanolic solutions of copper(II) chloride and copper(II) bromide indicates the halide-to-copper(II) charge-transfer (CT) responsible for the photoreduction. Quantum yields for the formation of copper(I) as a function of irradiating wavelength and copper(II) halide concentration show that [Cu(CH3OH)5Cl]+ and [Cu(CH3OH)4Cl2] have identical photoreaction efficiency, while [Cu(CH3OH)4Br2] is more photoreactive than [Cu(CH3OH)5Br]+. In the copper(II) chloride system the chloride-to-copper(II) CT band centered around 272 nm appears to be responsible for the photoreaction, while the bromide-to-copper(II) CT band centered around 245 nm effects the photoreaction in copper(II) bromide system.
New Amino-protective Reagents for t-Butoxycarbonylation and Benzyloxycarbonylation of Amines and Amino Acids
Authors: Kim Sunggak , Lee Jae In , Yi Kyu Yang
Published: July 2006

New amino-protective reagents for t-butoxycarbonylation and benzyloxycarbonylation of amines and amino acids have been developed. t-Butyl 2-pyridyl carbonate and t-butyl S-(2-pyridyl) thiocarbonate react cleanly with various amines and amino acids to afford N-Boc amines and N-Boc amino acids in high yields. Benzyl 2-pyridyl carbonate and O-benzyl S-(2-pyridyl) thiocarbonate are also found to be very effective in the benzyloxycarbonylation of amino acids.
Refractive Indices, Dielectric Constants, and Order Parameter of Four Alkyl/Alkoxyphenylcyclohexanecarboxylate Liquid Crystals in the Nematic Phase
Authors: Kali Krishnakali , Sen Sushmita , Roy Subir Kumar
Published: July 2006

The extraordinary and ordinary refractive indices, ne and no and the densities of four liquid crystals 4-pentylphenyl trans-4′-pentylcyclohexanecarboxylate, 4-ethoxyphenyl trans-4′-propylcyclohexanecarboxylate, 4-ethoxyphenyl trans-4′-butylcyclohexanecarboxylate, and 4-methoxyphenyl trans-4′-pentylcyclohexanecarboxylate have been reported at different temperatures. The effective polarizabilities αe and αo in the nematic phase have been calculated using 1) Neugebauer and 2) Vuks methods. The order parameter S calculated from the two methods were comparable. The dielectric constants ε|| and ε⊥, parallel and perpendicular to the long axis of the molecules have been measured at 1 kHz at different temperatures. The order parameters for the liquid crystals were then evaluated from dielectric anisotropy Δε(=ε||−ε⊥), polarizability anisotropy Δα(=αe−αo) and dipole moment μ, using Maier and Meier equation and were found only slightly less than those obtained from refractive indices method. It was concluded that Maier and Meier equation also could be used to evaluate the order parameter of liquid crystals of molecules having dipole moments 2 Debye or less.
Synthesis and Characterization of a Chloro-bridged Binuclear Iron(III) Complex
Authors: Matsumoto Naohide , Yoshimura Chikako , Maeda Yonezo , Okawa Hisashi , Ohyoshi Akira
Published: July 2006

A chloro-bridged binuclear iron(III)complex [Fe2ClL](BPh4), where [H4L] and BPh4− denote N,N,N′,N′-tetrakis(3-salicylideneaminopropyl)ethylenediamine and tetraphenylborate, respectively, was prepared and characterized by elemental analysis, electrical conductivity, Mössbauer spectrum, and cryomagnetic data. The magnetic susceptibility data of the complex was analyzed by the Heisenberg model on the basis of a binuclear structure \hatH=−2J\hatS1·\hatS2 (S1=S2=5⁄2), leading to an antiferromagnetic interaction parameter of J=−3.9 cm−1.
Preparation and Characterization of (Iminodiacetato)cobalt(III) Complexes with l-Methioninate and S-Methyl-l-cysteinate
Authors: Umehara Hideki , Isago Takashi , Okamoto Ken-ichi , Hidaka Jinsai
Published: July 2006

The (iminodiacetato)(l-methioninato or S-methyl-l-cysteinato)cobalt(III) complex was prepared and separated into three geometrical isomers by ion-exchange chromatography. The isomers were characterized from the electronic absorption, 1H NMR and CD spectra.
A New Gas Sampler for Pyrolytic Sulfurization Gas Chromatography
Authors: Kawai Itsuro , Hara Tadashi
Published: July 2006

A new gas sampler was designed and constructed by the use of a commercially available pyrolytic apparatus. This sampler made easier heating and crushing an ampoule, and introducing a liberated gas into a gas chromatograph than those by the conventional gas sampler.
Absolute Configurations of Novel Axially Dissymmetric 10,10′-Dihydroxy-9,9′-biphenanthryl and Its Related Compounds
Authors: Yamamoto Koji , Fukushima Hitoshi , Yumioka Hiroya , Nakazaki Masao
Published: July 2006

Stereoselective oxidative coupling of 10-hydroxy-1,2,3,4-tetrahydrophenanthrene derived from methyl 3-methoxy-2-naphthoate gave (−)-(S)-10,10′-dihydroxy-1,1′,2,2′,3,3′,4,4′-octahydro-9,9′-biphenanthryl which was converted into (+)-(S)-10,10′-dimethoxy-9,9′-biphenanthryl assigning the S configuration to (−)-10,10′-dihydroxy-9,9′-biphenanthryl.
A HPLC Study of Adsorption of Organic Solutes on Cellulose Acetate
Authors: Kiso Yoshiaki
Published: July 2006

The liquid chromatographic technique was useful for the measurement of adsorption of some nonionic organic solutes on cellulose acetate. It was recognized that there were linear correlations between logarithmic capacity factors measured by HPLC, logk′, and logarithmic 1-octanol: water partition coefficients, logP.
Extractability of Copper(II) and Zinc(II) with Crown Ethers as Picrates
Authors: Hasegawa Yuko , Tanabe Hiroaki , Yoshida Satoshi
Published: July 2006

The extraction of copper(II) and zinc(II) with picrate ion and 12-crown-4(1,4,7,10-tetraoxacyclododecane) or 15-crown-5(1,4,7,10,13-pentaoxacyclopentadecane) into benzene or chloroform has been measured. The extraction of copper(II) is better than that of zinc(II), in spite of the similar ionic size, although the difference is much smaller than that in the extraction of these metal ions with β-diketones.
A Novel Synthesis of Dihydropyranoflavonols
Authors: Takkellapati Sudhakar Rao , Mathur Hari Har , Trivedi Girish Kumar
Published: July 2006

Condensation of 6-formyl-7-hydroxy-2,2-dimethylchroman with ω-nitrostyrene in the presence of triethylamine yields 3-nitro-8,8-dimethyl-2-phenyl-7,8-dihydro-2H,6H-benzo[1,2-b:5,4-b′]dipyran which on treatment with hydrogen peroxide gives 3-hydroxy-8,8-dimethyl-2-phenyl-7,8-dihydro-4H,6H-benzo[1,2-6:5,4-b′]dipyran-4-one.
Spectrophotometric Determination of Cobalt(II) with Thiocyanate. A Modification for Increasing Sensitivity and Selectivity
Authors: Singh Ajai Kumar , Kumar Dinesh , Katyal Mohan
Published: July 2006

The ion association complex formed between [Co(SCN)4]2− and 3,3′-(1,1′-biphenyl-4,4′-diyl)bis[2,5-diphenyl-2H-tetrazolium] dichloride, commercially known as neotetrazolium chloride, has been extracted into isobutyl methyl ketone and used for the photometric determination of 2.5–9.8 μg cm−3 cobalt at pH 3.5–5.0 (acetate buffer). Sandell’s sensitivity of the method (0.02 μg cm−2) is better than most of the other thiocyanate methods known so far. Interference of diverse ions has been studied. Using the higher tolerances of anions, many cations interfering in the other thiocyanate methods have been masked, thus making the present procedure more selective. The method has been applied to wire alloys.
The Preparation of a Highly Active Raney Nickel Catalyst with Formation of a Recoverable Bayerite
Authors: Nishimura Shigeo , Ikeda Satoshi , Kinoshita Makoto , Kawashima Masaaki
Published: July 2006

In the presence of a properly prepared bayerite and a small amount of sodium hydroxide, Raney nickel–aluminium alloy is developed with water to give a highly active catalyst with formation of a recoverable bayerite. In hydrogenation of typical organic compounds the catalyst is even more active than the T-4 Raney nickel.
Characterization of Catalyst for Coal Liquefaction. Exchange of Hydrogen Attached to Condensed Aromatics with Deuterium in Heavy Water over Catalyst
Authors: Yokono Tetsuro , Kohno Taro , Sanada Yuzo
Published: July 2006

The H–D exchange reaction of hydrogen atoms attached to condensed aromatics with deuterium atoms in D2O over catalyst for coal liquefaction was studied by means of D-NMR. MoO3/ZrO2, MoO3/SiO2, Fe2O3–SO42−, SbCl3 and ZnCl2 showed a significant catalytic activity for the exchange reaction. The H–D exchange ability was discussed in terms of the acidic properties and concentration of Mo5+ over supports for coal liquefaction catalysts.
Formation Constants of Lanthanoid(III) Complexes with 4-(2-Thiazolylazo)resorcinol
Authors: Ohyoshi Emiko
Published: July 2006

The formation constants of the protonated (MHR) and normal (MR) complexes (1 : 1) of lanthanoids(III) with 4-(2-thiazolylazo)resorcinol (TAR, H2R) have been determined spectrophotometrically by estimation of the free ligand. The MR complexes of TAR were less stable than the corresponding 4-(2-pyridylazo)resorcinol (PAR) complexes, but the relative stabilities were reversed for the MHR complexes.
Structural Studies of Cyclo(l-histidyl-l-histidyl) and Its Metal Complexes
Authors: Kojima Yoshitane , Yamashita Tetsushi , Nishide Shinya , Hirotsu Ken , Higuchi Taiichi
Published: July 2006

The crystal structure of cyclo(l-histidyl-l-histidyl) was determined by X-ray diffraction techniques, and was refined to a final R index of 0.066 for 680 reflections. This showed that one imidazolyl group of this compound faces the piperazine ring(folded) whereas the other is kept away from the ring(unfolded). A calculation using the α-β coupling-constant data of this peptide obtained by an 1H NMR measurement shows that the ratio of a folded conformation to an unfolded one is 49:51 in D2O. Also, NMR investigations of zinc(II) and silver(I) complexes with this peptide were carried out in D2O.
The Effects of the pH and the Temperature on the Oxidation-reduction Properties of Adriamycin Adsorbed on a Mercury Electrode Surface
Authors: Kano Kenji , Konse Tomonori , Kubota Tanekazu
Published: July 2006

The effects of the pH and the temperature on the oxidation-reduction properties of the quinone moiety in adriamycin adsorbed on a mercury electrode surface have been investigated by means of cyclic d.c. voltammetry. The quinone waves have been fundamentally interpreted in terms of a two-step one-electron surface-redox reaction, even in a neutral or an alkaline solution, where the reduced product is liable to cause the following chemical reaction. The pH dependences of the standard surface-redox potential of the adsorbed adriamycin are −60 mV/pH (pH 2–6), −30 mV/pH (pH 7–8), and −60 mV/pH (pH 9–12). The semiquinone formation constant is 0.15 at pH 2–6 and 5 at pH 9–12. These results can be well explained by considering the protolytic equilibria of the phenolic hydroxyl groups among the oxidized, semiquinone, and reduced forms of adriamycin, the pKa’s of which are 8.53, 6.93, and 6.83 respectively. The thermodynamic constants of the semiquinone formation reaction at pH 4.5 have been determined to be ΔH=−24.6 kJ mol−1 and ΔS=−99.7 J K−1 mol−1.
The Near Infrared Emission Band Observed in Electron Irradiated Xe and Xe in Other Rare Gases
Authors: Tanaka Masako , Sasaki Susumu , Katayama Meiseki
Published: July 2006

The near-infrared emission spectra were studied for xenon diluted with krypton, argon, and neon, respectively, in order to estimate the origin of an emission band at 1260 nm which was previously observed at several hundred Torr(1 Torr=133.2 Pa) of pure Xe irradiated with pulses of high-energy electrons. A continuous band around 1260 nm was observed only in Xe-Ar mixtures. This band appeared at Xe pressures above 20 Torr(diluted in 600 Torr of Ar) while it was detected above 190 Torr in pure Xe. In Xe–Ar mixtures, three emission lines due to Xe 5d(3/2)1 were also observed at 1700, 2020, and 2650 nm. On the basis of the reported kinetic data for the reactions of rare gas mixtures, the present results led to the conclusion that the band at 1260 nm was due to emission from highly excited excimer states, of which the dissociation limits were higher Rydberg states above the energy level of the Xe2+ ion.
Asymmetric Transformation of Dl-p-Hydroxyphenylglycine by a Combination of Preferential Crystallization and Simultaneous Racemization of the o-Toluenesulfonate
Authors: Hongo Chikara , Tohyama Masanori , Yoshioka Ryuzo , Yamada Shigeki , Chibata Ichiro
Published: July 2006

The asymmetric transformation of Dl-p-hydroxyphenylglycine was achieved between two enantiomers by a combination of preferential crystallization of a desired enantiomer of p-hydroxyphenylglycine o-toluenesulfonate (HPG·o-TS) and the simultaneous racemization of the antipode. l-HPG·o-TS was easily racemized by heating at 100 °C in aqueous 95% (v/v) acetic acid in the presence of small amounts of salicylaldehyde and free Dl-HPG. A supersaturated solution of Dl-HPG·o-TS placed under such conditions for racemization was seeded with the crystals of d-HPG·o-TS, and added with Dl-HPG and o-toluenesulfonic acid in order to provide continuously the supersaturated state of Dl-HPG·o-TS as a driving force. As a result, 77.2% of Dl-HPG added was transformed to d-isomer.
Mössbauer Spectroscopic Studies of the Correlation between Molecular Structure and Sign of Quadrupole Splitting in Tris(β-diketonato)iron(III) Complexes Utilizing Paramagnetic Relaxation Effects
Authors: Yamauchi Shigeru , Sakai Yoichi , Tominaga Takeshi
Published: July 2006

The change of the Mössbauer line shape with the paramagnetic relaxation time was studied in several tris(β-diketonato)iron(III) complexes to determine the sign of the quadrupole splitting. The correlation observed between the molecular structure and the sign of the quadrupole splitting demonstrates that the sign should depend on the bond angle (∠O–Fe–O) in iron(III) complexes.
SH2 Reactions of Triethylgermyl Radical with Thiosulfonic S-Esters and Selenosulfonic Se-Ester
Authors: Kobayashi Michio , Kobayashi Masanori , Yoshida Masato
Published: July 2006

The triethylgermyl radical was found to react with thiosulfonic S-esters to generate sulfonyl radicals. The SH2 character of this new reaction was confirmed by a C-13 CIDNP study and products analysis. Selenosulfonic Se-ester reacts with germyl radical in a similar way.
A Comparative Study of Photoinduced Isomerizations between 1-exo- and 1-endo-Cyano-1a,7b-dihydro-1H-cyclopropa[a]naphthalenes
Authors: Kobayashi Hisako , Kato Masahiko , Miwa Toshio
Published: July 2006

The titled compunds 1-exo-Cyano-1a,7b-dihydro-1H-cyclopropa[a]naphthalenes(8a), 1-endo-Cyano-1a,7b-dihydro-1H-cyclopropa[a]naphthalenes(8b), were photolyzed in several solvents. The results were: (1) The isomerization proceeded faster in aprotic nonpolar solvents than in polar ones. (2) The 1-endo derivative (8b) rearranged faster than the 1-exo-isomer (8a). (3) 8b was isomerized through Berson-Willcott rearrangement by the fission of bonds C1–C7b and C1–C1a, while 8a gave 1-cyanomethylnaphthalene (5b) as a main product. (4) Examination with an optically active 1-exo derivative (8a) showed that the exo-endo interconversion occured by the simultaneous two centered (30%) and one centered (70%) epimerization.
The Synthesis of the Chloro and Dichloro Derivatives of 2,10-Dihydroxydicyclohepta[b,d]furan-3,9-diones
Authors: Kusaba Tomoyuki , Mori Akira , Takeshita Hitoshi
Published: July 2006

4,8-Dichloro- and 5,7-dichloro-2,10-dihydroxydicyclohepta[b,d]furan-3,9-diones were synthesized. Although the latter could be obtained by condensation of 4-chloro-p-tropoquinone and its hydroquinone, the former required the hydrolysis of condensate of 3-chloro-p-tropoquinone and 7-chloro-5-hydroxy-2-methoxytropone. This mixed condensation led to several unsymmetrically substituted derivatives in improved yields.
High Resolution 29Si Nuclear Magnetic Resonance Study on Gallosilicates with Zeolitic Structures
Authors: Hayashi Shigenobu , Suzuki Kunio , Shin Shigemitsu , Hayamizu Kikuko , Yamamoto Osamu
Published: July 2006

High resolution 29Si nuclear magnetic resonance spectra have been measured using magic angle sample spinning technique for several gallosilicates and aluminosilicates with zeolitic structures. The number of gallium atoms coordinating to the SiO4 tetrahedron was determined by the technique in the same manner as established for aluminium in aluminosilicates. The resonance lines were observed to shift to lower field by the substitution of silicon atoms with gallium as well as aluminium. The magnitudes of lower-field shifts were larger for the substitution by gallium than aluminium. The chemical shift ranges of 29Si nuclei are discussed for gallosilicates with the values for aluminosilicates compared.
Photochemical Electron-transfer Reaction between Aromatic Olefins and Metal Ions. Dependence of the Reaction Course on the Structure of the Olefins
Authors: Kojima Masanobu , Sakuragi Hirochika , Tokumaru Katsumi
Published: July 2006

To investigate the photochemical electron transfer from aromatic olefins to copper(II) or iron(III) ions, a series of substituted styrenes (1) was irradiated in the presence of copper(II) or iron(III) salts in methanol, which gave dimethoxylated monomers (2) and one or more of three types of dimethoxylated dimers [α,α- (3), α,β- (4), and β,β,-dimers (5)]. The formation of these products are reasonably attributed to the participation of the cation radicals of the olefins generated by electron transfer from the excited olefins to the metal ions. Substituents on the substrates are found to govern the reaction products.
Magnetic Properties of Conjugated Systems. Bond Orders and Imaginary Bond-Bond Polarizabilities of “Acyclic” Bonds
Authors: Mizoguchi Noriyuki
Published: July 2006

Within the London-McWeeny formalism of the π-electron magnetic properties, the contribution of each bond in a conjugated system to the London susceptibility is studied. By using the relations between the bond orders Prs and the imaginary bond-bond polarizabilities \barπ(rs)(tu) proved in a previous paper, it is shown that two equations, Prs+βπ(rs)(rs)=0 and π(rs)(vw)=0, hold for the “acyclic” bond r-s in a conjugated system. The equations show that no bonds in acyclic conjugated systems or in acyclic fragments of cyclic systems make any contributions to the London susceptibilities (or to the ring currents) of the systems. On the basis of these equations, the expression for the London susceptibility is simplified. Moreover, we will discuss the relationships between the above equations and some consequences of McWeeny’s unitary transformation.
Calorimetric Studies of the Interaction between the Lecithin and Copolymers of l-Lysine and l-Leucine
Authors: Nakagaki Masayuki , Okamura Emiko
Published: July 2006

The interaction between the dimyristoyl phosphatidylcholine (DMPC) bilayers and aqueous copolymers of l-lysine and l-leucine was investigated by means of differential scanning calorimetry. None of the copolymers had any effects on the transition temperature of DMPC, irrespective of the lysine/leucine ratio, although the pretransition peak disappeared. The transition enthalpy did not appreciably change upon the addition of copolymers if the leucine fraction was small (<0.25), but it remarkably decreased upon the addition of a copolymer with a large leucine content (>0.3). The latter case suggests the penetration of copolymers into the hydrophobic region (hydrocarbon-chain region) of DMPC as a result of the hydrophobic effect of leucine residues. On the contrary, copolymers of a small leucine content can penetrate at most into the polar region of DMPC because of the electric charge derived from lysine residues, indicating the effect of the copolymer composition on the penetrability of a copolymer into lipid layers.
The Electrical Properties of Calcium Sulfide Doped with Lanthanum Sulfide and Zirconium Sulfide
Authors: Adachi Gin-ya , Imanaka Nobuhito , Sato Mineo , Shiokawa Jiro
Published: July 2006

Calcium sulfides doped with tri- and tetravalent metal sulfides were prepared. Their electromotive forces (EMF) were measured on a galvanic cell(Fe+FeS| Solid Electrolyte| Cu+Cu2S) where the solid electrolyte was a material in a CaS–Ln2S3–MS2 system. The cell, using calcium sulfide doped with La2S3 and ZrS2, exhibited an EMF value as high as the one calculated for thermodynamical equilibrium. The CaS–La2S3–ZrS2 solid electrolyte showed, predominantly, an ionic conduction in the sulfur pressure range from 10−4 to 102 Pa with an activation energy of approximately 56.7 kJ·mol−1, which was lower than for CaS and CaS–La2S3.
Fluorescence Emissions of Cycloalkanes and Mono-olefin by Controlled Electron Impact
Authors: Kawazumi Hirofumi , Uchida Tsuneaki , Ogawa Teiichiro
Published: July 2006

Emission spectra of cyclohexane, methylcyclohexane, trans-decalin and tetramethylethylene were measured under the controlled electron-impact (5–100 eV) excitation. A broad band was observed in the ultraviolet region in addition to lines and bands from such fragments as H, CH, and C2. This broad band was assigned to the fluorescence emission from the excited parent molecule, since its peak and lineshape resemble the fluorescence measured for liquid and since the threshold energy agrees with the absorption onset. The emission cross sections for these emissions were determined at an electron energy of 50 eV.
Studies of the Complexes of Np(V) with Inorganic Ligands by Solvent Extraction with Thenoyltrifluoroacetone and 1,10-Phenanthroline. I. Carbonato Complexes
Authors: Inoue Yasushi , Tochiyama Osamu
Published: July 2006

The complex formation of Np(V) in a carbonate medium has been studied in 1 mol dm−3 NaClO4 at pH 6.5–8.3 and 25 °C using the solvent-extraction method with thenoyltrifluoroacetone (TTA) and 1,10-phenanthroline. The formation constants of the complexes of Np(V) with CO32− were log(β1/mol−1 dm3)=4.14±0.01 and log(β2/mol−2dm6)=6.78±0.01, with no indication of the formation of HCO3− complexes. Based on these constants, the distribution of chemical species of neptunium are discussed under various conditions encountered in natural water.
Über den Effekt der Schwingungsmühle auf Thermische Zersetzung von Ammoniumhydrogenamidophosphat
Authors: Shimasaki Choichiro , Ookawa Shigenobu , Ishizaka Ryuichi
Published: July 2006

Das von einer Schwingungsmühle gemahlte Ammoniumhydrogenamidophosphat (NH4HPO3NH2) hat es herausgestellt, daß nach einer Stunde Laufzeit die erste endotherme Spitze in DSC Kurven in zwei Teile geteilt wird. Die Absorption infolge NH und Zwitterions in IR Spektren wird vom EinfuB der Schwingungsmühle verändert. Das Ergebnis unterstützt eine Transformation von NH4HPO3NH2 nach einer Zwischenphase, die durch die starke Wasserstoffbindung zwischen NH und POH gebildet worden hat.
Orbital Phase Design of Acyclic Electron Localizing and Delocalizing π-Conjugated Poly ions and Related Systems
Authors: Inagaki Satoshi , Iwase Koji , Kawata Hirofumi
Published: July 2006

Acyclic localization-delocalization of electrons in π-conjugated hydrocarbon polyions was predicted in terms of the continuity-discontinuity of the phase of the component orbitals. Many pairs of electron-localizing and -delocalizing conjugated polyions were designed as the model systems of which the relative stabilities have not been explored so far.
Thermodynamic Analysis of the Potentiometric Titrations of Polypeptides Accompanying the Coil–Beta Conversion
Authors: Maeda Hiroshi
Published: July 2006

The stability of uncharged β-structure of polypeptides from potentiometric titrations is examined based on thermodynamic considerations with special references to the aggregation and/or precipitation of polypeptides and the irreversible nature of the titration. It is concluded that most of the reported data on various kinds of polypeptides approximately represent the stability of the β-structure. Diverse stabilities exhibited by reported data can be partly ascribed to different extents of the stacking of the pleated sheets.
ESR Spectra of Six-coordinate Cobalt(III) Tetraphenylporphyrin Cation Radicals Generated by Electrochemical Oxidation II. Axial Ligand and Solvent Effects
Authors: Ichimori Kohji , Ohya-Nishiguchi Hiroaki , Hirota Noboru , Yamamoto Kiyoko
Published: July 2006

The ESR spectra of the π-cation radical generated electrochemically from 5,10,15,20-tetraphenylporphyr-inatocobalt(II), [CoII(tpp)], have been observed in the presence of various anions and in solvents such as halo-genated hydrocarbons, nitriles, ethers, ethanol, and organic acids. From the analyses of these spectra, the TT-cation radical has been found to coordinate axially the anion or the solvent according to the order of its coordinating ability; BF4−, ClO4−, PF6−, NO3−<nitriles<halogen anions<ethanol<CF3COO−, AcO−, SCN−, CN−. The singly-occupied molecular orbital has been assigned to be always a2uπ orbital regardless of the axial ligands. The spin densities on N and Co much increase due to the axial ligation. It has been further confirmed that the spin polarization mechanism mainly contributes to the appearance of the spin density on Co. These axial-ligand effects are quantitatively explained by a model calculation of the CNDO/2 MO method.
Reactions of the [PtC2L2] Complexes (L=Sulfide or Tertiary Phosphine) with β-Diketonate Anions
Authors: Sasakura Fumiyo , Isobe Kiyoshi , Kawaguchi Shinichi
Published: July 2006

cis- and trans-[PtCl2(Et2S)2] as well as [PtCl2(EtSCH2CH2SEt)] reacted with thallium(I) β-diketonates, Tl(β-dik), to give complexes containing a central-carbon-bonded β-dik ligand. The reaction of cis-[PtCl2(PEt3)2] with Tl(acac) (acac=acetylacetonato) did not give an acetylacetonato complex, but resulted in [Pt(CO3)(PEt3)2], while trans-[PtCl2(PEt3)2] yielded [PtCl(acac)(PEt3)]. [Pt(PPh3)2(H2O)2](ClO4)2 derived from cis-[PtCl2(PPh3)2] reacted with K(acac) and K(tfac) (tfac=trifluoroacetylacetonato) to afford [Pt(acac)(PPh3)2]ClO4 and [Pt(tfac)(PPh3)2]ClO4, respectively. Bases such as Et3N, K(acac), and K(tfac) removed a proton from the latter complex to give [Pt(tfac(2–)-C,O)(PPh3)2] containing a C,O-chelated tfac dianion.
Chemistry of 1,2-Thiaphosphole 2-Sulfides I. Cycloaddition Reactions of 1,2-Thiaphosphole 2-Sulfides with Some Dienophiles
Authors: Tanaka Hideyuki , Kametani Shunichi , Saito Takao , Motoki Shinichi
Published: July 2006

2,9-Dithia-1-phosphabicyclo[4.3.0]nona-3,7-diene 1-sulfides have been prepared by the reaction of α,β unsaturated ketones with P4S10 in the presence of NEt3. 1,2-Thiaphosphole 2-sulfides generated by the thermolysis of the phosphabicyclo compounds underwent cycloaddition reactions with acrylonitrile, styrene, butyl vinyl ether and norbornene to give the [4+2]cycloadducts, respectively.
A Potent Pyridoxal Model Capable of Promoting Transamination and β-Elimination of Amino Acids
Authors: Kondo Hiroki , Kikuchi Jun-ichi , Uchida Shinji , Kitamikado Tatsuya , Koyanagi Eiji , Sunamoto Junzo
Published: July 2006

N-Dodecyipyridoxal chloride (1a) has been synthesized as a potent pyridoxal 5′-phosphate model. The equilibrium constant for Schiff base formation of 1a with phenylalanine (21000 M−1) in 3 mM hexadecyltrimethylammonium chloride (CTACl) micelle is over a thousand times larger than that for the N-methyl counterpart (1b). The Schiff base of 1a and phenylalanine exists over a broad pH range of 5–11 in two ionic forms, HSB and SB−, that differ in the protonation state at the azomethine group. These Schiff bases undergo transamination at 30 °C in the absence of a metal ion at considerably different rates; 1.33×10−3 and 1.5×10−5 s−1 for HSB and SB−1, respectively. Likewise, the former species exhibited 11 times higher reactivity in the β-elimination of O-phosphonoserine catalyzed by 1a in 3 mM CTACl at 40 °C. These results indicate unambiguously the importance of a positive charge on the azomethine nitrogen as well as the one residing on the pyridine nitrogen in vitamin B6 catalysis. The kinetic α-deuterium isotope effect of 5.1 in the transamiantion of phenylalanine with 1a at pH 7.7 and 30 °C revealed that α-hydrogen abstraction takes place in the transition state.
NAD(P)+–NAD(P)H Models. 53. Proximity Effect of Intramolecular Heteroatom on Reaction Rate
Authors: Ohno Atsuyoshi , Goto Takehiko , Kobayashi Hisami , Oka Shinzaburo
Published: July 2006

NAD(P)H-model compounds that have a sulfur or oxygen substituent in the molecule have been synthesized and kinetics for the reduction of both substituted and unsubstituted α,α,α-trifluoroacetophenones with these model compounds are studied. Reduction with the heteroatom-containing model compounds proceeds at a slower rate than the reduction with a model without any heteroatom substituents. Furthermore, the dependency of the kinetic isotope effect on the electron-deficiency of the substrate differs. Kinetic parameters reveal that the retardation caused by the heteroatom is due to the loss of entropy in the initial electron-transfer process. The enthalpic term favors the reduction with the heteroatom-containing model.
The BBGKY Equation in the Interaction Site Model for Polyatomic Molecular Fluids
Authors: Lee Lloyd Lieh-shen
Published: July 2006

We extend the atom-atom interaction site model to a fluid of polyatomic molecules in an external field by deriving the first Born-Bogoliubov-Green-Kirkwood-Yvon(BBGKY) hierarchy for a nonuniform system. It is shown that the intramolecular structure contributes to the density gradient as well as the intermolecular correlations. By invoking the mechanical equilibrium conditions for microscopic forces we also obtain new expression for the gradient of the pressure tensor in inhomogeneous fluids. The BBGKY equation provides a consistency check on any theories of the interaction site variety. An examination of the so-called RISM theory of uniform fluids shows that the latter is inconsistent with respect to the BBGKY condition.
Studies on Mixed-Ligand Complexes of Cadmium with 2,2′-Bipyridyl and Some Dicarboxylic Acids in Dioxane Medium
Authors: Kumari Rajani , Chandel Chandra Pal Singh , Gupta Chand Mai
Published: July 2006

The mixed-ligand complexes of cadmium with 2,2′-bipyridyl and dicarboxylic acids (tartaric, succinic, maleic, malonic, and malic) were studied polarographically in the 50% dioxane medium. The stability constants of simple systems were calculated by Deford and Hume method, and the values of stability constants of mixed-ligand complexes have been determined by the method of Schaap and McMasters. The overall stability constants have been evaluated with the help of Leden’s graphical extrapolation method and the values of β11, β12 and β21 are (5.24, 5.80, and 8.19) for Cd-bpy-tartarate system (5.62, 6.15, and 8.34) for Cd-bpy-succinate system (5.48, 6.10, and 8.32) for Cd-bpy-maleate system (5.57, 6.15, and 8.37) for Cd-bpy-malonate system, and (5.57, 6.15, and 8.34) for Cd-bpy-malate system.
The Phosphorescence Spectra of 9,10-Anthraquinone β- and β,β′-Sulfonates in an Aqueous Solution at 77 K
Authors: Kuboyama Akira , Matsuzaki Sanae Y
Published: July 2006

The nπ* phosphorescence spectra, and their excitation spectra and lifetimes of 9,10-anthraquinone-2-sulfonate, and -2,6- and -2,7-disulfonates in water–ethylene glycol 1:1 mixture at 77 K have been obtained. These phosphorescence spectra shift to the red with increases in the concentration of the solutions, and show an excitation-wavelength dependence. From the results obtained it is concluded that in the glassy solutions at 77 K an association of these quinones occurs, and that the phosphorescence state of the associates corresponds to the nπ* triplet excimer state, similar to that of the p-quinone aggregates in polycrystalline solutions at 77 K, previously studied.
X-Ray Photoelectron Spectroscopy of Sodium-doped Polyacetylene
Authors: Ikemoto Isao , Ichihara Toshihide , Egawa Chikashi , Kikuchi Koichi , Kuroda Haruo , Furukawa Yukio , Harada Issei , Shirakawa Hideki
Published: July 2006

The change of the C ls peak shape in an X-ray photoelectron spectrum was studied for sodium-doped polyacetylene. The C ls peak due to negatively-charged carbon atoms was found to appear on the low-binding-energy side of a peak due to neutral carbon atoms. An electron, which is transferred to a polyacetylene chain from the sodium atom, has been determined to reside over several carbon atoms.
Application of Laser Flash Photolysis to Determine Association Constants between Zn–TPPS3 and Viologens
Authors: Okura Ichiro , Aono Shigetoshi , Hoshino Mikio , Yamaha Akira
Published: July 2006

The association behavior between zinc 5,10,15,20-tetraphenylporphyrintrisulfonate (Zn–TPPS3) and viologens was investigated from the T-T absorption band of the triplet Zn–TPPS3 by laser-flash photolysis. The association constants of Zn–TPPS3 with methylviologen and propylviologen-3,3′-sulfonate (PVS) were 1.7×104 and 7.3×102 mol−1. dm3, respectively.
Triphenylmethyl-substituted Arylthioaminyl Radicals, An ESR Study of N-(Arylthio)triphenylmethylaminyls
Authors: Miura Yozo , Isogai Mamoru , Kinoshita Masayoshi
Published: July 2006

The title radicals have been studied by ESR spectroscopy. The radicals are fairly long-lived in solution and satellite lines due to the 33S atom at natural abundance could be observed in their ESR spectra.
The Electrochemical Behavior of BR2-linked Bis(glyoximato)nickel(II) Complexes in a Nonaqueous Solvent
Authors: Aihara Makoto , Nishi Yumiko , Omatsu Hiroko , Nonaka Yasuomi
Published: July 2006

Nickel(II) complexes with dioximers replaced by BF2 and B(C2H5)2 groups for bridging by the hydrogen atom were investigated by electrochemical methods. The nickel(II) complexes exhibited two distinct one-electron reduction waves in N,N-dimethylformamide. It was found that the electron-withdrawing effect of the replaced group is exerted on the electronic states of the nickel(II) complexes.
Stability Constants of Complex Formations between Divalent Metal Ions and Cyclic Dipeptides: Cyclo(glycyl–l-histidyl) and Cyclo(l-methionyl–l-histidyl)
Authors: Kojima Yoshitane , Ishio Noriaki , Yamashita Tetsushi
Published: July 2006

The values(logK1i and logK2 of the complex formations between divalent metal ions and two cyclic dipeptides of this title were determined by Bjerrum’s method. It is apparent from 1H NMR data that metal ions link exclusively to the nitrogen atom of the imidazolyl group of cyclo(l-methionyl-l-histidyl).
Synthesis of β-Alkylimino α-Cyano Dithiocarboxylic Acids, 3-Alkyl-1,3-thiazine-2,6-dithiones, and Related Compounds
Authors: Yamamoto Tatsuo , Hirasawa Shigeo , Muraoka Motomu
Published: July 2006

The title compounds 2 and 5 were synthesized by the reaction of β-alkylimino nitriles with carbon disulfide.
Sintered Iron (III) Oxide Photoanode Doped with Molybdenum
Authors: Oishi Shigero , Tajime Keiko , Hosaka Akeri
Published: July 2006

Sintered iron(III) oxide electrodes which contained about 0.01 atomic% of molybdenum showed considerable improvement in generating anodic photocurrent, particularly, in a cathodic potential region. 0.01 Atomic% doping level was found to be attained by sintering at 1200 °C for 12h using 0.2 atomic% of MoO2 or 1.0 atomic% of MOO3.
Synthesis of Lariat Ferrocenocrown Ethers and Their Alkali Metal Complexes
Authors: Akabori Sadatoshi , Habata Yoichi , Sato Masaru
Published: July 2006

Lariat ferrocenocrown ethers were synthesized by the reaction of disodium salt of 1,1′-dihydroxyferrocene with N-substituted bis(2-chloroethyl)amines and/or by the reaction of bis(2-chloroethoxy)ferrocene with disodium salts of N-substituted bis(2-hydroxyethyl)amines. Crystalline 1:1 complexes of N-(2-methoxyethyl)-4-aza-1,7-dioxa[7]ferrocenophane with LiClO4 and NaClO4 were also isolated.