Infrared spectra of hexachiorocyclohexane (BHC) isomers were precisely measured in CH stretching region as rnodel compounds for the investigation of CH stretching vibration of sugar.
One band whlch seems to be independent of the molecular structure appears at 2976 1cm-1 in the spectra of all the isomers measured except B-isomer, while the frequencies and numbers of the ether bands depend upon the configurations. Based on the normal vibrations of BHC igomers calculated by a simple method which takes into account only the stretching vibrations of CH bonds, the ebserved bands were assigned. The cenfiguratien-dependenee of the CH vibration was well interpreted as the result of 1, 2- anct 1, 3-diaxial interactions,

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13C NMR spectra were measured for eleven mono-substituted aceranilides in 10 mol dimethylsulfoxide solution and the electron densitiea for these compounds were calculate by means of CNDO/2 MO method. The 13C chemical shifts for sp2 carbons in m- and p-substitude compounds are in parallel with the electron densities at the positions (Figs. 4 and s) On the other hand, for the o-substituted compounds, the correlation is not so good and it is considered to be due to the effect of steric compression or intramolecular hydrogen bonding between the amide and the substituents.
Changes in chemical shifts for the carbonyl carbons due to the alternation of substituent in benzene ring are extremely small (belew 1, 5ppm) and this result is in good agreement with in the total electron den.sities obtained by CNDO/2 calculation.
In p-substituted acetanilides, the linear relationship between the chemical shifts of 13C at the para position with respect to substituted group and the total electron denslties are observed (Fig.6). While the chemical shifts and the -electron densities as not correlate to each other.
13C chemical shifts at the carbon to which the substituent attaches in m-and p-substituted acetanilides, are correlated well with Pauling's electronegativity of the atom bonded directly to the ring carbon, and it is in agreement with the behavior in mono-substituted benzenes (Fig.8).

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Influence of atmosphere on the dissolution of Li in molten LiCl was studied both. yviJth sealed-type and non-sealed-type cells (Fig. 1). True (physical) solubility of Li .could .be measure by using the sealed-type cell, It was O.66 mol% at 662"C. On the other hand, the amount of Li dissolved increased with time when non-sealed-type cell was used (Fig. 4), this was due to the effect of 02, N2 or moisture. Addition of Li20 into molten LiCl brought about a slight increase in the amount of Li dissolved (Fig. 5). These facts suggested that, in T rmaddition Yo the usual physical dissolution, there was also a possibility of colloidal. dissolution 6f Li due to the emulsifYirig action of Li20 and LisN which were produced by the reaction of Li with 02, N2, or moisture.
The conductivity data of Li-Licl system obtained with non-sealed-type cell supported this view.

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The effects of the shqpe and size of soil particle and fiber, as well as the effects of zeta potentials en the interaetion between a seil particle and fiber were theoretically investigated. An equation for potential energy of the interaction between dissimilar electrical double iayers was derived on the basis of a sphere/cylinder model. Equations of the interaction for three different models, i.e., sphere/cylinder, sphere/infinite flat plate and sphere/sphere were compared. As far as practical sizes of a soil particle and fiber in detergent solution is concerned, the difference of the potential energy among three models is very small (Table 1). The difference in the zeta potentials between a soil particle and fiber (Ci, Cs) has a large influence en the maximum value of the total potential energy (iVT, .). Despite a constant CieCz value, VT, . decreases rapidly with the increase of C2/Ci ratio (Figs. 2, 3). The effect of C2/Ci ratio on VT, max was expressed by an exponential function (Fig. 3), and the stability parameter for heterocoagulation, OH, was defined as
OH= 2, exp(-1 ( 1-1, )), 1
The relation between eH ancl VT, ... is linear (Fig. 4) and the value of OH corresponds to the amount of deposited Fe203 onto fabrics (Fig. 5).

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The molybdite-alumina catalysts calcinated at 4000C and reduced under a low hydrogen-pressure were fouRd to have high activity for ethylene polymerization. Polyethylene, which had the same high-density as one produced by a middle method, was obtained urder ethylene pressure of less than 200 mmHg and at reactioR-temperatures of O-v70"C, The average molecular-vy eight was 540000.
The kiRetic studies of ethylene polymerization showed that the initial reaction was of O-, O.3-, O.5- and 1 st-order, at O, 10, 20 and 35, w700C, respectively, under low, - ethylene .pressure. The value of the activation energy E was 7.82 kcal/mol between o and 70oc, The polymerization rate for propylene was one-tenth of that for ethylene with the catalysts. Molybdenum oxides on alumina were more active than those on silica-alumina for ethylene polymerizatien. These facts and IR results of chemisorbed ethylene on the catalyst were well explained in terms of coordination mechanism.

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2, 2'-Bipyridyl and 1, 10-phenanthroline complexes with lithium, sodium and potassium exchanged their hydrogen with gaseous deuterium at 100eC to form HD with respective different rates, V, .. The exchange of potassium complexes with deuterium gave 2, 2'-bipyridyl 6-d and 1, 10-phenanthroline 5-d, The rates of HD formation from H D2 mixture over those complexes, V.q, were mostly larger than V, ., as summarized in Table 1; this indicated that the reaction occurred which did not exchange hydrogen in this complex. The overall aetivity for the H2--D2 exchange increased with increasing V., q/V.. ratio, and with changes from 2, 2'-bipyridyl to 1, 10-phenanthroline as well as those from lithium to potassium complexes. This increase in activity from lithium to potassium complexes corresponded to the change in activation energy. The intensity of ESR spectra of the complex observed near g=2.00 decreased when hydrogen Was intreduced and increased when it was removed, suggesting an interact ion of hydrogen with the unpaired electron as observed by the ESR.

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Kinetics of disproportionation of propylene over several supported molybdenum oxide catalysts were investigated by means of the conventional differential reactor technique. The catalysts used were as follows: MoO3-A1203 and MoO3-SiO2 catalysts, prepared by wet mixing method containing various amount of MoO3, and MoO3-Y-A1203 and CoO-MoO3-r-A1203 catalysts, prepared by impregnation method.
The initial rate data obtained for all catalysts could be correlated with the rate equation based upon a dual site Langmuir-Hinshelwood mechanism. These results could be interpreted by introducing the following concepts to the adsorption equilibrium constants of olefine.
(1) The stepwise equilibrium constants of olefines K1 and K2 were not the same value with each other by considering the free energy of each interaction between a metal ion and two olefins.
(2) The active centeres were also retarded by the adsorbed species which were different from the intermediate of this reaction.
The compensation effect was observed between the activation energy E and the preexponential factor A in the rate expression of k=A exp(-E/RT).
As the degree of the dispersion of MoO3 on carriers increased, both the activation energy E and the heats of adsorption Q increased, and the relation, 2 Q E, was obtained for all catalysts used. It was concluded from all results that the inhibiting effect on the active center of the catalyst by non-intermediate adsorbates was very important, and also that the entropy change in forming the activated complex was more important than the enthalpy changes of this reaction.

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The oxidative dehydrogenation of 1-butene was studied with platinum group metal catalysts. The catalytic activity decreased in the following order: Pd>Rh>Pt>Ir>Ru. However, the order of catalytic activity for the oxidative dehydrogenation plus isomerization, which were considered to proceed via a common intermediate, was in agreement with that found for oxychlorination.
The effects of additives on palladium catalysis were also studied. Halogen ion markedly suppressed carbon dioxide formation. The extent of the suppression was in the following order: F<Cl<BrzI. This trend seems to reflect the affinity between palladium and halogen ion. When bromide ion was added (as sodium salt) the selectivity of butadiene formation was about 99.9%. Alkali metal ions suppressed the isomerization of 1-butene catalyzed by acid sites on the supports, whereas they accelerated the oxidative dehydrogenation catalyzed by palladium metal. Anions other than halogen ions did not exhibit any suppression effect on carbon dioxide formation.
The suppression of carbon dioxide formation by the addition of halogen ions was considered to be not caused by the poisoning of specific active sites but to be due to the inhibition of oxygen activation which causes complete oxidation.

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The mechanism of oxychlorination of propylene over supported metallic palladium catalyst was studied. The change in the products formation with time was observed after the supply of one of the reactants (oxygen or hydrogenchloride) was stopped. If the feed of oxygen was stopped, the rate of allyl chloride formatidn fell slowly to zero in about 30 miutes, whereas that of isopropyl chloride did not change. On the other hand, if the feed of hydrogenchloride was stopped the rate of allyl chloride formation fell $lowly to zero in about an hour, wbereas that of isopropyl chloride fell to zero in a few minutes. These observations suggested that the chloride species participating in allyl chloride formation were held strongly on palladium surface, but those related to isopropyl chloride were comparatively held weakly. The fact that considerable amount of palaladium chloride was formed in the catalyst during oxychlorination and the amount of it depended on the reaction condition suggested the chloride species concerning allyl chloride formation being chloride anion which has been oxidatively adsorbed on the palladium.
Some cocatalysts (active carbon, cupric chloride and nitric acid) which had been considered to promote the oxidation of palladium, accelerated the rate of allyl chloride formation.
The mechanism was analyzed by the kinetic method.

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The accomodation coefficients of argon at 305 1 K on nickel were determined by using a nickel ribbon at the temperature range from 345 to 5500K under the pressure of 2.v5 10- Torr of Argon. To elcidate the effect of surface conditions on the accommodation coefficierits, measurements were carried out on the surfaces which had been pretreated differently each other, and the thermal desqrption was measured at the surfaces before and after the measurements of the accommodatioh' coeficients to see the change of surface conditions owing to the measurements of the accomodation coedicients. As for surface pretreatment three methods were preferred; i.e. the exposure to hydrogen, the bombardment with argon ions and the treatment of oxidation and reduction.
The values of the accommodation coefllicients obtained in the present experiments lay in the range from O.50 to O.99. As the temperature difference (a T) between argon and nickel became larger, the accommodation coefficients decreased no matter which pretreatment was taken, however the rate of decrease varied with surface conditions. At the surface bombatded with argon ions the rate of the decrease was the largest, and moreover the most remarkable change of thermal desorption curves before and after the measurements of the accomodation coeMcients was obtained in this case. As compared at the same d T, the accommodation coemcients were larger when the cleanliness on the surface was thought to be inferior. she value proposed by Eucken, 2 the difference between the heat of adsorption and the activation energy of energy transfer was seen to be influenced greatly by the surface pretreatments.

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Reverse photochromic 1, 3, 3-trimethylspiro indoline-2, 2'-benzopyran-8'-carboxylic acid (1) turned from the colored to the colorless state on the addition of NaOH. This change was considered to occur by neutralization of the carboxylic acid group of (Z) with NaOH which resulted in the unstabilization of the colered structure by destruction of hydrogen bonding.
In the presence of NaOH, two colored isomers, (Bt) and (B2), were separated spectroscopically after fiash irradiation on the colorless species (A') of (1). lncreasing the concentration of NaOH added, another colored species (Bs) was formed, its quantity being proportional to the concentration of NaOH excess to the amount ef spiropyran (1).
Two colored species (B') and (Bs) in neutral ethanolic solution, and another colered (B6) species in basic solution were feund also in the case of 6'-carboxylic acid derivatives (2), and its reaction scheme was discussed.
In the absence of NaOH, relative photo-coloration efficiency of (2) was larger in polar alcohlic solvents than in nonpolar solvents. lt increased on the addition of NaOH. These results show great influences of the dissociative proton on cc. The effect of proton on co of C1 was also discussed.

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A porous oxide film having parallel pores is produced when aluminium is anodized in such a solution as phosphoric acid and a thin compact oxide layer called the barrier layer exists at the bottoms of pores, The thickness of pore-wall, which is a half of the distance between the adjacent pores, is nearly the same as that of the barrier layer, b (Fig. 1). lt has been known that a small amount of phosphate ion is included in the film as the result of coordination of these iions towards aluminium ions in the oxide.
In this investigation, the distribution of phosphate ion across pore-wall( =1000A) was measured for the film formed at 100 V (vs. SCE) in 4% HsPO kept at 250C, a technique of dissolving the film in 2 mol/l H2SOG solution being utilized. The dissolution of. the filrp proceedsYff the surface of pore-wall in such a manner that pore widens evenly. all thro.ugh ihe depth of the pore (Fig. 1), so that the distribution of, phosphate ion was determined-by measur the time-variations of the amounts of phosphate and aluminium ions in solutio4 during dissolution (Fig. 2). The concentration of phosphate izefo at 900 A (Fig. 4). The average concentration of phosphate be abeut O.14 mg-PO/rng-Al. The to that across the pore-waH, in view o eiectronmicroscepy. The mechani sm of film growth explaining described. nearly constant irrespective of, but increases gradually and decreases nearly equal to in the film was estimated to distribtition of phosphate across the barrier laYer was similar of the results of examination of the film by ESCA and the phosphate distribution is described.

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The effects of addition of Ag and Ag20 (5 or 10%e) on the characteristics of the positive plate (Ni(OH)2 50, graphite 35, polyethylene 15) of pressed-type Ni-Cd sterage battery were studied by measuring overpotential, capacity changes with charge-discharge eycle and the potential-current curves obtaind by the potential sweep method. The results are smmerized as follows:
(1) Availability of the active material at the initial cycle increased with the additien of Ag and Ag20. The increase exceeded 80%o when the content of Ag20 was 10%.
(2) The addition of Ag and Ag20 decreased the overpotential in charge and discharge processes. The effect of Ag20 was more appreciable than that of Ag,
(3) Capacity of the plates containing 10% Ag20 increased gradualy with charge-dischargecycles, while that of the plates containing Ag decreased suddenly and shedding was observed.

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Tetrachlorodiphenylphosphazene P3NsC14(CeHs)2 (CPP) was synthesized by Freidel-Crafts reaction, and the polycondensation reaction of CPP with aromatic dihydroxy or diamino compounds were carried out in pyridine solvent.
The polycondensation products obtained from the reaction of CPP with dihydroxy compounds were soluble in the most polar organic solvents, and molecular weight of the products was about 1100 to 3400. Since the polycondensation products of CPP an, d using diamine compounds was not suMcently soluble in the most organic solvents, molecular weight of them was unable to measured.
All of the products was amorphous, and had white, yellow, brown or orange color. The softening peint of all of the, products was measured, and it was found that the product obtained from CPP and P, Pr-dihydroxydiphenyl had the higest softening peint about from 260 to 270CC. Consequently, this product seemed to be the most stable for heat. Also, it was found that the products obtained from CPP and bisphenol-A or P, PLdihydroxydiphenylsulfonehad three dimentional network structure, though the other products had linear structure.

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In order to investigate the appropriate oxidizing conditions of chromite with rnolten salts, several chromites were treated with NaOH-NaNOs molten salts under various, conditions of temperature (300N700eC), time and atmosphere.
It was found that the Cr203 component in the chromite was oxidized to chromate by the reaction (1) below ca. 400C, and by the reaction (2) above 4000C.
Cr203 + 4 NaOH + 3 NaNO3 = 2 Na2CrO + 3 NaNO2 + 2 H20 (1)
5Cr20s + 14 NaOH +6NaNO3 =10 Na2CrO4 +3N2 +7H20 (2)
The appropriate conditions are shown below: ratio of sodium equivalent to Cr20s was about4.0, oxidant equivalent ratio, 1.ONI.3, reaction temperature, 450.v6000C, and reaction time, IN3 hrs. ln these conditions, a high degree of oxidation, more than 90%, was observed. There was no remarkable difference in reactivity among several chromites, and the change of atmosphere did not affect the degree of oxidation.

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Aseries of studies are being undertaken in order to clarify the variation of the layer structure in graphitization process. ln this paPer, on the 3, 5-xylenol-formaldghyde resin carbon samples heat-treated at 18000C to 3000C, themean-square displacement, ecl, and the mean-square thermal vibrational tV isplacement, li of cqrbon atems .per-pendlculqr to layer pianes Were calculated from X-ray diffraction intensities of 002, 004 and 006 reflections.
The value of u2 decreased abruptly with the decrease in co from 6.S6 A to 6.S5 A, and showed about O, 033 A2 up to 6.78 A, and then decreased again with the decrease in co(Fig.3)
The values of were in the range of O.015-O.012 A2 at 20o and increased with ambient temperature(Figs.2and 4).
The 3, 5-xylenol-formaldehydeuresin carbon was found to be less graphitizing than the petroleum coke studied previously from the variations of ce and L, with heat-treatment temperature. However the variatio:ns of with and of with ambient temperature were similaron both samples.

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2, 2t-Diaminebiphenyl(dabp) c6mplexes with transjtion mAetalS, CO(II), Ni(II) and Cu(II), were studied by various spectroscopic techniques such as reflect.ance s-petral .X-ray diffwraAction, IR and ESR spectra, 2, 2'-Diamin6phenyl as a bidentate ligand was located between.H2O and vly- in a spectrochemical series. Trans hexa-coordinated structure was estimated for disubstituted complex except (Ni(dabp)2(NO3)s), based on the reflectance, far-infrared, ESR spectras and powder X-ray diffraction data, while cis-structure was postulated for (Ni(dabp)2(NO3)2). From the ESR spectrum of (CU(dabp)2CL2), elongated trans-tetragonal structure was assumed for this compound. The covalent bond character between Cu2+ ion and N atom in dabp was ascertained from thr ESR spectrum of the methanol solution of Cu(dabp)2(H2O)(CIO4)2. The far-infrared spectra were measured for metal-dabp complexes and the assignments of the bands associated with metal-N stretching vibrations were made. The assignments were also made for those hands associated with metal-halogen and metal-oxygen stretching vibrations. On the basis of these vibrational assignments, the bonding nature between metal atoms and ligands was discussed, and considerable degree of ionic character of the bonds between metal atom and halogen or NO3- was presumed.

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Kinetics ef the substitution reactions ef the lead(ll) complexes of ethylenediamineN, N, N', N'-tetraacetate(EDTA), N-(hydroxyethyl)ethylenediamine-N, N', N'-triacetate(EDTAeOH), 1, 2-cyclohexanediaminetetraacetate(CyDTA) and diethylenetriamine-N, N, N', Nt', N"-pentaace-tate (DTPA) with gallium(III) In have been studiedover a pH range 2 0-4 0 at 200C and an ionic strength of O, 1 in the presence of an excess of lead(ll) ions.
The reacVtions were follow5d spectrophotometrically at the maximum absorPtion wavelengths of the lead complexes. The initialrate of the reaction (R) was expressed as
R=(k1+k4[Pb2+])/[H+]+(k2+k5/[Pb2+]+(k3+k6/[Pb2+][H+])[Pbx](Ga3+)
for the EDTA and EDTA e OH systems,
R=(k5+k6[H+])EPbX)[Ga3+]/[Pb2+]
for the CyDTA system, and
R=((k3+k6/[Pb2+])/[H+]+(k7+k8/[Pb2+]))[PbH2x](Ga3+)
for the DTPA system.
Contribution of each reaction path to the over-all rate of the reaction was estimated. The reactions for the EDTA, EDTAeOH and DTPA systems seemed to proceed through both stepsforming binuclear intermediate complexes PbXtGa and the dissociative paths in wbich the rapid dissociitive equilibria of lead complexes proceeded to form the gallium complexes, and the reaction for the CyDTA system proceeded through the disseciativepaths.
In addition, sinde it was estimated that in the dissociative path the reaction. s-pr-o-ggedeq through the bath involving GaOH2', the rate constants for the formation of G4X. GeHXAand GaH, X couldM be calculated For EDTA, EDTA.OH orCyDTA kG.x w-as 1-3xIP, 1, 5x196 gr 2.7x107mo1-1 l sec-1, and kG0Hx was 1.0x10, , 7, 8x103 r 2 9x10 mo1-1 se-1 espectively and for DTPA kgx or kG H2x was 2.4x106 or 4, 0x104 mor1, 1 sec-1 again respectively.

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The fluorine eontent was determined spectrophotometrically for seventy sedimentary roek samples from Niigata Prefecture. The arithmetic means of thedetermined values for various rock types were 200 ppm for sandstone, 370 ppm forsandy mudstone, 400 ppm for mudstene, and 410 ppm for shate. The results gerierally agreed with the previous information that pelitic rocks were richer in fluorine than psammitic ones. ln comparison with the previous data which were considered rb be reliable, the average fluorine contents of sandstones were almost atthe same level in various regions, while the averages for shales fiuetuated appreciably according to the locality. As a whole, abundance of fluorine in Japaneseshales tended to be rather lower than that found in those of other countries.
Although boring core samples in this region shovy'ed very high chlorine content by the addition of the element contained in oil-field brines, fluorine content seemed to be hardly affected by brines, showing a similar content range (300v500 ppm) to. that of weathered outcrep samples.

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Palladium(II) formed four kinds of stable 1:1 chelates with 4-(2-pyridylazo)resorcinol(PAR or II2R), i'e.at pH 4, a green chelate [Pd(H2R)OH2]2 (e=1.75x10' at 440 nm and e=8.63x103 at 580 nm), at pH 4N7 two kinds of red chelates [Pd(HR)OHa] (e=2.68x10' at 515 nm) and [Pd(R)OH2]e (e=2.89x10' at 525 nm) and at pH 8-11 a red chelate [Pd(R)OH]- (e=3.40x10' at 520 nm), (Fig. 1 and 4). The acid dissociation constants of the chelates were estimated as Kai=, Pd(HR)OH2 (H+)/[Pd(H3R)OH22 ]= 14 ss ho 5 and Kaa= [Pd(R)OH2 H+]/(Pd(HR) OH, ')=10-536 e5 in 5Q% aqueous dioxane solution at 25C, , ec=O.1 (Fig. 5 and 6)
At pH 6.vll, Pd(U)-PAR chelates reacted with tetradecyldimethylbenzylammonium chloride (Zephiramih, Zeph eCl-) to form an iorvassociation complex which was easily extracted into chloroform and had a maximal absorbance at 540 nm with molar absorptivity of 3.29x10 (Fig. 2).
Beer's law was confirmed over a range of Ov20 ptg Pd2/10 ml CHCIs and sensitivity which gave the absorbance of O. OOI was O.0032 ptg Pd2/cm2. Pd(II)-PAR chelate was more stable thanPd(II)-EDTA chelate so' that EDTA could be used as a masking agent for hindering metal ions. Among twenty kinds of diverse metal ions, only Fe(II II)and C (III)ions seriously interfered with the determination (Table 1). The role of EDTA was not restricted only as a masking agent, but also as an agent which accelerated the rate of the PAR chelate formationby preventing the hydrolysis of Pd2 ion.

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A modified null-point potentiometric method and a modified differential potentiometric method are compared with respect to precision with calibration curve method using a new sodium selective glass electrode.
The plot of the electrode potential vs. pNa .shows Nernstian response giving a straight line over the concentration range of 10-1 to 10-4 mol/l Na-. The presence of 20-100 times as many potassium and ammonium ions, and more than 1000 times as many calcium ion are tolerated. A PH value does not affect the electrode response at the pH range higher than (pNa+4.5). It is confirmed that the irradiation of ultra-violetlight on the glass membrane does .enot giye a meaningful change in electromotiveforce.
Of the three rfiethods tested, the modified differential potentiometric method i-s-.most precise, followed by the modified nuil-point potentiometric method, and then the calibration curve method.

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Ari X-ray diffraction method has been developed for the determination of silica content of B--eucryptite solid solution precipitated in glass-ceramics. B-Eucryptite solid solytions.of Varioug silica content were prepared by the crystallization of glass technique, and d-spacings corresponding to (514), (406), (220), (206) and (114) lines were measured to obtain cali.braQon curvesMDThe Tocalibtation curves, showing the correlation between lattice constaRts and silica content of the solid solution had bent at the composition of Li20-A1203e3 SiO2 and Li20.A1203e 4SiO2.This phenomenon was explained on the basis of repulsive fore betwee-n lith um.iops, or litAium ion'and other cations in the lattice.On the low silica content region, the lattice constants also depended upon the crystallizing temperature and time. However, it was foupd that the calibrat- ocurve, showing .the correlation of (406) interplanar spacing against the silicacontent was linear irrespective of the crystallizing temperature over all solid solutiqn ladday eO1ule time required for ari analysis was dbout one hour w.hep the ayerage -of .thre.e time measurgments the interplanar spacing was used. The absolute values of the lattice constants 6Et5ihed in this woik can bMe also used for the determination anywhere it. is required, if correction is made for systematlc error

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The rates of deoxygenation by trialkyl phosphites were measured for ev-phenyl-N-aikylnitrones.The reaction rates are of first order with both trialkyl phosphites and nitrones respectively.The Arrhenius plot of rate constants vs.temperature gives a straight line. The activation energy (dE), activation entropy (dS) afford 20.0 kca!/mol and -28.2 e.u. (at 1200C) respectively.The relative rates of n itrones with TEP t the Taft equation, 1o9(k/ko)= 2.47 *+1 53 E, and those of phosphites with N-ethylnitrone fit the Taft equation, log(k/kg)=-1.23 g*+2.86 E, .These facts seem to suggest that the deoxygenation reaction proceeds through nuleophilic attack of the phosphorus ato of phosphite on the nitrogen atomofnitrone.

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The reactions of nitrobenzenes with benzyl alcohols and aqueous alkaliLi hydroxide solution have been investigated, The yield of azoxy compounds wasaffected by the concentration of alkali hydroxide (Fig. 1 and 2). The reduction of nitrobenzenes was facilitated by.the electronwithdrawing substituents, such as nitro, carboxyl and halogen, and retarded with the electronreleasing substituents, such as hydroxyl, alkoxyl and alkyl (Table 1). A small quantity of benzylp-nitrophenyl ether was obtained as a byproduct in the reduction of p-chloro- and Pbebromo itrobenzenes. ln the reaction of P-nitroteluene, the yield of 4, 4'-azoxytoluene was poor, and the yellowish orange solid was obtained as a main product, and a small amount of azobenzene-4, 4'-dicarboxylic acid was also obtained The reactivity of substituted benzyl alcohols in the reduction of nitrobenzene increased i theorder: -CH3 -C6H5 -CH30 P-CH3 H -Cl(Table 2).

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The nitration and bromination of (1, 1, 2, 3, 3, 3-hexafluoropropyl)-oxy-(2) and -thio-benzene (3) were investigated. ln the nitration of (2), the para substitution was more predominant over theorthosubstitution comparing with those of the non- orinated alkoxybeRzenes. The nitration and bromination of (3) proceeded without diflliculty to give mono-substituted products.These results wereascribed to the inductive effect of the electron attractive -ZCF2CHFCF, (Z=O and S) groups. From the 9F NMR data of m and P-fluoro-(2).and (3), the 6, and oR values were determined for-ZCF2CHFCFs groups (Table 2) The most favorable condition for the preparation of (2) and (3) were also studied.

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The condensation reactions of 2-amino-5-chlorobenzophenone (1), 5-chloro-2-(N-methyF amino)benzophenone (2) and 5-chloro-2-(N, N-dimethylamino)benzophenone (3) with 2-hydrazinobenzothiazole in the presence of PPA gave the corresponding hydrazones-(4), (5) and (6) in 48.3, 64.9 and 33.1% yields, respectively.These hydrazones were found to be a mixture of geometrical isomers with respectto the C=N bond. The ratio of the E- to Zisomersformed were(4);1511, , (5);11/1, (6);5/1. The E-and Z-isomers were separated and their cenfiguration wras determined by spectral data. ln the NMR spectra, e-amino protons of benzene rings of (4E)and (5E) were deshielded compared to those of (4Z)+and (5Z), while the methylprotons of the dimethylamino group of (6E) were shielded more than those of (6Z).
The E- and Z-isomers were interconverted by irradiation of a 2x10-5 mol/1 solution with the tungsten lamp at 25eC. ln the cases of (4E) and (4Z), the rateof isomerization depended on the solvent, and decreased in the order: EtOH CHsCNcyclo-CgHi2.

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Reactions of phenols with Cyanuric chloride in the presence of aluminium chloride were carried out in e-dichlorobenzene and benzene. ln the reactionof p-chlorophenol with cyanuric chloride in a molar ratio of 3:1, only tris(P-chlorophenoxy)-s-triazine was obtained as a result of O-s-triazinylation ef chlorophenol, whi1e in the case of P-cresol, 2-(5-methyl-2-hydroxyphenyl)-4, 6-bis(P-tolyloxy)-s-triazine and 2, 4-bis(5-methyl-2-hydroxyphenyl)-6-(P-telyloxy)-s--triazine were obtained as the C-s-triazinylation preducts in addition to tris(p-tolyloxy)-striazine. ln the cases of m-cresol, resorcinol, ev-and B-naphthel, however, all the reaction products wereoftype, showing that the l course of these reactions depended mainly upon the reactivites of phenols towards electrophiles; theO-condensation predominated when phenol of low reactivity was used, while the C--condensation predominated when phenol of high reactivity was employed, and boththe O- and C-condensations occurred in the case of phenol of medium reactivity sueh as P-cresol. ln the cases of m-cresol, resorcinol and B-naphthol, the C-condensation took place at the ortho position of hydroxy group and condensation products centaining two or three phenol nuclei in one s-triazine ring were obtained, even when the reactions with cyanuric chloride were carried out in a mo!ar ratioof1:1. ln these cases it is suggested that the phenols reacted preferentially withprimary and/or secondary condensation products whese residual chlorine atoms areassumed to be more reactive than those of cyanuric chloride by the presence of achelate ring in the aluminium chloride eomplexes.

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Some of tin(ll) alkoxides and phenoxides, containing functional group which was of use to prevent the association of tin-tin or tin-oxygen bond, have been prepared by the reaction of tin(ll) ethoxide or chloropropoxide with corresponding alcohol or phenol. The degree (n) of association of these 2-alkoxyethoxides or 2-, 2, 4- and 2, 5-substituted phenoxides was low (n=1.v3). Thesure compounds were very soluble in organic solvents. such as benzene, toluene, and methylene chloride, and were susceptible to hydrolysis, but tin(rr) phenoxides were somewhat more stable to moisture than tin(U) alkoxides.
Further, the method of the direct preparation of tin(ll) compounds from stannous chloride has been examined by using the ring-opening reaction of propylene oxide.

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Vapor phase amination reaction of phenol to aniline was studied by. flow re.actor.met.hod undei atrdospheric pressure; the acidity of catalyst was measured by. n-butylamip.e titr4tiop NPeMpmwrmrmsolid a6ids, Zrb2-WO3 TiO2-Nb20s, and ZrO2-Nb20s, were found and the qcidit and acid strength of theSe acias weredetermined (Table 1). TiO2-SiOz auznd TiP2-ZrO2.-s-h-o-wgd strgnger 6htalyWticactivity than SiO, -A120g. Kinetic studies on TiO2 SiO2 catalyst at 450- C shgwgdtAh-aAt brmhrmen61 reactionrrate was pfoportional to PNM, 6ePpheH 8(at PNH3 O INO-7atm at PhothH O Ol rO 14htm). The activation energy was 23 kcal/mol.The reagtio-n radtek was rgasonably cor.relqsed with the acidity of catalysts, lnthe amination reaction of phenpl derivatives the aminatlon it 12 ele1i'-i-i as concluded 'that the reaction proceeded through the phenol adsorption on the acid-sites 6Tf'catalyst. sites of moderate acid strength were most effective in the reaction. catalysts having highly acidic sites were poisoned by phenol or aniline.

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A series of partially fluorinated alkane sulfonates (3 F), n-C3F7(CH2)nSOsNa (n:5N9) were synthesized. Some physicochemical properties.of these anionics were examined in comparison with those of the'follQwing three series of sulfenate containing a Similar number of carbon in the hydrophobe n-alkane (HC), . n-perfluoroalkane (PF) and to-trimethylsilylalkane (1 Si).
1) Krafft point of3 F was significantly lower than that of PF and close to those of HC and 1 Si.
2) CMC value of 3 F was nearly intermediate between that of PF and HC for the lowest member, h owever, the value was close to those of HC and 1 Si as the member inereased.
3) Ability of ioweriRg aqueous surface tension increased in theorder of HC 1 Si tsg; 3 F e PF and increased with increasing chain length among 3 F series.
4) Wetting efliciency (canvass disc test) increased in the order of HC ISi x 3 F and foaming power 3 F HC 1Si.
These results were discussed interms of the orientation and packing state of the to-perfluoroprepylated anionics adsorbed on aqueous surface and associated into micelle.

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A number of N-1, 3, 5-triazinyl derivatives of m- and Prsubstituted anilines containing -Cl, -OCHg, and -NEt2 groups in the 1, 3, 5-triazine nucleus 'were synthesized and their ultraviolet absorption spectra were measured in cyclohexane and methanol. ln every case, it was found that a linear re1ation holds between, the shifts (dy) of L.bands of substituted anilines upon 1, 3, 5-triazinylationand the a- values of substituents in aniline nucleus, and that the more the two substituents in 1, 3, 5-triazine nucleus becomes electron-attractive the more the reaction constants for the shift becomes large, Similar relations were also observed between the shifts upon 1, 3, 5-triazinylation and the d values of substituents of 4'-substituted 4-aminoazobenzenesi
In these N-1, 3, 5-triazinyl aromaticamines, linear relations were observed between the Zom values of twe substituentsint the 1, 3, 5-triazine nucleus and the wave numbers of La bands; slopes of thelines are considered to indicate the electron-withdrawing capacities ef the aromatic systems. When the slopes(cm-1/ b)of the lines are plotted against the values upon 1, 3, 5-triazinylation, an almost linear relation was obtained in every case, showing that the electron-attracting capacity of the aromatic system plays animportant role for the shift.

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Blue acid azo dyes (AB 92, AB 116, ABk 1 and AG) have been irradiated with monochropa. atic lights of various wavelengths, and the influences of flurescent brightening agentsts of stilbene (FBg) and pyrazoline type (FwG) on the photofading have been investigated.
The light from visible near ultraviolet region gave rise to s1ight fading of dyes. The rates of photodegradation increased sharply on irradiation with the light at the wave length shorter tAan 300Tnm. lrradiation with 252 nm light gave the quantum yield of 3x10dNl, 1x10ews for the air saturated solution. The fluorescent agents faded to a certain extent by the irradiation with the light of the 300-400nm region where the fluorescence had the excitation maximal and the rate of photofading was more rapidly at shorter wavelength. Dissolved oxygen depressed the degradation of the dyes and accelerated that of FwGi
T-heVfluorescent'agents'quenched the photofading reaction of thedyes when they were applied without oxygen. Oh the other hand, acceleration of the reaction was observed'.in thg.air sa.tur rated solutfoWn. The acceleration effects were most prominent on 300At400 nm, irradiation(cf.Figs. 5 and 6). The effect of Fwo was three times as strong as FBs. IMTdshe Effects of Fluorescent substances en the phetofading of Celers. 1.

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The behavior of gas fading of some aminoanthraquinonoid disperse dyes on eellulose acetate and triacetate films has been examined in terms of the specific fading constant to gas. The effect of substituents on the fading to gas and light of aminoanthraquinones were discgssed.A concentration dependence on thegas fading of dyes, ie., resistance to gas fading of the dyes increases with their increasing conentration on the substrate is shown in this series. 5, 6-'and 6, 7-benzo derivatives of 1, 4-diamino(and dimethylamino)anthraquinones are more resistant to gas fading and photofading than the compounds of original strncture.1-Amino-2-methoxy-4-amino(and hydroxy)anthraquinones and 1-amino-2-alkylthio-4-anilino-anthraquinones fade to gas much less and fade te.light more than corresponding-2-unsubstituted' frivatives. Gas fading and photofading of 1-amino-2-carbamoyl-4-methylaminoanthraquinon is more sensitive than those of 1-amino-4-methylaminoanthraquinon.

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The thermal unstableness of benzoyl peroxide (BPO) was investigated by means of pressure vessel test (PVT), ignition delay time, TG and DSC methods. ln addition, the analyses of thermal decomposition products and their reactions were carried out.
The PVT curves showed that BPO decomposed violently at about 1000C with the evolution of white smoke, and hence the hazard of this material is very large. The white smoke produced was found by IR analysis to be composed of benzoic acid, phenyl benzoate, terphenyls and biphenyl. The melting point and the decomposion temperature of BPO were dependent.upon heating rate, and the 50C/min was suitable to get the melting point of 105.5A-tlO7 C and the decomposition temperature of 108eC. The ignition delay time depended upon the amount of saMple, and the qnantity of 150 mg was used. lt was found by TG, DSC, IR and the activation energy estimated from ignition delay time that the termal decomposition of BPO at first occured suddenly and followed by a milder reaction. The analysis of IR, thi'n layer chromatography and the pyrolysis gas chromatography revealed that the thermal decomposition of the pure BPO gave carbon dioxide, benzoic acid and biphenyl as main products, together with some phenyl benzoate, benzene and terphenyls. After about 6 to 10%e weight less was perceived on TG curves, this decomposition reaction was accelerated by biphenyl whieh was produced by the decompositi6n of BPO.

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Inonenes of a general structure fomula, N(cH ) -(i cH ) N(c cH where(n m)are 2) (6, 5), (8, 8)and(10, 10)were prepaed. Specific resistance(p) and activation energy of conduction(E) of 7, 7, 8 -tetracyanqui dimethane(CQ)salts of these lonenes were measured
The values of p and E, of Ionene-CQ simple salts ipcreased as a number of methylene groups between ionic sites became larger within;(6 6) while th se f(8 8) (10 10)-lonene CQ simple salts were smaller than(6, 6)-lonene-CQ simple salt
As a whole the correlation of an interval between electric conductivity and ionic site on the Ionene was obseved from (2.5)-Inonene-CQ o(6.6)-Inonene-CQ salt. It was found that (6, 5)-Ionene was e m st effective at rixThe valuesof an ol the(6 5) 1 nene CQ complex salt[CQo]/[CQ7]=1.O were 77 n and O 4 eV, r6spectivglY.

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The sorption precess of methyl methacrylate (MMA)-2-diethylaminoethyl methacrylate (DEAEMA)copolymer(MMA/DEAEMA=9/1 in mole ratio)immersed in water'was pursued from the process of the lowering of 4-potential with time.
The C-potential estimated from the streaming potential method changed from positive to negative values, arriving finally at the negative equilibrium value (Fig. 1).
Below T, C-potential decreased with time exponentially and aEl=-25.8 kcal/mol was obtained from the Arrhenius plot of the rate constants (Fig. 3). ln addition, the points at which-potential curves intersected the time axls mlgrated to long timeside and the equili-brium values of potential increased with increaslng temperature. But above, Tg the lowering of ptential with time was not exponential and the migration of the intersectionson the time axis was not correlate with te:mperature(Fig, 1).
Further, it was found from the sorption experiments.that difference of sorption amQunts between below and above Tg was considerably Iarge(Fig, 2).

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The Cu(II)or Co(III)-Complexes of the two Schiff-base ligands, 3-(2-pyrrolylmethylenimino) propene-1(PIP) and p-(2-pyrrolylmethylenimino)styrene(PIS), were synthesized. The radical polymerizability of the vinyl groups in these comple, xes was studied.
The kinetic order with respect to the initiator was O.5 in the copolymerization of Cu(PIP)2 with AN and was 1.0 in the homopolymerization of Cu(PIS)2. These results suggested that the termination mechanisms changed with the difference of the conjugated system in the complexed monomers. Since transition metal ions acted as a kind of retarder, the polymerization rate was low and the molecular weight of the polymer c6mplexes obtained' was small. The inhibition effect of metal ions or complexes depended on their redex-potentials and electronic structures of d-orbital, so that the inhibition effect of Co(II)-complexes was greater than that of Co(III)-or Cu(I)-complex.
Large ri-values were obtained in both the copolymerization systems, i.e., Co(PIP)s (Mi)-AN (M2) and Cu(PIS)2 (Mi)-St (M2) systems. This may be due to the unchanged vinyl groups coordinated to the metal ions in the polymer.
On the polymerization of Cu(PIS)2 complex, the intramoleeular electron transfer mechanism was assumed and the formation of uncross-linked polymer could be explained in terms of this mechanism.

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To improve the solubility of Naphthol AS series polymeric dye intoresins and to investigate the effect of dye content in polymeric dye on light fastness, polymers containing the coupling component in various proportions were rst prepared by copolymerization of 3-hydroxy-2-naphth(m-methacrylamide)anilide.and methyl methacrylate(MMA)or stylene(St), second, MMA polymers, that was copolymerized 4-[2-methoxy-5-(diethylsulfamoy1)pheny1]azo-3-hydroxy-2-naphth(m-methacrylamide)anilide in the proportion of 43.0, 28.1, 18.4 and 9, 2 wt%, and third St polymers, ontaining t:he dye group in the proportion of 34.2, 20, 1, 11.4 and 6, 2wt%, were prepared by the coupling reaction of the copolymers with 2-CH30-5-(C2H5)2-NSO2CeHsN2BE in DMF.
The comparison of light-fastness of these polymeric dyes and the control monomeric dye was carried out by measuring the decrease in optical density at 512nm in casting film As a result, polymers which contained the dye Iess than 10 wt%Showed the best Iight fastness as well as that of mbnomeric dye, but Iight fastness of other polymeric dyes became poor with in.creasing dye content. It seemed the at light fastness of the polymeric dyes depended on the dye content.

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In connection with the utilization of 2, 3-naphthalenediscarboxylic acid (2, 3-NDCA) as a new industrial raw material, 2, 6-naphthalenedicarbaldehyde was prepared by the reduction reaction of 2, 6-NDCA which in turn was obtained by the Henkel rearrangement of K2-2, 3-NDCA.
Conversion of 2, 6-NDCA to the acid chloride, followed by the reaction with N-methylaniline gave 2, 6-naphthalenedicarbon-N-methylanilide (1). Reduction of (Z) with Li[AIH] (1.2 molar ratio to (1)) in THF for 2 hr at OeC, and cleavage of the resultant complex with dilute hydrochloric acid without previous isolation produced 2, 6-naphthalenedicarbaldehyde (2). The yields depend sharply on the reaction temperature and on the amount of Li[AIH] used At higher reaction temperatures, the yie1d of (2) decreases and 2, 6-bis(hydroxymethyl)naphthalene is formed as a side product.

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It has been reported that a durable fiameproofing property can be obtained by treating cellulose with erthophosphorib acid and cyanamide'. This study was carried out to elucidate the flarneproefing factors.
As a result, it was found that the cellulose treated contained much nitrogen and phospherus as shown in Table i, The reason was presumed as follows: The large contents of nitrogen and phosphorus were ascribed to the esterification promoted by cyanamide and to the condensed phosphoric acid which formed in the treating solution and acted as a prometer of the esterifieatien.

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It was confirmed by means of gas-liquid chrematograph aRd NMR spectroscopy that acrolein oxime obtained acording to Tuerck's and Koral'nik's procedures was a mixture of geemetrical isomers. The syn form (AOM-S), whih was a colorless and viscous liquid, was stable at room temperature. On the other hand, the anti form (AOM-A), which formed white needles having the melting point of 33 -v35eC, was stable at temperature below OeC, but unstable at room temperature. The NMR signals assignable te the C-CH=N of AOM-S and C=CH-C of AOM-A were shifted to lewer fields due to the spatial iRfluences of the hydroxy group.

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