The electric conductivity of aqueous Co(N113)511S04 solution was measured as a function of pressure (up to 3000 kg/cm2) for concentrations from 2.0x1O to 1.0 x 10 N at the temperatures of 15, 25 and 400C. The equivalent conductance at infinite dilution, A0, vs. pressure curve has a maximum. The pressure at this maximum conductance was found to be higher than that at the minimum viscosity of water at each temperature. These phenomena may be attributed to the decrease in the effective radii of the hydrated ions with increasing pressure.
Thehydration numbers of the ions estimated by the Robinson-Stokes method are littlechanged with pressure and temperature.
Both the closest approach distanceof the ion-pair, a, calculated by using the theoretical equation of Fuoss and the thermodynamic parameter, AVO, calculated from the pressure coefficient of the dissociation constant suggest that the ion-pair, Co(NH3)5NOj2 .S042, exists in closer contact as compared with that in a simple 2-2 electrolyte,

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The equilibrium and kinetics of ion exchang of adsorption of Pu(IV) (1.5x 10-7 mol/l) have been studied with a chelating resin, Dowex A-i (polystyrene-divinylbenzene copolymer containing iminodiacetic acid as a functional group).
The distribution coefficient, Kd of Pu(IV) increased with increasing pH ofthe solution until pH 3.5, beyond which the Kd decreased. The ionic strength which was varied from 0.01 to 0.5 did not affect the Kd value in the pH range of 2-3.5, whereas above pH 4 the Kd value varied with ionic strength. The mass-actionlow hold for the adsorption of Pu(IV) at pH 3, but not for the adsorption at pH 5. These results may probably be due to the fact that Pu(IV) is adsorbed on thisresin throughout the pH range of 2-3.5 by chelate formation mechanism between monomeric Pu(IV) ion and the iminodiacetic group of the resin, but Pu(IV) at abovepH 4 exists predominantly as polymeric species which is adsorbed on the resin surface by the colloidal adsorption mechanism.
The rate of the ion exchange adsorption of Pu(IV) was independent of the ionich strength and of the particle sizeof the resin, and was not explained by a kinetic equation with film or particle diffusion. These results support the view that rate determining step of the reaction is the chelate formation reaction between Pu(IV) and iminodiacetic group ofthe resin. The apparent activation energy obtained from the first-order rate constant was 18.4 kcal/mol at ionic strength of 0.1 and pH 3.

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The interactions between dodecylammonium salts and poly(vinylpyrrolidone) in aqueous solution were studied by means of the measurements of viscosity, electrical conductivity and equilibrium dialysist.
The viscosity and conductivity data indicate that an associatien complex is formed between dodecylammonium thiocyanate or iodide and the polymer, The thiocyanate binds strenger than theiodide to the polymer. Doclecylammonium bromide and chtoride do not bind to the polymer judging from the data of the reduced viscosity of the polymer solutioninthe presence of these salts. The binding is slight for tetrabutylammonium iodide, and no detectable binding for tetrabutylammonium bromide, cetykrimethylammonium bromide and potassium iodide was observed.
It is concluded that for alkylammenium salts the more the anions have strong water-structure-breaking effectandthe cations are hydrophobic, the more they bind onto poly(vinyl-pyrrolidone).

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The hydrogenation of r-butyrolactone over a comtnercial catalyst, nickel catalyst supported en kiesielguhr, has been investigated, in order to elucidate the reaction mechanism and find a desirable process for tetrahydrofuran pfodubt ibn from r-butyrolactone or maleic anhydride. The reactions were carried out batchwise under the following reaction conditions: temperatures; 180N290"C, pressure; 5e. 120 kg/cm2, catalyst concentration; 10 wt %.
The main product wastetrahydrofuran, and 1, 4-butanediel could not be detected even at the lower reaction temperature than 2000C. The by-products obtained were the lower alcohols, i, e., n-propanof and n-butanol and the lower organic acid, i.e. propionic acid and btttyric acid. The yields of these by-products increased remarkably with increase of the reaction temperature, but the yield bf tetrahydrofuran did not increase so much as the above by-products. The yield of tetrahydrofuran increased lirtearly with the reaction pressure up to 100 kg/gm2.
The reaction rate could be related linearly with the concentration of r-butyrolactone and with one half power of hydrogen pressure. lt was supposed that the water and the lower organic acids produced through the reactibn were strongly adsorbed on the surface of catalyst and caused to inhibit the reaction. The apparent activation energy of thisreaction was 11.7 kcal/mol.

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The catalytic dehydration and dehydrogenation of 2-propanol over thesilica-manganeset (II), -zinc(II)and-magnesium(II), which were prepared by the method of precipitation from homogeneous solution were compared with those over usual coprecipitated metals.
Dehydration took place to a large extent over the catalysts prepared by the homogeneous method, while dehydrogenate did only toa small extent at 300Cover the catalysts prepared by the both methods. The catalytic dehydration activities on the homogeneous catalysts were much higher than those on the coprecipitated catalysts, and the order of activity was Mg(II) Zn(II) Mn(II).
Kinetics studies using a fiow reactor indicated that the dehydration and the dehydrogenation were of both first-order irreversible reactions. From theArrhepius plots the activation energies for the dehydration Over the homogeneoussilica-manganese(E), -zinc(II) and -magnesium(E), were found to be 16.0, 17.9 and20.6kcal/mol.m2, respectively.
From the consideration, of the changes of relative activities by adding various amounts of KOH and of the differences of thepH titration curves for the catalysts and silica gel, it was concludedthat the active sites of the dehydration were. Lewis acid site, vi2., the metals with the vacant orbitals which combined with the silica gel and those of the dehydrogenation were the electron pair donor or the oxygen atom of the metallic oxide bended to the silica gel.

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The catalytic dehydrochlorinations of 1, 1, 2-trichloroethane(TCE) and1, 2dichloropropane (DCP) were studied at 3000C and 250"C, respectively on various metal fl uorides. The catalytic activities were found to be in order of AIF3 MgF2CaF2 =t CrFs ZrF4 LiF (Figs. 1, 2). Except for MgF2 this order corresponded, to that of the catalytic dehydroclorination of 1, 1, 1- trichloroethane. The selectivity for TCE dehydrochlorination showed that all of examined metal fluorides belonged to a solid acid group typified by silica-alumina(Fig.3).
The calytic activity of aluminum fluoride decreased with calcination temperature. And that ofaluminum fluoride which had been poisoned NaOH solution decreased with the concentration of NaOH, and a relation was found between its activity and acidity.br In the MgF2-AIF3 system, the catalytic activity for DCP dehydrochlorination showed maximum at 13 and 90 mol% AIFs, and minimum at about 60 mol% AIFs, which corresponded to the acid amount Ho +4.8.Some disagreements observed may be due to theinteraction of MgF2 considerably and produced HCI.
Infrared absorption spectra of pyridine adsorbed on AIF3 showed that AIFg has bothj Br6nsted (1540cm-1)andLewis (1450 and 1490cm-i) type acid sites.

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The behaviour of 3 MgO.VxO6 and 3(Ca, Mg)O.2V20if produced in MgO-CaO-A1203-NiO system catalyst used for cracking of petroleum in reducing atmospherewere examined by X-ray analysis.
In order to clarify the relations betweenthebehaviour of the produced metals and the activity decrease of the catalyst, the activities and the melting points of these vanadium compounds replaced with NiO were determind. As the results, the following reduction process were found.
3MgO.V20g --2 MgO.VO2 + O.5(MgO.V203) + O.5MgO
or 2.5MgO.V20g.s + O, 5MgO
3(Ca, Mg)O, 2 V20s -- 3(Ca, Mg)Ot2 V20g
Lattis constantsof the decomposed minerals were, 2 MgO.VO2; cubic a=8.4001, MgO eV20s; cubic a=8.4172, 3(Ca, Mg)O.2 V203; cubic a=15.0987.
It was found that all minerals had high activities while 3(Ca, Mg)O.2V20s had low melting point of 10800C, as compared with other minerals of which melting points were above 1250eC.
These facts lead to a following conclusion on the cause of decreasing of the catalytic activity.
During the oil gas craeking furnace is in air atmosphere at high temperature for short time, 3(Ca, Mg)O.2V20s in the catalyst becomes sintered or molten state and makes reduction of NiO contained in the catalyst minerals diflficult and the activity is gradually decreased.
But a direct poisoning action of vanadium to nickel catalyst is not considered.

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Reduced nickel-molybdenum supported on SiO2-Al2O0 was found to be a favorable catalyst for the production of tetrahydrofuran and T-butyrolactone from succinic anhydride or maleic anhydride.The favorable composition ratio of Mo to Ni range from 0.06 to 0.2. SiO2-A1203 and kieselguhr were used as the catalystsupport, and the former was better than the latter with respect to both the activity and selectivity for the production of tetrahydrofuran.
It was confirmed by X-ray diffraction for the catalyst of various composition that molyb- denumwas incorporated into the nickel crystal forming a solid solution with nickel. Simple relations were found among the Mo/Ni atomic ratio, the crystal size and the lattice constant of Ni(III) plaine. The catalytic activity increased with increase in the lattice constant and decreased with increase in the crystal size. Itmay be concluded that the lattice constant and crystal size affect the characterand number of active center of catalyst, respectively. Not only the composition ofcatalyst but also the temperature, hydrogen flow rate and water content ofreducing gases in the reduction procedure of catalyst influenced the nature of the ystal of Ni(III) plaine and the catalytic activity. The most favorable reductiontemperature was ranged from 600 to 8000C.

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The relations between structure and catalytic activity of vanadium-chromium oxide for the liquid phase oxidation of acrolein have been studied. The reaction was carried out in a gas sealed system and the rate of oxygen consumption was measured. The three kinds of binary oxide catalyst were prepared by calcining (at 450 C) the pastes made from different combinations of raw materials, such as NH, VOs + Cr(NO3)3 e g H20, NH4VOg3 + Cr(OH3)enH2O and V205 + Cr203, and they were denoted as V-Cr-A, V-Cr-B and V-Cr-C, respectively (Table 1). The following results were obtained. According to X-ray diffraction (Figs.2 and 3), V-Cr-C consists of only V20s and Cr20s, however, besides these oxides, there are recognized two other structures in V-Cr-A and V-Cr-B. One of these which is clarified to contain VS ion by measuring ESR (Figs.3 and 6) was denoted as Y and the other as, X. By means of DTA, etc., Y was ascertained to decompose to vanadium pentoxide, structure X and chromium orthovanadate at about 800C (Figs.5, 7 and 8). IR spectra (Figs.4. and 8) suggest. that X contqins only the bonding of -V-O-Cr-, but both bondings of -V-O-Cr- and. -V-O-V- are included in Y. In V-Cr-C, only V20s is thought te be active and the activity of this species is considered to be diluted with Cr20s which is inactive. The activity for oxidation can be put in the following order V-Cr-A- V-Cr-B- V-Cr-C (Fig.1). Furthermore, a catalyst obtained by washing V-Cr-A with NH3 in order to remove V20s and therefore thought to be mainly cemposed of structure Y, showed higher activity than the original catalyst V-Cr-A (Fig.3 and Table 2). Consequently, it is concluded that the structure Y is mainly. formed in the catalyst prepared from NHaVOs + Cr(NO3)3.9 H20 and, as V205, it has large contribution to the activity of the V-Cr catalysts.

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The desensitizing phenomena of phenosafranine (1), 9-methylthiacarbocyanine (2), and 5, 5 -diphenyl-9-ethyl-oxacarbocyanine (3) have been examined in the emulsions composed of cubic and octahedral AgBr grains (-O.7 ). The desensitization by (1) was stronger in the cubic AgBr emulsion than in the octahedral one. On the other hand, the desensitizations by (2) and (3) were stronger in the octahedral AgBr emulsion than in the cubic one. From the measurement of the visible-range refiction spectra of the dyed emulsions, it was found that (1) did not form its aggregate in these emulsions. Therefore, aggregate mechanism for desensitization by dyes is not adequate for dye (1). The aggregate of dye (2) (H-aggregate)was more easily formed in the octahedral AgBr emulsion than in the cubic one, whereas the aggregate of dye (3) (J-aggregate) was easily formed both in the cubic and octahedral AgBr emulsion. Therefore, the dependence of the desensitization by these dyes upon the crystal habit did not correspond to the depe, ndence of their aggregate formation upon the crystal habit. These phenomena were interpreted from the viewpoints of the dependence of the photQgraphic effects of an electron trap ((1)) and positive hole traps ((2) and (3)) upon the nature of AgBr grains.

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A hysteresis of the polarization curve on increasing and decreasing current was observed on the caihodic reaction of dissolved Qxygen in alkaline solution at liquid flow-through porous carbon electrodes.lt was presumed that thishysteresis was due to the hydrogen peroxide yielded by the reduction of oxygen.The time dependence of polarization pot-en"tia-1 was ineasured at various censtant current densities and at the same time concentration of hydrogen peroxide was analyzed quantitatively by colorimetry. The polarization pgtejntiql became noblewith increasing the concentration of hydrogen peroxide.Then, the polarization curyes were examined in I N KOH, after adding the various concentrations of hydrogen peroxide. The current was proportional to the concentration of hydrogen peroxide (10-S to 10 i.mol/1)I Accordingly, the 6haracteristics of the cathodic reaction of hydrogen peroxide as an oxidant of a fuel cell were examined.
The porous carbon electrode is mechariically fragile to make its thigkngss be restricted., while the porous nickel eleetrode can cover this defect. Pt and Pd were a-dded as-ca-talysts by the immersion method. The amount of catalyst needed to obtain the better polarization characteris tics was less on the occasion of porousnickelelectrode than in case of porous carbon electrode.

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Anodic reaction of hydrazine and cathodic reaction of hydrogen peroxide have been studied in alkaline solution by liquid flow-through electrodes. Ateven a considerable low concentration of the reactants, good polarization characteristics were obtained, and their polarization characteristics can be easily controlled by the variation of flow-through rate and of their concentrations.
Discharge characteristics of a single N2H4-H202 fuel cell (porous nickel electrode 0.6 mm, thick, 5X5 cm2, Pt-Pd mixed catalyst) was improved by the quick removal of N2 and H2, or 02 gas yielded at the electrodes. In connection with this problem, dependence of the discharge characteristics on a uniformity of electrolyte flow in the electrodes and on the distance between the electrodes were examined. Abattery in which three single cells were connected in parallel was made to obtain the maximum power of 7 W at 0.5 V (93 mWIcm2, 187 mA/cm2).

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Five speeies of hydreus mQlybdenum trioxide were prepared under various conditions and investigated by DTA-TGA, X-ray diffractemetry, IR and NMR spectrometries to tsvet detailed infermations regarding structures and their thermal behaviers.
Three ef these five hydrous oxides were confirmed to be hydratesof trioxide (yellew dihydrate sample A, yellow monohydratet sample B and white menohydrate sample D). Sftinple A transformed te sample B at 105 C by liberating one moleeule of water. Sffmple B transformed to MoO3, having a rhombie crystal structure, (rhombie MoO3) at 165 C by liberating residual one molecule of water, Sample D alse transformed to rhombic MoO3 threugh amerpheus trioxide and hexagonal MeOs by elevation of temperetture.
The remaining two were comfimed to be trioxide(hydrous rhombic MoO3 sample C and hydrous hexagenal MoO3 sample E), Sample C, which had a rhombic crystal structure, was prepared by treating sample A with hot water at about 70 for several hours. It was gradually dehydrated by heating from room temperature to about 400 without any struetural transformation. Sample E, wbich. had es hexagonal erystal strueture, was prepared by the hydrelysis of ammonium parenmolybdmte in 2-3 mole acidic solution at about 70. It was also dehydrated by heating frem room temperature te abeut 400 without showing any change in structure. Transformation te rhembic MoO3 took plaee at 420-430. This hexagonal MoO3 was newly found meta-stable oxide.These twe oxides were considered te ceclude water in interstitial position of crystal lattice.

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Five speeies of hydreus mQlybdenum trioxide were prepared under various conditions and investigated by DTA, -TGA, X-ray diffractemetry, IR and NMR spectrometries to tsvet detailed infermations regarding structures and their thermal behaviors.
Th-ree ef these five hydrous oxides were confirmed to be hydrates of trioxide (yelEew dihydrate sample A, yellow monohydratet sample B and white menohydrate sample D). Sftinple A transformed te sample B at 105 C by liberating one moleeule of water. Sffmple B transf6rmed to MoOg, having a rhombie crystal structure, (rhombie MoOa) at 165 C by liberating residual one mQlecule of water, Sample D also transformed to rhombic MoOg threugh amerpheus trioxide and hexagonal MeOs by elevation of temperetture.
The remaining two were comfirmed tobetrioxide hydrous rhombic MoO3 sample C and hydrous hexagenal MeOs sample E, Sample C, which had a rhombic crystal stru6ture, svas Rrgpa.red by tre-ating sample A with hot water at about 70K fer several hours.lt was gradually dehyclrated byheating from room temperature to about 400C without any struetural transformation, Sgemple E, which had a hexagonal erystal strueture, x, vas prepared by the hydrelysis of pampatonium parenmelybdmte in 2N3 mole eseidic solution at about70eeC, lt wMs ulso dehydrated by heating frem room temperature to about 400C without showing any change in stiucture. Transfermthtion te rhembic MoOs toek plaeeat420di-w i30 C, This he agonal MoOi was newlyfound meta-stable exide, These two oxides were eonsidered to ceclude water in interstititil position of crystal lattice,

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Synthesisof anhydrous Na-Huor-hectorite[Na1/3Mg2(2/3)(Si4O10)F2](1)was undertaken and its formation was confirmed. It was found that the swelling inclinations of(1)are Iarger than those of Na-taenio1ite(NaMg2Li(Si4O10)F2)(2). The three-layer hydrated state, 18.82A phase, is observed for(1)and so-called indefinite swelling seems to occuL It seems that such larger hydration properties of (1)can be attributed to the decrease of layer charge and the increase of interlayer vacancies. It is also found that the interlayer Na ions in(1)are base exchangeable.

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Synthesis and spectral properties of copper(ll)halide complexes withquinoxaline N-exides, N, N -dioxides and their derivatives have been investigated. Most of the obtained complexes were 2:1 complexes, while quinoxaline 1, 4-diexide and 2-methyl-3-phenylquinoxa1ine 1, 4- dioxide formed 1:1 complexes, Far infrared spectral analyses indicated that Cu-Cl stretching frequencies appear at 270v350 cm i, and Cu-Br frequencies at 226"v264 cm-w i. For the copper(E) halide-quinoxaline N, N -dioxides complexes the Cu-O stretching frequencies were observedin the range 329rv419 cm-i; however, omplexes of quinoxaline N-oxides (except that of 3-phenylquinoxaline 1-oxide) did not show any Cu-O frequencies.
The diffuse reflectance spectra of copper halide-quinoxaline N, N -dioxides complexes showed 3 bands in the region of 450.v900 nm. The d-d transition bands of these complexes appear at much longer wavelengthes (790.v900 nm) than those of the quinoxaline N-oxides complexes.
Furthermore, the in, frared spectra of quinexaline N-oxides and N, N -dioxides, and 14 kinds of their 2- and 2, 3-substitUted derivatives were measured. Their characteristic N-O stretching frequencies were observed in the region of 1280N1380 cmewi, and they were scarcely shifted by the hydrogen bond formation caused by addition of MeOH to their solutions in non-polar solvents.

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The complexes of N-(2-pyridylmethyl)-2-(dimethylamino)-acetamide(pdgH), M(pdg)XenH, O (M=Pt, Pd, Ni, Cu; X=Cl, Br, NCO, NCS, CIOs, 1/2 SO), were studied by means of magnetic moments, and infrared, electronic and NMR spectra (Tables 2 v5). The terdentate 1igand coordinates with deprotonated amide-N, pyridine-N, and amino-N atoms (Fig.1), The pletinum, palladium aRd nickel complexes arediamagnetic and square-planar, while the copper complexes have normal magnetic moments and their structure is a tetragonally distorted octahedron.
The trans-influence of the amide-N atom in infrared spectra Iis estimated to be as strong as the sulfide-S atem (Table 3). The chemical shifts of ligaind-hydrogens in thecomplexes vary with both anions and metal ions (Table 5 and Fig. 4) and, the ha16gen-dependent part of the chemical shifts of the pyridine ring 6-H is interpreted as arisin-g -fro, rp -sp-atial prowding between the hydrogen and halogen atoms.The oxygen atom ef the ampde groUp whosenitrogen is eoordinated to a metal ion under depretonatien has a slightlYts kkl, e.s ab.i lity of coordination than thatof a free acid amide. The nature of acid amide, groups aliphatic or aromatic, isreflected on electronic spectra, espeeially on those of the palla, dium and L platinum complexes.

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To study the behaviors of trace elements in shells during the process of fossilization, alumihum, titaRium and vanadium, containing in shells belonging to Pelecypoda colleeted from Miocene, Pliocene, Pleistocene and Recent deposits in the northeastern Japan, were determined by nondestructive neutron activation analysis.
The samples were irradiated in the TRIGA Mark ff Reactor of Rikkyo University (thermal neutron flux5*10ii n/cm2/sec)for 3 min. After coo1ing for 3 min, r-rays of 2sAl, Ti and S2V were measured, for 5 min using a 4096 channelGEOSCIENCE pulse height analyzer and a ORTEC Ge(Li) detector (effective volume 50ml).
The contents of aluminum, titanium and vanadium in Recpnt she11s havebeen found to correlate with the crystal-form of calcium carbonater and the she"structure: each content of the three elements in calcite type shells with foliated structure was higher than that in aragonite type shells and calcite type shells with homogeneous or complex prismatic structure.
Although the contents of aluminum, titanium and vanadium in fossil shells generally increased with increasing age contrary to the decrease in residual organic matters in shells, the pattern and the degree of increase changed with variation of the shell structure and the crystal-form of calci um carbona.te. Q, n the other hand, the V/Al ratio of fessil shells seemed to increase in Proportion to that of the environmental sediments, These results suggested that, aluminum, titanium and vanadium in fossil shells were supplied from the surrounding sediments during the progress of fossilization.

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The fact that the high-frequency po!arogram consists of the, positivesign wave (the wave of the positive rectification effect) and the negative sign wave (the wave of the negative rectification effect) being perceived, the absolute ratio of these two wave heights has been adopted as an index of the wave-shape. The present paper demopstrates the variation of the polarographic wave-shape with respect to frequency.
In case of transfer coeMcient (a) was more than O.5, the wave-shape of high-frequency polarogram shows that the positive rectification effect incrqases as frequency increases. Whereas if transfer cQef cient isless than, 0.5, the wave-shape of high-frequency po1arogram shows that the negative rectification effect incrcases according to the increase of frequency. The absolute ratio of the height of the positive sign wave (i...) to the height of the negative sign wave, (im ig), (imaxlimin) or (imin/imax), shows the linear relationship with regard to the square root of frequency (Fig. 7, 8).
Although thedependence of the wave-ShaPe variation on the electrode process with respect to frequency is complicated, it can generally basserted that the positive rectification effect becomes more remarkable as a indreases(, a 0.5)in the system where X(=wDo)is less than 10 (Fig. 9).
Sequential separation of multi-elements systemcould be attained by the ingenious application of the frequency dependence of each e!ectrolysis system.

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It was found that base-catalyzed Ia-elimination of ethyl 19-acetoxy-a-nitrocarboxylates (2) (threo : erythro = 70: 30) and ethyl a-acetoxy-I3-nitrocarboxylates C 5 J (threo erythro =50 : 50) gave a mixture of geometric isomers ((Z)-isomer (E)-isomer=70 : 30) of ethyla-nitro-a, - unsaturated carboxylates C313 and almost pure (E)-isomer of ethyl I -nitro--c, j -unsaturated carboxylates C6, respectively.
Irradiation of (E)-C 6 J with UV-light gave (Z)-C 6in ca. 50% yield.
From these results, it was deduced that base-catalyzed -elimination of C2J proceeded by E 2-trans elimination, while that of (5) by E 1 cB via the corresponding nitronate carbanion.

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The thermal addition of methyl acrylate (2) to rnyrcene (1) yieided a (2:3) mixture of two methylacrylate addtrcts, they were is61ated by gas, chromatography (GLC) and were determined to be 1-methoxycarbonyl-3-(4-methyl-3-pept.enyl)-3-qyclohexene, (4), and 1-methoxycarbonyl- 4-(4-methyl-3-pentenyl)-4-cyclohexene (7), , respectively, on the basis of their NMR spectral, data.
On the other hand the thermal addition of acrylaldehyde (3) to tu(1) also afforded a (2:3) mixture of two acrylaldehyde adducts, which were isdlated by GLC and were determined to be 1-formyi-3-(4-:methy1-3-pentenyl)-3-cyc1ohexene(5), and 1-formy1-4-(4-methy1-3-pe:ntenyl)- 4-cYclohexene(8).
The structures were confirmed on the basis of comparisons of their reduction products- with authentic samples of 1-hydroxymethyl-3-(4-methyl-3-pentenyl)-3-cyclohexene-(6) and 1-hydroxymethyl-4-(4-methyl-3-pentenyl)-4-cyclohexene (9).
(4), (5), (7), and (8) had a fresh wood like odor and also (6), (9) and esters of (9), which was derived from saturated lower fatty acids had a mild flowerly odor,

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The reactions of benzoic anhydride with excess cupric oxide are carried out in cyclohexane as an inert solvent at several temperatures for 1 hour.
The conversion of benzoic anhydride into a copper benzoate, which is different from the we11-known copper(I)or(II)benzoates, was determined by three methods(solvent extraction, elementary analyses and hydrolysis) which showed the consistent results (20.9 mol %o, 27.3 mol % and 23, 4 mol% respectively at 240eC, 1 hr).An increase in conversion was observed at temperatures higher than 240eC. The X-ray diffraction diagram of the product containing the above copper salt differed from those of cupric oxide, cuprous benzoate and cupric benzoate.

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New rhodium-acrolein complexes were obtained by the reaction of bis(cyclooctene)chloro, rhodium, [RhCl(CsHM)2]2 (1), with acrolein in the presence of 1, 2-bis(diphenylphos. phino)ethane (DPE) or ev, adipyridy1 (Dipy). Reaction with DPE gave a yellow crystalline. complex, Rh(COCI) (CH2=CH2) (CH2=CHCHO) (DPE) (2), which was presumed to have Rh-COCl bonds. (2) reacted with triphenylphosphine to give RhCI(CO) (PPh3)2 evolving ethylene gas. Red crystalline complex, [RhCl(DPE)]2, was obtained by recrystallization of -(2) tr. oAm.5cetone or h6t benzene. By use of Dipy instead of DPE, . a brown powder complex, RhCl (CH2=CHCHO)2 (Dipy) (3), was obtainedl The same complex (3) was also obta. ined by tT??@feaction of rhodium-acroleitn complex, RhCl(CH2=CH2) (CO) (CH2=CHCHO), with Dipy. However, the reaction of rhodium-acrolein complex with DPE did not yield the abovet copaplgx (2), but RhCl(DPE)2 or [RhCl(DPE)]2. These rhodium-acrolein-complexes-gatalyged. th e forination of diethyl ketone and ethyl vinyl ketone from acrolein, carbon monoxide and ethylene in low yield.

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The oxygen-containing functional groups and their contents in pyridine extracts prepared from a series of twelve Japanese coals were investigated toobtain some insight into their structures.
The estimation of the oxygen-containing functional groups (-OH, C=O, COON) in pyridine extracts was made by chemical methods which were applied previously to parent coals. The variation of thecontents of the oxygen-containing functional groups in pyridine extracts with respect to the carbon contents of parent coal was compared with those of parent coals. It was found that, in the case of relatively lower carbon content of coal, the contents of the hydroxyl and carbonyl groups in pyridine extract were lower than those of parent coals. As the coalification proceeded, the difference in thecontents between the parent coals and pyridine extracts diminished to disappear approximately at about 80% carbon or thereabouts.
It is to be mentioned that, in the proton NMR spectra of the pyridine extract of coal, the signals at c 3. 5to 5. 0 are assigned to the aliphatic hydrogens at the a position to the oxygen atom in the alkyl ethers. It may be concluded on this basis that the unreactive oxygen groups such as dialkyl and alkylaryl ethers are not important in coal andcoal derivatives with the exception of Ishikari peat pyridine extract which has the lowest carbon content. Therefore, it can be assumed that almost all unreactive oxygen functions in coal consist of heterocyclic or diphenyl ether types. By considering the results of structural analysis of aromaticity f in parent coal and their pyridine extracts, it can also be concluded that the hydroxyl groupsconsist of phenolic group.
Moreover, in the fraction isolated by various solventsfrom Sumiyoshi coal, the content of oxygen-containing groups was correlatedwith the character of these structures, especially with aromaticity. The conclusionsimilar to the one obtained above was found to hold true for the structure of the hydroxyl and unreactive oxygen functions in solvent fractionation products.

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Naphthalene was polymerized by the use of anhydorous aluminum chloride without solvents and the relation between the chemical structure of product and the reaction condition was examined.The reaction was curried out at 90, -v1600C for O.5.v2.0 hours with the molar ratio of anhydrous aluminum chloride to naphthalene of O.5 v2. 0.
The yield of polymerized product increased to more than900/e with increasing reaction temperature, reaction time and the amount of AICI3,
Based on the observed similarity in the IR and NMR speetra of resin and asphaltene fracge tionS of the products, it is suggested that their structural features are qualitatively similar.Moreover, it was found that the resins and asphaltenes obtained under various condition have quite similar average molecular weightof 300 to 370, and 410 to 520, respectively.This indicate that, on an average, 2.3N2.9 naphthalene units for resin and 3.2, y4.1 naphthalene units for asphalteneare present.
Thus the products consist of mixture of a greater part of aromatic and smaller part of alicyclic component.
Analysis- of IR spectra revealed that the products with more than three units of naphthalene consist of componentsbonded at the 2- and 6-position of naphthalene nucleus.

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Naphthalene was polymerized by the use of anhydrous aluminum chloride-cupric chloride at a reaction temperature of 90 C without solvent.
The polymerization prQductwas separated into five fractions(No, 1.to No. 5) by extraction with a series of binary solvents consisting of n-hexane and benzene.
The Product yield of polymeriz.ation of naphthalepe was a.bout 40 9% on the, basis of raw naphthalene. Fraction No. 1 soluble in n-hexane was obtained in abbut 400/oyield based on the total product. The added yield of fraction No.1 through No.3 was about 90 /e of the product. It is suggested that the product had a relatively low average degree of polymerlzation.
The average molecular structure of each fraction was estimated by the average moleculat weight, gel permeation chroMatography, elementary analysis, IR-, UV- and NMR-spectra.
IR- and NMR-spectra showed that product contained some aliphatic struqtures in addition-, to. the aromatic structure, Moreover, the aliphatic structure was found to contain a cycloparaffinic structure.
The results of structural analysis of each fraction are as follows. (1) With the descending order of fraction, the average molecular weight increased from 260 for No. 1 to 900 for No.5 and the aromaticity (A) of the fraction a1so showed an increase. (2) Since the numbers of the aromatic carbon (C.) increased gradually, the degree of polymerization of naphthalene was considered to increase with the descending order of fractions.
In summary the polymerization product was fractionated to a considerable extent byil the. present fractionation methodwith binary solvents.

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When an alcohol was oxidized in the presence of carboxylic acids, the rate constant of autoxidation, kI 2kD112, remarkably decreased and the extentof retardation was in dependent of the acidity of carboxylic acid except p-nitrobenzoic acid. The k/(2k)1'2 of autoxidation of 1-phenylethanol in the presence of0. 10 mol/l of any substituted benzoic acids presented the identical value, but extremely small value in the presence of p-nitrobenzoic acid. The k/(2k) 2 ofautoxidation of 1-phenylethanol in the presence of nitrobenzene was smaller thanthat in the absence of nitrobenzene.
The k/(2k)112 of autoxidation of an alcoholin the presence of phthalic acid, which subjected to form an intramolecular hydrogenThond, was greater than that in the presence of isophthalic acid, which was difficult to form an intramolecular hydrogen-bond.
The k/(2k)112 of hydroperoxyl radical in the autoxidation of 1, 4-cyclohexadiene decreased by the additionof acetic acid. When an aichohol was oxidized in the presence of 0. 20 mol/l 1, 2, 3, 4ttrahydro-1-naphthylhydrOperOxide, k I(2k) 2 was not affected by acetic acid.
It was suggested that carboxylic acids deactivated the hydroperoxylor a-hydroxyperoxyl radicals due to hydrogen-bonding but not alkylperoxyl radical. And it was presumed that a nitro group took part in the chain reaction and decreased the k/(2k) 2 in the autoxidation of alcohols.

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The behavior of photofading, of some azodisperse dyes containing nitr, group has been examined on polyester and o n polyamide films, The contributionof nitro group on the an, 4-nitro-4-hydroxy, malous photofading, of thesedyeswas discussed, 4rNitro-2 -hydroxy-4-, 4-nitro-2, , 4-dihydroxy-and 4-nitro-4-N-biscyan, ethyl in, az, benzenes, n p, lyamide fade It is observe thst there by light easier th he corresponding P ed deri is a correlation between the basicity of a dye and its sensitivity to the anomaleus photofading. Anomolous fading of a dye proceeds easily when it is less basic, and 4-nitro-4 -N, N-diethylaminoazobenzene dp. es not show the c, . haracter. The spec3. fioc anomqlous fading of 4-nitroazobenzenes on polyamide may be explained by the assumption that the nitro group can be photoreduced to amino group prior to photooxidation of azo group to azoxy group.2-Nitroazobenzenes on polyester and on polyamide fade by light much more easily than the corresponding 4-nitro derivatives. In anaerobic coRdition, 4-nitroazobenzenes are more resitant to fading than that in normal condition, however, the fading of 2-nitro-azobenzenes does not change practically in both conditions. The anomalous fading of 2-nitroazobenzenes is position specific and may be explained by the assumption that intramolecular photo-oxidation of azo group to azoxy group Proceeds exc usively by 2-nitro group. The behavior of fading of 2, 4-dinitroazobenZeneS has also been examined and discussed.

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Leaves of the sesquiterpene tree3, one kind of camphor tree, were extraeted with acetone. The extract, after concentration, was treated with hexane and the hexane solution was steam distilled in order to remove the volatile substances. The residue was extracted with hexane and, after concentration, was subjected to chromatography on an alumina column (selvent: n-hexane containing 200/e ethylacetate) and then on a siliea gel column (solventin-hexane cpntaining 150/o ethylaeetate), to isolate 9-oxenerolidol (1), cis- and trans-3, 7, 11-trimethyldo- decq-1, 7, 10-trien-3-ol-9rt-one (2), (3), 9-oxofarnesol (4) and its acetate(5).
The structure of each. go-mpoynq was tested by spectral qpd chemical analyses. The stereochemistry of 9-oxonerolidol, which was a major compound was determined as in (1) in relation to (+)in-nerolidol.

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Poly(m-phenyleneisophthalamide) films were drawn and heat-treated inglycol solution of N, N-dimethylformainide or N, N-dimethylacetamide, and the fine structure and mechanical properties of thus treated films were investigated, comparing them with those treated in aqueous solution.
It was found that filmscould be drawn in N, N-dimethylformamide solution at lower temperature and at lower concentration than in aqueous solution. Improvement of orientation, initial modulus and tensile stress at break by drawing or heat-treatment in glycol solution was of similar extent to those in aqueous solution, but the former solution was slightly more effective for improving the elongation at break and crystallinity than the latter.
In order to evaluate the degree of crystallinity and orientation, the amorphous X-ray diffraction pattern was determined and the intrinsic birefringence of poly(m-phenyleneisophthal-amide) was estimated; and the finestructure of films was discussed in more detail from the changes in the degree of crystallinity and orientation.

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The catalytic cycle of the polymerization of 2, 6-xylenol catalyzed by the copper-pyridine complex is divided into four elementary processes, the coordination of the substrate(1), the electrontransfer from the substrate te the cupric ion (k), the dissociation of the aetivated substrate (kd) and the reoxidation of the catalyst (ke). The rate constant of each elementary reaction was determined by means of the stoppedfiow spectrophotometric study of the copper complex, and the detailed mechanism of the catalysis was discussed. From the comparison of rate constants (Table 1), the process involning, either k. or kd was considered to be the ratedetermining step but the latter could not be measured in the present procedure. It was found that the oxygen molecule was involved in the cupric substrate omplex, promoting the k. process. The rate constants were affected by the components of the solvent. Except for a few cases where solvents having coordinating ability are used, k and ke increased and ke decreased with the increasing solvent polarity.

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The polymerization of vinyl monomers by the system of ferrocene (Fc)and carbon tetrachloride (Cptb14) was studied in the dark.lt was found that methyl methacrylate (MMA) and acryldnitrile (AN) can be polymerized without photoirradiation, while styren, e (St) was not polymerized under these conditions.
Thepolymerization Qf MMA by the Fc/CC14 system in the dark was also. investigatedkinetically, using benzene as a solvent. And the following equation was obtained:
R =const. [Fc]O, 6[CC14]e, 5[MMA]1, 5
This resu1t agrees with those of the usual photopolyrnerizations. Polymerization cpnversions decreased with hddition ofwater.The polymerization is assumed to proceed through a freeradical mechanism.The apparant overall energy of activation was estimated to be 13.O kcal/mol.

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The radical polymerizations and copolyrnerizations of 2, 4, 6-tribromophenyl acrylate (TBPA), pentabrornophenyl acrylate(PBPA)and 2, 4, 6-tribromophenyl methacrylate (TBPMA) were investigated. TBPA and PBPA were .easily polymerized in the presence of ev, al-azobisisobutyronitrile, but TBPMA was hardly homopolymerized (Table 1). From the results of their copolymerizatio.ns with styrene (M2) at 600C (Fig.1), the following copolymerization parameters were obtained (Table 2):
TBPA and PBPA (Ma):ri=O.10, r2=O.20, Qi=1.03, ei=1.18
TBPMA(Mi):ri=0.20, r2=O.15, Qi=1.48, ei=LO7
It was also found from the results of the copolymerizations of TBPMA with styrene or methyl methacrylate (M2) in substituted benzene solvents (Table 3) that the copolymerization parameters changed with solvents used: 1/ri increased with increase in electron density of benzene nucleus of the solveints, while 1/r2 was almost unchanged. These results might be explained by assuiming interactions between the tribromophenyl nucleus of TBPMA and thebenzene nucleus of the solvents.

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2, 6-Xylenol(XOH) was oxidatively polymerized by the Cu(II)-partially-quaternized poly (vinylpyridine) (QPVP) complexes in a homogeneous dimethylsulfoxide (DMSO) solution, and the electrostatic effects of the Cu-QPVP complex on the atalytic activity were discussed. The Cu-QPVP complex has a chelate structure in DMSO. The rate of polymerization of XOH by the Cu-QPVP catalyst was larger than that of the Cu-pyridine(Py) or the Cu-Poly(vinylpyridine) (PVP) catalyst. The results of the measurement of kinetic constants, the neutral salt effects and the infiuene of the monomer species, indicate that the higher activity of the CuQPVP catalyst was ascribed to the electrostatic action of the Cu-QPVP complex as a polycation. Moreover, the Cu-QPVP complex showed the higher catalytie activity when the degree of quaternization of QPVP was about 20-50. The catalytiactivity tends to become larger as increasing the degree of polymerization of QPVP.

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In order to obtain reactive ultraviolet absorbers possessing excellent fastness to waShing, phenyl methacrylate and naphtyl methacrylate were prepared and grafted onto cotton fibers by various initiators. The effects of ultraviolet light irradiation upon tensile strength were examined. It was found that the tensile strength of grafted fibers did not decrease when ultraviolet light was irradiated for many hours, if these monomers were grafted more than about 13 using ceric ammonium nitrate as initiator. Infrared spectral studies of the irradiated fibers confirmed tha t phenylester linkages in the grafted chains were converted to o-hydroxyphenylketon structure upon ultraviolet irradiation, which might enhance the ultraviolet protectiveproperty.

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By use of the emulsions composed of innert gelatin and octahedral or cubic silver bromide grains (about O.7pt), effects of sulfur and gold sens, itizations have been examined on the emission processes at liquid N2 temperature and photographic processes of the silver bromide grains. Both sulfur and geld sensitizations increased the photographic speeds, and decreased the emission intensities of both octahedral and cubic grains. This result has been interpreted by the view that both sulfur and gold sensitizations provide electron traps at the grain surfaces.

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The rearrangement scheme of potassium salicylate (SA-K) to p-hydroxybenzoic acid (POB) in a stream of N2 was clarified by microthermal and UV analyses.
In this paper, the effects of inert or active gases of atmospheric and elevated pressures which. are commonly used in this rearrangement was been investigated, The previously found rearrangement scheme, proceeding from SA-K to POB via 4-hydroxyisophthalic acid as a reaction intermediate, has been shown to hold for the rearrangement at elevated gaseous pressure.

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1-Methyl-4, 5-imidazole dicarbonyl dichloride (1) was obtained in a high yield by the Teaction of 1-methyl-4, 5-imidazole-dicarboxylic acid with an excess of thionyl chloride or with a stoichiometric amount of phosphorus pentachloride. (1) reacted with methanol, phenel, methylamine, aniline and several diamines to give the corresponding esters, amides and polyamides. Further reaction of (1) with an excess pf phosphorus pentachloride gave 1-methyl-4-triehleromethyl-5-imidazole carbonyl chloride.

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Reactions betvieen styrene oxide an, d methylene bis(magnesium iodide) CH2(Mgl)2 (Z) obtained from methylene iodide and magnesium turnings were investigated. Styrene, allylbenzene, by the reaction paths of Eq. (5), Nof phenylcyclopropane was, detected in. the reaction mixture which might be expected to be formed via the addition of the gem dimagnesium reagent to the epoxide followed by the a, r-elimination from the, adduc-t, (2). On the other hand, 1, 2-dibiroinoStyrene gave phenylcyclopropane on the treatment with. the gem-dimagnesium reagent (Eq. ( 2 )).

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Geometric isomers of 2, 6-dimethyl-2, 6-octadiene and ocimene were obtained from myrcene by the, hydrogenation and isomerization reaction using pentacyanocobaltate(g) as a catalyst. In the case of alloocimene, 2, 6-dimethyl-2, 4-octadiene was obtained. This octadiene was no more hydrogenated From these resglts, the reactivity of the conjugated double boad ih these reactions was discussed.

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The catalytic activity of the copper-pyridine comPlex on the, polymerization of 2, 6-xylenol was studied in var-ious solvents which, t were classified into two groups from the results in Fig.1 and Fig.2. One is composed of pyridine and an amphiprotic solvent, . and the other pyridine and an apretic solvent. In the former, the minimum catalytic activity appears at the intermediate composition, and this seems to be due to the ehange on the complex compdsition. From, the kinetic data it is suggested that the rate-determining step, of the polyn terizatien is the electron-transfer(k3) or the dissociatien of the activated substrate (kd). In benzene the high eatalytic activity of Cu-Py is due to the effect of the activation entropy.

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P-(2-Pyrrolylmethyleneamino) styrene(PIS) which is a monomer-ligand with two coordination sites was synthesized from p-aminostyrene and 2-formylpyrrole. The copolymerization parameters, Q and e values, of PIS were 2.8 and -1, 2, respectively. The large values of 2 and e are assumed to be due to the large r-conjugated system and excessive r-electrons of pyrrole ring. A yellowish green and insoluble polymer-chelate was synthesized from tetrahydrofuran solutions of PIS-St copolymer, and of Co(II)Cl2. The formation of polymer-complex was determined by IR spetra and. elemental analyses.

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It has been .shown that solid state sulfur is chemically activated or polymerized by irradiation with light. As a further example, silver-sulfur system is demonstrated in the present paper.The sulfurization of silver was accelerated by irradiation with light.
Electron microscopic analysis showed that a por6us layer formed at the interface between silver and Sulfur. The porosity depended upon the rate of sulfide formation.

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Colored materials which differed from the azo dye were formed, when the photocoloration systems consisting of diazonium salts and dye bases, such asstyryl bases and ind61e groups, were exposed to light.
The colored material producced from diazonium salt and 4-(p-dimethylaminostyryl)quinbline was identical with the dye from carbon tetrabromide and 4-(P-dimethylaminostyryl)quineline in the free radical-photography. The colored material formed in the diazonium salt-indole system was, different from the dye formed in the carbon tetrabromide-indole system.

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