bluuebunny/crossref_metadata_2025 huggingface dataset:
ASYMMETRIC SYNTHESES OF α-AMINONITRILES VIA CYANOSILYLATION OF SCHIFF BASES
Authors: Ojima Iwao , Inaba Shin-ichi , Nagai Yoichiro
Published: July 2006

Optically active α-aminonitriles were synthetized by using cyanosilylation of (−)-N-alkylidene-(1-methylbenzyl) amines followed by hydrolysis. The optical yield realized in the reaction was 57.0–69.6 %, which was determined on the basis of nmr spectroscopy.
CORRELATION OF MAGNETIC SUSCEPTIBILITY OF POLYMER–HEMIN COMPLEX TO THE STRUCTURE OF POLYMERIC LIGAND
Authors: Tsuchida Eishun , Honda Kenji , Hata Seiji , Suwa Hidenori , Kohn Kay
Published: July 2006

The electronic configuration of the polymer–hemin complex was at equilibrium between the high spin state and the low spin state and varied with the sort of the coordinating group and its neighbouring group of the polymer ligand bonded to the axial site of hemin.
OXIDATIVE DIMERIZATION OF (1-HYDROXYALKYL)FERROCENE WITH OXYGEN
Authors: Hisatome Masao , Koshikawa Sakae , Yamakawa Koji
Published: July 2006

Treatment of (1-hydroxy-1-phenylethyl)ferrocene (III) in hexane with O2 in the presence of SiO2 or acidic Al2O3 gave several oxidative dimerization products: butadiene (VIII), 1,4-dihydroxybutane (IX), and tetrahydrofuran derivatives (Xa and b). Production of these compounds suggests formation of an unisolated peroxide (XII) as an intermediate.
UTILIZATION OF THE PROTON SPIN-LATTICE RELAXATION TIMES FOR THE ASSIGNMENT OF METHYL SIGNALS OF SCHIFF BASE CHELATES
Authors: Sakaguchi Ushio , Yoneda Hayami
Published: July 2006

The proton spin-lattice relaxation times have been measured on diamminebis(acetylacetone)ethylenediimino-cobalt(III) ion in D2O using the pulsed Fourier transform method at 100 MHz. The shorter relaxation time of the methyl resonating at lower magnetic field indicates that this methyl signal should be assigned to the methyl groups adjacent to the diimine bridge.
8-HYDROXYQUINOLINE AS A REAGENT FOR PROTECTION OF PHOSPHATES IN OLIGONUCLEOTIDE SYNTHESIS
Authors: Takaku Hiroshi , Shimada Yoshifusa , Hata Tsujiaki
Published: July 2006

8-Hydroxyquinolyl group was used as a new protecting group on phosphates in the synthesis of oligonucleotides. This group was easily removed by treatment with cupric chloride in a mixture of dimethyl sulfoxide and water.
SELECTIVE DIMERIZATION OF ETHYLENE CATALYZED BY HALOGENOTRIS(TRIPHENYLPHOSPHINE)COBALT(I)-BORON TRIFLUORIDE ETHERATE IN HALOBENZENE
Authors: Kawakami Kiyoshi , Mizoroki Tsutomu , Ozaki Atsumu
Published: July 2006

Dimerization of ethylene is very selectively catalyzed by halogenotris(triphenylphosphine)cobalt(I) in the presence of Lewis acid in halobenzene. The catalytic activity is significantly affected by the solvent, bromobenzene being most effective.
FUNCTION OF PYRIDINIUM SALTS ON THE RATE OF AUTOXIDATION OF HYDROQUINONE AND ITS DERIVATIVES
Authors: Shirai Masamitsu , Koizumi Taizo , Iguchi Yoshio , Tanaka Makoto
Published: July 2006

Autoxidations of hydroquinone and its derivatives are catalyzed by pyridinium salts positively or negatively depending on the properties of the substituents of the pyridinium rings. Formation of charge–transfer complexes between hydroquinones and pyridinium salts plays an important role.
FACILE SYNTHESIS OF 1-ALKYL-2- AND 4-ALLYLIDENKDIHYDROPYRIDINE DERIVATIVES
Authors: Kakehi Akikazu , Ito Suketaka , Funahashi Takahisa , Ogasawara Norio
Published: July 2006

The reactions of 1-alkylpyridinium salts carrying a 2- or 4-methyl group with activated β-ethoxymethylene compounds in the presence of alkali gave the corresponding 2- or 4-allylidenedihydropyridine derivatives in good yields.
A SIMPLE METHOD FOR THE SYNTHESIS OF 5′-AZIDO-5′-DEOXYRIBONUCLEOSIDES
Authors: Hata Tsujiaki , Yamamoto Isamu , Sekine Mitsuo
Published: July 2006

Azido group was introduced selectively to 5′-position of nucleosides by one-step reaction using carbon tetrabromide, triphenylphosphine, and lithium azide.
REACTIONS OF DI-t-BUTYL THIOKETONE
Authors: Ohno Atsuyoshi , Nakamura Kaoru , Uohama Misao , Oka Shinzaburo
Published: July 2006

Several nucleophilic and electrophilic reactions of di-t-butyl thioketone are reported.
THE FACILE SYNTHESIS OF N-SUBSTITUTED PIPERIDINES FROM GLUTARALDEHYDE USING CARBONYLHYDRIDOFERRATE AS A REDUCING AGENT
Authors: Watanabe Yoahihisa , Shim Sang Chul , Mitsudo Take-aki , Yamashita Masakazu , Takegami Yoshinobu
Published: July 2006

Glutaraldehyde reacts with primary amines in the presence of tetracarbonylhydridoferrate to give the corresponding N-substituted piperidines.
THE ENERGY TRANSFER FOR AN ORIENTED DYE MOLECULES IN STRETCHED POLY(VINYL ALCOHOL) FILMS
Authors: Komiyama Tomoko , Mori Yuji
Published: July 2006

For various stretch ratios, the degrees of polarization(P) of Acridine Orange(AO) cations in stretched poly(vinyl alcohol) (PVA) films has been measured as a function of the concentration of AO cations. The plots of 1/P versus concentration are linear with the slope dependent on the stretching ratio, for concentrations ranging from 4×10−5to 10−4M. This has been interpreted as the results of energy transfer between partially oriented like molecules.
THE CONFIGURATION AT THE ANOMERIC CARBON OF THE ETHYNYLATED PRODUCTS OF 2,3,5-TRI-O-BENZOYL-d-RIBOFURANOSYL BROMIDE WITH MERCURIC AND CUPROUS PHENYLETHYNYLIDES
Authors: Arakawa Kiichi , Miyasaka Tadashi , Hamamichi Norimitsu
Published: July 2006

The substituent at the anomeric carbon of the major product of the ethynylation, one of the 1-phenyl-2-(2,3,5-tri-O-benzoyl-d-ribofuranosyl)-ethynes, have chemically been proved to be β-oriented. In the NMR spectra of 2,3-isopropylidene-ribofuranose derivatives the coupling constant of C1–H has been observed to be approximately 4 Hz in the 1-α-substituted anomers and almost negligible in the 1-β-substituted anomers.
THE REACTION OF 2-FLUOROPYRIDINIUM SALT WITH NEROL AND GERANIOL. NON-ENZYMIC BIOGENETICLIKE CYCLIZATION TO LIMONENE
Authors: Kobayashi Susumu , Tsutsui Mikio , Mukaiyama Teruaki
Published: July 2006

Treatment of nerol with 2-fluoropyridinium salt and tri-n-butylamine at −40°C afforded cyclic monoterpenes, mainly limonene, in high yields. The reaction of geraniol with 2-fluoropyridinium salt is also described.
THE ROLE OF THE CT FLUORESCENT STATE IN THE PHOTOSUBSTITUTION OF 1,2,4,5-TETRACYANOBENZENE-TOLUENE COMPLEXES
Authors: Ohashi Mamoru , Nakayama Noboru
Published: July 2006

The Stern–Volmer treatments of the photosubstitution of charge–transfer complexes of TCNB-toluene systems using trifluoroacetic acid as a quencher indicated that the reaction proceeds via the CT fluorescent state and that the rate constants of quenching and reaction were estimated to be 109 and 2×105 M−1s−1 respectively.
THERMAL DECARBONYLATION OF CATECHOL, HYDROQUINONE AND RESOLSINOL
Authors: Sakai Tomoya , Hattori Masayuki
Published: July 2006

Decarbonylation proceeded as the main primary process in thermal reactions of catechol, hydroquinone, and resorcinol at 500–600°C under H2 or He dilution. An accompanying minor process was dehydration to form phenol. The rate of decarbonylation of hydroquinone pyrolysis was smaller than that of p-benzoquinone pyrolysis under H2 dilution.
SOLID-PHASE THERMAL SYNTHESES OF CIS- AND TRANS-[CrBrIen2]Z ( Z = I AND CIO4 )
Authors: Tsuchiya Ryokichi , Imai Hiroyasu , Uehara Akira , Kyuno Eishin
Published: July 2006

The mixture of cis- and trans-[CrBrIen2]I was prepared via the solid-phase deaquation-anation of cis-[CrBr(H2O)en2]I2· H2O. Both the isomers were purely isolated from the mixture by using aqueous NaCIO4 solution (trans-[CrBrIen2]ClO4) and methanol (cis-ICrBrIen2]I).
CHELATION EFFECTS ON THE RATE OF THE METHYL-PROTON EXCHANGE IN ALKALI ACETOPHENOLATES
Authors: Kawato Toshio
Published: July 2006

The rate of the hydrogen-deuterium exchange of acetyl-methyl groups was determined for the alkali-metal salts of three acetophenolates by means of NMR measurement of the rate of the disappearance of the methyl-signals in D2O. The chelation of o-hydroxyacetophenone with the alkali-metal ions was found to influence the reaction rate.
LEWIS ACID-PROMOTED REACTION OF 2-ALKOXY-3,5-DINITROPYRIDINES WITH THIOLS. A NEW METHOD FOR THE SYNTHESIS OF UNSYMMETRICAL SULFIDES
Authors: Mukaiyama Teruaki , Masui Takashi , Izawa Toshio
Published: July 2006

2-Alkoxy-3,5-dinitropyridines, easily prepared from 2-fluoro-3,5-dinitropyridine and alcohols react with various thiols in the presence of Lewis acids to give the corresponding unsymmetrical sulfides in good yields.
ELECTRON PARAMAGNETIC RESONANCE STUDIES OF NITRIC OXIDE-HEME-POLYMER COMPLEX
Authors: Kobayashi Kazuo , Tamura Mamoru , Hayashi Koichiro
Published: July 2006

The electron paramagnetic resonance (EPR) spectra of nitric oxide-heme-polymer complex were measured under the various conditions. From the analysis of the hyperfine structure by second derivative display, it is suggested that the linkage between NO and heme-iron is altered greatly with the function of the extension of polymer chain.
SIGN AND MAGNITUDE OF ONE-BOND 195Pt–13C COUPLING CONSTANTS IN Pt(II)–OLEFIN AND–CARBONYL COMPLEXES
Authors: Iwayanagi Takao , Saito Yasukazu
Published: July 2006

The positive sign of 1J(Pt–C) in [Pt(C2H4)Cl3]− has been determined by the double resonance experiments, although both positive and negative signs are inferred for Pt (II)-cyclooctadiene π-complexes. The small magnitude of 1J(Pt–C) in [Pt(C2H4)Cl3]− compared with [Pt(CO)Cl3]− has been interpreted in terms of the s orbital coefficients of Pt and C.
DIVALENT AND TRIVALENT COBALT COMPLEXES OF 4-(2-PYRIDYLAZO)RESORCINOL IN AQUEOUS SOLUTIONS
Authors: Mochizuki Katsura , Imamura Taira , Ito Tasuku , Fujimoto Masatoshi
Published: July 2006

In the course of the reaction in aqueous solutions between Co2+ and 4-(2-pyridylazo)resorcinol (PAR), the formation of an intermediate Co(II)–PAR complex and the subsequent oxidation to the Co(III) complex are observed by a rapid-scan spectroscopic method combined with stopped-flow technique. The ligand substitution reaction of Co(II)–PAR complex with EDTA and that of Co(II)–EDTA complex with PAR are inferred.
STEREOCHEMISTRY OF HALOGEN EXCHANGE AND DEHYDROBROMINATION REACTIONS OF 2-BROMOBUTANE OVER COPPER(II) CHLORIDE
Authors: Ishikawa Makoto , Misono Makoto , Yoneda Yukio
Published: July 2006

Inversion of configuration and syn elimination were the favored steric paths, respectively for halogen exchange and for dehydrobromination of 2-bromobutane over CuCl2 at about 100°C. This stereochemistry and slow racemization of 2-bromobutane are in contrast to those observed for 2,3-dibromobutane, and support the idea that the reaction intermediates are sec-butyl cation for 2-bromobutane and a cyclic bromonium ion for 2,3-dibromobutane.
SILYL RADICALS XVI. AN ELECTRON SPIN RESONANCE STUDY ON THE HOMOLYTIC AROMATIC SILYLATION
Authors: Sakurai Hideki , Nozue Ikuo , Hosomi Akira
Published: July 2006

Seven 2,4-di-t-butyl-6,6-bis(organosilyl)cyclohexadienyl and two 2,4-di-t-butyl-6-organosilylcyclohexadienyl radicals, the intermediate radicals in homolytic ipso-substitution and silylation, respectively, are generated and characterized by esr spectroscopy. Spectral features, especially the large 29Si coupling constants are discussed.
DMSO OXIDATION Of CYCLOPROPYLMETHANOLS WITH REARRANGEMENTS. THREE CARBON CHAIN EXTENTION OF ALDEHYDES TO α,β-UNSATURATED ALDEHYDES
Authors: Nishida Shinya , Kataoka Fumio
Published: July 2006

A rearrangement of cyclopropylmethanols in hot DMSO followed by in situ oxidation and double bond isomerization gave conjugated enals. The transformation was performed in a single operation. Utilization of cyclopropylmagnesium bromide provides a new route for the three carbon chain extention of aldehydes.
ESTIMATE OF ELECTROSTATIC SOLVATION FREE ENERGY OF ELECTRON IN VARIOUS POLAR SOLVENTS BY USING MODIFIED BORN EQUATION
Authors: Yamashita Kazuo , Kitamura Mitsutaka , Imai Hideo
Published: July 2006

The modified Born equation was tentatively applied to estimate the electrostatic free energies of solvation of the electron in various polar solvents. The related data of halide ions and a datum of the hydration free energy of the electron obtained by radiation chemical studies were used for the numerical calculations.
VISCOSITY OF BIMOLECULAR FILM OF CIS-9-OCTADECENYLAMINE (OLEYLAMINE) IN AQUEOUS SOLUTION
Authors: Yoshida Tadayoshi , Itoh Takahiro , Okuyama Masataka
Published: July 2006

The viscosity of bimolecular film was estimated from the motion of an oil lens (diameter: ca. 0.2 mm) in film (thickness: ca. 5 nm). The oil lens consists of the bulk liquid remained as an island in large film (area: ca. 600 mm2). For the film formed from oleylamine/n-decane (0.2/1, v/v) solution, the two-dimensional film viscosity was 5.6×10−8 N s/m at 22°C.
A FACILE METHOD FOR THE BECKMANN REARRANGEMENT USING 2-FLUOROPYRIDINIUM SALT OR 2-CHLOROPYRIMIDINIUM SALT
Authors: Shiono Manzo , Echigo Yoshiaki , Mukaiyama Teruaki
Published: July 2006

The Beckmann rearrangement of ketoximes easily proceeds under mild conditions to afford various amides in high yields by treating the oximes with 2-fluoropyridinium salt or 2-chloropyrimidinium salt.
ORGANIC SYNTHESIS BY MEANS OF METAL COMPLEXES. XVI. EFFICIENT CATALYTIC OXIDATION REACTIONS OF o-PHENYLENEDIAMINE, DIHYDRAZONES OF α-DIKETONES, AND HYDRAZIDES OF CARBOXYLIC ACIDS USING COPPER SALTS
Authors: Tsuji Jiro , Takayanagi Hiroshi , Toshida Yomishi
Published: July 2006

Oxidations of o-phenylenediamine to cis,cis-mucononitrile, dihydrazones of α-diketones to acetylenes, and hydrazides of carboxylic acids to the corresponding acids can be carried out smoothly at room temperature and under atmospheric pressure of oxygen by using a catalytic amount of copper salts.
NEW PREPARATION METHOD OF EUROPIUM DIFLUORIDE
Authors: Adachi Gin-ya , Nishihata Toru , Uchiyama Katumi , Shiokawa Jiro
Published: July 2006

Silicon reduction of EuF3 to EuF2 is described. Optimum conditions to prepare EuF2 are as follows; quantities of Si and heating temperature to reduce 4 mol of EuF3 are 1.0∼1.05 mol and 900°∼1000°C for 6hr, respectively.
SELECTION OF BINDING SITES IN COENZYME A BY NICKEL(II) AND COPPER(II)
Authors: Sugiura Yukio , Tanaka Hisashi , Kuroda Yoshihiro
Published: July 2006

The sites of metal binding in coenzyme A(CoA) have been investigated in an aqueous solution bv visible absorption, proton magnetic resonance and electron spin resonance spectra, and compared with those in the related ligands. Spectroscopic results indicate that Ni(II) binding occurs at cysteamine-β-alanyl portion of CoA and that Cu(II) binding occurs at adenosine portion of CoA.
PHOTO-REACTIONS OF 2-HYDROXYCYCLOOCTATRIENONES (π-HOMOTROPOLONES)
Authors: Oda Masaji , Miyakoshi Shoichi , Nakanishi Shozo , Kitahara Yoshio
Published: July 2006

Irradiation of 2-hydroxy-2,4,6-cyclooctatrienone (1,7-π-homotropolone) (1) afforded 1-hydroxybicyclo[3.3.0]octa-3,6-diene-2-one (9), whereas 2-hydroxy-2,4,7-cyclooctatrienone (5,7-π-homotropolone) (2) did 1-hydroxybicyclo[3.3.0]octa-3,7-diene-2-one (12) and 3-hydroxybicyclo[3.3.0]octa-3,7-diene-2-one (13). 3-Bromo derivatives gave similar results. The mechanisms of these reactions as well as tropolone-photocyclization are discussed.
AMINO SUBSTITUENT EFFECT ON OXYGENATION OF ENAMINES CATALYZED BY CUPRIC CHLORIDE
Authors: Itoh Takashi , Kaneda Kiyotomi , Watanabe Iwao , Ikeda Shigero , Teranishi Shiichiro
Published: July 2006

In the cupric chloride-catalyzed oxygenation of isobutyraldehyde enamines and cyclohexanone enamines of various secondary amines, the amino substituent remarkably affects the reactivity and the relative rates correlate well with their 1st ionization potentials.
VIBRATIONAL ASSIGNMENTS OF RESONANCE RAMAN LINES OF NI(OCTAETHYLPORPHYRIN) ON THE BASIS OF A NORMAL COORDINATE TREATMENT
Authors: Abe Motoko , Kitagawa Teizo , Kyogoku Yoshimasa
Published: July 2006

Vibrational modes for the resonance Raman lines of Ni(OEP) have been obtained on the basis of a normal coordinate analysis. The Raman line at 1383 cm−1, which corresponds to an oxidation-state marker band of hemoproteins, is mainly due to the breathing mode of the pyrrole rings. The vibrations of the sixteen-membered inner ring contribute to the Raman bands sensitive to the spin-states of the heme iron.
DISPROPORTIONATION OF THE UNSATURATED ESTERS
Authors: Nakamura Ryuichi , Fukuhara Seiji , Matsumoto Shuichi , Komatsu Kooei
Published: July 2006

The disproportionation reactions of the unsaturated esters such as ethyl 3-butenoate, methyl 10-undecenoate, methyl oleate and 9-octadecenyl acetate were carried out using alkylborane-WCl6, -Mo(OEt)2Cl3 and various other catalysts. Both Et3B-WCl6 and Et3B-Mo(OEt)2Cl3 were found to be the effective catalysts for the above reactions.
LIQUID PHASE OXIDATION CATALYZED BY BISMUTH SULFATE. A NEW SYNTHESIS OF 1-CYCLOPENTENE-1-CARBOXALDEHYDE
Authors: Suzuki Shunichiro , Moro-Oka Yoshihiko , Ikawa Tsuneo
Published: July 2006

Autoxidation of cyclohexene catalyzed by insoluble bismuth sulfate in acidic solvents gave 1-cyclopentene-1-carboxaldehyde selectively. A new mechanism for the autoxidation involving isomerization of peroxyradical catalyzed by acidic site was presented.
THE ANODIC OXIDATION OF 1,3-DIENES
Authors: Shono Tatsuya , Ikeda Akihiko
Published: July 2006

The anodic oxidation of isoprene, piperylene, cyclopentadiene, or 1,3-cyclohexadiene in methanol or acetic acid brought about mainly the nucleophilic 1,4-addition of the solvent molecule to the diene. On the other hand, 1,3-cyclooctadiene gave a considerable amount of the product substituted at the allylic position along with the addition product.
CATALYTIC ACTIVITY AND SELECTIVITY OF Re2O7–Al2O3 FOR THE METATHESIS OF CYCLOOCTADIENE
Authors: Kumobayashi Hidenori , Ogura Toshimasa , Akutagawa Susumu , Saito Kaizaburo , Yamaguchi Tsutomu , Tanabe Kozo
Published: July 2006

The metathesis of cyclooctadiene was studied over fourteen kinds of oxides or binary oxides at 40°C in a liquid phase. Only Re2O7–Al2O3 was found to be active. The conversion was 100 % when the concentration of cyclooctadiene was low and the selectivity for the formation of C12, C16, and C20 cyclopolyenes was 64 %. The distribution of C12–C32 cyclopolyenes was entirely different from that in homogeneous catalyst system.
ISOMERIZATION OF d-LIMONENE OXIDE OVER ALUMINAS
Authors: Arata Kazushi , Tanabe Kozo
Published: July 2006

The title reaction was carried out over five different aluminas. One of them formed predominantly carbonyl compounds, while two gave more than 80 % allyl alcohols. Others produced both products.
NEW INTERCALATED COMPLEXES OF MPS3 (M=Mg, Zn, Mn) WITH n-ALKYLAMINES
Authors: Yamanaka Shoji , Kobayashi Hidejiro , Tanaka Masami
Published: July 2006

New types of intercalated complexes are synthesized by the reaction of MPS3 layer crystals (M=Mg, Zn, Mn) with n-alkylamines (CnH2n+1NH2, n=1–8). The amines are adsorbed on the interlamellar surfaces of the MPS3 crystals to form two different types of complexes of increased values in basal spacing. The spacing value of the first type of complexes is independent of the number of carbon atoms in alkyl chain of the amines, and the value of the second type of complexes increases with the number of the carbon atoms. The possible arrangements of the amines in the interlayer region are proposed for these types of complexes.
MOLECULAR STRUCTURE OF ETHYLENEDIAMINE-N,N,N′,N′-TETRAACETATO COMPLEX OF ANTIMONY(III): HSb(C10H12N2O8)·2H2O
Authors: Kita Itsuro , Uehiro Takashi , Iwamto Toschitake , Ouchi Akira , Yoshino Yukichi
Published: July 2006

The titled complex crystallizes in the monoclinic space group Pc with a=7.341, b=18.496, c=13.21 Å, β=123.8°, and z=4. The structure of crystallographically different molecules in the unit cell are almost identical. Two N and four O atoms of the sexadentate ligand and a lone electron pair form ψ-pentagonal bipyramid around the antimony atom.
MECHANISM OF THE REACTIONS OF METHOXYCARBONYLCARBENE STUDIED BY CIDNP. IV. DOES NOT METHOXYCARBONYLCARBENE INSERT INTO THE C–Br BONDS OF BROMOMETHANES ?
Authors: Iwamura Hiizu , Imahashi Yuzo , Kushida Katsuhiko , Aoki Kiyoshi , Satoh Shiroh
Published: July 2006

The main products of the photochemical reactions of methyl diazoacetate with CBrCl3 and CBr2Cl2 have been unambiguously characterized as CCl3CHBrCO2CH3 and CBrCl2 CHBrCO2CH3, respectively. These results,together with the 1H and 13C CIDNP spectra,support the formation of these products by recombination of radical pairs (Remark: Graphics omitted.) which in turn are formed by preferential attack of carbene :CHCO2CH3 on the bromine atom.
ABSOLUTE CONFIGURATION AND CIRCULAR DICHROISM OF S-o-METHOXYPHENYL-S-PHENYLSULFIMIDES AND SULFOXIMIDES
Authors: Moriyama Masaru , Kuriyama Kaoru , Iwata Tatsuo , Furukawa Naomichi , Numata Tatsuo , Oae Shigeru
Published: July 2006

(−)-S-o-methoxyphenyl-S-phenylsulfimides (1,3–6) exhibited negative Cotton effects around 232 and 283 nm, which correspond to (S)-configuration, like the analogous (S)-(−)-S-o-methoxyphenyl S-p-tolyl sulfoxide(2). The corresponding sulfoximides (7,8) show small Cotton effects near 272 and 240 nm. The observed solvent effects were ascribed to solvation.
SYNTHESIS AND STEREOCHEMISTRY OF 1,4-THIAPHOSPHORINANE 1,1-DIOXIDES
Authors: Nagao Yoshihiro , Sakurai Hiroshi
Published: July 2006

The reaction of bis(hydroxymethyl)phenylphosphine with distyrylsulfone proceeds stereoselectively to give only one of two possible stereoisomers of 3,4,5-triphenyl-1,4-thiaphosphorinane 1,1-dioxide. The preparation and stereochemistry of some other 1,4-thiaphosphorinane 1,1-dioxides are also described.
A SHORT FLASH OF MERCURY RESONANCE LINE AT 253.7 NM
Authors: Sato Shin , Okazaki Kiyoshi , Yamabe Masaki , Umemoto Hironobu , Tsunashima Shigeru , Ueno Takumi , Yokoyama Atsushi , Hatano Yoshihiko
Published: July 2006

When helium gas containing mercury vapor was irradiated by the electron pulse from a Febetron 706, an emission of mercury resonance line at 253.7 nm was observed, which consisted of two parts. The lifetime of the first emission agreed with the calculated apparent lifetime of the 6 3P1 state of mercury atoms. The second emission, the peak of which appeared at a few μsec, was completely quenched upon the addition of a small amount of sulfur hexafluoride. The first emission may be due to the direct excitation of mercury atoms by subexcitation electrons produced in helium, while the second emission probably results from the neutralization reaction of mercury ions produced.
SILVER ION-ASSISTED INTRAMOLECULAR NUCLEOPHILIC ADDITION-ELIMINATION OF VINYL BROMIDES; FORMATION OF BENZOTHIOPHENES FROM 2-(o-METHYLTHIOPHENYL)VINYL BROMIDES
Authors: Sonoda Takaaki , Kobayashi Shinjiro , Taniguchi Hiroshi
Published: July 2006

The reactions of 1-unsubstituted and 1-methyl-2-(o-methylthiophenyl)vinyl bromides in acetic acid in the presence of silver salt gave exclusively benzothiophenes, while the corresponding 2-methoxyphenyl analogues were unreactive under similar conditions. This cyclization is considered to involve an intramolecular nucleophilic attack of the sulfur atom at the carbon atom of the double bond activated by the silver ion with the elimination of the silver bromide.
FORMATION OF FORSTERITE(2MgO·SiO2) FROM THE MIXTURE PREPARED BY ALKOXY-METHOD
Authors: Yamaguchi Osamu , Nakajima Yoshiki , Shimizu Kiyoshi
Published: July 2006

Forsterite(2MgO·SiO2) was formed at low temperatures by heating the mixed powders prepared by the simultaneous hydrolysis of magnesium and silicon alkoxides.
SYNTHESIS AND CHARACTERIZATION OF 1-IMIDOYLIMINOPYRIDINIUM N-YLIDES
Authors: Kakehi Akikazu , Ito Suketaka , Uchiyama Kenji , Konno Yoshiaki
Published: July 2006

1-Imidoyliminopyridinium N-ylides were prepared for the first time by the reaction of pyridinium N-imines with ethyl benzimidate, and their thermal and photochemical reactivities were examined.
SYNTHESIS OF POLYMERIZABLE p-STYRENE SULFINATE
Authors: Kamogawa Hiroyoshi , Hayashi Tsuyoshi , Nanasawa Masato
Published: July 2006

Sodium p-styrene sulfinate, a novel redox monomer, was synthesized starting with 2-bromoethylbenzene with intention of preparing a novel class of redox polymer. The monomer was found to afford soluble polymers of high molecular weights by radical polymerization.
N-ALKYLPENTAMETHYLPHOSPHORAMIDES: NOVEL CATALYSTS IN TWO-PHASE REACTIONS
Authors: Tomoi Masao , Takubo Toyokazu , Ikeda Manabu , Kakiuchi Hiroshi
Published: July 2006

Phosphoramides having hydrophobic groups in the molecule, e.g. N-dodecylpentamethylphosphoramide or N-benzylpentamethylphosphoramide, can be used as phase-transfer catalysts in two-phase reactions. Polymeric phosphoramides, which were prepared by the copolymerization of N-(p-vinylbenzyl)pentamethylphosphoramide with styrene, were found to catalyze phase-transfer reactions more efficiently than their monomeric analogs.
A FACILE PREPARATION Of α-NITROOLEFIN OF CARBOHYDRATES
Authors: Tachihori Yoshifusa , Takamoto Tetsuyoshi , Sudoh Rokuro
Published: July 2006

d-Hexopyranosides involving β-nitro alcohol were readily converted to the corresponding α-nitroolefins via sulfonates when mainly treated with ca. 1 eq. mesyl chloride-ca. 2 eq. triethylamine in CH2Cl2 or THF, whereas methyl 3-deoxy-2-O-methylsulfonyl-3-nitro-α-d-glucopyranoside derivative 10 was isolated in 80% yield when 1 eq. Et3N was used.
THE FACILE SYNTHESIS OF LACTONES
Authors: Mukaiyama Teruaki , Usui Masahiro , Saigo Kazuhiko
Published: July 2006

Direct lactonization of ω-hydroxy acids, HO(CH22)nCOOH with n=5, 7, 10, 11, 14, has been successfully carried out under mild conditions in good yields by the treatment with 1-methyl-2-chloropyridinium iodide in the presence of triethylamine. In the case of the acid with n=6, only lactide has been produced.
A CONVENIENT PREPARATION OF MALTOL, ETHYLMALTOL, AND PYROMECONIC ACID FROM 2-ALKYL-6-METHOXY-2H-PYRAN-3(6H)-ONES
Authors: Torii Sigeru , Tanaka Hideo , Anoda Takuo , Simizu Yasuo
Published: July 2006

The efficient synthesis of 2-alkyl-3-hydroxy-4H-pyran-4-ones, e. g., pyromeconic acid (6a), maltol (6b), and ethyl maltol (6c), from 2-alkyl-4,5-epoxy-6-methoxytetrahydropyran-3-ones 5 by acid-catalyzed rearrangement is described. The key precursors 5 were obtained by epoxidation of 2-alkyl-6-methoxy-2H-pyran-3(6H)-ones 4, which were synthesized by three steps starting from furfuryl alcohols 1.
ELECTROPHILIC SUBSTITUTIONS OF OLEFINIC HYDROGENS II. ACYLATION OF VINYL ETHERS AND N-VINYL AMIDES
Authors: Hojo Masaru , Masuda Ryoichi , Kokuryo Yoshitsugu , Shioda Haruyuki , Matsuo Sachio
Published: July 2006

Reactions of vinyl ethers, N-vinyl carboxamides and N-vinyl sulfonamides with trifluoroacetic (or trichloroacetic) anhydride occurred quite easily at room temperature to give corresponding β-trifluoro- or trichloroacetylated compounds in high yields. Reactions with a mixed anhydride, CH3COOCOCF3, gave trifluoroacetylated compounds in high yields, acetyl compounds being not produced.
NOUVEAUX HETEROCYCLES THIOPYRANNIQUES
Authors: Croisy Alain , Ricci Adolfo , Jancevska Miroslava , Jacquignon Pierre , Balucani Dante
Published: July 2006

The thiopyranone-3 has been condensed with arylhydrazines, orthoamino acetophenone and orthoamino benzaldehyde to give some new indoles and quinolines.

The Bthoxycarbonyl-2 derivative has given some pyrazolones. RMN and Mass Spectra are examinated.
PHOTO-ELECTROCHEMICAL BEHAVIOUR OF THE TRIS(2,2′-BIPYRIDYL) RUTHENIUM(II) ION IN ACIDIC SOLUTION
Authors: Kobayashi Shigero O , Furuta Naoko , Simamura Osamu
Published: July 2006

A cathodic photocurrent was observed at an SnO2 electrode immersed in an acidic solution of tris(2,2′-bipyridyl)ruthenium(II) dichloride illuminated with visible light, and the current increased in the presence of methyl viologen. The photo-potential at the electrode was found to be positive enough for water to be oxidized; in fact, chemical species produced in a cell incorporating this photochemical system were identified with oxygen and hydrogen peroxide.
THE EFFECT OF EXTERNAL MAGNETIC FIELD ON THE PHOTOCHEMICAL REACTION OF ISOQUINOLINE N-OXIDE
Authors: Hata Norisuke
Published: July 2006

It was found that the magnetic field affected the photochemical isomerization of isoquinoline N-oxide to lactam in ethanol to cause an interesting variation in the yield of lactam. The results appear to indicate that there occurs a remarkable enhancement of the intersystem crossing from the excited singlet state of isoquinoline N-oxide by the magnetic field of approximately 10 kG.
THE REACTION OF α-SUBSTITUTED DEOXYBENZOINS WITH HEXAMETHYLPHOSPHORIC TRIAMIDE. FORMATION OF A NOVEL CYCLIC ENAMIDOPHOSPHATE
Authors: Monson Richard S , Baraze Adina
Published: July 2006

The reaction of benzoin and other substituted deoxybenzoins with HMPT has been investigated. Along with modest yields of tetraphenylpyridine, the major product in all cases is 2-dimethylamino-4, 5-diphenyl-3-methyl-1-oxa-3-aza-2-phosphacyclopent-4-ene 2-oxide (5). meso-Hydrobenzoin similarly gives 2-dimethylamino-4,5-diphenyl-1,3-dioxa-2-phosphacylopentane 2-oxide (4). The mechanism of formation of 5 and the pyridine is discussed.
A NEW METHOD FOR THE SYNTHESIS OF 5′-AMINO-NUCLEOSIDES AND THEIR PHOSPHORAMIDATE DERIVATIVES
Authors: Hata Tsujiaki , Yamamoto Isamu , Sekine Mitsuo
Published: July 2006

The reaction of nucleoside azides with trimethylsilyl phosphites is described. By use of the reaction, amino-nucleosides were obtained in high yields. The reaction can be also applied to the synthesis of dinucleoside phosphoramidate and nucleoside cyclic phosphoramidate.
THE STRUCTURES OF TWO MAJOR INTERMEDIATES IN TRIFLUOROMETHANESULFONIC ACID-CATALYZED REARRANGEMENT OF TRICYCLO[5.2.2.02,6]UNDECANE
Authors: Inamoto Yoshiaki , Takaishi Naotake , Fujikura Yoshiaki , Aigami Koji , Tsuchihashi Kiyoshi
Published: July 2006

Two major intermediates of unknown structure (unknown E and D) found in trifluoromethanesulfonic acid-catalyzed rearrangement of tricyclo[5.2.2.02,6]undecane (1) to 4-homoisotwistane (4) were identified as tricyclo[5.4.0.04,8]undecane (2) and tricyclo[5.3.1.04,11]undecane (3), respectively, by independent syntheses.
STRUCTURAL STUDY OF OPTICAL RESOLUTION III. THE CRYSTAL STRUCTURE OF CIS-DICHLOROBIS(ETHYLENEDIAMINE)COBALT(III) d-α-BROMOCAMPHOR-π-SULPHONATE
Authors: Kushi Yoshihiko , Kuramoto Masahiro , Yoneda Hayami
Published: July 2006

The crystal structure of the title compound has been determined by X-ray analysis. It has been found that a face-to-face type close contact of the (+)589-[CoCl2(en)2]+ cation with the bromocamphor moiety of the d-BCS anion is formed in this crystal.
STEREOCHEMISTRY AND REGIOSELECTIVITY OF HALOGEN EXCHANGE REACTIONS OF vic-DIHALOALKANES OVER METAL HALIDES
Authors: Misono Makoto , Ishikawa Makoto , Yoneda Yukio
Published: July 2006

Stereospecific substitution reaction of halogens with retention of configuration was found in the reaction of 2,3-dibromobutanes over metal halides at 100–200°C, although rapid racemization of optically active 2,3-dibromobutane took place. A reaction mechanism which involves a bridged bromonium-ion intermediate was proposed to explain these results and the regioselectivity of the substitution of 1,2-dibromopropane.
A CONVENIENT METHOD FOR THE PREPARATION OF OLEFINS BY REDUCTIVE DEMETHOXYLATION OF ALLYL METHYL ETHERS USING TiCl4–LiAlH4
Authors: Ishikawa Hiroshi , Mukaiyama Teruaki
Published: July 2006

The reductive demethoxylation of allyl methyl ethers using TiCl4–LiAlH4 afforded various olefins in good yields accompanied with double bond migration.
A SYNTHESIS OF PROSTAGLANDIN F2α (PGF2α)
Authors: Tanouchi Tadao , Kori Seiji , Hayashi Masaki
Published: July 2006

PGF2α 15 was synthesized via the δ-lactone aldehyde 2, which is much more stable than the Corey’s aldehyde 1.
THE REACTION OF THIOLANE WITH HYDROGEN ATOMS IN GAS PHASE
Authors: Horie Osamu , Kawamata Kazunori , Onuki Kaoru , Amano Akira
Published: July 2006

The title reaction was carried out in the temperature range of 300–670 K between the pressure of 5.5–11 Torr, using a discharge-flow apparatus. n-Butanethiol, n-butane, and 1-butene are the main products at room temperature. The results are explained by the ring opening reaction initiated by the H atom attack on sulfur atom. followed by the C–S bond dissociation.
NUCLEOPHILIC SUBSTITUTION REACTION VIA ONE ELECTRON TRANSFER PROCESSES. I A NEW SYNTHETIC METHOD FOR THE PREPARATION OF α,β-UNSATURATED NITRILES
Authors: Ono Noboru , Eto Hiromichi , Tamura Rui , Hayami Jun-ichi , Kaji Aritsune
Published: July 2006

An efficient one-pot synthesis of α,β-unsaturated nitriles consisting of the coupling reaction of α-bromonitroalkanes with the anions of ethyl α-alkylcyanoacetates followed by deethoxycarbonylation and elimination of the nitro group is described.
THE TITANIUM TETRACHLORIDE-PROMOTED REACTION OF KETENE ALKYL TRIALKYLSILYL ACETALS WITH ACETALS OR AN ORTHOFORMATE
Authors: Saigo Kazuhiko , Osaki Masaaki , Mukaiyama Teruaki
Published: July 2006

In the presence of TiCl4, ketene alkyl trialkylsilyl acetals reacted with acetals or an orthoformate at −78°C to afford the corresponding β-alkoxyesters or β,β-dialkoxyester in good yields, respectively.
LIQUID–LIQUID EXTRACTION OF COBALT(II) WITH POLYETHYLENEGLYCOL AND ITS DERIVATIVES
Authors: Sotobayashi Takeshi , Suzuki Toshio , Yamada Kohji
Published: July 2006

Polyethyleneglycol and its derivatives were found to be employed as new extracting reagents of trace amounts of Co(II) in liquid–liquid extraction. The extraction behavior of Co(II) with polyethyleneglycol alkylphenyl ether (Triton X-100) from thiocyanate solutions was studied, and the extracted chemical species was estimated to be (NH4)2Co(NCS)4(Triton X-100))2.
SYNTHESIS OF 2,15-HEXADECANEDIONE, A PRECURSOR OF MUSCONE, FROM BUTADIENE
Authors: Tsuji Jiro , Mizutani Kyoichiro , Shimizu Isao , Yamamoto Keiji
Published: July 2006

1-Acetoxy-2,7-octadiene obtained by the palladium catalyzed dimerization of butadiene in acetic acid was converted to 1-chloro-2,7-octadiene. Coupling of this allylic chloride with iron powder in DMF afforded 1,6,10,15-hexadecatetraene as a main product. Selective oxidation of the terminal double bonds to methyl ketones catalyzed by palladium chloride and cuprous chloride, followed by hydrogenation gave 2,15-hexadecanedione.
PHOTOSENSITIZED OXYGENATION OF 2-PHENYL-1,3-OXAZEPINE
Authors: Seshimoto Osamu , Tezuka Takahiro , Mukai Toshio
Published: July 2006

The dye-sensitized photooxygenation of 2-phenyl-1,3-oxazepine (1) in methylene chloride yields fragment products, 2, 3, 4, and 5. Among them, pyrrolinone (2) and butenolide (3) are assumed to originate from the 1,4-epidioxide (6), and ethylidene malonaldehyde (4) from dioxetane (10) or 1,6-epidioxide (11).
PHASE TRANSITIONS AND BROADENING OF CHLORINE NQR SPECTRUM OF 1,1,1-TRICHLORO-2-METHYL-2-PROPANOL HEMIHYDRATE
Authors: Hashimoto Masao
Published: July 2006

It was found that 1,1,1-trichloro-2-methyl-2-propanol hemihydrate exhibits two phase transitions at 192 K and 198 K. By quenching the compound from room temperature to 77 K, a metastable phase was obtained. The results of the dielectric and chlorine NQR measurements suggest a random orientation of molecules in the metastable phase.
DIMERIZATION OF THE TRYPTOPHYL MOIETY
Authors: Omori Yukako , Matsuda Yasuhiro , Aimoto Saburo , Shimonishi Yasutsugu , Yamamoto Masao
Published: July 2006

A compound isolated from solutions of N-acetyl-tryptophan methyl ester in hydrogen fluoride and trifluoracetic acid was found to be a dimer with the structure shown in Fig. 1.
3,3′-DIBROMO-4,4′,5,5′-TETRAHYDROXYBIBENZYL, A NEW BROMOPHENOL FROM THE RED ALGA, POLYSIPHONIA URCEOLATA
Authors: Kurata Kazuya , Amiya Takashi , Nakano Naomi
Published: July 2006

The new bromophenol, 3,3′-dibromo-4,4′,5,5′-tetrahydroxybibenzyl has been isolated from the red alga, Polysiphonia urceolata, and identified. Besides this phenol, three bromophenols have been obtained and shown to be 3,5-dibromo-4-hydroxybenzyl methyl ether, 3-bromo-4,5-dihydroxybenzyl methyl ether and 3-bromo-4,5-dihydroxybenzaldehyde, which were previously reported in the literature.
FORMATION OF BENZ[cd]INDAZOLE BY LOW-TEMPERATURE PHOTOLYSIS OF 1,8-DIAZIDONAPHTHALENE IN A RIGID MATRIX
Authors: Yabe Akira , Honda Koichi , Oikawa Setsuko , Tsuda Minoru
Published: July 2006

The absorption spectrum of benz[cd]indazole is observed by low-temperature matrix photolysis of 1,8-diazidonaphthalene and is identified tentatively on the basis of its chemical behavior and the prediction of the spectroscopic data by SCF MO-CI calculations.
THE EFFICIENT CATALYSIS OF THE AUTOXIDATION OF THIOPHENOL BY A TETRADEHYDROCORRINATOCOBALT(III) COMPLEX
Authors: Murakami Yukito , Aoyama Yasuhiro , Nakanishi Shigenori
Published: July 2006

The oxidation of thiophenol was effectively catalyzed by dicyano-8,12-diethyl-1,2,3,7,13,17,18,19-octamethyltetradehydrocorrinatocobalt(III) ((CN)2Co(III)TDHC) in methanol containing small amounts of acetic acid and sodium cyanide at room temperature. The reaction was consistent with the sequence: (1) (CN)2Co(III)TDHC is reduced to Co(I) with thiophenol without participation of molecular oxygen; (2) the Co(I) species is oxidized to Co(II)TDHC by oxygen and acid; (3) the Co(II) species is oxidized to (CN)2Co(III)TDHC by the cooperation of oxygen and cyanide ion. The Co(III) species was repeatedly used at a rate of 3–5 cycle per second as an electron transport mediator.
AN INITIAL INTERMEDIATE ON PULSED ELECTRON IRRADIATION OF AQUEOUS SOLUTIONS OF MERCURIC IODIDE
Authors: Fujita Shin-ichi , Horii Hideo , Mori Toshiaki , Taniguchi Setsuo
Published: July 2006

HgI2 was found to react rapidly with eaq− producing initially a very short-lived intermediate with an absorption maximum at 470 nm. It decays via first order kinetics with a half-life of 1 μs to form another transient, HgI, absorbing at 360 nm. The first intermediate is proposed to be an eaq− or an H atom adduct.
GRAPHITE FURNACE ATOMIC ABSORPTION SPECTROMETRY UTILIZING SELECTIVE ADSORPTION OF METAL IONS ONTO TUNGSTEN WIRE IN. AQUEOUS SOLUTIONS
Authors: Hoshino Yoshio , Utsunomiya Taizo , Fukui Keitarou
Published: July 2006

The graphite furnace atomic absorption spectrometry (AAS) is improved by utilizing tungsten wire as an adsorbing material. This method has 20 to 50 times higher sensitivity compared to the conventional aliquot-sampling flameless AAS. Interferences of large amounts of coexisting alkali salts can be effectively eliminated.
PALLADIUM POLYPYRAZOLYLBORATE COMPLEXES CONTAINING A Pd–C BOND
Authors: Onishi Masayoshi , Ohama Yushichiro , Sugimura Koji , Hiraki Katsuma
Published: July 2006

(N,N-Dimethylbenzylamine,2-C,N)(BPz4)Pd(II) (Pz=1-pyrazolyl), (2-phenylpyridine,2′-C,N)(BPz4)Pd(II), (azobenzene,2-C,N)(BPz4)Pd(II), [benzo(h)quinoline,2-C,N](BPz4)Pd(II), and (N,N-dimethylbenzylamine, 2-C,N)(HBPz3)Pd(II) were prepared. Pyrazolyl groups of these complexes were found to show a fluxional behavior on the basis of 1H-NMR spectra.
CONFORMATION OF COORDINATED AMINO ACIDS. II. LONG-RANGE SPIN–SPIN COUPLING IN HISTIDINE AND HINDERED INTERNAL ROTATION OF IMIDAZOLE GROUP IN PENTAMMINE(l-HISTIDINE)COBALT(III) ION
Authors: Sakaguchi Ushio , Taura Toshiaki , Yoneda Hayami
Published: July 2006

It is found that in the pentammine(l-histidine)cobalt(III) ion, the imidazole C(5) proton is coupled to only one of the methylene protons with 4JHH=0.9 Hz and the internal rotation of the imidazole ring around the Cβ–Cγ bond is hindered presumably due to an intramolecular hydrogen bonding.
MAGNETIC FIELD EFFECT ON THE EXCIPLEX FLUORESCENCE OF POLY-N-VINYLCARBAZOLE
Authors: Okamoto Ken-ichi , Itaya Akira , Kusabayashi Shigekazu
Published: July 2006

Magnetic fields were found to increase the prompt exciplex fluorescences in intensity in poly-N-vinylcarbazole films doped with dimethylterephthalate and N,N,N;N′-tetramethyl-p-phenylenediamine by up to 2 % at 500 G. This effect was independent of the intensity and the wavelength of the exciting light, the emission-wavelength, and applied electric fields, although slightly dependent on temperature. This effect was not observed for the exciplex fluorescences in solution.
AN EFFICIENT METHOD FOR THE PREPARATION OF ACYLSILANE AND α-HALOACYLSILANE
Authors: Kuwajima Isao , Abe Toru , Minami Naoki
Published: July 2006

On treating 1,1-bis(trimethylsilyl)alkan-1-ol with t-butyl hypochlorite, the corresponding acylsilane is obtained in good yield, while the reaction of the alcohol with NBS, in contrary, affords α-bromoacylsilane exclusively.
A NEW SYNTHETIC METHOD OF BIVALENT Rh(II) COMPLEX USING PHOSPHINATED POLYSTYRENE AND ITS CATALYTIC ACTIVITY FOR OLEFIN HYDROGENATION
Authors: Kaneda Kiyotomi , Terasawa Masami , Imanaka Toshinobu , Teranishi Shiichiro
Published: July 2006

A paramagnetic bivalent rhodium complex was selectively formed by the reaction of phosphinated polystyrene with RhCl3·3H2O in ethanol. The characterization of the rhodium complex was carried out by the use of IR, ESR, and ESCA spectrometers. This complex was active for hydrogenation of olefins. The remarkable features of the hydrogenation are described.
PHOTOCHEMISTRY OF 3-OXIDOPYRIDAZINIUM BETAINES ISOLATION AND REACTION OF NEW FUSED DIAZIRIDINES
Authors: Maki Yoshifumi , Kawamura Masao , Okamoto Hisanori , Suzuki Mikio , Kaji Kenji
Published: July 2006

Irradiation of 3-oxidopyridazinium betaines (4) and (9) in acetonitrile gave fused diaziridines (5) and (10) which are stable enough to isolate. The amido bond of (5) underwent alcoholysis and aminolysis with ease. Thus, apparent phototranspositions of (4) and (9) to pyridazinones (6) and (11) in water were proved facile hydrolysis of the amide bonds of the intermediates (5) and (10).
CYCLIZATION OF POLYENES XXVII. SYNTHESIS OF OXOCRINOL, dl-CAULERPOL, AND dl-CRINITOL
Authors: Kato Tadahiro , Takayanagi Hisao , Uyehara Tadao , Kitahara Yoshio
Published: July 2006

Novel terpene alcohols, oxocrinol (1a), caulerpol (3a), and crinitol (2a), isolated from marine algae, were synthesized by the alkylation of lithium salt of benzenesulfonyl derivatives, 5, 6, and 11 (R = THP; X = SO2Ph) followed by reductive cleavage of SO2Ph and the protecting groups. The present study confirms unequivocally the proposed structures of oxocrinol, caulerpol, and crinitol, respectively.
OXIDATION OF D:B-FRIEDO-OLEAN-5(10)-ENE. A COMMENT ON THE STRUCTURE OF “ALNUS-5(10)-EN-1-ONE” FROM EUPHORBIA NERIFOLIA
Authors: Akiyama Eri , Ogawa Keiichiro , Moriyama Yoshihiko , Tsuyuki Takahiko , Takahashi Takeyoshi
Published: July 2006

The Ratcliffe oxidation of D:B-friedo-olean-5(10)-ene (2) gave D:B-friedo-olean-5(10)-en-1-one (1), D:B-friedo-olean-5(10)-en-6-one (3), and D:B-friedo-olean-5(10)-ene-1,6-dione (4). The spectral data of the enone (1) are not identical with the corresponding values reported for a triterpene ketone “alnus-5(10)-en-1-one” isolated from Euphorbia nerifolia, indicating that the structure of this natural triterpene must be revised.
COMPETITIVE PHOTOSENSITIZED OXIDATION AT TiO2 PHOTOANODE
Authors: Inoue Tooru , Watanabe Tadashi , Fujishima Akira , Honda Kenichi
Published: July 2006

The rotating ring-disk electrode (RRDE) technique has been applied to the study of photosensitized oxidation of various redox agents in competition with the oxidation of water on a TiO2 photoanode. The results are discussed referring to the standard redox potentials of the reducing agents.
BASE-INDUCED REARRANGEMENT AND ELIMINATION OF 2-HALO-SUBSTITUTED 1-AMINOETHANE-1,1-DIPHOSPHONIC ACIDS
Authors: Fukuda Masahiro , Okamoto Yoshiki , Sakurai Hiroshi
Published: July 2006

A base-induced rearrangement involving a 1,2-shift of a phosphono group from carbon to carbon was found in 2-halo-substituted 1-aminoethane-1-1-diphosphonic acids. In 2,2-dichloro-substituted 1-aminoethane-1,1-diphosphonic acid, each of the geminal phosphono groups underwent a 1,2-shift and an elimination, respectively, to give phosphonoacetic acid.
REACTIONS OF THIOL ESTERS WITH HALOGENS AND SOME N-HALO AND O-HALO COMPOUNDS
Authors: Minato Hiroshi , Takeda Kazuyuki , Miura Takashi , Kobayashi Michio
Published: July 2006

S-Phenyl thioacetate (1) quantitatively reacted with 1/2 mole of bromine (or chlorine), yielding acetyl bromide (or chloride) and phenyl disulfide. With iodine, 1 formed a complex, which reacted with an alcohol (MeOH, Me3CCH2OH, PhCH2OH), forming the corresponding ester; a catalytic amount of iodine was sufficient for this transesterification. 1 reacted quantitatively with 1-chlorobenzotriazole. The reaction of 1 with t-butyl hypochlorite yielded t-butyl acetate (70%) and acetyl chloride(30%).
CHLORINATION OF PHENYLTHIOCYCLOPROPANES AND PHENYLSULFINYLCYCLOPROPANES WITH CHLORINATING AGENTS: PREPARATION OF 1-CHLORO-1-(PHENYLTHIO)CYCLOPROPANES AND 1-CHLORO-1-(PHENYLSULFINYL)CYCLOPROPANES
Authors: Masuda Toshiaki , Furukawa Naomichi , Oae Shigeru
Published: July 2006

1-Chloro-1-(phenylthio)cyclopropanes and 1-chloro-1-(phenylsulfinyl)cyclopropanes are readily prepared by the direct chlorination of phenylthiocyclopropanes or phenylsulfinylcyclopropanes with various chlorinating agents.
A TRANSIENT FORMATION OF N-SUBSTITUTED ISOINDOLE BY MEANS OF PHOTOCHEMICAL INTRAMOLECULAR HYDROGEN ABSTRACTION
Authors: Maruyama Kazuhiro , Kozuka Tadashi , Otsuki Tetsuo , Naruta Yoshinori
Published: July 2006

Isoindole derivative 2 was formed transiently by means of intramolecular hydrogen abstraction of 1. The intermediacy of 2 was confirmed by the good yields of Diels-Alder type adducts of it with dienophiles.
ASYMMETRIC SYNTHESIS BASED ON (Z)-(2R,3S)-6-BENZYLIDENE-3,4-DIMETHYL-5,7-DIOXO-2-PHENYLPERHYDRO-1,4-OXAZEPINE. SYNTHESIS OF OPTICALLY ACTIVE 3-SUBSTITUTED 3-PHENYLPROPIONIC ACIDS
Authors: Mukaiyama Teruaki , Takeda Takeshi , Osaki Masaaki
Published: July 2006

(Z)-(2R,3S)-6-Benzylidene-3,4-dimethyl-5,7-dioxo-2-phenylperhydro-1,4-oxazepine (I) was prepared in good yield from α-ethoxycarbonylcinnamic acid and l-ephedrine hydrochloride by the use of 2-chloro-1-methylpyridinium tosylate as a coupling reagent. The conjugate addition of n-butylmagnesium bromide to (I) in the presence of nickel chloride, followed by hydrolysis and decarboxylation gave highly enantiomerically pure (99%) 3-phenylheptanoic acid in high yield (92%).
DIRECT EVIDENCE OF PHOTODISSOCIATION OF CARBAZOLE VIA THE HIGHER EXCITED TRIPLET STATE BY A DOUBLE EXCITATION METHOD
Authors: Yamamoto Sada-aki , Kikuchi Koichi , Kokubun Hiroshi
Published: July 2006

Photodissociation of carbazole is investigated in cyclohexane at room temperature by a double excitation method which utilizes two successive excitation light pulses; the first flash L1 is used to populate the lowest excited triplet state T1 of carbazole and the second flash L1 to excite T1 into the higher excited triplet state Tn. Selective Tn←T1 excitation of carbazole by L2 brings about both the formation of carbazyl radical and the depletion of T1. Therefore, it is concluded that carbazyl radical is formed via Tn.
KINETIC STUDY ON THE ADDITION OF ETHYLENE TO DI-μ-CHLORO-TETRAKIS (TRIPHENYLPHOSPHINE) DIRHODIUM (I)
Authors: Ohtani Yoshimi , Yamagishi Akihiko , Fujimoto Masatoshi
Published: July 2006

The addition of ethylene to di-μ-chloro-tetrakis (triphenylphosphine)dirhodium(I) is studied by means of a stopped-flow and a rapid-scan spectroscopic method. The reaction is found to proceed in two successive steps: [RhCl(PPh3)2]2 (Remark: Graphics omitted.)[(C2H4) {RhCl-(PPh3)2}2] (Remark: Graphics omitted.)2[RhCl(C2H4)(PPh3)2];K1 = 2.1×102 and k2 = 1.1 mol−1dm3s−1.
SYNTHESIS OF 15,19-METHANO-ω-NOR-PROSTAGLANDINS
Authors: Niwa Haruki , Kurono Masayasu
Published: July 2006

15,19-Methano-ω-nor-prostaglandin F2α and E2 methyl ester, 4 and 5 were synthesized from (−)-Corey’s aldehyde 9 and the β-oxidoylide 6 via allylic rearrangement of the intermediate 17.
TWO TYPES OF INDIRECT CYCLODIMERIZATION OF BIACETYL VIA ITS ENOL SILYL ETHERS
Authors: Murai Shinji , Ryu Ilhyong , Kadono Yukio , Katayama Hajime , Kondo Kiyoshi , Sonoda Noboru
Published: July 2006

Silyl ethers of biacetyl enols, an enone 2 and a diene 3, were prepared. Cyclodimerization of 2 gave a dihydropyran 4, while reaction of 3 with 2, maleic anhydride, and ethyl acrylate gave Diels–Alder adduct 5, 8, and 9, respectively. The compounds 4 and 5 were desilylated to afford 6 and a mixture of 7 and 7′, respectively.