A series of nickel(II) complexes containing N-glycosides derived from the reaction of saccharides and polyamines have been prepared and characterized; the amine ligands act as anchors for the accumulation of sugar molecules on metal complexes. The real existence of the C-N bond in the N-glycoside ligand on cobalt (III) complexes was unambiguously proven by the application of the isotopic multiplets in the ¹³C-NMR spectra. The structures of the sugar units were analyzed by means of the semiempirical AM 1 calculations coupled with the conversion of the vicinal ¹H-¹H spin-spin coupling constants in the ¹H-NMR spectra into torsion angles of the corresponding H-C-C-H fragments. Aldoses are rapidly epimerized at C-2 by the cooperative effects of nickel(II) ion and N-alkylated diamines, involving a stereospecific 1, 2-carbon shift, and nickel(II) ions form complexes with only the mannosetype epimers stereoselectively. In the light of the results of NMR and EXAFS studies as well as electronic absorption and circular dichroism spetral data, we proposed a possible mechanism for the epimerization of _D-Glc to _D-Man with the nickel(II) -N, N, N', N' -tetramethylethylendiamine system in which the C-2 epimerization proceeds via a mononuclear nickel(II) intermediate complexes, where the carbinolamine-like adduct of aldose with diamine in an open-chain form is epimerized at C-2 by a stereospecific rearrangement of the carbon skeleton involving a cyclic transition state. The newly discovered sugar transformation reaction using nickel(II) -N-alkylated diamine system has been applied to the synthesis of the (1-6)-linked disaccharides having the mannose reducing terminal from their C-2 reducing terminal epimers which are abundant in nature. Aldoses are also epimerized at C-2 by combinations of certain metal ions (Co²⁺, Ca²⁺, Sr²⁺, and Pr²⁺) and N-alkylated diamines. In the system of Ca²⁺ and monoamine a novel C-2 epimerization of aldoses proceeds via the stereospecific rearrangement of the carbon skeleton and ketose forms without 1, 2-carbon shift.

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Phenol was formed photoelectrochemically when ZnO semiconductor powders suspended in mixed solution of benzene and water were irradiated by UV light. Rate of the phenol formation depended on the concentration of dissolved oxygen. Quantum efficiency for phenol formation was 7% when 1 the dissolved oxygen was saturated. Phenol formation was also observed in ZnO photoanodic reaction. The quantum efficiency was 64% under oxygensaturated conditions. The reaction mechanism was discussed.

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The adsorption of surface-active reagents on activated carbons has been studied in order to clarify the effects of surface oxide of activated carbon on the adsorption of surface-active reagents.
Poly(oxyethylene)nonylphenyl ether (PO), octadecyltrimethylammonium chloride (OT) and sodium dodecylbenzenesulfonate (DB) were used after purification as nonionic, cationic and anionic surface-active reagents, respectively. Activated carbons with different amounts of acidic and basic surface oxides were prepared by evacuating an original activated carbon, having 1.34 meclig of acidic surface oxide, at various temperatures.
The surface oxides of activated carbon exhibited no effect on the adsorption of PO (Fig.2). The adsorption by the van der Waals force was dominant in the adsorption of PO. The increase in adsorption of OT due to the dissociation of strong acidic surface oxide was found above pH 4 (Fig.4). Therefore, the electrostatic force between dissociated strong acidic surface oxide and OT cation contributes to the adsorption of OT as well as the van der Waals force. The agreement between the amount of strong acidic surface oxides (Table 2) and the increase in the amount of adsorption of OT (Fig.5) reveals that each strong acidic surface oxide captures one OT molecule at nearly neutral pH. In the case of DB, the presence of acidic surface oxides suppressed the adsorption of DB by electrostatic repulsion (Fig.6).
The activated carbon outgassecl at high temperature adsorbed an additional amount of DB in an acidic region (Fig.7). This increase in the amount of adsorption seems to be due to the interaction between basic surface oxide and DB anion.

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The dealumination from the framework of zeolite-Y during the protonation was studied by using a high-resolution solid-state MAS (Magic-Angle Spinning) NMR spectroscopy. In addition, the acidic properties were investigated. During the process from the Na-type to the NH₄-type, no remarkable changes were observed in the microenvironments of the framework, i. e., the distribution of the Si(nAl) configuration and the Al-O coordination states. When the NH₄-type was calcined in air at 550°C, the dealumination from the framework appreciably occurred. The dealumination results from the change of four-coordinated aluminum Al(tet) to six-coordinated aluminum Al(oct) and from the decrease in the concentration of Si(2 Al) and Si(3 Al) configuration.
The dealumination was contro lled by the atmosphere of calcination. It was inhibited in the calcination in vacuo, that is, in the low partial pressure of water. It was also. inhibited by the exchange from the NH₄-type to the type of the rare earth elements (La). There was no appreciable difference in the ratio of Al(tet) to Al(oct) between the H(vac)-type and La-type. However, the content of Brφnsted acid was larger than Lewis acid in the La-type. Therefore, the electronic influence by the presence of La³⁺ ion to the aluminum microenvironments is considered. Not only the La-exchange inhibit the dealumination, but also it may change the acidic properties.
The amount of the acid sites was related to the total amount of aluminum including dealuminated species from the framework. But no good correlation was found between the amount of acid and the Al/Si atomic ratio of the framework.

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The effects of platinum doping of praseodymium oxide on its catalytic activity have been examined. X-ray diffraction analysis showed that the doped platinum was incorporated into the lattice of praseodymium oxide. The catalytic activity of the oxide for CO oxidation was highly enhanced by platinum doping, and the activity maximum appeared at 0.2% Pt. Temperature-programmed desorption analyses revealed that the platinum doping depressed both absorption and desorption of the lattice oxygen in the oxide catalyst, while it enhanced the activity for reduction of the lattice oxygen by CO. These two effects must result in the appearance of the activity maximum. Since the, product of CO oxidation, CO₂, was incorporated into praseodymium oxide below 330°C and the catalytic activity was depressed, by CO₂, the reaction temperature should be kept higher than 330°C.

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The titration curves for thallium( I ) ion with halide ions(X^-) in 1, 3-dimethyl-2imidazolidinone (DMI) were found to have well-defined equivalent points at C_X^-/C_Tl⁺ =1(mole ratio). Precipitates of thallium( I ) halide (T1X) appeared in the range of 15 to 30°C soon after the halide ions were added in DMI. Redissolution of TlX was not observed in the presence of an excess of X^-. Based on the Gibbs energies (ΔG⁰) calculated from the solubility products of TlX in DMI, the stability of TlX was found to decrease in the order of TlCl>TlBr>TlI for X^-, as in propylene carbonate (PC) and N, N-dimethylformamide (DMF). This order was reversed in water. The order of the stability of TlX in PC, DMI and DMF was PC>DMI>DMF.
The differencesin the stability of TlX for X^- in transfer from water to DMI depended on the Gibbse nergies (ΔG⁰_tr) of X^- in transfer from water to DMI. On the other hand, the differences in the stability of TlX for three nonaqueous solvents depended on the Gibbs energies (ΔG⁰_tr) of Tl⁺ in transfer from water to these solvents.
From the ΔG⁰_tr values of T⁺ the donor number of DMI was assumed to be betweent hose of PC and DMF.
The donor number of DMI was estimated to be 20-23 by measurements of the half-wave potentials for polarographicr eduction of several uni- and bivalent metal ions referred to tetraphenylarsoniumion. By comparing the donor number of DMI with those of DMF and PC, the order of PC>DMI>DMF for the stability of TlX in three solvents was reasonably interpreted.

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The effect of inorganic salts on the color of tetra4romophenolphthalein ethyl ester anion (TBPE anion) has been studied using a photometric technique. The color of a 13 μM aqueous solution of TBPE anion changed to red violet from blue violet at pH 6.80 by addition of inorganic salts. The order of the effect on the absorbance change at 590 nm was NaClO₄<LiCl<KCl, and NaCl<NH₄Cl<MgCl₂_??_CaCl₂. The TBPE anion concentration depen dency of the spectrum in 2.44M CaCl₂ suggests the association of TBPE anion. The temperature dependency of the spectrum in 3.9M NaCl supported this idea. The spectrum change of TBPE anion induced by the addition of protamine was quite similar to those observed by the addition of inorganic salts. It is concluded that the color change of TBPE anion by inorganic salts is not caused by salting-out but by metachromasy.

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Methane is a major component of natural gas and obtainable all over the world. Methane is utilized as an energy source, but the chemical usefulness is not extensiye due to its low reactivity.
In the present study, the conversion of methane to a more valuable substance has been tried by the photochemical reaction. The photolysis of the gas mixture of CH₄, NH₃, and H₂O with a low-pressure mercury lamp (185nm light) gave methylamine, ethylenediamine, methanol, ethane, and hydrogen gas as the major products, In the first step of the reaction, methane is activated by hydrogen abstraction by the hydroxyl radicals which are formed by the photolysis of water vapor. Ammonia also splits into ⋅NH₂ and ⋅H by the absorption of the light of 185 nm. The formation of CH₃NH₂, CH₃OH, and C₂H₆, is ascribed to the mutual couplings of ⋅CH₃, ⋅NH₂, and ⋅OH. The activation energy for the formation of methylamine was estimated to be 4.4±0.4 kcal⋅mol^-1. The study by spin-trap-ESR method revealed that ⋅CH₂NH₂ was formed as a reaction intermediate in the photolysis of CH₄-NH₃-H₂O mixtures. It was therefore concluded that NH₂C₂H₄NH₂ is formed by the coupling reaction of ⋅CH₂NH₂.

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Amines were converted into isothiocyanates [1] at room temperature by an efficient and simple method via ammonium dithiocarbamates [2], which are readily obtained from carbon disufide and amines, using triphenylphosphine (TPP)-carbon tetrachloride [3]. Two procedures, a one-pot method and a two-step method including the isolation of [2] were examined. The aliphatic isothiocyanates were obtained in 70-90% yields by the former method, and aromatic isothiocyanates were in 50-80% yields by the latter method. The reaction was accelerated in polar solvents such as acetonitrile to give [1] in high yields. The yield of [1] was increased with increasing the concentration of the substrate, and also the molar ratio (TPP/CCl₄), but decreased with raising reaction temperature. One the basis of these data, the reaction mechanism was discussed in detail.

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Ethylene glycol was produced. directly from ethylene, oxygen (air), and water by means of so-called Hoechst-Wacker type redox system which comprises thallium chloride and iron or copper chloride in aqueous solUtion.
In the one-step process in which ethylene and air were reacted simultaneously with aqueous solution of the metal salts, a stationary state was reached and the concentration of products was increased with the reaction time. The yield of both ethylene glycol (EG) and its precursor 2-chloroethanol (ECH) was 80-90% in the reaction where iron chloride -Was a cocatalyst. The reaction rate was dependent upon the concentration of thallium( I ) (in case of unsaturation), the concentration of chloride ion (for concentration less than 4-6 mol/l), and the partial pressure of ethylene and oxygen.
The space-time yield of EG and EG+ECH were 0.5-1.0 mol/l⋅h and 1.0-1.5 mol/l⋅h respectively, under suitable reaction conditions.
The two-step process in which eth ylene and air were reacted separately and alternately with aqueous solution of the metal salts, was also examined.

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Oxidation of 3, 3'-methyienebis (guaiazulene)[1A₁] with peraceticacid in hexane at 25°C for 1h gave one major product : Namely, oxidation product of the nucleus, 5-isopropyl-3, 8-dimethyl-1- [(3-guaiazulenyl)methyl] -4(3aH)-azulenone [1B] (40.0% isolated yield). As minor products (0.5-7.5% isolated yield), twelve kinds of compounds were separated : benzofulvene [1A₂], 3, 3'-biguaiazulene [1A₃], 3-formylguaiazulene [1H], azulenylbenzofulvenes ([1A₄], [1A₅]), isomer of [1B] ([1D]), azulenylinclenols ([1F₁], [1F₂], [1G₁]), oxidationp roduct of [1B] ([G₂]), and other oxidation products with skeltal rearrangements ([1C1], [1C₂]) ; struuctures of these products were established on the basis of the spectroscopic (UV, MS, IR, and NMR) data. Possible reaction pathways are suggested for the formation of the thirteen kinds of products.

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It was found that the quinoline derivatives are formed by the reaction of benz[ c ]isoxazoles (anthranils) with enamines. For example, 2, 3-dihydro-1 H-cyclopenta[ b ]quinoline was obtained by the reaction of anthranil with 4-(1-cyclopentenyl)morpholine (70% yield). The reaction may proceed via a quinoline N-oxide, which was formed from the [4+2]cycloadduct of anthranil with the enamine. In fact, quinoline N-oxides were occasionally isolated.
In the presence of a low valence titanium salt (prepared from titanium(IV) chloride and zinc dust), the reaction proceeded smoothly under mild conditions, and 1, 2, 3, 4-tetrahydroacridine was easily synthesized from anthranil and 1-(1-cyclohexenyl)pyrrolidine (yield : 78%).

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The rearrangement of potassium 1- and 2-naphthoates was investigated in the presence of cadmium oxide under the pressure of carbon dioxide. The disproportionation of 1-naphthoate took place after it melted at 400°C. Various naphthalenecarboxylates were initially produced, and as the reaction proceeded the amounts of these carboxylates decreased rapidly, and simultaneously those of 2-naphthoate and 2, 6-naphthalenedicarkoxylate increased. When the reaction was carried out at a lower temperature around 400°C, the rearrangement virtually stopped to produce the 2-naphthoate.
Potassium 2-naphthoate was hardly fusible and thus less reactive. Even at 480°C for 3h, about 20mol% of 2-naphthoate remained unreacted. The poor fusibility of 2-naphthoate was much improved by addition of 1-naphthoate, and the rearrangement reaction proceeded very smoothly. This observation suggests, that the modified fusibility of the starting material is required for the rearrangement to take place.
A possible reaction mechanism for the rearrangement reactions is proposed.

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Network polymers which have highly ordered and dense crosslinkages are expected to be a new material with good mechanical properties. In order to obtain these polymers, a N, N'-dipropargylfumaramide dimer (FADD) was prepared to form an ordered and dense crosslinkage in the solid state, and their molding under hydrostatic pressure was studied.
( 1 ) This diacetylene compou nd has two functional groups, a diacetylene moiety and a terminal ethynyl group. These unsaturated groups are highly reactive toward thermally induced solid state reaction. IR spectra show that the two-step reaction composed of the polymerization of the diacetylene moieties and the reaction of the ethynyl groups occures in the solid state. Consequently crosslinking in this compound seems to occur through the two step reaction. The X-ray scattering pattern of the obtained polymer indicates that the crystalline structure is highly disordered. However, the solid-state reaction under high pressure (650 MPa) yields rather ordered and dense network polymers.
( 2 ) The powder compression molding of the com pound was investigated. The properties of moldings highly depend on the applied pressure and the molding temperature. These moldings are isotropic and have excellent properties, such as Young's modulus, ultrasonic velosity, thermal conductivity. The maximum value of Young's moduli reached 15.5 GPa. The thermal conductivities of the moldings are about two or three times larger than those of commodity polymers.

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Photoelectric properties of evaporated gallium phthalocyanine thin films under vacuum and dry atmosphere were investigated with a sandwich-typed cell configuration of SnO₂/GaClPc/Ag. The photoinduced current spectrum ; induced current with step steady state incident light without an applied voltage and rectification properties under the dark state were discussed.
When the cell was illuminated through the NESA electrode, the photoinduced current spectra agreed approximately with the absorption spectrum of the GaClPc. These results indicate that a potential barrier is formed in the PN heterojunction at SnO₂/GaClPc interface. Excellent rectification characteristics were observed under the dry atmosphere. In the vacuum, however, these characteristics were missed with passage of time. A series of these phenomena was reversible under the vacuum and the dry atmosphere. The energy band structure of the cell is estimated from these experimental results.

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The green Cu^₂+-PVA complex has been characterized mainly by thermal analyses and magnetic susceptibility measurements, together with isolated Cu(OH)₂ as a reference compound. An endothermic reaction due probably to dehydration of Cu(OH)₂ to CuO was found to occur at 160°C, and the complex 'showed a subnormal effective magnetic moment like the isolated polynuclear olated compound of Cu(OH)₂. These and other related observations present further evidence in support of our previous conclusion that the complex is a PVA complex of Cu(OH)₂. Cu(OH)₂ in the complex is probably in the form of amorphous ultrafine particles.

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10, 20-Dioxadinaphtho [1, 2-a : 1', 2'-j] perylene [1c] and 10, 20-dioxadinaphtho [2, 1-a : 2', 1'-j] perylene [1d] were synthesized by cyclization of 1, 5-bis (1- or 2-naphthyloxy) anthraquinones, which were prepared from 1, 5-dichloroanthraquinone and 2-naphthol (or 1-naphthol). The electronic absorption spectrum of [1c] or [1d] showed some resemblance to that of benzo [1, 2, 3-kl : 4, 5, 6-k'l'] dixanthene [1a] except for a considerable red shift (-30 nm). The photooxidation of the above red compounds [Ic] - [1d] at 541 nm gave colorless endoperoxides [2c] - [2d]. Photooxidati, on of [1c], which is the most sterically hindered derivative, proceeded about 2 times faster than that of [1a] or [1d]. The photochemical and thermal properties of [2c] - [2d] were also investigated.

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The adsorption of hydrazine formed in a nitrogen-hydrogen plasma prepared using radiofrequency discharge on sodium ion-exchanged zeolite (NaZ) or hydrogen ion-exchanged zeolite (HZ) was, studied. Although the adsorbed amount of hydrazine was two orders of magnitude less than that of ammonia, a hundred times larger amounts of hydrazine could be adsorbed on HZ than on NaZ (Table 1). Larger amounts of acidic sites on HZ would contribute to an increment of the amount of hydrazine adsorbed.

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Hematite was formed when mixtures of Bizen-clay and potassium chloride were heated to temperatures between 600°C and 1100°C. Clay minerals in Bizen-clay reacted with potassium chloride to liberate iron in the form of hematite. Above 1200°C, however, no hematite was detected within the glassy phase. When the glassy phase was cooled down slowly, hematite reappeared. This reappearing hematite could be responsible for Hidasuki, the red surface coloration characteristic of Bizen-yaki.

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It was found that amines added to the N-cyano group on cyanoguanidines in the presence of FeCl₃ or ZnCl₂ under mild conditions. For example, the reaction of cyanoguanidine [2a] with butylamine, proceeded at room temperature in the presence of FeCl₃ to give butylbiguanide [1a] in 99% yield. Similarly, [2a] or N-cyano-N'-phenylguanidine [2b] reacted with diethylamine, benzylamine, hexadecylamine, octadecylamine and aniline at room temperature or under reflux in dioxane or tetrahydrofuran to give the corresponding biguanides [1].
In the presence of ZnCl₂, [2] and two equivalents of amines were heated in refluxing dioxane. The initial products, biguanides [1]-ZnCl₂ complexes, were readily hydrolyzed by aqueous ammonia or amines to give hydropchlorides of [1].
When N-substituted-N'-cyano-S-methylisothioureas [3] reacted with primary amines in the presence of FeCl₃ or ZnCl₂ the addition to the cyano group and the substitution of the methylthio group with amines occurred at the same time to yield the corresponding [1].

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Partial oxidation of ethane was performed at moderate temperature using N₂O as a source of O(¹D) produced by ArF excimer laser irradiation. Investigated in more details was the effect of ArF excimer laser irradiation for attaining selective and high quantum yield of alcohols. In the absence of oxygen, shown in Table 1, the product selectivities for propane and butane which were presumed to be formed by the recombination of methyl and ethyl radicals, were very high. In the presence of oxygen, however, the selectivity for oxygencontaining compounds, such as alcohols, ethers and aldehydes, was increased. The chain lengthw asa lso l ongert han that in the absence of oxygen, indicating that a chainr eaction was significantly enhanced by oxygen molecules.

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9-(Acyloxy)anthracenes were synthesized by the reactions of anthrone (9(10 H)-anthracenone) with acyl chlorides.
Treatment of these substances with various metal halides in benzene under reflux gave the corresponding 10-acylanthrones and anthrone.

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The reaction of alkylbenzenes with benzenesulfonyl chloride in the presence of aluminum chloride was studied kinetically in nitrobenzene.
The rate constants k₃ were in good agreement with Hammett-type linear free energy relationships, that is, Yukawa-Tsuno equation (log f=ρ(σ+γΔσ_R+), ρ=-4.8, γ=0.6).
Differences in activation energies and activation entropies at the o- and p-positions and the m- and p-positions were -0.27 kcal/mol, -2.1 e.u./mol and 1.2, -1.4 for toluene, -1.2, -2.1 and 0.48, -2.3 for ethylbenzene, -1.9, -9.9 and 0.53, -1.9 for isopropylbenzene and and -, - and 0.1, -3.0 for t-butylbenzene, respectively.

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Radical polymerizations of styrene were carried out in the presence of poor solvents for polystyrene at 60°C. The 40 vol% addition of 2-propanol caused the solution turbid and precipitation of polystyrene, but no turbidity was observed below the 30 vol% addition. For both hexane and cyclohexane addition, turbidity and precipitate were not observed below the 50 vol%. Kinetic orders of the monomer in hexane, cyclohexane and 2-propanol were 1.6, 1.4 and 1.3, respectively. Kinetic orders of the initiator in these poor solvents were 0.5. The values of k_t/k_p² were derived from the slopes of 1/P_a vs R_p (rate of polymerization)plots. For the homogeneous solution systems k_t/k_p² was proportional to the reciprocal of the viscosity of the system. But at the 2-propanol concentration above 40 vol% the plots deviated from the relation to indicate the increase of termination rates.

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