bluuebunny/crossref_metadata_2025 huggingface dataset:
PHOTOREACTIONS OF HETEROAROMATIC COMPOUNDS VII. PROMOTION AND INHIBITION OF PHOTO-METHOXYLATION OF METHYL 2-PYRIDINECARBOXYLATE IN ACIDIC METHANCLIC SOLUTIONS BY ADDITIVES. SPECIFIC PROMOTION BY 4-SUBSTITUTED PYRIDINES
Authors: Miyazawa Yoshiyuki , Hasegawa Ryo , Tobita Etsuo , Furihata Toshikazu , Sugiyama Toru , Sugimori Akira
Published: July 2006

Photo-methoxylation of methyl 2-pyridinecarboxylate at 6-position is promoted specifically by 4-substituted pyridines. Substituted pyridines at 2- or 3-position have no effect or inhibit the process. Many other substances including sensitizers (singlet or triplet), electron donors and acceptors do not promote the photo-methoxylation.
PARTICIPATION OF ALLYLIC HYDROXYL GROUP IN THE BROMINE ADDITION TO CYCLOHEXENE DERIVATIVES, 1α- AND 1β-HYDROXY-2,3-DEHYDRO-5α-SANTANOLIDE
Authors: Yamakawa Koji , Azusawa Kazutoyo , Nishitani Kiyoshi
Published: July 2006

Addition of bromine to 1α-hydroxy-2,3-dehydro-5α-santanolide (6a) and its derivatives (6b and c) gave diequatorial 2α,3β-dibromides (9a, b, and c) as major products and diaxial 2β,3α-dibromides (10a, b, and c) as minor products, respectively. This bromine addition is all abnormal in the Früst-Plattner rule and its reaction mechanisms are proposed.
SYNTHESIS OF GRANULIBERIN R. AN APPLICATION OF THE ‘HOLD-IN-SOLUTION’ METHOD
Authors: Muramatsu Ichiro , Kimura Atsuko , Nozaki Sukekatsu , Nakajima Terumi , Yasuhara Tadashi , Hirai Yuko
Published: July 2006

Granuliberin R, a new dodecapeptide isolated from Rana rugosa, was synthesized. The ‘hold-in-solution’ method was applied to the preparation of the fragment peptides.
BIOGENETIC-LIKE CYCLIZATION OF FARNESOL AND NEROLIDOL TO BISABOLENE BY THE USE OF 2-FLUOROBENZOTHIAZOLIUM SALT
Authors: Kobayashi Susumu , Tsutsui Mikio , Mukaiyama Teruaki
Published: July 2006

Treatment of trans, cis-farnesol or nerolidol with 2-fluorobenzothiazolium salt in the presence of tri-n-butylamine afforded monocyclic sesquiterpenes, mainly α-bisabolene, in good yields.
THE SESQUITERPENES OF CACALIA SPECIES. II. THE STRUCTURE OF CACALAL AND THE INTERCONVERSIONS OF THE CONSTITUENTS
Authors: Naya Keizo , Takai Kunihiro , Nakanishi Mikihiko , Omura Kanji
Published: July 2006

Two known sesquiterpenes, cacalone (I) and decompostin (II), and one new, named cacalal (III), have been isolated from Cacalia delfiniifolia Sieb. et Zucc. The structure of III and cacalolide (XIVa) have been established by selective oxidation of cacalol (IV). The interconversions of the constituents were also investigated.
n-PROPENYL AND σ-ALLYL INTERMEDIATES IN THE HYDROGENATION OF METHYLACETYLENE AND ALLENE ON MoS2
Authors: Okuhara Toshio , Kondo Toshihiko , Tanaka Ken-ichi
Published: July 2006

The hydrogenation of methylacetylene on MoS2 proceeds through n-propenyl intermediate, (Remark: Graphics omitted.), however, the hydrogenation of allene occurs through σ-allyl intermediate, (Remark: Graphics omitted.). These two intermediates are in marked contrast with the intermediates for the hydrogenation of butadiene and olefins taking place via iso-butenyl and iso-alkyl intermediates on the MoS2 catalyst.
STUDIES ON PHOTOACTIVATED ELECTRON-TRANSPORT SYSTEMS. I. REDUCTION OF HEMIN AND ANTHRAQUINONESULFONATE AS MEDIATED BY PYRIDINIUM IONS AND PHOTOEXCITED RUTHENIUM(II) COMPLEXES
Authors: Takuma Keisuke , Kajiwara Makoto , Matsuo Taku
Published: July 2006

Photoexcited state of tris(2,2′-bipyridine)ruthenium(II) ion serves as a good reducing agent, if EDTA is present in the solution. Pyridyl radical and 4,4′-bipyridinium cation radical were obtained by this means of photoirradiation, and proved to be useful as mediators for catalytic reduction of Hemin and 9,10-anthraquinone-l-sulfonate.
RADIATION-INDUCED REACTIONS OF PYRIDINECARBOXYLIC ACID ESTERS IN ACIDIC ALCOHOLIC SOLUTIONS. SUBSTITUTION BY ALKYL AND HYDROXYALKYL GROUPS AND REDUCTION OF CARBOXYLIC ESTER TO ALCOHOL
Authors: Nakamura Kazuhito , Sugiyama Toru , Suzuki Toru , Sugimori Akira
Published: July 2006

The main reactions of pyridinecarboxylic acid esters induced by Co-60 γ-rays are 1) substitution on the pyridine ring by alkyl or hydroxyalkyl groups derived from solvent alcohols and 2) the reduction of carboxylic esters to alcohols (hydroxymethyl group). Substitution is dominant in methanol solutions and reduction is dominant in 2-propanol solutions.
PHOTOLYSIS OF 1,3,4-OXADIAZOLES IN ALCOHOLS
Authors: Tsuge Otohiko , Oe Koji , Tashiro Masashi
Published: July 2006

Irradiation of 2,5-diphenyl-1,3,4-oxadiazole in alcohols induces a heterolytic addition of alcohols to the C=N bond of the oxadiazole, followed by cycloelimination to yield benzoic acid ester and benzonitrile imine. The latter reacts with the oxadiazole to form 4-benzamido-3,5-diphenyl-1,2,4-triazole which is photochemically transformed into benzamide and 3,5-diphenyl-1,2,4-triazole. Upon irradiation of 2-phenyl-1,3,4-oxadiazole in methyl alcohol, the 1:1 adduct is obtained.
MEERWEIN-PONNDORF-VERLEY REACTION OVER MAGNESIUM OXIDE
Authors: Takezawa Nobutsune , Kobayashi Haruo
Published: July 2006

The hydrogen transfer reaction between ethanol and acetone CH3CH2OH + (CH3)2CO→CH3CHO + (CH3)2CHOH was studied over magnesium oxide by use of deuterium tracer. Ethanol transfered its hydrogen of CH bond to carbonyl carbon atom, suggesting that the hydride ion transfer from surface ethoxide anion is involved in the reaction. On the other hand, methyl hydrogens in acetone were rapidly exchanged with hydroxyl in ethanol.
SYNTHETIC APPROACH TO A NEW HETEROCYCLE, ISOINDOLO[2,1-c]THIAZOLE
Authors: Shimoharada Hiroshi , Ikeda Shigehiko , Kajigaeshi Shoji , Kanemasa Shuji
Published: July 2006

Isoindolo[2,1-c]thiazolium salt, a precursor of isoindolo[2,1-c]thiazole, was synthesized via four steps starting from o-(bromoacetyl)benzoic acid. This salt reacted with acetic anhydride to afford the 5-acetyl derivative which underwent intramolecular 10π cyclization upon treatment with triethylamine.
SILYL ANIONS VII. ELECTRON TRANSFER FROM TRIMETHYLSILYLPOTASSIUM TO BENZOPHENONE AND NAPHTHALENE. GENERATION OF ANION RADICALS IN NONPOLAR SOLVENTS SUCH AS n-HEXANE
Authors: Sakurai Hideki , Kira Mitsuo , Umino Hiroshi
Published: July 2006

Trimethylsilylpotassium, prepared in a nonpolar solvent by the reaction of hexamethyldisilane with potassium methoxide in the presence of 18-crown-6, is a useful reagent for efficient homogeneous electron transfer. The first esr spectra of anion radicals of benzophenone and naphthalene in n-hexane as well as those in THF and benzene were recorded.
A METHOD FOR A MEASUREMENT OF THE ELECTRON TRANSFER RATE CONSTANT IN ECL
Authors: Itoh Kiminori , Sukigara Mitsunori , Honda Kenichi
Published: July 2006

A simple method for measuring reaction rate constants of anion–cation annihilation reactions is proposed. The method is principally capable of obtaining an accurate value of the total reaction rate constant K in Eq. (4) . A preliminary result is given for the diphenylanthracene–benzonitrile system.
SELECTIVE REDUCTION OF OXIMES WITH PYRIDINE-BORANE
Authors: Kikugawa Yasuo , Kawase Masami
Published: July 2006

Pyridine-borane, which was readily prepared from pyridine hydrochloride and sodium borohydride, reduced oximes to the corresponding hydroxylamines in good yields with simple procedure. Other functional groups (ester, nitrile, nitro, amide, and halide) present in the same molecule of oximes were not reduced by this reagent.
NEW SYNTHETIC REACTIONS BASED ON 1-METHYL-2-FLUOROPYRIDINIUM SALTS. FACILE CONVERSION OF ALCOHOLS TO THIOALCOHOLS
Authors: Hojo Ko , Yoshino Hiroshi , Mukaiyama Teruaki
Published: July 2006

Facile conversion of alcohols to thioalcohols via thiolesters is described. The synthetic scheme involves (i) preparation of thiolesters (5) by the reaction of ethanethioate anion with 2-alkyloxypyridinium salts (3), formed from 1-methyl-2-fluoropyridinium salt (1) and alcohols, and (ii) subsequent reduction of 5 to thioalcohols. A clean inversion of configuration is noted.
BILAYER MEMBRANES PREPARED FROM MODIFIED DIALKYLAMMONIUM SALTS AND METHYLDIALKYLSULFONIUM SALTS
Authors: Kunitake Toyoki , Okahata Yoshio
Published: July 2006

Electron microscopy showed that modified dialkylammonium salts and methyldialkylsulfonium salts formed bilayers in dilute aqueous solutions. The effect of polar head groups on the aggregation properties of the amphiphiles was discussed.
SYNTHESIS AND CHARACTERIZATION OF CATIONIC DIAMINOCYCLOPROPENYLIDENE MERCURY COMPLEX
Authors: Yoshida Zen-ichi , Konishi Hisatoshi , Kamitori Yasuhiro , Ogoshi Hisanobu
Published: July 2006

Cationic diaminocyclopropenylidene mercury complexes (1) were synthesized by the reaction of diaminocyclopropenium perchlorate with mercury acetate. Coordination of two diaminocyclopropenylidenes to divalent mercury was confirmed on the basis of microanalyses and spectral measurements. The value of 13C–199Hg coupling constant in 1 indicates a diagnostic of sp hybridization of the C–Hg bond.
SYNTHESIS OF [3.3]PARACYCLOPHANE-5,8-QUINONE
Authors: Shinmyozu Teruo , Inazu Takahiko , Yoshino Tamotsu
Published: July 2006

[3.3]Paracyclophane-5,8-quinone I was synthesized. Its charge-transfer absorption maximum at 406 nm (ε 407) showed a marked red shift as compared with that of [2.2]- and [4.4]paracyclophanequinones.
SELECTIVE HYDROGENATION OF 1,3-BUTADIENE CATALYZED BY COBALT(I)-BIPYRIDYL COMPLEXES
Authors: Yamamoto Nobuyuki , Kanai Hiroyoshi , Tarama Kimio
Published: July 2006

1,3-Butadiene was selectively hydrogenated to cis-2-butene by cobalt(I)-bipyridyl complexes. The order of the addition of butadiene to cobalt complexes determined the distribution of products. The catalytic activity was affected by the bipyridyl/cobalt ratio and halide anions.
2,2-DIFLUORO-1-PHENOXYVINYLLITHIUM: A NEW REAGENT FOR THE PREPARATION OF 2-PHENOXY-2-ALKENOIC ACIDS FROM CARBONYL COMPOUNDS
Authors: Tanaka Kiyoshi , Nakai Takeshi , Ishikawa Nobuo
Published: July 2006

The title reagent 3, readily generated in situ from the reaction of 2,2,2-trifluoroethoxybenzene (1) with lithium diisopropylamide, was found to be useful for the preparation of 2-phenoxy-2-alkenoic acids (6) from various carbonyl compounds via facile acid hydrolysis of the initially formed difluorovinylcarbinols (5).
SYNTHESIS OF EVERNITROSE AND ITS ENANTIOMER
Authors: Yoshimura Juji , Matsuzawa Masafumi , Sato Ken-ichi , Funabashi Masuo
Published: July 2006

Evernitrose (1: 2, 3, 6-trideoxy-3-c,4-o-dimethyl-3-nitro-l-arabino-hexopyranose) and its enantiomer (17) were synthesized from methyl 2,6-dideoxy-4-o-methyl-α-l-erythro-hexopyranosid-3-ulose and methyl 4,6-o-benzylidene-2-deoxy-α-d-erythroa-hexopyranosid-3-ulose, respectively. In both cases, the unique nitro group attached to the tertiary branching carbon was introduced by oxidation of the corresponding amino derivatives prepared by Bourgeois’s method.
STEREOCHEMICAL STUDIES ON THE ELEMENE-TYPE SESQUITERPENES FROM ACORUS CALAMUS L.
Authors: Niwa Masatake , Terada Yukimasa , Iguchi Masanobu , Yamamura Shosuke
Published: July 2006

The absolute configuration of epi- and isoshyobunone was established as 2 and 3, respectively, on the basis of their chemical and spectral data together with base-catalyzed isomerization of shyobunone (1) affording natural isoshyobunone and the enantiomer of natural epishyobunone. In addition, conformations of the base-catalyzed isomerization products (3, 6, 8, 9, and 11) are also discussed.
ALKYLATION, ARYLATION, AND VINYLATION OF ACYL CHLORIDES BY MEANS OF ORGANOTIN COMPOUNDS IN THE PRESENCE OF CATALYTIC AMOUNTS OF TETRAKIS(TRIPHENYLPHOSPHINE)PALLADIUM(O)
Authors: Kosugi Masanori , Shimizu Yutaka , Migita Toshihiko
Published: July 2006

Alkylation, arylation, and vinylation of acyl chlorides by means of organotin compounds in the presence of catalytic amounts of tetrakis(triphenylphosphine)palladium(O) were demonstrated. The corresponding ketons were obtained in fairly good yields.
A HIGHLY ACTIVE NICKEL OXIDE CATALYST FOR ETHYLENE HYDROGENATION
Authors: Tsukada Kiyoshi , Ozaki Atsumu
Published: July 2006

A nickel oxide catalyst prepared by homogeneous precipitation with urea followed by decomposition in vacuo shows an extraordinarily high activity in ethylene hydrogenation. An evidence is given to indicate that the generation of active sites is associated with a partial reduction of oxide by the precipitant, urea, remained in the oxide.
CALORIMETRIC AND DIELECTRIC STUDIES OF PHASE TRANSITION IN TlNO2 CRYSTAL
Authors: Moriya Keiichi , Matsuo Takasuke , Suga Hiroshi , Seki Syûzô
Published: July 2006

The molar heat capacity of TlNO2 crystal has been measured between 14 and 355 K with an adiabatic calorimeter. A heat capacity anomaly due to a phase transition was found at (282.4±0.5) K. The enthalpy and entropy changes of the transition are 6400 Jmol−1 and 23.6 J K−1mol−1, respectively. The complex dielectric permittivity was measured in the frequency range between 200 Hz and 100 kHz. Dielectric dispersion and relaxation were found between 80 and 180 K. The activation enthalpy derived from the dielectric measurement is 19 kJ mol−1 and is possibly related to the reorientation of the NO2− ion.
A POSSIBLE SULFURANE: N-DIPHENYLSULFILIMINYL SULFONIUM SALT (

Remark: Graphics omitted.

)
Authors: Furukawa Naomichi , Takahashi Fujio , Akasaka Takeshi , Oae Shigeru
Published: July 2006

Sulfiliminyl sulfonium salts(IIIa,b) were prepared. NMR spectra indicate that III has a sulfurane structure.
AZIDOAZONETHINE-TETRAZOLE ISOMERISM IN TETRAZOLO[1,5-a]PERIMIDINE
Authors: Claramunt Rosa Ma , Elguero José
Published: July 2006

The equilibrium between 2-azidoperimidine and tetrazolo[1,5-a]perimidine is strongly shifted towards the latter reflecting the poor aromatic character of the perimidine ring. The title compound is the first example of a new class of condensed tetrazoles.
ENZYMATIC SYNTHESIS OF CLITIDINE
Authors: Tono-Oka Shuichi , Sasaki Akio , Shirahama Haruhisa , Matsumoto Takeshi , Kakimoto Shichiro
Published: July 2006

Clitidine (1) was synthesized by successive enzymatic cleavages of a new NAD-analogue, which was in turn prepared in a good yield from β-NAD and methyl 4-aminonicotinate utilizing the trans-glycosidation action of pig-brain NADase. The present synthesis establishes the β riboside structure of 1.
A SYNTHETIC APPROACH TOWARDS THE CLERODANE DITERPENOIDS, A VERSATILE SYNTHON
Authors: Apsimon John W , Yamasaki Kazuyuki
Published: July 2006

A potential synthetic route to the trans-clerodane diterpenes is described. Two key features involved in the synthesis are a unique acid-catalyzed Michael additioncyclization sequence developed by G. Saucy, and an opening of the cyclic hemiketal intermediate 10 by thioketalization. A known steroidal synthetic intermediate 7 prepared in a series of reactions from 4 confirmed the trans-decalin structure of our intermediates.
CATALYTIC ACTIVITY OF ALKALINE EARTH METAL OXIDES FOR ISOMERIZATION OF 1-N-PYRROLIDINO-PROP-2-ENE TO 1-N-PYRROLIDINO-PROP-1-ENE
Authors: Satoh Akiko , Tanabe Kozo , Hattori Hideshi
Published: July 2006

Isomerization of 1-N-pyrrolidino-prop-2-ene to 1-N-pyrrolidino-prop-1-ene was carried out at 40°C over alkaline earth metal oxides. MgO and CaO exhibited high activity and selectivity, while SrO and BaO degradated their activities during the reaction.
ABNORMALITY OF THE ACTIVATION ENTROPY OF THE ROTATION OF A SPIN PROBE IN A SDS MICELLE
Authors: Yoshioka Hisashi
Published: July 2006

The ESR spectra of a spin probe, 2-(14-carboxytetradecyl)-2-ethyl-4,4-dimethyl-3-Oxazolidinyloxyl (16NS), dissolved in a SDS micelle were measured at various temperatures. The rotational correlation time was analysed by the theory of absolute reaction rate. The activation entropy of the rotation of the probe in the micelle was abnormally small compared with that in water, though the activation enthalpies were nearly equal in two cases.
THE ISOLATION OF OPTICALLY ACTIVE COMPLEX OF LITHIUM CIS-DIAMMINEDICARBONATOCOBALTATE(III)
Authors: Muramoto Satoru , Shibata Muraji
Published: July 2006

From an aqueous solution of Li(±)[Co(CO3)2(NH3)2] in the presence of (−)589[Co(ox)(en)2](C2H3O2), Li(−)589[Co(CO3)2(NH3)2] has been isolated with a ca. 70% yield. The CD spectrum of the complex has been measured.
EMISSIONLESS DIFFUSE REFLECTANCE IR SPECTROSCOPY AT HIGH TEMPERATURE
Authors: Hattori Tadashi , Niwa Miki , Takahashi Mamoru , Murakami Yuichi
Published: July 2006

New diffuse reflectance spectrometer in the infrared region was made to eliminate the emission spectrum, and emissionless spectra of powder CaCO3 were measured in the temperature range from room temperature to 450°C.
SOLVOLYSIS OF BUTATRIENYL HALIDES: EVIDENCE OF AN AMBIDENT VINYL CATION
Authors: Kobayashi Shinjiro , Sonoda Takaaki , Taniguchi Hiroshi
Published: July 2006

The reactions of butatrienyl halides 4 and 5 in aqueous ethanol exclusively gave bis(benzofuranyl)acetylene 6. The first-order kinetics, the leaving group effect, kBr⁄kCl=52, and the Grunwald–Winstein’s m value of ca. 0.5 show that 4 and 5 are solvolyzed by an SN1 mechanism. The intermediate carbenium ion 7 is a new type of ambident vinyl cations.
REVERSE DI-π-METHANE REARRANGEMENT. MINOR PRODUCTS OF PHOTOLYSIS OF 3-METHYL-3-PHENYL-2(3H)-OXEPINONE
Authors: Sato Kazuhiro , Hagiwara Hisahiro , Uda Hisashi
Published: July 2006

The structures of two minor products from the sensitized photolysis of 3-methyl-3-phenyl-2(3H)-oxepinone have been confirmed to be 3-methyl-5-phenyl-2(5H)-oxepinone and 4-methyl-1-phenyl-2-oxabicyclo[3.2.0]hept-6-en-3-one, respectively. Both of them are shown to be produced, on direct photolysis, from the major photoproduct, 4-methyl-7-phenyl-2-oxabicyclo[4.1.0]hept-4-en-3-one, through the formal reverse di-π-methane rearrangement.
PREPARATION AND REACTIONS OF DIPHENYL PHOSPHITE
Authors: Yamazaki Noboru , Iguchi Tadao , Higashi Fukuji
Published: July 2006

Diphenyl phosphite was prepared by direct esterification of monophenyl phosphite with phenol by using catalysts for esterification of carboxylic acids. Triphenyl phosphite, though could not be obtained by the direct esterification, was obtained from diphenyl phosphite through disproportionation by tertiary amines.
NUCLEOPHILIC SUBSTITUTION REACTION VIA ONE ELECTRON TRANSFER PROCESSES. II A NEW SYNTHETIC METHOD FOR THE PREPARATION OF α,β-UNSATURATED ESTERS AND KETONES
Authors: Ono Noboru , Tamura Rui , Hayami Jun-ichi , Kaji Aritsune
Published: July 2006

An efficient one-pot synthesis of α,β-unsaturated esters and ketones consisting of the coupling reaction of α-chloronitroalkanes with the anions of diethyl α-alkylmalonates or ethyl α-alkylacetoacetates followed by deethoxycarbonylation and concomitant elimination of the nitro group is described.
ABSORPTION OF NITROGEN OXIDES WITH AMMONIUM SALTS
Authors: Osa Tetsuo , Fujieda Shigeaki , Abe Yasuhiko , Ohkatsu Yasukazu
Published: July 2006

Absorptions of an equimolar mixture of NO and NO2 in an aqueous solution of ammonium salts and with a cation-exchange resin substituted by ammonium ion were investigated by a flow method. Ammonium salts such as phosphate, benzoate, and oxalate were found effective for the removal of nitrogen oxides. Effects of temperature and time of contact were examined.
REACTION OF PENTACYANOCOBALTATE(II) WITH THALIUM(I) CHLORIDE
Authors: Hisamatsu Yoshiharu , Iguchi Masaakira
Published: July 2006

Hydrogen uptake of a solution containing pentacyanocobaltate(II) ions was found to be inhibited by Tl(I) ions. It was confirmed by a rapid-scan spectroscopic method that pentacyanocobaltate(II) ions react with Tl(I) ions in an aqueous solution to give the dimeric complex, [(CN)5CoTlCo(CN)5]5−. The dimeric complex containing Co-Tl-Co linkage was successfully isolated as a solid state.
A FACILE RING CONTRACTION OF WIDDROL INVOLVING PHOTOLYSIS OF THE NITRITE ESTER
Authors: Takahashi Hajime , Ito Masaaki , Suginome Hiroshi
Published: July 2006

A facile three-step ring contraction of sesquiterpene widdrol (1) is described. The steps involve the first known example of the photoreaction of a 7-membered cyclic homoallyl alcohol nitrite to afford four isomeric α,β-unsaturated oximes (3), (4), (5) and (6).
REACTION OF β-KETOSULFOXIDES WITH ALKYL GRIGNARD REAGENTS IN TETRAHYDROFURAN
Authors: Nokami Junzo , Kunieda Norio , Kinoshita Masayoshi
Published: July 2006

The reaction of (+)-(R)-α(p-tolylsulfinyl)acetophenone(1) with alkyl Grignard reagents in tetrahydrofuran is described. When 1 was treated with 2 equiv of ethylmagnesium iodide in tetrahydrofuran at 0°C, (−)-ethyl p-tolyl sulfoxide and α(ethylsulfinyl)acetophenone were obtained.
THE OXIDATION OF N,N-DIALKYLANILINES BY PALLADIUM(II) ACETATE
Authors: Sakakibara Tsutomu , Kotobuki Junko , Dogomori Yoko
Published: July 2006

The reaction of N,N-dialkylanilines with palladium(II) acetate gave N,N,N′ ,N′-tetraalkyldiaminodiphenylmethanes (II) as major products. The origin of –CH2– in II seems to be the methyl group of palladium(II) acetate and the compound II may be derived from further oxidation of N,N-dialkyltoluidine primarily formed.
THE CRYSTAL STRUCTURE OF SARABAUITE CaSb10O10S6, A NEW OXIDE SULFIDE MINERAL
Authors: Nakai Izumi , Koto Kichiro , Nagashima Kozo , Morimoto Nobuo
Published: July 2006

Sarabauite is monoclinic: a=25.33(2), b=5.655(3), c=16.88(1) Å and β=117.51(6)° and C2/c. Z=4 and ρc=4.99 g/cm3. The Sb is essentially coordinated by three atoms of oxygen and/or sulfur. SbO3 pyramids of the Sb(1), Sb(2) and Sb(3) share corners forming a slab parallel to (100). The four membered ring consisting of Sb(S,O)3 pyramids of the Sb(4) and Sb(5) links to the slab through the O(2). The Ca is coordinated by eight oxygen atoms in the slab.
t-BUTYLATION AND ISOPROPYLATION OF TOLUENE WITH t-BUTYL AND ISOPROPYL CHLORIDES CATALYZED BY CALCINED IRON SULFATE TREATED WITH HYDROGEN CHLORIDE
Authors: Hino Makoto , Arata Kazushi
Published: July 2006

The title reaction was carried out at room temperature over catalysts prepared by calcining FeSO4, Fe2O3 and Fe(OH)3 in air at various temperatures, followed by treating with HCl. The FeSO4 catalyst heat-treated at 700°C showed surprisingly high activity and selectivity, whereas other catalysts were almost inactive.
AUTOXIDATION OF 4H-5-OXAZOLONE
Authors: Tajima Kiyohiko
Published: July 2006

α-Methoxy-N-(phenylacetyl)phenylglycine methyl ester was obtained in 37% yield by the treatment of N-(phenylacetyl)phenylglycine with dicyclohexylcarbodiimide in methanol under an oxygen atmosphere. The mechanism and the generality of this oxidative alkoxylation are discussed.
THE IMPORTANCE OF GENERAL ACID CATALYSIS IN THE DIHYDRONICOTINAMIDE REDUCTION OF CARBONYL SUBSTRATES
Authors: Shinkai Seiji , Kunitake Toyoki
Published: July 2006

The reduction of hexachloroacetone by 1-benzyl-1,4-dihydronicotinamide in absolute ethanol and acetonitrile is general acid catalyzed. This mechanism is important in connection with the function of some NADH dependent enzymes in which the reaction can be aided by a general acid catalysis.
APPLICATION OF THE PFEIFFER EFFECT TO PARTIAL RESOLUTION OF TRIS(ACETYLACETONATO)COBALT(III)
Authors: Miyoshi Katsuhiko , Wada Yoshiaki , Yoneda Hayami
Published: July 2006

Partial resolution of neutral [Co(acac)3] was performed by extracting into 1,2-dichloroethane the complex formed when racemic Li[Co(acac)3] was mixed with Δ- or Λ-[Co(phen)3]Cl3 in water. This system is the first Pfeiffer-active system in which a dissymmetric metal complex serves as a chiral environment compound.
ISOLATION OF TWO NEW ENT-KAURANE CLASS DITERPENOIDS FROM PORELLA DENSIFOLIA (LIVERWORT)
Authors: Matsuo Akihiko , Uto Seiryû , Nakayama Mitsuru , Hayashi Shûichi
Published: July 2006

Two kinds of new diterpene keto-alcohols were isolated from Porella densifolia. The structures including absolute configurations were elucidated to be ent-18-hydroxykauren-15-one(I) and (16R)-ent-18-hydroxykauran-15-one(II) in combination of chemical reaction and spectroscopic analysis.
EVIDENCE FOR A BOND RUPTURE MECHANISM IN TRANS-TO-CIS ISOMERIZATION OF [CrCl2bn2]Cl·HCl·2H2O IN SOLID-PHASE
Authors: Tsuchiya Ryokichi , Yoshikuni Tadatsugu , Nakagawa Shigeo , Uehara Akira , Kyuno Eishin
Published: July 2006

The trans-to-cis isomerization of [CrCl2bn2]Cl·HCl·2H2O (bn = d,l-2,3-diaminobutane) was investigated in the solid-phase. A bond rupture mechanism was proposed for the isomerization from the fact that the trans-complex (green) is converted into cis-[CrCl2bn2]Cl (violet) via the intermediate [CrCl3bn2] (bluish violet) in which one of d,l-2,3-di:aminobutanes is coordinated as unidentate toward chromium(III) ion.
SYNTHESIS OF α,β-UNSATURATED ALDEHYDES BY MEANS OF 3-METHOXY-1-PHENYLTHIO-1-PROPENE
Authors: Wada Makoto , Nakamura Hideo , Taguchi Takeo , Takei Hisashi
Published: July 2006

3-Methoxy-1-phenylthio-1-propene (3), obtained by the reaction of 1-phenylthio-2,3-epoxypropane (1) with sodium hydride in tetrahydrofuran (THF) and successive treatment with methyl iodide, was lithiated with lithium diisopropylamide at −78°C. The lithio derivative reacted with alkyl halides regioselectively at the α-position of sulfur atom, and hydrolysis of the products at room temperature in the presence of mercuric chloride afforded the corresponding α,β-unsaturated aldehydes in good yields.
ORGANO-MODIFIED CARBON ELECTRODES. I. STUDIES OF MODIFIED LAYER VIA AMIDE BONDS BY CAPACITANCE MEASUREMENTS AND ESCA
Authors: Fujihira Masamichi , Tamura Akiko , Osa Tetsuo
Published: July 2006

The electrochemical characteristics of chemically modified glassy carbon electrodes via amide bonds have been correlated with the results of surface analysis by X-ray photoelectron spectroscopy (ESCA). The double layer capacitance measurements were proved to be useful to determine the extent of surface modification as well as ESCA analysis.
REACTION OF trans-Mo(N2)2(Ph2PCH2CH2PPh2)2 WITH HYDROAROMATIC COMPOUNDS, ALCOHOLS, AND METHYL FORMATE; THE FORMATION OF CARBONYL AND HYDRIDE COMPLEXES OF MOLYBDENUM
Authors: Tatsumi Takashi , Tominaga Hiroo , Hidai Masanobu , Uchida Yasuzo
Published: July 2006

Reaction of trans-Mo(N2)2(DPE)2(DPE=Ph2PCH2CH2PPh2) with tetrahydrofuran, MeOH, EtOH, and HCOOMe gives the molybdenum carbonyls, trans-Mo(CO)(N2)(DPE)2 and cis-Mo(CO)2(DPE)2; in the case of tetrahydrofuran the hydride MoH4(DPE)2 is also formed. The hydride is selectively obtained from pyrrolidine, indoline, and 2-propanol.
A REACTION OF SELENONIUM YLIDES WITH EPISULFIDES
Authors: Tamagaki Seizo , Tamura Katsuyuki , Kozuka Seizi
Published: July 2006

Dialkylselenonium cyano(methoxycarbonyl)methylides reacted catalytically in CHCl3 at room temperature with aliphatic episulfides to give mainly the reduced selenides and dicyanofumarate.
FORMATION OF THE BILAYER MEMBRANE FROM A SERIES OF QUATERNARY AMMONIUM SALTS
Authors: Kunitake Toyoki , Okahata Yoshio , Tamaki Kiyoshi , Kumamaru Fumiko , Takayanagi Motowo
Published: July 2006

A series of dimethylammonium salts having two long alkyl groups were shown by electron microscopy to form in water lamellar and vesicle structures which are composed of the bilayer structure similar to that of biomembranes.
COMPELLED AZEPINE RING FORMATION IN THERMAL RING EXPANSION OF 2H-AZIRINE
Authors: Isomura Kazuaki , Taguchi Hiroshi , Tanaka Tatsuyoshi , Taniguchi Hiroshi
Published: July 2006

Thermolyses of three β-(benzofuran-2-yl)vinyl azides, 1a, 1b, and 1c, in which the benzofuran ring bears a hydrogen, a methyl, and a phenyl group at the 3-position, gave a benzofuropyrrole 2, a benzofuropyridine 3, and a benzofurobenzazepine 4, respectively. Photolyses of these azides gave the corresponding 2H-azirines, 7a, 7b and 7c, which on heating afforded the same heterocyclic compounds as the products of the thermolyses of the vinyl azides.
NEW SYNTHETIC REACTIONS BASED ON 1-METHYL-2-FLUOROPYRIDINIUM SALTS. STEREOSPECIFIC PREPARATION OF THIOALCOHOLS FROM ALCOHOLS
Authors: Hojo Ko , Yoshino Hiroshi , Mukaiyama Teruaki
Published: July 2006

Treatment of various alcohols with 1-methyl-2-fluoropyridinium salt and sodium N,N-dimethyldithiocarbamate afforded alkykl N,N-dimethyldithiocarbamates of inverted configuration. The latter compounds were converted to thioalcohols with retention.
SPIN-LABELED METACHROMATIC DYES. III. INTERACTION OF SPIN-LABELED PROFLAVINE WITH NATIVE AND HEAT-DENATURED DNA
Authors: Yamaoka Kiwamu , Noji Sumihare
Published: July 2006

The binding of spin-labeled Proflavine to native and denatured DNA was evidenced by the line broadening and anisotropic pattern in ESR and by the absorption changes and extrinsic Cotton effects in optical spectra. The tilt angle and rotational diffusion constants of the bound spin-label were obtained by the simulation of ESR spectra.
THE VIBRATIONAL SPECTRA OF α, β, AND γ-PICOLINES ADSORBED ON AEROSIL SILICA
Authors: Hirokawa Takeshi , Ohno Keiichi , Kimura Tomoyuki , Murata Hiromu
Published: July 2006

The vibrational spectra of α, β, and γ-picolines adsorbed on aerosil silica were measured in the regions of 2800–4000 cm−1, 1300–1650 cm−1, and 950–1100 cm−1. At high coverage, two kinds of the surface species were found, which were assignable to the liquid-like species and the hydrogen-bonded species persisting at low coverage.
BIOSYNTHETIC STUDIES OF ALOENIN. THE INTERMEDIATE AND THE BIOSYNTHETIC SEQUENCE INVOLVED IN THE BIOSYNTHESIS
Authors: Hirata Toshifumi , Koshitani Osamu , Suga Takayuki
Published: July 2006

Incorporation of the labels from 3H/14C-labeled 4-methoxy-6-(2′,4′-dihydroxy-6′-methyl)phenyl-2-pyrone (II) and 3,5-dioxo-5-(2′-o-glucopyranosyl-4′-hydroxy-6′-methyl)phenylpentanoic acid (III) into aloenin (I) in the Aloe plants demonstrated that the biosynthetic intermediate of aloenin is the pyrone (II) and not the diketo acid (III), and the formation of the aglycone (II) by cyclization of a biological polyketide (IV) and creation of the methoxyl group through methylation is followed by glucosylation which results in the formation of aloenin.
PREPARATION OF ESTERS AND AMIDES USING HEXAFLUORO-1,2-EPOXYPROPANE-TRIETHYLAMINE SYSTEM
Authors: Ishikawa Nobuo , Sasaki Shigekuni
Published: July 2006

Hexafluoro-1,2-epoxypropane-triethylamine system was found to be a useful condensing agent for the preparation of esters, thioesters, and amides.
VIBRATIONAL STRUCTURE OF THE LIGAND FIELD ABSORPTION BAND OF SOME Co (III) COMPLEXES
Authors: Fukuda Kunimasa , Urushiyama Akio
Published: July 2006

The vibrational structures of the ligand field absorption bands of the Co (III) complexes, [Co(NH3)6]3+, [CoF(NH3)5]2+, [CoCl(NH3)5]2+, trans-[CoCl2(NH3)4]+, and trans-[CoBr2(NH3)4]+were studied at 4.2 K. It was found that the vibrational structures observed in the present studies consist of the uniquantal progressions of the totally symmetric CoN stretching vibrations of the complexes.
SOLVENT EFFECTS ON NMR SPECTRA OF 8-HYDROXYQUINOLINE DILUTION COEFFICIENTS
Authors: Katayama Seizi , Akahori Yukio
Published: July 2006

The dilution coefficients (Δδ/Δc)solv. are introduced from the dilution shifts of PMR spectra of 8-hydroxyquinoline in various solvents, and correlations between these values are examined. There are good correlations between the dilution coefficients of every pair of H-2, H-3, H-4, H-6, H-7, but not between the dilution coefficients of H-5 and the other protons.
ARYLAZO GROUP EXCHANGE IN THE REACTION OF 5-ARYLAZOTROPOLONES WITH ARYLDIAZONIUM SALTS
Authors: Ide Tsutomu , Imafuku Kimiaki , Matsumura Hisashi
Published: July 2006

5-Phenylazo-, 5-(p-tolylazo)-, and 5-(p-methoxyphenylazo)tropolones reacted with aryldiazonium salts to give products which derived from arylazo group exchange at the C-5 position of the tropolone ring.
REACTIONS OF NAD+-MODEL COMPOUNDS WITH BASE. THE REVISED STRUCTURE OF DITTMER’S TRIMER
Authors: Ohnishi Yutaka , Minato Hiroshi , Okuma Kentaro , Kobayashi Michio
Published: July 2006

The structure of the cyclic trimer obtained by the reaction of N-benzylnicotinamide cation with base was established. A plausible mechanism involves the removal of the amide hydrogen with base, the attack of the amide anion at C-4 of another pyridinium ion, and the formation of a 12-membered ring.
A NEW EVIDENCE FOR ACID-CATALYTIC ACTION OF SINGLET EXCITED 2-NAPHTHOL ON THE GROUND STATE REACTION
Authors: Hisaoka Motoyuki , Tokumaru Katsumi
Published: July 2006

A new evidence to demonstrate acid-catalytic action of excited 2-naphthol on the ground state reaction is presented for the production of acetals from irradiation of alkanals in alcohols in the presence of 2-naphthol.
STEREOCHEMISTRY OF THE HYDROGENATION OF 5α- AND 5β-CHOLESTAN-3-ONES OVER PLATINUM METALS. AN UNUSUAL ASPECT WITH PALLADIUM AND PLATINUM
Authors: Nishimura Shigeo , Ishige Masayoshi , Shiota Michio
Published: July 2006

Hydrogenation of 5α-cholestan-3-one with palladium gives an equatorial 3β-o1 while hydrogenation of 5β-cholestan-3-one under the same condition affords an axial 3β-o1 with high stereoselectivities in alcohols and tetrahydrofuran. This unusual hydrogenation stereochemistry is also seen with platinum in alcohols, but not with platinum in tetrahydrofuran nor with ruthenium, osmium and iridium in t-butyl alcohol. With rhodium in ethanol, the both ketones afford the axial alcohols in high selectivities.
REACTION OF POTASSIUM SUPEROXIDE WITH PHENOXY RADICALS. ON THE MECHANISM OF BASE-CATALYZED OXYGENATION OF PHENOLS
Authors: Nishinaga Akira , Shimizu Tadashi , Matsuura Teruo
Published: July 2006

Superoxide ion (O2−) hes been found not to couple with 2,6-di-tert-butylphenoxy radicals but to reduce the radicals giving rise to the corresponding phenolates. Molecular oxygen attacks predominantly the para position of the phenoxy radicals and the regioselectivity is not affected by the nature of the reaction medium. A new mechanism involving an ionic process for the base-catalyzed oxygenation of 2,6-di-tert-butylphenols is proposed.
DECARBOXYLATION REACTION VI. REACTION OF α-ALKYLIDENEMALONONITRILES WITH TRICHLOROACETIC ACID. A NEW 1,1-DICHLOROCYCLOPROPANE FORMATION THROUGH β-TRICHLOROMETHYLATION
Authors: Nanjo Katsumi , Suzuki Kunio , Sekiya Minoru
Published: July 2006

It has been found that highly electron-deficient carbon-carbon double bond conjugated, in the main, with two cyano groups undergoes 1,1-dichlorocyclopropane formation by reacting with trichloroacetic acid. This reaction is presumed not to involve dichlorocarbene, but trichloromethylated intermediate.
THE ISOLATION AND STRUCTURE OF C19-OBTUSILACTONE DIMER
Authors: Niwa Masatake , Iguchi Masanobu , Yamamura Shosuke
Published: July 2006

C19-Obtusilactone dimer, a cytotoxic substance, has been isolated from Lindera obtusiloba Blume, and its structure also been elucidated on the basis of its spectral data coupled with chemical evidence.
A NEW METHOD FOR THE SYNTHESIS OF 3-DEOXY SUGARS BY GRIGNARD REACTIONS WITH METHYL 5,6-O-CYCLOHEXYLIDENE-3-O-MESYL-α- AND -β-d-ALLOFURANOSIDE
Authors: Kawana Masajiro , Emoto Sakae
Published: July 2006

The 3-deoxy sugars were easily prepared in good yield by the reaction of t-butylmagnesium bromide with the title compounds. The same reaction with 1-O-benzoyl- or -mesyl-cis-cyciododecane-1,2-diol gave cyclododecanone.
DYE-SENSITIZED PHOTOOXIDATION OF SPIROCYCLIC VINYLCYCLOPROPANES IN THE PRESENCE OF SODIUM AZIDE
Authors: Hatsui Toshihide , Takeshita Hitoshi
Published: July 2006

The effects of azide ion in the sensitized photooxygenation of spirocyclic vinylcyclopropanes, suitable substrates for stereochemical analysis of the mechanism, were investigated. Two types of products, azidoalcohols and an epoxide, obtained were different from the genuin products of singlet oxygen oxidation : The formers were shown to be formed by an initial attack of azide radical non-selectively to the both double bonds, and the latter, being formed by no skeletal rearrangement, was shown to be oxygenated at the norbornene moiety.
PYROLYSIS OF 1,2-ETHANEDITHIOL: MICROWAVE SPECTROSCOPIC DETECTION OF VINYL MERCAPTAN, CH2=CHSH
Authors: Tanimoto Mitsutoshi , Saito Shuji
Published: July 2006

Vinyl mercaptan was identified in the thermal decomposition (600–950°C) products of 1,2-ethanedithiol and thiirane. A microwave spectroscopic study of CH2=CHSH and CH2=CHSD showed that the molecule is planar with the total dipole moment of 0.896±0.007 D and has the syn-form.
THE REACTION OF POLYNITROHALOBENZENES WITH CARBOXYLIC ACIDS. USE OF 2-FLUORO-1,3,5-TRINITROBENZENE (FTNB) AS A NEW CONDENSING REAGENT
Authors: Kotake Hiroshi , Inomata Katsuhiko , Kinoshita Hideki , Tanabe Kumiko , Miyano Osamu
Published: July 2006

The reaction of polynitrohalobenzenes with carboxylic acids in the presence of a base was examined, and it was found that 2-fluoro-1,3,5-trinitrobenzene (FTNB) was the most reactive polynitrohalobenzene. Various carboxanilides were prepared under mild conditions in excellent yields using FTNB as a new condensing reagent.
PREPARATION AND CHARACTERIZATION OF OXO(2,3,17,18-TETRAMETHYL-7,8,12,13-TETRAETHYLCORROLATO)MOLYBDENUM(V)
Authors: Murakami Yukito , Matsuda Yoshihisa , Yamada Sunao
Published: July 2006

Oxo(2,3,17,18-tetramethyl-7,8,12,13-tetraethylcorrolato)molybdenum(V) was prepared from the corresponding corrole by the reaction with either molybdenum pentachloride or molybdenum hexacarbonyl. Spin Hamiltonian parameters were evaluated as g = 1.967, AMo=41.8×10−4 cm−1, and AN=2.3×10−4 cm−1. The results from ESR and ESCA measurements indicate that the molybdenum complex has a compressed tetragonal structure of N4O-coordination.
A CONVENIENT METHOD FOR THE PREPARATION OF ISOCYANIDES
Authors: Echigo Yoshiaki , Watanabe Yutaka , Mukaiyama Teruaki
Published: July 2006

Treatment of formamides with 2-chloro-3-ethylbenzoxazolium tetrafluoroborate affords various isocyanides in good yields at room temperature in neutral media.
STEREOSELECTIVITY IN ION-PAIR FORMATION. II. THE ADDITIVITY OF INDUCED CIRCULAR DICHROISMS OF Λ-[Co(en)3]3+ BY THE ROTATIONAL ISOMERS OF l-MALATE ANION
Authors: Taura Toshiaki , Yoneda Hayami
Published: July 2006

The changes in the CD spectrum of Λ-[Co(en)3]3+ have been observed upon the addition of some dicarboxylate anions (maleate, l-malate, and fumarate). The results demonstrated the additivity of circular dichroisms induced by the gauche and trans rotational isomers of the l-malate anion.
SYNTHESIS OF dl-MUSCONE
Authors: Nokami Junzo , Kusumoto Yoshihisa , Jinnai Kiyoharu , Kawada Mikio
Published: July 2006

dl-Muscone was prepared in a good yield by cyclization of β-keto ω-halo sulfoxide (3), followed by thermolysis and methylation.
DIAZO-COUPLING REACTION OF 5-METHYLTROPOLONE. THE FORMATION OF 3,7-DIARYLAZOTROPOLONES
Authors: Ide Tsutomu , Imafuku Kimiaki , Matsumura Hisashi
Published: July 2006

5-Methyltropolone reacted with aryldiazonium salts to give either 3-arylazo-5-methyltropolones or 3,7-diarylazo-5-methyltropolones according to the electrophilicity of the attacking species.
STUDY ON RACEMIZATION IN OXIDATION-REDUCTION CONDENSATION BY THE COUPLING REACTION FOR THE FORMATION OF BOC-LEU-ILE-ASP(NH2)-LEU-OBUt
Authors: Matsueda Rei , Takahagi Hidekuni , Mukaiyama Teruaki
Published: July 2006

Racemization in the oxidation-reduction condensation was studied by the coupling reaction for the formation of Boc-Leu-Ile-Asp(NH2)-Leu-OBut , recently reported for the detection of racemization in the azide, dicyclohexylcarbodiimide +1-hydroxybenzotriazole methods, etc. The coupling reaction using triphenylphosphine and 2,2′-dithiodipyridine-1,1′-dioxide gave favorable results to the present racemization test on solid support as well as in solution synthesis.
THE STRUCTURE OF EPILUBIMIN, A STRESS METABOLITE FROM DISEASED POTATO TUBERS
Authors: Katsui Nobukatsu , Yagihashi Fujio , Matsunaga Akira , Orito Kazuhiko , Murai Akio , Masamune Tadashi
Published: July 2006

The structure of epilubimin, a stress metabolite isolated from diseased potato tubers, was determined as shown in formula 1 on the basis of the chemical and spectral data.
TETRABRIDGED FERROCENOPHANES AND A PRECURSOR OF PERFERROCENOPHANE
Authors: Hisatome Masao , Watanabe Naoyuki , Yamakawa Koji
Published: July 2006

[4] [4] [4] [3] Ferrocenophanes (5a and 5b) , tetrabridged ferrocenophanes, have been synthesized via lactic acid derivatives of [4] [4] [3] ferrocenophanes. A precursor of perferrocenophane, 5-(3-carboxypropyl)[4] [4] [4] [3] ferrocenophane (7), has been derived from 5a.
SYNTHESIS OF CLADINOSE ANALOGUES OF CARBOMYCIN B
Authors: Tatsuta Kuniaki , Tanaka Akihiro , Kinoshita Mitsuhiro , Umezawa Sumio
Published: July 2006

Cladinose analogues (2 and 8) of carbomycin B have been synthesized by regio- and stereoselective introduction of cladinose instead of mycarose into the ethylene acetal (3) of demycarosylcarbomycin B. Their antimicrobial activities are also presented.
OXIDATION OF NITROALKYLBENZENE WITH ELECTRO-GENERATED SUPEROXIDE ION
Authors: Sagae Hiromitsu , Fujihira Masamichi , Osa Tetsuo , Lund Henning
Published: July 2006

THe oxidation of nitroalkylbenzene with electro-generated superoxide ion was studied by cyclic voltammetry and controlled potential macro-electrolysis. The electrochemical reduction of oxygen in the presence of nitrotoluenes (o- and p-) and p-nitroethylbenzene yielded under mild conditions the corresponding nitrobenzoic acids from the former and p-nitroacetophenone plus 1-(p-nitrophenyl)ethanol from the latter.
ISOLATION OF TWO DIASTEREOMERS OF DICHLORO{2-(S)-[(n-BUTYLPHENYLPHOSPHINO)METHYL]PYRROLIDINE}PALLADIUM(II)
Authors: Kinoshita Isamu , Kashiwabara Kazuo , Fujita Junnosuke
Published: July 2006

A pair of new diastereomers, the isomerism of which came from a pair of chiral phosphorus atoms were obtained for [PdCl2L], where L denotes 2-(S)-[(n-butylphenylphosphino)methyl]pyrrolidine prepared from (S)-proline. The absolute configurations of these isomers were suggested on the basis of the PMR spectra.
SELECTIVE ALKYLATION AND DESELENENYLATION OF CYANOMETHYL PHENYL SELENIDE IN AQUEOUS MEDIUM, AND AN APPLICATION TO 1-CYANOCYCLOPROPENE SYNTHESIS
Authors: Masuyama Yoshiro , Ueno Yoshio , Okawara Makoto
Published: July 2006

The alkylation followed by the deselenenylation of cyanomethyl phenyl selenide (1) gave α,β-unsaturated nitriles. The method was applied to generate 1-cyanocyclopropene, which was trapped using anthracene.
PHOTO-LIGAND-SUBSTITUTION REACTION OF TRIS(ETHYLENEDIAMINE) COBALT(III) ION WITH N-BIS(2-HYDROXYETHYL)DITHIOCARBAMATE ION
Authors: Nakashima Michio , Kida Sigeo
Published: July 2006

Tris(ethylenediamine)cobalt(III) ion underwent a ligand substitution with N-bis(2-hydroxyethyl)dithiocarbamate ion(=L−) to form [CoL3] in aqueous solution, when the light (460–585nm) was irradiated. The quantum yield (0.343–0.845) of the reaction is unusually high compared to those of the photo-ligand-substitution reactions of cobalt(III) complexes so far known.
CONFORMATIONAL EQUILIBRIA OF 8-HALOGENO-8,9,10,11-TETRAHYDRO-7H-CYCLOOCTA(de)NAPHTHALEN-9-ONES
Authors: Kamada Toshihiro , Yamamoto Osamu
Published: July 2006

The titled α-haloketones (1–3) were prepared and the conformations were studied based on the NMR spectra. It was found that 1–3 exist as an equlibrium mixture of axial-boat (ab) and equatorial-boat (eb) conformers in solution with the ab overwhelmingly predominant (−ΔG°(101°C)=−1.6 kcal/mol). The conformation ab is in a puckered form in all of 1–3 as a result of steric compression effect.
STEREOSELECTIVE PUMMERER REARRANGEMENT OF PHENYLSULFINYLCYCLOPROPANES WITH ACETIC ANHYDRIDE
Authors: Masuda Toshiaki , Numata Tatsuo , Furukawa Naomichi , Oae Shigeru
Published: July 2006

The Pummerer reaction of cis- and trans-2-phenyl-1-(phenylsulfinyl)cyclopropanes and cis, syn- and cis, anti-2,3-dimethyl-1-(phenylsulfinyl)cyclopropanes afforded the stereoselective products.
AZAFULVENES 7. CYCLOADDITION REACTION OF 8-AZAHEPTAFULVENE TO KETENE
Authors: Yamamoto Kikuo , Kajigaeshi Shoji , Kanemasa Shuji
Published: July 2006

8-alkyl- and 8-aryl-8-azaheptafulvenes reacted with diphenyl-and biphenyleneketene affording the corresponding [8+2] cycloadducts in good yields. Similarly the reactions with phenylketene gave only trans [8+2] cycloadducts.
PHOTOCHEMISTRY OF 2-PHENYLATED CYCLOHEPTA-3,5-DIENONES
Authors: Ushiyama Hidehiko , Hagiwara Hisahiro , Sato Kazuhiro , Uda Hisashi
Published: July 2006

Acetone sensitized photolysis of 2-phenyl- and 2-methyl-2-phenylcyclohepta-3,5-dienones gives in about equal yield 2-substituted bicyclo[3.2.0]hept-6-en-3-ones and 6-substituted cyclohepta-2,4-dienones as the major products, while on direct irradiation both dienones undergo mainly decarbonylation to produce unstable trienes.
ORTHO-METHYLATION OF 2,3-XYLIDINE OVEP SOLID CATALYSTS
Authors: Matsumoto Tadashi
Published: July 2006

The methylation of 2,3-xylidine with methanol was carried out over various solid catalysts. Silver-alumina showed 70% selectivity in the methylation at the ortho-position. The activity and the selectivity of catalysts were briefly discussed in view of the acidic and basic properties of the catalysts.
A NOVEL ETHYNYLATION OF α-SUBSTITUTED MESITYL OXIDES
Authors: Fujita Yoshiji , Wada Fumio , Onishi Takashi , Nishida Takashi
Published: July 2006

The ethynylation of ketone (2) in liquid ammonia at −33°C with stoichiometric sodium acetylide afforded the corresponding alcohol (3 and 4). Similar treatment of 1 resulted in only a little isomerization to 2. Favorskii ethynylation under pressure at 0°C yielded a mixture of 1, 2, 3 and 4 without any detectable 5, whichever ketone 1 or 2 being used.
STEREOSELECTIVE TOTAL SYNTHESES OF (±)-RECIFEIOLIDE AND (R)-(+)-RICINELAIDIC ACID LACTONE
Authors: Narasaka Koichi , Yamaguchi Masahiko , Mukaiyama Teruaki
Published: July 2006

The naturally occurring macrolide, (±)-recifeiolide, was synthesized stereoselectively. (E)-11-Hydroxy-8-dodecenoic acid (5) was obtained stereoselectively from 11-hydroxy-8-dodecynoic acid by the reduction with lithium, and the acid (5) was cyclized to (±)-recifeiolide in excellent yield via its 6-phenyl-2-pyridyl ester. Similarly, (R)-(+)-ricinelaidic acid was lactonized to afford the corresponding lactone in high yield.
COPPER-CATALYZED OXIDATIVE COUPLING OF DIPHENYLMETHANIMINE PROMOTED BY BICYCLOAMIDINES
Authors: Hayashi Hiromu , Tanaka Toshikazu , Shigemoto Naoya , Okazaki Tatsuya
Published: July 2006

Benzophenone azine was obtained in a high yield by copper-catalyzed oxidative coupling of diphenylmethanimine in the presence of bicycloamidines, 1,8-diazabicyclo[5.4.0]undecene-7(DBU) or 1,5-diazabicyclo[4.3.0]nonene-5(DBN) in tetrahydrofuran or 1,4-dioxane as a solvent.
THE COBALT–BISDEHYDROCORRIN COMPLEX AS A VITAMIN B12 MODEL
Authors: Murakami Yukito , Aoyama Yasuhiro , Nakanishi Shigenori
Published: July 2006

The (AD-bisdehydrocorrinato)dicyanocobalt(III) complex [Co(III)(CN)2(BDHC)] was reduced with sodium borohydride to give the corresponding cobalt(I) complex, which underwent alkylation with an alkyl bromide or iodide at the axial position. The second-order rate constants for reactions of Co(I)(BDHC) with alkyl halides in aqueous THF at 25.0±0.1°C reveal that an extra steric effect, which is not expected for the cobalt corrinoid, is exerted by the 1,3-diaxial-type interaction between angular methyl groups placed at C1 and C19 of BDHC and an alkyl groups bound to the nuclear cobalt. The present complex bears a resemblance to the cobalt corrinoid in various aspects.
TOTAL SYNTHESIS OF 14-FLUOROPROSTAGLANDIN F2α AND 14-FLUOROPROSTACYCLIN
Authors: Grieco Paul A , Yokoyama Yuusaku , Nicolaou Kyriacos C , Barnette William E , Smith J Brian , Ogletree Martin , Lefer Alan M
Published: July 2006

The synthesis of (±)-14-fluoroPGF2α methyl ester (1), (±)-15-epi-14-fluoroPGF2α methyl ester (12), and (±)-14-fluoroprostacyclin (2) is detailed. Prostaglandins 1 and 12 have been evaluated for pregnancy interruption in the hamster and smooth muscle stimulating effects on gerbil colon and hamster uterine strips. Prostacyclin 2 was evaluated for inhibition of human blood platelet aggregation and dilation of the isolated perfused cat coronary artery.
A SYNTHESIS OF 1,3-DIKETONES BY ELIMINATION OF SELENIUM FROM Se-ACYLMETHYL SELENOCARBOXYLATES
Authors: Ishihara Hideharu , Hirabayashi Yoshio
Published: July 2006

Se–Acylmethyl selenocarboxylates, prepared by a reaction of potassium selenocarboxylates with α-bromoketones, readily extruded elemental selenium by a treatment with potassium tert-pentoxide to form 1,3-diketones in good yields.