C-NMR spectra were measured for eighteen mono-substituted carboxylic acids in 10 mol% DMSO solutions and total electron densities for m- and p-substituted compounds were calculated by means of CNDO/2 MO method.
Values of plCa, of m- and p-substituted benzoic acids are respectively in parallel with the total electron densities at oxygen atom which hydrogen atom bonded to. As seen in Fig.2, there exist good linear relationships of negative slope between the chemical shifts of carboxyl carbons and pIC-values in DMSO for m- and p-substituted compounds, respectively. '3C chemical shifts at the ring carbon to which the carboxyl group attaches in p-substituted compounds show a good linear relationship of positive slope with piCa-values (Fig.3) The chemical shifts of carboxyl carbons in p-substituted compounds show a roughly linear relationship of positive slope with 7r-electron densities at the carbons, while in m-substituted compounds the relationship of negative slope is found (Fig.4).
These results suggested that in p-substituted carboxylic acids the changes of the physical values are influenced by the resonance effect between the substituent and the benzene ring, while in m-substituted compounds the inductive effect of the substituent seem predominant.

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For the purpose of studying Donnan membrane equilibria across liquid ion exchangers, an apparatus has been designed so that a liquid ion exchanger circulates in drops through two different aqueous solutions alternatively. This dropping method has the following advantages; (1) the time to attain equilibrium is shorter compared with other methods, (2) complete separation of different liquid phases can be achieved, and (3) it is not necessary to use stirrers. Membrane equilibria in systems composed of 0.5 mol/l ammonium chloride/liquid anion exchanger/ 0.5∼4 mol/l sodium nitrate were determined by using this method.

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Isopiestic vapor pressure measurements were carried out on binary solutions of sodium glucuronate (NaGlcA) and glucosamine hydrochloride (GlcNH₃Cl) and on ternary solutions of NaG1cA and urea at 25° C. The activity coefficient of GlcNH₃Cl showed minimum at 1.3 mol/l, while that of NaGlcA decreased monotonously in all the concentration range studied. The activity coefficient of NaGlcA was decreased by the addition of urea. The lowering effect of urea largely depended on the concentration of NaGlcA.
The free energies of the transfer, ziGt, of NaGlcA from water to urea solutions with various concentration have been calculated. The values of ΔG, of NaGlcA from water to 5 m urea solution are 60 (J/mol) at infinite dilution of NaGlcA and 140 (J/mol) at 1 m NaG1cA. Partial molar volumes at infinite dilution, calculated from the density measurements, are 94.4 (ml/mol) for NaGlcA and 131 (ml/mol) for GlcNH₃Cl.
No difference was found in the hydration of GlcA- ion and GlcNF13+ ion at infinite dilution. The concentration dependence of the activity coefficients and that of apparent molar volumes of these salts, however, were dissimilar owing to the contribution of counter ions and non ionic parts of the sugar ions.
Two effects act on the activity coefficients of the solutes in the system NaG1cA-urea-water. One lowers the activity coefficients of the solutes and the other increases them. The lowering effect which includes the interaction of glucose part in GlcAT, is predominant at low concentrations.

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In order to confirm the results obtained from hydrodynamic and thermodynamic studies on aqueous solutions of guanidinium salts, in which guanidinium ion was concluded to be a structure breaking ion, NMR studies were carried out on the aqueous solutions of various guanidinium salts at varied temperatures, concentrations and pHs. As shown in Fig.1, the chemical shifts of water proton in sulfate, acetate and carbonate solutions appear toward lower magnetic field, while in nitrate, chloride, bromide, iodide and thiocyanate solutions toward higher magnetic field than that in pure water. The molar chemical shift of guanidinium ion is 0.044 (negative value means high field shift) and the sign of temperature dependence of molar ion shift is positive as shown in Fig.2. These results agreed with those obtained in the previous papers.
The proton exchange reaction catalyzed by OH- was also studied by measuring the half band width of water proton signal in the pH region of slow exchange. The reaction rate is proportional to the guanidinium ion concentration and the rate constants are 1.5 x 10¹⁰, 4.6 X 10¹⁰ and 1.4 X 10¹¹ l/molec at 15, 32 and 45° C, respectively. The activation energy of the reaction is 15 kcal/mol.

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Real density ρr (Tables 1 and 2) and sorption property (Table 3) of porous alumina and silica were measured by use of several kinds of liquid. The pore structure of each sample was diversified by calcination at different temperatures. No difference in pr was detected for silicas with different immersing liquids. But for aluminas, unless calcined at higher temperature, a large difference in ρr was observed.
If this difference in pr is due to the compression of the immersing liquid, the decrease in volume by compression, ΔV, can be expressed by ΔVr=1/ρ. -1/ρ, (Table 4); where pHe is the true density measured with helium gas. A linear relationship between 417, and the volume of BET capacity m, viz. the surface area of the solid (Fig.1) demonstrates that the compres- sion of liquid in a capillary takes place on the solid surface.
The total pore volume evaluated from the saturated amount of the sorption using bulk density of liquid was nearly independent of the kind of liquid used (Table 3). The value became more satisfactory when the compression effect was taken into account (Table 5). Present results imply that the compression of the adsorbed layer takes place in the measurement of sorption as well as in the measurement of density.

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Kinetic study of the esterification of propionic acid with ethanol was carried out at 120° C in the gaseous phase with use of sulfonated styrene-divinylbenzene copolymer as a catalyst. The kinetics at initial stage revealed that the reaction is bimolecular one of the Langmuir-Hinshe-lwood type.
Further, behavior of active sites was closely examined by replacing the hydrogen ions of the catalyst resin a variety of metallic ions; sodium, potassium, lithium, magnesium, calcium, manganese, nickel and aluminium ions. The catalytic activity was found to be affected by the ionic valencies of the metallic cations (Me⁺ <Me²⁺ <Me³⁺).

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1-Pyrenylnitrene formed by the photolysis of 1-azidopyrene in degassed methanol gave 1- aminopyrene and 1, 1'-azopyrene while it gave only 1, 1'-azopyrene in degassed benzene. When phenol exsisted in degassed benzene, N- (1-pyrenyl) -p-benzoquinone monoimine was formed in addition to 1-aminopyrene and 1, 1'-azopyrene.1-Aminopyrene, 1, 1'-azopyrene and a quinone imine compound were formed by the photolysis of 1-azidopyrene in phenol resin matrix. The formation of quinone imine compound was due to the reaction of 1-pyrenylnitrene with phenol group of the resin, and resulted in the insolubilization of phenol resin in alkaline water. When oxygen exsisted in the solution, 1-nitropyrene and 1, 1'-azoxypyrene were produced besides the compounds described above. The rate constants of hydrogen abstraction of 1- pyrenylnitrene from the solvents were determined from the amount of 1-aminopyrene formed by a flash photolysis of 1-azidopyrene in toluene, p-xyrene, ethylbenzene, cumene, methanol, diphenylmethane and phenol as follows; 1.1 x 10³, 1.8 X 10³, 3.7 X 10³, 1.8 x 10³, 4.0 X 10⁸, 6.0 X 10⁴, x 10⁵ (l mol^-1 sec^-1) Hydrogen of benzene was not abstracted by 1-pyrenylnitrene. N(1-P y r eny) -2, 6-dimethyl-p-benzoquinone monoimine, N- (1-pyrenyl) -2, 4-dimethyl-o-benzoquinone monoimine and N- (1-pyrenyl) -4-benzyl-o-benzoquinone monoimine were formed by the reaction of 1-pyrenylnitrene with 2, 6-xylenol, 2, 4-xylenol and p-benzylphenol, respectively.

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The electroedposition of zinc from the alkaline zincate bath containing a small amount of lead was carried out under galvanostatic or potentiostatic condition. The lead content of the electrodeposit was determined from polarogram, and electronmicroscopic observation of the deposit was conducted. The lead content of the deposit was 0.1∼1%, and it was relatively high in the initial stage of low current (C. D.10 mA/cm²) electrolysis, while it was almost independent of the cathodic potential. The cathodic polarization increased with an increase in the lead ion content of the bath. Charging or discharging process of the cell was accompanied with deposition or dissolution of zinc, respectively. The charging-discharging cycle was found to be much prolonged by the codeposition of lead. From the results obtained, it was found that the growth of the dendritic deposit of zinc was inhibited by a relatively large amount of codeposited lead.

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The reaction between propylene oxide (PO) and TiO₂ was studied in order to elucidate the reactivity of cyclic ether towards TiO₂. Physico-chemical properties of reaction product was also investigated.
The reaction was carried out by both circulating method at the boiling point of PO and ampoule method at higher temperature. The degree of reaction was mainly controlled by the amount of surface OH group of TiO₂. TiO₂ being calcined at lower temperature and kept plenty of OH groups on its surface reacted with PO to proceed polymerization reaction besides simple reaction between PO and the surface OH groups. At higher temperature polymerization reaction took place more favorably and average degree of polymerization over 10 was attained. Based on IR spectra, the structure of the reaction product was estimated as
The product was susceptible to the attack of H₂O, but it was reasonably stable up to 250° C.

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Correlation between the preheating temperature and hydrothermal treatment at 90° C of Shirasu-Na₂0 mixture (Na₂0: Si0₂=. O.6-1.2: 1) and the, formation rate of faujasite was studied. The formation of faujasite was affected by the particle size of the preheated ShirasuNa₂0 mixture, Na₂0/Si0₂ molar ratio and the preheating temperature. Hydroxy sodalite was formed by the evapolation of aquous NaOH solution with Shirasu to dryness. When the preheating temperature was lower than 800° C, the crystalline phases in Shirasu (albite and quartz) and hydroxy sodalite remained in the heated mixture, and the amount of faujasite formed by the hydrothermal treatment at 90° C was small. In the temperature range from 700° to 800° C, hydroxy sodalite changed to carnegieite. From the mixture preheated at these temperature, zeolite species p(cubic) and faujasite were formed by the hydrothermal treatment at 90° C. From the mixture preheated at above 800° C, faujasite and small amount of zeolite species p (cubic) were obtained.
The result of X-ray diffraction of solid phase and the chemical analysis of liquid phase after the hydrothermal treatment of the preheated mixture at 90° C suggested that the formation of faujasite proceeded in solid phase and the formation of zeolite species p (cubic) proceeded in liquid phase.
Finally, it was found that the solid phase containing 62.5%- of faujasite was synthesized from the glassy Shirasu-Na₂0 mixture (Na₂0: Si02=1.2: 1) preheated at 1000° C.

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In order to develop fireproof materials, an attempt was made to prepare the hybrid heterocompounds PO (X)₂OR'OPO (X)₂ (I) and (PDXOR'O-) (II) (R' = aromatic group, X =alkoxyl group or amide group) by means of a simple process. The conditions for the synthesis and the chracteristics of the products have been investigated.
As an aromatic diols (HOR'OH), 2, 2-bis (p-hydroxyphenl) propane was suitable for the syntheses of (I) and (II). As the intermediate compound of (I), POCl₂OR'OPOCl₂ (I) was formed by the reflux of a mixture of 2 mol of POCl₂ and 1 mol of HOR'OH. An oliy (I) was obtained by the esterification or the amidation of (I '). The addition of dehydrochlorination catalyst such as AlCl3 accelerated the reaction, and resulted a product containtng some cross linkage simultaneously. The intermediate compound of (II), (POClOR'0-)7, (IV), was obtained by the reflux of the equivalent mixture of POCl₂ and HOR'OH dissolved in a small volume of dioxane. (U') could also be formed by the thermal dehydrochlorination of POCl₂OR'OH, which was obtained by the exclusion of excess POCl₂ from the reaction mixture, which is consisted of several mol of POCl₂ and 1 mol of HOR'OH. A viscous oily produst was directly obtained by the esterification or the amidation of 01. However, the lump or powder of (I) and (II) could be obtained by the exclusion of a slight solvent included in the oily products.
The products thus obtained were soluble in various organic solvents. P contents were 13∼14% in (I) and 8∼9% in (II), respectively. N contents were less than that of the expected as the result of the incomplete amidation. All the products contained traces of Cl. From the measurements of molecular weights, solubilities in organic solvents and the IR spectra, the products were estimated to be the condensation products of phosphate group with aromatic group. The resin containing more than ten percent of the products exhibited the incombustibility.

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Kinetics of the substitution reactions of the lead (II) complexes of ethylenediamine-N, N, N', N'-tetraacetic acid (EDTA), N- (hydroxy ethyl) ethylenediamine-N, N', N'-triacetic acid (EDTAH), 1, 2-cyclohexanediamineteraacetic acid (CyDTA) and dietylenetriamine-N, N, N', N", N" -pentaacetic acid (DTPA) with yttrium (W) ion have been studied in the pH range 2.5-, 5.6, at 20° C and an ionic strength of 0.1 in the presence of excess lead (II) ion.
The inital rate equations of the forward and reverse reactions were obtained by observing the change in absorbance. Contribution of each reaction path way to over-all rate of the reaction was estimated. The reactions for the EDTA, EDTAH and DTPA systems seemed to proceed through two path ways: (1) forming binuclear intermediate complexes and (2) dissociating metal complexes. In the forward reactions the rapid dissociation of lead complexes precedes the formation of yttrium complexes, and in the reverse reactions the dissociation of yttrium complexes is the rate-determining step. The reactions for the CyDTA systems proceed merely through the dissociation of the metal complexes.
The rate constants for the formation of YHX (kyllx) were found to be 1.0 x109, 1.9 x 107, 2.4 X 107 and 4.3 x 10mol-sec for EDTA, EDTA H, CyDTA and DTPA (H, X), respec- tively, where HnX represents the polyamine-N-polyacetic acids.

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The interactions of ethylendiamine (en), diethylenetriamine (dien), N- (2-aminoethyl) -1, 3- propanediamine (aepd) and triethylenetetramine (trien) chelates of copper (II) or nickel (II) ion with various concentrations of hydroxide ion were investigated by measurements of volume changes.
Volume changes due to the hydroxo-complex formation were calculated from the density. The results indicated the presence of a correlation between the formation of hydroxo-complex and the volume change.
Then, the stability constant for the following equilibrium was determined:

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Removal methylmercury (II) chloride (MMC) from waste water was carried out by flotation method using N-amidinothiourea derivatives (N-methyl-N'-amidinothiourea, N-ethyl-N'-amidinothiourea and N-phenyl-N'-amidinothiourea) as collectors for MMC and sodium dodecylbenzenesulfonate (DBS) as a surfactant. Hg atom in MMC combines by coordination with sulfur containing group in the collectors and forms cationic complexes. Resulting complexes and an anionic surfactant DBS make new chemical species and then MMC complexes are removed by the flotation.
Among these N-amidinothiourea derivatives, N-phenyl-N'-amidinothiourea (Ph-ATU) is the most effective collector for MMC in the flotation.
Effects of pH, concentrations of DBS and Ph-ATU and coexisting salts on the removal of MMC were studied. Optimum pH is If waste water contains enough DBS to make bubbles continuously, the percentage removal of MMC increases with increasing concentration of Ph-ATU. When concentrations of coexisting salts: sodium chloride, calcium chloride and magnecium chloride, were less than 50-100 ppm, no effects of these salts on the flotation of MMC were observed.
Under the condition of 1 ppm of MMC, 100 ppm of DBS, 25 ppm of Ph-ATU, pH 5.5 and 80 ml/min of gas (N₂ gas) flow rete, MMC was removed from waste water to the level of 1 ppb by the flotation. From these results, Ph-ATU can practically be used as a collector of MMC in the flotation.

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In N, N-dimethylformamide (DMF) Water media, dechlorination waves and a reduction wave of pyridine nucleus were shown for chloropyridines at the dropping mercury electrode. The elimination wave of a chlorine corresponds to irreversible two-electron wave. The reduction wave of pyridine nucleus corresponds to irreversible one-electron wave in DMF and to irreversible two-electron wave in water containing DMF. The process of dechlorination was studied by controlled potential electrolysis and number of electrons transfered during the electrode reaction was determined. The UV spectra of the solution after controlled potential electrolysis were also examined.
The kinetic parameter of the dechlorination process were determinded by cyclic voltammetry. ks= (0.72-1.20) x105 cm and a = 0.1-0.2.
The present data indicate that mechanisms for the electrode reaction in DMF, DMF-water media are as follows ;

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In order to investigate the fragmentation pattern in mass spectrometry, a parameter, ΔH⁺ which is defined by equation (1) has been introduced by consideration of the excited states.
Here Hprod and Hreact stand for the enthalpy of the products and the reactants in the excited states, respectively.
The quantity ΔH⁺ corresponds to the distribution of fragment ions, and it is found that the ion which has a smaller ΔH⁺ value appears preferentially in mass spectra.
On the basis of this theory, mass spectra of unsaturated hydrocarbons have been explained quasi-quantitatively.

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The dechlorination of concentrated (4.4 X 10^-1 mol/l) PCB solution in alkaline 2-propanol by UV-irradiation brought about white deposition of sodium chloride on the surface of quartz jacket contacting the PCB solution. Consequently, penetration of light into the reaction mixture greatly decreased, whereas such deposition was not observed in the case of PCB concentration less than 4.6 X 10^-2 mol/l. From the discussions of the output characteristics of light source (100 W high pressure mercury lamp), the molecular extinction coefficient of PBC, and the wavelength dependence of the quantum yield of dechlorination, it was found that dechlorination occurred in the neighbourhood of less than O.92 mm and 8.00 mm from the jacket wall in 4.4 x 10^-1 mol/l and 4.6 X 10^-2 mol/l of PCB solution, respectively. Several attempts were made to allow the photodechlorination of an increased amount of PCB without the growth of deposition on the jacket. By supplying PCB step by step or continuously into the alkaline alcoholic solution from outside of the reactor under irradiation, 8 times of PCB by weight could be successfully dechlorinated (99.5%) with the rate acceleration by a factor of 1.6 in comparison with those of the reaction of PCB (4.6 X 10^-2 mol/l) in a batch.

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The reactions of vinyl Grignard reagent with carboxylic acids have been studied in detail in various solvents.
The order for the ease of formation of ketone [1] is (CH), CCOOH, HOOH> C, H, COOH> (CH, ) 2CHCOOH> CH₃ (CH₂), COOH> CH, (CH₂) 2COOH > CH, COOH. Pivalic and cyclohexanecarboxylic acids having bulky alkyl groups yield ketone [1]quantitatively.
This result may be explained in terms of the steric hindrance of alkyl groups. It was found that the formation of ketone [1] becomes further difficult with increasing solvent basicity. The reactivity of vinyl Grignard reagent with a, 0-unsaturated carbonyl compouds was found to be similar to that with carboxylic acids. From the result obtained, it was found that the reaction of vinyl Grignard reagent with carboxylic acid proceeds via corresponding alkyl vinyl ketone intermediate.

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1- (2-Benzofuryl)-2- (3-benzofuryl) ethylenes [7] were prepared in good yields (70-75%) by heating a mixture of acetic anhydride, sodium acetate, and a-[2-(8-benzofuranylacryloy1)- phenoxy]alkanecarboxylic acids [6] which were obtained by the condensation of the corresponding 2-formylbenzofurans with the corresponding ethyl ce-(2-acetylphenoxy)alkanecarboxylates. Palladium-carbon-catalyzed hydrogenation of [7] in ethanol or benzene at ambient temperature and pressure gave the corresponding ethanes [3]. [3] were subjected to additional hydrogenation under the same condition; [3 a] yielded bis(dihydrobenzofuranyl)derivative [12] via dihydrobenzofuranyl drivative [11 a], whereas [3 b] gave a mixture of two isomers of dihydrobenzofuranyl derivatives ([13] and [11 b]).
When [3] were treated with hydrogen chloride or sulfuric acid in ethanol, intramolecular cyclization occurred with the formation of the corresponding tetrahydrobenzofurano[2, 3-a] dibenzofurans ([4] and [5], respectively), in almost quantitative yields.

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The condensation of 2-acetylbenzoic acids with salicylaldehydes has been studied.2-Hydroxy2'-carboxychalcones were obtained in the alkaline condensation. Dehydration by heat or by usual dehydrating agents gave spiro[2 H-1-benzopyran-2, 3'-phthalides] [1]. In the acidic condensation, [1] was obtained directly. [1] was also obtaned by the reaction of 3-methylenephthalide with salicylaldehyde in sulfuric acid. Similarly spiro[3 H-naphtho[2, 1-b]pyran-3, 3'- phthalide] [2] was prepared by the condensation of 2-acetylbenzoic acid with 2-hydroxy-1- naphthaldehyde in the presence of alkali, while selfcondensation product of 2-acetylbenzoic acid was obtained in place of [2] in the acidic condensation.

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The reactions of spiro[2 H-1-benzopyran-2, 3'-phthalides] [1] with acid, alkali and hydrazines were studied. The equilibrium between spiropyran form [1] and the open form (2'-carboxyflavylium salts [2]) in acidic condition was discussed. Its ring opening was found to be affected strongly by substituents; electro-donating groups favoring the open form [2] on the equilibrium.
The spiro compounds [1] were hydrolyzed by aqueous alkali to give 2-hydroxy-2'-carboxychalcones, which further decomposed to 2-acetylbenzoic acids and salicylaldehydes.
The reaction of [1] with hydrazines afforded spiro[2 H-1-benzopyran-2, 1'-tetrahydrophthalazine]-4'-ones.

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The reaction routes to N, N'-disubstituted o-ureidobenzamides [ 1 ] and 3-substituted quinazoline-2, 4-diones [ 2 ] by the reaction of N- (mesyloxy) phthalimide (MSOP) with various amines have been investigated. The reaction of MSOP with aniline at room temperature using pyridine as an acid acceptor gave o- (N'-phenylureido)benzanilide [1 a], while the reaction in the presence of triethylamine afforded 3-phenylquinazoline-2, 4-dione [2 a]. MSOP reacted with benzylamine in the presence of triethylamine to form N-benzyl-o- (N'-benzylureido) - benzamide 11 131 The reaction solvents had almost no influence on the proportion of the reaction products, [1] and [ 2 ] while it was affected by basicity of both the amines and the acid acceptors used in the reaction. Based on these results, it can be concluded that the reaction follows path A in which [ 1 ] is formed by the intermolecular addition of the intermediate o-isocyanatobenzamides C 6 with another molecule of the amine, and path B forming [ 2 ] by the intramolecular addition of [6]. On the other hand, the reaction of N- (mesyloxy) succinimide with aniline and benzylamine under various reaction conditions was found to proceed almost exclusively through path A to yield 3- (N'-phenylureido)propionanilide [8 a] and N-benzy1-3- (N'-benzylureido)propionamide C8 bp, respectively.

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Syntheses of homopolymers of Naphthol AS series azo dyes containing polymerizable group in diazo component and the relationship between tautomerism and light fastness of the dyes have been investigated. Homopolymers of 3-hydroxy-4- (m-methacrylamidophenylazo) -2-naphthanilides were prepared by the polymerization of monomeric dyes which in turn were synthesized by the coupling reaction of m-methacrylamidophenyldiazonium chloride with 3- hydroxy-2-naphthanilides. The aryl groups are C₆H₅, 3-NO₂C₆H₅, 2-CH₃C₆H₄, 2-CH₃0C₆H₅, 4-Cl0₆H₄, and β-C₁₀H₇.
It was proved from GPC analysis that the polymeric dyes consisted of dimerecamer, the main components being tetramerentamer. Their visible and infrared absorption spectra showed that a content of keto form in the polymeric dye was smaller than that in the monomeric dye.
Examination of light fastness of the dyes in poly (methyl methacrylate) film revealed that, while the ratio of keto/enol forms in the monomeric dye remained almost constant during fade, the content of keto form remarkably decreased with increasing fade in the polymeric dye. Therefore, poor light fastness of the polymeric dyes appeared to be due to partial interference in the tautomerization between keto and enol form by polymerization.

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A new organic pigment, 3'-hydroxy-5, 6, 7, 8-tetrabromobenzo[ b ]quinophthalone, has been developed as a substitute for cadmium yellow (CdS) which is forbidden to use because of its toxic property. This brominated quinophthalone is quite similar to CdS in color and has excellent pigment properties, being resistant to light, acid and alkali, heat, migration and organic solvents.
A number of brominated 3'-hydroxybenzo[ b ]quinophthalones were synthesized by the reaction of brominated 2, 3-naphthalenedicarboxylic anhydride with brominated 3-hydroxy-2-methylquinoline-4-carboxylic acid.
The contribution of the bromo substituents to some pigment properties of these compounds was also discussed. The thermal behavior of these compounds was estimated by means of the thermal gravimetric and differential analyses.
The bromo substituent on naphthalene ring improved markedly the pigment properties. However the additional bromo substituent on quinoline ring did not show any appreciable effect but decreased drastically the pigment properties in some cases.

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The binding reaction of 4-aminoazobenzene derivatives (one anionic and seven nonionic dyes) with β-cyclodextrin (abbreviatted as XD) has been studied spectrophotometrically There is only one site in βCD available to the dye. The values of binding constants (K) are fairly large as shown in Table 1. It is deduced from the spectra of bound dyes (Fig.1 and Table 2) and the thermodynamic parameters for the reaction (Table 1) that the benzene ring without the amino substituted in the dye molecule should be included in a hydrophobic cavity of βCD by the binding.
The effects of βCD on the dyeing properties of the nonionic dyes have also been studied. The addition of βCD in an infinite dye bath leeds to a marked decrease in the concentration of the dye at the surface of the Nylon 6 rolled film, but the distance of the penetration of the dye is kept unchanged (Fig.4). The concentration of the dye at the surface is proportional to that of unbound dye in the bath. Therefore, it is concluded that only the unbound dye can be adsorped on the rolled film.
8CD in a finite dye bath behaves as a retarder which reduces the rates of dyeing and the equilibrium exhaustions of the dyes (Fig.5, 6).
If a nonionic dye bound with βCD has no affinity for a hydrophobic fiber and the concentration of βCD in a finite dye bath is far greater than that of the bound dye, the equilibrium exhaustion A. is expressed by following equation.
A. = K+ L (1 + bK9), where K is partition coefficient, L is liquor to goods ratio, and b is the initial concentration of βCD. The change in the rate of dyeing caused by the presence of βCD can be estimated using the value of A. calculated by the above equation.
The change of A. and the rates of dyeing calculated theorically agree well with those deteamined experimentally.
Finally, the action of retarder possesing affinity for a dye has been discussed using βCD as a model compound. The retarder is concluded to be usefull for a dye having very great affinity for a fiber but small diffusion coefficient in the fiber.

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In order to disclose side reactions in the diazotisation of aromatic primary amines of weak basicity, the reactions of 6-bromo-2, 4-dinitrobenzenediazonium [1] and 6-chloro-2, 4-dinitrobenzenediazonium compounds C_2C'D with some inorganic salts in sulfuric acid have been investigated. In the reaction with NaNO₂, [1'] gives not only 2, 3, 5-trinitrobromobenzene but also 1, 2- dibromo-3, 5-dinitrobenzene under a preferential replacement of the -NZ group even in the absence of copper catalyst in strong sulfuric acid. In the reactions with inorganic halides (KF, NaCI, NaBr, KI), [1] gives the corresponding halogen compounds by the replacement of -N2 group except in the case of KF. The yield of the halogen compound varies in the order: FCCl < Br <I.
Similar results are obtained also in the reactions of C_2C'. The reactions of dazonium compounds derived from 2, 4-dinitroaniline, p-nitroaniline, and aniline with inorganic halides have also been carried out. However, the, yield of the corresponding halogen compound decreases with decreasing number of the nitro groups on the aromatic nucleus.
These results suggest that the replacement of -N, group in these reactions takes place by a bimolecular mechanism. Nucleophilic reagents of weak basicity and moderate nucleophilicity appear to react even in sulfuric acid with C. M and C_2C'D under a cleavage of N2 group to give the corresponding substitution products.

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Disproportionation of the equimolar mixtures of two C4 olefins has been investigated over a WO^3-SiO₂ catalyst at a total pressure of about 1 atm and at 450° C in a quartz reactor. The ratios of the initial rate of each primary metathesis were determined: in the reaction of 1- butene with isobutylene, r1B-1B:r1B-tB:riB-iB=90:50:1, in the reaction of cis-2-butene with isobutylene, rcB-tB:riB-1B=100:1, and in the reaction of trans-2-butene with isobutylene, riB-1D:r1B-tB=120:1. In the reactions of 1-butene with cis-2-butene and 1-butene with trans-2-butene, the ratios of initial rates were r1B-1B:r1B-CB=1B-1B:r1B-iB=1:6.
Under the conditions of these experiments, the disproportionation was accompanied with the migration of double bonds, which affected the distributions of products considerably. As shown in Fig.8, the linear velocity of feed affected the rate of disproportionation but did not change the rate of isomerization. The higher linear velocity was preferable to the selective dispro- portionation. In the reaction of 2-butenes with isobutylene, high selectivity to isoamylenes was attained when the concentration of isobutylene in the feed was considerably high.

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In the course of our chemosystematic investigation of the chrysanthemum native in Japan, the essential oils from Ch. boreale Makino and Ch. makinoi Matsum. et Nakai have been analyzed in detail.
The essential oils were separated into individual components by means of a combination of fractional distillation and preparative GLC or elution chromatography. Thirty compounds were identified on the ground of chemical and spectral evidences. The essential oil from Ch. boreale contains sabinene, a-thujone, pinenes and chrysanthenone as the characteristic compo- nents, while camphene, camphor, borneol and monoterpene esters such as trans-chrysanthenyl, linalyl and bornyl acetate are present in the oil from Ch. makinoi.

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Camphor tree (Cinnamomum Camphora Sieb.) is classified into five subgroups in view of the major components (parenthesized below) in the leaf oil: eucamphor tree (camphor) (1), linalool tree (linalool) (2), cineole tree (cineole) (3), sesquiterpene tree (nerolidol) (4), and safrole tree (safrole) (5). Among them, the leaves of (2)(4) contain considerable amount of lignans, but that of (5), whose leaf oil consists mainly of safrole (a C₆-C₃ compound), contains no lignan. Six lignans were isolated: dimethylmatairesinol [1] (major component), dimethylse coisolariciresinol kusunokinin [3], kusunokinol [4], cinnamonol [5] and hinokinin [6], among which, [1] and [2] have first been found in natural products and [3], [4] and [5] are now substances.

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Hexagonal and circular crystals have been obtained by the evaporation of the hot o-dichlorobenzene solution containing a small amount of poly (isobutylene oxide).
It was confirmed that hexagonal crystals are single crystal consisting of chain folded lamellae and that a central hole within the crystals is formed at an early stage of the growth, which is created by a screw dislocation mechanism as suggested by Frank. The circular crystals consist of chain folded lamellae, however, they differ from the hexagonal crystal both in not having a central hole and having the structure with a radially oriented lamellar texture, which is similar to a two dimensional spherulite, usually known.
Hexagonal fences and concentric rings grown around the central crystals consist of radially oriented narrow lamellae under the influence of the central crystals, having hexagonal or circular shape, and it was found that these growth pattern show a periodic difference in thickness depending on the distance from the centre.
The circular crystals and the rings show negative birefringence toward radial directions, and it has been recognized very weak bright and dark concentric rings superimposed on the extinction pattern with a Maltese Cross. It was concluded that the pattern could be explained in terms of a half twist model of the lamellar crystals to the radial directions.

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Under sufficiently drying condition when ramie was oxidized by NO₂ gas, it was found that its crystallinity and its crystallite size in a [101] direction increase with increasing degree of oxidation after the first stage in which the crystallinity decreses. At the degree of oxidation of 250 mmol-COOH/100 g, the crystallinity becomes about 1.3 times of its original ramie and the same is true for its crystallite size. However, from this point, both turn out to decrease with increasing degree of oxidation.
When the NO₂ oxycellulose was converted into CA²⁺ or Ag+ salt, the crystallinity and the crystallite size decreased with increasing degree of oxidation. By desalting with dilute aq. HCI solution, they return to have the values of the original oxycellulose.
In our previous paper, it was suggested that the molecular group in the (101) plane of cellulose is a structure unit, the planes are connected together by intermolecular hydrogen bond participating in the -OH at C, and forming a crystallite, and an amorphous part shows the (101) plane lattice structure having disorder in the regularlity between the planes.
NO₂ oxidizes selectively the -OH at CB in cellulose. It was confirmed that the stereochemical arrangement of CB, oxidized to -COOH, does not differ from that in the crystallite of cellulose. Therefore, it was considered that the -COOH in the NO₂ oxycellulose incorporated the (101) planes in amorphous part into the crystallite of cellulose in terms of its high ability of intermolecular hydrogen bond, and brougnt about the increase in the crystallinity and the crystallite size in the [101] direction. These effects are eliminated in its salt. The hypothesis was very available for the interpretation of the characteristic behaviors of the NO₂ oxycellulose which are dependent on the large resistance to esterification and to the solubility of the ester, on the high solubility in a alkali solution and on the regeneration in high yield from the solution. The HI04-HCl02 oxycellulose in which -OH at C_2C and C, position are oxidized, does not show the behavior like NO₂ oxycellulose.

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The temperature-dependence of ESR absorption intensity (I) of 7, 7, 8, 8-tetracyanoquinodimethane (CQ) salts with polycation in the following general formura, was discussed in relations to electrical conductivity.
In the CQ simple salts, the relationship between I and absolute temperature T was expressed by I cc (1/ T) at temperature lower than 210° K and by I cc (1/ T) [3 + exp (J I kT)]-1 at temperature higher than 210° K. It was suggested from this result that the degenerate states of singlet and triplet changed into the separate ones as the temperature was raised. However, from the disagreement between the separation energy J and the activation energy Efor electrical conductivity, the conclusion was drawn that the triplet state didn't contribute to the conduction through the CQ simple salts.
On the other hand, in the CQ complex salts, the state in which I was independent to T was observed with increasing CQ° molecules and the singlet and triplet states were separated at a temperature above 320° K, where strong interactions between the unpaired electrons were recognized.

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The reactions of 3-phenoxypropylene diacetate (P0Ac2), and 3-phenoxypropyl acetate (POAc) with formaldehyde (F) catalyzed by perchloric acid have been carried out in acetic acid, and the influence of the reaction conditions on the molecular weight of the formed resins has been investigated. The molecular weights of the POAc2 and POAc. resins formed in the mole ratio of 1.2. (F/P) at 90° C were found to be 3300 and 5020, respectively.
The reactions of the Monomers and their resin model compounds with F have been kinetically studied by measuring the consumed amount of F, and the initial rate was found to be expressed by the equation:
where P=P0Ac2, 3-(p-tolvloxy)propylene diacetate (TOAc2)
The values of the rate constant (k) and the activation energy for POAc2, POAc, TOAc2, and 3- (p-tolyloxy)propyl acetate (TOAc) are listed in Table 4.
The curves of consumed amount of F in the reactions of the dimeric compounds of POAc and TOAc with F differ from those of the monomers.

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The polymerization of methyl methacrylate (MMA) initiated by tributylborane (TBB) -metal acetylacetonate systems has been studied in dioxane at 25° C. It was found that metal acetylacetonates, especially vanadyl acetylacetonate (VO (AcAc) 2), stabilized TBB by the formation of a complex with TBB, which can still initiate the polymerization of MMA. The polymer is obtained in maximum yield at 1: 1 mole ratio of TBB/VO (AcAc) 2. The rate of polymerization is expressed by the folowing equation:
The total activation energy was calculated to be 5.5 kcal/mol. A possible initiation mechanism was discussed in terms of kinetic studies and spectoscopy. It was suggested that the TBBVO(AcAc)2 complex formed radicals by the interaction between this and MMA as shown in the rate expression.

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Study was made on the effect of valence states of nickel (0) and (I) complexes catalysts on the polymerization products of methylacetylene.
Bis (1, 5-cyclooctadiene) nickel, bis (zr-ally1) nickel, bis (acrylonitrile) nikel, bis (t-butyl isocyanide) - nickel and their derivatives were used as the catalyst of nickel (0) complex and (ir-ally1) nickel halides were used as that of nickel (I) complex.
Oligomer of methylacetylene was mainly obtained by using nickel (0) complex. The structural analyses of dimers and trimers showed the presence of two linear dimers (2-methyl1-penten-3-Sine, 2-hexen-4-yne), two cyclic and two linear trimers (1, 3, 5- and 1, 2, 4-trimethylbenezene, 2, 4-dimethyl-1, 3-heptadien-5-yne, 5-methyl-2, 4-octadien-6-yne) in the reaction products.
Methylacetylene catalyzed by nickel (I) complex forms single polymer (close upon eicosamer of methylacetylene). Molecular weight and yield of the polymer were effected by halogen atom in (r-a1ly1) nickel halides. The polymer obtained using (r-cinnamyl) nickel chloride instead of (r-ally1) nic61 chloride, was found to contain phenyl group. Thus, the polymeriza- tion was probably initiated by 7r-cinnamyl group in (z-cinnamyl) nickel chloride.

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The thioetherification of poly (vinyl chloride) (PVC) in ethylenediamine or ethylenediaminetetrahydrofuran has been compared with the reactions of model compounds e. g., s-butyl chloride, 1, 3- and 1, 4-dichlorobutane to. elucidate a polymer effect of this reaction. The rate of the thioetherification of PVC is proportional to [PVC] and [thiols] and is almost similar to that of s-butyl chloride. As the thioether group first formed activates remaining chlorine atom during the thioetherification of 1, 3- and 1, 4-dichlorobutane, chlorine atoms is PVC would presumably be activated by the thioether group introduced and probably by the formation of sulfonium salts. In addition, such a neighboring effect of aliphatic thioether group seemed to be stronger than that of aromatic thioether group.

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The preparation of Ni(II) silk fibroin (Bombyx mori) complex was carried out under various conditions of pH and TNI2+/THL (molar ratio of reacting species) in an aqueous solution at 25° C, and the secondary structure of the products was investigated. In an aqueous fibroin solution, the galation was observed in the presence of Ni (II) ion and the pH range below 9. The infrared and X-ray diffraction pattern of these gels showed that the crystals formed in the gel are cross / structure. Furthermore, the Ni (II) (N4) planar chelated structure of inner polymer molecular complex is formed in the pH range above 10. The viscosities of an aqueous silk fibroin solution decrease with increasing amount of nickel biuret complex. The films obtained from an aqueous silk fibroin solution gave X-ray pattern of the random coil structure.

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The differences among the Fe (III) and Fe (II) -halide complexes produced in three solvents with different donor numbers, i. e. dimethyl sulfoxide, N, N-dimethylformamide and propylene carbonate were studied. The number of complex species formed in these solvents decreased in the order of propylene carbonate> N, N-dimethylformamide> dimethyl sulfoxide, and the case of formation of higher complexes decreased in the order of >Br^- >I-. The compositions of the complexes which are in equilibrium with Fe" ion in each solvent were determined by the observation of isobestic points.

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Polytypism has been observed among delafossite-type compounds; AgFe02, AgCoO₂ and AgCrO₂. This phenomenon was also observed in Cu3TiO₄. The crystal structure of Cu3TiO₄ (2 H) has been reported in the previous paper. A polytype-Cu3TiO₄ (3 R) has a trigonal lattice with the unit cell dimensions; a0=5.995 A and a=29.27°.
The 3 R-type of Cu3TiO₄ was synthesized by heating the mixture (3 mol Cu0+1 mol Ti02) at 1050° C in an oxygen stream for several hours followed by rapid quenching. The above two types usually coexist and their ratio depends on the oxygen pressure. At higher oxygen pressure and at lower one, Cu3TiO₄ (3 R) and Cu3TiO₄ (2 H) are mainly produced, respectively.

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Imidazole-4-carboxylic acid [1] and imidazole-4, 5-dicarboxylic acid [2] reacted with phosphorus pentachloride or thionyl chloride to give diimidazo[1, 5-a, 1', 5'-d]pyrazine-4, 9-dione [3] and 4, 9-dioxo-4, 9-dihydrodiimidazo[1, 5-a, 1', 5'-d]pyrazine-1, 6-dicarbonyl dichloride [4], respectively. The dioxopyrazine rings of the resulting dimers [3] and [4] were cleaved in their reactions with methanol or amines, giving the corresponding esters or amides of imidazole4-carboxylic acid and imidazole-4, 5-dicarboxylic acid.

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The oxidation of prenyl chloride [1], prenyl acetate [2] and prenyl methyl ether [3] by selenium dioxide in acetic acid, dioxane and/or ethanol was investigated. [1] was oxidized in dioxane to give 4-chloro-2-methyl-2-butenal [4] selectively. From [2] and [3], 4-acetoxy-2- methyl-2-butenal [6] and 4-methoxy-2-methyl-2-butenal [10] were obtained respectively.

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The study of oxidation of ethylene in liquid medium in terms of Wacker-process was carried out experimentally in wetted-wall column.
The average absorption rate of ethylene in wetted-wall column, estimated by using the reaction rate constant obtained in an agitated vessel, was in good agreement with that obtained experimentally.
It was found that this reaction can be dealt with as gas absorption accompanied by pseudofirst order reaction and that the constant rate of gas absorption observed in an agitated vessel can be regarded as that of initial absorption.

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