bluuebunny/crossref_metadata_2025_split huggingface dataset:
The Acylation of bz-Hydroxy- and bz-Methoxy-2,3-dimethylbenzofurans and the Synthesis of Furobenzopyranone Derivatives
Authors: Kawase Yoshiyuki , Yamagughi Seiji , Oki Nobuo , Okumura Fumiko 
Published: July 2006

Abstract
The action of acetic acid, phenylacetic acid, or β-phenylpropionic acid and polyphosphoric acid on 5-, 7-, and 6-hydroxy-2,3-dimethylbenzofurans afforded 6-acyl-5-hydroxy-, 6-acyl-7-hydroxy-, and 5-acyl-6-hydroxybenzofurans, some of which were also obtained by the Friedel-Crafts acylation of the corresponding methoxybenzofurans. The hydroxyketones thus obtained were converted to dimethylfuro derivatives of 4-hydroxycoumarins and isoflavones, and 3-benzyl-4-hydroxyfurocoumarins were also prepared by the thermal condensation of the hydroxybenzofurans and diethyl benzylmalonate.
Tetraaminoethylenes. I. The Preparation and Some Reactions of Tetrapiperidino- and Tetramorpholinoethylene
Authors: Tsuge Otohiko , Yanagi Kiyoshi , Horie Masako 
Published: July 2006

Abstract
The preparation of new tetraaminoethylenes was attempted by the reaction of chlorotrifluoroethylene (CTFE) with several amines. It has been found that CTFE reacted with piperidine and morpholine to give tetrapiperidino- (TPE) and tetramorpholinoethylene (TME) in moderate yields respectively, although no tetraaminoethylenes were formed in the reactions with diethylamine, pyrrolidine, aniline, N-alkylaniline, and diphenylamine. Also, it has been made clear that the compounds whose structures were previously assigned to the tetraaminoethylenes, obtained from 1,1-dimethoxytrimethylamine or ethyl orthoformate and secondary amines are the corresponding triaminomethanes. It has been found that TPE and TME reacted with halogens, halogen-, nitrocompounds, and aromatic carboxylic acids to form mainly the corresponding oxamidinium salts.
Optical Activity of Bis-1,1′-spiroindanes. II. Absolute Configuration of Optically Active 5,5′- and 6,6′-Disubstituted-bis-1,1′-spiroindanes and Their Circular Dichroism Spectra
Authors: Hagishita Sanji , Kuriyama Kaoru , Shingu Keiji , Nakagawa Masazumi 
Published: July 2006

Abstract
An unequivocal determination of the absolute configuration of 5,5′- and 6,6′-disubstituted bis-1,1′-spiroindane and the behavior of the CD spectra of some 5,5′-disubstituted ones are described.
Synthesis of Poly Substituted cis-Hydrindanes
Authors: Yamamoto Kagetoshi , Sohda Takashi , Kawasaki Ichiro , Kaneko Takeo 
Published: July 2006

Abstract
cis-4-Carboxy-5-isopropyl-8-methylhydrindane-1,6-dione was synthesized from cis-1-hydroxy-8-methylhydrindanone-5 as a useful intermediate for the synthesis of picrotoxin and dendrobine.
Electronic Spectra of Square-Planar Bis(tertiary phosphine)dialkynyl Complexes of Nickel(II), Palladium(II), and Platinum(II)
Authors: Masai Haruo , Sonogashira Kenkichi , Hagihara Nobue 
Published: July 2006

Abstract
Electronic spectra of trans-[L2M(C≡CR)2], (L=tertiary phosphine or tertiary stibine, and M=Ni, Pd or Pt) have been studied in solution from 220 mμ to 360 mμ. Nickel and platinum complexes showed three intense absorption bands. The lowest energy band was particularly sensitive to substituents of alkynyl groups. This band was assigned empirically to the transition between the molecular orbitals involved in metal-alkynyl bonds. The possibility of π-interaction between the two alkynyl groups through central metal was discussed in relation to the influence of R.
Electron-transfer Phenomena in Some Three-dimensional Complex Thiocyanate Semiconductors
Authors: Hashimoto Masao , Kawai Shichio , Kiriyama Ryôiti 
Published: July 2006

Abstract
Measurements of the electrical conductivity, the photoconductivity, the electronic spectra, and the magnetic susceptibility were carried out with powder samples of CuHg(SCN)4 and (CuxZn1−x)Hg(SCN)4. The electrical conductivity (σ) of the compounds has been found to obey the usual exponential equation of electrical conduction, σ=σ0exp(−Et⁄KT). It was found that there was a close relation between the photocurrent spectra and the electron-transfer bands in both compounds. In terms of the band model, the nature of the semiconductivity and the photocurrent in their intrinsic region are discussed in connection with the electron-transfer phenomena.
Elimination Reaction on Solid Acid Catalysts. IV. A δR LFER Study of the Esterification of Alcohols with Carboxylic Acids over Solid Acid Catalysts
Authors: Mochida Isao , Anju Yasuhide , Kato Akio , Seiyama Tetsuro 
Published: July 2006

Abstract
The esterification between eight alcohols and seven carboxylic acids was studied over sodium-poisoned silicaalumina at 250°, using a microcatalytic gas chromatographic technique, in order to elucidate the mechanism of the esterification on a solid acid catalyst on the basis of a LFER (Linear Free-Energy Relationships) approach. Alcohols showed fairly close reactivities for the esterification with acetic acid, whereas, for the olefin formation by intramolecular dehydration and ethylether formation with ethanol, their reactivity varied very much according to the kind of alcohol. In contrast, the reactivities of carboxylic acids for the esterification varied with the structure and were correlated with Es, Newman’s steric-effect parameter, as was observed in the homogeneous acid catalysis, although the reactivity difference under the present conditions was small indeed. It is probably due to the elevated reaction temperature. No ethylacetate, but only thiolacetate, was found in the reaction of acetic acid with ethanethiol. From these facts, it may be concluded that the esterification over a solid acid catalyst may proceed through the attack of an oxonium ion from a carboxylic acid on an adsorbed alcohol, in the manner similar to that in the homogeneous acid-catalyzed esterification.
Rearrangement and Decomposition of Phosphoranyl Peroxides Produced in situ from Alkylidenephosphoranes and t-Alkylperoxy Anions
Authors: Yamada Koh-ichi , Akiba Kin-ya , Inamoto Naoki 
Published: July 2006

Abstract
The reactions of alkylidenephosphoranes(I), produced in situ from the corresponding phosphonium salts and sodium ethoxide, with sodium salt of t-butyl hydroperoxide (II) were carried out in absolute ethanol. Carbanion (III) of phosphoranyl peroxide, formed by the reaction of I with II, underwent a rearrangement to produce t-butyl phenyl ether, alkyl t-butyl ether, and two kinds of phosphine oxides. Phosphoranyl peroxide (IV), formed by abstraction of proton from ethanol, decomposed in homolytic fashion to yield t-butyl alcohol and hydroxyphosphorane (V) as an intermediate, the decomposition of which gave benzene, hydrocarbon and corresponding phosphine oxides. Homolytic decomposition of IV was supported by the reaction of tetraphenylphosphonium bromide with II. The contribution of III was confirmed by the effect of base concentration on the amounts of rearrangement products. The reaction with cumylperoxy anion gave similar results. The mechanisms of these reactions were discussed.
Cyclopropenones. IV. The Reactions of Diphenylcyclopropenone with Water, Carboxylic Acid, Phenol, and Amide
Authors: Toda Fumio , Kataoka Toshiaki , Akagi Katsuhiko 
Published: July 2006

Abstract
The pyrolysis of diphenylcyclopropenone monohydrate (II) at 150°C afforded α-phenyl-trans-cinnamic anhydride (VI). It was proved that the reaction consists of two main steps, the nucleophilic attack of water on I to yield α-phenyl-trans-cinnamic acid (IV), and the reaction of I with IV, thus finally yielding VI. The same type of reaction as that of I with IV was also observed when I was heated in phenol to afford phenyl α-phenyl-trans-cinnamate (XII). The reaction of I with the weak nucleophilic reagent, α-phenyl-trans-cinnamamide (XIV), afforded a monoimino derivative of VI (XVI), which is believed to be produced by the nucleophilic attack of the amide-oxygen of XIV on the carbonyl-carbon of I.
The Preparation of Geometrical Isomers of β-Nitrostyrene and Their Addition Reactions with Ethanol
Authors: Yamamura Kimiaki , Watarai Setsuo , Kinugasa Toshio 
Published: July 2006

Abstract
The preparation of the geometrical isomers of ethyl α-nitrocinnamate and α-nitrochalcone is described. Ethyl (E)-α-nitrocinnamate and (Z)-α-nitrochalcone were obtained by the thermal- or photoisomerization of the corresponding geometrical isomers, which were themselves produced predominantly through the Knoevenagel reaction. The facile addition of ethanol to the double bonds of β,β-dinitrostyrene, ethyl α-nitrocinnamates, and α-nitrochalcones without any catalyst at room temperature is also described.
The Preparation of Amino-s-triazines with Amino- or Nitrophenyl Groups
Authors: Yuki Yasuo , Kakurai Toshio , Noguchi Tatsuya 
Published: July 2006

Abstract
Amino-s-triazines with nitro groups were prepared by the reaction of biguanide derivatives with appropriate carboxylic acid derivatives (acyl chloride, anhydride, or ester) or by reaction between dicyanodiamide derivatives and nitrile. Amino-s-triazines with aminophenyl groups were prepared by the reduction of the corresponding nitro-compounds. Acylamino-s-triazines have been found to be formed when an excess of acyl chloride or anhydride is used.
Syntheses and Thermal Isomerizations of Bicyclo[3.2.2]nona-2,6,8-triene and Its Benzo Analog
Authors: Tsuji Teruji , Ishitobi Hiroyuki , Tanida Hiroshi 
Published: July 2006

Abstract
A convenient synthesis of bicyclo[3.2.2]nona-2,6,8-triene (1) was devised starting from the cycloheptatrienemaleic anhydride adduct. Benzo[f]bicyclo[3.2.2]nona-2,6,8-triene (2) was prepared starting from benzo[f] bicyclo[3.2.2]nona-3,6,8-trien-2-one. Heating 1 in n-hexane at 160–180°C gave almost quantitatively 3-vinyl-cycloheptatriene (9) besides a trace of 7-vinylcycloheptatriene (10). It was found however that 10 undergoes thermal isomerization into 9 under milder conditions. The result from 1 is thus rationalized by the existence of an equilibrium between 1 and 10 preceding the conversion of 10 into 9. On the other hand, benzo analog 2 does not isomerize in a similar manner and instead, is transformed by heating at 270–290°C into benzobarbaralane (14) and hydrobenzindene (15). The contrast in behavior is discussed.
The Reactions of β-Ketosulfonium Salts with Sulfenamide Derivatives
Authors: Mukaiyama Teruaki , Hosoi Kazuo , Inokuma Shun , Kumamoto Takanobu 
Published: July 2006

Abstract
2-Phenylthio-2-(dimethylsulfuranylidene)acetophenone was obtained in good yield by the reaction of dimethylphenacylsulfonium bromide with N,N-diethylbenzenesulfenamide. The reaction of dimethyl-α-methylphenacylsulfonium bromide with N,N-diethylbenzenesulfenamide gave α-phenylthioacrylophenone in good yield. The reactions of α-phenylthioacrylophenone thus obtained with various active methylene compounds were investigated.
Synthesis and Properties of Two Annelated Annulenes
Authors: Endo Katsusuke , Sakata Yoshiteru , Misumi Soichi 
Published: July 2006

Abstract
Two annelated tridehydrof[18]annulenes, trinaphtho[1,9,8,7-abc: 1′,9′,8′,7′-ghi:1″,9″,8″,7″-mno]- and tribenzo[a,g,m]-5,11,17-tridehydro[18]annulenes (VI and VII), were synthesized by the Castro reaction of cuprous salts of 1-ethynyl-7-iodonaphthalene (IX) and 4-[o-iodophenyl]-3-buten-1-yne (XIV), respectively. The UV spectra of these annelated annulenes revealed an extended delocalization of π-electrons around the inner eighteen membered ring. However, from the chemical shifts of the inner protons (HA and HB) it is concluded that both VI and VII are non-aromatic compounds.
Decomposition of m-Nitrobenzenesulf onyl Peroxide in Several Solvents
Authors: Yokoyama Yasukazu , Wada Hiroko , Kobayashi Michio , Minato Hiroshi 
Published: July 2006

Abstract
Rates of decomposition of m-nitrobenzenesulfonyl peroxide in chloroform, nitrobenzene, chlorobenzene, and benzene were determined, and activation parameters were calculated. Products of decomposition in nitrobenzene were m-nitrophenyl m-nitrobenzenesulfonate and m-nitrobenzenesulfonic acid, whereas those in chloroform were m-nitrobenzenesulfonic acid, hexachloroethane, and phosgene (when air is present). Activation parameters and reaction products indicate that the reaction in chloroform involves homolytic cleavage of the O–O bond, whereas that in nitrobenzene involves electrophilic attack of the peroxide on aromatic nuclei. When sulfonyl-18O labeled m-nitrobenzenesulfonyl peroxide was decomposed in benzene, about 35–36% of the label was found in the phenolic oxygen of m-nitrophenyl m-nitrobenzenesulfonate. This finding could be accounted for by a mechanism which involves a loose π-complex prior to the formation of a σ-complex.
Phenylazo p-Tolyl Sulfone as a Source of Phenyl Radical
Authors: Kobayashi Michio , Minato Hiroshi , Kojima Minoru , Kamigata Nobumasa 
Published: July 2006

Abstract
Mechanism of the decomposition of phenylazo p-tolyl sulfone(I) was investigated. Orientations and partial rate factors of substituted biphenyls produced by the decomposition of I in benzene-substituted benzene mixtures were used as the criteria for judging the nature of the decomposition. When CaO- or MgO-suspension was present, autocatalytic heterolysis of I was suppressed to some extent, but for complete suppression 20–40 w/v % CaO or MgO was necessary. Pyridine and quinoline were found to be effective for suppression of the autocatalysis. When sufficient amount of pyridine, quinoline, MgO or CaO were present, orientations and partial rate factors for phenylation of substituted benzene were similar to those obtained by phenyl radical produced by benzoyl peroxide on N-nitrosoacetanilide. The rate of decomposition of I was determined in PhC2H5, PhOCH3, PhCl, PhNO2, pyridine and DMF in the presence of pyridine. An isokinetic relationship was found to hold for activation parameters for the decomposition in these solvents, and the isokinetic temperature was 88.6°C. Values of activation enthalpy and entropy were rather large; ΔH\eweq=39.6 kcal/mol and ΔS\eweq=34.4 e.u./mol in DMF.
Photoconduction of Polystyrylpyrimidines
Authors: Hirohashi Ryo , Hishiki Yasushi , Haruta Masahiro 
Published: July 2006

Abstract
Eight polystyrylpyrimidines were synthesized from p-xylylpyrimidine with p-phenylene diisothiocyanate (DIT), terephthaloylchloride (TPC), p-xylylenedibromide (XDB), p-phenylenediamine (PDA), 4,4′-diaminodiphenyl (BD), 4,4’-diamino diphenylsulfone (DPS), hexamethylene diamine (HMD), and 4,4′-diaminodiphenylmethane (DPM). These polymer films have a fairly large photoconductive character; using a surface-type photoconductive cell, the logarithmic relation of the photo-current (Ip) to the applied potential was found to be linear. Further, it was found that the slopes (n) obtained from the logarithmic relation (Ip=kLn) of the photo-current to the light intensity (L) have values from 1.0 to 2.4. The peaks of the spectral response of the photo-current of the eight samples exit around 500–600 mμ and/or near the ultraviolet wavelength region. The photoconduction of these polymers was enhanced by the bridging groups attached to xylylpyrimidine; the enhancement is in the following order;
(Remark: Graphics omitted.)
The Preparation of Fukinane, A New Skeletal Sesquiterpene Hydrocarbon
Authors: Naya Keizo , Kobayashi Masakazu 
Published: July 2006

Abstract
A novel skeletal sesquiterpenic hydrocarbon, fukinane (I), has been prepared by conversion from an eremophilane type, fukinone (VIII), via fukinan-8-ol (IX). A rearrangement of the fukinane skeleton into an eremophilane type through fukinan-8-ol tosylate (X) has been studied.
The Measurement of Reaction Rates under Pressure by using a Manganin Pressure Gauge
Authors: Moriyoshi Takashi 
Published: July 2006

Abstract
An apparatus capable of following reaction rates under pressure without sampling has been designed and constructed. The pressure change due to the progress of a reaction in a closed system could be accurately measured to about 0.08 atm by means of a “fixed bridge” combined with a manganin pressure gauge, in which the unbalanced e.m.f. generated at a constant bridge current was potentiometrically determined to 0.1 μV. The rates of the acid-catalyzed inversion of sucrose and the base-catalyzed decomposition of diacetone alcohol, with the expansion in volume and the contraction respectively, were measured in order to verify the applicability of this apparatus. The agreement between the results obtained by this method and those obtained by the analytical method was satisfactory. From these results, it has been confirmed that the method is sufficiently applicable to the measurement of reaction rates under pressure.
Stochastic Formulation of Entropy Production due to Second-Order Reaction
Authors: Ishida Kenji 
Published: July 2006

Abstract
Entropy production, originated from an ideal gas second-order reaction taking place in a closed system, has been stochastically formulated by defining the entropy in a form similar to the conditional entropy used in the theory of information. The entropy is introduced in the natural way as a result of the partial factorization of joint probability for reaction states devised for the approximate solution of the stochastic process of the second-order reaction. The entropy production has also been discussed in comparison with the usual one.
The Reactions of Mobile Electrons in the Frozen Solution of Ethylene Glycol-Water at 77°K
Authors: Sasaki Teikichi , Ohno Shin-ichi 
Published: July 2006

Abstract
The yield of trapped electrons produced in ethylene glycol-water glass at 77°K increased linearly with the gamma dose up to 1.5×1020 eV/g, and the G value was estimated to be 2.8±0.2. The relative reaction rates of mobile electrons with various inorganic ions at 77°K were determined by competition kinetics. The observed relative reaction rates with simple inorganic ions corresponded to those of hydrated electrons obtained at room temperature. For complex ions, however, the reactivities of the mobile electrons were larger than those of hydrated electrons. The reaction products, such as bromine dioxide, Cr(V) species, and the pentacyano Co(II) ion, all of which are unstable at room temperature, could be detected by optical and ESR spectroscopies at 77°K.
The Electronic Character of the π-Allylic Group of π-Allylic Palladium Complexes
Authors: Takahashi Yasutaka , Akahori Hiroyuki , Sakai Shizuyoshi , Ishii Yoshio 
Published: July 2006

Abstract
The substituent constants of the 2- and 1-positions of the π-allylic group of acetylacetonato (a) and cyclopentadienyl (b) derivatives of π-[2-(p-substituted phenyl)allyl]-(I) and π-(p-substituted cinnamyl)-palladium complexes(II) were estimated from their NMR spectra. The differences in the chemical shift (Δν, Hz) between the p-phenylene ring protons H1 and H2 of the complexes was found to be dependent upon the ligand and the substituent X. The plot of Δν against the substituent constant σp+, of X gave a fairly good linear relationship, and from the intercept of the straight line at Δν=0, the substituent constants of the 1-and 2-positions of the π-allylic group in the IIa or IIb complex and the Ia or Ib complex were estimated: σp: at the 1-position, 0.27 (IIa) or 0.24 (IIb), and at the 2-position, 0.21 (Ia) or 0.03 (Ib).
A Convenient Method for the Preparation of Primary Amines by the Use of Bisbenzenesulfenimide and Bis-p-chlorophenylsulfenimide
Authors: Mukaiyama Teruaki , Taguchi Takeo , Nishi Mineo 
Published: July 2006

Abstract
A convenient method for the preparation of primary amines by the use of bisarylsulfenimide has been established. Primary amines were obtained in good yields under mild reaction conditions by treating N-substituted bisarylsulfenimides with hydrochloric acid or mercaptan. The N-substituted bisarylsulfenimides were prepared in good yields by the reactions of lithium bisarylsulfenimide with alkyl halides or alkyl p-toluenesulfonates or by the addition reactions of bisarylsulfenimide to olefinic compounds.
Aminocyclitols. XXVII. Preparation of Deoxyinosamines from vibo-Quercitol
Authors: Suami Tetsuo , Ogawa Seiichiro , Yabe Kenji , Uchida Masaru 
Published: July 2006

Abstract
On bromination with acetyl bromide and acetic anhydride at 130°C, vibo-quercitol (1) gave tetraacetyl 1-bromo-1-deoxy-scyllo-quercitol (2) in 23% yield. Treatment of 2 with sodium azide in an appropriate solvent afforded three azido compounds, from which, by hydrogenation, corresponding three deoxyinosamines were obtained: 1-deoxy-scyllo-2, 5-deoxy-chiro-1 and 1-deoxy-myo-2-inosamine. The latter two are new compounds and their structures were established by their proton magnetic resonance (PMR) spectra and the reaction sequences.
Selective p-Toluenesulfonylation of myo-Inositol Derivatives
Authors: Suami Tetsuo , Ogawa Seiichiro , Oki Shuichi 
Published: July 2006

Abstract
Attempt to know the reactivities, toward sulfonylation, of the hydroxyl groups in myo-inositol was carried out using partially sulfonylated derivatives of myo-inositol. The present studies indicated that the order of reactivity of the hydroxyl groups is 1-OH and 3-OH&gt;4-OH and 6-OH&gt;5-OH&gt;2-OH. From a preparative standpoint, 1,3–di-O-p-toluenesulfonyl-myo-inositol was readily obtained in 59% yield from 1-O-p-toluenesulfonyl-myo-inositol by a selective sulfonylation.
Stereochemical Studies of Monoterpene Compounds. XII. The Acid-Catalyzed Rearrangements of 2α-Bromo-10β-pinan-3-one
Authors: Hirata Toshifumi , Suga Takayuki 
Published: July 2006

Abstract
In connection with the bromination of 3-acetoxy-pin-2-ene (II), the acid-catalyzed rearrangement of 2α-bromo-10β-pinan-3-one (I) was investigated under several conditions. The bromoketone (I) was thus found to yield (+)-6-endo-bromocamphor (III), (−)-α-carvone (V), (−)-8-hydroxycarvotanacetone (VI), carvacrol (VII), (+)-dihydro-β-campholenolactone (VIII), and (+)-campholenic acid (IX). It also became clear that the bromocamphor (III) and the (V), (VI), and (VII) products are directly formed from the bromoketone (I), whereas the γ-lactone (VIII) is obtained via α-campholenic acid (IX) from the bromocamphor (III). The mechanistic implications of the rearrangements are discussed.
Studies of N-Sulfinyl Compounds. VI. The Preparation of N-Sulfinylbenzamide and Its Reaction with Styrene Oxide
Authors: Tsuge Otohiko , Mataka Shuntaro 
Published: July 2006

Abstract
The reaction of benzamide with thionyl chloride in the presence of pyridine gave N-sulfinylbenzamide and N,N′-dibenzoylsulfurdiimide. It has been found that N-sulfinylbenzamide reacted with styrene oxide in the presence of tetraethylammonium bromide to give 4-oxo-5-benzoyl-2,6-diphenyl-1,4,3,5-oxathiadiazepine as the main product, accompanied by lesser quantities of two N-benzoyl-phenylaminoethanols, 2,5-diphenyloxazoline, benzonitrile, and benzamide. The pathways for the formation of the products are suggested.
Reaction of Methanol with Accelerated Rare Gas Ions
Authors: Kotoyori Takashi , Takahasi Makoto , Ichinose Akira 
Published: July 2006

Abstract
Reaction of methanol with accelerated rare gas ions was studied. The yields of the reaction products, H2, CO, CH4, HCHO, and ethylene glycol, were determined, varying the initial kinetic energy of ion (2–6 kV), ionic species, (Ar, Xe, and Kr), and pressure of methanol ((2–14)×10−3 Torr). No appreciable effect on the product yields was observed by adding carbon tetrachloride as electron scavenger or propylene as radical scavenger. The product yields are found to be linear against In Ei, (Ei is initial kinetic energy of ions). Although the detailed reaction mechanism is left for future investigation, the reaction seems to be interpreted in terms of billiard model, momentum of ion being transferred directly to a local part of the target molecule at the contact time.