bluuebunny/crossref_metadata_2025 huggingface dataset:
Nickel(II) Complexes of N,N′-Polymethylenebis(o-mercaptobenzylamine)
Authors: Koyama Hiroyuki , Murase Ichiro
Published: July 2006

N,N′-Polymethylenebis(o-mercaptobenzylamine) ligands (polymethylene=ethylene 1,2-cyclohexylene, trimethylene, and tetramethylene) have been synthesized by the reduction of the corresponding amides, which were prepared by the condensation of 2,2′-dithiodibenzoyl chloride and polymethylenediamines, and then their nickel(II) complexes have been prepared and characterized. The elemental analyses and the magnetic and spectroscopic data indicate that all of the complexes are monomeric with metal-ligand ratio of 1: 1, and their geometries are essentially square-planar. When the bridging carbon chain was replaced from ethylene up to tetramethylene, the electronic spectra of the complexes exhibited pronounced change in the d-d bands.
Circular Dichroism Studies of a Series of (Ammine)[(RR)-2,4-pentanediamine]cobalt(III) Complexes
Authors: Kojima Masaaki , Fujita Miho , Fujita Junnosuke
Published: July 2006

The circular dichroism spectra of a series of complexes of the type [Co(NH3)2n(RR-ptn)3−n]3+(n=0, 1,2), where the RR-ptn is (RR)-2,4-pentanediamine, were recorded in aqueous solutions with and without the addition of electrolytes such as chloride or sulfate, and in DMSO solutions. The circular dichroism spectra in the region of the first absorption band of Δ-[Co(RR-ptn)3]3+ and cis-Δ-[Co(NH3)2(RR-ptn)2]3+ were extremely sensitive to the environment of the complexes and showed a remarkable variation, while those of the corresponding diastereomers, Λ-[Co(RR-ptn)3]3+ and cis-Λ-[Co(NH3)2(RR-ptn)2]3+ were little affected by the given environment. The other complexes, trans-[Co(NH3)2(RR-ptn)2]3+ and [Co(NH3)4(RR-ptn)]3+ exhibited small variations in the circular dichroism spectra. These variations seem to be accounted for by the conformational change of the flexible sixmembered chelate ring brought about by ion-pair formation between the complex cations and anions.
Mechanism of Photochemical Reaction of Friedelin with Diethyl Ether and with Acetone
Authors: Shirasaki Hidekazu , Tsuyuki Takahiko , Takahashi Takeyoshi , Stevenson Robert
Published: July 2006

Photo-irradiation of friedelin (1) in diethyl ether gave a keto ether (2), a hydroxy ether (3), and an alcohol (4). A hydroxy ketone (5) was formed by the photo-irradiation reaction of 1 in diethyl ether containing acetone. In the latter case, labeled experiments showed that the photo-produced ketene (12) reacted with 1-hydroxy-1-methylethyl radical derived from acetone to give 5. The formation of 2 could be explained by an attack of an α-radical derived from diethyl ether to 12. Both 3 and 4 were shown to be derived from a norseco-aldehyde (11) which was produced from the ketene (12).
A New Method for the Synthesis of 1-Cycloalkenyl Alkyl Sulfides
Authors: Akiyama Fuminori
Published: July 2006

2-Isopropyl-5-methyl-1-cyclohexenyl alkyl sulfides were obtained in about a 60% yield by the reaction of 2-isopropyl-5-methylcyclohexanone with thioacetals or thiols in the presence of aluminum chloride. 1-Cycloalkenyl ethyl sulfides, (Remark: Graphics omitted.) (n=4, 5, or 6, R=H or alkyl) were obtained in good yields by the reaction of cycloalkanones with ethanethiol in the presence of diphosphorus pentaoxide. However, an attempt to apply this method to acyclic vinyl sulfides was unsuccessful.
Synthesis of Optically Active Bis(1-mesitylethyl) Ethers
Authors: Nakatani Munehiro , Kamikawa Tadao , Hase Tsunao , Kubota Takashi
Published: July 2006

The racemic and meso bis(1-mesitylethyl) ethers were synthesized. The optical resolution of the dicarboxylic acid derivative showed that the high-melting compounds were racemic in form and the low-melting isomers meso in form.
Amidrazones and Related Compounds. V. The Formation of Pyrazole, 1H-1,2,4-Triazepine, and 4H,11H-[1,5]Diazocino-[2,3-e: 6,7-e′]di[1H-1,2,4]triazepine Derivatives
Authors: Takahashi Masahiko , Sugawara Noriyuki , Yoshimura Kaoru
Published: July 2006

Amidrazones RC(NH2)=NNH2 (1a, b) (R=2-pyridyl, phenyl) reacted with EtOCH=CR1R2 (2a–d) (R1R2=CN, CO2C2H5, COCO2C2H5) to give RC(NH2)=NNHCH=CR1R2 (3a–g). 3,4-Disubstituted pyrazoles (4a, b) were obtained on the heating of 3a, b, e, and f (R=2-pyridyl, phenyl, R1=CN, R2=CN, CO2C2H5) in toluene. However, the heating of 3c (R=2-pyridyl, R1=R2=CO2C2H5) gave a dimer, the 2,3,7,9,10-pentaazadodeca-1,4,8,11-tetraene derivative (9), instead of 4. 5-Amino-6-ethoxycarbonyl-3-(2-pyridyl)-1H-1,2,4-triazepine (10) was obtained by the reaction of 3a (R=2-pyridyl, R1=CN, R2=CO2C2H5) with ethanolic hydrogen chloride. The treatment of 10 with alkaline gave 2,9-di-2-pyridyl-6,7,13,14-tetrahydro-4H,11H-[1,5]diazocino-[2,3-e:6,7-e′]di[1H-1,2,4]triazepine-6,13-dione (11). Triazepine (10) reacted with hydrazines to give 5-hydrazino-1H-1,2,4-triazepine derivatives (13a, b).
Synthesis of a Masked Derivative of 3′-Deoxydihydrostreptobiosamine, a Precursor for the Synthesis of 3″-Deoxydihydrostreptomycin
Authors: Sano Hiroshi , Tsuchiya Tsutomu , Kobayashi Shigeru , Umezawa Hamao , Umezawa Sumio
Published: July 2006

2′-N-Acetyl-4′,6′-di-O-acetyl-3,3a-O-carbonyl-3′-deoxydihydrostreptobiosamine (15), a precursor in the synthesis of 3″-deoxydihydrostreptomycin, was prepared from benzyl α-dihydrostreptobiosaminide. The synthesis involves formation of l-allo compound (5) with inversion of the 3′-hydroxyl group of l-gluco derivative (2) in order to facilitate 3′-chlorination, dechlorination, of the 3′-chloro-l-gluco derivative (7 or 11) with tributyltin hydride, and utilization of cyclic 3,3a-O-carbonyl group instead of 3,3a-O-isopropylidene group which was unstable in the later reactions.
A Semi-empirical Calculation of the Substituent Effects on the 1H Chemical Shifts of 1-Substituted Naphthalenes
Authors: Niwa Jun
Published: July 2006

A semi-empirical equation for predicting the 1H chemical shift induced by substituents in an aromatic system (J. Niwa, Bull. Chem. Soc. Jpn., 48, 118, 1637 (1975)) has been applied to the ring protons of 1-substituted naphthalenes. The predictions of the equation are tested against the available experimental data for six representative substituents and are also compared with those of the electric-field model.
Effects of Pressure on the Disproportionation of Olefins over MoO3–Al2O3 and Re2O7–Al2O3 Catalysts
Authors: Sodesawa Toshiaki , Ogata Eisuke , Kamiya Yoshio
Published: July 2006

The disproportionation of propylene and 1-butene over MoO3–Al2O3 and Re2O7–Al2O3 catalysts was carried out in order to investigate the effects of reaction pressure in the range from 1.0 to 130 kg/cm2. The effects of the pressure on the reaction can be identified as two independent of the reaction phase; the catalytic activity increased with the reaction pressure, and the time needed to reach the maximum conversion (Tmax) as well as the time when the conversion falls to half the maximum value (τ1⁄2) decreased with the increase in the reaction pressure. It can be concluded that the catalytic activity by the polymers formed over the catalyst falls off rapidly with the increase in the pressure. In both phases, the disproportionation of olefins over the Re2O7–Al2O3 catalyst exhibits the following features as compared with that over the MoO3–Al2O3 catalyst: (1) a much higher activity at temperatures of 0–140 °C; (2) a much higher selectivity for disproportionation, and (3) a lower apparent activation energy.
Radiation Chemical Reactions in Carbon Dioxide–Propane System. III. Formation of Oxygen Containing Products
Authors: Ikezoe Yasumasa , Sato Shoichi
Published: July 2006

The G value of water and 2-propanol as well as that of carbon monoxide decreased with decrease in propane concentration below 0.5%, the value of acetone remaining constant. Considering the effects of dose rate and irradiation temperature on the product yields, the results indicate that the formation of water and 2-propanol competes with the back reaction, or the reoxidation of carbon monoxide. A clustered negative ion, O−(CO2)n seems to be the oxidizing species responsible both for the back reaction and the formation of water and 2-propanol. The G value of O−(CO2)n was estimated to be 1.3. The formation of acetone is independent of the back reaction.
Viscoelastic Behavior of Some Di(normal alkyl) Phthalates
Authors: Kinjo Noriyuki , Nakagawa Tsurutaro
Published: July 2006

The viscoelastic behavior of a homologous series of di-n-alkyl phthalates varying in alkyl chain length from methyl- to nonyl- was studied by means of torsional braid analysis (TBA). The glass transition temperatures, Tg were determined as the temperature at loss maximum. The Tg decreases with increasing alkyl chain length in the di-n-alkyl phthalates, up to dibutyl. Thereafter, the Tg increases gradually with further increase in the alkyl chain length. This behavior can be explained by taking into account two factors which determine the Tg, the molecular weight and the intermolecular interaction. The increase in the number of methylene groups in the phthalates brings about two effects: first, the Tg is increased with increasing molecular weight and, second, the Tg is decreased owing to shielding of the interaction between polar carbonyl groups due to the presence of non-polar methylene groups. When the number of methylene groups is four, the two effects counterbalance each other and the Tg of dibutyl phthalate is the lowest of the di-n-alkyl phthalate series.
Absorption Spectra of Inter- and Intramolecular Exciplex Systems of Pyrene and N,N-Dimethylaniline in Alcoholic Solutions
Authors: Hinatu Junji , Masuhara Hiroshi , Mataga Noboru , Sakata Yoshiteru , Misumi Soichi
Published: July 2006

Absorption spectra of inter- and intramolecular exciplex systems of pyrene and N,N-dimethylaniline in alcoholic solution were obtained by means of ns laser photolysis. The spectra of intermolecular systems can be reproduced by the superposition of bands of the pyrene anion and the N,N-dimethylaniline cation. Similar results were obtained with intramolecular systems of P1 and P2, where Pn is (1-pyrenyl)-(CH2)n-(p-dimethylaminophenyl). The absorption band of P3 exciplex is structureless and very broad, the position of the maximum remaining unchanged. From the relation between absorption spectra and conformation of intramolecular systems, it is concluded that the broad band is due to the sandwich type of structure of the donor cation and the acceptor anion. Anomalous behavior of intermolecular exciplexes in alcoholic solutions is discussed on the basis of their absorption spectra.
Kinetics of Oxidation of 4-Hydroxy-4-methyl-2-pehtanone by Sodium N-Chloro-p-toluenesulfonamide
Authors: Uma K V , Mayanna S M
Published: July 2006

The kinetics of oxidation of 4-hydroxy-4-methyl-2-pentanone (diacetone alcohol) by sodium N-chloro-p-toluenesulfonamide (Chloramine-T, RNClNa) in presence of hydrochloric acid (0.05–0.6 M) has been studied at 30 °C. The reaction follows first order kinetics with respect to chloramine-T. The reaction rate depends on the square of the [H+] and independent of the alcohol concentration. The energy and entropy of activation have been found to be 65.56 kJ mol−1 and −73.81 JK−1 respectively. The rate of reaction has been affected by the addition of potassium chloride and dioxane to the reaction mixture. A mechanism has been proposed involving diacetone alcohol and H2OCl+ formed by the hydrolysis of chloramine-T. Applying steady state condition to RNHCl, a rate expression has been given to account for the observed results. Kinetic data have been used in the analytical estimation of diacetone alcohol in acidic medium.
Japanese Tea Leaves: A Possible Biological Standard Reference Material
Authors: Fuwa Keiichiro , Notsu Kenji , Tsunoda Kin-ichi , Kato Hideaki , Yamamoto Yuko , Okamoto Kensaku , Dokiya Yukiko , Toda Shozo
Published: July 2006

Japanese Tea Leaves, prepared by pulverizing with an agate ball mill and sieving with a Saran fiber sieve (50 mesh) were assessed as a possible biological standard reference material for elemental analysis. The metal content of the tea leaves was determined independently at two laboratories using atomic absorption and flame emission spectrometry. Neutron activation analysis was also performed to determine the content (21 elements) of Tea Leaves. For some elements the result from the various methods were compared. The characteristics of Tea Leaves are discussed and the elemental composition is compared to that of Orchard Leaves (NBS SRM, 1571). The most significant characteristic of Tea Leaves was the high manganese content.
Trimethylenediamine Complexes. IV. Kinetics and Mechanism of Acid and Base Hydrolysis of Tetranitro(ethylenediamine)- and Tetranitro(trimethylenediamine)cobaltates(III)
Authors: Ito Yoshiaki , Kawaguchi Shinichi
Published: July 2006

Hydrolysis of Co(NO2)4(AA)− (AA=en or tn) was studied in acidic and basic aqueous solutions by the spectrophotometric method. In faintly acidic solution (6>pH>4) the aquation proceeds reversibly to attain an equilibrium with Co(NO2)3(H2O) (AA), Keq being (1.71±0.03)×10−2 and (3.55±0.06)×10−2 mol·1−1 for AA=en and tn, respectively, at 25.0 °C and μ=0.1. With increasing concentration of hydrogen ion the acid-catalyzed pathway becomes increasingly important. In basic solution (12.2>pH>9.5) Co(NO2)3(OH)(AA)− was formed irreversibly as the first product. Kinetic data of these hydrolysis reactions are interpreted in terms of the dissociative mechanism involving a five-coordinate intermediate Co(NO2)3(AA). The rates of nitrite release from Co(NO2)4(tn)− ((9.27±0.03)×10−4s−1) and deaquation from Co(NO2)3(H2O)(tn) ((3.95±0.12)×10−4 s−1) are several times greater than those for the corresponding ethylenediamine complexes ((2.08±0.01)×10−4 and (5.46±0.10)×10−5 s−1, respectively.
The Stereochemistry of 3-Hydroxy-2-methylbutyric Acid
Authors: Tai Akira , Imaida Motomasa
Published: July 2006

Four stereoisomers of methyl 3-hydroxy-2-methylbutyrate (I), (+)-threo-I, (−)-threo-I, (+)-erythro-I, and (−)-rythro-I, were prepared, and their absolute configurations were determined. The configurations of (+)-threo-I, [α]D20+36.80° (c 5, methanol) and (+)-erythro-I, [α]D20+14.32° (c, 5, methanol) were assigned to (2S, 3S) and (2S, 3R) respectively.
Structural Studies of the Interaction between Indole Derivatives and Biologically Important Aromatic Compounds. I. The Crystal and Molecular Structure of the Indole-3-acetic Acid-Nicotinamide (1:1) Complex
Authors: Inoue Masatoshi , Sakaki Toshimasa , Fujiwara Takaji , Tomita Ken-ichi
Published: July 2006

The title complex crystallizes in the monoclinic space group P21/c. The unit-cell dimensions are a=11.287(5), b=5.110(3), c=26.391(3) Å, and β=107.07(2)°. The crystal structure was solved by a direct method. By block-diagonal least-squares refinements, the R-value dropped to 0.069. All the nitrogen and oxygen atoms in the complex participate in the hydrogen bonding. No prominent overlapping between pyridine and indole rings is observed in the crystal. Both molecules are hydrogen-bonded to form infinite-layered structures perpendicular to the c-axis; those structures are held together by van der Waals contacts.
Oxidative Degradation of Polymers. V. Ozonization of Polypropylene and Polystyrene in Carbon Tetrachloride
Authors: Saito Tsuneo , Niki Etsuo , Shiono Takeo , Kamiya Yoshio
Published: July 2006

The rates and products of ozonization of atactic polypropylene and polystyrene were studied in carbon tetrachloride at 30 and 70 °C. Atactic polypropylene underwent cleavage statistically by ozone to give oxygenated products. The molecular weight of polypropylene decreased with the progress of ozonization. Most chain ends of ozonized polypropylene were suggested to be carboxylic acids. Ozonization of polystyrene brought about crosslinking as well as chain scission, giving rise to broadening of molecular weight distribution. The major product from polystyrene was carboxylic acid.
Gel Chromatography of β-Diketones and Their Metal Complexes. IV. The Partition Concept in Gel Chromatography
Authors: Saitoh Koichi , Suzuki Nobuo
Published: July 2006

A new theoretical treatment of the solute distribution in gel chromatography is proposed. Practical gel chromatography can be regarded as one based on a combined function of the molecular sieve effect and the partition effect. Introducing the concept of a regular solution to the column system of gel chromatography, the contribution of the partition effect can be estimated from the data on the physical properties of the solute, the solvent, and the gel matrix. The argument being proposed is supported by the experimental data on the gel chromatography of metal (II, III) chelates with acetylacetone and normal alkanes previously obtained in the systems of a poly(vinyl acetate) gel and various eluting solvents.
The Relative Rates of Ene Reaction of Benzyne with Cyclic Olefins: The Stereochemical Course
Authors: Kato Masahiko , Okamoto Yukio , Chikamoto Takeji , Miwa Toshio
Published: July 2006

The benzyne reaction of cyclic olefins, in competition with that of cyclohexene has been studied. The relative reactivities for ene reaction and the stereoselectivity of the reaction with 4-t-butylcyclohexene, which afforded trans-5-t-butyl-3-phenylcyclohexene and cis-3-t-butyl-6-phenylcyclohexene, are consistent with the stereochemical requirements along the reaction pathway.
Reactions of Tetramethylbenzenedicarbonitriles and Tetramethylbenzonitriles with Fuming Nitric Acid. A New Route to Some Substituted Phthalides and 1,3-Dihydroisobenzofuran-1-imines
Authors: Suzuki Hitomi , Koge Mamie , Inoue Akiyoshi , Hanafusa Terukiyo
Published: July 2006

The reaction of tetramethylbenzenedicarbonitriles and tetramethylbenzonitriles with fuming nitric acid (d=1.5) has been investigated at room temperature in the dark. 2,4,5,6-Tetramethylbenzene-1,3-dicarbonitrile and 2,3,5,6-tetramethylbenzene-1,4-dicarbonitrile gave, after aqueous work-up, 4-cyano-5,6,7-trimethyl- and 5-cyano-4,6,7-trimethylphthalides, respectively, in high yields, while 3,4,5,6-tetramethylbenzene-1,2-dicarbo-nitrile produced appreciable amounts of two cyanonitro-3-cyclohexen-1-ones in addition to 7-cyano-4,5,6-trimethylphthalide. Similarly, 2,3,4,6- and 2,3,5,6-tetramethylbenzonitriles afforded 4-nitro-5,6,7-trimethyl- and 5-nitro-4,6,7-trimethylphthalides, respectively, along with the expected nitro compounds. In contrast, 2,3,4,5-tetramethylbenzonitrile underwent normal nitration, giving 6-nitro derivative as the sole product. The phthalide formation was found to proceed through 1,3-dihydroisobenzofuran-1-imines presumably derived from the initially formed o-cyanobenzyl nitrates. The reaction appears to provide potential utility in the synthesis of some substituted phthalides and 1,3-dihydroisobenzofuran-1-imines.
Asymmetric Reactions. III. The Asymmetric Synthesis of Methyl 2-Phenylpropionate in the Presence of Chiral Polymers
Authors: Yamashita Tetsushi , Yasueda Hiroshi , Nakatani Noriyuki , Nakamura Nobuo
Published: July 2006

The asymmetric addition of methanol to phenylmethylketene was carried out in the presence of a chiral polymer obtained by the co-polymerization of N-benzyl-2-pyrrolidinylmethyl acrylate with methyl acrylate. The products obtained for the above co-polymer showed a correlation between logkR⁄kS and 1⁄T deviating from linearity, while those for poly(N-benzyl-2-pyrroIidinylmethyl acrylate) exhibited a linear relationship. N-Benzyl-2-pyrrolidinylmethyl butyrate, hexanoate, and stearate were also used as catalysts; they showed asymmetric efficiencies intermediate between those of N-benzyl-2-pyrrolidinylmethyl propionate and poly(N-benzyl-2-pyrrolidinylmethyl acrylate). The use of several high- and low-molecular-weight catalysts derived from cinchonine was similarly attempted in order to examine the polymer effect with regard to the stereoselectivity.
The Effect of Macrocyclic Polyethers on the Alkylation of Sodium 2-Naphtholate
Authors: Akabori Sadatoshi , Tuji Hiroyuki
Published: July 2006

The alkylation of sodium 2-naphtholate, in the presence of benzo-18-crown-6 or 4,7,13,16,21,24-hexaoxabicyclo[8.8.8]hexacosane is found to give high ratios of O/O+C alkylation when conducted in THF, in benzene, and in water. The striking increase in the product ratio is attributed to a specific complexation of the macrocyclic polyethers, which facilitate the dissociation of the ion-pair aggregate of the sodio-derivative which exists in benzene or THF. The polyethers may act as phase-transfer catalysts when the reaction is run in water. In support of this conclusion, the reaction in DMF or acetonitrile, in which the dissociation of sodium 2-naphtholate takes place, fails to show any effect of the macrocyclic polyethers on the product ratio.
Photolyses of S,S-Dimethyl-N-(ethoxycarbonyl)sulfimide in Hydrocarbons and in Oxygen Compounds
Authors: Torimoto Noboru , Shingaki Tadao , Nagai Toshikazu
Published: July 2006

The behavior of ethoxycarbonylnitrene (3), generated photochemically from S,S-dimethyl-N-(ethoxycarbonyl)sulfimide (1), upon insertion into the C–H bonds and the O–H bonds was compared with that of 3 generated from ethyl azidoformate (2). Ethoxycarbonylnitrene generated from 1 was inserted preferentially into the α C–H bonds of cyclic ethers. The relative reactivity toward 3 of the primary, secondary, and tertiary C–H bonds in 2,4-dimethylpentane is in the ratio of 1 : 9 : 35. The insertion of 3 into the tertiary C–H bonds of cis- and trans-1,4-dimethylcyclohexanes proceeded stereospecifically. The reaction of 3 with alcohols gave the O–H insertion products. These results show that the insertion of 3 generated from 1, as well as that of the nitrene from 2, into the hydrocarbon C–H bo nds and the O–H bonds proceeds only for the singlet.
Synthesis of 2,3 : 7,8-Bis(polymethylene)-4H,9H-benzo[1,2-b : 4,5-b′]dipyrans and Their Oxidation to the Corresponding Benzodilactones
Authors: Mahajan Jaswant Rai , Monteiro Maria Beatriz
Published: July 2006

Four members of a new series of the title benzodipyrans have been synthesized through the alkylation of the pyrolidine-enamines of 6,7,8- and 12-membered cycloalkanones with 2,5-bis(dimethylaminomethyl)hydroquinone, followed by hydrolysis and subsequent cyclization of the intermediate products. Oxidation of these benzodipyrans with m-chloroperbenzoic acid (MCPBA) afforded the corresponding benzodilactones in 10–65% yield, the rest of the material being a mixture of hydroxylated carbonyl compounds.
Semi-Empirical Configuration Interaction Studies on the π-Electron Spectra of Nonbenzenoid Molecules
Authors: Das Gupta N K , Birss F W
Published: July 2006

A modification of the method of Yamaguchi et al. has been used to predict the π-electronic spectra of a number of nonbenzenoid molecules containing five- and seven-membered rings. Good correlation of the theoretical and experimental transition energies is found. The calculated intensities are also reasonably consistent with experiment, to the extent of raising questions as to the source of intensity in the bands of some molecules.
Unusual Products of the Leuckart Reaction of 1-Acenaphthenone
Authors: Tatsugi Jiro , Okumura Michio
Published: July 2006

In the reaction between formamide and 1-acenaphthenone, 1,1′-biacenaphthenyliden-2-one was obtained instead of 1-acenaphthenamine which is expected to be formed by the Leuckart reaction. When formic acid was incorporated in the reaction, besides 1,1′-biacenaphthenyliden-2-one two new nitrogen-containing compounds were isolated; their structures were identified to be acenaphtho[1,2-d]pyrimidine and diacenaphtho[1,2-b: 1′,2′-d]pyridine by independent syntheses.
Micellar Effects on Base-Catalyzed Isomerization of Prostaglandin A1 and Prostaglandin A2
Authors: Uekama Kaneto , Hirayama Fumitoshi , Yamasaki Shyukou
Published: July 2006

Micellar effects on base-catalyzed isomerization of A-type prostaglandins to B-type prostaglandins were studied. Cationic and non-ionic micellar systems increased the rate of isomerization, but anionic systems either decreased or had negligible effects on the rate constants. Incorporation of the prostaglandins into the hydrophobic interior of the micelles was suggested by circular dichroism spectra.
The Reactions of the (ZrO)2P2O7–NiO System and the ZrP2O7–NiO System
Authors: Kinoshita Makio , Baba Saburo , Kishioka Akira , Amagasa Michio
Published: July 2006

The reaction between (ZrO)2P2O7 and NiO at elevated temperatures up to 1340 °C yielded Ni3(PO4)2 and ZrO2 over the whole composition. The reaction between ZrP2O7 and NiO yielded NiO·4ZrO2·3P2O5 and Ni3(PO4)2 in the molar ratios up to equimolarity.
The Nitrogen Oxide Complex of the Iron(II) Protoporphyrin IX Dimethyl Ester
Authors: Yoshimura Tetsuhiko
Published: July 2006

A nitrogen oxide complex of the iron(II) protoporphyrin IX dimethyl ester was synthesized and characterized by means of its infrared spectrum and electron paramagnetic resonance (EPR) spectra at the X- and Q-band frequencies. The EPR spectra in the glass state and in the polycrystalline powder state distinctly indicated the existence of three g-values, showing a rhombic symmetry.
The Concentration and Separation of a Trace Amount of Cobalt(II) in Sea Water as Its 1-Nitroso-2-naphtholate by Extraction Chromatography
Authors: Honjo Takaharu , Abe Shuhei , Kiba Toshiyasu
Published: July 2006

The behavior of a trace amount of cobalt(II) in extraction and back extraction has been examined with 1-nitroso-2-naphthol in carbon tetrachloride, and the results have also been applied to the concentration and separation of a trace amount of cobalt(II) in sea water as its 1-nitroso-2-naphtholate by extraction chromatography.
Synthesis and Spectral Studies of Dichloroacetates of Lanthanoids
Authors: Singh Megh , Bhutra M P , Vaishnava P P , Misra S N
Published: July 2006

Dichloroacetates of lanthanoids (Pr, Nd, Sm, Ho, and Er) have been synthesized and characterized by elemental analysis, absorption and IR spectral data, and the X-ray power patterns. Magnetic moments of these derivatives have been measured. Molecular weights determined ebullioscopically in acetic acid showed them to be dimeric.
Asymmetric, Partial Acetylation of dl-1-Phenylethanol by Means of Chiral Polymers
Authors: Yamashita Tetsushi , Yasueda Hiroshi , Nakamura Nobuo
Published: July 2006

The partial esterification of dl-1-phenylethanol with acetic anhydride was carried out in the presence of poly (O-acryloylquinine), poly (N-benzy 1-2-pyrrolidinylmethylacrylate), and poly(O-acryloyl-N-benzylephedrine). The propionyl esters of quinine, N-benzyl-2-pyrrolidinylmethanol and N-benzylephedrine were also used as low molecular weight catalysts. The above polymeric and monomeric catalysts showed poor, asymmetric efficiencies for this esterification.
Conformational Analysis of 9,14-Dihydrotribenzo[a,c,f]cyclooctene and Its Derivatives
Authors: Shigemitsu Yasuo , Juro Masayoshi , Mukuno Yuji , Odaira Yoshinobu
Published: July 2006

9,14-Dihydrotribenzo[a,c,f]cyclooctene, 9,14-dihydrotribenzo[a,c,f]cycloocten-9-one, and 9,14-dihydrotribenzo[a,c,f]cyclooctene-9,14-dione, which are all new bridged aroma tics containing a biphenyl moiety, have been prepared. Saddle conformations have been suggested for all of them on the basis of the spectra data.
New Synthetic Methods for Benzyloxycarbonyl-l-arginine-p-nitroanilide, Benzoyl-l-arginine-p-nitroanilide, and Acetyl-l-arginine-p-nitroanilide
Authors: Somorin Oyin , Nishi Norio , Noguchi Junzo
Published: July 2006

The optically active substrates for two peptidases, benzoyl-l-arginine-p-nitroanilide hydrochloride (l-BAPA·HCl) and acetyl-l-arginine-p-nitroanilide (l-AAPA·HCl), were readily prepared through the synthesis of benzyloxycarbonyl-l-arginine-p-nitroanilide hydrochloride (l-ZAPA·HCl). Benzyloxycarbonyl-l-arginine and p-nitroaniline were directly coupled without any racemization. The product, l-ZAPA·HCl, was quantitatively debenzyloxycarbonylated with hydrogen chloride in glacial acetic acid at 50 °C to l-arginine-p-nitroanilide dihydrochloride(l-APA·2HCl) which gave, on benzoylation or acetylation, l-BAPA·HCl or l-AAPA·HCl respectively.
Formation of (4S,5R)-4-(Nitrovinyl)-2-phenyl-1,3-dioxan-5-yl Formate from Methyl 4,6-O-Benzylidene-2-deoxy-2-nitro-β-d-glucopyranoside
Authors: Sakakibara Tohru , Sudoh Rokuro
Published: July 2006

Acetylation of methyl 4,6-O-benzylidene-2-deoxy-2-nitro-β-d-glucopyranoside with acetic anhydride–pyridine afforded a mixture of the expected 3-O-acetate and the title compound in a ca. 1:1 ratio; the structure of the latter compound was confirmed by conversion into an adduct with hydrazoic acid.
The Reaction of Benzeneseleninic Acid with Olefins in Acetic Acid. A New Method of Acetoxyselenation
Authors: Miyoshi Noritaka , Takai Yoshitsugu , Murai Shinji , Sonoda Noboru
Published: July 2006

The reaction of benzeneseleninic acid with olefins in acetic acid gave 2-acetoxyalkyl phenyl selenides in good yields.
Static and Kinetic Studies of the Interaction of Toluidine Blue with Ghondroitin-4-sulfate
Authors: Takahashi Kojiro , Horiuchi Zengo , Yasunaga Tatsuya
Published: July 2006

The binding of Toluidine Blue to chondroitin-4-sulfate was investigated by absorption spectra, titration curves, and temperature-jump relaxation spectra. The results were well interpreted by a basic model of binding to a linear lattice, where the cooperative interaction is restricted to the nearest-neighbor binding sites. The parameters g (number of binding sites per disaccharide repeating unit), K (cooperative binding constant), and q (strength factor of cooperativity) in 0.015 M phosphate buffer (pH 7.0) were determined to be 2, 1.02×105 M−1, and 270±60, respectively. The fastest process of the three relaxations observed in the system of Toluidine Blue-chondroitin-4-sulfate, could be interpreted as the aggregation process for cooperative binding. The rate constant \ ildekR was determined to be 1.6×108 M−1 s−1 at 28 °C.
Isotope Effect in Thermal Ionic Reactions of Isomeric Transition-Activated 80Br and 82Br in the HBr–CH4 System
Authors: Kondo Kenjiro , Yagi Masuo
Published: July 2006

The reactions of isomeric-transition activated 82Br were studied in the gaseous H82mBr–CH4(HBr/CH4=0.1±0.01) system. CH382Br and CH282BrBr were identified as the reaction products; their absolute yields were 0.8% for CH382Br and 3.7% for CH282BrBr respectively. The results were compared with those obtained in the H80mBr–CH4 and 80mBr2 (or 82mBr2)–CH4 systems. The effect of Krand Xe additives showed that these products were formed only through kinetic energy-independent (thermal-ionic) reactions, as opposed to the results obtained in the 80mBr2 (or 82mBr2)–CH4 system. This difference was explained on the basis of the kinetic energies initially acquired by the bromine atoms in the molecular-explosion process. In addition, an outstanding isotope effect resulting from the difference in the decay schemes of 80mBr and 82mBr was observed between the I. T.-activated 80Br and 82Br reactions in the H80mBr–CH4 and H82mBr–CH4 systems, and it was pointed out from the analysis of the 80mBr-data that the two successive internal conversions in the 80mBr decay were responsible for this isotope effect. It was considered that the second internal conversion started in a liquid-like condition such as ion-clusters containing the 80Br in the intermediate state; this idea is supported by the experimental results obtained in the condensed phase.
Synergistic Effect of Pyridine and Ammonia in the Extraction of Copper(II) Fixed on the Ion Exchange Resin with 2-Thenoyltrifluoroacetone
Authors: Ohzeki Kunio , Nozawa Katsunori , Kambara Tomihito
Published: July 2006

The composition of hydrated copper(II), copper-pyridine, and -ammine species fixed on the cation exchange resin was determined by chemical and thermogravimetric analyses. Provided that all the water and bases were coordinated to copper(II) ion, the species on the resin were estimated to be [Cu(H2O)5]2+, [Cu(py)(H2O)3]2+, and [Cu(NH3)3(H2O)3]2+, respectively. The removal of copper(II) ion from the resin with 2-thenoyltrifluoroacetone (Htta) was studied in various organic solvents. The rate of reaction was accelerated with the replacement of water molecules coordinated to the metal ion with pyridine or ammonia.
The Kinetics of the Radiation-induced Chain Dechlorination of Hexachloroethane in Alcohols
Authors: Sawai Takeshi , Ohara Naoki , Shimokawa Toshinari
Published: July 2006

The kinetics of the radiation-induced dechlorination of hexachloroethane was investigated in deoxygenated alcohol solutions. The major products were hydrogen chloride, pentachloroethane, 1,1,2,2-tetrachloroethane, tetrachloroethylene, and aldehydes or acetone. No 1,1,1,2-tetrachloroethane was observed. The radiationchemical yields of these products and the disappearance of hexachloroethane were quite high; these facts indicate that a chain reaction is involved in these processes. After the hexachloroethane had effectively dechlorinated down to tetrachloro compounds, there were no marked changes in the lower chlorinated compound upon continuous irradiation. Tetrachloroethane was formed via pentachloroethane, but tetrachloroethylene was produced by means of C2Cl5→C2Cl4+Cl reaction and the yield was paticularly high in methanol compared with the other alcohols. The chain length of the dechlorination from hexachloroethane to pentachloroethane and from pentachloroethane to tetrachloroethane increased in the order of 2-propanol>ethanol>methanol. The G(−C2Cl6) and G(products) were proportional to (dose rate)−1⁄2, and the ratio of G(C2HCl5) to G(C2Cl4) was a constant in each alcohol solution, regardless of the dose rate. The α-hydroxy alkyl radical is the chain carrier for the dechlorination reaction of hexachloroethane in alcohol solutions. The relative rates of the dechlorination were found to be 1, 3, and 14 for \dotCH2OH, CH3\dotCHOH, and (CH3)2\dotCOH, respectively. The order in the rate is in agreement with that of the redox potential of these radicals. The effect of the irradiation temperature on the products yields was also examined.
Conductometric Studies on the Ion-pair Formations of [Cr(NH3)6]3+, [Co(NH3)6]3+, [Cr(en)3]3+, and [Co(en)3]3+ with Several Anions in Aqueous Solutions
Authors: Takahashi Tatsuo , Koiso Takefumi
Published: July 2006

The thermodynamic ion-association constants (K) of [Cr(NH3)6]3+, [Co(NH3)6]3+, [Cr(en)3]3+, and [Co-(en)3]3+ with several anions in aqueous solutions were determined using the conductometric method. The logK values obtained at 25.0 °C are 1.17 for [Cr(NH3)6]3+–SCN−, 1.34 for [Cr(en)3]3+SCN−, 1.30 for [Co(NH3)6]3+–SCN−, 1.34 for [Co(en)3]3+–SCN−, 1.68 for [Co(en)3]3+–Br−, 1.46 for [Co(en)3]3+–I−, 1.37 for [Co(en)3]3+–ClO4−, 3.20 for [Cr(NH3)6]3+–C2O42−, and 2.97 for [Cr(en)3]3+–C2O42−. The results indicate that the SCN− ion has less of a tendency to associate with the complex cations than do other univalent anions, the K values of SCN− being of the same order of magnitude as those of ClO4−, and that the K values of chromium(III) complex cations with several anions are slightly smaller than those of the corresponding cobalt(III) complex cations.
Light Scattering Study of Local Structure in Solution. Double-Layered Structure Formation in Chloroform Solution of Surfactant
Authors: Kato Tadashi , Fujiyama Tsunetake
Published: July 2006

Light scattering spectra have been observed for binary solutions of chloroform–tetrabutylammonium chloride (TBACl) and chloroform–hexadecyltrimethylammonium chloride (HTACl) at various concentrations. The Rayleigh intensities have been reduced to concentration fluctuations. The observed concentration dependence of the concentration fluctuation was explained in terms of the existence of aggregates which were composed of a few surfactant molecules and several decades of chloroform molecules. Using the infrared data, the structures of the aggregates were demonstrated to be double-layered. In HTACl solution, a singular concentration dependence of concentration fluctuation was observed in the concentration range below 0.004 mole fraction.
The Reactions of Dichlorotriazinyl Reactive Dyes with Cellulose and Simultaneous Diffusion in Cellulose
Authors: Motomura Hiromi , Morita Zenzo
Published: July 2006

The diffusion coefficients and rate constants of the reactions of C. I. Reactive Yellow 4, Orange 1, and Red 1 were measured at 30 °C by means of a cylindrical cellophane film roll. The diffusion coefficients of the three hydrolyzed dyes were nearly constant at all the pH values examined. The apparent diffusion coefficients of all the active species of Orange 1 and Red 1 except Yellow 4 were gradually decreased with an increase in the pH of the dyebath; this decrease was due to the hydrolysis of the active species in the cellulose substrate. The rate constants of the reactions with cellulose were of a pseudo-first-order; i.e., the second-order rate constants of reactions with cellulose were constant up to a certain pH, and thereafter they decreased with an increase in the pH of the dyebath. The pH dependence of the reactivity with cellulose was similar to that of the hydrolysis reported previously. The concentration profiles of the removed and immobilized species in cellulose dyed from a weakly alkaline dyebath agreed with the theoretical profiles of active and reacted species respectively. From a highly alkaline dyebath, those of the immobilized species agreed with the theoretical profiles of reacted species, while those of the removed ones did not agree with theoretical profiles of active species because of hydrolysis.
Analysis of Tin Corrosion Products Using Conversion Electron Mössbauer Spectroscopy, Transmission Mössbauer Spectroscopy, and X-Ray Diffractrometry
Authors: Shibuya Mamoru , Endo Kazutoyo , Sano Hirotoshi
Published: July 2006

Tin plates corroded by various acids were nondestructively analyzed by a 119Sn conversion electron Mössbauer spectroscopy, a transmission Mössbauer spectroscopy, and an X-ray diffractometry. The conversion electron method was shown to be useful for analysis of some corrosion products which could not be easily observed by the transmission method. By using both the Mössbauer spectroscopy and the X-ray diffractometry, the corrosion products formed by 6.7M-HNO3, 5.7M-HCl, and 9.0M-H2SO4 were determined to be SnO2·nH2O, Sn4(OH)6Cl2, and SnSO4, respectively.
Raman and Infrared Spectra of μ-O2 Dicobalt(III) Complexes
Authors: Shibahara Takashi , Mori Masayasu
Published: July 2006

Raman and infrared spectra of μ-hyperoxo and μ-peroxo ammine and cyano dicobalt(III) complexes have been studied and isotopic shifts of ν(OO) and ν(CoO) examined using 18O. A μ-hyperoxo complex, [(NH3)5Co(O2)Co(NH3)5]X5 shows peaks around 1110, 620, and 440 cm−1 assignable to ν(OO), sν(CoO), and asν(CoO), respectively, whereas a μ-peroxo complex, [(NH3)5Co(O2)Co(NH3)5]X4 shows peaks around 805, 645, and 545 cm−1 assignable to ν(OO), sν(CoO), asν(CoO), respectively. These observed values are best reproduced, when the following force constants are assumed in the UBFF calculation: K(OO)=5.6, K(CoO)=1.40 mdyn/Å for μ-hyperoxo complexes and K(OO)=2.7, K(CoO)=2.15 mdyn/Å for μ-peroxo complexes. The calculated isotopic shifts are in good agreement with the observed ones. Raman and infrared spectra of dibridged μ-amido-μ-O2 (both peroxo and hyperoxo) dicobalt(III) complex have also been characterized. A linear relationship has been found between ν(OO) and the bond order of the O2 moiety in O2-complexes in different oxidation states including alkali hyperoxide, alkali peroxide, hydrogen peroxide, oxygen, and O2+ species.
Relative Intensities of the Ligand-field Transition Bands in Tetragonal Chromium(III) and Cobalt(III) Complexes
Authors: Fujinami Shuhei , Shibata Muraji , Yamatera Hideo
Published: July 2006

On the basis of a tetragonal (D4h) model, the procedures for calculating the vibronically induced transition moment have been described, and a correlation in the band intensity between two nondegenerate transition components (A2 and B2) has been shown. The correlation has then been applied to understanding the characteristic absorption spectra of the trans-[CrClF(NH3)4]+ and trans-[CrF2(NH3)4]+ complexes. Furthermore, an effect upon the band intensity caused by the configuration interactions among the E states has been proposed in order to explain the characteristic spectra of the trans-[Co(C2O4)2(py)2]− and trans-[Co(CO3)2(py)2]− complexes. This treatment has been applied also to the spectra of cobalt(III) complexes with C4V symmetry.
ESR Studies of an Oxo-Bridged Manganese(III. IV) Complex of 2,2′-Bipyridine
Authors: Inoue Motomichi
Published: July 2006

ESR spectra were recorded on the single crystal of di-μ-oxo-tetrakis(2,2′-bipyridine)dimanganese(III,IV) perchlorate trihydrate. ESR signals attributable to the excited quartet state were observed in addition to an ESR signal due to the ground doublet state. From the temperature dependence of the signal intensities, the exchange integral was determined as J⁄k=−207 K. The spectrum of the quartet state exhibits a fine structure: |D| and |E| were estimated to be equal to 0.39 and 0.12 cm−1, respectively. The constants are interpreted in terms of the dipole-dipole interaction and the crystal-field effect; the anisotropic part of the exchange interaction is negligibly small. The hyperfine structure in the spectrum of the doublet state indicates that odd electrons are distributed unequally on two manganese atoms in the dimer. This is due to an odd e electron (in the t23-t23e1system) localized mostly on one of the paired manganese atoms.
Application of Electrochemical Recycle of Ti4+-Ti3+ to Additive Dimerization of Butadiene with Hydroxylamine
Authors: Chiba Toshiro , Takata Yoshiyuki
Published: July 2006

The electrolytic recycle of Ti4+-Ti3+ has been employed for a redox-system consisting of hydroxylamine and Ti3+ which can produce amino radicals. From electroanalytical measurements, it was found that titanium(IV) chloride in hydrochloric methanol was reducible to Ti3+ with a sufficient current efficiency at the platinum electrode and the reduction was speeded up by an addition of hydroxylamine. On macro-scale electrolysis using a small amount of titanium(IV) chloride in the presence of 1,3-butadiene and hydroxylamine, the generated amino radical undergoes additive dimerization with butadiene and gives diaminooctadienes in reasonable yields.
Catalytic Hydrogenolysis of Phenothiazine, Thianthrene, and Phenoxathiin
Authors: Nagai Masatoshi , Sakikawa Noriyuki
Published: July 2006

Catalytic hydrogenolysis of phenothiazine, thianthrene, and phenoxathiin as appropriate model reactants in the competing reactions of sulfur, nitrogen, and oxygen removal over NH4Y zeolite, pre-sulfided Co–Mo–Al2O3, and Ni–W–SiO2Al2O3 catalysts has been carried out using the batch method. The cleavage patterns and the schemes in the hydrogenolysis of the three compounds and the active sites of an NH4Y zeolite for the hydrogenolysis are discussed. The C–S bond in phenoxathiin was more prone to cleavage than the C–O bond, and the C–N bond in phenothiazine was not broken in our experiments. Sulfur removal from the three compounds took place more than the removal of nitrogen or oxygen. The reactivity over the zeolite Y, pre-sulfided Co–Mo–Al2O3, and Ni–W–SiO2Al2O3 catalysts decreased in the order of phenothiazine>phenoxathiin>thianthrene, but in the absence of the catalyst the thermal stability was phenoxathiin>thianthrene>phenothiazine. In the hydrogenolysis of the three compounds over the NH4Y catalyst the desulfurization activity of the zeolite Y catalyst was maximized when calcined at 500 °C. The reaction of phenoxathiin was found to be accelerated by Brönsted acid, but this did not hold true in the case of phenothiazine and thianthrene.
Boron Trifluoride Hydrate-catalyzed Ethylation of Benzene with Ethyl-1-13C Fluoride and Ethyl-1,1-d2 Fluoride
Authors: Oyama Toshiyuki , Hamano Toshio , Nagumo Katsuyuki , Nakane Ryohei
Published: July 2006

In the ethylation of benzene with ethyl-1-13C fluoride and ethyl-1-d2 fluoride in boron trifluoride hydrate, almost a 50% isotope position rearrangement in the ethyl group of ethylbenzene was found, whereas in the boron trifluoride-catalyzed ethylation in excess benzene no rearrangement was observed. Based on these results, it was suggested that an electrophile is an ethyl cation in the ethylation of benzene in excess boron trifluoride hydrate and a nonionized polar complex in the boron trifluoride-catalyzed ethylation in excess benzene.
A Monte Carlo Study of the Intrachain Reaction on a Poly(oxyethylene) Chain
Authors: Sisido Masahiko , Imanishi Yukio , Higashimura Toshinobu
Published: July 2006

Monte Carlo calculation was performed to estimate the ring-closure probability of a poly(oxyethylene) chain. The calculation was made for various chain lengths on the basis of a rotational isomeric state model in which the intrachain atomic overlaps were excluded in terms of the hard-sphere model. The chain-length dependence of the ring-closure probability thus obtained was compared with that of the rate-constant ratio of the intrachain reaction vs. the intermolecular reaction previously reported. For longer chains, the calculation agreed well with the experimental data. For shorter chains, the agreement was less satisfactory; this discrepancy was attributed to the effect of the bulky terminal groups of the poly(oxyethylene) chain. The thermodynamic parameters for the cyclization were determined, and it was found that the chain-length dependence of the ring-closure probability is mainly governed by the conformational enthalpy.
Liquid Phase Peptide Synthesis by the Fragment Condensation on Soluble Polymer Support. I. Efficient Coupling and Relative Reactivity of a Peptide Fragment with Various Coupling Reagents
Authors: Narita Mitsuaki
Published: July 2006

The fragment condensation on the soluble polymer support using dicyclohexylcarbodiimide (DCCI) plus 1-hydroxy-1H-benzotriazole (HOBt), diethoxyphosphoryl cyanide (DEPC), and triphenylphosphine (Ph3P) plus di-2-pyridyl disulfide ((PyS)2) as coupling reagents gave rise to efficient coupling (86–99% yield) of the peptide fragment, t-butyloxycarbonyl-l-O-benzyl-tyrosylglycylglycyl-l-phenylalanine [Boc-l-Tyr(Bzl)–Gly–Gly–l-Phe–OH], to the amino free terminal of Leu anchored to the soluble polymer support, H–l-Leu–OCH2–resin. Relative reactivity ratios of Boc–amino acids and Boc–l-Tyr(Bzl)–Gly–Gly-l-Phe–OH with H–l-Leu–OCH2–resin in the coupling reaction using the three coupling reagent systems could be easily determined by use of amino acid ratios in the acid hydrolysates of the resulting peptide resins in which they were taken. The peptide chain length of Boc–l-Tyr(Bzl)–Gly–Gly–l-Phe–OH has no influence on the reactivity of C-terminal amino acid in the coupling reaction using DCCI plus HOBt or DEPC as a coupling reagent when Boc–l-Phe–OH was replaced with Boc–l-Tyr(Bzl)–Gly–Gly–l-Phe–OH. The coupling reagent, Ph3P plus (PyS)2, brought about a marked decrease in the reactivity of the fragment peptide acid.
The Reaction of 1,3,5-Triazine with Aromatic Nitrile Oxides. A New Synthesis of 3-Substituted 1,2,4-Oxadiazoles
Authors: Kurabayashi Masahiro , Grundmann Christoph
Published: July 2006

The cycloaddition of aromatic nitrile oxides(2a=benzo-; 2b=p-tolu-; 2c=mesitylenecarbo-) with 1,3,5-triazine(1) is reported. The corresponding 3-substituted 1,2,4-oxadiazoles(3a,b,c) are obtained in fair yields only when BF3 is added. It was stoichiometrically confirmed that one mol of 1 behaves so as to supply three mols of azomethine radicals. A reaction scheme initiated from a two-step cycloaddition of 2 to 1 activated by BF3 is suggested. The mixture, 1 : 2c : BF3=1 : 3 : 1, afforded a better yield of 3c(69%) than an equimolar mixture of 2c with ethyl formimidate or formamidine.
Reactions of Aromatic Compounds in Molten Salts. II. The Rearrangement of Phenylhydrazine to Give o-Phenylenediamine in a Molten Mixture of AlCl3–NaCl–KCl
Authors: Imaizumi Hisao , Hashida Yoji , Matsui Kohji
Published: July 2006

Phenylhydrazine gave o-phenylenediamines as the major product upon heating in a molten mixture of AlCl3–NaCl–KCl. In the molten mixture, some aromatic compounds gave the corresponding aromatic amines in good yields in the presence of phenylhydrazine, suggesting that the method provides a novel direct process for the preparation of aromatic amines.