Substituent effect on the electronic spectra of fluorene [F] and N-methylcarbazole [NMC] was examined. Their L_b absorption bands were very sensitive to the substituent at the 2- position The wavenumber of L_b bands was related to the parameter |σ_R| of the substituent at the 2-position. From the comparison of the present results with those for dibenzofuran [D] which were reported previously, the intramolecular interaction of the oxygen 2ρ-electrons of [D] with the π-electron system was discussed. The substituent effect at the 3-position on the L_a band of [F] was also examined and compared with the results for [D].

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The equivalent conductances of tetradecyldimethylbenzyl-, octadecyldipolyoxyethylenemethyl-, and dioctadecyldimethylammonium chlorides have been determined. There was no anomaly in the conductance-concentration curve for the aqueous solutions of tetradecyl dimethyl benzylammonium chloride, but that for octadecyldipolyoxyethylenemethylammoniurn chloride showed a maximum at a concentration below the critical micelle concentration. Much lager equivalent conductances of dioctadecyldimethylammonium chloride in very dilute solutions than expected indicate that a maximum is also present. These maxima may be explained as follows. Owing to the steric hindrance of the long-chain substituents of surfactant ions, the counter ions can not form non-conducting ion-pairs with micellar ions and the tendency of surfactant ions to associate with each other is strengthened. Thus, the formation of multi-valent surfactant ions will cause a sharp rise in conductance in dilute solutions.

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The surface area covered by adsorbed dye molecules on the fiber, which is determined from the slope of the surface day adsorption vs. total dye adsorption curves C potential method-, was investigated for nylon 6 fiber treated under different conditions of spinning, drawing and heat-setting, in acid dye solution. The surface area was compared with the BET specific surface area of the fiber determined by the adsorption of nitregen and water vapor. It was suggested that both surface areas are independet of spinning temperature and dependent on draw ratio and heat-setting condition, and that they are governed by the change in the crystallinity and the birefringence. The surface area covered by adsorbed dye molecules was always larger than that determined by the adsorption of nitrogen (about 10³ cm²/g-fiber). Moreover, the former was of the same order as that determined by the adsorption of water vapor (about 10⁶ cm²/g-fiber), but it had slightly larger value than the above. The surface area of wet-heat-set fiber covered by adsorbed dye molecule and determined by the adsorption of water vapor gave abnormally high values.

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The promoting effect of CoO on the activity of Al2O^2-MoO^2- catalyst was investigated, by the extraction experiment for the catalyst by aqueous ammonia and the measurement of the isomerization rate of 1-butene over the catalyst.
The results in extraction of MoO₃ from Al2O^2-MoO^3-Co0 and MoO^2-Co0 catalysts by aqueous ammonia indicate that mixed oxides of CoO and MoO^2- are formed in both catalysts and CoO in MoO^2-Co0 catalyst combines quantitatively with MoO₃ and formes the mixed oxide correspond to CoMoO^2- (Fig.2). In Al2O^2-MoO^2-Co0 catalyst, however, CoO combined with a portion of MoO₃ (Fig.1).
The isomerization of 1-butene was accelerated by the addition of CoO to Al2O^2-MoO^2- catalyst but was not by MoO^3-Co0 catalyst (Fig.5). These results suggest that the mixed oxide formed in Al2O^2-MoO^3-Co0 catalyst is different essentially from that of MoOs-CoO catalyst.
The addition of CoO to Al2O^2-MoO^2- catalyst results in increasing the reactivity of active site which is considered to be surface oxygen in the oxide such as Co8O^2- or a mixed oxide of CoO and MoOs.

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For the oxychlorination of 1, 3-butadiene to obtain, 3, 4-dichloro-1-butene and 1, 4-dichloro2-butene, copper (II) chloride supported on sintered alumina-silica was found to be a suitable catalyst. The conversion of 1, 3-butadiene and the selectivity for dichlorobutenes were found to be improved by the addition of alkali metal chlorides. Phosphoric acid was effective for the improvement of selectivity. The addition of both compounds gave a better result.
The conversion and the selectivity obtained by a catalyst composed of CuCl2, LiCl, H₂PO₄ and carrier, for example, with a weight ratio of 1.86 x 10-2, 1.96 X 10-3, 1.51 x 10-8 and 1.0, were 72% and 92%, respectively, at 2509C and a space velocity of 210 hr'. for the effect of alkali ions, butadiene conversion at 200'C decreased in the following order, Csfrz-, R. b>Na> Li, while the selectivity for dichlorobutenes at 250°C showed different order, Li > Na > Rb> Cs, although the effect of KCI was somewhat different.
The butadiene conversion was independent of reactant gas pressure in the case of alkali promoted catalysts, but dependent on HCl in the case of unpromoted catalysts. Therefore, the addition of alkali metal chloride seemed to speed up the velocity of oxychlorination by activation of HCI.

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The oxychlorination of 1, 3-butadiene over CuCl2-H3P0, -LiCl supported on commercial carriers such as active carbon, silica-gel, r-alumina, celite, silicon carbide and five samples of sintered alumina-silica has been studied. The reaction temperature was 130-275°C and the space velocity was 210 Among the carriers studied, sintered alumina-silica was the best with respect to the selectivity to dichlorobutene and the conversion of butadiene. Other carriers of high surface area were less effective. In the case of sintered alumina-silica, the presence of β-alumina lowered the selectivity and ZrO₂ contained as impurity exhibited a favourable effect.
On the basis of these results, we prepared a catalyst by using as the carrier base a-alumina which contained 0.O^2-5 wt % Zr on the surface and by treating it for 15 hours at 300°C and obtained a maximum conversion of 79% and a 92% selectivity to dichlorobutene. The effect of Zr, however, was restricted to the LiCl promoted catalyst. The increase in the conversion by Zr may be attributed to the increase in the number of effective active because the catalysts with and without Zr gave practically equal activation energies of 30.2 kcal/mol and 31.6 kcal/ mol, respectively, and the difference in the selectivities to dichlorobutene was undetectable.

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When some kinds of diazonium compounds were partly photolyzed by UV or visible light, the remaining diazonium compounds decomposed at an accelerated rate. This enhanced thermal decoMposition of diazonium compounds was remarkable especially after the dye-sensitized photolysis. The decomposition rate was affected by the chemical structure of the diazonium compound, the extent of exposure and other factors such as-the pH of the solution; the amount of dissolved oxygen and the temperature. Benzene diazonium compounds with p-amino substituents showed notable enhanced thermal decomposition at a pH from 6 to 7 under an aerobic condition, where the dissolved oxygen played a significant role. After UV exposure, 4-diazodiphenylamine hydrogensulfate (4-DS) acceleratedly decomposed with a pseudo first-orderrate (activation energy: 26 kcal/mol). The species responsible for the enhanced thermaldecom, posi- tion was proposed to be p-hydroxydiphenylamine which was the main product of the UV photolysis.

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The electrolytic reduction of a variety of amino, aliphatic, and aromatic nitriles was investigated by means of constant current electrolysis in aqueous sulfuric acid at palladium black, mercury, and lead cathodes. Amino nitriles were 2 H-reduced at a palladium black cathode, while those were 4 H-reduced at mercury and lead catt: iodes. On the other hand, aliphatic and aromatic nitriles were 4 H-reduced at all cathodes. For all nitriles, it was also found that the reduction efficiency is increased by electron-releasing substituents at a palladium black cathode and by electron-attracting substituents at mercury and lead cathodes. On the basis of the results, it was supposed that the electrolytic reduction of nitrile proceeds by the catalytic hydrogenation at a palladium black cathode and by the electrochemical electron-transfer at a mercury or lead cathode.

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The tellurium content of the crystal deposited by electrolysis of zinc ion in alkaline solution containing a trace of tellurium ion was determined under galvanostatic or potentiostatic condi tions, and the deposits were observed by an electron microscope. The content of tellurium of the deposit was about 10-3-10-2 per cent of that of zinc and it was relatively high in the initial stage of the deposition and in the range of low current density (10-20 mA/cm²) or low overpotential (-20 mV). The deposition overpotential of "zinc increased with ion concentration in the bath. Further, The deposit with laminar structure was obtained by electrolysis in the bath containing small amount of tellurium ion.

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The effect of temperature on the anodic behavior of zinc has been studied under galvanostatic or potentiostatic condition in an aqueous KOH solution saturated with ZnO. Passivation time became longer as bath temperature was higher up to about 50°C and revealed a peak at the temperature. Temperature of the peak was shifted from 50 to 56°C by the increased current density. Passivation of zinc was scarcely influenced by the existence of Cl- in the bath. The anodic polarization curves indicated that the anodic dissolution of zinc was accelerated by raising the bath temperature. A dark film was formed on the anode in the low temperature range while the film became blue in the temperature above 50°C. From the results obtained, it was considered that the anodic process of zinc and the properties of the anodic film might be changed at about 50°C.

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The ionic conduction in sintered oxides with hollandite-type structure, Ka, MrTi8s016 (M=Al, Fe, Co, Cr), was investigated. These oxides have tetragonal lattice and contain tunnels along the c axis. In the case of KzAlsTi8x0, 6, well sintered products were obtained when K2CO₃, r-Al2O^2- and TiO₂ were fired at 1200°C for 5 hr after prefired at 950°C for 10 hr. On the basis of the powder X-ray diffraction patterns, fluorescence X-ray analyses and lattice constants, the composition range where the tetragonal single phase of KxA4Ti8_s016 appeared was determined to be 1.6 <=X<=2.0.
Tablets about 11 mm in diameter and 2 mm in thickness were prepared from the sintered oxides with the compositions 1.4<=x<=2.2. The conductivities of the specimens were measured by using 10 kHz A. C. impedance bridge in the temperature range from 200° to 400°C. Gold plates of 0.05 mm thick were used as electrodes. The conductivities increased from 10-5 to 10-s mho. cm^-1 with increase in x of the single phase. The charge carrier was clarified to be potassium ion from analyses of D. C. polarization curves and of the weight change of the tablets before and after the electrolysis and the qualitative analysis of cathode products. The conductivities of K2M2T40, 8 (M=Fe, Co, Cr) measured by the similar method as in the case of KrA1xTi8, 016 showed that the conduction was mixed ionic and electronic character. The potassium-ion conduction in the hollandite type structure was discussed.

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For the clarification of the physiCo-chemical position of hydrated melt in the electrolytewater system, viscosity, electro-conductivity, density, refractive index, laser Raman spectrum, near infrared spectrum and visible spectrum were measured in the various concentration of hydrated FeCl₃.
Bending points or maxima were found in physical properties and concentration relationship at the FeCl₃ concentration 5 to 6 mol/l. For higher and lower concentration region of these singular points, different peak profile were obtained in Raman, near infra-red and visible spectra. The bending points and maxima were greatly influenced by the H+ concentration and temperature, and the increase of the H+ concentration and temperature shifted singular points to the lower concentration.
The dependence of the physical properties and peak profile on the composition of FeCl₃-H₂0 system was interpretated to be based on the change of the coordination number of Fe₃ from six to four. The hydrated melt, of FeCl₃.6 H₂O situated in the four coordination region of FeCl₃-F120 system.

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The reaction between solid sodium aluminate, one of the binary metal oxides, and SO₂ was studied by using a gas flow reactor. - The sodium aluminates were obtained by evaporating sodium aluminate solutions with Na₂0/Al2O^2- ratios (mole) between O.5 and 3.0, which were prepared by dissolving various amounts of metallic aluminum in sodium hydroxide solution. The reaction behavior and mechanism of sodium aluminate with SO₂ were examined at 330°C and 130°C.
In the case of reaction of sodium aluminate containing excess sodium, it was found that the rate of initial stage was fast, and the reaction in this initial stage occured between SO₂ and NaOH involved in the sample. An approximately linear relationship existed between the amount of initial reaction and the amount of NaOH in the sample. On the other hand, the rate of later stage was slow, and in this region the reaction between Na₂Al2O^2-, involved in the sample, and SO₂ occured. 'The rate of the reaction increased with an increase of the reaction temperature.
The results of X-ray diffraction and IR analysis of the samples before and after the reaction suggested that the reaction was expressed by the following four equations,
2 NaOH SO₂ -4- Na₂SO^2- + H₂0
Na₂Al2O^2- + SO₂ Na₂SO^2- + Al2O^2-
2 Na5A1O^2- + 5 SO₂ 5 Na₂SO^2- + Al2O^2-
2 Na₂SO₃ + O^2- -3.2 Na₂SO₄
For Na₂SO₄ formation, it was recognized that Al2O^2-, which was formed from the reaction between Na₂Al2O^2- and SO₂, promoted the oxidation of Na₂SO^2-.

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It is important to determine the flow rate of mercury in designing a large capacity amalgam cell of 500-800 kA, because its operation is disturbed by the formation of the film and discharge of hydrogen ion on the mercury cathode. In the case of high flow rate of mercury, the cathode potential in amalgam cell was measured, and the results were summarized as follows:
( 1 ) The cathode overvoltage is only 30 to 80 mV.
( 2 ) Sodium concentration on the surface of the mercury cathode is appreciably high at high current density.
( 3 ) The thickness of the boundary layer was an order of 10-3 cm under high flow rate of mercury as 50 to 110 cm/sec.

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The compressed mixture of calcium hydroxide and silica gel powder was treated hydrothermally at various temperatures between 140°C and 300°C, in an autoclave filled up 12% water. The influences of CaO/SiO^2- ratio, moulding pressure, reaction period, reaction temperature, the amount of unreacted lime, the morphology and the kinds of reaction products on the compressive strength of cured bricks were inverstigated.
The compressive strength of the cured bricks varied with the CaO/SiO₂ ratio, and at the temperature below 180°C the maximum values were obtained in the bricks with CaO/SiO^2- ratio of 2/3 and 1/3. The maximum value was found in the lower CaO/SiO^2- ratio (1/3) bricks cured at an elevated temperature. For example, the maximum strength was 280 kg/cm² for 2/3 ratio cured at 140°C, and 560 kg/cm' for 1/3 ratio at 300°C. The bulk specific gravity and combined water content in bricks decreased with an increase of the curing temperature and the treating period. The unreacted lime in the reaction product decreased with the increase of the curing period, but it was not the case in product with CaO/SiO^2- ratio under 2/3. From the result of X-ray diffraction analysis, a compound like CSH (1) was found in the products cured below 180°C, and xonotlite or gyrolite were found in the product cured above 250°C. The highest compressive strength was attained in the brick containing gyrolite.
Polarizing microscopic observation made it clear that at lower temperature the reaction products were scattered around the original silica gel particles, and at higher temperature the boundary of silica gel disappeared and the products dispersed in the matrix. The bricks cured at high temperature gave good heat resistivity. The bricks with CaO/SiO^2- ratio 1/3 cured at 300°C for 6 hrs revealed only 3% contraction after heating at 800°C.

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This work was undertaken to prepare and to characterize a binderless carbon article (pitch carbon) with a high density. In order to prepare the variant pitch material, coal tar pitch was distilled at 500°C for 20 minutes by blowing nitrogen gas through it. The variant pitch material was pulverized by use of ball mill and, was moulded into the rods under high pressure of 1600 kg/cm². The pitch carbon (12 x 12 x 95 mm) having about 1.8 g/ml in bulk density was prepared by heat treating above 2200°C without any damages. The pitch carbon was analogous to glassy carbon in mechanical properties such as shore hardness, transverse breaking strength and compressive strength.. The electrical resistivity, thermal conductivity, graphitizability and preferred orientation of the pitch carbon were similar to those of the conventional artificial graphite. In view of its overall properties, the pitch carbon was characterized as intermediate carbon product between the other two carbon products. Moreover, it was confirmed that the moulding of the variant pitch material under high pressure is appropriate for the preparation of the large sized pitch carbon with a high density.

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The purpose of the present study is the elucidation of the chemical characteristic of the water quality of the streams around Rokko Mountains, based on the inorganic chemical analyses of the samples taken from June in 1972 to November in 1973.
As shown in the geological maps by Ueji (1937) and Fujita-Kasama (1971), the major portion of the mountain body is composed of granite which is furthermore classified into biotite granite and granodiorite. In the limited region, Chichibu Paleozoic strata are distributed and Mt. Kabuto is composed of pyroxene andesite.
The average concentrations of the main components of the streams-water over the whole granite region are very close to that of river-water in Japan as reported by Kobayashi (1960). The correlation coefficients between the components elucidate a mechanism of chemical weath- ering process of the rock by carbon dioxide reported by Kitano and others (1967). The amounts of the main components in granodiorite region dissolved in the water are more than those in biotite granite region, except for fluoride. This should be due to the relative higher contents of the components and the relative chemical unstability of the rock.
A characteristic of the streams in the Paleozoic strata region is due to relative high content of magnesium, and in the streams at the pyroxene andesite area its tendency becomes more noticeable.
The quality difference of the streams-water in each region mentioned above is clearly expressed by the plots of the equivalent ratios of magnesium and calcium to total cations, as shown in Fig.2.
In the north-eastern Rokko region some high co ntent of fluoride in streams- and wells-water has been recognized by Tsurumaki (1962) and others. Based on the present author's considerations concerning the correlation coefficients between the content of the fluoride and that of other main components, it is concluded that the fluoride in the streams-water in this region is mainly derived from the granite rocks with relatively high content of fluorine.

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Copper (II) was found to react with 6-hydroxy-5-nitroso-1, 3-dimethyl-1, 2, 3, 4-tetrahydropyrimidine-2, 4-dione (HNDU) to form a water-soluble yellow complex easily, and the optimum conditions for the spectrophotometric determination of copper (II) have been studied. The Cu (II)-HNDU complex has an absorption maximum between 420 and 430 nm and shows a definite absorbance over the pH range from 5.5 to 6.8. Beer's law was obeyed up to 10.0 Azglml of copper (II), the molar extinction coefficient of the complex and the sensitivity of the determination being 5.3x 10⁸l/mol cm and 1.2X 10-2 pg Cuicm² for log (I₀/I) = 0.001, respectively. Several ions such as cobalt (II), iron (II), citrate and tartrate interfered with the determination. The molar ratio of copper (II ) to HNDU has been confirmed to be 1: 1 by the mole ratio method.

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With an aim of its application to the analysis of chromium in soil and sea-sediment, the interference of diverse ions on the absorbance of chromium and its elimination with air-acetylene flame was investigated.
Chromium in the sample was eluviated by decomposing it with hydrochloric acid prior to the atomic absorption spectrophotometric procedure.
The condition recommended for chromium determination were as follows, wavelength; 357.9 nm, air pressure; 1.5 kg/cm² (flow rate; 7.1 l/min), acetylene pressure; O.28 kg/cm² (flow rate; 1.4 //min), beam height above burner top; 18 mm.
The depression of chromium absorption was observed in the coexistence of iron, titanium, vanadium, nickel, cobalt, magnesium and barium. The interference of iron, titanium, vanadium, nickel and cobalt could be eliminated by the addition of potassium sulfate to the unknown and standard samples. The interference of magnesium and barium could be eliminated by the addition of aluminum.
Naturally, soil and sea-sediment are rich in interfering elements, such as iron, titanium and vanadium, and contain, much potassium and aluminum. Thus, chromium in soil and seasediment could be determined by directly atomizing the eluviated solution into the air-acetylene flame without being interferred by the presence of several coexisting elements.

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Zincon(2-carboxy-2'-hydroxy-5'-sulfoformazyl benzene) reacts with cobalt(II) and forms a chelate anion which is extractable into chloroform by the presence of zephiramine (Z+Cr, benzyl-dimethyl-tetradecyl-ammonium chloride). When pyridine coexists with zephiramine, the quarternary complex, which is also extractable into chloroform, is formed. The molar absorptivity of the quarternary complex is about four times that of the ternary complex. The ternary complex shows the broad absorption band from 660 to 700 nm in the chloroform extract. On the other hand, the quarternary complex having blue coloration shows the absorption maximum at 675 nm in the chloroform extract. The optimum pH range for the extraction of the quarternary complex is 8.3-9.0. When the amou nts of zincon, zephiramine and pyridine are more than one and half times, ten times and a thousand times, respectively, that of cobalt, cobalt is extracted quantitatively into chloroform as the quarternary complex. Beer's law holds for the quarternary complex extracted under the optimum condition in the concentration range of 1.85--24.7 pg cobalt/10 ml. The molar absorptivity is (2.16+-0.O3) x 1O⁴ cm-2 mol-1 l.
Cobalt is oxidized to cobalt(III) in ammonia-buffered, aqueous media, and cobalt(1I) complex formed is extracted into chloroform as the quartenary complex. In the absence of pyridine, the ternary complex of cobalt(I11) is not extracted into chloroform. However, the absorption spectrum obtained for the extract of cobalt(II) in the presence of pyridine coincides with that of quarternary complex in which the oxidation state of cobalt was +3. The oxidation state of cobalt in the extractable ternary complex was, therefore, +2.

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The fundamental parameters which affect normal pulse 'polarographic wave have been investigated comparing with those of sampling DC polarography (tast polarography), and various phenomena observed in DC polarography migration current, maxima, kinetic wave and adsorption wave (prewave and postwave) have also been studied using normal pulse polarography.
Regardless of whether the reduction process is reversible or not, the limiting currents of normal pulse polarography for diffusion-controlled wave are about 2 to 6 times greater than those of tast polarography in the drop time range of 0.5 to 5 sec. On the other hand, in the case of formaldehyde kinetic wave, the wave heights of normal pulse polarography for cathodic and anodic scans are only about 10% higher than those of tast polarography over the drop time range used.
The migration current causes a round peak on the rising portion of the limiting current on normal pulse potarogram.
The "negative" maxima, which are observed for the solution of 1 mmol/l of Zn (11) and Ni (II) in ammoniacal medium at the absence of maximum suppressor, cannot be found on normal pulse polarogram. However, the "positive" maxima, which are observed for Cu (II) wave and the first wave of oxygen, are found on both normal pulse and tast polarographic waves.

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Mechanism of initial dehydration of ZrOCl2.8 H₂O was investigated by isothermal heating and X-ray diffraction studies. In the range of 50°C to 66.5°C, two molecules of three-coordinated lattice water are lost in the first step of dehydration and subsequently one molecule of four-coordinated lattice water is lost. After the loss of three molecules of lattice water, the rate of thermal decomposition become slow and the crystal structure changes. It seems that above 66.5°C, both dehydration and chemical reaction which produces HCl presumably occur competitively. Activation energy of the initial dehydration is estimated to be 12.9 kcal/mol.

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A method has been developed for the determination of traces of gold in pure zinc by neutron activation analysis using ion exchange preconcentration.
Five grams of sample was transferred to a 50 ml beaker and dissolved in a least amount (about 30 ml) of 9: 1 mixture of HNO₃ and HCl. The sample solution was slowly cooled to room temparature, on standing, then diluted to 50 ml with water, and then passed through a small column packed with 150 mg (wet basis) of Dowex 1-X 8 AG anion exchange resin (Clform, 100-200 mesh) to separate gold from zinc (see Fig.1). Then, the resin was treated with 15 ml of 0.2 N HNO₃ solution to convert to NO^3-form, and finally washed with water. The resin was transferred into a polyethylene bag and dried in an electric oven at 75°C for about 10 hours, and heat-sealed off.
The resin samples together with standards were irradiated with pneumatic tube system of JRR-2 reactor at a flux of 7x 10" n/cm²/sec for 20 minutes. After being cooled for about 5 hours to allow 28Cl to decay out, the irradiated resin was slurried with water and transferred into a column previously packed with 50'-.400 mg of non-irradiated Dowex 1-X 8 resin (Cl-form, 100-200 mesh), then treated with 20 ml of 0.5 N HCl solution to elute out the interfering nuclides (see Table 1). 198Au remained on resin was then counted with a Ge (Li) detector after cooling for about 7 hours, or with a NaI (T1) detector after cooling for about 1 day.
The chemical yield of gold was about 98%, and the concentration factor was 2.2 X 107. The blank was 0.05 ng on an average. The minimum determinable and detectable masses are thus presumed to be about O.5 ng (10-fold of blank) and 0.1 ng (2-fold. of blank), respectively.

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Irradiation of phenylacetylene [1] in tetrahydrofuran in the presence of acetophenone or benzophenone using high pressure mercury lamp resulted in the formation of 1: 1 adducts β- (tetrahydro-2-furyl) -styrene [2 a and 2 b] and 1, 2-ethanediols. However, the reaction hardly tookplace in the presence of naphthalene or phenanthrene, or by nonsensitized irradiation with low pressure mercury lamp (Table 1). From the results, the reaction is considered to proceed via hydrogen abstraction by the excited keton sensitizers followed by addition of tetrahydrofuryl radical to [1].
In the photoreaction of methyl phenylpropiolate C 3 J with tetrahydrofuran, 1: 1 adducts, methyl a- (tetrahydro-2-fury1)-cinnamate (4 a and 4 b) were also obtained. The reaction was quenched by 1, 2-pentadiene and a\ Stern-Volmer plot (Fig.1) gave a straight line. The photoreaction of C 3 J and photoisotherization of the mixture of (4 a) and (4 b) were carried out by use of various triplet sensitizers (Table 2 and 3). From the results thus obtained, it was found that the triplet excited state of ( 3) has an impprtant role in the reaction, and the lowest triplet excitation energies of ( 3) and (4 b) (trans isomer) were estimated at 56.9-61.8 and approximately 59.5 kcal/mol, respectively.

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The reaction of camphene with o-cresol was carried out under various temperatures in the presence of such catalysts as boron trifluoride etherate, activated earth, aluminium chloride and cation exchange resin.
The gas chromatogram of the crude reaction product showed formation of six products and their contents varied over a wide range with the change in the catalysts and the reaction temperature.
When boron trifluoride etherate was used as a catalyst, the ratio of ortho-substituted products (CO-1, CO-3, CO-4) to para-substituted products (CO-2, CO-5, CO-6) in the adducts was 3.O4: 1.
In the case of activated earth, aluminium chloride or cation exchange resin, the ratio of the ortho to para was O.35: 1, O.51: 1, O.61: 1, respectively. The reaction at elevated temperatures gave the products which contained more para isomer in all case.
The adducts (C0-3, CO-4, CO-5, CO-6) were identified on the basis of their spectral data (NMR, 'IR, Mass) as 6-isoborny1-2-methylphenol, 6- (6'-exo-isocamphyl)-2-methylphenol, 4- camphenyly1-2-methylphenol, 4- (6'-exo-isocamphyl)-2-methylphenol respectively.
A mechanism to account for the observed results is presented.

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Addition reactions of aliphatic alcohols to tetrachloroethylene using organic peroxides, as an initiator yielded 1: 1-adducts and the corresponding unsaturated compounds. Their yields, in general, were found to be lower than those observed previously for the reactions initiated by r-ray.
The saturated chlorine-containing alcohols thus obtained were acetylated in yields from 62 to 89%. The yields decreased in the order:
Isopropyl>Ethyl, Methyl>n-Propyl
Behavior of the acetates of the ethanol-adduct and the corresponding unsaturated compound towards treatment with bromine under UV-irradiation was also examined. A monobrominated compound was obtained in 61% yield from the acetate of the saturated adduct. From the unsaturated acetate, another bromine adduct was obtained in 65% yield. Synthesis of Oxygen-containing Halogenated Compounds. V.

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A novel synthetic method of cyanqdienes (2, 4-pentadienenitriles) from 1, 4-dibromo-2-butenes was found.1, 4-Dibromo-2-butenes (1 mol) was treated with 1.2 mol of potassium cyanide and 1.2 mol of potassium hydroxyde in a water-acetone mixture.1-Cyanobutadiene C 1 J was obtained from 1, 4-dibromo-2-butene (71%, Table 3). From 2-methyl-1, 4-dibromo-2-butene, the mixture of 1- and 4-cyanoisoprene [2 and 3] was obtained (91%, [2]/[3]=22/78, Table 4). The photosensitized dimerizations of the above nitriles were also studied. Each dimerized product by these reactions had a six-membered ring. Furthermore, in the presence of radical trapping reagents, the reactions were retarded. Therefore, these reactions seem to proceed on the stepwise radical mechanism.

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Reactions of the title compound [1] with nitric acid (d=1.38) have been investigated in chloroform, carbon tetrachloride, nitromethane, methanol, and acetic acid. In every case, [1] underwent facile nitrative cleavage and nitrodecarboxylation to yield 2-hydroxy-3-methy1-5- nitrobenzoic acid [2] as the major isolable product. Other products obtained include 4, 4'- dihydroxy-3, 3'-dimethyl-5, 5'-dinitrodiphenylmethane [3], 4-hydroxy-3-methyl-5-nitrobenzyl nitrate [4], and 4, 6-dinitro-o-cresol [5].
Substantial amounts of [3] were formed in the reactions in acetic acid. In addition to these, 4-hydroxy-3-methy1-5-nitrobenzyl methyl ether [7] and 4-hydroxy-3-methyl-5-nitrobenzyl acetate [8] were obtained from the reactions in methanol and acetic acid, respectively. These benzylic compounds probably arose from the solvolysis of the initial product [4].
With increase in the amount of nitric acid, formation of [5] and unidentified carbonyl compounds became prominent. Further addition of nitiric acid upon C 3 3 in chloroform led to similar cleavage, giving [4], [5], and 4-hydroxy-3-methyl-5-nitrobenzaldehyde [9]. By heating in acetic acid under, gentle reflux, [4] was readily converted into a mixture of [5] and [8]. Possible pathway from [1] to [2] has been suggested.

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cis- and trans-Tetrahydrofuran-3, 4-diacetic acid [6 a and 6 b] were prepared by the ozonization of cis- and trans-8-oxabicyclo[4.3. O]non-3-ene [5 a and 5 b] and subsequent oxidative cleavage of the resulting ozonides with formic acid and hydrogen peroxide mixture. [6 a] was easily converted to anhydride [8 a] and the Dieckmann reaction of the diethyl ester of [6 a] gave cis-2- (ethoxycarbonyl) -7-oxabicyclo[3.3. O]octane-3-one [11 a], however, the same reaction of [6 b] did not proceed. Pyrolysis of [6 a] gave meso-β, β'-bibutyrolactone [9 a] and cis-7- oxabicyclo[3.3.0]-octane-3-one [12], while [6 b] gave dl-β, β'-bibutyrolactone [9 b] only.

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In the deep-hydrodesulfurization of Khafji atomospheric residue over a cobalt-molybdenumalumina catalyst in the fixed-bed cocurrent up-flow reactor, hydrocracking of the residue occurring simultaneously with the desulfurization was studied under the following experimental conditions; total pressure: 50-200 kg/cm², temperature: 400-460°C, LHSV=1-6, and hydrogen-oil ratio: 500-3000.
The relation between hydrocracking and hydrodesulfurization, the reaction order of hydrocracking, its dependence upon the reaction pressure and temperature, and the hydrogen consumption in it are examined here.
The value indicating the extent of hydrocracking, such as the amount of produced gaseous C_1-4 saturated hydrocarbons, density and viscosity, fractional ratio of 300°C cut distillate and residue, and asphaltene content in the product oil, changed markedly near the point of desuclfurization of 85-90% except for the viscosity. This observation suggests that rapid hydrocraking reaction occurred in the region of desulfurization above 85-90%. The reaction order of hydrocracking appears to be the 2nd order in the region of comperatively low desulfurization, which agrees well with that of the hydrodesulfurization reaction reported in our previous paper. But, in the region of higher desulfurization, where the effect of desulfurization reaction on hydrocracking can be eliminated, the reaction order was found to be the 1 st which is considered to be proper as the reaction order of hydrocracking of the heavy oil. The reaction rate of hydrocracking appears to have a maximum value at the pressure around 150 kg/cm². It seems to be most probable that the hydrogen consumption have a linear corelation with the fractional ratio of hydrocracking as follows: z11-12=17 z+4.

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In order to take the progress of deactivation into consideration in the rate equations derived in the previous paper, the cracking of butane over a silica-alumina catalyst in a tubular flow reactor was investigated at 600°C, under atomosperic pressure and with feed rates of butane of 16 to 59 m//min. Particular attention was paid to the changes of the amount and the atomic ratios of hydrogen to carbon of coke (Figs.1 and 2) and the distributions of gaseous products (Figs.3 and 4) as a function of process time.
The stoichiometric equations derived in the previous paper were modified by introducing the two-step reactions of coke formation which could explain the observed decrease in the H/C ratios in coke with increasing process time (Table 1). By solving simultaneously the rate eqUations (Eq. ( 1 ) ) and the process equations containing the position of reactor and the process time as the variables by Marquardt method, the rate parameters were obtained (Table 2). These values explain satisfactorily the changes in coke formation and gaseous product distributions with process time.

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Mononitration of toluene with nitric acid in the mixture of aromatic sulfonic acids and phosphoric acid in place of sulfuric acid on the usual nitration method with mixed acid (nitric acid and sulfuric acid) was studied. The distribution of mononitro-isomer was examined by means of GLC. It was found that the yield of mononitrated products was favorable and the content of p-isomer wes higher than that on the usual method.
Thus, the liquid mixture (water content 1.0-1.5%) of m-benzenedisulfonic acid-H₃PO₄ (1: 3 weight ratio), toluene-2, 4-disulfonic acid-H₃PO₄(1: 3) or nitrobenzene sulfonic acids (nitrated products of benzenesulfonic acid)-H₃PO₄(1: 2) and toluene (CH, C, FISHNO, : 1.5 (mole ratio)) was violently stirred and 98% nitric acid (HNOSaeid mixture: 1/20-1/30 (weight ratio)) was added dropwise at 0-2°C. The yield and pi° ratio in the mononitrotoluene mixtures was 94-97% and 1.5-1.6, respectively.

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The partial methylation of 3, 4, 6-trimethoxycatechol [2] with dimethyl sulfate yielded 2, 3, 5, 6-tetramethoxyphenol [3] and 2, 3, 4, 6-tetramethoxyphenol [7] which was easily oxidized to quinone [8] with ferric chloride solution. The Friedel-Crafts acetylation of isopropyl ether [12] of [3] in ethyl ether afforded 2-hydroxy-4-isopropyloxy-3, 5, 6-trimethoxyacetophenone [l4], 1-acetoxy-2, 3, 5, 6-tetramethoxybenzene [IO] and 1-acetoxy-2-ethoxy-3, 5, 6- trimethoXybenzene [l5].
2-Hydroxy-4-isopropyloxy-3, 5, 6-trimethoxy-w-aroylacetopheriones [20] were obtained from [l4] and substituted benzoyl chlorides by the Baker-Venkataraman transformation. The cyclyzation of w-aroylacetophenones [20] with sodium acetate in acetic acid affcried 7-isopropyloxy-5, 6, 8-trimethoxyflavones [21] (Table 6). The hydrogenolysis of [21 a, b] yielded 4'- hydroxyflavones [22 a, b]. The partial dealkylation of flavones ([22 a, b] and [21 c, d]) with anhydrous aluminm chloride in acetonitrile gave 5, 7-dihydroxy-6, 8-dimethoxyflavones: sudachitin [1 a], demethoxysudachitin [1b], hymenoxin [1 c], and nevadensin [1d] (Table 7).

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Aralkyl and aliphatic diisocyanates are now increasingly important as starting materials for non-yellowing polyurethane resins. The present investigation was undertaken to determine the chemical shifts of the NH proton of aralkyl and aliphatic isocyanate derivatives using the NMR spectroscopy in polar solvent like N, N-dimethylacetamide (DMA), dimethyl sulfoxide (DMSO) and pyridine.
It was found that the chemical shifts of the NH protons in the urea linkage derived from xylylene diisocyanate (XDI) and benzyl isocyanate fall into the region from 6.40 to 7.42 (in DMSO), while those for the urethane around 8 7.50. On the other hand, the NH proton signals in the allophanate and the biuret are expected to appear at slightly lower field than those in the urethane and the urea due to intramolecular hydrogen-bonding with carbonyl oxygen. Actually, 1, 3, 5-tribenzylbiuret showed the NH signal at 5 8.75 (in DMSO). Ethylcx, T-dibenzylallophanate also showed the NH signal at 8 9.O2.
The NMR in the region of methylene group can also be used for the discrimination of XDI derivatives. The isomer ratio of XDI (ni-XDI and p-XDI) can be determined by their ring proton signals when the NMR measurement of their urethane derivatives is made in DMA containing lithium chloride. Further, in the case of aliphatic isocyanate derivatives, the NH proton signal was observed at fairly higher field than those of aromatic and aralkyl isocyanate derivaties.
It is now clear that aromatic, aralkyl and aliphatic isocyanate derivatives afford the NH signal at the increasing field in this order and can be distinguished from each other by their NMR in the region of NH proton. This results suggest that XDI has an intermediate proper- ties between the aromatic and the aliphatic diisocyanates.

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The complex formation of bivalent metal ion, Co (II), Ni(II), Cu (II), Zn (II), or Cd (II), with isotactic or syndiotactic poly (rnthacrylic acid) (PMA) in aqueous solution was investigated by the pH titration method at 25°C and the ionic strength of 0.1. The stability constants of the PMA-metal(II) complexes were calculated by a modified Bjerrum method. The forma- tion curves of the complexes show that the Bjerrum spreading factors for isotactic PMA are smaller than those for syndiotactic PMA (Figs.3-6); in a high pH region, the complexes involving two carboxylate groups per each bivalent metal ion are more favorably formed in the case of isotactic PMA. The stability of the PMA complexes with the different bivalent cations increases in the order of Co (II) <Ni(II) <Zn(II) <Cd (II) <Cu(II), irrespective of the stereoregularity of PMA (Table 1 and 2). The overall stability constants, log β₂, indicate that the complexes with isotactic PMA are more stable than those with syndiotactic PMA (Table 2). These results can be ascribed to the more compact conformation of isotactic PMA, where the ionic groups are more closely spaced with each other.

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Polyguanamine was prepared in dipo!ar aprotic solvent such as dimethylsulfoxide (DMSO) or dimethylformamide (DMF) from aliphatic or aromatic dicarbo, xylic acid diphenylester and dibiguanide. Polymer from aliphatic diester had reduced viscosity 0.40-0.80 dl/g in DMSO and formed a hard flexible film from DMF or formic acid solution. A solution of this polymer in formic acid showed high viscosity and the electrolytic fashion. The above polymer was soluble in sulfuric acid, m-cresol and dipolar aprotic solvent and softened at 230-280°C, whereas aromatic polyguanamine was slightly soluble and softened above 330°C. A good thermal stability of polyguanamine was observed by TG measurement.
Glass transition point of polyguadamine determined by dynamic viscoelastic measurement was 100-110°C and its specific gravity was 1.25-1.30. The influence of guanamine structure on the various properties of the polymer was discussed.

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In order to elucidate the mechanism of aldehyde polymerization catalyzed by organoaluminum compounds, the polymerization of acetaldehyde catalyzed by triethylaluminum-r-methylthiobutanol (1: 1 or 1: 3) was examined. In the polymerization (1: 1 catalyst) at -78°C, a mixture of the crystalline and amorphous polymers was obtained. Whereas in the polymerization (1: 3 catalyst) a mixture of the liner oilgomers together with the crystalline polymer was obtained. In the bulk polymerization (1: 3 catalyst) at -40°C, only a mixture of the linear oligomers was formed (Table 2). The oligomer mixture (MW 2500, by VPO) was a liquid or- a semisolid, which was soluble in common organic solvents including aliphatic hydrocabons and more stable than the polymer.
IR and NMR analyses showed that the end groups of the oligomer consisted of acetyl group, ethoxy group, as well as r-methylthiobutoxy group but not hydroxyl group (Fig.1 and 2). These observations were explained in terms of coordinated anionic propagation and chain transfer.

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The effect of additive on the radiation-induced polymerization of extremely dry acrylonitrile was studied at -78°C. Water, hydrogen bromide and carbon tetrachloride remarkably retarded the rate of the polymerization, and triethylamine, dimethylformamide, nitrous oxide and benzoquinone somewhat reduced the rate of polymerization. These results indicate this mechanism is anionic. By the kinetic analysis using hydrogen bromide as a retarder, an upper limit of the propagation rate constant was estimated to be 4x 10⁷l/mol sec. This suggests the propagating ion is a free anion.

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Under the assumption that HX elimination reaction occurred in vinyl polymer, where A and B are end groups which do not relate to the elimination reaction and X is a substituent group, proceeds at random, the fraction of the substituent groups which remains as isolated state at the termination of the reaction was calculated. Of course, double bonds are introduced into the polymer by the elimination.

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The most suitable conditions to obtain diamino cellulose (DAmC) as a cationic polymer were investigated. Details of the experiment are as follows :
( 1 ) Preparation of dialdehyde cellulose (DAC): 1 g of cotton wool was soaked in 25 ml of aqueous solution containing 1.390 X 10-2 moles of H1O^2- and 1.575 X 10-2 moles of CH₃COONa and was oxidized in the dark place for 14 days at 8°C.
( 2 ) Preparation of dioxime cellulose (DOC): 1 g of DAC was soaked in 120 ml of 1.5 moles aqueous solution of NH₂OH·HCl for 15 hrs. at 5°C and its aldehyde groups were converted to oximes.
( 3 ) Preparation of DAmC: 2 g of DOC was soaked in 100 ml of CHs0H containing O.05 moles of NaBH4 and was reduced for 2 hrs 10°C, and this procedure of reduction was repeated again.
Next the electrolytic dissociation in the aqueous solution of this DAmC was investigated and found that a formula pH =pK+ n log(where K is equilibrium constant of the ionization, n is constant and a is the degree of ionization which is approximately regarded as the degree of neutralization) was applicable in the region where the neutralization of DAmC with 0.1 N HCl solution proceeded more than 27%, and that n and K were 1.55 and 4.68 X 10-8, respectively, at 25°C.
Furthermore, DAmC was allowed to react with CH, I to obtain the compound having methylamino groups, and the neutralization curve of this compound with HCl solution by the use of pH-meter was determined and investigated. t Studies on the Cationic Polymer. I.

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As one of studies on the effect of proton donor on the half-wave reduction potential, DC polarographic behavior of N-benzylideneaniline (BA) and N- (diphenylrnethylene) aniline (DA) was investigated in DMF solution in the presence of cx-cyclodextrin (CD) by the three-electrode system. The half-wave reduction potential of the 1 at wave shifted to a less negative potential (100-150 mV) by the addition of CD. As a most plausible interpretation on the results, the formation of hydrogen bond was suggested between BA or DA and CD.

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Although the standard addition method using a nitrate-selective electrode brought positive errors in the coexistence of chlorate, it was experimentally shown that the linearity of Y={(V+ vs)/V.10e/s} vs. vs plotting was still kept (V: sample volume, vs: standard solution volume, e: difference between potentials before and after addition of the standard solution, S: response slope of ion-selective electrodes). In an attempt to elucidate the influence of the interfering effect on the standard addition method, investigation was carried out by numerical calculations, to know what factors affect the linearity of Y vs. vs plotting and accuracy. As a result, it was shown that the interfering effect affects most the accuracy and the linearity of Y vs. vs plotting is maintained even under a large interfering effect. When the ratio of the standard solution concentration to the sample concentration is large, the Y vs. vs plotting is figured by a straight line, whereas it is figured by a gentle curve, yielding greater concentration-errors, when the ratio is small. The electric charge of ions does not much affect the linearity as well as the concentration-error. A great concentration error occurs also due to the error of the response slope q. At q>0, positive errors occur, whereas negative ones occur at q<0. Even if errors in the response slope exist, the Y vs. vs plotting is figured by a very gentle curve (by two straight lines, in the approximate sense). Positive errors attributable to the interfering effect are compensated in the range of q<0, and cancelled to be zero in apparently at a certain value of q.

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Pentachlorophenylmagnesium chloride and pentamethylphenylmagnesium iodide, prepared in tetrahydrofuran solutions from hexachlorobenzene and pentamethyliodobenzene, respectively, were treated with opper( 1 ) iodide below 0°C. A given polymethyliodobenzene was then added to the resulting dark solution and the mixture was heated under gentle reflux for 6 to 8 hr. Removal of the solvent followed by the Soxlhet extraction of the residue and chromatography on activated alumina gave the corresponding unsymmetrical biphenyl in fair to good yields.
Biphenyls thus obtained include 2, 3, 4, 5, 6-pentachloro-2', 3', 4', 5', 6'-pentamethylbiphenyl; 2, 3, 4, 5, 6-Pentachloro-2', 3', 4', 5'-tetramethylbiphenyl; 2, 3, 4, 5, 6-pentachloro-2', 3', 4', 6'-tetra, T: methylbiphenyl; 2, 3, _4, 5, 6-pentachloro-2', 3', 5', 6'-tetrarnethylbiphenyl; 2, 3, 4, 5, 6-pentachloro 2', 4', 6'-trimethylbiphenyl; 2, 3, 4, 5, 6--pentachlorobiphenyl; 2, 2', 3, 3', 4, 5, 5', 6, 6'-nonamethyl biphenyl; and 2, 2', 3, 4, 4', 5, 6, 6'-octamethylbiphenyl,

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1-Amino-7-naphthol and 3, 5-xylidine were prepared by amination of potassium 2-naphthol8-sulfonate and m-xylene-5-sulfonate, respectively.
Potassium 2-naphthol-8-sulfonate was allowed to react with sodium amide in liquid ammonia at 160°C for 16 hours to give 1-amino-7-naphthol in a 84.5% yield, whereas sodium 2-naphthol6-sulfonate did not undergo the amination under these conditions.3, 5-Xylidine was obtained by the amination of potassium m-xylene-5-sulfonate at 155°C for 9 hours in a 82.7% yield.

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The purpose of this work is to determine the harmful substances described below eluted from the gelled soil stabilizer. The amounts of sulfuric acid, formaldehyde, and KMnO⁴- consuming substances eluted with water were more than 99%, 3-6%, and 6-14% of the respective amounts in the ungelled soil stabilizer solution (Table 2). These values did not decrease even when the soil stabilizer was gelled in the presence of wet or dry sand (Table 2).

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