bluuebunny/crossref_metadata_2025 huggingface dataset:
SYNTHESIS AND PROPERTIES OF TRIS(3-HYDROXY-2-METHYL-4-PYRONATO) COMPLEXES OF CHROMIUM(III), MANGANESE(III) AND IRON(III)
Authors: Morita Hideyoshi , Hayashi Yasuhisa , Shimomura Shigeru , Kawaguchi Shinichi
Published: July 2006

Tris(3-hydroxy-2-methyl-4-pyronato)complexes of chromium(III), manganese(III) and iron (III) have been prepared. Comparison of their IR spectra suggests that a Jahn–Teller distortion is operative in the Mn(III) complex. The electronic spectrum of this complex is also consistent with a tetragonal structure caused by the Jahn–Teller effect.
THE REACTION OF LITHIUM TRIBUTYL-1-PROPYNYLBORATE WITH OXIRANE. STEREOSELECTIVE SYNTHESIS OF (Z)- AND (E)-3-METHYL-3-OCTEN-1-OL
Authors: Utimoto Kiitiro , Furubayashi Toshiki , Nozaki Hitosi
Published: July 2006

The title reaction in dichloromethane affords (Z)-3-methyl-3-octen-1-ol in good yield after the usual protonolysis, while the predominant product in THF has been found to be the (E)-isomer.
SOLVENT EFFECT ON THE REACTION OF 2,6-DIBROMOCYCLOHEXANONE WITH MORPHOLINE
Authors: Sato Kikumasa , Inoue Seiichi , Ohashi Masao , Kuranami Shin-ichi
Published: July 2006

The reaction of 2,6-dibromocyclohexanone (1)with morpholine gives 1-cyclopentenecarboxymorpholide (2) and 2-morpholino-2-cyclohexenone (3) . The ratio of 2 :3 is remarkably affected by the reaction solvent, and the amide 2 or the enaminoketone 3 is obtained selectively when chloroform or HMPA was used, respectively.
CYCLOADDITION REACTIONS OF 1,3-OXAZEPINE AND 1,2-DIAZEPINES TO 2,5-DIMETHYL-3,4-DIPHENYLCYCLOPENTADIENONE
Authors: Mukai Toshio , Yamashita Yoshiro , Sukawa Hiroshi , Tezuka Takahiro
Published: July 2006

This report describes the first example of a cycloaddition reaction of 1,3-oxazepine derivatives. 2-Phenyl-l,3-oxazepine (I) added thermally to 2,5-dimethyl-3,4-diphenylcyclopentadienone (II) to give [4+2] adducts IV and V. Irradiation of V afforded VI, a novel type of the cage compound containing oxygen and nitrogen atoms. For comparison, the cycloaddition reactions of N-substituted 1H-1,2-diazepines (IIIa and IIIb) and lH-azepine (XII) were examined.
DEPOLARIZATION RATIOS OF I2 RAMAN LINES IN THE RESONANCE REGION
Authors: Matsuzaki Susumu , Maeda Shiro
Published: July 2006

Depolarization ratio(ρl) of I2 Raman lines in the resonance region was observed in several solutions, and appreciable dependence of ρl. on exciting wavelengths was found out. The origin of the observed ρl changes was discussed on the basis of the composite nature of the visible band.
γ-RADIOLYSIS OF AN OLEFIN-LIQUID CARBON DIOXIDE MIXTURE
Authors: Sakurai Hiroshi , Akimoto Koichi , Toki Susumu , Takamuku Setsuo
Published: July 2006

Radiolysis of an aliphatic olefin(0.01 mol)-liq. CO2(1 mol) mixture has been investigated at room temperature. The main products were the corresponding epoxide and carbonyl compounds. A biradical intermediate which is formed by addition of oxygen atom to olefinic double bond is proposed. The nature of the oxidizing species is discussed.
NUCLEAR MAGNETIC RESONANCE STUDY OF EXCHANGING SYSTEMS. VII. 13C NMR SPECTRA OF BARBARALONE AND ITS DEGENERATE COPE REARRANGEMENT
Authors: Nakanishi Hiroshi , Yamamoto Osamu
Published: July 2006

13C NMR spectra of barbaralone were measured at several temperatures. Spin-lattice relaxation times and nuclear Overhauser enhancement factors were also determined. Complete line shape analyses of 13C spectra were made by the simulation method to obtain the accurate activation parameters of the Cope rearrangement of barbaralone.
PHOTOCHEMICAL REACTION OF 3-HEXENE-2,5-DIONE WITH TETRAMETHYLETHYLENE: STEREOSPECIFIC SYNTHESIS OF TRANS-1,2-DIACETYL-3,3,4,4-TETRAMETHYLCYCLOBUTANE
Authors: Yoshida Zen-ichi , Kimura Makoto , Yoneda Shigeo
Published: July 2006

Photochemical reaction of 3-hexene-2,5-dione (1) with tetramethylethylene has been found to lead to stereospecific formation of trans-1,2-diacetyl-3,3,4,4-tetramethylcyclobutane. No evidence for oxetane formation has been obtained.
A NEW SYNTHESIS OF ETHYL CYCLOPENTADIENE FROM CYCLOPENTADIENE AND ETHYLENE
Authors: Akimoto Masamichi , Minomiya Ei-ichi , Echigoya Etsuro
Published: July 2006

An equimolar mixture of 1-, and 2-ethyl cyclopentadiene was formed in vapor-phase thermal reaction of cyclopentadiene with ethylene.
VAPOR GROWTH OF ZnO NEEDLE CRYSTALS
Authors: Kodaira Kohei , Matsushita Toru , Saito Junji , Yoshida Ryoichi
Published: July 2006

Needle crystals of zinc oxide were obtained by the oxidation of zinc vapor produced from the reduction of ZnO powder with carbon. The reduction of ZnO powder was the rate-determining step in the crystal growth. The growth direction of the crystals was along a-axis.
STUDIES ON HYDROXY AMINO ACIDS V. SYNTHESIS AND N-ACYLATION OF 3-METHYL-l-AZYLYLGLYCINE BENZYL ESTER
Authors: Okawa Kenji , Nakajima Kiichiro , Tanaka Takumi , Kawana Yuriko
Published: July 2006

Optically active 3-methyl-l-aziridinecarbonyl glycine ester was successfully obtained from the corresponding N-trityl derivative by the careful treatment with formic acid and Z-Gly-3-Me-l-Azy-Gly-OBzl was also prepared without cleavage of aziridine ring by the usual DCC method.
SYNTHESIS OF 2-HYDROXYDENDROBINE AND NOBILINE
Authors: Suzuki Masaaki , Yamada Kiyoyuki , Hirata Yoshimasa
Published: July 2006

An efficient method of introducing a hydroxy group at the C-2 position of the dendrobine skeleton using a keto lactam (1) is described. By means of this method 2-hydroxydendrobine (9) was synthesized from a keto lactam (4). Further, 2-hydroxydendrobine was transformed into nobiline (10).
HETERA-p-CARBOPHANES. VI. LONG-RANGE ASYMMETRY EFFECT ON THE PROTON MAGNETIC RESONANCE SPECTRUM IN DIOXATHIA[17]PARACYCLOPHANES
Authors: Sakamoto Kazuhiko , Oki Michinori
Published: July 2006

PMR spectrum of a dioxathia[17]paracyclophane derivative showed the nonequivalence of protons of methylene groups which are separated by 8 bonds from an aromatic ring constituting the center of plane asymmetry. The barrier to rotation of the aromatic ring was obtained as 11–12 kcal/mol.
REDUCTION OF AZOBENZENE AND BENZYLIDENEANILINE BY THE COMBINED USE OF COPPER AND N,N-DIETHYLDITHIOCARBAMIC ACID
Authors: Sato Toshio , Inoue Tan , Mukaiyama Teruaki
Published: July 2006

Azobenzene or benzylideneaniline was reduced by the combined use of copper and N,N-diethyldithiocarbamic acid to afford hydrazobenzene or 1,2-dianilino-1,2-diphenylethane in good yield, respectively.
THE REACTIONS OF N,N-DICHLOROAMINE AND -AMIDES WITH IRON CARBONYL COMPLEXES. METAL-ASSISTED NITRENE GENERATION
Authors: Suzuki Hiroharu , Itoh Kenji , Matsuda Isamu , Ishii Yoshio
Published: July 2006

Reactions of N,N-dichloroamine or -amides with diiron enneacarbonyl yield isocyanates via carbonylation of iron nitrenoid. N,N-Dichloro-p-chlorobenzamide gives complex whose composition is (p-Cl–C6H4–CO–N)2Fe(CO)2(maleic anhydride)Cl2 in the reaction with maleic anhydride iron tetracarbonyl in an excellent yield.
SYNTHESIS OF THE FLUORIDE GARNETS {Na3}[M23+](Li3)F12 (M=Al, Cr, Fe)
Authors: Naka Shigeharu , Takeda Yasuo , Sone Masahiro , Suwa Yoshiko
Published: July 2006

The synthesis of the fluoride garnets, {Na3}[M23+](Li3)F12, in aqueous solution is studied. The garnet for M=Al obtained is identical with that prepared in the solid reaction. Garnets for M=Cr and Fe contain a given amount of water removable at 250° and 235°C, respectively, at temperatures of which the garnet structure remains unaltered but the color and cell constants change.
INFRARED SPECTROSCOPIC STUDIES ON THE SHIFT REAGENT-SUBSTRATE COMPLEXES
Authors: Hirota Minoru , Otsuka Soichi
Published: July 2006

The shift reagent-substrate complexes were studied by infrared spectroscopic methods. The composition of the Eu(dpm)3-2-methyl-2-propanol complex was determined to be 1:1, and the enthalpy and the entropy of its formation were calculated from the temperature dependence of the intensities of the free and the complexed O–H bands of the alcohol. The ΔH and ΔS are −9.6 kcal·mol−1 and −21 cal·mol−1·deg−1, respectively.
A CARBON-13 NMR STUDY OF THE DIRECTION OF ENOLIZATION OF TRIFLUOROACETYLACETONE
Authors: Niwa Jun , Yamazaki Mitsuru , Takeuchi Tsugio
Published: July 2006

Solvent shifts of the chelated carbonyl carbons of trifluoroacetylacetone reveal the predominance of the enol form which is enolized toward the trifluoroacetyl group.
SOME ADDUCTS OF OXOBIS(ACETYLACETONATO)VANADIUM(IV) WITH PHENOL OR ITS PARA-SUBSTITUTED DERIVATIVES
Authors: Taguchi Hiroshi , Isobe Kiyoshi , Nakamura Yukio , Kawaguchi Shinichi
Published: July 2006

Oxobis(acetylacetonato)vanadium(IV) reacts with phenol or its para-substituted derivatives in methanol, affording a stable adduct of the composition VO(acac)2(p-XC6H4OH), where X=H, NO2, CHO, COOH, Cl or CH3. The magnetic and spectral data reveal that these are vanadium(IV) complexes containing the phenol as a neutral ligand. They show an unusually low ν(V=0) frequency of ∼900 cm−1 compared to a value of 1000 cm−1 for the parent complex, and are presumed to have a polymeric structure with a phenol molecule connecting with an adjacent vanadyl oxygen via the hydrogen bond. The behavior of the adduct in solution is also reported.
WOLFF REARRANGEMENT OF 2-DIAZO-3,4-BIS(DIPHENYLMETHYLENE)CYCLOBUTMONE INTO 1,2-BIS (DIPHENYLMETHYLENE) CYCLOPROPMES
Authors: Ueda Kozaburo , Toda Fumio
Published: July 2006

Irradiation of 2-diazo-3,4-bis(diphenylinethylene)cyclobutanone (2) in the presence of alcohol and amine afforded 1-alkoxycarbonyl- and 1-carbamoyl-2,3-bis(diphenylmethylene)cyclopropane respectively.
ISOMERIZATION OF 1-BUTENE OVER POTASSIUM
Authors: Ikefuji Yoshio , Yoshioka Norihiko , Noumi Hisayuki , Tsuchiya Susumu
Published: July 2006

The isomerization of 1-butene takes place over potassium; trans-2-butene and cis-2-butene are formed. The ratio, trans/cis, was 0.1–0.2 in the temperature range 20–40°C, and was about unity in the range 90–140°C.
MECHANISM FOR NOVEL HOMOLYTIC AROMATIC SUBSTITUTION BY DIPHENYLMETHANIMINYL RADICAL IN PHOTOLYSIS OF BENZOPHENONE O-ACYLOXIMES IN AROMATIC SOLVENTS
Authors: Ishikawa Syun-ichi , Sakuragi Hirochika , Yoshida Masayuki , Inamoto Naoki , Tokumaru Katsumi
Published: July 2006

Irradiation of benzophenone O-acyloximes (I) in benzene or toluene effects aromatic substitution on the solvents by diphenylmethaniminyl radicals (IV) to give N-diphenylmethyleneaniline (II) or N-diphenylmethylenetoluidines (VIII) unless concurrently formed acyloxyl radicals facilely decarboxylate. A mechanism involving a participation of sufficiently lived acyloxyl radicals is proposed for the above substitution reactions.
PHOTOREACTION OF 1,2,4,5-TETRACYANOBENZENE WITH TETRAHYDROFURAN
Authors: Ohashi Mamoru , Tsujimoto Kazuo
Published: July 2006

Irradiation of 1,2,4,5-tetracyanobenzene in tetrahydrofuran underwent photosubstitution to give tetrahydro-2-(2,4,5-tricyanophenyl)furan. The reaction is scarecely affected by trifluoroacetic acid and hence it appears to belong to a novel class of photoelectrophilic substitution.
FREQUENCY RESPONSE METHOD FOR DETERMINATION OF DIFFUSION COEFFICIENT OF HYDROGEN IN METAL
Authors: Sekine Kyoichi
Published: July 2006

A new electrochemical method for the study of the diffusion process of hydrogen in metal foils is proposed. In the bielectrode system when hydrogen charging direct current is overlapped with sinusoidal current, there appears a phase lag in permeation current. This phase lag is related mathematically to the diffusion coefficient D of hydrogen in metal. The values of D obtained by this method are in good agreement with those by other methods in α-phase palladium-hydrogen system.
A PHOTOCHEMICAL REACTION OF 2-ALKOXY-3-BROMO-1,4-NAPHTHOQUINONE WITH 1,1-DIARYLETHYLENE—A NOVEL SYNTHETIC METHOD OF 5-ARYL-7,12-BENZ (a) ANTHRAQUINONES
Authors: Maruyama Kazuhiro , Otsuki Tetsuo
Published: July 2006

5-Aryl-7,12-benz[a]anthraquinone derivatives (6) was obtained in good yields in the photochemical reaction of 2-alkoxy-3-bromo-1,4-naphthoquinone with 1,1-diarylethylene.
AMINOALUMINUM HYDRIDE AS NEW REDUCING AGENTS. III SELECTIVE REDUCTION OF CARBOXAMIDES TO ALDEHYDES
Authors: Muraki Masayoshi , Mukaiyama Teruaki
Published: July 2006

Bis(4-methyl-1-piperazinyl)aluminum hydride was found to be a useful reagent for reduction of various N,N-disubstituted carboxamides, such as N-acylmorpholines and N,N-dimethylcarboxamides, to provide the corresponding aldehydes in fairly good yields.
PHOTO-CONTROL OF ENZYME ACTIVITY WITH A PHOTOCHROMIC SPIROPYRAN COMPOUND —MODIFICATION OF α-AMYLASE WITH SPIROPYRAN COMPOUND—
Authors: Namba Kenryo , Suzuki Shuichi
Published: July 2006

A photochromic α-amylase was prepared by chemical modification with a spiropyran compound and isolated with DEAE-Sephadex chromatography. The modified α-amylase showed the reverse photochromism in water. UV- or VS-light irradiation caused a decrease in enzyme activity of the modified enzyme. The initial activity could be recovered when the modified enzyme irradiated was kept in the dark.
A NOVEL, CYCLOBUTANONE-FORMING CARBENE INSERTION REACTION. TETRACYCLO[7.3.1.02,5.05,10]TRIDECAN-4-ONE FROM 1-(TRICYCLO[5.3.1.03,8]UNDEC-3-YL)-2-DIAZOETHAN-1-ONE
Authors: Takaishi Naotake , Fujikura Yoshiaki , Inamoto Yoshiaki , Ikeda Hiroshi
Published: July 2006

Decomposition of 1-(tricyclo[5.3.1.03,8]undec-3-yl)-2-diazoethan-1-one (IV) in toluene gave predominantly tetracyclo[7.3.1.02,5.05,10]tridecan-4-one (V) under silver oxide catalysis, while tetracyclo-[5.4.1.11,9.05,13]tridecan-11-one (VI) was the major reaction product in the presence of cupric sulfate.
PHOTOINJECTION OF ELECTRONS AND HOLES INTO p-TERPHENYL FROM METALLIC CONTACTS
Authors: Kotani Masahiro , Ohno Shigeru
Published: July 2006

The photoconduction excitation spectrum was measured in the energy range of 1.0–6 eV for p-terphenyl single crystals. The photoconduction by photons hν < 2.4 eV was attributed to the injection of excited holes from the gold electrode. The ionization energy of p-terphenyl was estimated to be 6.0 eV.
CARBOXYLATION REACTION OF ALCOHOLS HAVING SHORT CARBON CHAINS WITH CARBON MONOXIDE IN THE PRESENCE OF HF–SbF5
Authors: Takahashi Yukio , Tomita Nobu , Yoneda Norihiko , Suzuki Akira
Published: July 2006

Alcohols with short carbon chains, one to four, which are not carboxylated under the usual Koch conditions, were carboxylated with carbon monoxide in the presence of HF–SbF5 as a catalyst. This was carried out at temperatures from −20 to 30°C under atmospheric pressure. Except for methanol, such alcohols were found to react readily with carbon monoxide to give corresponding carboxylic acids in high yields.
PHOTOLYSIS AND ASSOCIATION OF 1-BENZYL-4-METHOXYCARBONYLPYRIDINYL
Authors: Ikegami Yusaku , Watanabe Hidetoshi
Published: July 2006

A neutral free radical, 1-benzyl-4-methoxycarbonylpyridinyl is stable in the dark, but decomposes by light irradiation to generate benzyl radical. Association of the radical at low temperature has been investigated.
CIRCULAR DICHROISM OF COBALT(III) COMPLEXES CONTAINING OPTICALLY ACTIVE 1,3-DIPHENYL-1,3-PROPANEDIAMINE
Authors: Arakawa Sumio , Kashiwabara Kazuo , Fujita Junnosuke , Saito Kazuo
Published: July 2006

Four optical isomers of [Co(en)2(rac-dppn)]3+(en = ethylenediamine, rac-dppn = (R,R)- or (S,S)-1,3-diphenyl-1,3-propanediamine) and a pair of enantiomers of [Co(NH3)4(rac-dppn)]3+ were prepared and circular dichroism (CD) spectra obtained. The calculated vicinal effect curve for the dppn in [Co(en)2(dppn)]3+ differs greatly from that in [Co(NH3)4(dppn)]3+. Such a difference was not observed between those of the corresponding new stilbenediamine (stien) complexes, [Co(en)2(l-stien)]3+ and [Co(NH3)4(l-stien)]3+.
NOVEL SYNTHESIS OF THE TAUTOMERIC ISOMER OF THE AZIRINOMYCIN ETHYL ESTER AND ITS ANALOGUES
Authors: Shin Chung-gi , Yonezawa Yasuchika , Yoshimura Juji
Published: July 2006

The new and facile syntheses of ethyl 2-azido-2-alkenoate (4) and ethyl 3-azido-2-alkenoate (5) and the subsequent photolysis or pyrolysis of 4 and 5 to 2-alkyl-3-ethoxycarbonyl-2H-azirines and 3-alkyl-2-ethoxycarbonyl-2H-azirines, respectively, were accomplished.
QUENCHING OF EXCIPLEX WHICH EMITS VERY WEAKLY OR IS NOT EMISSIVE: EVIDENCE FOR EXCIPLEX INTERMEDIACY IN FLUORESCENCE QUENCHING AND PHOTOCYCLOADDITION
Authors: Pac Chyongjin , Sakurai Hiroshi
Published: July 2006

Pyridine quenched the exciplexes of 2-naphthonitrile–2-methylfuran and –2,3-dimethylbut-2-ene which emit very weakly and that of 9-cyanophenanthrene–2,3-dimethylbut-2-ene which is not emissive. There was provided evidence demonstrating that these exciplexes are the intermediates in the photoreactions and reversibly formed.
NUCLEOPHILIC ION PAIRS. FACILE CLEAVAGE OF AN AMIDE SUBSTRATE BY HYDROXAMATE ANIONS
Authors: Shinkai Seiji , Kunitake Toyoki
Published: July 2006

An amide substrate(N-methyl-2,4-dinitroacetanilide) is readily cleaved by tetraethylammcnium hydroxamate ion pairs in dry, aprotic solvents at room temperature, and the reaction is efficiently suppressed by minute amounts of water. This is the first example of efficient nucleophilic catalysis of amide cleavage at ambient conditions.
CONVENIENT SYNTHESES OF ALKYL THIOCYANATES AND ALKYL SELENOCYANATES FROM STERICALLY HINDERED OLEFIN VIA HYDROBORATION. SELECTIVE REACTIONS OF SECONDARY OR TERTIARY ALKYL GROUP IN MIXED TRIALKYLBORANES WITH FERRIC THIOCYANATE OR FERRIC SELENOCYANATE
Authors: Arase Akira , Masuda Yuzuru
Published: July 2006

Mixed trialkylboranes, prepared by the successive reactions of BH3 in THF with a sterically hindered internal olefin and a terminal olefin, reacted with either aqueous ferric thiocyanate or aqueous ferric selenocyanate to give corresponding secondary or tertiary alkyl thiocyanates or selenocyanates selectively.
STEREOCHEMISTRY OF PETASITENINE, THE CARCINOGENIC ALKALOID FROM PETASITES JAPONICUS MAXIM. AND TRANSFORMATION OF PETASITENINE TO SENKIRKINE
Authors: Yamada Kiyoyuki , Tatematsu Hiroshi , Hirata Yoshimasa , Haga Masanobu , Hirono Iwao
Published: July 2006

Stereochemistry at C-18 of petasitenine, the carcinogenic alkaloid isolated from Petasites japonicus Maxim. was established by chemical and spectral means: the structure of petasitenine was thus determined completely, which is represented by (1). Transformation of petasitenine (1) into senkirkine (3) was achieved by low valent tungusten complexes.
MONOMER AND DIMER BANDS IN THE VISIBLE SPECTRUM OF ALKALI METAL DIBENZOSUBERONE KETYL
Authors: Nakamura Kazuo
Published: July 2006

The visible spectra of the alkali metal (M+) dibenzosuberone (D−) ketyl were measured and assigned to the three species, the ion pair D−M+, its ionic dimer (D−M+)2, and the free anion D−. The wave numbers of the absorption maxima are linearly correlated to Z/R, where Z is a cationic charge and R Pauling’s cationic radius. The coordination of dibenzo-18-crown-6 to the cation causes dissociation of (D−M+)2 into a contact ion pair.
HYDROMETALATION AND ISOMERIZATION OF OLEFINS BY THE TITANIUM COMPLEX
Authors: Isagawa Kakuzo , Tatsumi Kimio , Otsuji Yoshio
Published: July 2006

The reagent system generated from Cp2TiCl2(Cp=cyclopentadienyl) and LiAlH4 promoted the catalytic hydrometalation and isomerization of olefins, the catalytic ability of the reagent system for both reactions strongly depending on the composition of two reagents in the reagent system. The hydrometalation occurred in the anti-Markownikoff fashion. By these two catalytic reactions, 1-octene was effectively converted to 1-bromooctane and 2,3-dibromooctane.
A POLYION COMPLEX-SUPPORTED PALLADIUM CATALYST FOR SELECTIVE HYDROGENATION OF CONJUGATED DIOLEFINS TO MONOOLEFINS
Authors: Nakamura Yoshio , Hirai Hidefumi
Published: July 2006

A colloidal palladium supported on the polyion complex composed of polyacrylic acid and polyethylene imine catalyzes highly selective hydrogenation of conjugated diolefins to monoolefins at 30°C under an atmospheric hydrogen pressure.
HOMOLYTIC AROMATIC ipso-SUBSTITUTION IN ARYL ETHERS BY BENZOXYL RADICALS
Authors: Nowada Keiko , Sakuragi Hirochika , Tokumaru Katsumi , Yoshida Masayuki
Published: July 2006

Thermal decomposition of dibenzoyl peroxide and bis(4-substituted benzoyl) peroxides in diphenyl ether or anisole affords phenyl benzoate and 4-substituted benzoates, respectively, arising from ipso-substitution in the aryl ethers by the corresponding benzoxyl radicals.
CHEMICAL TRANSFORMATION OF KAURENE-I. SYNTHESIS OF RING C AND D FUNCTIONALIZED KAURENOIDS
Authors: Fukazawa Nobuyuki , Funamizu Makoto , Kitahara Yoshio , Kato Tadahiro
Published: July 2006

The naturally occurring kaurenoids oxygenated at C11 and C15-positions (II and III) have been selectively synthesized from (−)-kaurene (I).
DECOMPOSITION REACTIONS OF UNSATURATED α-PHENYLSULFONYL-α-DIAZO KETONES
Authors: Kuwajima Isao , Higuchi Yasushi , Iwasawa Hiroyuki , Sato Toshio
Published: July 2006

Thermal decomposition of unsaturated α-phenylsulfonyl-α-diazo ketones afforded various types of cyclization products derived from the phenylsulfonylketene intermediates, along with ones from the usual ketocarbene intermediates, which are dependent closely on the position and alkyl substitution of the olefinic parts.
A GENERAL ASYMMETRIC CYCLIZATION. ASYMMETRIC SYNTHETHIS OF OPTICALLY ACTIVE 2-OXO-5-PYRROLIDINEACETIC ACID DERIVATIVES
Authors: Wakabayashi Toshio , Kato Yoshinori , Watanabe Kenzo
Published: July 2006

Novel asymmetric intramolecular Michael addition by chiral amide anion to α,β-unsaturated ester was performed for the asymmetric synthesis of (S)-2-oxo-5-pyrrolidineacetic acid. The acid was related to (S)-(−)-ecgoninic acid in order to determine its absolute configuration. Much higher diastereoselectivity of the chiral amide than that of the chiral ester was also demonstrated.
LIQUID CRYSTALS COMPOSED OF N-ACYLAMINO ACID. I. CIRCULAR DICHROISM IN LIQUID CRYSTALS COMPOSED OF N-LAUROYL-l-GLUTAMIC ACID AND AROMATIC SOLVENTS
Authors: Sakamoto Kazutami , Yoshida Ryonosuke , Hatano Masahiro
Published: July 2006

Amorphous powdered N-lauroyl-l-glutamic acid (LGA) soaked into aromatic solvents such as benzene showed birefringence under a polarizing microscope and a positive CD band. An achiral dye molecule dissolved in this system showed induced CD. From these results it is concluded that the LGA-benzene system is a cholesteric liquid crystalline phase.
PREPARATION OF CARBOXYLIC ACID FLUORIDES USING HEXAFLUORO-1,2-EPOXYPROPANE
Authors: Ishikawa Nobuo , Sasaki Shigekuni
Published: July 2006

Carboxylic acid fluorides were prepared by treating free carboxylic acids with hexafluoro-1,2-epoxypropane in the presence of triethylamine or N,N-dimethylaniline under mild conditions.
THE r1-r1 INTRACONFIGURATIONAL ELECTRONIC TRANSITION WITHIN t2g4 OF THE CHLORO–BROMO MIXED HALOGENO COMPLEXES OF Os(IV)
Authors: Urushiyama Akio
Published: July 2006

The electronic spectra of the chloro–bromo mixed halogeno complex anions, [OsBrxCl6−x]2− (x=0–6), in K2SnCl6 matrix were measured in the region of 16000–18000 cm−1. In this region, intraconfigurational electronic transition within t2g4 was observed in the absorption and emission measurements. The mixed halogeno complex anions showed band features markedly different from those of the complexes in Oh symmetry.
DIMERIZATION OF ANION RADICAL IN MICELLES
Authors: Yamagishi Akihiko , Watanabe Fumiyuki
Published: July 2006

Sodium salt of 2,3-dichloro-5,6-dicyano-p-benzoquinone is found to dimerize in chloroform when it is solubilized by dodecylpyridinium chloride micelles. The enthalpy and entropy changes of dimerization equilibrium have been determined at various surfactant concentrations (0.003–0.07 M). The temperature-jump measurements show that the relaxation time of dimerization is less than 1.5×10−5 s. The results indicate that the dimerization occurs in the micelle interior.
THE TERMINAL-CARBON-BONDED PALLADIUM(II) COMPLEXES OF ACETYLACETONE
Authors: Kanda Zenjiro , Nakamura Yukio , Kawaguchi Shinichi
Published: July 2006

Dichlorobis(benzonitrile)palladium(II) reacts with acetylacetone in acetone at room temperature to afford an insoluble product PdCl (C5H7O2) [1]. The reactions of 1 with a base L such as triphenylphosphine and triphenylarsine, or lithium chloride yield PdCl(C5H7O2)L or PdCl2(C5H7O2)−, respectively. The σ,η-coordination of the acetylacetonate ligand in these complexes was deduced by the IR and NMR studies. The compound 1 reacts with 2,2′-bipyridine to produce PdCl(C5H7O2)(bipy), in which the terminal-carbon-bonded acetylacetonate ligand attains the keto-enol equilibrium in solution.
FORMATION AND SOLUBILITY OF BASIC LEAD CHLORIDES AT DIFFERENT PH VALUES
Authors: Kiyama Masao , Murakami Kenso , Takada Toshio , Sugano Izuru , Tsuji Toshiro
Published: July 2006

Suspensions prepared by mixing solutions of NaOH and PbCl2 in various mol ratios were subjected to aging at 25, 50 and 80°C. Formation of three kinds of basic lead chlorides takes place, depending mainly on the pH. Their solubilities in the suspension media with various pH values at 25°C were determined.
FORMATION OF CARBONYL YLIDE BY THE INTRAMOLECULAR CARBENIC REACTION. DISROTATORY RING CLOSURE OF CARBONYL YLIDE TO EPOXIDE
Authors: Ibata Toshikazu
Published: July 2006

Copper acetylacetonate catalyzed decomposition of 8-methoxycarbonyl-1-α-diazoacetylnaphthalene in benzene solution gave 2-hydroxy-3-methoxyphenalenone and 2,3-dihydroxyphenalenone via thermally forbidden disrotatory ring closure of intermediate carbonyl ylide to epoxide and successive cleavage of the epoxide.
2-HALO-3-ETHYLBENZOTHIAZOLIUM SALTS AS REACTIVE COUPLING REAGENTS
Authors: Mukaiyama Teruaki , Hojo Ko
Published: July 2006

2-Halobenzothiazolium fluoroborate, when treated with a mixture of equimolar amounts of carboxylic acids and alcohols in the presence of base such as tertiary amines, gave the corresponding carboxylic esters in good yields.
PHOTOCHEMICAL CYCLOADDITION OF 5-METHYL-2,3-DIHYDRO-3-FURANONE TO OLEFINS
Authors: Ogino Toshio , Kubota Tetsuo , Manaka Kiyoshi
Published: July 2006

Photochemical reactions of 5-methyl-2,3-dihydro-3-furanone 1 with methyl acrylate, vinyl acetate, and cyclopentene have been examined and found to give adducts having 4-oxa-bicyclo[3.2.0]heptanone structure in all the cases. Orientation and stereochemistry of the adducts were deduced on the basis of NMR studies using shift reagent. Stereospecificity was observed with the head-to-head adducts of the acyclic olefins. The cyclopentene adducts were transformed to a bicyclic enonealdehyde 22 by subsequent modification.
A NEW METHOD FOR THE PREPARATION OF α-KETO CARBOXYLIC ESTERS BY THE PHOTO-OXIDATION OF 1-(1-ETHOXYCARBONYLALKYL)PYRIDINIUM IODIDES
Authors: Takeda Takeshi , Mukaiyama Teruaki
Published: July 2006

α-Keto carboxylic esters were obtained in good yields by the photo-oxidation of 1-(1-ethoxycarbonylalkyl)pyridinium iodides in the presence of tetra-n-butylammonium iodide. Similarly, 1-methyl-2-(1-ethoxycarbonylalkylthio)pyridinium iodides were oxidized to give α-keto carboxylic esters.
MICROWAVE SPECTRA OF FLUOROMETHYLMETHYLETHER
Authors: Nakagawa Jun , Hayashi Michiro
Published: July 2006

Microwave spectra of fluoromethylmethylether and its two deuterated species were studied. This molecule is mainly in the gauche form with the skeletal dihedral angle of 69°. The CH3 internal rotation barrier was calculated from the observed splittings of the spectra as 1500 ±30 cal/mol and the dipole moment was determined by the Stark effect measurements of the spectra as 1.744 ± 0.029 D for the normal species.
METAL-CATALYZED ORGANIC PHOTOREACTIONS PHOTOREACTION OF AROMATIC NITRILES IN METHANOL IN THE PRESENCE OF TITANIUM(IV) CHLORIDE
Authors: Sato Tadashi , Yoshiie Shigeo
Published: July 2006

Aromatic nitriles, upon irradiation in methanol in the presence of TiCl4, afforded substituted oxazolidines, probably through electron transfer from methanol to nitriles mediated by titanium.
MOLECULAR WEIGHT DISTRIBUTION OF POLYCARBOSILANE AS A STARTING MATERIAL OF THE SILICON CARBIDE FIBER WITH HIGH TENSILE STRENGTH
Authors: Yajima Seishi , Liaw Chiu-fong , Omori Mamoru , Hayashi Josaburo
Published: July 2006

Polycarbosilane was fractionated by fractional solution. Relation between MW distribution and spinnability of polycarbosilane was obtained.
THE PREPARATION AND REACTIONS OF UNSYMMETRICAL THIOCARBONYL DISULFIDES
Authors: Katada Tomonori , Tsuji Sadaaki , Sugiyama Tatsushi , Kato Shinzi , Mizuta Masateru
Published: July 2006

Unsymmetrical thiocarbonyl disulfides (3) have been easily synthesized in good yields by the reaction of piperidinium dithiocarboxylates with sulfenyl chlorides. In the reaction of these disulfides with nucleophiles (amine and metal alkoxide), both thiocarbonyl carbon and sulfenyl sulfur atom seem to be attacked by nucleophiles. By desulfurization with triphenylphosphine thiocarbonyl disulfides converted into corresponding dithioesters in high yields.
THE ISOTOPE EFFECT IN THE Cd-PHOTOSENSITIZED REACTION OF METHANOL
Authors: Tsunashima Shigeru , Morita Kuniko , Sato Shin
Published: July 2006

The isotope effect in the Cd-photosensitized reaction of methanol has been investigated using CH3OH, CH3OD, and CD3OD. The quenching efficiencies for the 326.1 nm resonance line were 1 : 0.31 : 0.31 in the order of CH3OH, CH3OD, and CD3OD. The intensity of the emission from the intermediate complex between an excited cadmium atom and methanol was also measured. The intensity ratio was 1 : 3.1 : 3.1 in the order of CH3OH, CD3OD, and CD3OD. The band-shape of the emission was not affected by the substitution of D atoms. These results are compared with the isotope effect recently reported in the study of the Hg-photosensitized reaction of methanol.
LINEAR DICHROIC SPECTRA OF DNA-CRYSTAL VIOLET COMPLEXES UNDER FLOW FIELDS
Authors: Yamaoka Kiwamu , Hashimoto Hideko
Published: July 2006

The linear dichroic spectra of DNA-Crystal Violet complexes under flow were measured in the visible absorption region of Crystal Violet at three mixing ratios. The reduced dichroism was both positive (>620 nm) and negative (620–400 nm). The average angles between the transition moments and the orientation axis were estimated.
STUDIES OF NITROGEN–PHOSPHORUS COMPOUNDS. XXVII.THE HYDROLYSIS OF TETRAMERIC PHOSPHORUS NITRIDE DIAMIDE
Authors: Kobayashi Etsuro
Published: July 2006

When an aqueous solution of N4P4(NH2)8 was refluxed at 100°C, the compound was initially hydrolyzed to PO(NH2)3 and P2O2NH(NH2)4, and they were converted into PO(ONa)(NH2)2. The rate of hydrolysis was remarkably slow at room temperature, however, the composition of the hydrolysis products was similar to that at 100°C. In a sosium hydroxide solution, N4P4(NH2)8 was converted directly into PO(ONa)(NH2)2 at an elevated temperature. An acid-hydrolysis behavior was resembled that in the neutral-hydrolysis, but the reaction was accelerated with an acid strength. The formation of tetrametaphosphimate by the hydrolysis of N4P4(NH2)8, that had been hitherto claimed, could not be recognized in this study.
ONE-STEP SYNTHESIS OF 4-METHYLCHROMANS FROM PHENOL DERIVATIVES AND 3-BUTENYL OR 3-METHYL-3-BUTENYL DIPHENYL PHOSPHATE
Authors: Butsugan Yasuo , Tsukamoto Hideshi , Morito Naoya , Bito Tadaaki
Published: July 2006

3-Butenyl or 3-methyl-3-butenyl diphenyl phosphate reacted with phenols or phenyl ethers in the presence of a Lewis acid under mild conditions to give selectively 4-methyl or 4,4-dimethylchromans in 10–53% yields.
MAGNETIC PROPERTIES OF Dl-PENICILLAMINE-Cu(I,II) COMPLEX
Authors: Miyoshi Kiyonori , Ishizu Kazuhiko , Sugiura Yukio
Published: July 2006

The complex, Dl-penicillamine-Cu(I,II), was investigated by ESR in solution. The spin Hamiltonian parameters determined are g|| = 2.414, g⊥ = 2.080, and A|| = 123 G. The paramagnetic susceptibility of the solid complex measured from 77°K to 230°K followed the Curie–Weiss law with a Curie constant of 0.45°Kemu/mol, a Weiss constant of −1.5°K. A spin concentration is obtained to be 99% as pure doublet, S = 1/2, based on the molecular composition proposed by Sugiura.
NEW EQUILIBRIA IN ALLYL(CHLORO)PLATINUM(II) COMPLEXES
Authors: Yoshida Gohei , Numata Shigeaki , Kurosawa Hideo
Published: July 2006

The complexes, Pt(allyl)ClL2 (allyl= CH2CH=CH, CH2CH=CHMe, CH2CMe=CH2; L= PPh3, AsPh3, show varying degrees of equilibrium processes, depending on the nature of the allyl moieties, L, and solvents. A convenient method to synthesize complexes of the type, Pt(π-allyl )CIL, is also described.
SOLVENT, TEMPERATURE, AND PRESSURE EFFECTS ON THE REACTION BETWEEN TETRACYANOETHYLENE AND STYRENE
Authors: Nakahara Masaru , Tsuda Yasutaro , Sasaki Muneo , Osugi Jiro
Published: July 2006

A new absorption band discovered in the region 300–350 nm by varying solvents, temperature, and pressure was assigned to the zwitterionic intermediate postulated so far in the thermal (2+2) cycloaddition. The PMR spectrum was taken at low temperature. The rate of the intermediate formation depended strongly on solvent polarity.
HIGH STEREOSELECTIVITY IN N,N′-(S,S)-1,2-CYCLOHEXYLENEBIS(SALICYLIDENEIMINATO) (sal2-(S,S)-chxn) COBALT (III) COMPLEXES CONTAINING AMINO ACIDS AND OPTICAL RESOLUTION OF AMINO ACIDS WITH COBALT(II)-sal2-(S,S)-chxn
Authors: Fujii Yuki , Sano Mitsuo
Published: July 2006

A series of new mixed ligand cobalt(III) complexes with the general formula of [Co (sal2-(S,S)-chxn) (aa)] (aa = anion of gly, ala, val, leu, or thr) has been prepared. They take stereoselectively Λ-cis-β1(fac)-structure. The optical resolution of eleven amino acids with cobalt(II)-sal2-(S,S)-chxn complex has been examined. The optical purities of the amino acids resolved in 1 : 2 reaction molar ratio have been 8–50%.
TRIFLUOROMETHANESULFONIC ACID CATALYZED REARRANGEMENT OF HOMOADAMANTANE
Authors: Takaishi Naotake , Inamoto Yoshiaki , Fujikura Yoshiaki , Aigami Koji , Golicnik Bogdan , Mlinaric-Majerski Katica , Majerski Zdenko , Osawa Eiji , Schleyer Paul von Ragué
Published: July 2006

Homoadamantane (1) rearranges under CF3SO3H catalysis to 1- and 2-methyladamantane (2, and 3, respectively), tricyclo [5.3.1.03,8] undecane (4), exo-tricyclo[5.3.1.01,5] undecane (5), tricyclo[6.3.0.01,5] undecane (6), exo-tricyclo[5.3.1.02,6] undecane (7), and an unknown tricycloundecane (8). That the 2-homoadamantyl cation (11) is the key intermediate in going from 1 to 4 is indicated by the result of hydride transfer reduction of 2-homoadamantanol (17) in H2SO4.
PHOTOLYSIS OF SILYLDIAZOMETHANE. THE MIGRATING TENDENCIES OF THE GROUPS ON SILICON ATOM
Authors: Ando Wataru , Sekiguchi Akira , Migita Toshihiko
Published: July 2006

Photolysis of silyldiazomethane in alcohols gave alkoxysilanes. The reaction probably involves isomerization of silylcarbene to Si=C double bond intermediates. The migrating ability of the groups on silicon atom decreases in the order; methyl > phenyl≈benzyl group.
LABILE HALOGENATED MONOTERPENES FROM DESMIA (CHONDROCOCCUS) JAPONICUS HARVEY
Authors: Naya Yoko , Hirose Yoshio , Ichikawa Nobutaka
Published: July 2006

Structures of labile halogenated monoterpenes (V, VI) have been established as (Z)- and (E)-10-bromo-3-chloro-α-myrcene by spectroscopic methods.
THE CONFIGURATION OF OXYLUBIMIN
Authors: Katsui Nobukatsu , Kitahara Haruo , Yagihashi Fujio , Matsunaga Akira , Masamune Tadashi
Published: July 2006

The configuration of oxylubimin was determined on the basis of the NMR spectrum in the presence of the shift reagent and the CD spectrum of oxylubimin derivatives.
A NOVEL METHOD OF PREPARATION FOR ORTHOCARBOXYLATES FROM DITHIOCARBOXYLATES AND DIALKOXYDIBUTYLSTANNANES
Authors: Sakai Shizuyoshi , Fujinami Tatsuo , Kosugi Kunio , Matsnaga Kaoru
Published: July 2006

The reaction of methyl dithiocarboxylates with dialkoxydibutylstannanes at 60-95°C afforded the corresponding trialkyl orthocarboxylates in good yields.
COLLOIDAL RHODIUM IN POLYVINYL ALCOHOL AS HYDROGENATION CATALYST OF OLEFINS
Authors: Hirai Hidefumi , Nakao Yukimichi , Toshima Naoki , Adachi Koichi
Published: July 2006

A colloidal rhodium has been prepared by reduction of rhodium(III) chloride with methanol in the presence of polyvinyl alcohol. The particle size distribution of the metallic rhodium is narrow ranging from 30 to 70 Å with a maximum at 35 Å. The colloidal dispersions in methanol-water solutions are effective for the hydrogenation of olefins at 30°C under an atmospheric hydrogen pressure.
SYNTHESIS OF CYCLOPROPYL ESTERS FROM SILYL ENOL ETHERS
Authors: Ryu Ilhyong , Murai Shinji , Otani Shoji , Sonoda Noboru
Published: July 2006

Cyclopropyl esters are conveniently prepared by direct addition of acid halides to the reaction mixture of Simmons–Smith reagent and silyl enol ethers. In this reaction, zinc iodide, a by-product of the Simmons–Smith reaction, operates as a Friedel–Crafts-type catalyst to activate acid halides.
A NEW METHOD FOR THE TRANSFORMATION OF 1,2-EPOXIDES TO 1,2-DICHLOROALKANES
Authors: Echigo Yoshiaki , Watanabe Yutaka , Mukaiyama Teruaki
Published: July 2006

Treatment of 1,2-epoxides with 2-chloro-3-ethylbenzoxazolium tetrafluoroborate and tetraethylammonium chloride affords 1,2-dichloroalkanes in good yields under mild conditions with good stereospecificity.
SYNTHESIS OF A NEW HEXADENTATE LIGAND AND MEASUREMENT OF STABILITY CONSTANTS OF ITS METAL CHELATES
Authors: Tanaka Norio , Kobayashi Yukiko , Takamoto Susumu
Published: July 2006

A new macrocyclic hexamine ligand, 1,2-di(1,4,7-triaza-1-cyclononyl)ethane, was synthesized and its protonation and chelate formation constants with manganese(II), cadmium(II), cobalt(II), zinc(II), and nickel(II) were measured at 25°C in 1 M KNO3.
HOMOGENEOUS SELECTIVE HYDROGENATION OF CYCLODODECATRIENE, CYCLOOCTADIENE, AND 1,6-DIENES TO THE CORRESPONDING MONOENES CATALYZED BY RuCl2(PPh3)3
Authors: Tsuji Jiro , Suzuki Hirohisa
Published: July 2006

Cyclododecatriene was hydrogenated to cyclododecene with a high selectivity by using RuCl2(PPh3)3 as catalyst at room temperature. Selective hydrogenation of cyclooctadiene to cyclooctene was also achieved. Ethyl 2-acetyl-4,9-decadienoate was converted to 2-acetyl-4-decenoate with 100% selectivity at room temperature.
NOVEL ASPECTS OF ASYMMETRIC BROMOLACTONIZATION REACTION
Authors: Terashima Shiro , Jew Sang-sup , Koga Kenji
Published: July 2006

Asymmetric bromolactonization reaction was found to proceed highly stereo- and regiospecifically via the transition state such as 5II when (S)-N-(α,β-unsaturated acyl)-α-amino acid, where two alkyl groups are located at the α and β positions in a cis relationship and free rotation of the bond between asymmetric carbon and nitrogen is prohibited due to cyclic structure, is used as a reaction substrate.
NOVEL KINETIC RESOLUTION OF 2-DIMETHYLAMINOPROPIOPHENONE DURING ASYMMETRIC CATALYTIC HYDROSILYLATION
Authors: Yamamoto Keiji , Tsuruoka Katsuhiko , Tsuji Jiro
Published: July 2006

Kinetic resolution was observed when (±)-2-dimethylaminopropiophenone was allowed to react with one-half equivalent of diphenylsilane in the presence of rhodium(I)-(−)-DIOP as catalyst. The recovered amino ketone was found to be (R)-(+)-enantiomer of 23% optical purity, while asymmetrically hydrosilylated products, after hydrolysis, were (1S, 2S)-(+)-pseudomethylephedrine and (1R, 2S)-(−)-methylephedrine in 27% and 20% ee, respectively.
PREPARATION OF ALCOHOLS VIA HYDROALUMINATION OF OLEFINS BY USE OF THE Cp2TiCl2–LiAlH4 REAGENT SYSTEM
Authors: Isagawa Kakuzo , Tatsumi Kimio , Otsuji Yoshio
Published: July 2006

The oxidation of lithium alkylhydroaluminates, which are produced by the catalytic hydroalumination of 1-olefins with the Cp2TiCl2–LiAlH4 reagent system, gives the corresponding 1-alcohols. By a similar method, dienes having a double bond at the terminal position can be converted selectively to the corresponding alken-1-ols, in which the internal double bond remains intact. The yields of alcohols depend on the oxidizing agents used.
CATALYTIC ACTIVITY AND THE GLASS TRANSITION OF POLYMER-BOUND METAL COMPLEX CATALYST
Authors: Uematsu Takayoshi , Saito Fumiyoshi , Miura Masatoshi , Hashimoto Hidehisa
Published: July 2006

Rhodium(I)-complex was bound on a ternary copolymer of styrene (ST), divinyl benzene (DVB) and diphenyl-p-styrylphosphine (DPSP). The hydrogenation of ethylene was studied over this polymer-bound metal complex, at 40∼90 °C in gas phase. The catalytic activity changed abruptly at around 68 °C due to the reversible discontineous change In the pre-exponential factor, which was ascribed to the glass transition of the polymer.
13C NMR SPECTRA OF 1,3-DITHIOLYLIUM TETRAFLUOROBORATE AND RELATED COMPOUNDS
Authors: Sakamoto Kazuhiko , Nakamura Nobuo , Oki Michinori , Nakayama Jyuzo , Hoshino Masamatsu
Published: July 2006

13C NMR spectra of 1,3-dithiolylium tetrafluoroborate and related compounds are recorded. The 13C spectra offer firm proof for the presence of aromatic character in the 1,3-dithiolylium ring, which was deduced from the 1H NMR spectral data.
THE DIELS–ALDER REACTION OF 2,4-DIPHENYLTHIOPHENE AND 2,5-DIPHENYL-1,4-DITHIIN WITH DIMETHYL ACETYLENEDICARBOXYLATE. NOVEL FORMATIONS OF THE NAPHTHO[2,1-b] AND [1,2-b]THIOPHENES
Authors: Kobayashi Keiji , Mutai Kiyoshi
Published: July 2006

The naphtho[2,1-b]thiophene 5 was obtained by the reactions of dimethyl acetylenedicarboxylate (2) with 2,4-diphenylthiophene (1) and with 2,5-diphenyl-1,4-dithiin (6) as well, whereas the reaction of 6 with 2 under the mild conditions yielded the naphtho[1,2-b]thiophene 8.
THERMOCHROMISM OF METAL CHELATES WITH TRIPHENYLMETHANE COMPLEXONS IN AQUEOUS SOLUTIONS
Authors: Nakada Shoji , Yamada Mutsuo , Ito Tasuku , Fujimoto Masatoshi
Published: July 2006

Reversible thermochromisms are found for about thirty kinds of metal complexes of triphenylmethane complexons in aqueous solutions. The color changes are primarily due to the equilibria between the complex having an uncoordinated phenolic hydroxyl group and the complex having a coordinated phenolate group.
2,3:6,7:8,9:12,13-TETRABENZO[13]ANNULENYL ANION
Authors: Willner Itamar , Gamliel Asher , Rabinovitz Mordecai
Published: July 2006

2,3:6,7:8,9:12,13-tetrabenzo[13]annulenyl anion 1 was prepared from the corresponding hydrocarbon 2. The effect of benzannelation and the spatial structure of the anion is derived from its proton nmr spectrum.
PROTON-TRANSFER REACTION OF 2,4-DIHYDROXYAZOBENZENE IN AQUEOUS SOLUTION
Authors: Yoshida Noboru , Fujimoto Masatoshi
Published: July 2006

The recombination reaction of 2,4-dihydroxyazobenzene (DAB;H*HA) with the hydroxide ion is investigated by temperature-jump method in 2% (v/v) ethanol-water solution. The presence of the minimum observed in the τ−1 vs. \barCOH plot is interpreted by assuming a pre-equilibrium involving an intermediate H*A− with an undissociated para-OH, which has not been pointed out so far.
SOME PALLADIUM(II) AND PLATINUM(II) AMINE COMPLEXES CONTAINING β-DIKETONATE ANIONS IN THE OUTER SPHERE
Authors: Okeya Seichi , Onuki Yukio , Nakamura Yukio , Kawaguchi Shinichi
Published: July 2006

Bis (β-diketonato)palladium(II) reacts with excess amines(L) to afford [Pd(β-dik)L2] (β-dik) or [PdL4] (β-dik)2 depending upon whether L is a secondary or a primary amine, respectively. These reactions are reversible and the relative stability in solution of the complexes containing the β-diketonate anion in the outer sphere is in the order: acac < tfac < hfac.
CHARGE TRANSFER INTERACTION IN SOME TROPYLIOCYCLOPHANE TETRAFLUOROBORATES
Authors: Horita Hisanori , Otsubo Tetsuo , Misumi Soichi
Published: July 2006

Three isomeric [2.2]tropyliocyclophanes were synthesized. The similarity of their structures to those of [2.2]metapara- and meta-cyclophanes and a relationship between the structures and the intramolecular CT interaction are discussed on the basis of the NMR and electronic spectra, respectively.
α-HALO-β-DICARBONYL COMPOUNDS. NOVEL CARBOXYL PROTECTING REAGENTS. THE APPLICATION TO THE SYNTHESIS OF CEPHALEXIN FROM PENICILLIN
Authors: Ikeda Hitoshi , Nitta Hajime , Hatamura Mariko , Hatanaka Minoru , Ishimaru Toshiyasu
Published: July 2006

α-Halo-β-dicarbonyl compounds are successfully used as the carboxyl protective reagents in the synthesis of cephalexin from penicillin.
INTERACTION OF ANTHRAQUINOID ACID DYES WITH NONIONIC SURFACTANTS
Authors: Tuong Tran Dinh , Hayano Shigeo
Published: July 2006

The interaction of an anthraquinoid acid dye with a nonionic surfactant of the nonylphenol ethylene oxide type has been investigated by spectroscopic measurements and gel permeation chromatography. The results are interpreted by assuming that the dye is adsorbed on the surfactant micelles and the Freundlich isotherm has been found to correlate well the data.
PREPARATION OF THE THERMODYNAMICALLY LESS STABLE ALTROPYRANOSIDE FROM A NITRO-SUGAR WITH ACETYLACETONE
Authors: Sakakibara Tohru , Seta Akinori , Tachimori Yoshifusa , Takamoto Tetsuyoshi , Sudoh Rokuro
Published: July 2006

The Michael reaction of the 3-nitro-2-enopyranoside 1 with ethyl malonate in THF or with acetone in the presence of small amounts of NaOH gave the mannopyranoside 2 or 3, respectively, whereas the similar reaction with acetylacetone afforded a mixture of the mannopyranoside 4 and the altropyranoside 5.
RADICAL POLYMERIZATION OF METHYL METHACRYLATE INITIATED WITH THE SYSTEM OF SODIUM CHONDOROITIN SULPHATE, Cu(II)-ION AND WATER
Authors: Ouchi Tatsuro , Yamada Takeshi , Imoto Minoru
Published: July 2006

It was found that an aqueous solution of sodium chondroitin sulphate (ChS-Na) can initiate a radical polymerization of methyl methacrylate (MMA) in the presence of Cu(II)-ion. The kinetic behavior with respect to ChS-Na and MMA was studied. The initiation mechanism was considered to be as follow: ChS-Na forms a hydrophobic area in water. MMA is incorporated into the area, where the complex of ChS/Cu(II)-ion/MMA/H2O generates free radicals of MMA, which initiate the polymerization.
INSERTION OF DIMETHYL ACETYLENEDICARBOXYLATE AND 2,5-NORBORNADIENE INTO THE Pd–C BOND OF THIOMETHOXYMETHYL-PALLADIUM DERIVATIVES
Authors: Yoshida Gohei , Kurosawa Hideo , Okawara Rokuro
Published: July 2006

Insertion of RC≡CR (R= COOCH3) or 2,5-norbornadiene into the Pd–C bond of Pd(Ph3P) (CH2SCH3) (OCOCF3) gave the corresponding cis-addition product in good yield. Pd(Ph3P) (CH2SCH3)Cl was unreactive toward RC≡CR (R= COOCH3), however, the reaction between these two compounds occurred readily by addition of catalytic amount of AgClO4 to give [Pd(CR=CRCH2SCH3)Cl]2 (R= COOCH3).
CONFORMATIONS ANALYSIS OF SOME CYCLIC PEPTIDES USING DIFFERENTIAL N-METHYLATION
Authors: Kawai Masao , Nagai Ukon
Published: July 2006

Partial N-methylation of peptides with CH3I–Ag2O in DMF constitutes a new potential method of conformational analysis. Reactivity of peptide NH′s with the methylating reagent reflects their degree of exposure to the solvent. The method was applied to the samples of micromolar quantities of a Gramicidin S derivative and two destruxins.
REARRANGEMENT OF CEPHALOSPORINS TO A PENICILLIN NUCLEUS BY THE REACTION WITH BENZYLSULFONYL CHLORIDE THROUGH A NEW EXTRUSION REACTION OF SULFUR DIOXIDE
Authors: Kobayashi Takeo , Hiraoka Tetsuo
Published: July 2006

Cephalosporins rearranged to penicillin derivatives on treatment with α-toluenesulfonyl chloride in the presence of a silylating reagent via 2,3-sigmatropic type reaction after extrusion of sulfur dioxide. This reaction also proceeded in the case of alkyl allylsulfide.
THE PARTIAL REDUCTION OF CARBOXYLIC ACIDS TO ALDEHYDES via 3-ACYLTHIAZOLIDINE-2-THIONES WITH DIISOBUTYLALUMINUM HYDRIDE
Authors: Izawa Toshio , Mukaiyama Teruaki
Published: July 2006

3-Acylthiazolidine-2-thiones (1), prepared from free carboxylic acids and thiazolidine-2-thione by using 2-chloro-1-methylpyridinium iodide in the presence of triethylamine, were reduced to the aldehydes with diisobutylaluminum hydride (DIBAH) in good yields even when excess amount of DIBAH was used.
FACILE OXIDATION OF THIOPHENOL BY ISOALLOXAZINE(FLAVIN) BOUND TO A CATIONIC MICELLE
Authors: Shinkai Seiji , Ando Reiko , Yoneda Fumio
Published: July 2006

Oxidation of thiophenol by isoalloxazines(flavin analogs) was found to proceed readily in a cationic micelle solution. The observed rate enhancement was related to the activation of the thiophenol anion in the hydrophobic environment of the micelle.
A NEW ROUTE TO OLEFINS FROM DITHIOCARBAMATES VIA S-ALKYLATION-ELIMINATION PROCESS. APPLICATION TO A STEREOSELECTIVE SYNTHESIS OF NATURALLY-OCCURRING TRIENES
Authors: Hayashi Toshio , Sakurai Akio , Oishi Takeshi
Published: July 2006

Alkyl 1-pyrrolidinecarbodithioates, when treated with an excess of methyl iodide in hexamethylphosphoric triamide, afforded trans-olefins stereoselectively in high yields. Naturally-occurring 2,4,6- and 1,3,5-undecatrienes and allo-ocimene were prepared.