By use of nuclear magnetic resonance, the binding site of cytidine and thymidine nucleosides to various divalent metal ions was determined in dimethyl sulfoxide (DMSO). In Mg²⁺ and Ca²⁺ -cytidine systems the metal ions are bound to 3N and 4NH². On the other hand, Sr²⁺, Ba²⁺, Zn²⁺, Cd²⁺, and Hg²⁺ are bound to either 3N or 4NH₂.
In all cases the peaks of the 4NH² group in cytidine was found to split into two peaks, which indicate non-equivalence of amino protons as the result of hindered rotation of amino group.
The IIa metal ions such as Mg²⁺, Ca²⁺, Sr²⁺, and Ba²⁺ form weak complexes with thymidine base, but the IIb metal ions such as Zn²⁺, Cd²⁺, and Hg²⁺ do not form complexes with thymidine in DMSO.
Concerning the conformation about the glycosideic bond of the cytidine Ca²⁺ and the thymidine-Ca²⁺ comlpex, it is concluded from the results of nuclear Overhauser effects (NOE) that syn-like conformation is predominant in the cydine Ca²⁺ complex and the intermediate-range conformation is preferred in thymidine Ca²⁺ complex.

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Walden's rule predibts that the specific conductivity, k, of solution of an electrolyte of a low molecular weight decreases with increasing viscosity of the solution, n. By analysing the experimental data, it was concluded that the hydrated volume of neutral substances added as visous-forming agent interrupts the transport of ions.
When the viscous-forming agent is of a low molecular weight substance, the specific conductivity, k, decreases linearly, regardless of the kind of added substances, with the volume fraction of the hydrated solute, o, calculated from Einstein's equation, as shown in Fig. 5.This means that the hydrated substance hinders the ionic transport.
This theory is extended to the case of nonionic polymers, poly(vinyl pyrrolidone)(PVP) and poly(vinyl alcohol)(PVA), the hydration numbers, N(mole H₂O/base mole), were calculated to be 2-5 and 1.5-2.0, respectively, as shown in Fig. 8.
It has been concluded that ions are transferred thr ugh the poly er coil and that only the volume occupied by hydrated polymers disturbs the transport of the ions and decreases the ionic mobility, while the velume of expanded polymer coils contributes to the viscosity of these polymer solutions.
Both hydration number, N, and intrinsic viscosity, [n], decrease in accordance with the lyotropic series as shown in Figs. 9 and 10. ln the case of LiCl'and Na₂SO₄, however, the ppparent.abnormality of hydration number was observed because the radii .of these hydrated.ions are large.

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The temperature of phase transitien of Br2(CHs)C-C(CH3)g (1) was determined to be -59 C by the differential thermal analysis. High values of the dielectric constant were observed in the high temperature solid phase, although in the low temperature phase it was low (see Fig.1), The infra-red spectra showed no remarkable charige at temperatures both above and belew the phase transition, as shown in Fig. 2. An X-ray study showed that the crystal structure at room temperature was a body-centered cubic lattice with a 7.71 A and Z=2. From ornparisons between symmetries of the molecule and the crystal, it was concluded that the molecular axis should run parallel to eaeh of the four body-diagonals of the unit cell with equal ststistical weight and that the C-C axis at the same time acquired at least a statistical symrnetry of 3. Reinvestigation of the molecular from of Br(CH3)2C-C(CHg)2Br(2) was made by the spectroscopic method(see Table 2). lt was confirmed that only trans-fermed molecule existed in the solid phase (-89-90C)and in CCl solution. Mehanism of the phase transitions for these two crystals was studied from an entropy analysis. ln the case of (1), the statistical orientation of the molecule mentioned above and the intra-molecular rotation should eccur at the trasition point. At the lower transitien peint (-89 C) of (2), the molecule should have the orientational freedom which satisfied a statistical symmetry 4 about the Br-Br molecular axis.

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Relation between the degree pf dispersion and the flow properties of calcium carbonate in water suspensions have been sthdied rmby using sodium lauryl sulfate and sodium pyrophosphate as dispersing agents.
Suspensions of good dispersion showed Newtonian flow and those of bad one showed pseudoplastic flow. All flow curves of these suspensions were expressed by the equatien, Ti2 kiDtM +ke, given by Casson. The constants ev and B in the equation, 1=ev+3(neD)i2, were calculated from the values ef the constants ki and kg.
As given in Figs. 9 and 10, the values of ev, which express the state of the unit partiele in the suspension, were constant irrespective of the concentratien of the dispersing agents, that is, the degree of dispersion, The values of B, which relate to the aggregation force of the particles in the suspension, changed with those of the median diameter of aggregate particles.It is concluded that the constants in the equation of Casson express fairly well the relation between the degree of dispersion and the fiow properties of suspensions.

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Experimental results for the adsorption of nitrogen-oxygen on two natural zeolite tuffs and M.S.5.A are reported. Mordenite tuff from shirasawa, Miyagi Prefecture and clinoptilolite tuff from Futatsui, Akita Prefecture were used in the present experiments. Adsorption of nitrogen oxygen was medsured at 25, 50, 75 and 1000C, and 1, 3 and 5 kg/cm². Also the adsorption isotherms were obtained for pure nitrogen and oxygen on the three zeolites at 25, 50, 75 and 100C, and in the range of pressure from 0 to 7 kg/cm². Separation factors of mordenite tuff, clinoptilolite tuff and M.S.5 A at 25C, 3 kg/cm² and O.5 equilibrium nitrogen mole fraction in gas phase were 4.7, 3.0 and 3.3 respectively. The thermodynamic prediction method of predictig binary adsor ption data from the pure gas isotherms has been examined. The prediction at 25C and 3kg/cm² was good for mordenite tuff but not for clinoptilolite tuff and M.S.5.A.

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The effect of the aminoethyl derivatives of cellulose, starch, and pelyvinylalcohol on the flocculation of the dilulte suspensions of microcrystalline cellulose and kaolin was studied asfunctions of their molecular weight, amino group density, and polymer structure. The -degree of flocculation was evaluated from the supernat t rbidities measured after the suspensions had been stood for 30 minutes. The adsorption of the polyamines onto the suspended Particles and the electrophoretic behavior of the particles were also investigated to elucidate the flocculation mechanism.
The flocculating ability ef the polyamines increases reughly in proportion to their amino group density (Figs. 4, 5), while the effect of melec lar weight (in the range from about 2 10 to 8 10) is not so large (Fig. 6), and the flexibility of polymer chain seems to play no important role in flocculating action (Table 1).
The flocculation of the suspensions occurs under a wide range of polyamine dosage, and the minimum amount of polyamine required to cause the fiocculation correspends to about 100050 of the saturation adsorption capacity (Figs. 8, 9). The electrophoretic behavior of the suspensions indicates that positively charged particles coexist with negatively charged ones in the region where fairly good fiocculation occurs (Fig.12).
These observatiens suggest that (1) the unequal adsorptien of polyamine onto the suspended particles occurs, causing the presence of pesitively eharged particles and negatively charged ones, or polarized ones, and (2) thus the electrostatic force ef attraction between the positively charged parts and the negatively charged parts causes the flocculation of the partiles.

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The dehydration reactions of 2-propanol and the deuterated one (i-PrOH-ds) on alumina and silica-alumina were carried out by employing a closed circulation method at 1600C and 1700C and in the pressure range of 2-propanol from 5 to 18 mmHgt The hydrogen isotope effects were obtained by analyzing the observed data by the use of a Langmuir type rate equation. ln the case of alumina, the values of the primary isotope effect were found to be large (4.06 at 160Cand 3.47 at 1700C), whereas, in the case of silica-alumina, the isotope effect was certainly small, though the exact values could not be determined. lt was concluded from these results that, on alumina, 2-propanol is dehydrated via E 2-ideal type reaction intermediates and, on silicaalumina, the dehydration reaction proceeds via E l type reaction mechanism, in agreement with our previous conclusion.

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Disproportionation of propylene over MoO₃-Al₂0₃ and MoO₃-SiO₂ prepared by wet mixing has been investigated by means of a conventional flow method.
As the concentration of molybdenum oxide was increasedon the alumi a support, the activityof the catalyst pretreated with nitrgenat 500 Cf or several hours increased considerably and then decreased consecutively. The maximum activity appeared at an atomic ratio of Mo/A1=10/90, whereas it appeared at Mo1A1=5/95 in the case of the impregnated MoO₃-γ-SiO₂ catalysts which were less active than the wet-mixed catalysts.
On the other hand, MoO₃-SiO₂ catalysts, prepared by the wet mixing, did not show any activity by treatme:nt with nitrogen. By reducing all these catalysts the catalytic activity largely increased and the maximum activity was obtained at an atolnic ratioof Mo/Al=20180 and Mo/Si=10/90.
The acidity, BET surface area, the relative intensity of Mo5 ESR signal of the catalyst and the degree of reduction of molybde moxide with hydrogen were measured From the investigation on the physical properties and activities of the catalyst, the close relationships between the degree of dispersion of the supPorted molybdenum oxide(whose valency is lower than 5)and the catalytic activity were found.

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The purpose of this work is to clarify the origin of an ESR absorption with a g value of 1.94 and its relation to the polymerization activity of titanium trichloride. The spectrum with a g value of 1.94 was observed by the addition of such compounds as alkylaluminums and triethylamine to TiCls, which have the ability to abstract ehlorine from TiCis or when TiCl₃ was exposed to electric disharge. Both number of spins with a g value 1.94 and the stationary pOlymerization rate are proportional to the surface area of TiCl₃ and the number of spins is found to be nearly equal to the number of polymerization centers. From the above results it was concluded that the species showing this absorptiPn spectrum was a chlorine vacancy on TiC13 and was connected with the polymerization centers. The ESR spectrum of g value 1.94 is asymmetric because of the anisotropy of the g values, and it was concluded that TiS in the species shewing this absorption spectrum was the octahedral environment with trigonal distortien.

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The oxidative dehydrogenation of ethylbenzene to styrene was investigated over uranium oxide and its mixed catalysts with' ai203, Sb20s, KaO or P20s. X-ray patterns and infrared spectra were measured to characterize the structure of catalyst. The following results were obtained.
(1) The catalytic activities of the mixed catalysts were higher than the catalyst without additives. The, U-P catalysts having the P-to-U atomic ratio from O.7 to 1.0 yielded styrene very selectively, with side-reactions of CO2 and C6Hs formation retarded. Retardation of the complete oxidation to CO2 was also observed for the U-K catalysts, but the dealkylation to C6H6 increased in this case. (2) The reaction rate over tke U-P catalyst was approximately of first order in ethylbenzene pressure and of zero-th order in 02 pressure. (3) The uranium oxide catalyst without additives was a mixture of U30g-and UO3. The addition of P206 component lowered the oxidation state of uranium oxide to the level'of U30s, while K20 promoted it te the level of UO3. The composition of U-P catalysts, containing U30s or uranium oxide phosphate, or both, depended upon the ratie of P-to-U of the catalyst. A qualitative relationship between the catalyst structure and the catalytic selectivity has.been discussed.

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The oxidation of butene and acetic acid as well as the isomerization of butene iR the presence of excess air were carried out over V20s-MoO3 catalysts contain1ng O.-v30 atom%e of Mo. Then, the activity for dehydration of isopropylalcohol (IPA) which was adopted as, a measure of acidity of the catalysts was also examined, in order to elucidate the addition effect of MoO3 on the catalyst activities. The activities for both the oxidation and isomerization of butene correlated fairly well with the IPA dehydration activity (Fig. 8) which inereased with increasing MoO3content, reached a maximum at Mo=15N20 atom%e (Fig. 1) and then decreased. The reaction order of the butene oxidation with respect to butene eoncentratien decreased from O.9 to O.5, with addition of 10.v20 atem% of Mo (Table 1). However, the activity for the decomposition of acetic acid remained constant (Fig. 6). lt is considered that at least in the case of partial oxidation of such electron-donoptype compounds as olefin, the main role of MoO3 added to V20ti is not an ativation of surface oxygen, but an increase of acidity which promotes the adsorption or activation of the reactant on the surface.

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Complexation reacti ns of Fe io with salicylic acid a d 5-sulf salicylic acid on p1 tinum electrode in acidic aqueous selutions were investigated by means of voltammetry, lt was found for the solutions containing salicyli acicl that the complexation reaction proceeds between Fe(M)ion, formed by anodic oxidation of.Fe ion, and salicylic acid i the st stage of dissociatio HZ(CeH (OH)COOww). The reaction was first-order with respect to Fe(M) ion and secondorder with respect t HZ4 the range of pHs fr m 2, 54 to 2, 70 while it is firs Qrder with respect to HZ at pH about 2.15. The rate censtants of the reaction were estimated respectively to be 2.3 107 mole 2 12 sec-i for the former pH range and about 104 mol p i 1-sec i for the latter pH. Fer the solution of pH 1.8 to 2.2 containing 5-sulfosalicylic acid, it was inferred that 5M- sulfosalicylic acid in the second stage of disseciation, HZ (C6Hs(OH)(SOs-)COO-), forms a complex with Fe i and that the reaction has first order dependence b th f r Fe and HZ. The rate constant ef the reaction was calculated to be 5.5 10S rnoli 1 sewa i.

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In previous papers on amine hydrochloride flux action of soldering, it has been shown that electrochemical action of fiux (ZnC12-NH Cl system) and elimination of oxides play an important role in spreading of Sn-Pb alloy solder on copper plate. However, the basic factors controlling flow and wet are not well understood.
In this report, aniline hydrochloride flux actien of soldering was studied in relation to the reaetion of flux with base metal (Cu) or with Sn-Pb alloy solder and spreading phenomenon.
The fiux action of aniline hydrochloride may be considered as follows; Molten aniline hydrohleride reacts with copper te give CuC12 and copper complex, which react with molten Sn-Pb alloy solder to give metallic copper. Copper dissolves immediately into the molten solder and a thin Cu-rich layer at the outer surface of molten soider is formed.The wetting of Sn-Pb alloy solder on cepper plate is improved by the reaction and the dis, -so!ution of Cu into molten solder. So, Sn-Pb alloy solder spreads over cepper plate.

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In order to develop reproof materials, an attempt is made to prepare the linear alkoxyphosph rus nitride polymers with applying a simple process. It is also found that the product containing a sma11 amount of phenyl radicals is formed by adding benzene in the reaction system.
The reaction between phosphorus pentachloride, ammonium chloride, benzene, and metal powder(Al, Zn, C), added as a catalyer for dehydrochloriation, is performed in a medium of 5 -tetrachloroethane. The reaction temperature is kept at 100-108 C in the begining in consideration f the start of phosphorus pentachloride reaction with be zene, continuously, the dehydr chlorination reaction is impleted by the re ux at 118-130C. The deposits of an excess ammonium chloride and metal chloride, formed throughout the reaction with hydrogen chloride, are separated from the reactant solution by ltration. Avari us kind of alcohol is added to the 1trate, and the mixture is heated in the reflux. Aresinous product results by the distillation of solvent, and it is converted to powder rlump by vacuum drying.
The obtained products are dissolved in a water-ethan 1 solution. They contained 18-28%P, 9-13%N, and O.7-20%CL The products obtained by the use of AI or Zn scarcely contained the meta1, and in the case f Co, etal is slightly contained in a resultant product.The molecular weights of products are in the range from 300 to 500. The existence of pheny1 adical connected to polymer has not yet been ascertained by the IR spectra. The resin ester containing several percent f the product exhibits an exebllent inc mbustibility.Therefore, the a1koxyph sph rus nitride polymers can be utilized as an useful name regarders of r plastics.

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It is widely recognized that supporting electrolyte has an important effect on adsorption, but few syStematie studies have been done hitherto. The authors investigated the effect of supporting electrolyte on the adsorption of organic compounds at electrode. Tensammetriq waves were measured by Yanagimoto Polarograph PA-102, and drop time-potential curves, were used for analyses of the effect.
Tensammetric waves of O.05 mol/l of t-pentyl alcohol (constant coneentratlQp). were measured varying the supperting electrolyte conentration. ln such a case, two effects are considered. One is salting out effect which increases the adsorption of organic compounds on electrode. The other is ionic specific adsorption which either reduces the adsorption of organic compounds on electrode or narrows the adsorption potential region-potential region between two adsorption desorption peak, poten-tLigls (E, r, E-p)
In the solution of KF or NH₂SO₄, salting out effect outweighed the other, so that the adsorption potential region and adsorptio:n-desorption peak heights lp, Ip increased with the elevation of electrolyte concentration (Fig. 1, Fig. 2 and Fig. 4). ln the solution of KI or KSCN, ionic specific adsorption outweighed the other, so that the adsorption potential region and peak heights decreased with the elevation of electrolyte concentration (Fig. 5, Fig. 6 and Fig. 7). ln the solution of KCI or KBr, both effects existed. Up to about 1 N solution, ionic specific adsorption narrowed the adsorption potential region (Fig. 8 and Fig.9), while salting out effect increased the surface excess in the adsorption potential region (Fig.10). Above 1 N solution, salting effect outweighed the other and both surface excess and adsorption potential region increased.

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Distribution equilibria of aniline derivatives, such as toluidine (T), nitroaniline (NA) andnitro-N, N-dimethylaniline (NDA) isomers, between nonaqueous solvents and a macroreticularsulfonic acid resin were investigated bver a wide range of concentration. These bases weredistributed onto the resin by acid-base equilibria, RSO3-H B RSOs-BH, which obeyed ac/lassical mass action law expression in nonpolar as well as polar solvents. The observed equilibrium constants (K) were related to the acid dissociation constants (Ka) of bases in waterthrough the following equations.
The slope of a plot of log K vs. PKa(ei, o) was regarded as a measure of relative strength ofbases for the sulfonic acid resin in nonaqueous media The K value was affected by strengthand structure of bases and properties of solvents.
On the basis of these results, chromatographic separation of aniline derivatives were performedin nonaqueous media. NA and NDA isomers were successfully separated using pure or mixedsolvents as eluate which allowed to change the acid-base equilibrium.

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Selenium dioxide oxidation of isoprene was investigated. The oxidation products identified were 2-hydroxymethyl-1, 3-butadiene(1), 2-acetoxymethyl-1, 3-butadiene(2), 3-acetoxymethylfuran(3), 1-formyl-3 or 4-methyl-1-vinylcyclohex-3-ene(4), 2-methyl-1, 4-diacetoxy-2-butene (5), 2-formyl-4-acetoxy-2-butene(6), 3-hydroxy-4-methylenetetrahydroselenophene(7), 3-acetoxy-4-methylenetetrahydroselenophene(8), 4-acetoxy--3-hydroxy-3-methyltetrahydroselenophene(9) and 3, 4-djacetoxy-3-methyltetrahydroselenophene.(10)
The composition of these products was dependent on the molar ratio of iseprene to selenium dioxide and the solvents when the ratio was (10), the main product was (1) and when it was 2, (8) and (9) were mainly obtained in acetic acid at 100-105c for 1hr. In the case of acetic anhydride, (6) was obtained as the main product.
The selenium dioxide oxidations of (1) and (5) were also studied.
From these results, the reaction scheme was discussed.

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The liquid phase air oxidation of 1-butanol at 15-100C in the presence or absence of six catalysts (manganese naphthenate, ferrous naphthenate, stannic acetate, dupric acetate, cobalt acetate, and chromium acetate), using acetaldehyde as a reaction initiator, was attempted and the influences of the reaction conditions on the yields of products or the conversion to products were investigated. By this oxidation, n-butyraldehyde and butyric acid were produced and nbutyl acetate was obtained as a by-product. Among six catalysts, manganese naphthenate and ferrous naphthenate were not active catalysts, while cobalt acetate and chromium acetate were found to catalyze the oxidation of 1-butano1. Under the optimum condition in the presence of chromium acetate, 72% of 1-butanol was converted to 2% of n-butyraldehyde, 67% of butyric acid, and 3% of n-butyl acetate. The liquid phase air oxidation of 1-butanol in the presenee of chromium acetate catalyst was investigated kinetically and this oxidation was found to be a simultaneous reaction resulting from the esterifieation of 1-butanol and a consecutive oxidations ef 1-butanol to 1-butyraldehyde and of 1-butyraldehyde to butyric acid. The rates of these reactions were found to be expressed by a first order equations of corresponding reactants.The rate constants of these reactions were in the range from 10^-2 to 1(hr^-1) and the activation energies were less than 10 kcal/mol.

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The electrolytic benzoyloxylation of N, N-dimethylamides, (CH₂)₂NCOR, with benzoic acid has been studied. At first, the electrolytic benzoyloxylation of N, N-dimethylformamide(DMF) with benzoic acid was investigated in benzene, dimethylsulfoxide(DMSO) and acetonitrile. The acetonitrile-DMF system using tetraethylammonium perchlorate as a supporting electrolyte gave the highest conversion at a low bath voltage. Therefore, acetonitrile was used as a solvent.
Electrolysis of benzoic acid in acetonitrile-(CH₂)₂NCOR gave selectively N-beRzoxymethyl-Nmethylcarboxamides(2), similarly to the electrolysis in DMF. Studies on the effect of R groups indicated that the current eMciency for the formation of (2) was not affeted by bulky groups such as isopropyl and cyclohexyl. The current efficiency for the'formation of (2) was remarkably decreased by the substitution of phenyl group. However, the introduction of methylene group between phenyl and carbonyl group showed the tendency of increasing current efficiency slightly.

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The reduction of naphthaIene in hexamethylphosphoric triamide(HMPA)-alka1i meta1-p on donor systems was examined.
The order of reagent addition did not affect the conversion of naphthalene and the selectivityof reaction.
The kind of alkali metals affected the conversion, the selectivity(Table 3), and the effectiveness of alkali metals (Table 4). Therefore, the active species are supposed to be the solvated electrons formed in the HMPA solution of alkali metals, and the complexes of alkali metal iens and solvated electrons.
There is no close correlation between the acidity of proton denors and the degree of reduction, the conversion (Table 1), and the effectiveness (Table 2). Thus, the direct reaction of alkali metal with the proton donor must be considered asst a side reaction when a strongly acidic proton donor was used (Equation(1'))
1, 2-Dihydronaphthalene was obtained selectively when cyclohexylamine was used as a hydrogen source (Table 7). The reaction would proeeed in two succesive steps (Fig. 2).
The selectivity of reduction varied with the change of the molar ratio ef alkali metal to the proton donor in the reaction system (Tables 5 and 7). However, the result did not agree with that of the reduction of benzene in liq. NH₃-Na-H₂O systems.

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The reduction of toluene and tetralin in hexamethylphosphoric triamide-alkali metal-proton donor systems was examined. The results are as follows.
Various kinds of proton donors such as alcohols and amines were used, but there was no close correlation between the acidity of proton donors and the degree of reduction, or the conversion (Table 1); this is the same result as that on the reduction of naphthalene.
The klnd of alkali metals affected the selectivity of the reduction, but little affected the conversion (Table 3).
When the molar ratio of Na to ethanol was larger than unity, tetrahydro products were obtained selectively (Table 5). This is not the case of the reduction of naphthalene under the similar condition. The molar ratio of alkali metal to ethanol which affords maxiraum yields of dihydro products is different from Li te Na (Table 5 and 7).
It was supposed from these results that the active species are not only the solvated electrons, but also the complexes of alkali metal ions and solvated electrons.
The time change ef the composition of products under the reaction condition, which was expected to produce dihydro products selectively, was measured and the resu1t was different from that of the reduction of naphthalene (Fig. 1).
It should be noted that the conjugated dienes were formed as dihydro products, even in the reaction system containing the solvated electrons.

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The reacton of nitriles with hydrazine hydrate in the presence of sulfer compounds offers a convenient synthetic method of 3, 6-disubstituted-1, 2-dihydro-s-tetrazines. Sulfur, mercaptans, disulfides and polysulfides are effective catalysts for the reaction at temperatures in the range of about 20° to 80°C. Mercaptoacetic acid and mercaptoethanol were the most effective catalysts among them. Their catalytic ro1e is discussed in terms of neighboring group participation.The additions of large amounts of amines in the reaction mixture of benzonitrle, hydrazine hydrate and mercaptoacetic acid did not affect the yield of the product, but, when sodium hydroxide was added, none of the products was formed.On the basis of these observatlons, a mechanism of the reaction and also the catalytic role of some sulfur compounds were discussed.

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The continuous Iiquid-phase isomerization and the disproportionation reaction of z-xylene were carried out over a silica-alumina catalyst undopressure in the presence of O.1-0.2%of hydrogen chlloride, where hydrogen chloyide was supplied by the catalytic decomposition of ethylchloride dissolved in reactant m-xylene. The addition of hydrogen chloride toreactant 3-xylene resulted in the increase in the both yields of the disproportionating react on and the isomerization, as shown in Fig.1. And the addition resulted in the decrease in the ratio of the yield of high boiling by productl the yield of toluene, and depressed the decline in catalytic activity with reaction time. While the addition of either diphenylmethane or anthracene to reactant -xylene resulted in the decrease in the activity for the isomerization, as shown in Figs.5and 6. In the case of the addition of diphenylmethan, when the reactant was re-placed by the solution of the z -xylene qontainingonly hydrogen chloride, the decreased acti vity was recovered to the original one, and Fig.7 and Table1 show that most of diphen y1-methane was recovered as po1ymethyldiphenylmethane. On the basis of the above results it was discussed that the active sites available for the isomerization, the disproportionation reaction of xylene and the chemisorption of diphenylmethane were common and have both acidic characters, f.8, protonic and Lewis, as was shown in Fig.8.

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Transalkylation between t-butylbenzene and phenol in the presence of AICIs-CHsNOs catalyst (molar ratio of AICIs/CHsNO2=O.574) and BFs catalyst at a temperature 20.v609C was studied. In both cases, p-t-butyl phenol and benzene were obtained along with a small amount of dit-butylbenzene. p-t--Butyl phenol was obtained in better yield by the use of BFs than that of AICIs-CHsNO2 as the catalyst.
The reaction shows the first order reaetion with respect to t-butyl benzene under our experimental conditions. The values of activation energy and apparent A factor were found to be 18 4 kcal/mol and 1.1 109 secl' respectively for both catalysts.

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Thermal decomposition of 1-pentene was studied in a flow apparatus under an atmospheric pressure, at temperatures ranging from 480 to 750C, with residence times from 0.05 to 48 sec and nitrogen/1-pentene mole ratios of 6 and 15. The overall reaction was fourid to obey the first order rate equation with the rate constant ef log k (sec)=12.2-52000/4.575T. The reaction products were, in the decreasing order, ethylene, propene, butadiene, 1-butene, methane, ethane, hydrogen, 1, 5-hexadiene and 1, 3-pentadiene. More ethylene and propene were formed at higher temperatures and lower partial pressure of 1-pentene, while the amount of butadiene was found to decrease under these conditions.
The main reaction can beL accounted for by the free-radical chain process in which decomposition and isomerization of alkenyl as well as alkyl radicals compete. The experimentally observed product distributions as well as reaction rates generally agreed with those calculated by the proposed chain scheme. lt is found, however, that ethylene and propene are formed not only through chain process but also via molecular proess or direct fission of 1-pentene, The latter reaction becomes more important at lower temperatures. At 500C, the centribution of this reaction is estimated to be about 20%e cf the total decomposition.

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Decomposition reactions of stilbene fluoreseent brightening agents (FBA) by action of active chlorine under dark were studied by the changes in UV-spectra and thin layer chromatograms, the analyses of the ionic species produced, and the measurement of the changes of active ehlorine concentration and pH of the reaction. The results are as follows.
Each derivative (5 -vlO ppm aqueous solution) was decomposed by action of sodium hypochlorite (active chlorine concentration 20 ppm) to a non-fluorescent initial decomposition product in a short time, the half-life time (ri) of the reaction being ca. 30 min. One atomic equivalent of active chlorine was consumed per 1 mole of FBA in the reaction, but pH did not change appreciably.
The non-fiuorescent initial decomposition product of each derivative contained one chlorine atom in its molecule and absorbed UV-light around 270 nm.
The product was degraded gradually to NH3, HSO4m, SO2, COs2-, and carbexylic acid residues, the half-life time (T2) of the reaction being ca. 30 hr. A large amount of active chlorine in the reaction was consumed and pH of the solution changed from 9 to 7, indicating the formation of the said ionic species.
The isosbestic points were observed in UV-spectra at the beginning of the reaction, which could be explained by the following relationship.
(FBA)(the initial decompesition product) constant was established because of T2 ri.

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In order to obtain some fundamental information on disperse dyeing in tetrachloroethylene as a medium, the equilibrium adsqrption of seventeen dyes on cellulose lacetate has been investigated from the view points of isotherm, partitien coefficient and solubility.
The adsorption isotherms were determined at temperatures from 45C to 75C and found to obey the distribution law. The partition coefficients and the heats of dyeing were calculated from them.
The solubilities of the dyes in tetrachloroethylene were measured at temperatures from 30C to 60C, and the heats of solution were calculated from the Arrhenius plots of the solubilities.
The larger the solubility, the smaller is the partition coefficient.
An approximate correlation with a negative coefficient is shown between the logarithms of both parameters.
In the case of anthraquinone dyes, the heat of dyeing is closely correlated to the heat of solution by the equation, AHdyeing, +a AH, .in.=const. where a is a constant for numbers of amino groups.

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The essential oils of L, Makinei and L. auratum were examined in detail. From L. Makinei 12 compounds were isolated and confirmed by direct comparison with the authentic samples, and 4 trace components were identified by GLC-MS method. Among them 2, 6, 6-trimethyl-2-vinyl-5-ketotetrahydropyran (2) was newly isolated as natural product. On the other hand, 25 compounds were isorated from L, auratecm and characterized, and 6 trace components were also identified.
The essential oil of L. Makinoi. contained cis-2, 6, 6-trimethyl-2-vinyl-5-hydroxytetrahydropyran (1) as the'main component, along with small amount of linalool relatively large amounts of the other oxidation compounds of linalool, and small amounts of a few phenolic compounds. The essential oil of L. auratum, on the contrary, contained linalool, many phenolic compounds in large guantities, and some oxidation compounds of linalool in smail quantities.

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The absolute structures of linalool (1), trans- and cis-linalyloxides (2)and(3), trans- and cis-2, 6, 6-trimethyl-2-vinyl-5-hydroxytetrahydropyran (4) and (5), and 2, 6, 6-trimethyl-2-vinyl-5-ketotetrahydropyran (6) obtained from Lilium Makinoi Koidz. were determined. In the compounds (2)-(6) the absolute configurations at C(2) position retaine that of co-existent linalool (1) which is presumed to be a biosynthetiC precursor.
It was pointed out that the diretions of the specific rotations of (3) and (5) were reported erroneously by Klein et al.

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The viscoelasticity of vulcanized blend rubber which attended by chemieal reaction was investigated. lt is well known that the blend rubber was consist of the heterogeneous system of the small particles or the plates. Many papers on the viscoelasticity of blend rubber has been published but no reported about the viscoelasticity which attended the chemical reaction. Then we researched using chemorheological technique for NR-NBR, and NR-SBR systems.
In the two compenent systems, three types of network will be produced of blend materials, that is, the networks of the homopolymers A, B and the third compopent of co-crossiinked rubber was appeared. Some informations were obtained from the chemorheological investigations and it is suggested that many co-crosslinkage exist in NR-NBR blend system.
Consequently, the elastic enthalpy of NR-NBR blend system decreased when compared with the vulcanized each homopolymers.

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The viscosity of concentrated solutions of rubbers was measured, and effects of molecular weight, molecular weight distribution and branching were discussed. Characterization of the sameples were made by the calculation with a computor combined GPC and intrinsic viscosity measurements. The measurements of the solution vlscosities of the samples were carried out with a cone and plate viscolneter at concentrations ranged from l to 12 wt%in diethy1-benzene. The fractionated samples of styrene-butadiene copolymer(SBR), two kinds of 5-1, 4-polybutadiene(BRA and BRB), asticated samples of cis-1, 4 polyisoprene(IR) a naturaI rubber(NR)were used as the samples, fro the GPC a alysis, BRA was fo d to be almost linear, while SBR and BRB contained branched polymers in high molec 1ar weight reg on (Table 1, 2, 3). The zero-shear solution viscosity was proportional to M forelinear polyms independent of molecular weight distribution(Fig.5). B t for branched polymers o was lower than that for the linear polymers at the same molecular weight, and the difference was welhnterpreted by Bueche's theory(Fig.4, 5). For the masticated samples of the sol fractions of IR and NR, 1nolecular weight decreased with increasing number of passes and also the branched polymers generated d ing mastication. Soluble parts obtained by mastica g the gel fractions were almost branched polymers. These results were found in both GPC data (Table 4, 5, 6)and the relation between, and Mw(Fig.6). The plot of solutio vis6o6 ty against shear rate for the linear polymers fit well to Graessley, s theoretical durve calcurated by considering molecular weight distrib tion(Fig.7). The plot for the branched polymers deviated slightly from the theoretical curve(Fig.8).

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In the photopolymerization of acrylamide sensitized by acidopentaamminecobalt(M) complexes [CoL(NH3)6] X2 in aqueous solutions, their sensitizing abilities are dependent on the nature of the acid-ligands (L) greatly. Neither the chloro- nor the bromo-complex can initiate the photopolymerization without ultraviolet irradiation. But the complexes containing such acidligand as N3-, NCS- or NO2- can sensitize the Polymerization even under irradiation with visible light(470nm).
In the latter cases, the polymerization rates (Rp) are dependent on the light intensities (I0)and on the concentrations of the complexes (c) and the monomer([M])variously. For the azido-complex Rp=, for the thiocyanato-complex and for the nitro-complex R . The initiation effciencies, that is, the ratio of the number of radicals initiating the polymerization to the total number of radicals produced from the complex, are only 0.15 and 0.06 for the azido-and nitro-complexes, respectively.
From these results it is concluded that the polymerization sensitized by the azido-complex is slightly retarded by the complex itself and that in the case of the thiocyanato-and the nitro- complexes the radidals formed by the interaction between the ligand-radical and the monomer initiate the polymerization and the primary radical termination by nitro-radicals takes place predominantly in the case of the nitro-complex.

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Zinc-methylene iodide reagents were prepared in THF from the various amounts of methylene iodide and zinc, and the reactiqns with benzaldehyde were examined. The zinc-methylene iodide reagent(reagent A)prepared by the reaction with more than 2 molar amounts of zinc did not afford methyl iodide on the hydrolysis, but gave methylene iodide on treatment with iodine (No.1, No.2 in Table 1). This observation seems to indicate that reagent A contained no ICH2Zn-unit b.ut-ZnCH2Zn-unit. Reagent A reacted with benzaldehyde to give styrene, but the Simmons-Smith reaction did not occur with the reagent.
After the preparation of feagent A, the residual zinc was removed by ltration and an additional amount of methylene iodide was added to the reaction mixture. The mixture gave ethyl iodide on the hydrolysis, and norcarane in the reaction with cyclohexene(No.7), The reagent(reagent B)prepared from less than 1molar amount of zinc also gave norcarane with cyclohexene in poor yields, but styrene was not formed with benzaldehyde(No.3, No.4).
These facts suggest that the active organozinc species which converts benzaldehyde into styrene may be represented as CH2(Znl)2. The presence of the following reversible reaction between the Simmons-Smith reagent ICH Znl, and the"CH2(Znl)2"is also suggested.

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The poly(vinyl alcohol) (PVA)-copper(ll) complexes in aqueous solutions were formed at varing ratio of the concentration of copper ion to the ligand (Tcu2V T=O.0125.vO.125) in pH 10.5, where ion strength was kept at O.1 (Table 1). These solutions were stood for 24 hr at 30C, after which dialysed to remove the excess reagents, The films from these solutions were obtained on polyethylene films by casting. The co-ordinated structure of copper(II) ion with hydroxy groups of PVA molecule in the film was confirmed by electronic and infrared spectra.The effects of Tc.2+/THL ratios on crystallinity, and thermal properties for these films were as follow;(1) The crystallinity, the size of semicrystalline and the melting points decreased with increaseing Tc.2+/THL ratios of higher than O.031 (Fig, 2, 3). (2) Activation energies for thermal degradation decreased with increasing Tcu2 ratios(Table 3). It is concluded from these results that the formation of intra-molecular crosslinking complexes distorts orientation of polymer chain and prevents the crystallization of PVA.

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The properties of the po1y(vinyl alcohol)(PVA)-copper(II) complex films prepared by dipping the polymer ligand films into cupric ammine complex aqueous so1ution have been investigated. The co-ordination bond between copper(II) ion and hydroxyl groups of PVA molecules in the film was confirmed by electronic and infrared spectra. The increase in the amounts of copper(II) ion bounded with PVA resulted in decrease in crystallinity, melting points, swelling index and Solubility in water of the complex films. As annealing temperature of the ligand films is raized, the amounts of copper(II) ion bounded with PVA decreased steadly up to 190c, after which were kept constant. On the other hand, in the films drawn by the monxial stretching, the amounts of copper(II) ion bounded with PVA were influenced by the drawn ratio and that maximum was observed in about 2.O drawn ratio. These results show that the complex formation between PVA films and copper(II) ion is affected by micro-structure of the ligand films.

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The quaternary salts from N, N-dimethylalkyl-amines (R: dodecyl, hexadecyl and octadecyl)and 4-nitro- or 4-chloro-benzylchloride were prepared and their physico-chemical, antibacterial and antifungous properties were studied. The results obtained were as follows.
(1) 4-Chloro-derivatives were supetior to 4-nitro-derivatives in such surface active properties as lowering of surfae tension, emulsifying of liquid paraMn and wetting of cloth.
(2) The long alkyl chain derivatives were more powerful in lowering of surface tension, increasing of 'a' mmounts of solubilized Orange OT, emulsifying and wetting as compared with the short chain"'derivatives.
(3) A linear telationship Was observed between alkyl chain length and log CMC for a homologous series.
(4) The growth retardati6n by the homologous compounds for mildew became progressively greater as. the carbon number of straight chain decreased.
(5) The substituents, chloro and nitro group on benzene ring decreased antibacteria aRd antimildew actions against our expectations.

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The experiment dealing with the emulsion polymerization of vinyl acetate has been carried out in the presence of poly(vinyl alcohol) as emulsifier using hydrogen peroxide as initiator, and the effect of the initiator amount on the properties of polymer emulsion has been investigated. The monomer was dropped by means of a continuous addition, process, and the initiater was added just before the start of monomer dropping and then at intervals of 30 min during a period of polymerization. With increasing initiator amotmt, an apparent viscosity of polymer emulsion inereased, reached a maximum, and then decreased. The effect on the viscosity of the initiator amount added just before the start of monomer dropping was significantly higher than that of initiator amount added during a peripd of polymerization. From the variation in the particles of polymer emulsions obtained by the polymerizations and the properties of the polymer firms, it seems that these results are caused by the interaction between poly(vinyl alcohol) and, the hydroxyl and groups of the polymer molecules coming from initiators or poly(vinyl alcohol)parts in graft polymers, which exist on the surface of the poly(vinyl acetate) particles.

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A copolymer of ethylacrylate(EA) and 2-chloroethylacrylate(CEA)(95/5 wt%), one of polyacrylate rubbers, has been vulcanized by using tetraethylenepentamine (TEPA) as a curing agent (Table 2, Table 3).
The molecular weight M_c, between crosslinks of vulcanized rubber was plotted against the number average molecular weight M_n of the uncured sample (Table 4, Fig. 1, Fig. 3). For fractionated samples, the critical primary molecular weight, above which the effect of polymer ends does not occur, was estimated from the relation between logM_c and logM_n (Fig 1). The critical primary molecular weight decreased with increasing amount of TEPA or degree of cross linking, on account of the effect of network imperfection resulting from chain ends (Fig. 3).
M_c, the corrected values of M_c for imperfection resulting from chain ends for samples of low molecular weight and those obtained by using small amounts of curing agent, were smaller than those of the vulcanized samples obtained from rubber with high primary moleeular weight and those obtained by using large amounts of curing agent (Fig. 1, Fig, 3, Fig. 6), because the M_c values were affected by the number (fraction) of chain ends of cured rubber. The sol fraction of cured sample has been investigated with respect to primary molecular weight of sample (Fig. 2) and amounts of curing agent (Fig, 4). The sol fraction was nearly zero with respect to the sample having molecular weight above the critical primary molecular weight. The critical molecular weight decreased as the amount of the curing agent increased(Fig. 4). Effects of curing time on properties ef cured samples have been investigated by using the curves between M_c and M_n, and those between sol fraction and M_n (Fig.5, 7), The cross linking efficiency of TEPA was about 50 percent (Table 5). The rate of formation of cross linking was constant for samples in the wide range of primary molecular weight (Fig. 6).

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The catalytic reduction of sulfur dioxide with carbon monoxide [SO2+2CO-1/ySy(elemental sulfur)+2CO2] was studied using a flow reactor (inside diameter:12.0mm) at atmospheric pressure and temperatures of 300 to 550C (mainly 550C).
In the absence of H20 and 02, sulfur, CO2 and COS were formed by the catalytic reaction. 50Co304-50Al203 showed the highest apparent activity, but was more inferior in the selectivity for sulfur. CuO-A1203 with less content of copper was the preferable catalyst in the selectivity for sulfur. For example, 10CuO-90Al203 showed about 100% selectivity.
However, in the presence of H20 and 02, in adition to COS, formed by the reaction of sulfur with CO, H2S was considerably formed by the side reactions:CO+H20-CO2+H2, 3H2+SO2-H2S+2H20, etc. Furthermore, the marked deactivation of the catalysts was found to be dependent on the temporary poisoning due to the adsorption of water vapor and on the formation of oxide and sulfate of reduced metal (copper, cobalt, etc.) in the catalyst.

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The dehydration of ethanol on porous glasses which were exchanged with several metal ions was investigated with respect to varieus ion-exchanged degrees. Besides, the residual surface hydroxyl groups on the catalysts were also studied by infrared spectroscopic method.
The present results show that the catalytic active groups are the hydrogen-bonded surface hydroxyl groups, while the catalytic inactive groups are the free surface hydroxyl groups.

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Oxidation of palladium metal by Cu(II) salts has been investigated in acetic acid solvent. The rate of Pd(II) formation was proportional to the surface area of the palladium metal (Fig. 1), and incteased with the elevation of reaction temperature (Fig. 2). The reaction rate was approximately 1.5 order with respect to chloride ion concentration (Fig. 4), and decreased upon addition of LiOAc or Mn(OAc)₂ (Fig. 5, 6).

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Selenocyanate ion (0.01-0.0001N) was precisely titrated with a silver nitrate solution in the presence of 0.01N ammonia and 0.1N potassium nitrate by means of a short-circuit amperometry using a rotating (1000 rpm) platinum wire electrode and a mercury-mercuric iodide electrode (-0.23V vs. SCE).
Selenocyanate and thiocyanate ions in their mixture were determined as follows. Selenocyanate was titrated under the same conditions mentioned above, then, thiocyanate was titrated at the petential of SCE after acidification of the solution with dilute nitric acid.

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