The ultrasonic velocity in chlorobenzene and nitrobenzene was measured by a pulse technique of fixed-path type at a frequency of 1MHz. Measurements were carried out at 10 to 60 C (283.15-333.15K) under pressures up to 2100 bar (=105Pa), with an estimated accuracy better than 0.20%
The ultrasonic velocities in both liquids increase parabolicrlly with increasing pressure and linearly with increasing density at each temperature, as shown in Figs.2 and 3.
By useof the measured values of ultrasonic velocity and the P-V-T relations in the literature, the adiabatic compressibility, the specific heat ratio and the specificheat at constant pressure have been calculated under at each temperature and pressure.
It is found that the specific heats at atmospheric pressure increase with increasing temperature and the values are in satisfactory agreement with those in the literature, which were obtained by the usual calorimetric method.
The isobaric specific heats of chlorobenzene and nitrobenzene are also found to decrease with increasing pressure, and at 30 C these values under 1000 bar are less than those under the atmospheric pressure by 6 and 5%, respectively.

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Solid complex formation of malonic acid with several α-amino acids was studied by X-ray powder diffraction, infrared spectroscopy, differential thermogravimetry and differential scanning calorimetry.
Malonic acid forms solid complexes with dl-α-alanine, α-amino-isobutylic acid, dl-norvaline, dl-norleucine, and dl-isoleucine in a molar ratio of 1:1, while it does not form a solid complex with dl-leucine. The solid complexes have a peritectic point and the point is lower than the melting point of malonic acid.
It was inferred that the solid complexes was formed through intermolecular hydrogen bonds between the carboxyl group in malonic acid and the carboxyl group of α-amino acids.

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Irradiations of three kinds of methyl-phenyltrisiloxanes, 1, 2, 2, 3-tetramethyl, 1, 1, 3, 3-tetraphenyltrisiloxane (F-4), 1, 2, 3-trimethyl, 1, 1, 2, 3, 3-pentaphenyltrisiloxane (FT5), 1, 3-dimethly, 1, 1, 2, 2, 3, 3-hexaphenyltrisiloxane (F-6), were carried out. Yields of gaseous products, changes of molecular weights of the trisiloxanes, effect of oxygen on the changes of molecular weights and liquid chromatogram of the trisiloxanes were measured.
Gaseous products were mainly hydrogen, methane and benzene. The yields of hydrogen and methane decreased withthe increasing content of phenyl groups in trisiloxane. The yield of benzene, onthe other hand, increased with the increasing content of phenyl groups in trisiloxane. G(benzene) of F-6 was considerably high, i.e., 0.22, while G(benzene) of F-4 and F-5 were 0.03 and 0.05, respectively. G(polymerization) of F-4, F-5 and F-6 were shown to be 0.41, 0.28 and 0.36, respectively. These results were considered to be due to an ease of scission of the bonds between phenyl groups and trisiloxane groups by steric hindrance in the case of the F-6, in which two large phenyl groups bonded to the central silicon atom.
Molecular weights of trisiloxanes increased by the irradiation and the increments were depressed in the presence of oxygen. It was concluded that radical processes participated in the polymerization of the trisiloxanes.

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Aromatic amines were hydrogenated or competitively hydrogenated overpalladium supported on activated carbon under an atmospheric of hydrogen at 30-60 C in an acetic acid solvent. When the nuclear electron density was higher, the nuclear hydrogenation was easier. The competitive hydrogenation of several aromatic amines revealed that the order of the strength of adsorption was N, N-dimethylaniline N-methylaniline o-toluidine aniline p-toluidine m-toluidine. The introduction of methyl group at N-position of the aromatic amine leads to an increase in the strength of adsorption. It was shown that the relative ease of adsorption depends mainly on the strength of the adsorption of C1-N position. Then it has been concluded that aromatic amine is adsorbed on the metal at the nucleus andthe C1-N position, and the later adsorption is stronger than the former. It was shown that the adsorption of the C1-N position has a significant effect on thefirst adsorption step of the substrate on the metal, since the relative ease of adsorption is not in accord with the relative ease of the nuclear hydrogenation ofthe individual aromatic amine. These facts suggest that the adsorbed species is a complex, such as the following;

Under the conditions studied the nucleus of aromatic amine was hydrogenated more readily than benzen itself. Then the easy hydrogenation of the aromatic amine may be due to the strong adsorption of amino group on the metal, because which increase the interaction of the nucleus with the metal. Furthermore, in order to examine an intermediate formed in the hydrogenation or competitive hydrogen of aromatic amines, the hydrogenative condensation of some amines with cyclohexanone are studied.

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A complex of diphenylmethanimine (Im) with cuprous chloride, CuCl.Im[1], absorbs 1/4 mol of O2 in solution to form an oxygen-containing copper(II) complex [5], whi6h acts as an intermediate of the oxidative coupling of lm. Complex [5] contains N-H bond of coordinated lm, which implies that the dehyrogenation of lm does not occur in the formation of [5]. The decomposition of [5] in solution under the atmosphere of N2, by heating up to 200 C resulted in conversion of [5] to benzophenone azine (Az) accompanied by the reduction of Cu(II) to Cu(I).Similar behavior was observed both in air and in O2, where Az was formed above 120 C (Fig.3). The rate of formation of Az was proportional to the partial pressure of O2 at 200 C (Fig.4), whereas independent of the oxygen pressure up to 120C. It has been concluded that the equilibrium, Complex [1]+1/4 Complex [5], favors the formation of [5] at lower temperature, and the decomposition of [5] should be rate-determining in the oxidative coupling of Im, while at higher temperature, where the decomposition of [5] is fast enough, the equilibrium shifts to the opposite side and the concentration of [5] proportionally increases. with partial pressure of O2. The results obtained were applied to settle the optimum condition for the direct synthesis of Az starting from benzophenone, ammonia and oxygen in liquid-phase.

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To clarify the surface property of V2O5 reduced by hydrogen in a temperature range between 200 and 500 C, crystal structure, paramagnetic behavior and reaction of the reduced V2O5 on the surface with DPPH have been investigated by means of X-ray diffraction, IR, UV and ESR absorption. The results are as follows: (1) The concentration of V4+ on the surface of reduced V2O5 at 425 C is highest in the all samples. (2) The activation energy is 20-23 kcal/mol for the reaction between DPPH and the surface V2O5 reduced at 200-300 C, while 2-3 kcal/mol for the V2O5 reduced at 450-500 C. It was concluded that surface species, V5+=O, V4+ and V3+ on the reduced V2O5 behave as adsorption sites of hydrogen depending on the temperature.

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The anodic oxidation of benzoic acid in the potential region where platinum oxides form on the surface was examined in connection with the adsorption behavior of benzoic acid by means of potentiostatic and potentiodynamic techniques. Results obtained indicated that the adsorbed benzoic acid is oxidized catalytically by the surface platinum oxide. When adsorption were measured by the linear potential-sweep method at 60 C, both the apparent coverage and the charge Qox due to the anodic oxidation of the adsorbed benzoic acid showed usual bellshape dependences on the potential Vads in the potential region from 0.05 to 0.55V (vs.SEC). On the other hand, the dependences were different with each other at 20 C.
These results are explained by assuming two different types of adsorption of benzoic acid, one of which is active in the oxidation and the other inactive.The adsorption of benzoic acid on the platinum surface was found to obey Furumkin's isotherm and the adsorption rate is controlled by the diffusion process.

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Polarographic investigation was carried out on solutions containing tantalum pentachloride in molten potassium chloride and tantalum subchlorides inmolten sodium-potassium chlorides (1:1, in mole scale) in the temperature range of 775-875 C and 750-850 C respectiveiy. A ramp wave pulse generator specially designed for the fused salt polarography was used.
The peak potentials of tantalum ions were referred to that of silver ion.
It was found that the reductionprocess for tantalum pentachloride gave a two-step reduction wave; the first peak was ascribed to the reduction of Ta(V)to Ta(II), and the second peak to the reduction of Ta(II) to Ta(0).
Under the existence of Ta metal, two types of tantalum subchlorides were observed in the molten state (Ta(IV) + Ta=2Ta(II)). Inthe reduction process, two peaks were observed. The first peak was attributedto the reduction of Ta(IV) to Ta(II) and the second peak Ta (II) to Ta(0).

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The time dependence of resistivity of (ZrO2)1-x(Y2O3)x(x=0.06-0.10) was measured at 800 C in air. Problems related to the measuring method was investigated, and the kinetic equations were discussed briefly.
The specimens usedin this measurement were sintered at 2000 C for 4hr, to which the Pt paste electrodes were applied by baking at 1400 C for 30 min. The resistivity of specimens was evaluated by the method of complex impedance plot, in which the frequency ranged from 20 Hz to 20 kHz.
In all compositions the resistivity increased withtime. The order of the rate of resistivity increase was 7 6 8 9 10mol% Y2O3, increase after about 300hr being 39% with 7 mol% Y2O3 and 20% with 10 mol% Y2O3. The resistivities of specimens of 8-10 mol% Y2O3 reached respectiveiy constant values after about 100hr. After about 300hr the conductivity maximum was obtained with 8 mol% Y2O3 specimen(2.89X10-2 cm-1).

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The electric conductivities of the silver iodide-substituted sulfonium iodide systems were examined and high conductivity silver-ion electrolytes were found in three systems, viz., C5H11SI-AgI, Me3SI-AgI and Me2EtSI-AgI.
Theseelectrolytes were prepared from AgI and sulfonium iodide' in the molar ratio of n as
MI + n AgI=MAgnIn+1
The dependence of electrical conductivity on the composition showed that the maximum conductivity appeared at 84 mol% AgI for all these three systems. The highest conductivities of the systems, C5H11SI-AgI, Me3SI-AgI and Me2EtSI-AgI, were 0.04, 0.06 and 0.02(Ωcm)-1 at 25 C, respectively. The activation energies for conduction obtained from the temperature dependence of electrical conductivity was 12.6kJ/mol for the C5H11SI-AgI and Me3SI-AgI systems and 16.8kJ/mol for Me2EtSI-AgI. The electronic conductivity of thesesystems measured by Wagner's polarization method was found to be negligibly small, so that the conduction in these systems is essentially ionic.

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In order to obtain the fundamental data for separational and condensing processes in urea syntheses, the vapor-liquid equilibria for the ternary system of ammonia-carbon dioxide-water were studied from 70 C to 99 C at the pressure of 20 kg/cm2. Comparing the data with those in previous work, isothermal solubility curves and the following empirical equations to estimate the relations ofvapor-liquid equilibrium were obtained for 70 C to 130 C.
log rNH3=(-1.077 x2co2 + 0.0839 x2H2O + A0xCO2xH2O)/(xNH3 - 3.694 xCO2 - 2.887 xH2O)2(1)
log rH2O=(-0.00349 x2NH3 + B0x2CO2 + C0xNH3xCO2)/(xH2O - 0.3464 xNH3 + 1.280 xCO2)2 (2)
where
A0=-3.694 AH20, CO2 - 0.7382(3)
B0=1.637 AH2O, CO2(4)
C0=-0.2708 AH2O + 1.0934(5)
AH2O, CO2=8.909 - 3143/T, at 70-95 C(6)
AH20, CO2=14.705 + 5276/T, at 95-130 C(7)

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Alumina was prepared by the reaction of solid sodium aluminate with SO2 in a gas flow reactor and its catalytic characteristic was studied. The reaction conditions were as follows; reaction temperature: 100-500 C, particle size of sodium aluminate: <80 mesh, gas: air + SO2 (1:1 mixture in volume, flow rate; 100 ml/min), reaction time: 2hr. After the reaction, residual sodium aluminate was washed away with water and alumina obtained was heated at 600 C for 1hr. In such treatment, η-Al2O3 was produced at reaction temperature below 200 C, and e-Al2O3 and η-Al2O3 above 300 C. The amount of e-Al2O3 obtained increased with the elevation of reaction temperature.
In order to examine the reactivity of the aluminas prepared, the catalytic activity for the Claus reaction was studied by using a pulse reactor at 100-600 C. The reaction proceeds between SO2adsorbed on alumina and H2S in gas phase. The degree of reaction increased with a decrease in reaction temperature and was directly proportional to the specificsurface area, having no relations with the kind of aluminas prepared. The catalytic activity of alumina for the Claus reaction was supposed to closely relate toadsorptive activity of SO2 on alumina.

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The oxidation reaction of pyrolusite with KOH-KNO3 molten salts for the preparation of potassium manganate(V) has been studied in the temperature range of 200-240 C.
2MnO2 + 6KOH + KNO3=2K3MnO4 + KNO2 + 3H2O
The grain sizes of pyrolusite ores were gradually reduced with the progress of oxidation reaction. The analysis of kinetic curves in terms of a core-model revealed that thechemical reaction on the unreacted core surface was the rate-determining step ofthe reaction and that the rate was expressed by the following equation,
1 - (1 - x)1/3=kt
where x was degree of oxidation of MnO2, k was constant and t was reaction time. The apparent activation energies were found to be about 36kcal/mol for Indian pyrolusite and 32kcal/mol for Gabonian one.
The appropriate oxidation conditions of pyrolusite were investigated by treating it with KOH-KNO3 molten salts under various conditions of alkali and nitrate molar ratio to MnO2, temperature (250-400 C) and reaction time, and found that oxidation of pyrolusite proceeded most favorably at the following condition:
Alkali molar ratio:about 5, Nitrate molar ratio: about 1,
Reaction temperature: 300-350 C, Duration of reaction: 1-2 hrs.
About 95% of pyrolusite was oxidized at the condition.

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By-product of silane (Table 1), which resulted from the reaction among magnesium silicide, ammonium chloride and ammonia, consisted of ammonia magnesium chloride adduct MgCl2.6NH3(AMC) with small amounts of ammonium chloride, magnesium silicide and silicon. AMC was found to have a cubic lattice (a=10.20A, Table3) and seems to be a complex salt, Mg(NH3)6Cl2. Heating in gaseous ammonia changed AMC into MgCl2.2NHs at 140 C, MgCl2.NH3, at 280 C, and then into MgCl2 at350 C (Fig.1). MgCl2.2NH3 was found to have a tetragonal lattice (Table 4). AMC readily reacted with moisture in atmosphere releasing ammonia and gave amorphouscompound and ammonium chloride at first, and then a double salt MgCl2.NH4Cl.6H2O(Fig. 2).
When the by-product was treated with sulfuric acid, a double salt, MgSO4.(NH4)2SO4.6H2O and ammonium sulfate formed, while treatments with phosphoric acid gave MgNH4PO4.H2O and MgNH4PO4.6H2O (Table 6).
Magnesium silicide reacted with the acids to form magnesium salts and amorphous silica.

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The kinetics of extraction of nickel(II) ion from aqueous solution, using chloroform solution of 8-quinolinol (oxine), was studied in the pH range 6.2-8.1 and at the ionic strength μ=0.1.
In a sufficiently high shaking speed region (above 330 strokes/min), the rate of extraction was controlled by a chemical reaction in the aqueous phase. The reaction was of first-order with respect to nickel(II) and oxine. The relation between the rate of extraction and hydrogen ion concentration in the aqueous phase at constant oxine concentration gavestraight line with a positive intercept, as shown in Fig.1. From these results, it was found that the formation reaction of the 1:1 chelate in aqueous phase is the rate-determining step and the reaction proceeds through two reaction paths: the first, the-reaction between dissociated oxine (R-) and nickel(II), : the second, the reaction between undissociated oxine(HR) and nickel(II). The rate expression is as follows:
- d[Ni2+]/dt=(kHR + kR-.Ka.1/[H+])[Ni2+][HR]0/KDR
The estimated rate constants, kR- and kHR are 5.4X105 l.mol-1.sec-1 and 3.6X103l.mol-1.sec-1 at 298 K, respectively.
The temperature dependence of these reaction ware determined and thermodynamic data have been calculated.

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Compositions, stability constants, maximum, wavelengths of absorption and molar extinction coefficients of the following complexes were determined spectrophotometrically : 1, 4, 7-triazacyclononane (2, 2, 2), 2, 2'-diaminodiethylamine(2, 2), N-(2-aminoethyl)-1, 3-propanediamine (2, 3) and 3, 3'-diaminodipropylamine(3, 3) chelates of copper(II) or nickel(II) ion.
The measurements were carriedout in terms of a new technique for the preparation of solution without using buffer solution at 25.O C and ionic strength O.1.
These triamines were found toform chelates of the type ML and ML2. However, in the case of copper-(3, 3) or nickel-(3, 3) ML2 species were not found with excess ligand.
Stability constantsand visual absorption bands are shown Tables 1 and 2 respectively.
KML valuesof (3, 3) chelates are lower than those of (2, 2) and (2, 3) chelates due to the six membered chelate rings.

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The CoSO4-catalyzed pyrolysis gas chromatography was employed for the determination of a trioxocane (TOC) unit in the formaldehyde-trioxocane copolymer (FATOC) which was prepared by the insertion reaction of TOC into polyformaldehyde, catalyzed by BF3-Et2O.
Dioxolane (DOL), 2-methyldioxolane (2-MeDOL), dioxane (DOX) and ethylene oxide (EO) as well as TOC were found in the pyrolysis products by GC-MS method.
At the pyrolysis temperature between 400 and 500 C and with the catalyst (more than 3%) contained in the copolymer, the majority ofTOC were rocovered as a monomer accompanied by a minute transformation into DOL, 2-MeDOL and DOX and without a formation of EO. The amount of TOC in the copolymer was calculated from the yields of these compounds. The suitable condition and the reproducibility for this method are described.
Although the NMR spectrum of FATOC in deuterated DMF showed the presence of EFE triad (Fig.4), it failed to identify any pyrolysis product which contains a EFE unit that proves the presence of the two neighboring TOC units in the polymer chain.

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Simple and small size oxygen sensor with fast response was designed on the base of oxygen concentration cell with solid electrolyte. The sensor can be used as a detector for various gas analysers independently or with combination of other gas detectors such as thermal conductivity detector.
The sensor consists of two elements, a furnace and a thermocouple. The element is a stabilized zirconia pipe (4φ X 2-3φ X 150 mm) coated with porous platinum electrodes on both sides of the pipe (Fig.2). Two elements (reference and measurment cell) are located in the furnace (40 mm long) and heated to 800-1OOO C. The carrier gas is divided into two streams; one runs through the reference cell and the other is led into the measurment cell via the reactor containing a sample. The differential motive force between two electrodes is measured continuously (Fig.3).
The sensitivity of the sensor increases with the decrease of oxygen pressureof a carrier gas and 1X10-4 ml-O2 at Po2=10-3 atm (Fig.4) can be detected.
Though the sensor is not sensible to inert gases, gases, such as nitrogen oxides, affect the response through the dissociation and evolution of oxygen at high temperatures. The combustible gases, such as H2 and CO, react with oxygen at high temperature and reduce the oxygen concentration in a carrier gas (Fig.7).
This report describes the applications of the sensor for the study of oxidation andreduction reaction of cobalt oxide (Fig.5) and thermal decomposition of caluciumoxalate monohydrate (Fig.7).

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1-Aryloxy- and 1, 1-bis(aryloxy)polyfluoroolefins were prepared by the nucleophilic reaction of hexafluoropropene (HFP) and octafluoroisobutylene (OFIB) with sodium aryloxides.
Sodium phenoxide and p-methoxyphenoxide in tetrahydrbfuran reacted readily with HFP, giving 1-aryloxypentafluoropropene (cis-andtrans- 3a and 3b) and 1, 1-bis(aryloxy)tetrafluoropropene [4a and 4b], whereas sodium p-nitrophenoxide reacted in dimethylformamide only to give 1-(p-nitrbphenoxy)pentafluoropropene [3c] as a major product. The reaction between phenol and HFPin dimethylformamide, in the presence of excess sodium hydroxide, gave [4a] ina good yield.
The reaction of sodium aryloxides with OFIB took place readily indiethyl ether, yielding a mixture of 1-aryloxy-2-(trifluoromethyl)tetrafluoropropene[5a-5c] and 1, 1-bis(aryloxy)-2-(trifluoromethyl)trifluorepropene [6a-6c].

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1, 1-Dichloroethylene (VD) was formed in a good yield by the co-pyrolysis of 1, 1, 2-trichloroethane (TCE) and methanol on activated alumina. As the calcination temperature of activated alumina rose, the conversion of TCE decreased.The ratio of VD to 1, 2-dichloroethylene (DE) and that of trans-DE to cis-DE were approximately constant under various conditions. The reaction kinetics at a low temperature was reasonably interpreted by assuming longer residence time than that of the actual time factor. It seemed reasonable to assume that the reactionat a 1ow temperature proceeded slowly in the pores of alumina pellets.
The co-pyrolysis of TCE and methanol on activated alumina was first order in TCE. The rate constant of TCE consumption(kTCE) and the rate constants for the formation of VD, trans-DE and cis-DE (kVD, kt-DE and kc-DE, respectively) are expressed bythe following equations.
kTCE/(g-mol/g.hr)=1.02 X 105 exp(-19900/RT)
kVD/(g-mol/g.hr)=5.18 X 104 exp(-19700/RT)
kt-DE/(g-mol/g.hr)=5.34x104 exp(-21000/RT)
kc-DE/(g-mol/g.hr)=1.17x104 exp(-19300/RT)

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A study was conducted to determine the kinetics of oxidation of p-xylene in acetic acid solution catalyzed by cobalt acetate. The data of the oxdation carried out in the autoclave was analyzed with a digital computer, The reaction was found to be a chain reaction where p-xylene is progressively oxidized as follows:
p-xylene → p-Toluic aldehyde → p-Toluic acid
→ 4-Carboxy benzaldehyde → Terephthalic acid.
The chain initiation is the reaction of hydroperoxide and cobalt(II) ion Co2+. The chain propagation are the oxidation by Co3+ and the reduction of radicals and hydroperoxide by cobalt(II) ion Co2+. Namely,
φCH3 + Co3+ → φCH2+ + Co2+ + H+ φCH2+ + O2 → φCH2O2+
φCH202+ + Ce2+ → φCHO + Co3+ + OH-φCHO + Co3+ → φCO + Co2+ + H+
φCO + O2 → φCO3+φCO3+ + RH → φCO3H + R+
φCO3H + Co2+ → φCO2+ + Co3++ OH-φCO2+ +RH → φCO2H + R+
Cobalt ion is the chain carrier. The oxidation with hydroperoxy-radical,
φCH3(orφCHO) + φCH2O2+ → φCH2+ (orφCO) + φCH2O2H,
is much slower than that by Co3+.
These reactionschemes were examined around the concentrations of PX, PTAL, PTA, 4- CBA, TA, Co3+ and water, and the absorption rate of oxygen, and it was found that the reactin schemes are valid. In addition, the reactions of Co3+ with the hydrocarbons and the aldehydes was found to follow the Hammett rule.

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4-Azido-3-nitrobenzoic acid [3] and 2-azido-5-nitrobenzoic acid [4a]were prepared from the reaction of sodium azido with 4-chloro-3-nitrobenzoic acid 2-chloro-5-nitrobenzoic acid, respectively, in aprotic polar solvents, such ashexamethyl phosphoramide (HMPA).
The 4-azido-3-nitrobenzoic acid [3] obtainedwas changed by heat or light even in the solid state to give 5-carboxybenzofurazane-1-oxide.
From the results of IR and UV spectra, it was a estimated that the 2-azido-5-nitrobenzoic acid [4a] in the solid state has a ring structure formed between the azido and the carboxyl group.

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Phenol [1a], o-[1b], m-[1c] and p-cresol [1d], o-[1e], m-[1f] and p-nitrophenol[1g], p-acetaminophenol [1h], o-[1i], m-[1j] and p-methoxyphenol [1k], p-aminophenol [1l] and o-hydroxybenzyl alcohol [1m] were methylenated in a noncatalytic heterogeneous reaction system. The reaction was carried out in DMSO as a solvent, the cheapest methylenation agent, methylene chloride being used. The present authors have found extreme prominent results for a short reaction period, while concentrations of [1a-m] were regulated to be lowered in the reactien system according to a procedure devised by the present authors.

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1, 2, 4-Triazole derivatives were synthesized in good yie1ds by the reaction of 2-pyridinecarboxamidrazone with heterocumulenes or homophthalic anhydride.
3-(2-Pyridyl)-1, 2, 4-triazol-5-one [6a] was obtained by the reaction of phenyl isocyanate [2a] or benzoyl isocyanate [2b] with 2-p, yridinecarboxamidrazone [1] through the isolated intermediate [3a] and [3b]. 3-(2-Pyridyl)-1, 2, 4-triazol-5-thione [6b] was similarly obtained from isothiocyanate [2c] or [2d]. N-(2, 2-Diphenyl-1-p-tolylimino)-ethyl-2-pyridinecarboxamidrazone [10a], which was derived from diphenyl ketene p-tolylimine [9a], was cyclized with hydrochloric acid to 3-diphe:nylrnethy1-5-[2-pyridy1]-4-[p-tolyl]-1, 2, 4-triazole[11].[1] was allowed to react with diphenyl ketene [9b] to give N-diphenylacetyl-2-pyridinecarboxamidrazone [10b], which was cyclized on treatment with polyphoshoric acid to 5-diphenylmethyl-3-(2-pyridyl)-1, 2, 4-triazole [12]. The reaction of [1] with homophthalic anhydride [13] gave 3-(o-carboxybenzyl)-5-(2-pyridyl)-1, 2, 4-triazole [14], which was dehydrated on heating in acetic acid to afford 2-(2-pyridyl)-(1, 2, 4)-triazolo[1, 5-b]isoquinolin-5-one [16].

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Nenitzescu et al. had reported that 2, 3-epoxypropylethylmethylsulfonium iodide [1a] was obtained from the reaction of 2, 3-epoxypropyl ethyl sulfide with methyl iodide. This investigation showed that the compound obtained should be (1, 4-dioxan-2, 5-ylenebismethylene)bis(ethylmethylsulfonium iodide) [2a-1] which was formed by the dimerization of [1a].
On the other hand, the sulfonium salts [2] such as sulfonium perchlorate or sulfonium fluoroborate were easily prepared from the reaction of dimethyl sulfide with 1-chloro-2, 3-epoxypropane at room temperature in aqueous NaClO4 or in aqueous NaBF4, respectively.
The reaction of [2] with dialkylamine led to (1, 4-dioxan-2, 5-ylenebismethylene)bis(alkyl sulfide) [3]. The sulfide [3] was converted into the corresponding sulfoxide [5]or sulfene [6] by oxidation with H2O2. Particularly, the reaction of (1, 4-diexan-2, 5-ylenebismethylene) bis(methyl sulfide) [3b] with one equivalent of H2O2 or HNO3 afforded two isomeric products of(1, 4-dioxan-2, 5-ylenebismethylene)bis(methylsulfexide); [5b-1](mp 211-212 C) and [5b-2] (mp 160-190 C). Furthermore, thereaction of [5b] with one equivalent of HNO3 led to (1, 4-dioxan-2, 5-ylenebismethylene)bis(methylsulfoxinium nitrate)[7b].

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(1, 4-Dioxan-2, 5-ylenebismethylenen)bis(dimethylsulfonium perchlorate)[2a] was previously prepared by the reaction of dimethyl sulfide with 1-chloro-1, 3-epoxypropane [1a] in aq. NaClO4 in this laboratory.
Now, it has been found that [2a] is also prepared by the reaction of dimethyl sulfide with [1a] in aq.HClO4, followed by the treatment with aq. NaOH. This procedure is more useful synthetic method of [2a] than the previous one.
By this method, a number of sulfonium perchlorates [2] were synthesized by using several dialkyl sulfides and 1-chloro-2, 3-epoxypropane derivatives [1].
The derivatives [2] were easily converted into (1, 4-dioxan-2, 5-ylenebismethylene)bis(alkyl sulfide) derivatives [3] by refluxing with aq. dialkylamine.

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In the presence of amine, the reaction of bis(3-anilino-1-phenyl-2-propen-1-onato)copper(II) [1a] and bis(3-anilino-1-phenyl-2-buten-1-onato)coPPer(II) [1b] with benzoyl chloride in benzene has been investigated. [1a] reacted with benzoyl chloride in benzene at 50-55 C or under reflux in the presence of pyridine (Py) or 4-methylpyridine (4-MePy) for 2 hours to give the C-benzoylated product, 3-anilino-2-benzoyl-1-phenyl-2-propenr-1-one [2a], the corresponding N-benzoylated product, benzanilide [3], and the amine adducts [6] of copper(II) chloride. In the presence of 2, 6-dimethylpyridine (2, 6-Me2Py), 2, 4, 6-trimethylpyridine (2, 4, 6-Me3Py), or tri-n-propylamine ((n-Pr)3N), [1a] reacted with benzoyl chloride to give [2a], [3], the chlorinated product, 3-anilino-2-chloro-1-phenyl-2-propen-1-one [4a], and [6] except (n-Pr)3N-copper(II) chloride adduct (Table 1).The reaction of [1a] with 2, 6-Me2Py-copper(II)chloride adduct [6c] in benzene under reflux for 2 hours gave [4a] in 7% yield. [1b] reacted with benzoyl chloridein the presence of Py or 2, 6-Me2Py at 50-55 C to give the C-benzoylated product, 3-anilino-2-benzoyl-1-phenyl-2-buten-1-one [2b] in high yields (Table 1). A mechanism for the reaction of the enaminoketone-copper(II) complexes [1] with benzoyl chloride in the presence of amine is discussed.

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Catalytic hydrodesulfurlzation of dibenzothiophene, one of high-molecular-weight aromatic sulfur compounds in residual oils, over NH4Y zeolite catalyst pretreated at 200 to 650 C has been studied, the batch method being used.
The acidity and the desulfurization activity of decationated Y zeolite pretreated at 500 C was proportional to the degree of NH4+ ion exchange. The desulfurization activity increased with the rise of pretreatment temperature, reaching a maximum at 500C, and then began to decrease. Toluene, which arised from the products obtained over decationated zeolite, was not obtained when the protonic zeolite pretreated at 200 or 350 C was used. The poisoning effect of basic nitrogen compounds on decationated zeolite was increased in the following order regardlessof the degree of basicity, and no further decrease in the catalytic activity could be brought about by the addition of more than 0.004mol of pyridine or 0.003molof indole.
Diphenylamine < n-Butylamine < Aniline < Pyridine < Indole
Solid phosphoric acid and alumina catalysts did not show the activity for the hydrodesulfurization of dibenzothiophene, but platinum supported on NH4Yand alumina showed considerable activity.
From the results, it is considered that the hydrodesulfurization of dibenzothiophene needs both the Lewis acid sitesand the protonic acid sites. Dibenzothiophene is first adsorbed on a Lewis acid site and then the C-S bond is broken by a transfer of hydrogen atom from adjacent hydroxyl groups. The C-S bond fission is likely to precede ring hydrogenation.

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Finely powdered copper phthalocyanine was synthesized by the reaction of phthalonitrile with urea and Cu(CH3COO)2.H2O in glycerine for about 15 min in two stages. In the first stage phthalonitrile (1mol) and urea (2-3mol) were heated in glycerine at 135-140 C for 5min. In the next stage powdered Cu(CH3COO)2.H2O or urea-glycerine solution of Cu(CH3.COO)2.H2O was added to this reaction mixture at 150-160 C during 10 min. under vigorous agitation.
Subsequently, glycerine was removed and the filter cake of pigment was washed to obtain fine powder copper phthalocyanine pigment for practical use. The Products was polymorphous metastable α-form with greenish blue color (λ=478.Onm) and the average particle size of the product was 0.25μ.

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For the synthesis of optically active d, l-camphor [5] from d, l-2-pinene [1] a conventional method was presented. In the hydration of [1] with cationexchange resin in the presence of monochloroacetic acid [1] gave d, l-borneol [4b, 4c] in moderate yields, which was dehydrogenated over copper-zinc catalyst to give [5]. Its selectivity to [5] was mainly dependent on the reaction temperatureand [5] was obtained with selectivity of 100% at 265 - 270 C/25-40mmHg. This syntheticd or l-camphor [5] shows [ev] -19.80 or +24.75 (c=10, ethanol), respectively.

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The relation between electrophoretic mobility and viscosity of sodium polyacrylate with different molecular weight (Mn) was investigated. The mobilities and viscosities were measured at 25 C and in the pH range of 3.2-8, using buffer solution of CH3COOH-CH3COONa and Na2HPO4-KH2PO4 at the ionic strength of O.2.
The limiting mobilities (Uc-0) are dependent on pH in this pH range and not on Mn. The intrinsic viscosity ([η]) is plotted against average Uc-0 obtained from the samples of different Mn at constant pH in order to express the dependence of [η] on Uc-0. The plots of [η] vs. Uc-0 are straight lines passing through the origin, and their gradients increase in proportion to MaO.767. On the basis of the above-mentioned results, the relation between [η] and Uc-0 is expressed as follows;
[η]=6.61 X 10-1 Uc-0 Mn0.767
This relation is discussed in comparison with Flory-Fox theory.

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The polymerization of some alkyl methacrylates and styrene in the presence of sodium tetrapropylenebenzenesulfonate (ABS) was investigated in an aqueous medium without any ordinary radical initiators. Although the effect of the concentration of ABS on the rate of the polymerization of styrene was different from that of alkyl methacrylates, the approximately linear relationship was found between the rate of the polymerization of styrene or methacrylates and the concentration of micelles of ABS as shown in Fig.2. We already reported that methylmethacrylate in the presence of sodium oleate does not polymerize in an aqueous medium. But higher alkyl methacrylates such as n-butyl methacrylate, as well as styrene, polymerized markedly in the presence of sodium oleate as shown in Table4.The relationship between the rate of the pvlymerization and the concentration of micelles in the presence of sodium oleate is the same as that in the case of ABS. Moreover, as shown in Table 6 and Fig.4, Michaelis-Menten's equation is applicable to the present case in order to elucidate the initiation mechanism.

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Vinyl monomers polymerize markedly in an aqueous medium in the presence of an anionic surfactant without any ordinary radical initiators. This paperdeals with the emulsion polymerization of styrene or methyl methacrylate using small amounts of benzoyl peroxide (BPO) as an initiator and its comparison with the case in which any ordinary initiators are absent in order to clarify the effect of the peroxides of monomers or surfactants on the mechanism of polymerization reaction.
The effects of addition of BPO changed with the kinds of surfactant used and it was noticed that a specific behavior appears by the use of anionic surfactants as shown in Fig.2 and Table 4.
The peroxides of monomers and surfactants of high concentrations have similar activities for initiation as thatof BPO radicals. However, it seemed that in this case the interaction of micellesand solubilized monomers plays an important role for the initiation when the concentrations of peroxides of monomers and surfactants are extremely low.

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Adsorption capacity of NO2 on poly (vinylpyridine) resins and its mechanism were examined by gravimetric method and spectral analysis. Adsorption ability of resin decreased in the following order: poly-4-vinylpyridine=poly-2-methyl-5-vinylpyridine > poly-2-vinylpyridine=poly-5-ethyl-2-vinylpyridine. Differential heats of adsorption were found to be 4.1 to 5.0kcal/mol for poly-4-vinylpyridine, 1.0 to 1.9kcal/mol for poly-5-ethyl-2-vinylpyridine resin. The adsorption characteristic of NO2 on resin was expressed in terms of Henry's type adsorption isotherm. Infrared spectrum of NO2 adsorbed on 4-vinylpyridine homopolymer film showed asymmetrical and symmetrical stretching bands of NO2 at 1630 cm-1 and 1325 cm-1, respectively, whereas characteristic absorption band of N2O4 disappeared. The characteristic absorption band attributed to coordinated molecular complex with pyridine group or to nitrous ester was not observed. From these results, it was concluded that adsorption occurred in terms of dipole-dipole interaction between NO2 and pyridyl group. Poly-4-vinylpyridine resin which was exposed to NO2 for twenty five minutes at 23mmHg exhibited an anisotropic electron spin resonance signal whose g value was 2, 022, 2.004, and 1.983 at room temperature. As the resin was saturated with NO2, g value of 2.022 and 1.983 decreased, and simultaneously anisotropic signal whose g value was 2.014, 2.004, and 1.988 appeared. The spectra observed were not due to the signal of NO2, but to a radical formed on ethyl benzene or divinyl benzene which was used as a crosslinking reagent in the preparation of the resin.

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2-Isopropenyl-1, 3, 4-dioxazolin-5-one [2] was obtained in excellent yield by treating methacrylohydroxamic acid with phosgene. Monomer [2] was polymerized by means of a radical initiator and copolymerized with styrene (Alfrey-Price's values, Q=1.20 and e=O.25). The copolymer with styrene [4] decomposed at ca.200 C to afford NCO pendant polymer [10], and [10] reacted with amine and alcohol at 100 C to give urea- and urethane-derivatives, respectively. [4] and its model compound reacted with amines at room temperature to yield O-carbamoylated hydroxamic acids, which afforded hydroxamic acids with additional amine and urea derivatives by heating. [4] did not react with water at room temperature, but thecopolymer of [2] with hydrophilic N-vinyl pyrrolidone easily reacted with water to give hydroxamic acid derivative. Thus, the copolymer having [2] structure wasproved to be an interesting reactive polymer capable of exhibiting isocyanate function and reacting with active hydrogen compounds.

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Ultrasonic absorption coefficients in critical binary mixture of nitrobenzene-n-hexane have been analyzed by the method of D'Arrigo et al. based on Fixman's multi-relaxation theory. Characteristic parameters due to the rate of decay of critical fluctuation have been estimated from these data as a function of the temperature.
For our purposes it is convenient to write the results of the Fixman's theory in the following form
/f2 = af-1[fD-1/4[d1/2Tm[f(d)]]] + B
where fD is acharcterisitic frequency due to the rate of decay of critioal fluctuation, d is a reduced variable (fD/f)1/2 and A is a parameter of reiaxation absorption as a function of the thermodynamic quantity.
Present results of the dependency of characteristic frequency fD upon the temperature has been supported by Scaling Law's prediction and by Mictura's results analyzed in terms of the Fixman-Kawasaki's theory. But it has been found that the temperature dependence of the parameter A can not be explanined by Fixman theory.

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The telomerizations of 1, 1, 1, 3-tetrachloropropane (TCP) with α-olefins were carried out in the presence of triethyl phosphite (TEP)-FeCl2 or FeCl3. The main products were the simple adducts of TCP with α-oleins, which were identified as 1-substituted 1, 3, 3, 5-terachloropentanes, ClCH2CH2CCl2CH2CClRR'. The result indicates that the reaction proceeds by abstraction of chlorine atom of TCP. The conversion of the olefin to the adduct was found to increase with an increase in TCP/olefin ratio.

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(1, 4-Dioxan-2, 5-ylenebismethylene)bis(dimethylsulfonium salt)[2] hadalready been prepared from the reaction of dimethly sulfide with -chloro-2, 3-epoxypropane[1a] in an aqueous solution conction NaClO4 or NaBF4.
The reaction of dimethyl sulfide with 1-chloro-3-deutero-2, 3-epoxypropane[1b] in aqueous NaClO4 led to [1, 4-dioxan-2, 5-ylenebis(monodeuteromrthylene)]bis(dimethylsulfonium perchlorate)[2b].
From the resuls it was proved that the sulfonium salt [2] wa formed by ring-opening of the epoxy compound, Which was caused by nuclephlic attack of sulfur atom of dimethyl sulfide to position 3 of [1a], followed by dimerization.

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Alkyl 2-cyanoethyl sulfides [2] were prepared by the reactions of mercaptans with acrylonitrile with the aid of Triton B. The reactions of [2] with 1-chloro-2, 3-epoxypropane in the presence of aq. HClO4 (60%) led to aqueous solutions of alkyl(3-chloro-2-hydroxypropyl)(2-cyanoethyl)sulfonium prechlorates [3].The additions of aq. NaHCO3 to the above solutions caused the Hofmann Degradation of [3], and afforded alkyl 3-chloro-2-hydroxypropyl sulfides [4] in good yields.
Further, bis(3-chloro-2-hydroxypropyl)sulfide [6], which can be one of starting materials of epoxy resins containing sulfur atom, was also synthesized bythis method.

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The dark- and photo-conductivities of the mixture [1-2] of 1, 6-diaminophenazine [1] and 1, 6-dinitrophenazine [2] ([1]:[2]=1:1.3) and the mixture [3-4] of 1, 6-dimethoxyphenazine [3] and 1, 6-dichlorophenazine [4] ([3]:[4]=1:1.6) have been investigated. The dark conductivity of [1-2] (p20:1015 Ω-cm, Δ ε : 1.5eV) is better than that of [1] or [2], while [3-4] is similarin its dark conductivity to [3]. The photocurrent spectrum of [1-2] has two peaks at 430 and 560 nm, although no photocurrent peak at 560 nm is detected for itsmatrix, [1] or [2]. No distinctive difference of photoconductivity could be found among [3], [4] and [3-4].

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